CZ60198A3 - 2-cyklohexan-1,3-dionbenzoylderiváty - Google Patents
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- C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
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- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
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- C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
- C07D333/62—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
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- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
- C07D333/62—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero ring
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- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
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Description
2-cyklohexan-1,3-dionbenzoylderiváty
Oblast techniky
Tento vynález se týká nových benzoylderivátú s herbicidními účinky, postupů výroby těchto benzoylderivátú, prostředků které je obsahují a použití těchto derivátů nebo prostředků které je obsahují pro boj proti plevelům.
Dosavadní stav techniky
Z literatury jsou známy 2-aroylcyklohexandiony s herbicidními účinky, uvedené např. v EP 283261, EP 90262, EP 135191, EP 186118, EP 186119, EP 186120,
EP 319075, WO 9005712, WO 9404524, WO 9408988, J030528632 a JO
3120202.
Herbicidní vlastnosti těchto známých sloučenin jakož i tolerance kulturních rostlin vůči těmto látkám nejsou však zcela uspokojivé.
Proto bylo nutno hledat nové 2-aroylcyklohexandiony se zlepšenými vlastnostmi.
Podstata vynálezu
Byly nalezeny benzoylderiváty formule I,
kde jednotlivé substituenty mají následující význam:
L,M vodík, alkyl C1-C6, alkenyl C2-C6, alkinyl C2-C6, alkoxyl C1-C4, přičemž tyto skupiny mohou být případné substituovány jedním až pěti halogenovými atomy nebo alkoxyly C1-C4; halogen, kyanoskupina, nitroskupina, skupina -(A)m-S(O)nR1 nebo skupina
-(A)m-CO-R2;
Y skupina kterou tvoří C=O, C=N-R3, CR7-NR5R6, CR7OR8,
CR10R11, CR7SR8; 1,3-dioxanyl nebo 1,3-dioxolanyl substituovaný vodíkem nebo alkylem C1-C4; heteroatom ze skupiny kyslík, síra a dusík;
skládá se z řetězce (-CR12R13-), (-CR12R13-CR21R22-), vazba mezi X a Y může být nasycená nebo nenasycená;
A O, NR14;
m nula nebo jedna;
n nula, jedna nebo dvé;
R1 C1-C4 alkyl, C1-C4 haloalkyl nebo NR14;
R2 C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxyl nebo NR14;
R3 vodík, -NR9R4; C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkoxyl,
C1-C6 haloalkoxyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkinyl;
jednou až několikanásobně substituovaný fenyl, přičemž těmito substituenty mohou být C1-C4 alkyl, C1-C4 alkoxyl, C1-C4 haloalkoxyl, C1-C4 haloalkyl, halogen, kyanoskupina, nitroskupina;
jednou až několikanásobně substituovaný benzyl, přičemž těmito substituenty mohou být C1-C4 alkyl, C1-C4 alkoxyl, C1-C4 haloalkoxyl, C1-C4 haloalkyl, halogen, kyanoskupina, nitroskupina;
jednou až několikanásobně substituovaná benzoyloxyskupina, přičemž těmito substituenty mohou být C1-C4 alkyl, C1-C4 alkoxyl,
C1-C4 haloalkoxyl, C1-C4 haloalkyl, halogen, kyanoskupina, nitroskupina;
R4 vodík, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 alkinyl,
C=O-NR14;
jednou až několikanásobně substituovaný fenyl, přičemž těmito substituenty mohou být C1-C4 alkyl, C1-C4 alkoxyl, C1-C4 haloalkoxyl, C1-C4 haloalkyl, halogen, kyanoskupina, nitroskupina;
• · • ♦
| • · ·· ·· · · · · · · .····· ·· “θ'— ······· ·· ·· ·· jednou až několikanásobně substituovaný benzyl, přičemž těmito substituenty mohou být C1-C4 alkyl, C1-C4 alkoxyl, C1-C4 haloalkoxyl, C1-C4 haloalkyl, halogen, kyanoskupina, nitroskupina; | |
| R9 | vodík, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 alkinyl, C=O-NR14; jednou až několikanásobné substituovaný fenyl, přičemž těmito substituenty mohou být C1-C4 alkyl, C1-C4 alkoxyl, C1-C4 haloalkoxyl, C1-C4 haloalkyl, halogen, kyanoskupina, nitroskupina; jednou až několikanásobně substituovaný benzyl, přičemž těmito substituenty mohou být C1-C4 alkyl, C1-C4 alkoxyl, C1-C4 haloalkoxyl, C1-C4 haloalkyl, halogen, kyanoskupina, nitroskupina; |
| R5, R6 | nezávisle na sobě vodík, C1-C6 alkyl, C2-C6 alkenyl, C1-C4 haloalkyl, C2-C6 haloalkenyl, C1-C6 alkoxyl, C1-C6 haloalkoxyl; jednou až několikanásobně substituovaný fenyl, přičemž těmito substituenty mohou být C1-C4 alkyl, C1-C4 alkoxyl, C1-C4 haloalkoxyl, C1-C4 haloalkyl, halogen, kyanoskupina, nitroskupina; jednou až několikanásobně substituovaný benzyl, přičemž těmito substituenty mohou být C1-C4 alkyl, C1-C4 alkoxyl, C1-C4 haloalkoxyl, C1-C4 haloalkyl, halogen, kyanoskupina, nitroskupina; |
| R7 | vodík, C1-C6 alkyl,C1-C4 alkoxyl, C1-C4 haloalkyl, C1-C4 haloalkoxyl; případně substituovaný fenyl, přičemž jako substituenty mohou být jeden až tři halogeny, C1-C4 alkyl, C1-C4 alkoxyl, C1-C4 haloalkoxyl, nitroskupina; vazbu mohou tvořit R7 a R21 nebo R7 a R23 nebo R7a R21; |
| R8 | vodík, C1-C6 alkyl, C1-C4 halogenalkyl, substituovaný fenyl, přičemž těmito substituenty mohou být C1-C4 alkyl, C1-C4 alkoxyl, C1-C4 haloalkoxyl, C1-C4 haloalkyl, halogen, kyanoskupina, nitroskupina; substituovaný benzyl, přičemž těmito substituenty mohou být C1-C4 alkyl, C1-C4 alkoxyl, C1-C4 haloalkoxyl, C1-C4 haloalkyl, halogen, kyanoskupina, nitroskupina; |
···· «·· · · • · ····· ♦ · • · ·· ·· ·· ···
A ······· — 4 “ ······· ·· ·· ··
R10,R11 nezávisle na sobě vodík, C1-c|e alkyl; fenyl případné substituovaný jedním až třemi halogeny, C1-C4 alkylem, C1-C4 alkoxylem, C1-C4 haloalkoxylem, nitroskupinou; vazbu mohou tvořit R10 a R12 nebo R10aR23nebo R10a R21;
R12,R13 nezávisle na sobě vodík, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxyl, C1-C6 haloalkoxyl; případně substituovaný fenyl, přičemž jako substituenty mohou být C1-C4 alkyl, C1-C4 alkoxyl, C1-C4 haloalkoxyl, C1-C4 haloalkyl, halogen, kyanoskupina, nitroskupina;
R14 C1-C4 alkyl;
R21 vodík, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxyl, C1-C6 haloalkoxyl; případně substituovaný fenyl, přičemž jako substituenty mohou být C1-C4 alkyl, C1-C4 alkoxyl, C1-C4 haloalkoxyl, C1-C4 haloalkyl, halogen, kyanoskupina, nitroskupina;
R22 vodík, C1-C6 alkyl, C1-C6 haloalkyl, C1 -06 alkoxyl, C1-C6 haloalkoxyl; případně substituovaný fenyl, přičemž jako substituenty mohou být C1-C4 alkyl, C1-C4 alkoxyl, C1-C4 haloalkoxyl, C1-C4 haloalkyl, halogen, kyanoskupina, nitroskupina;
R23 vodík, C1-C6 alkyl, C2-C6 alkenyl, C1-C6 alkoxyl; případně fenyl nebo benzyl substituovaný C1-C4 alkylem, C1-C4 alkoxylem, C1-C4 haloalkoxylem, C1-C4 haloalkylem, halogenem, kyanoskupinou nitroskupinou;
Q v poloze 2 vázaný cyklohexan-1,3-dionový kruh formule II
II ······»
5“· ······· ·· ·· ·· kde
R15, R16, R18 a R20 představují vodík nebo alkyl C1-C4,
R19 představuje vodík, C1-C4 alkyl nebo skupinu -COOR14;
R17 představuje vodík, C1 až C4 alkyl, C3-C4 cykloalkyl, přičemž tyto skupiny mohou případně nést jeden až tři z následujících substituentů: halogen C1-C4 alkylthio nebo C1-C4 alkoxyl, nebo
R17 představuje tetrahydropyranyl-3, tetrahydropyranyl-4 nebo tetrahydrothiopyranyl-3, nebo
R17 a R20 vytvářejí vzájemnou vazbu nebo tvoří tří- až šestičlenný karbocyklický kruh, přičemž v případě, že Y = C=0, není X rovno NR23, jakož i zemědělsky využitelné soli sloučeniny I.
Sloučeniny formule la-le se získají tak, že sloučeniny formule II reagují s derivátem kyseliny benzoové formule III za vzniku benzoylderivátú formule la-le.
Schéma 1
I • ·
Ve výšeuvedeném schématu 1 znamená T v uvedených formulích halogen nebo OH a L, Μ, X a n mají význam uvedený dříve.
Prvním krokem tohoto sledu reakcí je acylace, která se provádí všeobecně známým způsobem např. přidáváním chloridu kyseliny formule III (T = Cl) nebo karboxylových kyselin III (T=OH) aktivovaných např. DCC (dicyklokarbodiimid) nebo jinými prostředky popsanými v literatuře, jako je např. trifenylfosfin/DEAD = diethylazodikarboxylát, 2-pyridindisulfid/trifenylfosfin, k roztoku nebo suspenzi cyklohexandionu II případné za přítomnosti pomocné báze. Reaktanty a pomocná báze se přitom používají v odpovídajících ekvimolámích množstvích. Podle okolností může být někdy výhodné použít nepatrný přebytek pomocné báze, např. 1,2 až 1,5 molámího ekvivalentu, vztaženo na II.
Jako pomocná báze jsou vhodné terciární alkylaminy, pyridin nebo alkalické uhličitany. Jako rozpouštědlo je možno používat např. methylenchlorid, dioxan, diethylether, toluen, acetonitril nebo ethylacetát.
V průběhu přidávání chloridu kyseliny je vhodné reakční směs chladit na teplotu 0 až 10°C, potom se reakce provádí při teplotě 20 až 100°C, zejména 25 až 50°C za míchání až do jejího skončení. Další zpracování se provádí běžným způsobem, např. vlitím reakční směsi do vody a extrakcí požadovaného produktu např. methylenchloridem. Po vysušení organické fáze a odpaření rozpouštědla je možno surový enolester bez dalšího čištění použít k další reakci. Příklady přípravy benzoylenolesteru cyklohexan-1,3-dionů jsou uvedeny např. v EP-A 186118 nebo US 4,780,127.
Přeměna enolesterů na sloučeniny formule la-le se provádí výhodně při teplotách 20 až 40 °C v rozpouštědle a za přítomnosti pomocné báze a s použitím kyanosloučeniny jako katalyzátoru.
Jako rozpouštědlo je možno používat např. acetonitril, methylenchlorid, 1,2dichlorethan, ethylacetát nebo toluen. Preferovaným rozpouštědlem je acetonitril.
* · • · · · · · ·· «······ ·· · · · ·
Jako pomocná báze jsou vhodné terciární alkylaminy, pyridin nebo uhličitany alkalických kovů, které se používají zpravidla vekvimolámím množství nebo v množství až do čtyřnásobného přebytku, vztaženo na benzoylenolester. Preferovanou bází je triethylamin ve dvojnásobném přebytku.
Jako katalyzátor se používají kyanid draselný, acetonkyanhydrin a trimethylsilylkyanid, zpravidla v množství 1 až 50 molárních procent, vztaženo na enolester. Přednostně se přidává acetonkyanhydrin, např. v množství 5 až 15, nejlépe 10 molárních procent. Příklady přeměny enolesterů katalyzované kyanidy jsou uvedeny např. v EP-A 186118 nebo US 4,780,127.
Zpracování reakční směsi se provádí známým způsobem např. okyselením reakční směsi zředěnými minerálními kyselinami jako např. 5%ní kyselinou chlorovodíkovou nebo sírovou a extrakcí organickým rozpouštědlem jako je např. methylenchlorid nebo ethylacetát. Čištění se provádí tak, že se extrakt vymývá chladným 5 až 10%ním roztokem uhličitanu alkalického kovu, přičemž konečný produkt přejde do vodné fáze. Po okyselení tohoto vodného roztoku se produkt formule la-le vysráží a znovu se extrahuje methylenchloridem nebo ethýlacetátem, extrakt se vysuší a nakonec se odpaří rozpouštědlo.
1,3-Diketony formule II, použité jako výchozí materiál, jsou známé a je možno je připravit známými postupy, popsanými např. v EP-A 71707, EP-A 142741, EP-A 243313, US 4,249,937 a WO 92/13821. Cyklohexandion a dimedon jsou komečné dostupné sloučeniny.
Benzoové kyseliny formule III je možno připravit následujícím způsobem:
Benzoylhalogenidy jako je např. benzoylchlorid formule III (T=CI) se připravují známým způsobem reakcí benzoových kyselin formule III (T=OH) s thionylchloridem.
Benzoové kyseliny formule III (T=OH) je možno vyrobit známým způsobem kyselou nebo bázickou hydrolýzou zodpovídajících esterů formule III (T= C1-C4 alkoxyl).
* · • ·
Meziprodukty formule III jsou částečně známy nebo je možno je připravit postupy uvedenými v literatuře.
Schéma 2
Rovněž je možno provést např. podle schématu 2 reakci aryithiosloučenin IV se substituovaným haloalkenylem podle J.Med.Chem. 1984, 27, 1516, se substituovanými alkinylkarboxylovými kyselinami podle J.Org. Chem. 1980, 45, 4611 nebo J.Am.Chem.Soc. 1983, 105, 883, substituovanými haloalkylkarboxylovými kyselinami podle Chem. Ber. 1925, 58, 1612 za přítomnosti báze jako jsou hydroxidy alkalických kovů, hydridy alkalických kovů nebo uhličitany alkalických kovů. Vzniklé sloučeniny V se cyklizují za podmínek Friedel-Craftsovy reakce za přídavku Lewisovy kyseliny nebo protonové kyseliny na sloučeninu VI. Jako Lewisovy kyseliny se používají především AICI3 nebo SnCI4, jako protonové kyseliny se používají zejména kyselina polyfosforečná a sírová podle Can.J.Chem.1981, 59,199; Chem.Ber. 1925, 58, 1625; Chem.Ber. 1926, 59,1074; Phosp. and. Sulf. 1984, 19, 31.
* · · ·
Thiochromenonkyseliny je možno připravit např. odštěpením halogenovodíku z 3halogenthiochromanonkyselin nebo např. reakcí substituovaných thiofenolkyselin se substituovanými estery α-alkyloctových kyselin za přítomnosti oxidu fosforečného podle Ann.Chem. 1964, 680, 40.
Arylthiosloučeniny IV je možno získat např. Sandmeyerovou reakcí z odpovídajících anilinů, které je možno připravit redukcí příslušných nitrosloučenin podle Organikum, 19. vydání 1992, 552ff.
V případě, že např. X je (-CR12R13-) resp. (-CR12R13CR21R22-), Y je C=O a T je C1C4 alkoxyl, je možno thiochromanonester resp. dihydrobenzothiofenester připravit podle schématu 2 alkylací arylthiosloučeniny IV za přítomnosti některé z dříve uvedených bází v rozpouštědle nebo ve vodě s halogenpropionovou kyselinou resp. halogenoctovou kyselinou a cyklizací získat sloučeninu VI.
Reaktanty a báze se přitomn zpravidla používají v ekvimolámích množstvích. Reakční směs se přitom míchá při tepolotě zpravidla 20 - 100°C, přednostně při teplotě 20-40°C. Zpracování reakční směsi se zpravidla provádí tak, že se reakční směs vlije do vody, vodná fáze se okyselí minerální kyselinou jako např. kyselinou chlorovodíkovou nebo sírovou a produkt se odsaje nebo získá extrakcí methylenchloridem nebo ethylacetátem, extrakt se vysuší a rozpouštědlo se odpaří. Získaný ester je možno použít bez čištění k další reakci.
Mícháním V např. v polyfosforečné kyselině při teplotě 40-140°C, přednostně při 70-100°C, nebo aktivací karboxylové kyseliny jejím převedením na chlorid kyseliny a mícháním s 2-6, přednostně 3,5 až 4,5 molámími ekvivalenty Lewisovy kyseliny jako je např. AICI3 nebo SnCI4 v rozpouštědle nebo mícháním se sírovou kyselinou nebo v sírové kyselině se získá podle známého způsobu zpracování, t.j. po přídavku vody s ledem a po odsátí produktu nebo jeho extrakcí z vodné fáze ethylacetátem nebo methylenchloridem, po vysušení extraktu a po odpaření rozpouštědla meziprodukt formule III.
• · · · · · · · · · v • · · · · · · · · · · • · ·· ·· · · ···· · ·· · · · · ··· ··♦ ···· ·· ·· ·· ··
- 10 V případě, že např. X je ethylenová skupina (-CR12=CR13-), Y je C=0 a T je C1-C4 alkoxyl, je možno thiochromenonester připravit např. reakcí arylthiosloučeniny s derivátem acetylenkarboxylové kyseliny ve vodě nebo v rozpouštědle při teplotě 0-140°C. Zpracování reakční směsi se provádí známým způsobem přídavkem vody a zředěné minerální kyseliny jako např. chlorovodíkové kyseliny. Produkt se získá buď odsátím nebo extrakcí methylenchloridem nebo ethylacetátem po vysušení extraktu a po odstranění rozpouštědla.
Meziprodukty formule III je možno dále funkcionalizovat reakcemi známými z literatury jako jsou redukce podle knihy Jerry March:“Advanced Organic Chemistry, 4. vyd., např. str. 91 Off, oximace podle Jerry March:“Advanced Organic Chemistry, 4. vyd., např. str. 934, 935, 1039, 1226, 405ff, převedení na iminy a aminy podle Jerry March:“Advanced Organic Chemistry, 4. vyd., ketalizace, alkylace, halogenace, eliminace a oxidace podle Jerry March:“Advanced Organic Chemistry, 4. vyd.
Kyseliny od 3-alkoxy-1,2-benzisothiazol-1,1-dioxidu nebo 3-alkoxy-1,2benzisothiazolu je možno získat z odpovídajících derivátů sacharinu nebo z 1,2benzisothiazolů např. reakcí s PCI5, POCI3 nebo reakcí s chlorem a alkoholem případně za přítomnosti pomocné báze jako je např. triethylamin, což je popsáno např. V US 4,571,429, Arch.Pharm. 1984, 317,807, US 4461901, US 450916, J.Med.Chem. 1986, 29, 359. Sacharinkarboxylové kyseliny je možno získat postupy známými z literatury podle Ann.Chem. 4327, 231, 1922, Chem.Ber. 13, 1554, 1980, Chem.Ber. 25, 1740, 1892, DE-OS 3607343, Německá přihláška patentu P 44 27 995.7.
Deriváty benzo-1,4-oxathiinových kyselin jsou zčásti známy, např. v J.Org.Chem.
1968, 33, 456 nebo je možno je získat např. reakcí odpovídajících fenolderivátú postupem podle Chem.Comm., 1975, 451, J.Org.Chem. 1974, 39, 1811,
J.Am.Chem.Soc 1954, 76, 1068 nebo kombinací např. substituční reakce halogensubstituovaných thiofenolových derivátů a dalších reakcí jako je např.
oxidace, redukce nebo adice podle J.Het.Chem. 1983, 20, 867.
···· · · · · · · · • · · ···· · - · · • · ·· e « ·· ··»· · ·· · · « · · · · ······· ·· · · ·· ··
Benzoové kyseliny formule III je možno získat i tak, že reaguje odpovídající bromnebo jodsubstituovaná sloučenina formule VII
Schéma 3
T
Y,L,M,X
OH, C1-C4 alkoxy mají význam uvedený drive za přítomnosti katalyzátorů obsahujcících přechodové kovy jako je palladium, nikl, kobalt nebo rhodium a báze s oxidem uhelnatým a vodou za zvýšeného tlaku.
Katalyzátory obsahující nikl, kobalt, rhodium a zejména palladium je možno přidávat v kovové formé nebo ve formě běžných solí, jako jsou např. halogenidy, např. PdCI2, RhCI3.3H2O, acetáty, např. Pd(OAc)2, kyanidy a pod. ve známých stupních mocenství. Rovněž je možno přidávat komplexy těchto kovů s terciárními fosfiny, metalalkylkarbonyly, metalkarbonyly, např. CO2(CO)8, Ni(CO)4, (PPh3)2Ni(CO)2, nebo komplexy těchto přechodových kovů s terciárními fosfiny. Tato posledně uvedená forma je preferována zejména při použití palladia jako katalyzátoru. Druh fosfinových ligandů je ve značné šíři variabilní. Je možno je znázornit např. následujícími formulemi:
R26 nebo ---(CH2)n---p <*26 r25^ R27 přičemž n je rovno 1, 2, 3 nebo 4 a substituenty R24 až R27 odpovídají nízkomolekulámímu alkylu, jako je např. C1-C6 alkyl, arylu, C1-C4 alkylarylu, jako • · je např. benzyl, fenetyl nebo aryloxyskupina. Jako aryl může být např. naftyl, anthryl a zejména případně substituovaný fenyl, přičemž je třeba dbát na to, aby substituenty byly inertní vůči karboxylační reakci, jinak je možnost jejich volby široká a zahrnuje všechny inertní C-organické zbytky jako jsoiu C1-C6 alkyly, např. methyl, karboxylové zbytky jako je COOH, COOM (M je např. alkalický kov, kov alkalických zemin nebo amonná sůl), nebo C-organické zbytky vázané přes kyslík jako C1-C6 alkoxylové zbytky.
Přípravu fosfinových komplexů je možno provádět známými způsoby, např. uvedenými v citovaných dokumentech. Vychází se např. z komerčně dostupných kovových solí jako jsou PdCI2 nebo Pd(OCOCH3)2 a přidá se fosfin, např. P(C6H5)3, P(n-C4H9)3, PCH3(C6H5)2,1,2-bis(difenylfosfino)ethan.
Množství fosfinu, vztaženo na přechodový kov, bývá zpravidla 0 až 20, přednostně 0,1 až 10 molámích ekvivalentů, zvláště preferované množství je 1 až 5 molámích ekvivalentů.
Množství přechodového kovu není kritické. Je samozřejmé, že z cenových důvodů se používají spíše malá množství, např. 0,1 až 10 molámích procent, zejména 1 až 5 molámích procent, vztaženo na výchozí látku II resp. III.
Výroba benzoových kyselin III (T=OH) se provádí reakcí s oxidem uhelnatým a minimálně ekvimolámím množstvím vody, vztaženo na výchozí látky VI. Voda jako reaktant může být zároveň použita jako rozpouštědlo, t.zn., že maximální množství vody není kritické.
V závislosti na druhu výchozích látek a na použitých katalyzátorech může být výhodné používat jako reaktant jiné inertní rozpouštědlo nebo používat jako rozpouštědlo bázi používanou pro karboxylaci.
Jako inertní rozpouštědla se mohou pro karboxylační reakce používat běžná rozpouštědla jako jsou uhlovodíky, např. toulen, xylen, hexan, pentan, ···· · · ♦ · · · · • · · ···· · · · ·
Í · ····*······· »— ·· · · · · ··· ······· ·· ·· ·♦ ·· cyklohexan, ethery, např. methyl-terc.butylether, tetrahydrofuran, dioxan, dimethoxyethan, substituované amidy jako je dimethylfomnamid, persubstituované močoviny jako jsou tetra-C1-C4-alkylmočoviny nebo nitrily jako jsou benzonitril nebo acetonitril.
Při preferovaném provedení tohoto postupu se používá reaktant, zejména báze, v přebytku, takže není třeba používat žádné další rozpouštědlo.
Bázemi vhodnými pro tento postup jsou všechny inertní báze, mající schopnost vázat jodovodík resp. bromovodík, který se uvolňuje při reakci. Jako příklad je možno uvést terciární aminy jako jsou terc.-alkylaminy, např. trialkylaminy jako triethylamin, cyklické aminy jako je N-methylpiperidin nebo N,N'dimethylpiperazin, pyridin, uhličitany nebo hydrogenuhličitany alkalických kovů, nebo tetraalkylsubstituované deriváty močoviny jako je tetra-C1-C4alkylmočovina, např. tetramethylmočovina.
Množství báze není kritické, zpravidla se používá 1 až 10, spíše 1 až 5 mol. Při současném používání báze jako rozpouštědla se toto množství zpravidla určuje tak, aby reaktanty byly rozpuštěny, přičemž z praktických důvodů se nepoužívají zbytečně velké přebytky, a to proto, aby se ušetřily náklady, aby bylo možno používat malé reakční nádoby a aby byl zajištěn maximální kontakt reaktantů.
V průběhu reakce se tlak oxidu uhelnatého reguluje tak, aby byl vždy zajištěn přebytek CO, vztaženo na VI. Tlak oxidu uhelnatého při laboratorní teplotě je zpravidla 1 až 250 bar, přednostně 5 až 150 bar CO.
Karbonylace se provádí zpravidla při teplotách 20 až 250°C, přednostně při 30 až 150 °C kontinuálním nebo diskontinuálním způsobem. Při diskontinuálním provozu se zpravidla pro udržení konstantního tlaku připouští oxid uhelnatý pod tlakem k reakční směsi kontinuálně.
Arylhalogensloučeniny VII používané jako výžchozí látky jsou známy nebo je možno je snadno vyrobit kombinací známých syntéz a podle dříve popsaných reakčních sledů.
• · ···· · *·· • · · · · · · · · · * · • · · · · · · · * · · · · · · · · · ·
Z hlediska cíleného použití benzoylderivátů obecné formule I přicházejí v úvahu následující substituenty:
L,M vodík
C1-C6 alkyl jako je methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1.ethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3dimethylbutyl, 3,3-dimethylbutyl, 1 -ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2trimethylpropyl, 1-ethyl-1-methylpropyl, nebo 1-ethyl-2-methylpropyl, zejména methyl, ethyl, 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1,1dimethylethyl a 1,1-dimethylpropyl
C2-C6 alkenyl jako 2-propenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2methyl-2-propenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 3-methyl-2-butenyl, 1methyl-2-butenyl, 2-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-4-butenyl, 3methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-2propenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-2-pentenyl, 2methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4pentenyl, 1,1 -dimethyl-2-butenyl, 1,1 -dimethyl-3-butenyl, 1,2-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl.-3.-butenyl, 2,3-dimethyl-2-butenyl, 2,3dimethyl-3-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-2-butenyl, 2-ethyl3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl a ethyl-2methyl-2-propenyl, zejména 1-methyl-2-propenyl, 1-methyl-2- butenyl, 1,1-dimethyl-2-propenyl a 1,1dimethyl-2-butenyl.
·· · · · · *·· ······· ·· ·· ·· ··
C2-C6 alkinyl jako je propargyl, 2-butinyl, 3-butenyl, 2-pentinyl, 3-pentinyl, 4pentinyl, 1-methyl-3-butinyl, 2-methyl-3-butinyl, 1-methyl-2-butinyl, 1,1 dimethyl-2propinyl, 1-ethyl-2-propinyl, 2-hexinyl, 3-hexinyl, 4-hexinyl, 5-hexinyl, 1-methyl-2pentinyl, 1-methyl-3-pentinyl, 1-methyl-4-pentinyl, 3-methyl-4-pentinyl, 4-methyl-2pentinyl, 1,1-dimethyl-2-butinyl, 1,1 -dimethyl-3-butinyl, 1,2-dimethyl-3-butinyl, 2,2dimethyl-3-butinyl, 1-ethyl-2-butinyl, 1 -ethyl-3-butinyl, 2-ethyl-3-butinyl, a 1-ethyl1 -methyl-2-propinyl.
C1-C4 alkoxyl jako je methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1methylpropoxy, 2-methylpropoxy, a 1,1-dimethylethoxy, zejména C1-C3 alkoxyly jako je methoxy, ethoxy, i-propoxy, přičemž tyto skupiny mohou být případně substituovány jedním až pěti halogenovými atomy jako je fluor, chlor, brom a jod, zejména fluor a chlor nebo C1-C4 alkoxyly, uvedenými dříve.
Výšeuvedená skupina -(A)m-S(O)nR1 znamená např.
C1-C4 -alkylthio jako je methylthio, ethylthio, n-propylthio, 1-methylethylthio, nbutylthio, 1-methylpropylthio, 2-methylpropylthio, a 1,1-dimethylethylthio, zejména methylthio;
C1-C4-alkylsulfinyl jako je methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, 1methylethylsulfinyl, n-butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl a 1,1 -dimethylethylsulfinyl, zejména methylsulfinyl;
C1-C4-alkylsulfonyl jako je methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, 1-methylethylsulfonyl, n-butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl, a 1,1-dimethylethylsulfonyl, zejména methylsulfonyl;
C1-C4-alkoxysulfonyl jako je methoxysulfonyl, ethoxysulfonyl, n-propoxysulfonyl,
1-methylethoxysulfonyl, n-butoxysulfonyl, 1-methylpropoxysulfonyl, 2-methylpropoxysulfonyl a 1,1-dimethylethoxysulfonyl, zejména methoxysulfonyl;
• · • ·
N-C1-C4-alkylsulfamoyl jako je N-methylsulfamoyl, N-ethylsulfamoyl, N-n-propylsulfamoyl, N-1-methylethylsulfamoyl, N-n-butylsulfamoyl, N-1-methyl propylsulfamoyl, N-2-methylpropylsulfamoyl a N-1-1-dimethylethylsulfamoyl, zejména
N-methylsulfamoyl;
N-C1-C4-alkylsulfinamoyl jako je N-methylsulfinamoyl, N-ethylsulfinamoyl, N-N-propylsulfinamoyl, N-1 -methylethylsulfinamoyl, N-n-butylsulfinamoyl, N-1 -methylpropylsulfinamoyl, N-2-methylpropylsulfinamoyl, N-1 -1 -dimethylethylsulfinamoyl, zejména N-methylsulfinamoyl;
Di-C1-C4-alkylsulfamoyl jako je dimethylsulfamoyl, diethylsulfamoyl, dipropylsulfamoyl, dibutylsulfamoyl, N-methyl-N-ethylsulfamoyl, N-methyl-N-propylsulfamoyl, N-methyl-N-1-methylethylsulfamoyl, N-methyl-N-1,1-dimethylethylsulfamoyl, di-1methylethylsulfamoyl, N-ethyl-N-1-methylethylsulfamoyl a N-ethyl-N-1,1 -dimethylethylsulfamoyl, zejména dimethylsulfamoyl;
Di-C1-C4-alkylsulfinamoyl jako je dimethylsulfinamoyl, diethylsulfinamoyl, dipropylsulfinamoyl, dibutylsulfinamoyl, N-methyl-N-ethylsulfinamoyl, N-methyl-Npropylsulfinamoyl, N-methyl-N-1-methylethylsulfinamoyl, N-methyl-N-1,1 -dimethylethylsulfinamoyl, di-1 -methylethylsulfinamoyl, N-ethyl-N-1-methylethylsulfinamoyl a N-ethyl-N-1,1-dimethylethylsulfinamoyl, zejména dimethylsulfinamoyl;
C1-C4-alkylsulfinyloxy jako je methylsulfinyloxy, ethylsulfinyloxy, n-propylsulfinyloxy, 1-methylethylsulfinyloxy, n-butylsulfinyloxy, 1-methylpropylsulfinyloxy, 2-methylpropylsulfinyloxy a 1,1-dimethylethylsulfinyloxy, zejména methylsulfinyloxy;
C1-C4-alkylsulfonyloxy jako je methylsulfonyloxy, ethylsulfonyloxy, n-propylsulfonyloxy, 1-methylethylsulfonyloxy, n-butylsulfonyloxy, 1-methylpropylsulfonyloxy, 2-methylpropylsulfonyloxy a 1,1-dimethylethylsulfonyloxy, zejména methylsulfonxyloxy;
• * • · • · · · · · · • » ·· · · ” « · • · · * * · • · · · · ·
C1 -C4-alkylsulfinylamino jako je methylsulfinylamino, ethylsulfinylamino, n-propylsulfinylamino, 1 -methylethylsulfinylamino, n-butylsulfinylamino, 1-methylpropylsulfinylamino, 2-methylpropylsulfinylamino a 1,1 -dimethylethylsulfinylamino, zejména methylsulfinylamino;
C1-C4-alkylsulfonylamino jako je methylsulfonylamino, ethylsulfonylamino, n-propylsulfonylamino, 1-methylethyl sulfonylamino, n-butyl sulfonylamino, 1methylpropylsulfonylamino, 2-methylpropylsulfonylamino a 1,1-dimethylsulfonylamino, zejména methylsulfonylamino;
N-C1 -C4-alkylsulfinyl-N-methylamino jako je N-methylsulfinyl-N-methylamino, N-ethylsulfinyl-N-methylamino, N-n-propylsulfinyl-N-methylamino, N-1 -methylethylsulfinyl-N-methylamino, N-n-butylsulfinyl-N-methylamino, N-1 -methylpropylsulfinyl-N-methylamino, N-2-methylpropylsulfinyl-N-methylamino a N-1,1-dimethylethylsulfinyl-N-methylamino, zejména N-methylsulfinyl-N-methylamino;
N-C1-C4-alkylsulfinyl-N-ethylamino jako je N-methylsulfinyl-N-ethylamino, N-ethylsulfinyl-N-ethylamino, N-n-propylsulfinyl-N-ethylamino, N-1 -methylethylsulfinyl-N-ethylamino, N-n-butylsulfinyl-N-ethylamino, N-1 -methylpropylsulfinyl-Nethylamino, N-2-methylpropylsulfinyl-N-ethylamino a N-1,1-dimethylethylsulfinylN-ethylamino, zejména N-methylsulfinyl-N-ethylamino;
N-C1-C4-alkylsulfonyl-N-methylamino jako je N-methylsulfonyl-N-methylamino, N-ethylsulfonyl-N-methylamino, N-n-propylsulfonyl-N-methylamino, N-1 -methylethylsulfonyl-N-methylamino, N-n-butylsulfonyl-N-methylamino, N-1 -methylpropylsulfonyl-N-methylamino, N-2-methylpropylsulfonyl-N-methylamino a N-1,1 -dimethylethylsulfonyl-N-methylamino, zejména N-methylsulfonyl-N-methylamino;
N-C1-C4-alkylsulfonyl-N-ethylamino jako je N-methylsulfonyl-N-ethylamino,
N-ethylsulfonyl-N-ethylamino, N-n-propylsulfonyl-N-ethylamino, N-1 -methylethylsulfonyl-N-ethylamino, N-n-butylsulfonyl-N-ethylamino, N-1 -methylpropylsulfonyl-N-ethylamino, N-2-methylpropylsulfonyl-N-ethylamino a N-1,1-dimethylethylsulfonyl-N-ethylamino, zejména N-methylsulfonyl-N-ethylamino;
• · · ·
C1-C4-halogenalkylthio jako je chlormethylthio, dichlormethylthio, trichlormethylthio, fluormethylthio, difluormethylthio, trifluormethylthio, chlorfluormethylthio, chlordifluormethylthio, 1-fluorethylthio, 2-fluorethylthio, 2,2-difluorethylthio, 2,2,2-trifluorethylthio, 2-chlor-2,2-difluorethylthio, 2,2-dichlor-2fluorethylthio, 2,2,2-trichlorethylthio a pentafluorethylthio, zejména trifluormethylthio.
Výšeuvedená skupina -(A)m-COR2 znamená např.
C1-C4-alkylkarbonyl jako je methylkarbonyl, ethylkarbonyl, n-propylkarbonyl, 1methylethylkarbonyl, n-butylkarbonyl, 1-methylpropylkarbonyl, 2-methylpropylkarbonyl a 1,1.-dimethylethylkarbonyl, zejména methylkarbonyl;
C1-C4-alkoxykarbonyl jako je methoxykarbonyl, ethoxykarbonyl, n-propoxykarbonyl, 1-methylethoxykarbonyl, n-butoxykarbonyl, 1-methylpropoxykarbonyl, 2methylpropoxykarbonyl a 1,1-dimethylethoxykarbonyl, zejména methoxykarbonyl;
N-C1-C4-alkylkarbamoyl jako je N-methylkarbamoyl, N-ethylkarbamoyl, N-npropylkarbamoyl, N-1-methylethylkarbamoyl, N-n-butylkarbamoyl, N-1-methylpropylkarbamoyl, N-2-methylpropylkarbamoyl a N-1,1-dimethylethylkarbamoyl, zejména N-methylkarbamoyl;
Di-C1-C4-alkylkarbamoyl jako je dimethylkarbamoyl, diethylkarbamoyl, dipropylkarbamoyl, dibutylkarbamoyl, N-methyl-N-ethylkarbamoyl, N-methyl-Npropylkarbamoyl, N-methyl-N-1 -methylethylkarbamoyl, N-methyl-N-1,1 -dimethylethylkarbamoyl, di-1-methylethylkarbamoyl, N-ethyl-N-1-methylethylkarbamoyl a N-ethyl-N-1,1-dimethylethylkarbamoyl, zejména dimethylkarbamoyl;
C1-C4-alkylkarbonyloxy jako je methylkarbonyloxy, ethylkarbonyloxy, n-propylkarbonyloxy, 1-methylethylkarbonyloxy, n-butylkarbonyloxy, 1-methylpropylkarbonyloxy, 2-methylpropylkarbonyloxy a 1,1-dimethylethylkarbonyloxy, zejména methylkarbonyloxy;
• · • · · *
C1 -C4-alkylkarbonylamino jako je methylkarbonylamino, ethylkarbonylamino, n-propylkarbonylamino, 1 -methylethylkarbonylamino, n-butylkarbonylamino, 1-methylpropylkarbonylamino, 2-methylpropylkarbonylamino a 1,1-dimethylethylkarbonylamino, zejména methylkarbonylamino;
N-C1-C4-alkylkarbonyl-N-methylamino jako je N-methylkarbonyl-N-methylamino, N-ethylkarbonyl-N-methylamino, N-n-propylkarbonyl-N-methylamino, N-1 -methylethylkarbonyl-N-methylamino, N-n-butylkarbonyl-N-methylamino, N-1 -methylpropylkarbonyl-N-methylamino, N-2-methylpropylkarbonyl-N-methylamino a
N-1,1-dimethylethylkarbonyl-N-methylamino, zejména N-methylkarbonyl-Nmethylamino.
X např. znamená:
CH2, CH(CH3), C((CH3)2), CH(C2H5), C((C2H5)2), CH(CeH5), ch2-ch2) CH2-CH(CH3), CH2C((CH3)2), CH(CH3)-CH(CH3), CH(CH3)-C(CH3)2i C(CH3)2-C (CH3)2i
CH2-CH(C2H5), CH2-C(C2H5)2, CH(C2H5)-CH(C2H5), CH(C2H5)-C(C2H5)2, C(C2H5)2-C(C2H5)2i CH2-CH(C3H7), CH2-CH(íC3H7), CH2-CH(C4H9), CH2-CH(íC4H9), CH2-CH(Br), CH2-C((Br)2), CH(Br)-CH(Br), C((Br)2)-C((Br)2),
CH2-CH(CI), CH2-C((CI)2), CH(CI)-CH(CI), C((CI)2)-C((CI)2), CH2-CH(C6H5), CH(C6H5)-CH(C6H5), CH2-CH (p-NO2C6H5)]
CH=CH, C(CH3)=CH, C(CH3)= CCH3, CH=CBr, CH=CCI, CBr=CBr, CCI=CCI, CH=C(OCH3), CH=C(C6H5), C(C6H5)=C(C6H5), C(C2H5)=CH, C(C2Hs)= C(C2Hs), CH=C(C3Hs), CH=C(C4H7), CH2-CH=CH, CH(CH3)-CH=CH, C((CH3)2)-CH=CH, CH2-CH=C(CH3), CH2-C(CH3)=CH, CH2-C(CH3)=C(CH3), CH(CH3)-C(CH3)=C(CH3), C((CH3)2)-C(CH3)=C(CH3), n-h, n-ch3, n-c2h5, n-c3h7, n-c4h9, N-íC3H7) N-OCH3i N-OC2H5) N-CH2CeH5, N-C6H5;
Y např. znamená
C=O, CH-OH, CH-OCH3) CH-OC2H5) CH-OC3H7,CH-OiPr, CH-OC4H9, CH-OiBu,
CH-OCsHn, CH-OCeHi31 CH-OC6H5, C(CH3)-OCH3, C(CH3)-OC2H5, C(CH3)-OC3H7,
C(CH3)-OC4H9, C(CH3)-OiPr, C(CH3)-OiBu, C(CH3)-OtBu, C(CH3)-OPh, CH2,
CH(CH3), C((CH3)2) ,c=n-ch3, c=n-c2h5, c=n-c3h7, c=n-c4h9, C=N-íC4H9,
C=N-tC4H9, C=N-iPr, C=N-OCH3, C=N-OC2H5| C=N-OC3H7i C=N-OC4H9i • · • · · ·
- 20 — ......
······· · · ··
C=N-OiC4H9, C=N-OtC4H9l C=N-OCH2CH=CH2, C=N-OCH(CH3)CH=CH2, C=N-OCH2CH=CHCH3, C=N-OCH2CH=C(CH3)2t C=N-0CH2CH=CHBr, c=n-och2ch=chci, c=n-och2ch=chc2h5, c=n-och2och, C=N-OCH2C^CCH3, C=N-OCH2C6H5, CH-NH(0CH3), CH-NH(OC2H5), CH-NH(OiPr), CH-NH(OnPr), CH-NH(OC6H5), CH-NCH3(OCH3), CH-NCH3(OC2H5), CH-NCH3(OiPr), CH-NCH3(OnPr), CH-NCH3(OC6H5), CH-NHCH3, CH-NH(C2H5), CH-NH(C3H7), CH-NH(C4H9), CH-NH(iPr), CH-NH(iBu), CH-NH(tBu), CH-NH(C6H5), CH-N(CH3)2i CH-NCH3(C2H5), CH-NCH3(C3H7), CH-NCH3(C4H9), CH-NCH3(iPr), CH-NCH3(iBu), C=N-NH2, C=N-NHCH31 C=N-N(CH3)2, C=N-NH(C2H5), C=N-NCH3(C2H5), C=N-N((C2H5)2), ch-sch3, CH-SC2H5) CH-SC3H7, CH-SC4H9, CH-SPr, CH-SiBu, CH-SH, C(CH3)-SCH3, C(CH3)-SC2H5, C(CH3)-SC3H7, 1,3-dioxanyl, 1,3-dioxolanyl, 5,5-dimethyl-1,3-dioxolanyl • · • ·
- 21 Preferovány jsou benzoylderiváty formule Ia,
kde L znamená vodík, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkinyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 halogenalkyl, C1-C4 halogenalkoxy, C1-C4 halogenalkylthio, C1-C4 alkylsulfonyl, halogen, nitroskupinu nebo kyanoskupinu a
M znamená vodík, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkinyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 halogenalkyl, C1-C4 halogenalkoxy, C1-C4 halogenalkoxy, C1-C4 halogenalkylthio, C1-C4 alkylsulfonyl, halogen, nitroskupinu nebo kyanoskupinu a Q, X, n a Y mají význam uvedený v patentovém nároku 1, přičemž v případě, že Y = C=O , není X rovno NR23.
Dále jsou preferovány benzoylderiváty formule Ib
Ib kde L znamená C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkinyl, C1-C4 alkoxy, C1-C4 halogenalkyl, C1-C4 halogenalkoxy, halogen, nitroskupinu nebo kyanoskupinu a M znamená vodík, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkinyl, C1-C4 alkoxy, C1C4 halogenalkyl, C1-C4 halogenalkoxy, halogen, nitroskupinu nebo kyanoskupinu a Q, X, n a Y mají význam uvedený v nároku 1, přičemž v případě, že Y = C=0 , není X rovno NR23.
• · • ·
Preferovány jsou benzoylderiváty formule Ic, (Q)n
II R21
O M
Q
Ic kde L znamená vodík, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkinyl, C1-C4 alkoxy, C1-C4 halogenalkyl, C1-C4 halogenalkoxy, halogen, nitroskupinu nebo kyanoskupinu a M znamená vodík, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkinyl, C1C4 alkoxy, C1-C4 halogenalkyl, C1-C4 halogenalkoxy, halogen, nitroskupinu nebo kyanoskupinu a Q, X, n a Y a dále R22, R21, R12 a R13 mají význam uvedený v patentovém nároku 1.
Rovněž jsou preferovány benzoylderiváty formule Id,
kde L znamená vodík, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkinyl, C1-C4 alkoxy, C1-C4 halogenalkyl, C1-C4 halogenalkoxy, halogen, nitroskupinu nebo kyanoskupinu a M znamená vodík, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkinyl, C1C4 alkoxy, C1-C4 halogenalkyl, C1-C4 halogenalkoxy, halogen, nitroskupinu nebo kyanoskupinu a Q, X, n a Y a dále R12 a R13 mají význam uvedený v patentovém nároku 1.
• ·
Rovněž jsou preferovány benzoylderiváty formule Ie,
kde L znamená vodík, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkinyl, C1-C4 alkoxy, C1-C4 halogenalkyl, C1-C4 halogenalkoxy, halogen, nitroskupinu nebo kyanoskupinu a M znamená vodík, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkinyl, C1C4 alkoxy, C1-C4 halogenalkyl, C1-C4 halogenalkoxy, halogen, nitroskupinu nebo kyanoskupinu a Q, X, n a Y a dále R12 a R13 mají význam uvedený v patentovém nároku 1.
Preferovány jsou i benzoylderiváty formule I podle nároku 1, kde n je jedna nebo dvě a Y znamená CR7-0R8, přičemž R7 a R8 mají význam uvedený v patentovém nároku 1.
• · • ·
- 24 Tabulka 1: Sloučeniny formule
| iNr. | R17 | Ria | R19 | □ | R12 | R13 | Y | L | M |
| LI | H | H | H | 0 | H | H | C=O | H | H |
| i 12 | H | H | H | 2 | H | H | oo | H | H |
| ;L3 | H | H | H | 0 | H | H | choch3 | H | H |
| 1.4 | H | H | H | 2 | H | H | CHOCH3 | H | H |
| |13 | H | H | H | 0 | H | H | CHOC2H5 | H | H |
| i 1.6 | H | H | H | 2 | H | H | CHOC2H5 | H | H |
| i 1.7 | H | H | H | 0 | H | H | CHOiPr | H | H |
| '1.8 | H | H | H | 2 | H | H | CHOiPr | H | H |
| 1.9 | H | H | H | 0 | H | H | CHOH | H | H |
| 1.10 | H | H | H | 2 | H | H | CHOH | H | H |
| 1.11 | H | H | H | 0 | H | H | C-NOCH3 | H | H |
| 1.12 | H | H | H | 2 | H | H | c»noch3 | H | H |
| 1.13 | H | H | H | 0 | H | H | C-NOC2H5 | H | H |
| 1.14 | H | H | H | 2 | H | H | C=NOC2H5 | H | H |
| 1.15 | H | H | H | 0 | H | H | ONOiPr | H | H |
| 1.16 | H | H | H | 2 | H | H | ONOiPr | H | H |
| 1.17 | H | H | H | 0 | H | H | ONOCH2CH«CHa | H | H |
| 1.18 | H | H | H | 2 | H | H | ONOCH2CH«CHC1 | H | H |
| 1.19 | H | H | H | 0 | H | H | ONOCH2C6H5 | H | H |
| 120 | H | H | 2 | H | H | ONOCH2C6Hs | H | H | |
| 121 | H | H | 0 | H | H | C(CH3)2' | H | H | |
| 122 | H | H | 2 | H | H | C(CH3)2 | H | H | |
| 123 | ch3 | H | 0 | H | H | 00 | H | H | |
| 124 | ch3 | H | H | 2 | H | H | 00 | H | H |
| 125 | ch3 | H | H | 0 | H | H | CHOCH3 | H | H |
| 126 | ch3 | H | H | 2 | H | H | CHOCH3 | H | H |
| 127 | ch3 | H | H | 0 | H | H | CHOC2H5 | H | H |
| 128 | ch3 | H | H | 2 | H | H | CHOC2H5 | H | H |
| 129 | ch3 | H | H | H | H | CHOiPr | H | H | |
| 1JÓ | ch3 | H | H | 2 | H | H | CHOiPr | H | H |
| 131 | ch3 | H | H | H | H | CHOH | H | H | |
| 132 | ch3 | H | H | 2 | H | H | CHOH | H | H----1 |
0050/46142
| Nr. | R17 | rI8 | R19 | n | R12 | R13 | Y | L | M |
| 1.33 | ch3 | H | H | 0 | H | H | c=noch3 | H | H |
| 1.34 | ch3 | H | H | 2 | H | H | c=noch3 | H | H |
| . 135 | ch3 | H | H | 0 | H | H | c=noc2h5 | H | H |
| 136 | ch3 | H | H | 2 | H | H | c=noc2h5 | H | H |
| 137 | ch3 | H | H | 0 | H | H | C=NOiPr | H | H |
| 138 | ch3 | H | H | 2 | H | H | C=NOiPr | H | H |
| 139 | ch3 | H | H | 0 | H | H | C=NOCH2CH=CHC1 | H | H |
| 1.40 | ch3 | H | H | 2 | H | H | C=NOCH2CH=CHC1 | H | H |
| 1.41 | ch3 | H | H | 0 | H | H | C=NOCH2C6H5 | H | H |
| 1.42 | ch3 | H | H | 2 | H | H | C=NOCH2C6H5 | H | H |
| 1.43 | ch3 | H | H | 0 | H | H | C(CH3)2 | H | H |
| 1.44 | ch3 | H | H | 2 | H | H | C(CH3h | H | H |
| 1.45 | ch3 | ch3 | H | 0 | H | H | c=o | H | H |
| 1.46 | ch3 | ch3 | H | 2 | H | H | c=o | H | H |
| 1.47 | ch3 | ch3 | H | 0 | H | H | choch3 | H | H |
| 1.48 | ch3 | ch3 | H | 2 | H | H | choch3 | H | H |
| 1.49 | ch3 | ch3 | H | 0 | H | H | choc2h5 | H | H |
| 130 | ch3 | ch3 | H | 2 | H | H | choc2h5 | H | H |
| 131 | ch3 | ch3 | H | 0 | H | H | CHOiPr | H | H |
| 132 | ch3 | ch3 | H | 2 | H | H | CHOiPr | H | H |
| 133 | ch3 | ch3 | H | 0 | H | H | C=NOCH3 | H | H |
| 134 | ch3 | ch3 | H | 2 | H | H | c=noch3 | H | H |
| 135 | ch3 | ch3 | H | 0 | H | H | c=noc2h5 | H | H |
| 136 | ch3 | ch3 | H | 2 | H | H | c=noc2h5 | H | H |
| 137 | ch3 | ch3 | H | H | H | ONOiPr | H | H | |
| 138 | ch3 | ch3 | H | 2 | H | H | C=NOiPr | H | H |
| 139 | ch3 | ch3 | H | 0 | H | H | C=NOCH2CH=CHC1 | H | H |
| 1.60 | ch3 | ch3 | H | 2 | H | H | c=noch2ch=chci | H | H |
| 1.61 | ch3 | ch3 | H | H | C=NOCH2C6H5 | H | H | ||
| 1.62 | ch3 | ch3 | H | 2 | H | H | C=NOCH2C6Hs | H | |
| 1.63 | ch3 | ch3 | H | H | H | C(CH3)2 | H | ||
| 1.64 | ch3 | ch3 | H | 2 | H | H | C(GH3)2 | H | |
| 1.65 | H | H | H | H | H | c=o | H | ch3 | |
| 1.66 | H | H | 2 | c=o | ch3 | ||||
| 1.67 | H | H | CHOCH3 | ch3 | |||||
| 1.68 | H | 2 | choch3 | cr3 | |||||
| 1.69 | H | choc2h5 | ch3 | ||||||
| 1.70 | H | 2 | CHOC2H5 | μ | ch3 | ||||
| 1.71 | H | I | CHOiPr | ch3 | |||||
| 1.72 | 2 | CHOiPr | ch3 | ||||||
| 1.73 | 5 | c=noch3 | ch3 |
0050/46142
| Nr. | R17 | R18 | R19 | n | R12 | R13 | Y | L | M |
| 1.74 | Η | H | H | 2 | H | H | c=noch3 | H | ch3 |
| 1.75 | Η | H | H | 0 | H | H | c=noc2h5 | H | ch3 |
| . 1.76 | Η | H | H | 2 | H | H | ONOC2H5 | H | . ch3 |
| 1.77 | Η | H | H | 0 | H | H | C=NOiPr | H | ch3 |
| 1.78 | Η | H | H | 2 | H | H | C=NOiPr | H | ch3 |
| 1.79 | Η | H | H | 0 | H | H | C=NOCH2CH=CHC1 | H | ch3 |
| 1.80 | Η | H | H | 2 | H | H | c=noch2ch=chq | H | ch3 |
| 1.81 | Η | H | H | 0 | H | H | ONOCH2C6H5 | H | ch3 |
| 1.82 | Η | H | H | 2 | H | H | C=NOCH2C6H5 | H | ch3 |
| 1.83 | Η | H | H | 0 | H | H | C(CH3)2 | H | ch3 |
| 1.84 | Η | H | H | 2 | H | H | C(CH3)2 | H | ch3 |
| 1.85 | ch3 | H | H | 0 | H | H | c=o | H | ch3 |
| 1.86 | ch3 | H | H | 2 | H | H | 00 | H | ch3 |
| 1.87 | ch3 | H | H | 0 | H | H | choch3 | H | ch3 |
| 1.88 | ch3 | H | H | 2 | H | H | choch3 | H | ch3 |
| 1.89 | ch3 | H | H | 0 | H | H | CHOC2H5 | H | ch3 |
| 1.90 | ch3 | H | H | 2 | H | H | CHOC2H5 | H | ch3 |
| 1.91 | ch3 | H | H | 0 | H | H | CHOiPr | H | ch3 |
| 1.92 | ch3 | H | H | 2 | H | H | CHOiPr | H | ch3 |
| 1.93 | ch3 | H | H | 0 | H | H | c=noch3 | H | ch3 |
| 1.94 | ch3 | H | H | 2 | H | H | c=noch3 | H | ch3 |
| 1.95 | ch3 | H | H | 0 | H | H | ONOC2H5 | H | ch3 |
| 1.96 | ch3 | H | H | H | H | ONOC2H5 | H | ch3 | |
| 1.97 | ch3 | H | H | H | H | ONOiPr | H | ch3 | |
| 1.98 | ch3 | H | H | 2 | H | H | ONOiPr | H | ch3 |
| 1.99 | ch3 | H | H | H | H | ONOCH2CH=CHQ | H | ch3 | |
| 1.100 | ch3 | H | H | 2 | H | H | C=NOCH2CH=CHa | H | ch3 |
| 1.101 | ch3 | H | H | H | H | ONOCH2C6H5 | H | ch3 | |
| 1.102 | ch3 | H | H | 2 | ONOCH2Q5H5 | H | ch3 | ||
| 1.103 | ch3 | Η | H | H | H | C(CH3)2 | ch3 | ||
| 1.104 | ch3 | H | H | 2 | H | C(CH3)2 | ch3 | ||
| 1.105 | ch3 | ch3 | H | 00 | ch3 | ||||
| 1.106 | ch3 | ch3 | H | 2 | 00 | ch3 | |||
| 1.107 | ch3 | ch3 | H | choch3 | ch3 | ||||
| 1.108 | ch3 | ch3 | H | 2 | 1 | choch3 | ch3 | ||
| 1.109 | ch3 | ch3 | H | CHOC2H5 | ch3 | ||||
| 1.110 | ch3 | ch3 | H | 2 | CHOC2H5 | ch3 | |||
| 1.111 | ch3 | ch3 | H | CHOiPr | ch3 | ||||
| 1.112 | ch3 | ch3 | H | 2 | CHOiPr | ch3 | |||
| 1.113 | ch3 | ch3 | a | CHOH | ch3 | ||||
| 1.114 | ch3 | ch3 | a | l | CHOH | ch3 |
0050/46142
X.:, • · · · · • · • ·
| Nr. | R17 | r18 | R19 | n | R12 | R13 | Y | L | M |
| 1.115 | ch3 | ch3 | H | 0 | H | H | onoch3 | H | ch3 |
| 1.116 | ch3 | ch3 | H | 2 | H | H | onoch3 | H | ch3 |
| . 1.117 | ch3 | ch3 | H | 0 | H | H | onoc2h5 | H | ch3 |
| 1.118 | ch3 | ch3 | H | 2 | H | H | onoc2h5 | H | ch3 |
| 1.119 | ch3 | ch3 | H | 0 | H | H | ONOiPr | H | ch3 |
| 1.120 | ch3 | ch3 | H | 2 | H | H | ONOiPr | H | ch3 |
| 1.121 | ch3 | ch3 | H | 0 | H | H | ONOCH2CH=CHQ | H | ch3 |
| 1.122 | ch3 | ch3 | H | 2 | H | H | C=NOCH2CH=CHC1 | H | ch3 |
| 1.123 | ch3 | ch3 | H | 0 | H | H | C=NOCH2C6Hs | H | ch3 |
| 1.124 | ch3 | ch3 | H | 2 | H | H | C=NOCH2C6H5 | H | ch3 |
| 1.125 | ch3 | ch3 | H | 0 | H | H | C(CH3)2 | H | ch3 |
| 1.126 | ch3 | ch3 | H | 2 | H | H | C(CH3)2 | H | ch3 |
| 1.127 | H | H | H | 0 | H | H | oo | H | a |
| 1.128 | H | H | H | 2 | H | H | c=o | H | a |
| 1.129 | H | H | H | 0 | H | H | choch3 | H | a |
| 1.130 | H | H | H | 2 | H | H | choch3 | H | a |
| 1.131 | H | H | H | 0 | H | H | choc2h5 | H | a |
| 1.132 | H | H | H | 2 | H | H | choc2h5 | H | a |
| 1.133 | H | H | H | 0 | H | H | CHOiPr | H | a |
| 1.134 | H | H | H | 2 | H | H | CHOiPr | H | a |
| 1.135 | H | H | H | 0 | H | H | c=noch3 | H | a |
| 1.136 | H | H | H | 2 | H | H | onoch3 | H | a |
| 1.137 | H | H | H | 0 | H | H | c=noc2h5 | H | a |
| 1.138 | H | H | H | 2 | H | H | c=noc2h5 | H | a |
| 1.139 | H | H | H | H | H | ONOiPr | H | a | |
| 1.140 | H | H | H | 2 | H | H | ONOiPr | H | a |
| 1.141 | H | H | H | H | H | ONOCH2CH=CHQ | H | a | |
| 1.142 | H | H | H | 2 | H | H | ONOCH2CH=CHQ | H | a |
| 1.143 | H | H | H | 0 | H | H | ONOCH2CeH5 | H | a |
| 1.144 | H | H | H | 2 | H | H | ONOCH2C6H5 | H | a |
| 1.145 | H | H | H | 0 | H | H | C(CH3)2 | H | a |
| 1.146 | H | H | H | 2 | H | H | CíCHsh | H | a |
| 1.147 | ch3 | H | H | 0 | H | oo | H | a | |
| 1.148 | ch3 | H | H | 2 | H | oo | H | a | |
| 1.149 | ch3 | H | H | H | choch3 | H | a | ||
| 1.150 | ch3 | H | 2 | H | choch3 | H | a | ||
| 1.151 | ch3 | H | H | CHOC2H5 | H | a | |||
| 1.152 | ch3 | H | 2 | H | CHOC2H5 | H | Cl | ||
| 1.153 | ch3 | H | H | CHOiPr | H | □ | |||
| 1.154 | ch3 | H | 2 | H | CHOiPr | H | □ | ||
| 1.155 | ch3 | H | H | c=noch3 | □ |
. 0050/46142
| Nr. | R17 | R18 | R19 | Π | R12 | rI3 | Y | L | M |
| 1.156 | ch3 | H | H | 2 | H | H | c=noch3 | H | a |
| 1.157 | ch3 | H | H | 0 | H | H | c=noc2h5 | H | a |
| 1.158 | ch3 | H | H | 2 | H | H | c=noc2h5 | H | a |
| 1.159 | ch3 | H | H | 0 | H | H | C=NOiPr | H | a |
| 1.160 | ch3 | H | H | 2 | H | H | O=N0iPr | H | a |
| 1.161 | ch3 | H | H | 0 | H | H | C=NOCH2CH=CHC1 | H | a |
| 1.162 | ch3 | H | H | 2 | H | H | c=noch2ch=chci | H | a |
| 1.163 | ch3 | H | H | 0 | H | H | C=NOCH2C6H5 | H | a |
| 1.164 | ch3 | H | H | 2 | H | H | C=NOCH2QíH5 | H | a |
| 1.165 | ch3 | H | H | 0 | H | H | C(CH3)2 | H | a |
| 1.166 | ch3 | H | H | 2 | H | H | C(CH3)2 | H | a |
| 1.167 | ch3 | ch3 | H | 0 | H | H | c=o | H | a |
| 1.168 | ch3 | ch3 | H | 2 | H | H | 0=0 | H | a |
| 1.169 | ch3 | ch3 | H | 0 | H | H | choch3 | H | a |
| 1.170 | ch3 | ch3 | H | 2 | H | H | choch3 | H | a |
| 1.171 | ch3 | ch3 | H | 0 | H | H | choc2h5 | H | a |
| 1.172 | ch3 | ch3 | H | 2 | H | H | choc2h5 | H | a |
| 1.173 | ch3 | ch3 | H | 0 | H | H | CHOiPr | H | a |
| 1.174 | ch3 | ch3 | H | 2 | H | H | CHOiPr | H | a |
| 1.175 | ch3 | ch3 | H | 0 | H | H | c=noch3 | H | a |
| 1.176 | ch3 | ch3 | H | 2 | H | H | c=noch3 | H | a |
| 1.177 | ch3 | ch3 | H | 0 | H | H | c=noc2h5 | H | a |
| 1.178 | ch3 | ch3 | H | 2 | H | H | c=noc2h5 | H | a |
| 1.179 | ch3 | ch3 | H | H | H | ONOiPr | H | a | |
| 1.180 | ch3 | ch3 | H | 2 | H | H | ONOiPr | H | a |
| 1.181 | ch3 | ch3 | H | H | H | ONOCH2CH=CHQ | H | a | |
| 1.182 | ch3 | ch3 | H | 2 | H | H | ONOCH2CH=CHd | H | a |
| 1.183 | ch3 | ch3 | H | H | H | onoch2c6h5 | H | a | |
| 1.184 | ch3 | ch3 | H | 2 | H | H | C=NOCH2CeH5 | H | a |
| 1.185 | ch3 | ch3 | H | H | : | C(CH3)2 | : | a | |
| 1.186 | ch3 | ch3 | H | 2 | H | C(CH3)2 | a |
• · • ·
Tabulka 2: Sloučeniny formule
Zbytky R12 od X a R7 od Y vytvářejí vazbu
| |Nr. | R18 | R19 | n | R13 | Y | L | M | |
| 2.1 | H | H | H | 0 | H | coch3 | H | H |
| 22 | H | H | H | 2 | H | coch3 | H | H |
| 23 | H | H | H | 0 | H | COC2H5 | H | H |
| 2.4 | H | H | H | 2 | H | COC2H5 | H | H |
| 23 | H | H | H | 0 | H | COiPr | H | H |
| 2.6 | H | H | H | 2 | H | COiPr | H | H |
| 2.7 | ch3 | H | H | 0 | H | coch3 | H | H |
| 2.8 | CHj | H | H | 2 | H | coch3 | H | H |
| 2.9 | ch3 | H | H | 0 | H | COC2H5 | H | H |
| 2.10 | ch3 | H | H | 2 | H | COC2H5 | H | H |
| 12.11 | ch3 | H | H | 0 | H | COiPr | H | H |
| 2.12 | ch3 | H | H | 2 | H | COiPr | H | H |
| ,2.13 | ch3 | ch3 | H | 0 | H | coch3 | H | H |
| 2.14 | ch3 | ch3 | H | 2 | H | coch3 | H | H |
| 115 | ch3 | ch3 | H | 0 | H | COC2H5 | H | H |
| 2.16 | ch3 | ch3 | H | 2 | H | COC2H5 | H | H |
| 2.17 | ch3 | ch3 | H | 0 | H | COiPr | H | H |
| 2.18 | ch3 | ch3 | H | 2 | H | COiPr | H | H |
| 2.19 | H | H | H | 0 | H | COCHj | H | ch3 |
| 220 | H | H | H | 2 | H | COCH3 | H | ch3 |
| 221 | H | H | H | 0 | H | COC2H5 | H | ch3 |
| 222 | H | H | H | 2 | H | COC2H5 | H | ch3 |
| 223 | H | H | H | 0 | H | COiPr | H | ch3 |
| 224 | H | H | H | 2 | H | COiPr | H | ch3 |
| 225 | ch3 | H | H | 0 | H | coch3 | H | ch3 |
| 226 | ch3 | H | H | 2 | H | coch3 | H | ch3 |
| 227 | ch3 | H | H | 0 | H | coc2h3 | H | CH3 |
| 228 | ch3 | H | H | 2 | H | COC2H5 | H | ch3 |
| 229 | ch3 | H | H | 0 | H | COiPr | H | ch3 |
| 230 | ch3 | H | H | 2 | H | COiPr | H | ch3 |
0050/46142
| Nr. | R17 | r18 | r19 | n | R13 | Y | L | M |
| 231 | ch3 | ch3 | H | 0 | H | coch3 | H | ch3 |
| 2.32 | ch3 | ch3 | H | 2 | H | coch3 | H | ch3 |
| 2.33 | ch3 | ch3 | H | 0 | H | coc2h5 | H | ch3 |
| 2.34 | ch3 | ch3 | H | 2 | H | COC2H5 | H | ch3 |
| 2.35 | ch3 | ch3 | H | 0 | H | COiPr | H | ch3 |
| 236 | ch3 | ch3 | H | 2 | H | COiPr | H | ch3 |
| 2.37 | H | H | H | 0 | H | COCH3 | H | a |
| 238 | H | H | H | 2 | H | coch3 | H | a |
| 239 | H | H | H | 0 | H | COC2H5 | H | a |
| 2.40 | H | H | H | 2 | H | COC2H5 | H | a |
| 2.41 | H | H | H | 0 | H | COiPr | H | a |
| 2.42 | H | H | H | 2 | H | COiPr | H | a |
| 2.43 | ch3 | H | H | 0 | H | coch3 | H | a |
| 2.44 | ch3 | H | H | 2 | H | coch3 | H | a |
| 2.45 | ch3 | H | H | 0 | H | COC2H5 | H | a |
| 2.46 | ch3 | H | H | 2 | H | COC2H5 | H | a |
| 2.47 | ch3 | H | H | 0 | H | COiPr | H | a |
| 2.48 | ch3 | H | H | 2 | H | COiPr | H | Cl |
| 2.49 | ch3 | ch3 | H | 0 | H | coch3 | H | a |
| 230 | ch3 | ch3 | H | 2 | H | coch3 | H | a |
| 231 | ch3 | ch3 | H | 0 | H | COC2H5 | H | a |
| 232 | ch3 | ch3 | H | 2 | H | COC2H5 | H | a |
| 233 | ch3 | ch3 | H | 0 | H | COiPr | H | a |
| 2.54 | ch3 | ch3 | H | 2 | H | COiPr | H | a |
Tabulka 3: Sloučeniny formule
| Nr. | R1^ | R1Š | R1^ | a | Rii | r13 | Y | L | M |
| 3.1 | H | H | H | 0 | H | H | C-0 | ch3 | H |
| 32 | H | H | H | 2 | H | H | C-0 | ch3 | H |
| 33 | H | H | H | 0 | H | H | CHOCH3 | ch3 | H |
| 3A | H | H | H | 2 | H | H | CHOCH3 | CH3 | H |
| 33 | H | H | H | 0 | H | H | CHOC2H5 | ch3 | H |
| 3.6 | H | H | H | 2 | H | H | CHOC2H5 | ch3 | H |
| 3.7 | H | H | H | 0 | H | H | CHOiPr | ch3 | H |
| 3.8 | H | H | H | 2 | H | H | CHOiPr | ch3 | H |
| 3.9 | H | H | H | 0 | H | H | c=noch3 | ch3 | H |
| 3.10 | H | H | H | 2 | H | H | ONOCH3 | ch3 | H |
| 3.11 | H | H | H | 0 | H | H | C-NOC2H5 | ch3 | H |
| 3.12 | H | H | H | 2 | H | H | O-NOC2H5 | ch3 | H |
| 3.13 | H | H | H | 0 | H | H | C-NOiPr | ch3 | H |
| 3.14 | H | H | H | 2 | H | H | C-NOiPr | ch3 | H |
| 3.15 | H | H | H | 0 | H | H | C-NOCH2CH“CHC1 | ch3 | H |
| 3.16 | H | H | H | 2 | H | H | C-NOCH2CH-CHCI | ch3 | H j |
| 3.17 | H | H | H | 0 | H | H | C-NOCH2C6H5 | ch3 | H | |
| 3.18 | H | H | H | 2 | H | H | ONOCH2C6H5 | ch3 | H i |
| 3.19 | H | H | H | 0 | H | H | C(CH3)2 | ch3 | H ! |
| 320 | H | H | H | 2 | H | H | C(CH3)2 | ch3 | H |
| 321 | ch3 | H | H | 0 | H | H | C-0 | ch3 | H |
| 322 | ch3 | H | H | 2 | H | H | C-0 | ch3 | H |
| 323 | ch3 | H | H | 0 | H | H | CHOCH3 | ch3 | H |
| 324 | ch3 | H | H | 2 | H | H | choch3 | ch3 | H |
| 325 | ch3 | H | H | 0 | H | H | CHOC2H5 | CH3 | H |
| 326 | ch3 | H | H | 2 | H | H | CHOC2H5 | CU3 | H |
| 327 | ch3 | H | H | 0 | H | H | CHOiPr | ch3 | H |
| 328 | ch3 | H | H | 2 | H | H | CHOiPr | ch3 | H . |
| 329 | ch3 | H | H | 0 | H | H | C-NOCH3 | ch3 | H |
| 330 | ch3 | H | H | 2 | H | H | C-NOCH3 | ch3 | H |
| 331 | ch3 | H | H | 0 | H | H | C-NOC2H5 | ch3 | H |
| 332 | CH3 | H | H | 2 | H | H | C-NOC2HJ | ch3 | H |
| 333 | CHj | H | H | 0 | H | H | C-NOiPr | ch3 | H |
0050/46142
9 • · ·· · · · · · * 9 9 9 e s • * • · · ·
| Nr. |R17 | R18 | R19 | n | R12 | r!3 | Y | L | M | |
| 334 | ch3 | H | H | 2 | H | H | (ONOiPr | ch3 | Η |
| 335 | ch3 | H | H | 0 | H | H | C=NOCH2CH=CHC1 | ch3 | H |
| _ 336 | ch3 | H | H | 2 | H | H | c=noch2ch=chci | ch3 | H |
| 337 | ch3 | H | H | 0 | H | H | ONOCH2C6H5 | ch3 | H |
| 338 | ch3 | H | H | 2 | H | H | c=noch2qh5 | ch3 | H |
| 339 | ch3 | H | H | 0 | H | H | C(CH3)2 | ch3 | H |
| 3.40 | ch3 | H | H | 2 | H | H | C(CH3)2 | ch3 | H |
| 3.41 | ch3 | ch3 | H | 0 | H | H | c=o | ch3 | H |
| 3.42 | ch3 | ch3 | H | 2 | H | H | c=o | ch3 | H |
| 3.43 | ch3 | ch3 | H | 0 | H | H | choch3 | ch3 | H |
| 3.44 | ch3 | ch3 | H | 2 | H | H | choch3 | ch3 | H |
| 3.45 | ch3 | ch3 | H | 0 | H | H | CHOC2H5 | ch3 | H |
| 3.46 | ch3 | ch3 | H | 2 | H | H | CHOC2H5 | ch3 | H |
| 3.47 | ch3 | ch3 | H | 0 | H | H | CHOiPr | ch3 | H |
| 3.48 | ch3 | ch3 | H | 2 | H | H | CHOiPr | ch3 | H |
| 3.49 | ch3 | ch3 | H | 0 | H | H | c=noch3 | ch3 | H |
| 330 | ch3 | ch3 | H | 2 | H | H | c=noch3 | ch3 | H |
| 3.51 | ch3 | ch3 | H | 0 | H | H | c=noc2h5 | ch3 | H |
| 332 | ch3 | ch3 | H | 2 | H | H | c=noc2h5 | ch3 | H |
| 333 | ch3 | ch3 | H | 0 | H | H | C=NOiPr | ch3 | H |
| 3.54 | ch3 | ch3 | H | 2 | H | H | ONOiPr | ch3 | H |
| 335 | ch3 | ch3 | H | 0 | H | H | C=NOCH2CH=CHC1 | ch3 | H |
| 336 | ch3 | ch3 | H | H | H | c=noch2ch=chci | ch3 | H | |
| 337 | ch3 | ch3 | H | 0 | H | H | ONOCH2QH5 | ch3 | H |
| 338 | ch3 | ch3 | H | 2 | H | H | C=NOCH2C6H5 | ch3 | H |
| 339 | ch3 | ch3 | H | H | H | C(CH3h | ch3 | H | |
| 3.60 | ch3 | ch3 | H | 2 | H | H | C(CH3)2 | ch3 | H |
| 3.61 | H | H | H | H | H | 00 | a | H | |
| 3.62 | H | H | H | 2 | H | H | 00 | a | H |
| 3.63 | H | H | 0 | H | H | choch3 | a | H | |
| 3.64 | H | H | H | 2 | H | H | choch3 | a | H |
| 3.65 | H | H | H | 0 | H | H | CHOC2H5 | a | H |
| 3.66 | H | H | H | 2 | H | CHOC2H5 | a | ||
| 3.67 | H | 0 | H | CHOiPr | a | ||||
| 3.68 | H | 2 | H | CHOiPr | a | ||||
| 3.69 | 0 | H | c=noch3 | a | |||||
| 3.70 | 2 | H | onoch3 | □ | |||||
| 3.71 | 0 | 1 | H | ONOC2H5 | □ | ||||
| 3.72 | H | 2 | El | ONOC2H5 | □ | ||||
| 3.73 | ) | 9 | ONOiPr | □ | |||||
| 3.74 | l | Ei | ONOiPr |
0050/46142 • · • · • · · · · · · • ·
| Nr. | R17 | r18 | R19 | n | R12 | r13 | Y | L | M |
| 3.75 | H | H | H | 0 | H | H | C=NOCH2CH=CHC1 | a | H |
| 3.76 | H | H | H | 2 | H | H | c=noch2ch=chci | ci |h | |
| _ 3.77 | H | H | H | 0 | H | H | C=NOCH2C6H5 | ci |h | |
| 3.78 | H | H | H | 2 | H | H | C=NOCH2QíH5 | a |h | |
| 3.79 | H | H | H | 0 | H | H | C(CH3)2 | Cl |H | |
| 3.80 | H | H | H | 2 | H | H | C(CH3)2 | ci |h | |
| 3.81 | ch3 | H | H | 0 | H | H | c=o | Cl |H | |
| 3.82 | ch3 | H | H | 2 | H | H | c=o | Cl |H | |
| 3.83 | ch3 | H | H | 0 | H | H | choch3 | Cl |h | |
| 3.84 | ch3 | H | H | 2 | H | H | choch3 | a |h | |
| 3.85 | ch3 | H | H | 0 | H | H | choc2h5 | a |h | |
| 3.86 | ch3 | H | H | 2 | H | H | choc2h5 | ci |h | |
| 3.87 | ch3 | H | H | 0 | H | H | CHOiPr | a |h | |
| 3.88 | ch3 | H | H | 2 | H | H | CHOiPr | Cl |H | |
| 3.89 | ch3 | H | H | 0 | H | H | c=noch3 | a |h | |
| 3.90 | ch3 | H | H | 2 | H | H | c=noch3 | ci |h | |
| 3.91 | ch3 | H | H | 0 | H | H | c=noc2h5 | Cl |H | |
| 3.92 | ch3 | H | H | 2 | H | H | C=NOC2Hs | ci |h | |
| 3.93 | ch3 | H | H | 0 | H | H | C=NOiPr | Cl |H | |
| 3.94 | ch3 | H | H | 2 | H | H | ONOiPr | Cl |H | |
| 3.95 | ch3 | H | H | 0 | H | H | C=NOCH2CH=CHC1 | a |h | |
| 3.96 | ch3 | H | H | 2 | H | H | c=noch2ch=chq | Cl |H | |
| 3.97 | ch3 | H | H | 0 | H | H | C=NOCH2C6H5 | ci |h | |
| 3.98 | ch3 | H | H | 2 | H | H | c=noch2qh5 | a |h | |
| 3.99 | ch3 | H | H | H | H | C(CH3)2 | a |h | ||
| 3.100 | ch3 | H | H | 2 | H | H | C(CH3)2 | a |h | |
| 3.101 | ch3 | ch3 | H | 0 | H | H | c=o | a |h | |
| 3.102 | ch3 | ch3 | H | 2 | H | H | c=o | Cl |H | |
| 3.103 | ch3 | ch3 | H | 0 | H | H | choch3 | Cl |h | |
| 3.104 | ch3 | ch3 | H | 2 | H | H | choch3 | a |H | |
| 3.105 | ch3 | ch3 | H | H | H | CHOC2H5 | Cl |H | ||
| 3.106 | ch3 | ch3 | H | 2 | CHOC2H5 | a |h | |||
| 3.107 | ch3 | ch3 | H | 0 | CHOiPr | a |h | |||
| 3.108 | ch3 | ch3 | H | 2 | CHOiPr | a |h | |||
| 3.109 | ch3 | ch3 | H | 0 | H | c=n-och3 | a |h | ||
| 3.110 | ch3 | ch3 | H | 2 | ONOCH3 | a |h | |||
| 3.111 | ch3 | ch3 | H | C=NOC2H5 | □ |h | ||||
| 3.112 | ch3 | ch3 | H | 2 | onoc2h5 | a |h | |||
| 3.113 | ch3 | ch3 | H | ONOiPr | □ |h | ||||
| 3.114 | ch3 | ch3 | H | 2 | ONOiPr | □ |h | |||
| 3.115 | zh3 | dh3 | a | ONOCH2CH=CHC1 | □ |h |
. 0050/46142 • · • ·
| Nr. | R17 | R18 | R19 | n | R12 | R13 | Y | L | M |
| 3.116 | ch3 | ch3 | H | 2 | H | H | C=NOCH2CH=CHC1 | Cl | H |
| 3.117 | ch3 | ch3 | H | 0 | H | H | C=NOCH2C<5H5 | a | H |
| . 3.118 5 _ | ch3 | ch3 | H | 2 | H | H | C=NOCH2QH5 | Cl | H |
| 3.119 | ch3 | ch3 | H | 0 | H | H | C(CH3)2 | Cl | H |
| 3.120 | ch3 | ch3 | H | 2 | H | H | C(CH3)2 | a | H |
| 3.121 | H | H | H | 0 | H | ch3 | c=o | ch3 | H |
| 3.122 | H | H | H | 2 | H | ch3 | c=o | ch3 | H |
| 3.123 | H | H | H | 0 | H | ch3 | choch3 | ch3 | H |
| 3.124 | H | H | H | 2 | H | ch3 | choch3 | ch3 | H |
| 3.125 | H | H | H | 0 | H | ch3 | CHOC2H5 | ch3 | H |
| 3.126 | H | H | H | 2 | H | ch3 | CHOC2H5 | ch3 | H |
| 3.127 | H | H | H | 0 | H | ch3 | CHOiPr | ch3 | H |
| 3.128 | H | H | H | 2 | H | ch3 | CHOiPr | ch3 | H |
| 3.129 | H | H | H | 0 | H | ch3 | c=noch3 | ch3 | H |
| 3.130 | H | H | H | 2 | H | ch3 | c=noch3 | ch3 | H |
| 3.131 | H | H | H | 0 | H | ch3 | c=noc2h5 | ch3 | H |
| 3.132 | H | H | H | 2 | H | ch3 | ONOC2H5 | ch3 | H |
| 3.133 | H | H | H | 0 | H | ch3 | C=NOiPr | ch3 | H |
| 3.134 | H | H | H | 2 | H | ch3 | C=NOiPr | ch3 | H |
| 3.135 | H | H | H | 0 | H | ch3 | C=NOCH2CH=CHC1 | ch3 | H |
| 3.136 | H | H | H | 2 | H | ch3 | c=noch2ch=chci | ch3 | H |
| 3.137 | H | H | H | 0 | H | ch3 | C=NOCH2C6H5 | ch3 | H |
| 3.138 | H | H | H | 2 | H | ch3 | c=noch2qh5 | ch3 | H |
| 3.139 | H | H | H | 0 | H | ch3 | C(CH3)2 | ch3 | H |
| 3.140 | H | H | H | 2 | H | ch3 | C(CH3)2 | ch3 | H |
| 3.141 | ch3 | H | H | H | ch3 | c=o | ch3 | H | |
| 3.142 | ch3 | H | H | 2 | H | ch3 | 00 | ch3 | |
| 3.143 | ch3 | H | H | H | ch3 | choch3 | ch3 | H | |
| 3.144 | ch3 | H | H | 2 | H | ch3 | choch3 | ch3 | H |
| 3.145 | ch3 | H | H | H | ch3 | CHOC2H5 | ch3 | H | |
| 3.146 | ch3 | H | H | 2 | H | ch3 | CHOC2H5 | ch3 | H |
| 3.147 | ch3 | H | 0 | H | ch3 | CHOiPr | ch3 | H | |
| 3.148 | ch3 | H | H | 2 | ch3 | CHOiPr | ch3 | ||
| 3.149 | ch3 | H | ch3 | c=noch3 | ch3 | ||||
| 3.150 | ch3 | H | 2 | ch3 | c=noch3 | ch3 | |||
| 3.151 | ch3 | H | ch3 | c=noc2h5 | ch3 | ||||
| 3.152 | ch3 | H | 2 | ch3 | ONOC2H5 | ch3 | |||
| 3.153 | ch3 | H | ch3 | ONOiPr | ch3 | ||||
| 3.154 | ch3 | H | 2 | ch3 | ONOiPr | ch3 | |||
| 3.155 | ch3 | H | ch3 | ONOCH2CH=CHC1 | ch3 | H | |||
| 3.156 | ch3 | H | • < | 2 | 5H3 | ONOCH2CH=CHC1 | 5H3 |
0050/46142 • ·
| Nr. | R17 | r18 | R19 | n | R’2 | R13 | Y | L | M |
| 3.157 | ch3 | H | H | 0 | H | ch3 | C=NOCH2C6H5 | CH3 | Η |
| 3.158 | ch3 | H | H | 2 | H | ch3 | C=NOCH2C6H5 | ch3 | H |
| . 3.159 | ch3 | H | H | 0 | H | ch3 | C(CH3)2 | ch3 | H |
| 3.160 | ch3 | H | H | 2 | H | ch3 | C(CH3)2 | ch3 | H |
| 3.161 | ch3 | ch3 | H | 0 | H | ch3 | c=o | ch3 | H |
| 3.162 | ch3 | ch3 | H | 2 | H | ch3 | c=o | ch3 | H |
| 3.163 | ch3 | ch3 | H | 0 | H | ch3 | CHOCH3 | ch3 | H |
| 3.164 | ch3 | ch3 | H | 2 | H | ch3 | choch3 | ch3 | H |
| 3.165 | ch3 | ch3 | H | 0 | H | ch3 | CHOC2H5 | ch3 | H |
| 3.166 | ch3 | ch3 | H | 2 | H | ch3 | choc2h$ | ch3 | H |
| 3.167 | ch3 | ch3 | H | 0 | H | ch3 | CHOiPr | ch3 | H |
| 3.168 | ch3 | ch3 | H | 2 | H | ch3 | CHOiPr | ch3 | H |
| 3.169 | ch3 | ch3 | H | 0 | H | ch3 | c=noch3 | ch3 | H |
| 3.170 | ch3 | ch3 | H | 2 | H | ch3 | c=noch3 | ch3 | H |
| 3.171 | ch3 | ch3 | H | 0 | H | ch3 | c=noc2h5 | ch3 | H |
| 3.172 | ch3 | ch3 | H | 2 | H | ch3 | onoc2h5 | ch3 | H |
| 3.173 | ch3 | ch3 | H | 0 | H | ch3 | C=NOiPr | ch3 | H |
| 3.174 | ch3 | ch3 | H | 2 | H | ch3 | C=NOiPr | ch3 | H |
| 3.175 | ch3 | ch3 | H | 0 | H | ch3 | C=NOCH2CH=CHC1 | ch3 | H |
| 3.176 | ch3 | ch3 | H | 2 | H | ch3 | c=noch2ch=chci | ch3 | H |
| 3.177 | ch3 | ch3 | H | 0 | H | ch3 | C=NOCH2C6H5 | ch3 | H |
| 3.178 | ch3 | ch3 | H | 2 | H | ch3 | ONOCH2C6H5 | ch3 | H |
| 3.179 | ch3 | ch3 | H | H | ch3 | C(CH3)2 | ch3 | H | |
| 3.180 | ch3 | ch3 | H | 2 | H | ch3 | C(CH3h | ch3 | H |
| 3.181 | H | H | H | 0 | H | ch3 | 00 | Cl | H |
| 3.182 | H | H | H | 2 | H | ch3 | 00 | a | H |
| 3.183 | H | H | H | 0 | H | ch3 | choch3 | Cl | H |
| 3.184 | H | H | H | 2 | H | ch3 | CHOCH3 | a | H |
| 3.185 | H | H | H | 0 | H | ch3 | CHOC2H5 | a | H |
| 3.186 | H | H | H | 2 | H | ch3 | CHOC2H5 | a | |
| 3.187 | H | H | H | H | ch3 | CHOiPr | a | ||
| 3.188 | H | H | H | 2 | H | ch3 | CHOiPr | a | |
| 3.189 | H | 0 | ch3 | c=noch3 | a | ||||
| 3.190 | H | H | 2 | ch3 | c=noch3 | a | |||
| 3.191 | H | H | H | ch3 | c=noc2h5 | a | |||
| 3.192 | 2 | ch3 | c=noc2h5 | a | |||||
| 3.193 | ch3 | ONOiPr | □ | ||||||
| 3.194 | l | ch3 | ONOiPr | □ | |||||
| 3.195 | ch3 | C=NOCH2CH=CHC1 | □ | ||||||
| 3.196 | > | zh3 | >NOCH2CH=CHC1 | □ | |||||
| 3.197 | 3H3 | >NOCH2C6H5 |
0050/46142 • · • ·· ·· ·· ··· · · ·· í · · · · · · • · · · · · • · · « · ...........
| Nr. | R17 | R18 | R19 | n | R12 | R13 | Y | L | M |
| 3.198 | H | H | H | 2 | H | ch3 | C=NOCH2C6H5 | Cl | H |
| 3.199 |H | H | H | 0 | H | ch3 | C(CH3)2 | a | H | |
| . 3.200 |H | H | H | 2 | H | ch3 | C(CH3h | a | H | |
| 3.201 |CH3 | H | H | 0 | H | ch3 | c=o | a | H | |
| 3.202 |CH3 | H | H | 2 | H | ch3 | c=o | a | H | |
| 3203 |CH3 | H | H | 0 | H | ch3 | choch3 | a | H | |
| 3.204 |CH3 | H | H | 2 | H | ch3 | choch3 | a | H | |
| 3.205 | CH3 | H | H | 0 | H | ch3 | CHOC2H5 | a | H | |
| 3.206 1CH3 | H | H | 2 | H | ch3 | CHOC2H5 | Cl | H | |
| 3.207 |cH3 | H | H | 0 | H | ch3 | CHOiPr | Cl | H | |
| 3208 |cH3 | H | H | 2 | H | ch3 | CHOiPr | a | H | |
| 3209 CH3 | H | H | 0 | H | ch3 | c=noch3 | a | H | |
| 3210 |CH3 | H | H | 2 | H | ch3 | o=noch3 | a | H | |
| 3211 |CH3 | H | H | 0 | H | ch3 | ONOC2H5 | a | H | |
| 3.212 1CH3 | H | H | 2 | H | ch3 | C=NOC2H5 | Cl | H | |
| 3213 |CH3 | H | H | 0 | H | ch3 | C=NOiPr | a | H | |
| 3214 |cH3 | H | H | 2 | H | ch3 | C=NOiPr | a | H | |
| 3.215 |CH3 | H | H | 0 | H | ch3 | C=NOCH2CH=CHCl | Cl | H | |
| 3216 1CH3 | H | H | 2 | H | ch3 | c=noch2ch=chci | Cl | H | |
| 3217 1CH3 | H | H | 0 | H | ch3 | C=NOCH2CeH5 | a | H | |
| 3.218 |cH3 | H | H | 2 | H | ch3 | ONOCH2QH5 | a | H | |
| 3219 1CH3 | H | H | 0 | H | ch3 | C(CH3h | a | H | |
| 3220 1CH3 | H | H | 2 | H | ch3 | C(CH3)2 | Cl | H | |
| 3221 |cH3 | ch3 | H | 0 | H | ch3 | 00 | a | H | |
| 3222 |cH3 | ch3 | H | 2 | H | ch3 | c=o | a | H | |
| 3223 |CH3 | ch3 | H | 0 | H | ch3 | choch3 | a | H | |
| 3224 |CH3 | ch3 | H | 2 | H | ch3 | choch3 | Cl | H | |
| 3225 |CH3 | ch3 | H | 0 | H | ch3 | CHOC2H5 | a | H | |
| 3226 1CH3 | ch3 | H | 2 | H | ch3 | CHOC2H5 | a | H | |
| 3227 |cH3 | ch3 | H | 0 | H | ch3 | CHOiPr | a | H | |
| 3228 1CH3 | ch3 | H | 2 | H | ch3 | CHOiPr | a | H | |
| 3229 1CH3 | ch3 | 0 | H | ch3 | c=noch3 | a | |||
| 3230 | CH3 | ch3 | H | 2 | H | ch3 | c=noch3 | a | ||
| 3231 CH3 | ch3 | 0 | H | ch3 | ONOC2H5 | a | |||
| 3232 |CH3 | ch3 | 2 | H | ch3 | ONOC2H5 | Cl | |||
| 3233 |cH3 | ch3 | 0 | H | ch3 | ONOiPr | a | |||
| 3.234 |cH3 | ch3 | 2 | H | ch3 | C=NOiPr | a | |||
| 3235 |CH3 | ch3 | 0 | ch3 | C=NOCH2CH=CHC1 | □ | ||||
| 3236 |CH3 | ch3 | 2 | ch3 | >NOCH2CH=CHa | □ | ||||
| 3237 |cH3 | ch3 | a | 2H3 | >NOCH2C6H5 | □ | ||||
| 3238 | CH3 | ch3 | 2 | DH3 | >NOCH2C6H5 | □ |
0050/46142 • · * · • · • · · · • ·
- 37 ♦ ♦ · · · · · • ·
| Nr. | R17 | r18 | R19 | n | R12 | R13 | Y | L | M |
| 3.239 | ch3 | ch3 | H | 0 | H | ch3 | C(CH3)2 | a | H |
| 3.240 | ch3 | ch3 | H | 2 | H | ch3 | C(CH3)2 | a | H |
| . 3.241 | H | H | H | 0 | H | ch3 | c=o | ch3 | ch3 |
| 3.242 | H | H | H | 2 | H | ch3 | c=o | ch3 | ch3 |
| 3243 | H | H | H | 0 | H | ch3 | choch3 | ch3 | ch3 |
| 3.244 | H | H | H | 2 | H | ch3 | choch3 | ch3 | ch3 |
| 3245 | H | H | H | 0 | H | ch3 | CHOC2H5 | ch3 | ch3 |
| 3246 | H | H | H | 2 | H | ch3 | CHOC2H5 | ch3 | ch3 |
| 3.247 | H | H | H | 0 | H | ch3 | CHOiPr | ch3 | ch3 |
| 3.248 | H | H | H | 2 | H | ch3 | CHOiPr | ch3 | ch3 |
| 3249 | H | H | H | 0 | H | ch3 | coch3 | ch3 | ch3 |
| 3250 | H | H | H | 2 | H | ch3 | coch3 | ch3 | ch3 |
| 3251 | H | H | H | 0 | H | ch3 | COC2H5 | ch3 | ch3 |
| 3252 | H | H | H | 2 | H | ch3 | COC2H5 | ch3 | ch3 |
| 3253 | H | H | H | 0 | H | ch3 | c=noch3 | ch3 | ch3 |
| 3254 | H | H | H | 2 | H | ch3 | c=noch3 | ch3 | ch3 |
| 3255 | H | H | H | 0 | H | ch3 | c=noc2h5 | ch3 | ch3 |
| 3256 | H | H | H | 2 | H | ch3 | c=noc2h5 | ch3 | ch3 |
| 3257 | H | H | H | 0 | H | ch3 | ONOiPr | ch3 | ch3 |
| 3258 | H | H | H | 2 | H | ch3 | ONOiPr | ch3 | ch3 |
| 3259 | H | H | H | 0 | H | ch3 | onoch2ch=chci | ch3 | ch3 |
| 3260 | H | H | H | 2 | H | ch3 | onoch2ch=chci | ch3 | ch3 |
| 3261 | H | H | H | 0 | H | ch3 | C=NOCH2C6H5 | ch3 | ch3 |
| 3262 | H | H | H | 2 | H | ch3 | c=noch2qh5 | ch3 | ch3 |
| 3263 | H | H | H | H | ch3 | C(CH3)2 | ch3 | ch3 | |
| 3264 | H | H | H | 2 | H | ch3 | C(CH3)2 | ch3 | ch3 |
| 3265 | ch3 | H | H | H | ch3 | 00 | ch3 | ch3 | |
| 3266 | ch3 | H | H | 2 | H | ch3 | 00 | ch3 | ch3 |
| 3267 | ch3 | H | H | 0 | H | ch3 | choch3 | ch3 | ch3 |
| 3268 | ch3 | H | H | 2 | H | ch3 | choch3 | ch3 | ch3 |
| 3269 | ch3 | H | H | 0 | H | ch3 | CHOC2H5 | ch3 | ch3 |
| 3270 | ch3 | H | H | 2 | ch3 | CHOC2H5 | ch3 | ch3 | |
| 3271 | ch3 | H | H | H | ch3 | CHOiPr | ch3 | ch3 | |
| 3272 | ch3 | H | H | 2 | ch3 | CHOiPr | ch3 | ch3 | |
| 3273 | ch3 | H | H | ch3 | c=noch3 | ch3 | ch3 | ||
| 3274 | ch3 | H | H | 2 | ch3 | c=noch3 | ch3 | ch3 | |
| 3275 | ch3 | H | ch3 | ONOC2H5 | ch3 | ch3 | |||
| 3276 | ch3 | H | 2 | ch3 | ONOC2H5 | ch3 | ch3 | ||
| 3277 | ch3 | H | ch3 | ONOiPr | ch3 | ch3 | |||
| 3278 | ch3 | H | 2 | ch3 | ONOiPr | ch3 | ch3 | ||
| 3279 | ch3 | H | ch3 | ONOCH2CH=CHC1 | 2H3 | ch3 |
0050/46142
• · · • · · ♦
| Nr. | R17 | r18 | R19 | n | R12 | R13 | Y | L | M |
| 3.280 | ch3 | H | H | 2 | H | ch3 | C=NOCH2CH=CHC1 | ch3 | ch3 |
| 3281 | ch3 | H | H | 0 | H | ch3 | C=NOCH2C6H5 | ch3 | ch3 |
| 3282 | ch3 | H | H | 2 | H | ch3 | C=NOCH2C6H5 | ch3 | ch3 |
| 3283 | ch3 | H | H | 0 | H | ch3 | C(CH3)2 | ch3 | ch3 |
| 3284 | ch3 | H | H | 2 | H | ch3 | C(CH3)2 | ch3 | ch3 |
| 3285 | ch3 | ch3 | H | 0 | H | ch3 | c=o | ch3 | ch3 |
| 3286 | ch3 | ch3 | H | 2 | H | ch3 | c=o | ch3 | ch3 |
| 3287 | ch3 | ch3 | H | 0 | H | ch3 | CHOCH3 | ch3 | ch3 |
| 3288 | ch3 | ch3 | H | 2 | H | ch3 | choch3 | ch3 | ch3 |
| 3289 | ch3 | ch3 | H | 0 | H | ch3 | CHOC2H5 | ch3 | ch3 |
| 3290 | ch3 | ch3 | H | 2 | H | ch3 | CHOC2H5 | ch3 | ch3 |
| 3291 | ch3 | ch3 | H | 0 | H | ch3 | CHOiPr | ch3 | ch3 |
| 3292 | ch3 | ch3 | H | 2 | H | ch3 | CHOiPr | ch3 | ch3 |
| 3293 | ch3 | ch3 | H | 0 | H | ch3 | c=noch3 | ch3 | ch3 |
| 3294 | ch3 | ch3 | H | 2 | H | ch3 | c=noch3 | ch3 | ch3 |
| 3295 | ch3 | ch3 | H | 0 | H | ch3 | C=NOC2H5 | ch3 | ch3 |
| 3296 | ch3 | ch3 | H | 2 | H | ch3 | ONOC2H5 | ch3 | ch3 |
| 3297 | ch3 | ch3 | H | 0 | H | ch3 | ONOiPr | ch3 | ch3 |
| 3298 | ch3 | ch3 | H | 2 | H | ch3 | ONOiPr | ch3 | ch3 |
| 3299 | ch3 | ch3 | H | 0 | H | ch3 | ONOCH2CH=CHC1 | ch3 | ch3 |
| 3300 | ch3 | ch3 | H | 2 | H | ch3 | C=NOCH2CH=CHa | ch3 | ch3 |
| 3301 | ch3 | ch3 | H | 0 | H | ch3 | ONOCH2QH5 | ch3 | ch3 |
| 3302 | ch3 | ch3 | H | 2 | H | ch3 | ONOCH2QH5 | ch3 | ch3 |
| 3303 | ch3 | ch3 | H | H | ch3 | C(CH3)2 | ch3 | ch3 | |
| 3304 | ch3 | ch3 | H | 2 | H | ch3 | C(CH3)2 | ch3 | ch3 |
- 39 Tabulka 4: Sloučeniny formule
| s | X | X | X | X | X | X | X | x‘ | X | X | X | X | X | X | X |
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| i | 8 | 8 | § 5 | i δ | f δ | Λ X u | X § δ | í δ | i δ | f o δ | Ϊ δ | £ δ δ | £ 1 6 | £ § δ | |
| a | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| δ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | 1 X í |
| en w· fii | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| ΓΜ w. fii | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| s | e | CM | o | CM | o | CM | o | «· | CM | e | CM | ||||
| Ot •Mi Pí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| «0 PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| r* PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| z | ^M | * | * | so | Os | o • | •4 | CM M? | «·> < | jř • •M· | « Φ· |
0050/46142 • ♦
| 3 | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| m | X | X | X | s | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
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| a | X | X | X | s | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| cn PÍ | X | X | X | Ύί | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| Zl* | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| a | CM | CM | o | CM | o | CM | o | CM | o | CM | o | ||||||||
| O\ pí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 Pí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| Γ* PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
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0050/46142
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• ·
0050/46142
- 42 • · • · · • · · · • * · • · · • · · · · ♦ ·
| 3 | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
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| δ | x | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
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| PÍ | x | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
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| r* ·—* PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
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0050/46142
| x | m | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
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• ·
0050/46142 • ·
| x | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
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| fc | x | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
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| s | CM | CM | o | CM | o | CM | o | •“4 | CM | o | CM | o | CM | |||||||
| o\ (X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| oo P4 | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
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0050/46142
| 3 | ffi | X | X | X | X | X | X | X | X | X | X |
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• ·
0050/46142
| 3 | « | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
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0050/46142
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0050/46142
- 48 • · · · ·
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• · • · · ·
0050/46142
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• · • · · ·
0050/46142 • · • · · ·
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0050/46142
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• ·
0050/46142
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0050/46142
| 3 | ě | 5 | á? u | ď u | á? Q | X o | m X o | ď O | cn X o | X u | en X o |
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0050/46142
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0050/46142 • · · · 'x.b<.·
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0050/46142
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| 0050/46142 | - 57 - | « «· · * x ‘ í : : 1 .· · ϊ i ···«··< · · |
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| δ | X | X | X | X | X | X | X | X | X | X | X |
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| (3 | o | CM | o | CM | o | <N | o | ||||
| O\ Pí | X | X | X | X | X | X | X | X | X | X | X |
| 00 1* PÍ | X | X | T | X | X | X | X | X | X | X | X |
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0050/46142 • ·
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0050/46142 » · « 4 • · ·
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0050/46142
| 3 | m X υ | 5? υ | X u | m X o | X υ | c*s δ | X o | X o | X ω | £ Q | cn X υ | <n X o | m X o | X u | δ | en X υ | rf? u | X o | m X υ | ť*S X υ | £ U |
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| m | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
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0050/46142 • « • · · · • · · · ·
| >1 | rn X u | X o | á? o | X Q | m X u | m X u | í1 o | m X u | m X o | <*> X Q | <*» δ |
| X | X | X | X | X | X | X | X | X | X | X | |
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| 04 | X | X | X | X | X | X | X | X | X | X | X |
| oá | X | X | X | X | X | X | X | X | X | X | X |
| m PÍ | X | X | X | ΊΠ | X | X | X | X | X | X | X |
| n PÍ | X | X | X | X | X | X | X | X | X | X | X |
| ta | 04 | o | 04 | o | 04 | o | 04 | o | |||
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| r* | X o | X o | m X o | m X o | m X o | X Q | r> X o | X u | X u | X u | n X o |
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• ·
0050/46142
| 5 | § | CA X u | 5? o | X o | CA X Q | CA X o | CA X Q | CA X O | CA 5 | X o | CA X o | g | CA X υ | CA X υ | β | § | ď o | X u | X u | CA X u | g |
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| δ | Ti | X | ►g | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| m | X | X | X | τ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
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| a | CM | o | CM | o | CM | o | CM | o | CM | o | •M | CN | o | •M | CM | o | |||||
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0050/46142
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0050/46142 *
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0050/46142
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0050/46142
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0050/46142 ·· 0 0 ··· « · · · • · · ···· 0 · · 0 • · 0 · · 0 · · 0 • 00 ···· ·· ·· ·· ··
| 3 | G | ϋ | g | G | G | G | G | G | □ | G | G | G | G | G | G | G | G | •Mj O | G | G | G |
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0050/46142 • *
| 5 | υ | υ | υ | o | o | ΰ | o | G | u | Q | o |
| X | X | X | X | X | X | X | X | X | X | X | |
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0050/46142
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| £ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
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• · • ·
0050/46142
| G | M«4 u | G | G | R O | G | G | G | G | G | G | G | G | «4 O | G | G | G | G | G | G | 0 | |
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0050/46142 • · • ·
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| a | CM | o | CM | CM | o | CM | o | ^4 | CM | o | lH | CM | o | CM | |||||||
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0050/46142
| G | G | G | G | G | G | G | G | G | G | G | ^4 O | G | |
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0050/46142 • · • · · ·
| 3 | □ | G | G | G | g | •—4 Q | u | G | G | G | G | u | 0 | G | □ | G | G | G | |
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0050/46142
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0050/46142
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• · • · · ·
0050/46142 • ·
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0050/46142 • ·
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• · • · • · · · * 9 9 • · · · · · ·
0050/46142
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• · • ·
0050/46142
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0050/46142
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0050/46142
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• · · • ♦
0050/46142
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0050/46142 • · · ·
| 3 | 5 z | $ | § | ď z | Ó* z | ď z | ď z | § | $ | ď z | £ | £ | ď z | ď z | ď z | ď z | ó1 z | f | £ | ||
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0050/46142 • · • 9 • 9 9 9 9
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0050/46142 • · ·
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0050/46142
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0050/46142
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• · • · · · • ·
0050/46142 • ·
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0050/46142 • · · · ·
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0050/46142
| 3 | £ o | £ u | § | § | ř*» X o | m X u | cn X Q | £ u | £ o | £ υ | £ o | £ υ | m X o | § | m 5 | £ υ | m X u | m δ |
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0050/46142 • ·
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0050/46142
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0050/46142
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0050/46142 < s · ·
| X o | m X Q | 8 | m 8 | m X y | m X o | X O | m X y | m X o | en X o | § | en X y | c*s X y | r*> X y | 3? y | g | X y | X y | |
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• · ·· • · • · · ·
0050/46142 • ·
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| % | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
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| CM PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| a | CM | o | CM | o | CM | o | CM | o | «s | © | CM | o | CM | o | |||||||
| Os PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 PÍ | X □ | m X o | o | £ u | £ u | m X u | cn X Q | <*» X u | 5 | £ u | c*s δ | en X o | <*s δ | £ υ | £ υ | £ o | g | m X u | £ υ | m X u | X |
| r* PÍ | m X o | Í*J X o | £ o | m X u | A δ | m X o | cn δ | m X υ | r*» X υ | m X υ | £ u | £ u | m X υ | £ υ | «*» X u | £ o | m δ | m X o | X o | £ υ | X |
| ž* | oo oo o A | Ox 00 o r—4 xr | 8 o | Os O ·* | S o | m Os o | & o ^4 | *A Os O Tř | 8 o * | r* Os O | 00 Os O | βχ σχ o | S | O | CM O »4 | m O ^4 | A o P»4 »•4 | Ό o | r* O *«4 | 00 o ^4 •4Ť |
0050/46142 • · • ·
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| o | G | G | G | G | G | G | G | G | G | G | rH Q | G | G | G | G | G | G | O | G | G | G | |
| 0 | G | G | G | G | G | G | G | G | G | G | G | G | G | G | G | G | G | G | G | «H O | G | |
| o δ | o δ | X £ o | •n X § u | m X 8 X Q | M* 8 X Q | Wk £ i 5 | «η f X υ | & § o | £ 5 | £ s X o | £ 8 3 o | X 8 l | £ 8 ! | «Λ X 1? z δ | «Λ X í? z δ | w> X | £ 1 G> | £ δ l | δ o Ϊ | g l £ 8 l | 8 ŽĚ g 8 l | |
| CM a | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| cn PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| es PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 0 | Γ4 | o | CM | o | r-M | CM | o | CM | o | H4 | CM | o | CM | o | Π4 | CM | o | ·« | ||||
| os PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 ** PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| r* Pí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| Ž | Os O M* | o rH ·—< e | cm r-H | m ^-4 xr | Xf «*< •4 Xt | Xt | \O «Μ xfr’ | F- xt | 00 ^4 xř | Os xT | O xř | es v* | CM CM •»h Mf | en CM rH rH xř | xí- CM ^4 M* | CM ^h xt | s© CM * | o; xí | 00 CM •M | Os CM Π4 *« xř | o m Mt |
0050/46142 • ·
| 3 | G | ^4 υ | G | G | G | g | G | G | G | G | 0 | G |
| G | G | G | G | G | G | G | G | G | G | G | G | |
| >· | § £ δ | a σ £ 8 u | X (3 X 8 l | V» X ž % | CM n X u o | CM z·—» £ y. o | CM X y. o | cs X u ťC ''rí X X u o 1 1 o o v. y' o | CM X X u u 1 1 o o u | CM u «< X X u u 1 1 o o | ro <-> X X O u X X X u o 1 1 o o o | m m X X u O X X X υ o 1 1 o o o |
| CM PÍ | X | X | X | X | X | X | X | X | X | X | X | X |
| X | X | X | X | X | X | X | X | X | X | X | X | |
| m Pt | X | X | X | X | X | X | X | X | X | X | X | X |
| X | X | X | X | X | X | X | X | X | X | X | X | |
| a | CM | o | CM | o | CM | o | w4 | CM | o | •—4 | ||
| Os fit | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 fit | X | X | X | X | X | X | X | X | X | X | X | X |
| X | X | X | X | X | X | X | X | X | X | X | X | |
| Nr. | cn *«4 | CM m ”T | C**> m | M“ m e—M | w> cn | SO m tT | tm | 00 m ^4 4-4 | Os cn ^4 ^4 | o 4^4 'T | M* w>4 | CM mt rř |
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| 5 | δ | δ | δ | δ | δ | δ | «4 O | δ | δ | δ | δ | δ | δ | δ | δ | δ | δ | δ | δ | δ | δ | |
| δ | δ | υ | δ | u | δ | δ | δ | δ | δ | o | δ | δ | δ | δ | δ | δ | δ | δ | O | δ | ||
| rs | rs | |||||||||||||||||||||
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| < | X | x | ||||||||||||||||||||
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| Λ X o | cs X u | WS X $ | £ | £ | £ | WS (M | ws X Μ | £ | -Χί | £ | Λί £ | X g | X g | X g | O £ | o /*-s £ | ||||||
| 1 o | 1 o | m | rs | f | WS I | WS X ď | g | g | -NHC | g | g | g | £ | £ | 1 | |||||||
| z | z | z | z | z δ | J, | SE | CH- | X | X | X | jg | ώ | X | X | ||||||||
| u | δ | li Q | δ | δ | δ | u | υ | υ | o | u | Q | u | o | o | u | u | o | u | ||||
| CM £ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| 2 | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| m »“* | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| <M PÍ | 32 | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| S | CM | o | CM | o | CM | o | CM | © | CM | O | CM | o | CM | o | —1 | |||||||
| 61* | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| 00 Pí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| rPí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| Nr. | 4.1143 | 4.1144 | 4.1145 | 4.1146 | 4.1147 | 14.1148 | 14.1149 | 4.1150 | 4.1151 | 4.1152 | 4.1153 | 4.1154 i | 4.1155 | 4.1156 | 4.1157 | 4.1158 | 4.1159 | 4.1160 | 4.1161 | 4.1162 | 4.1163 |
0050/46142
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| G | G | G | g | G | G | G | G | G | G | G | G | G | G | G | G | *A O | G | ••A u | G | G | G | |
| υ | G | 0 | G | G | G | G | G | G | G | 0 | G | G | G | G | G | G | G | G | G | G | G | |
| CA | Q | cm 1 u | CM 1 υ | 4? 1 II o | CM Z“s CA X 52 I II u | PA 1 δ | λ £ 52 U O | IA X Ό £ £ O ? X u | •A % X 8 £ 52 i u | •A X CO £ 8 £ u i o | IA X £ £ o, o | £ CA X 52 o | £ CA X 52 o | o | o | o | o δ | o δ | o δ | £ 8 X υ | IA X 8 X o | CA X 8 X o | |
| CM pk | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| UÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| m PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| CM PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| s | CM | o | ^A | CM | o | CM | o | A | CM | o | CM | o | A | CM | © | A | CM | o | wA | CM | ||
| Pí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 8IÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| Ílí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | CA X o | CA X o | £ o | CA X Q | £ ω | CA X υ |
| Nr. | 3 ^A -<r | m so A XT | 3 χτ | Γ* \O χτ | 00 s© »>a XT | ©s c© A xř | © r~ ^A A xr | r* A xr | CM r- A xr | cn r^A A XT | ? xr | VA r- xT | Ό r•A XT | C r*> | 00 r- A*4 XT | ©s r* wA xf | o 00 A a Xt | 00 xt | CM 00 ^A ^A ^T | CA 00 A A xr | 3 A xr | UA 00 ^A |
0050/46142 • · • ·
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| 3 | G | G | g | CJ | G | G | G | G | G | G | G | G | G | G | G | G | G | G | G | G | G | G |
| G | G | G | G | G | G | G | G | G | G | G | G | G | G | G | G | G | G | G | CJ | G | G | |
| ž X u | «Η I o | w> 1 X o | £ δ X o | £ δ X cj | £ <p4 O X CJ | X 8 l | £ l | £ 8 Ϊ | X § | v> X í | X g 5 cj | w s l | Im 04 • «4 O l | á o CJ | 8 l | 8 l £ 8 Š | 8 l £ 8 l | V» X ž i | *A X ž 8 l | m X σ £ 8 l | CM £ g | |
| CM a | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| iztf | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| <*» PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| CM | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| β | o | CM | o | CM | o | CM | o | CM | o | CM | o | ^4 | CM | o | CM | o | ||||||
| 0 PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| r- PÍ | ř*i X υ | <Λ X cj | m X u | m X o | r> u | m X o | m X o | en X o | £ cj | £ u | £ u | m X cj | m X o | £ u | cn X o | <*) X o | ř*> X cj | £ cj | £ cj | £ CJ | cn 3 | £ u |
| ž | Ό 00 V | r* 00 | 00 00 »~4 | 0 00 | »-4 | Os | CM 0% »·< | cn Ov | S e | U-) 0 «4 | so os xr | r* 0 M* | 00 0 | 0 0 w-4 | 8 CM | o CM ^•4 | 8 CM rr | n O CM | i | W> 0 CM | 3 CM xř | o CM ••4 |
0050/46142
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| 3 | y | Q | y | o | y | y | y | y | y | y | •M y |
| y | U | o | y | y | y | y | y | y | **« y | ^4 y | |
| cm ί* 8 | rs X £ υ | CM δ X X u o 1 1 o o | cs X u << X X o u 1 1 o o Z· o | P) X u fť X X υ υ 1 1 o o x. O | n m X X υ o X X X u o 1 1 o o o | m m X X o u X X X O o 1 1 o o u | m m X X u o X X X υ u 1 1 o o 'S o | X i t> | m z ó | m i | |
| CM fc | X | X | X | X | X | X | X | X | X | X | X |
| w4 fc | X | X | X | X | X | X | X | X | X | X | X |
| CO fc | X | X | X | X | X | X | X | X | X | X | X |
| X | X | X | X | X | X | X | X | X | X | X | |
| 0 | CM | o | •—4 | CM | © | CM | © | •—4 | CM | ||
| os PÍ | X | X | X | X | X | X | X | X | X | X | X |
| 00 r·* «X | X | X | X | X | X | X | X | X | X | X | X |
| £1* | m X υ | m o | X y | cn X y | <*» X y | X y | m X y | cn X u | cn X y | X u | m X y |
| •JN | § CM *4 Tt | δ CM Tt | © »^4 CM xr | •r CM Tfr | CM CM TT | m CM | r“4 CM | WJ CM Μ | \o 1—4 CM Tt | r* CM Tf | 00 *4 CM Tf* |
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| s | G | G | G | G | w4 o | G | G | G | G | G | G | G | 0 | G | G | G | G | G | G | G | G | G |
| u | 0 | G | O | G | G | >4 O | G | G | G | G | 0 | G | G | o | G | G | O | G | G | G | G | G |
| <r> | VJ | |||||||||||||||||||||
| X | X | X | ||||||||||||||||||||
| ri | CS | |||||||||||||||||||||
| «Η | Q | Q | Q | rs | ||||||||||||||||||
| x ď | X | *n X | x u | SÉ? o | sff o | X u | X ó* | X ď | «s Ě | Λ! £ £ | X £ | X g | 1 | X I | O | O sc o | O z·—\ £ £ | rc | rs | rs | sc | |
| o | ď | [z | z | z | z | Z | z | <4 | 1 | Ϊ | 5ί | 2; | z | I | ||||||||
| l | z δ | z δ | 5 | X o | i u | sc υ | X o | se Q | δ | ώ o | o | o | u | o | G | o | o | δ | δ | δ | ||
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| •-«4 | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| (*) ^•4 PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| cs | o | cs | o | cs | o | rs | o | ^4 | cs | o | es | o | rs | o | ^“4 | cs | o | |||||
| <h ·* fit | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 | ||||||||||||||||||||||
| fit | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| rPí | X o | cn X o | cn X o | r» X o | X o | X u | X o | cn X o | cn X o | cn X u | £ υ | rn X υ | cn δ | cn X υ | cn X u | cn X Q | £ o | cn X u | cn δ | § | cn X υ | cn δ |
| !Z | 4.1219 | 4.1220 | 4.1221 | 4.1222 | 4.1223 | 4.1224 | 4.1225 | 4.1226 | 14.1227 | 4.1228 | 4.1229 | 4.1230 | 4.1231 | 4.1232 | 4.1233 | 4.1234 | 4.1235 | 4.1236 | 4.1237 | 4.1238 | 4.1239 | 4.1240 |
0050/46142 • ·
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| s | u | G | G | G | G | G | G | «•“4 O | G | G | G | G | G | G | p—« u | G | G | G | G | PM Q | G | 0 |
| t-4 | G | G | G | G | G | G | G | G | G | G | G | G | G | G | G | G | G | G | G | O | G | G |
| d z <5 | d Z o o | V» X g £ a 1 o | *n z \© £ 4? X U Ϊ o | Z ď X 8 z-s cn X u >·✓ Ϊ Q | m X X u, u | Z X υ u | z ď g | o | o | o | o II υ | o δ | o II u | m z 8 z u | m X 8 X o | <*> X 8 X o | »n X d 8 X u | d 8 X o | z 8 X u | £ o z o | & δ z Q | |
| CM | X | X | X | X | X | X | X | z | X | X | X | X | X | X | X | X | z | X | X | X | z | Z |
| % | X | Ti | X | X | X | X | X | z | X | X | z | X | X | X | z | X | z | X | X | X | z | Z |
| ει* | X | X | X | X | X | X | X | z | X | X | z | X | X | X | z | X | z | X | X | z | z | z |
| π* | X | X | X | X | X | X | X | z | X | X | z | X | X | X | z | X | z | X | X | z | z | z |
| Q | CM | o | CM | o | CM | o | CM | © | CM | o | CM | © | CM | © | _ | |||||||
| fit | X | X | X | X | X | X | X | Z | X | X | z | X | X | X | z | X | z | X | X | z | z | z |
| OO «p« »4 | X | X | X | X | X | X | X | z | X | X | z | m X Q | m X Q | en z o | § | c*» X Q | z o | Z o | en X u | m δ | z υ | m z o |
| Z.lH | m X o | ř*» X o | m X υ | f*» X Q | <n X υ | m X u | cn X o | m z υ | tn X o | o | c*» X υ | X u | Z u | m u | m 5 | m X u | «*> X u | c*l X υ | X u | d z u | m X u | cn z Q |
| Nr. | Φ* CM Φ | CM 3 Φ· | m Φ* CM pW Φ* | 5 CM Φ | «η φ· CM Φ | $ CM Φ·“ | r* φCM Φ* | 00 φ> CM ΦΤ | o 3 ΦΓ | 8 CM p«M Φ* | ΙΑ CM Φ· | CM ΜΊ CM pH Φ* | m <n CM Φ | a CM Φ- | ΙΛ ΙΛ CM Φ* | Ό ui CM Φ” | r* <A CM Φ | 00 ΙΛ CM p“M Φ' | O\ tn CM p*4 Φ* | 8 CM p«M Φ | Ό CM pM Φ- | cm CM Φ* |
0050/46142 • 0 0 • *
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- 108 -
| G | O | G | G | G | G | G | G | G | G | G | G | «M u | G | G | 0 | G | G | G | G | |
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| £ o X u | X y ύ | ď 8 s | X u | vs X g o | X g l | VS I l | «Μ ĎH l | £ l | Im l | S £ 3 X 8 % υ | X Ϊ δ X 8 1 | l ? u | vs X ž 8 Ž | vs X % & | vs X £ | Λί m X y Q | ÍN /—s (*S δ Srn/ o | CN M y u | ^HO--0χ CHD D ^H0 01 | |
| CN | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| pí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| c | CN | o | CN | o | CN | o | CN | o | CN | o | CN | o | CN | o | ||||||
| 0S PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 Pí | X o | X Q | § | X o | rs X u | δ | <n X u | en X o | r*s 8 | X u | m X u | m X Q | cn 8 | rs 8 | g | rs δ | o | ť*S X u | X υ | g |
| rs X υ | (*S 3 | X υ | m X υ | X u | r*s X u | X u | m X υ | X o | n X o | m X u | rs X u | X u | X o | δ | X u | X u | X u | X Q | en δ | |
| ž | en s© CN Nr | 3 CN Ν’ | *o \© CN »“< Ν’ | 3 CN Ν’ | δ CN «Μ •e | 3 CN Ν’ | 0S Ό CN Ν’ | O rCN Ν’ | ·* ř* CN Ν’ | CN r* CN Ν’ | m r* CN N* | s CN Ν’ | VS r· CN Ν’ | s© r* CN •M Ν’ | § Ν’ | 00 r* CN N* | Os rCN Ν’ | 8 CN Ν’ | M·* 00 CN •H Ν’ | oo CN Nr |
| 0050/46142 | - 109 - | ♦ · • · • · • · · · · · · |
| 3 | G | G | G | G | G | G | G | G | **4 O | G | G | G | G |
| G | G | G | G | G | G | G | G | G | G | G | 4 o | G | |
| CN X o C< ^CN X X o o 1 1 o o | CN X o c< ^cn X X υ υ 1 1 o o υ | m cn X X o u X X X o υ 1 1 o o >s. u | tn <n X X O o X X X u u 1 1 o o o | cn cn X X o υ X X X υ υ 1 1 o o υ | X l | cn 5 Ϊ | cn 5 o | vs X t | <Λ X o l | X £ z ó | X y X o | cn X y i u | |
| CN PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X |
| Pí | X | X | X | X | X | X | X | X | X | X | X | X | X |
| <n Pí | X | X | X | X | X | X | X | X | X | X | X | X | X |
| CN oí | X | X | X | X | X | X | X | X | X | X | X | X | X |
| c | »-R | CN | o | CN | o | CN | o | CN | o | ||||
| Os PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 PÍ | cn X υ | cn X u | cn X u | 5 | m X u | g | cn X u | cn X o | cn X o | cn X υ | δ | X o | cn X o |
| Ípl | cn X o | m o | cn X υ | cn X o | cn X o | X o | cn X o | cn X υ | X Q | cn X υ | cn 5 | cn u | cn 5 |
| ž' | m 00 CN | 3 CN •*r | m 00 CN NT | s© 00 CN | r~ oo CN e | 00 00 CN M* | Os 00 CN xť | g CN | •“4 σ> ÍN Nt | CN Os CN | Os CN | s CN | OS CN •M |
• · • · · · • · · · • · · · • · · · ·
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| G | G | G | 0 | G | G | 3 | G | G | G | G | G | G | G | «*4 G) | G | G | G | G | G | G | G | |
| G | G | g | G | G | •M G> | G | G | G | G | G | G | G | G | ^4 G) | G | G | G | G | G | G | G | |
| «Λ | ||||||||||||||||||||||
| X | X Ό | |||||||||||||||||||||
| «Α | vs | vs | % | |||||||||||||||||||
| X | X | X | X | X | X | |||||||||||||||||
| CM | r s | rj | u | |||||||||||||||||||
| vs X f | srs I | v> X I | 4? r> X o | CM £ £ | A? £ G> Z | *rs X g | £ § 1 | vs X g | 8 § | 8 £ | 8 /*X 4? δ | ^gl | £ | d | CM X o, I | £ | <M *rs X o, I | 8 £ | 8 z-s δ | 8 i | ||
| Q | gT | Q | υ | i u | i Q | o | G) | u | g | u | G) | ir G) | δ | δ | H U | δ | δ | υ | ||||
| cm a | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| Ph | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| rs PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| CM PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| a | CM | o | CM | O | CM | o | *4 | CM | o | CM | o | CN | o | w4 | CM | o | **4 | CM | ||||
| Os PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 | £ u | X o | rs X G) | rs X Q | rs X G> | rs X u | £ G) | rs X G> | š | rs 5 | £ u | £ G> | rs δ | rs X G) | rs X G) | rs X G> | £ u | £ G) | £ G) | § | £ Q | £ G) |
| r* PÍ | rs X G> | X G> | rs X o | rs X G> | rs X G) | rs X G> | rs X G) | £ G) | rs X G) | £ G) | rs X υ | £ G) | rs X o | £ G) | rs X G) | £ G) | rs X G) | rs X G> | £ G) | £ Q | £ υ | £ G> |
| Nr. | £ CN Ν’ | oš ^4 Xf | CM Ν’ | Os a\ (N ^4 Ν’ | 8 rs •4 NT | ^4 O m e | CM O rs w«4 Ν’ | rs o rs Nr | 3 rs N | trs O rs N* | Ό O eo *^4 Ν’ | O n ^4 N* | s m N* | 8 Π N | o R4 rs Ν’ | ^4 «*4 rs ^4 Ν’ | CM rs N* | rs rs Ν’ | N* w4 rs w4 N* | trs ^4 rs ^4 N* | v© rs N“ | r* n Ν’ |
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| 3 | G | G | G | G | G | G | f*1 X υ | £ u | m X υ | ť*S δ | £ o | § | en X o | m X u | <*s X ω | ř*> X o | rs X u | cn X u | rs X o | rs X u | £ u |
| u | □ | G | G | g | G | G | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| £ £ u | r*s X $ m X o, o | e*s X £ £ u | o | o | o | o δ | o δ | o δ | £ X Q | £ 8 X Q | § X o | WS 1 X u | WS X CM 8 X o | WS 1 3 | & o X o | w &4 O X u | o X u | £ § II u | J? s 8 ¥ υ | £ 8 u | |
| CM | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| δ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| m fit | X | X | X | X | X | X | £ u | £ o | £ u | m X o | <*s δ | m 3 | <n 3 | £ o | £ υ | £ | cn X u | «η X o | rs X u | £ u | 3 |
| CM | X | X | X | X | X | X | £ Q | § | £ Q | £ o | £ o | í | £ o | £ o | £ Q | £ o | £ o | m δ | £ o | § | £ o |
| a | o | CM | o | CM | O | CM | o | CM | o | •»4 | CN | o | 4*4 | CM | o | CM | |||||
| Os fit | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| OO fit | rs X o | f*S δ | £ υ | en X u | m X o | X Q | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| r* Pí | f*» O | Γ*Ί X o | <*» δ | cn X o | FA X o | m X u | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| ž | 00 *4 en ^4 | OS ^4 en ^4 | 8 m ^4 | «Μ4 CM m w«4 tT | CM CM c*s -T | m CM m MT | S <*> | WS CM cn •»4 | v© CM cn | C*· CM m *•4 | 00 CM m Xt | as CM m *«4 V | o m cn | rH cn m »*< | CM en m | m m cn M· | M· cn f*S Mr | m m m | S© <*) cn | c— cn m 4·' | 00 cn c*> |
• ·
0050/46142
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| £ u | £ y | £ y | £ y | δ | § | en δ | «*> X u | m X y | c*s δ | £ u | § | X u | £ y | £ o | £ y | ||
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| V> X g 5 O | VI X ? y | l | u § i | £ <5 l | i ? u | y X Ϊ Ϊ | 8 s | 8 Ϊ II y | m X í l | VI X ď £ | VI δ £ 8 % | 45 £ U y | δ y | CM z“κ £ y y | CM δ << x x o o 1 1 o o u | OJ X o X X u u 1 1 o o | |
| CM * | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| m 9-* PÍ | £ u | m X y | (*) X y | £ u | £ y | £ y | m X o | £ y | § | § | § | «*1 X y | m δ | δ | r*i 5 | m y | n δ |
| cm «-Μ Pí | £ y | £ y | £ y | £ y | X y | £ y | £ U | £ y | £ y | £ u | £ u | § | £ y | £ y | <*l δ | ||
| a | o | CM | o | CM | © | n | © | *·< | CM | o | CM | © | ^4 | ||||
| Ol 3Í | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| co ••4 (X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| r* PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| u z | Os m m | ? m | m | 3 m | ? m | 4 m | £ m | S m ^4 | 5 cn ^4 ^r | 00 ^r cn ^4 * | Os m v*4 rř | 8 m ^4 | pw4 in cn rH sf | CM Ό cn | m wn cn tŤ | 3 m w>4 xr | »n V» cn |
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| £ o | £ o | cn X Q | cn X u | m X u | £ υ | £ u | cn X u | cn X o | £ | £ Q | £ o | £ u | § | ||
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| fN 5 << X X o υ 1 1 o o v. u | <n m X X u o X X X o o 1 1 o o u | m <n X X O U X X X u u 1 1 o o | m m X X o u X X X o υ 1 1 o o | cn | u | tn 1 | WS X $ z II O | WS u | WS i δ | £ o 8 | í u | £ o | ď CN u o | WS sc X u | |
| CN % | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| Sí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| cn PÍ | £ ω | cn X o | cn X o | cn 6 | cn u | £ u | £ u | cn X u | cn X u | § | cn 8 | cn 8 | cn X o | cn X u | £ o |
| CN ··< tA | £ o | cn X o | cn X u | £ Q | £ u | £ u | £ υ | £ o | g | £ u | £ o | £ Q | £ o | § | £ u |
| s | CN | o | CN | o | w4 | <N | o | v—4 | CN | o | CN | o | ·—4 | ||
| OS PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| r* —— Pí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| ž’ | v© «Λ cn N* | r* vn cn Ν’ | 00 κη m N* | Ov wn cn Ν’ | 3 m Ν’ | 3 m Ν’ | S m Ν’ | cn SO cn —1 Ν’ | 3 cn «—4 Ν' | wn Ό cn Ν’ | $ cn Ν’ | 5o m Ν’ | 3 cn Ν’ | ov v© m Ν’ | o r* m Ν’ |
0050/46142
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| 2 | X u | X u | X u | X G> | CA X G) | CA X G> | CA 5 | CA X G> | CA X G) | CA X G) | CA X G) | X G) | CA X G> | X □ | CA X G) | X G) | tt? G> | £ u | CA X o | X G> | X G) | X o |
| u | X | X | X | X | X | X | T | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| Ά | »A | |||||||||||||||||||||
| X | X | xe | ||||||||||||||||||||
| m | «Α | *a | fc | fc | fc | |||||||||||||||||
| X í | CM z*s X fc | /£J ca X ω | CM Z**\ X o | «Λ X I | *A X | | sa | I X % | g1 £ | X g X fc z | §. | £ o, | -S X fc 5 | X 8 z*\ δ z | X 8 z—s g 3? | 8 i | CA X CA X | CA 1 CA X | m 1 CA X | ||||
| o | δ | X u | 7 X υ | i G) | X G) | u | l | Q | 3 o | δ | δ | δ | I | δ | i | 1 | X u | i | G) >»/ o | fc G> | fc G> | |
| CM fc | X | ΎΙ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| fc | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| cn | δ | X Q | X u | X G> | CA X o | CA X u | X G) | CA X G) | X G) | X G) | δ | CA X o | CA δ | CA X G> | CA X Q | CA X G) | g | CA X G> | CA X G> | X Q | X u | X G> |
| Pí | X o | X u | § | £ G) | X G> | X Q | 5? G> | g | x1 G) | X G) | g | g | g | CA X Q | X G) | g | ď u | X O | £ u | X Q | g | ÍC u |
| a | CM | o | CM | o | CM | o | CM | o | ^•4 | CM | o | CM | o | •—4 | CM | o | «-4 | CM | ||||
| Os fc | X | X | m | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 | ||||||||||||||||||||||
| fc | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| r* fc | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| ž | i> en | CM r* ca | ca r* ca | rt ca | »n r* <n w4 | Ό rm Tt | rrm 4 | 00 Γ* ca ^4 | Os Γ* ca | S ca | —4 00 cn mt | CM 00 ca | ca 00 ca w—4 | 3 ca w4 xt | 00 CA | 8 CA rř | 00 ca 1-4 xř | 3 CA ^4 TT | Os 00 CA | 8 CA | Ss CA ^4 Μ | SJ CA ^4 |
0050/46142
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| 3 | rs X o | X u | rs X o | X Q | £ u | rs X o | rs δ | £ Q | £ o | X u | £ o | £ u | rs 5 | rs X u | £ u | rs X u | § | rs X u | £ Q | rs X o | ||
| u | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| o | o | o II Q | O II o | o ó | rs X 8 X o | rs § X o | rs X 8 X o | ws w § X Q | WS X 8 X u | » es 8 5 | £ o X u | £ i Q | £ δ X o | £ | £ 8 5 O | £ 8 u | £ í o | WS X l | WS X l | £ o o | 1 | |
| CM a | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| a | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| m fit | X Q | rs g | X o | X o | rs X u | rs g | rs δ | X u | £ u | rs X CJ | rs X u | rs δ | X u | g | rs X υ | £ u | rs δ | X u | rs δ | rs X u | rs δ | |
| CM PÍ | 4? X U | X u | § | X Q | £ u | £ Q | £ o | g | £ Q | £ o | £ o | £ O | § | £ Q | X u | £ Q | £ u | X u | £ u | £ o | £ o | £ Q |
| 0 | O | CM | o | ^4 | CM | o | CM | o | CM | o | *4 | n | o | *«4 | CM | o | CM | o | ||||
| Os PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 4·* PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| r** fit | X | X | rs » | X o | rs X o | rs X u | r> X o | rs X υ | £ o | rs X u | £ u | rs X o | rs X u | rs X ω | rs 5 | £ o | £ o | £ u | rs X o | rs X u | rs X u | £ u |
| ž | m Os m | 3 m Mř | S m | Ό Os m M* | r* Os <*s | co Os m •M | a m 4“< | M* | o ’φ | | M· | m xř | »•4 M- | un § xf | ^“4 Xfr | 8 *»•4 ’Φ | o 4· | š *4 | o A 4·' | 4—4 ^4 •4· ^4 -Φ | CM 44 4·4 4·’ | c*s R4 | 'φ· 4»H M· |
• · • · • ·
0050/46142 • · · · ·
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| É | X o | rs X Q | § | rs X Q | rs X o | m X u | £ o | £ u | ď o | £ o | rs X o | X u | ||
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| £ ! | g l l | 8 % £ 8 s | g 1 δ | WS X ž | ws X ž 8 Z δ | WS í | Λ X υ υ | λ X υ υ | Λ rs X y. o | n δ ''CM X X υ υ 1 1 o o o | CM X u 'CM X X u u 1 1 o o x. ' O | cm X υ e< δ 8 1 1 O o \ r· o | n m X X u u X X X u u 1 1 o o z' u | |
| CM % | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| δ | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| m PÍ | £ o | X o | X Q | § | X u | ř? | X o | X o | X u | § | rs 5 | rs « | X u | rs X o |
| CM PÍ | £ Q | x1 o | § | £ Q | ž | § | X o | X Q | X o | š | 5? U | g | £ o | |
| 0 | CM | o | <M | o | CM | o | *-4 | CM | o | ·—í | CM | o | ||
| Os PÍ | T | *T| | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 Pí | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| r* PÍ | X Q | rs X o | rs X o | n X u | rs X u | X Q | «η X o | rs X o | rs X o | rs X u | rs 8 | rs X o | £ u | x1 o |
| <n •4· F4 xř | Ό xT xř | r- Μ ^4 | 00 xt ^4 xř | o ^4 xř | 8 xr «Η xř | «—4 CM xr *>4 xr | CM CM Mr xř | m CM s xr | 3 xr *•4 xř | WS CM 3 xř | S© CM xT ^4 xř | r* CM 2 xř | 00 «ř |
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| 3 | m X u | cn X o | n X o | X υ | X Q | £ υ | £ o | c*·» X o | £ o | m X u | £ o | £ u | m X o | £ o | m X υ | δ | <*> X u | £ o | m X υ | ||
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |||
| ť*> w | r*> X | m rc | Λ a | ||||||||||||||||||
| u > | o ! | u | o ! | V> | m | ||||||||||||||||
| X u | X o | X o | X u | X | £ | £ | £ | «η w CM | «Η ,CM | »n X | <s z** £ | £ | <M | X g | X g | ||||||
| I | 1 | | | m X | m X | X | V» X | z | y | y | y | O | o | y | ||||||||
| 1 Q | 1 o | o | o | 9 | 9 | g | $ | g | z | Jz: | !z | z | z | ? | % | z | z | ||||
| z | ? | z | Ϊ | r/i | ii | X | i | X | s | X | X | X | X | X | |||||||
| o | u | δ | δ | δ | δ | u | u | o | u | o | u | o | o | u | o | o | u | ||||
| cm a | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | ||
| r-4 | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | ||
| m PÍ | ť*J g | § | £ o | ř*^ 5 | £ o | £ o | r*> δ | £ u | m X o | t*) δ | £ o | tn X | «*» X o | m δ | m X u | £ o | § | m X o | |||
| CM pt | £ u | £ U | £ o | υ | £ o | £ o | § | m X o | £ o | § | § | § | £ υ | £ u | £ u | § | § | § | § | ||
| a | CM | o | CM | o | CM | o | CM | o | CM | o | ••M | CM | o | ||||||||
| Ox Pt | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | ||
| 00 PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | ||
| r- PÍ | m X o | m X u | m X υ | <*> X υ | m X u | £ u | £ υ | £ Q | X u | £ o | X o | £ U | £ u | £ u | m X o | tn X u | en X □ | en X υ | X υ | ||
| ž’ | O\ CM φ φ· | o «*) φ φ | m Φ ^4 Φ | CM m Φ ^4 Φ | m m Φ *4 Φ | 3 Φ **4 Φ | <n m Φ· •>•4 ΦΓ | Ό en φ •φ | r·* cn Φ ··♦ Φ | 00 cn 3 Φ | ©\ m 3 φ· | 4·' | 3 φ | 5 Φ* | ? φ· | ^4 Φ* | <n 5 φ’ | <5 Φ’ | r* ^»4 Φ |
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| 3 | rs X υ | g | rs X u | 3? y | rs X y | £ y | X y | rs X y | X y | X y | x“ y | rs δ | rs X y | X y | £ y | g | £ y | rs X y | £ y | rs X u | X y | X y |
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| vs | vs | vs | ||||||||||||||||||||
| X | X | X | ||||||||||||||||||||
| vs | vs | vs | \© fc | I | O fc | |||||||||||||||||
| X g | fc 8 | fc | X | X | δ | |||||||||||||||||
| VS a | 8 | Λ | λ | 8 | 8 | 8 | £ | x | ||||||||||||||
| g | £ y | /**» X y | X 3? o | 4<* 1 | £ fc | X y. | g | £ fc δ | £ y. | s | £ rs δ | £ X y | 1 X y | o | o || | o δ | X 8 X | |||||
| y | X u | y | X y | δ | δ | δ | δ | δ | δ | y | y | S.X y | y | y | o | o | δ | δ | y | |||
| η fc | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| fc | X | X | X | X | Tl | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| r*s ^4 PÍ | rs X y | X y | X y | rs X y | rs X y | £ u | X y | rs δ | g | g | X y | g | £ y | X y | g | rs δ | £ y | rs X y | g | rs δ | £ y | |
| n PÍ | g | X y | ď y | £ u | rs X y | g | ď y | g | £ y | £ y | ď y | g | £ y | X y | 3? y | g | X y | £ y | g | g | £ u | £ y |
| a | CM | o | CM | o | CM | © | CM | o | ^4 | CM | © | CM | O | CM | o | ^4 | CM | © | ||||
| OS fc | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| rs | rs | rs | ||||||||||||||||||||
| 00 | X | X | X | X | ||||||||||||||||||
| fc | T | X | X | T | X | X | X | X | X | X | X | X | X | X | X | X | X | X | u | y | y | y |
| C* Pí | rs X y | rs X y | rs X y | rs X y | X y | X y | rs 8 | rs X y | δ | £ y | rs X y | g | X y | rs X y | X y | X y | X y | g | X y | g | g | rs X y |
| 00 | 1 | 8 | WS Tfr *4 | CM WS Tf r·* | cn ws xt | 3 ^“4 | ws ws Xf *4 | S© WS 2 | r* ws xt | 00 ws xť ^4 | Os WS xr ^4 | S -4· | *4 | CM Ό 2 | (8 *4 | 3 to· 4·« | $ rr »—t | $ | í | 58 '«r | OS s© ^4 « | |
| z | xf | xř | Μ* | e | xť | xř | xf | X* | M· | xt | -M·' | xt | xt | xt | xr | xí |
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| 3 | 5 | £ Q | £ u | m X u | r*> X o | £ υ | m X o | £ u | m 5 | £ Q | £ o | m X o | £ u | en X o | <*> X u | £ u | X u | £ u | δ” | f*» X u | m X Q | en X Q |
| u | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| >* | £ 8 X o | £ £ 5 | m * § o | i υ | £ 8 X υ | £ s X Q | £ •z o X u | eu δ X o | 5 υ | £ l | Ví X í | «Λ l | V» Ϊ | Iz & o l | l | 1-4 O* • z< O l | X £ δ £ 8 l | y δ | 8 Ϊ δ g l | «Λ X 8 l | tn X tf £ 8 o | |
| CM fc | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| fc | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| PÍ | £ o | <*> X u | cn 5 | m u | £ u | £ Q | 5 | í*> X u | £ o | £ | £ o | £ o | m X υ | X u | m X u | £ υ | cn δ | £ u | X o | m X u | £ u | δ |
| CM PÍ | g | £ o | £ u | £ o | £ o | § | £ u | £ u | g | £ u | £ G> | § | £ u | m δ | £ υ | £ u | g | £ o | £ o | § | £ υ | £ o |
| a | CM | o | ^4 | CM | o | CM | o | *z | CM | o | CM | o | ••z | CM | O | ^4 | CM | O | l | |||
| Λ fc | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 PÍ | X o | <n 8 | m X Q | m X o | £ u | cn X o | £ υ | X u | g | £ u | m δ | £ u | í*í δ | en X Q | £ u | δ | £ υ | £ Q | £ u | £ u | m X υ | «*> X u |
| r* p4 | m u | m X o | cn X o | cn X υ | « X o | m X u | m u | m X o | en X υ | £ u | m δ | £ u | tn X o | X u | cn X o | en X o | £ u | m δ | £ u | § | £ υ | £ u |
| u z | R M-Z | «Μ Γ* Tř •4 *e | CM ^4 | m c- xr | ? | νΊ r* xř | ie 4 4 | r** 5 | 00 r* »z | σ\ r* tT ^1* | ^4 MT | •z 00 --4 mT | 00 mT | cn 00 2 M· | s xr T“Z | 00 s Xt | 8 3 XT | § w Xf | 3 4 zZ xt | a oo 4 4 | 8 *r | σ» 4- 4 |
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| 3 | £ Q | £ o | en X υ | £ o | m X u | cn X Q | en X o | cn X o | £ o | £ υ | cn X Q |
| u | X | X | X | X | X | X | X | X | X | X | X |
| ΙΛ X i | z« cn X u | CN cn X u | u o | CM X u y X X u u 1 1 o o u | CN s y X X o u 1 1 o o \ s- u | CM X u y X X o o 1 1 o o X z* u | <n m X X u u X X X u o 1 1 o o o | n m X X Q O X 3 3 1 1 O o •x z· U | <*> <n X X o o X X X u u 1 1 o o o | cn 5 Ϊ | |
| CN | X | X | X | X | X | X | X | X | X | X | X |
| a | *τϊ | X | X | X | X | X | X | X | X | X | X |
| cn PÍ | £ o | £ o | £ u | en 5 | en o | cn 5 | £ o | £ u | § | § | cn δ |
| π PÍ | § | § | í | 5 | £ u | £ o | § | § | £ o | § | £ Q |
| a | CN | o | CN | o | CN | o | CN | o | |||
| O* PÍ | X | X | X | X | X | X | X | X | X | X | X |
| 00 PÍ | £ Q | en X o | δ | £ Q | •n δ | en X Q | en X u | 4? δ | £ u | £ υ | § |
| ř* PÍ | cn X O | en X o | £ u | £ u | £ u | cn X Q | en δ | en δ | en X o | £ □ | £ o |
| ž | S Ν’ ••4 Nr | cn Os Ν' n· | *r | Ά cr> <t «<4 Ν’ | so Os N* •M Ν' | ro •μ· *•4 N* | s Os S Ν’ | Os a\ Nj N· | S «Λ w>4 N* | O IA Ν’ | s wn W4 Ν’ |
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| g | ca X u | £ Q | £ υ | £ u | CA X u | CA X o | CA X o | £ o | £ u | g | CA δ | CA X u | £ Q | £ o | CA δ | £ υ | £ u | CA X o | £ u | £ Q | CA δ | |
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| IA | IA | |||||||||||||||||||||
| X | X | X | ||||||||||||||||||||
| CM | CM | |||||||||||||||||||||
| CA | ΙΑ | Q | Q | Q | ||||||||||||||||||
| £ | £ | £ | UA a CM | »A | IA | CM a | Λ £ | CM z“s a | X § | X g | X g | O £ | O £ | O z—\ £ | CM | ΟΪ | ||||||
| £ 9 | g | m 5 | £” £ | X £ | y | z | O | u | y | δ | y | Q | 1 | u | o | í | ! | |||||
| z δ | l | % o | l | Z | X u | s u | o | δ | o | X Q | u | i | u | o | δ | δ | o | o | δ | δ | ||
| cm | X | X | X | TÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| ca ¢4 | r> X u | £ u | CA X o | CA 5 | CA X u | £ u | 4? X O | CA δ | £ u | £ u | £ υ | g | CA δ | g | £ u | £ u | g | g | £ Q | CA δ | £ Q | £ u |
| CM AŽ | £ u | £ Q | g | £ o | £ u | £ o | g | £ o | g | £ u | £ o | g | £ o | £ u | £ o | £ Q | g | £ o | £ o | g | £ u | g |
| a | CM | o | A | CM | © | A | CM | © | CM | o | A | CM | © | A | CM | O | •A | CM | © | |||
| Os PÍ | X | X | T | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 Pí | g | CA X o | £ Q | CA X o | CA X υ | CA δ | CA X o | £ υ | £ u | CA X υ | CA 5 | CA δ | £ u | £ o | g | g | CA δ | § | £ u | g | CA X u | £ υ |
| r* A f* | ca X o | CA X υ | CA X u | CA X u | «Λ X o | CA X o | CA 5 | £ Q | £ u | CA X o | CA X u | £ o | £ o | £ υ | a o | CA X o | CA X o | £ υ | CA X o | g | £ o | £ u |
| ž | 8 ua A τΤ | 3 UA xř | UA O UA A xř | 3 UA A xr | o UA xT | 00 O UA »“4 Xt | 3 UA x# | © •A UA A | w< A UA Xt | CM •A UA A | CA A UA xf | xr A«t UA A xr | UA UA A Xt | C© »A Ά A4 Xt | r* a4 UA xf | 00 UA A>4 | O* UA xr | 8 UA xř | «Α CM UA xt | a UA A xt | CA CM IA A xr | 3 UA xí |
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| 5 | £ o | £ u | cn X o | £ Q | m X υ | m X υ | £ ο | r*s X u | m X Q | £ o | £ υ | o | O | u | G | c | c | ΰ | u | o | ^•4 u | |
| u | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| *Λ | ||||||||||||||||||||||
| X ί | ¾ $ | |||||||||||||||||||||
| £ | δ | X Ο | X y | m | ||||||||||||||||||
| Λ | δ | Ο | Ο | X | X | X | ||||||||||||||||
| CM | £ y | £ y | X y | § | £ υ | £ U | £ | i | Ϊ | cn ps | £ | £ | •n § | m | & | |||||||
| i | 5 | Ϊ | ! | X υ | 1 | m X y | m X u | m X y, | o δ | o | o II | 8 X | y | 8 X | o X | 8 X | δ X | |||||
| >* | δ | δ | δ | δ | U | u | O | y | o | o | δ | δ | u | u | u | o | u | u | o | |||
| CM ‘Sí | T | X | X | X | X | ΓΤΐ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| X | X | X | T | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| m PÍ | £ Q | £ u | r» 8 | í | •η 8 | § | <*» X U | rs X u | £ u | £ o | m X u | £ o | X | X | X | X | X | X | X | X | X | X |
| CM PÍ | £ U | § | 8 | § | £ υ | £ ο | £ y | £ o | £ y | £ u | § | £ y | § | j? δ | £ □ | o | ř | 5 | § | β | § | £ y |
| « | CM | o | CM | ο | CM | o | CM | © | cs | © | ^4 | CM | o | CM | © | W4 | <s | o | ||||
| Os PÍ | m | T | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 Pí | £ u | m 8 | § | § | £ Ο | £ υ | <*» X u | f*S X u | § | m X υ | £ υ | X | X | X | X | X | X | X | X | X | X | |
| r* cd | £ o | m X o | £ o | £ u | Π X ο | m X ο | m X y | £ o | m X o | £ o | cn X y | £ u | X | X | X | X | X | X | X | X | X | X |
| !Z | ia CM <A | 8 <A ^4 | Γ* CM IA | 00 CM IA ** | σ> <Ν <Λ Μ | ο ca <α | ca IA | CM CA IA e | (A CA m | 3 m | IA CA IA | s© <A IA | Γ- CA IA | 00 CA IA | Os CA IA w-< ’Ί* | IA ^4 | 3 wM M* | S e | CA 2 | 5 Tt | WA TT | ž |
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| 3 | G | G | G | G | G | G | G | G | G | G | G | G | G | G | G | u | G | 0 | G | G | G |
| z | a | a | a | a | a | a | a | X | a | X | X | z | a | z | z | z | X | z | X | z | |
| £ o a o | £ <5 a o | £ δ | £ 8 z II O | í*» a 8 l | a £ l | a g l | a § 5 O | ,¾ o l | & o u | ϊ-« l | 8 l £ 8 l | 8 l £ 8 t | 8 Ϊ 3 s£* 8 z II O | «Λ X í l | z ž 8 Z II Q | <n X ž 8 Z δ | CM z*s cn X o | CM <*> Z ω u | m z o o | CM X u dT ^CM X X u o 1 1 o o o | |
| CM | a | a | a | a | a | a | a | a | X | X | X | X | Z | Z | z | Z | X | X | z | z | z |
| % | a | a | a | a | a | a | a | a | X | X | X | X | z | Z | z | Z | z | X | z | z | z |
| C*1 Pí | a | TI | a | a | a | a | a | a | X | X | X | z | X | X | X | X | X | X | z | z | z |
| CM ai | z u | § | £ u | £ u | £ u | £ u | £ o | g | £ o | £ o | £ o | £ o | g | g | g | £ o | £ Q | £ u | £ | £ o | £ 8 |
| a | CM | o | CM | o | *«4 | CM | © | CM | O | d | o | CM | © | _ | CM | O | |||||
| 0 | a | a | a | a | a | a | a | a | X | a | X | z | X | X | X | X | X | z | X | Z | z |
| OO «· PÍ | a | Ti | a | a | a | a | a | a | X | X | X | X | X | z | X | X | X | X | X | z | z |
| £1« | z | a | a | a | a | a | a | a | X | X | X | z | a | z | z | X | X | X | X | z | z |
| Ž | δ ^•4 | 00 3 ^4 ''t | Os •e m | 8 | t-4 vn wn Tt | CM <n un xt | m UH to | 3 ΙΛ «^4 4·· | »A Vk •4 xř | ve | r* <n 4<M | 00 xř | Os <n ΙΓ» 4·· | 8 »—4 xt | 3 «η •'t | oř >e *Λ Mř | m ve m ^4 xí | 3 ΙΛ F—· xř | >e ΟΊ | 3 *Λ w<4 | δ ΜΊ |
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| 3 | G | •«4 O | G | R«4 Q | G | «>4 □ | G | *w« o | O | ••4 u | G | •mR u | G |
| u | X | X | X | X | X | X | X | X | X | X | X | X | X |
| CN X u C< ^CN X X o u 1 1 o o u | CN X u C< ^CN δ 8 1 1 O o | cn cn X X u u X 8 8 1 1 o o X x* u | m m 8 8 X X X υ u 1 1 o o | m rs 8 8 X X X υ υ 1 1 o o | í | cn δ 5 O | cn δ l | vs X í υ | vs l δ | V> X í | £ 8 | 1 8 | |
| (N | s | X | X | X | X | X | X | X | X | X | X | X | X |
| X | X | X | X | X | X | X | X | X | X | X | X | X | |
| m Pí | X | X | X | X | X | X | X | X | X | X | X | X | X |
| CN Pí | £ o | <? δ | § | δ | £ υ | £ o | £ υ | £ υ | £ u | £ υ | § | £ u | £ u |
| c | CN | o | CN | o | CN | o | CN | o | |||||
| Os Pí | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X |
| £1* | X | X | X | X | X | X | X | X | X | X | X | X | X |
| $ • Nf | Os s© un R>R Nf | g vn fM | r* wn Ν' | CN r* m •—i | cn r* wn | í un 1*4 xř | *n r* <Λ *«*4 | s© r* »Λ NT | r* r* ΙΛ N | ?2 vn •>w NT | Os r* wn •Ί· | S ^R |
0050/46142 ···« ··· · · · · • · · · · · · · · · · • · ·· ·· ·· ···· · ·· · · · · ··· ······· · · · · · · · ·
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| G | G | G | G | G | ·—·* o | G | G | G | G | G | ^•4 O | G | G | ^4 O | G | G | G | G | 0 | G | G | |
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| sn | «Η | »0 | ||||||||||||||||||||
| X | X | |||||||||||||||||||||
| »n | vn | <n | <x | % | ||||||||||||||||||
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| cs | cs | Q | ||||||||||||||||||||
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| bí | 5? | z | 5*4 | ? | 4 | 4 | ZI | Z | í | |||||||||||||
| >< | X u | u | o | o | i Q | o | u | X o | G | ^4 O | X ω | i o | X u | ir Q | δ | H O | ii o | '11' ω | II Q | u | X Q | Q |
| es a | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| % | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| <n | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| es fit | £ u | £ u | £ u | X u | X u | £ u | £ o | cn X o | X u | £ υ | £ u | £ u | X u | £ Q | £ u | £ o | X | £ u | £ υ | g | X u | £ o |
| a | cs | o | es | o | *4 | CS | o | 4 | es | o | es | o | 4-4 | n | o | es | 0 | es | ||||
| os PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| oo ^4 fit | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| Γfit | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| ž | S «»4 Φ | ¢3 00 un e | cn 00 ΜΊ Φ | 3 ¥Ί Φ | m 00 <Λ xr | £ un | S VH «-4 Φ | 8 ΙΛ Φ | s m Φ | g un *Φ | ox un •e | es Os *n Φ | cn Os un Φ | »n Φ | wn Os un Φ | s© Os IC Φ | cOs m Φ | 00 Os un Φ | 8 un Φ | *φ | S Φ | § |
• · ··· ···· • · ···· · ··· • · · ·· ·· · · · · · • ···· ··· ····· · · ·· ·· · ·
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| 3 | □ | y | δ | Ο | δ | •Μ* y | δ | δ | δ | δ | δ | ^4 Ο | δ | δ | δ | δ | δ | δ | ^•4 Ο | δ | ·—«· y | y |
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| m X m X 9 o | m X £ £ y | m X £ | ο | ο | ο II y | ο II y | ο δ | £ 8 X ο | £ ο | £ 8 X y | *Λ fc y ο | fc 8 X y | fc 8 5 | £ δ X ο | £ δ X υ | £ δ X Q | £ ι | £ | V» X í δ | 55 ? y | ||
| ΓΗ fc | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| fc | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| m fc | X | X | Τι | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | « | X |
| CM fc | X y | £ Ο | g | X ο | <*» X ο | £ y | X y | £ y | X y | £ ο | £ ο | £ ο | £ y | £ y | £ y | £ ο | £ ο | £ ο | g | g | £ y | £ y |
| 0 | o | CH | ο | η | ο | ΓΗ | ο | <Μ | ο | ΓΗ | ο | ΓΗ | ο | CH | © | |||||||
| Os PÍ | 5ΰ | *τ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | a | X |
| 00 Pí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | a | X |
| r* Pí | X | X | X | X | X | m X y | «*» X ο | η X ο | m X y | m X ο | «η X y | ΓΊ X y | 5 | 5 | m X υ | £ Q | g | m X ο | «η X ο | m X y | en a y | X y |
| ž | ’Ο’ | •4 | 3 | Γ- 3 | 1 «Μ | ο 3 xř | Ό | ΓΗ 5 | m «Μ <© | «Μ | »η *4 Μ· | \© *Μ \ο 4· | Γ\ο 4· | οο | 0\ S© •4 | ο γη \© Μ- | ^4 ΓΗ V© ^4 | ΓΗ CH V© | m rn Ό ^4 | 8 o nr |
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| G | G | G | G | G | G | G | G | G | G | G | G | G | G | G | G | |
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| *o X w l | o* o g | £ o z δ | Ut z δ | g l 8 υ | g δ | s a 8 ? u | «Λ X ž 8 Z II u | »n X o á* g II υ | x o u § g | m X υ | CM cn X υ u | 5? U U | CM δ << X X υ υ 1 1 o o X o | CM s «Γ X X o o 1 1 o o x. S u | n X U << '-n X X υ υ 1 1 o o x. s u | |
| CM | 3* | X | X | m | X | X | X | X | X | X | X | X | X | X | X | X |
| «*« | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| m Oí | X | X | X | 32 | Tf | X | X | X | X | X | X | X | X | X | X | X |
| CM ^•4 p4 | § | x1 υ | X u | X Q | <? X Q | X O | X O | rn X Q | X u | Z o | ď υ | X u | X ω | Z Q | 3? o | Z u |
| ca | CM | o | CM | o | w·* | CM | o | CM | o | «Ν | o | P4 | CM | |||
| Os »4 | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| QO | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| rr* PÍ | cn X Q | m X υ | X o | X o | <n X u | m X υ | X o | m 5 | D X o | Z u | í | X o | en X Q | Z u | cn X o | «η X υ |
| u z | in CM SO Φ* | SO CM s© p4 ΦΓ | Γ* CM sO Φ* | 00 CM SO ΦΤ | Os CM Ό Φ* | O cn so p*M | P»M cn SO ««4 Φ· | CM CA sO Φ· | m m so Φ | Φ· cn so Φ* | m cn sO Φ“ | so m \O p—4 Φ*' | ΓΓη SO PM Φ· | 00 co so ^4 Φ* | Os m \o φ· | P^ Φ* |
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| a | G | G | G | G | G | G | G | G | *4 u | —•4 u | —“4 O | G | G | G | G | G | G |
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| CN | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| <n PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| CN PÍ | X u | g | £ υ | £ υ | £ u | g | £ υ | £ Q | £ υ | g | g | g | g | £ o | g | £ υ | g |
| CJ | o | ^4 | CN | o | CN | o | cs | o | •»4 | CN | o | CN | o | ««4 | |||
| Os & | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
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| 3 | G | G | G | G | G | G | G | G | G | G | u | G | G | G | G | G | G | G | G | G | G | G |
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| £ o | g | g | g | £ o | £ o | i | rs | cji | . rs | X y | X & | X y | X y | £ u | £ o | X | 1 | |||||
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| 3 | G | G | G | G | G | G | G | G | G | o | G | G | HR Q | G | «•4 Q | G | <« o | G | G | G | •»4 O | G |
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| CM a | X | X | X | X | X | ΓΓΐ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 1·* Pí | T | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| cn | X | X | X | X | X | τ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| CM fit | £ Q | £ u | g | £ o | £ o | £ u | £ o | § | £ Q | g | £ o | 4? δ | § | £ υ | £ Q | £ Q | g | £ o | £ u | g | £ o | £ υ |
| s | CM | o | CM | o | CM | o | «R | CM | o | r4 | <N | o | rR | CM | o | CM | o | — | ||||
| Os oí | *Tl | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
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» · • ·
0050/46142 «
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| 5 | y | y | M4 y | MM y | y | y | MM u | y | y | y | y | y |
| u | Ti | X | X | X | n | X | X | X | X | X | X | X |
| 8 Ϊ y £ y y | X <3 £* 8 y | Vl X tf f Ϊ | 4Λ X | CM Z“\ m oc y y | CM z-*» m δ y | CM z** £ y y | ra X u c4* ''cc x X u o 1 1 o o | CM u <4” X X u u 1 1 o o u | X o c4 X X u o 1 1 o o | <n <*> X X u u X X X υ y 1 1 o o u | m <*> X X u o X X X u o 1 1 o o o | |
| cm £ | X | X | X | X | X | X | X | X | X | X | X | X |
| pí | X | X | X | X | X | X | X | X | X | X | X | X |
| <n PÍ | X | X | X | X | X | X | X | X | X | X | X | X |
| CM «•4 Pí | § | £ y | £ y | s | r*> X u | £ y | £ y | £ y | £ y | 4? δ | £ y | £ y |
| e | CM | O | m<4 | CM | o | «4 | CM | o | CM | O | ||
| σι Pí | X | X | X | Ti | X | X | X | X | X | X | X | X |
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| G | G | G | G | G | G> | G | G | G | G | G | *4 U | G | G | y | y | y | M4 y | G | G | m4 u | ||
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| 5 | υ | G | o | o | ΰ | 0 | u | O | o | 0 | υ | u | o | o | u | £ u | £ o | en X o | £ o | cn δ | £ u | £ u |
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| 3 | X υ | rs X o | rs X o | X u | § | X υ | rs X u | rs X o | X o | rs X o | rs X o | rs X u | rs X o | X u | rs X o | X υ | 5 | § | X o | £ u | £ o | |
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| 3 | £ o | m 8 | m X u | δ | m X o | rn X u | £ Q | £ Q | £ u | £ 0 | cn X υ |
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• · • · • · • · · · • · · * • · · * · • · ·
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| § l | X l | «Α i | v-» X g | X í δ | M O• —4 O 1ř υ | £ í | kx § υ | l 8 g | 8 s 8 ϊ u | s 8 Ϊ | <A X š 8 g | ffi ž 8 o | £ δ | z£? í | Λ! ě o | Λ £ fc o | X u X X o u 1 1 o o | d X O ď '''es X X υ υ 1 1 o o Zu | |
| CM fc | X | X | X | X | T | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| fc | CA 5 | g | CA δ | CA δ | g | g | g | g | CA δ | g | § | CA δ | g | g | g | cn δ | g | CA 8 | |
| m fc | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| CM fc | X o | X Q | X o | £ u | g | £ u | £ o | £ u | £ u | £ o | £ o | £ o | £ u | £ o | g | £ u | g | £ Q | £ |
| s | CM | o | •4 | CM | o | CM | o | CM | o | <s | o | CM | o | t | |||||
| Os fc | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 fc | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| fc | CA O | m X u | CA X u | cn X Q | tn X o | CA δ | £ o | CA X u | CA X o | £ υ | £ o | £ o | CA X o | CA X υ | CA X u | £ υ | cn X o | g | £ u |
| u z | 3 00 | 0Ί en oo | SO cn 00 MŤ | r* cn 00 —4 | 00 cn oo | Os m 00 Tř | 4· | «•4 | CM s ^4 | m 3 | t—4 | «η 3 | 3 **4 4·’ | oo 3 w4 | Os 3 w4 | 5? oo | <n 00 ^4 | CM »n 00 ^4 |
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| 3 | £ u | £ o | CA X Q | CA X υ | CA X u | g | £ u | CA X u | CA X Q | g | CA X u | CA X o | £ u | CA X Q | CA X Q |
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| CÍ a u X X o u 1 1 o o Xo | íA CA ώ a u u X X X u u 1 1 o o υ | CA «Α 5 δ X δ δ 1 1 o o o | <*> M X X o u X X X u u 1 1 o o \ x· O | CA X 9 z u | g Ϊ o | CA § | £ u | ua i | UA X í δ | CA i l o | £ o | £ X o | 1 u | V» X í o | |
| CM a | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| A % | g | CA X υ | £ u | g | g | g | CA 5 | g | CA δ | g | CA X u | g | g | g | CA δ |
| m PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| CM ••A Pí | £ υ | g | £ u | £ u | £ u | £ o | g | g | g | £ Q | £ u | £ u | £ Q | £ υ | £ u |
| a | CM | o | •A | CM | o | A | CM | o | CM | 0 | CM | © | A | ||
| Os Pí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| OO Pí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| r* PÍ | <a X υ | CA O | CA X o | CA X o | g | m X o | £ u | 4? δ | £ u | CA X o | CA X o | CA δ | CA X o | CA X o | £ υ |
| u z | cn VA oo •A xf | 3 00 | VA VA 00 ^4 Xt | Ό UA 00 ^A xt | r* VA 00 xr | 00 VA 00 A •e | o\ «Λ 00 «Α xr | s 00 A xr | A \© 00 Xt | CM \© 00 Xt | CA *© 00 ^4 xt | 3 00 xr | <n s© 00 Xt | « 00 •<r | sO 00 |
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| a | £ Q | £ u | g | £ u | £ o | £ o | £ o | £ o | m a o | m a u | m a u | £ o | m a o | m a o | £ u | £ u | £ u | g | £ u | en a o | m a u | £ υ |
| a | a | a | Ti | a | a | X | a | a | a | a | a | a | a | a | a | a | a | a | a | a | a | |
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| u | 7 a u | 5 o | s υ | 1 o | u | 1 o | δ | ti u | T a o | T u | δ | H Q | δ | δ | B U | g | a u | δ | y Q | 52 u | 52 υ | |
| CM a | a | a | m | a | a | a | Stí | a | a | a | a | a | a | a | a | a | a | a | a | a | a | a |
| PÍ | § | § | m s | 4? δ | cn δ | «*> a Q | g | § | £ <D | m δ | m δ | g | m s | g | g | <*» δ | § | § | g | g | g | |
| cn | ΓΓΪ | a | a | a | T* | a | a | a | a | a | a | a | a | a | a | a | a | a | a | a | a | a |
| CM Pí | £ o | £ Q | £ u | £ u | <*» a υ | £ o | £ o | £ u | g | £ o | £ Q | £ u | £ u | £ u | £ u | £ u | £ o | £ u | g | £ Q | £ u | g |
| a | CM | o | CM | O | w4 | CM | o | CM | o | ^4 | CM | o | w4 | CM | © | CM | © | ^4 | CM | |||
| Ok PÍ | a | K | T | *T* | a | a | a | a | a | a | a | a | a | a | a | a | a | a | a | a | a | a |
| oo fit | a | a | a | a | a | a | a | a | a | a | a | a | a | a | a | a | a | a | a | a | a | a |
| t- *4 Pí | m a u | £ o | m a o | £ u | a u | <*> a u | £ o | m δ | £ O | cn a υ | cn 5 | c*t a Q | PH a o | c*> z o | cn a CJ | «η a Q | £ o | £ u | <n a o | £ Q | Λ 5 | g |
| 3 00 φ’ | ©X X© 00 ^4 4 | R 00 Φ* | w4 t00 φ· | R 00 t»4 φ’ | cn ΓΟΟ φ· | OO ^4 | w-> ΓΟΟ Φ* | x© ΓΟΟ φ- | rroo ^4 Φ | 00 oo *4 Φ* | σ» Γοο «4 4 | 8 00 Φ* | 00 00 ^4 φ· | 00 00 φ· | m 00 00 φ· | 3 00 •4 Φ | ΙΛ 00 00 φ· | 3 00 4- | ΓΟΟ 00 ΦΤ | 3 00 4 | s 00 Φ* |
···· · · · ·*·· • · · · · · · · ··· • · ·· ·· ·· · · · · · • · ···· · · · ··· ···· ·· ·· ·· ··
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| 3 | rs X o | rs X o | rs X y | rs X y | X y | X y | rs X y | rs X y | rs X u | g | g | rs X y | rs X u | rs X y | rs X y | rs X u | rs X y | rs X y | rs X y | rs X y | rs X y | rs δ |
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| o | o | o δ | o δ | o δ | 3? 8 X y | X 8 X y | rs X 8 X y | vs I X y | vs s CM 8 X y | á* CM 8 X u | £ s X y | £ • •4 O X y | £ δ X y | rs X 8 y | á? 8 Z δ | 35 8 y | VS X g z II y | vs X g i | vs X g i | w • •4 O z II y | ©4 • *4 O % y | |
| CM fc | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| fc | § | g | x y | g | rs δ | g | X y | g | g | g | g | rs δ | g | rs δ | g | g | rs δ | X y | g | g | g | g |
| cn ^4 & | X | s | X | X | T | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| CM fc | 3? U | X y | s? y | g | 3? y | X y | £ y | £ y | g | ď y | 3? y | X y | X y | 3? y | X y | g | £ y | 3? y | X y | X y | 35 y | £ y |
| a | o | CM | O | CM | o | CM | o | »4 | CM | o | CM | o | ^4 | CM | o | ^4 | CM | o | ||||
| Os ^4 & | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 (X | T | X | rs X y | £ y | £ y | rs 5 | rs X y | X y | rs X y | X y | g | rs X y | rs X y | X y | rs δ | rs X y | rs X y | rs X y | rs X y | rs X y | rs X y | rs δ |
| r- ©4 | rs 5 | rs X y | m X y | rs X y | rs δ | rs X y | rs δ | rs X y | rs X y | rs X y | rs X y | rs X y | rs δ | 3? y | £ y | rs X y | rs X y | rs X y | X y | rs X y | X y | X y |
| 8 00 ^4 xt | Os 00 ^4 xř | S! 00 XT | m o* 00 xt | £ 00 xr | WS Os 00 •^4 Xt | 8 00 xř | r* Os 00 | 00 Os 00 •4 | o Os oo m·’ | ^4 | s | § ^4 Μ* | O Os ^4 | WS o Os 'e | Ό §? «M | | | ^4 | Os ^4 | o ^4 9 | W«4 0\ <r |
0050/46142 • *
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| a u | £ o | cn 5 | £ o | £ o | £ O | cn δ | cn X o | £ u | £ u | cn X u | cn 8 | cn X Q | ||
| ») | a | a | a | a | X | T | a | X | X | X | a | X | X | |
| w & o l | 8 Ϊ | 8 l | g Ϊ 5 £ 8 l | § g 8 l | wn a I 6 | «Λ X ž 8 f u | X g 8 l | a; m ξ υ | CM m X y o | CM rs X y υ | CM δ a a G> U 1 1 o o tX | CM δ a a O O 1 1 o o υ | CM 5 a a u u 1 1 o o X. X” u | m <·> a a o o X a a υ o 1 1 o o -v' | |
| CN •Sí | a | Ύ! | a | a | X | X | X | X | X | X | X | X | X | X |
| r—« PÍ | f | 4? 5 | 5 | f | £ υ | <? | cn δ | § | 4? δ | 8 | í | s | § | |
| cn Pí | a | TI | a | a | X | *τΐ | X | X | X | X | X | X | X | X |
| CM Pí | £ Q | β | £ υ | £ u | £ υ | £ u | § | £ u | í | £ υ | § | § | £ o | § |
| a | CM | o | (M | o | CM | o | CM | o | CM | O | ||||
| Os Pí | a | T | a | a | X | X | X | X | X | X | X | X | X | X |
| 00 Pí | cn 5 | cn a u | § | £ o | cn X o | £ u | £ u | 8 | £ u | cn X υ | cn 8 | υ 8 | cn X u | cn 8 |
| r* *«· Pí | m a o | m a υ | £ ω | cn a υ | cn X u | cn X o | cn X o | £ υ | cn X Q | £ υ | £ o | cn X υ | cn δ | cn 8 |
| Ž* | CN ^•4 Os Tř | CA Os A | M- Os | m o> | sO Os «4 | r- Os | 00 ·—« Os | Os Os W< | 8 Os | CM Os A* | CM £? Os | cn CM Os | 8 Os | WA CM Os |
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| rs X u | rs X υ | cn X u | rs X u | rs 5 | rs X u | rs X o | £ o | £ υ | rs 5 | rs X u | rs X u | rs X υ | rs X o | rs X o | £ Q | rs X o | rs X Q | rs X u | ||
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | ||
| <n r> X X u υ X | r> X υ > | rs 5 ! | WS | |||||||||||||||||
| c< ^cs X X o o | X O | *^rí X o | WS % | £ | £ | £ | WS X -CN | WS W , CN | WS -CM | CM z“*\ X | £ | CN £ | X § | X g | ||||||
| | | | | | I | £ | £ | cn X | WS X | WS X | y | y | y | y | y | ω | 9 | 9 | 9 | ||||
| n fs | o | 1 o | 9 | 9 | 9 | ď | & | $ | 9 | fe: | !z | 4 | *1 | |||||||
| <r o | O | X* | l | l | z II o | l | % | á | X o | 8 | st o | 8 | á | X o | é | 8 | 8 | s | ||
| CN | X | 5* | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| PÍ | rs 8 | £ u | rs 8 | rs 8 | rs 8 | í | rs 5 | g | rs 8 | g | rs 8 | rs 8 | £ o | g | g | rs 8 | g | g | g | |
| cn Pí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| CN Pí | X Q | £ o | £ o | £ u | £ o | £ u | £ υ | g | £ u | £ υ | £ o | £ o | £ u | £ o | £ υ | £ u | £ o | £ u | £ υ | |
| s | CN | o | —4 | CN | o | —M | CN | O | CN | o | Π | o | w*4 | Ol | o | —4 | ||||
| Os Pí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| 00 Pí | rs X u | £ u | rs 8 | £ u | rs X u | rs X u | g | £ u | rs X u | £ O | £ u | £ u | £ o | £ o | rs 8 | rs X Q | rs X ω | rs 8 | g | |
| Γ* PÍ | rs X o | en X u | rs X u | rs X u | rs X o | rs X o | £ o | *9 X o | rs X u | rs X o | rs X u | cn X o | rs X o | rs X u | £ □ | rs X υ | cn X o | rs X o | g | |
| V© CN Os | r* CN Os | 00 CN Os | o> cs Os | o m Os | cn Os | CN cn Os | cn cn Os «< | 3 Os | ΙΛ cn Os —4 | V© m Os | r* m Os | 00 cn Os | Os cn Os | •—4 | 3 —4 | <F*M | 3 ^4 Ν’ | í | ||
| Ž | Ν’ | •o | Ν’ | •o | Ν’ | Ν' | N* | Ν’ | Ν’ | Ν’ | •o | Ν’ | Ν’ | Ν' | M· | Ν’ | Ν’ | N |
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| £ Q | £ u | £ υ | Z Q | m X Q | £ u | c*> δ | g | £ o | £ υ | cn X o | m δ | cn X o | £ o | g | cn X o | £ u | ca δ | G | G | G | G | |
| X | X | X | Z | X | z | X | z | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
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| % | X | « | ||||||||||||||||||||
| v> | Ví | IA | y. | ý. | y | |||||||||||||||||
| % | | | % | z | z | X | £ | ||||||||||||||||
| 4? | 8 | 8 | Λ! | 8 | 8 | 8 | £ | £ | ||||||||||||||
| t | § | Z*\ § | g | CM | £ y | X | δ | t | £ | £ 0 | ||||||||||||
| % u | δ | Ϊ o | δ | δ | δ | δ | $ | i | Q | •í δ | δ u | X o <««/ o | § u | o | o | 0 11 u | 0 δ | 0 II u | 0 X 0 | |||
| CM fc | X | X | X | Ί1 | X | X | X | X | z | X | X | X | X | X | X | X | X | X | X | X | X | X |
| fc | g | § | í | g | g | cn δ | g | ca δ | g | δ | § | m δ | CA δ | ca δ | ca δ | ca δ | CA δ | ca δ | g | g | g | |
| m fc | X | z | X | m | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| CM fc | £ υ | g | g | g | z o | g | £ o | tn δ | £ u | g | £ o | £ u | £ o | £ S | g | £ o | g | £ u | £ u | £ o | £ o | CA δ |
| CM | CM | o | CM | o | CM | o | ZM | CM | o | zM | CM | o | CM | 0 | CM | o | ||||||
| © fc | X | T | T | X | X | X | X | X | z | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 ZZ Pí | m X υ | <*í δ | cn X Q | m δ | *n X o | <*> X u | £ u | g | m δ | £ u | δ | ca δ | <a X Q | ca X u | ca δ | ca δ | £ υ | £ 0 | X | X | X | X |
| r* fc | f*í X o | m X o | ť*í 5 | fH X o | cn X o | CA X o | cn X u | CA δ | m z o | £ u | g | CA X u | m X υ | ca X υ | ca X u | ca X Q | ca X υ | ca X υ | X | X | X | X |
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0050/46142 • · • ·
145
| s | y | y | y | u | y | y | y | y | y | W«4 y | y | y | y | y | y | y | y | y | y | y | y | H Cl |
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | ||
| £ £ y | X 8 X y | <n 1 X y | <Λ i X y | «Λ X CH § y | £ δ X y | £ δ y | £ δ δ | £ 8 | «*» X | EC | £ 1 δ | «η X g | Im A. δ y | £ δ l | £ δ y | X V X y f 5 y | y 5 X ž | 8 V X y g 5 y | X σ y | V» 5 £ 8 g | ||
| CH fc | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| fc | m δ | g | m δ | g | cn 8 | en δ | g | g | cn δ | g | P*> δ | δ | g | g | m δ | 3 | g | cn δ | g | g | g | g |
| m | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| CH | g | X y | X y | X y | g | £ y | £ y | £ y | £ y | £ y | £ y | £ y | g | £ y | g | g | £ y | g | g | £ y | £ y | £ y |
| 0 | CH | o | CH | o | CH | © | CH | © | W4 | CM | o | CH | o | CH | © | ^4 | ||||||
| OS PÍ | X | X | Ύ* | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 ^>4 & | X | X | rt | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| r©3 | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
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• · • · • · • ·
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| G | G | G | G | G | G | G | G | G | G | G | |
| ►J | z | X | X | X | X | X | X | X | X | X | X |
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| OS PÍ | X | X | X | X | X | X | X | X | X | X | X |
| 00 PÍ | X | X | X | X | X | X | X | X | X | X | X |
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| Os PÍ | X | T | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 | ||||||||||||||||||||||
| Pí | X | X | T | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| r* Pí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| u z | N | 4.2001 | 4.2002 | 42003 | 14.2004 | 14.2005 | 4.2006 | 4.2007 | 42008 | 4.2009 | 42010 | O | CN o CN e | (42013 | 142014 | 142015 | 42016 | 42017 | 4.2018 | (4.2019 | 42020 | 4.2021 |
···· · · · · · * · • · · · · · · · * · · • · · · ·· · · ···* · • · ···· · » · ······· ·· ·* · · ··
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| 3 | G | y | G | G | G | y | G | G | y | •M y | G | G | u | y | y | y | o | G | y | y | o | G |
| u | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| N δ | 45 £ £ δ | 45 £ δ | CM § y, I | ď £ 8 z*s g y | VI X Ό £ 8 £ y X u | VI % 8 £ o 5 | £ £ y. u | £ σι X y y | σι X y u | o | o | o δ | o δ | o δ | £ 8 8 | £ § y | 1 y | VI X CM 8 X y | VI X y | f X y | £ • v4 8 y | |
| CM | X | X | X | X | m | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| PÍ | g | § | 4? 5 | £ | σι δ | σι δ | § | g | g | g | g | g | σι δ | g | g | g | g | g | g | § | f | g |
| CA | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| CM PÍ | § | £ y | X y | £ υ | £ o | £ y | £ u | £ y | g | £ y | £ y | £ y | £ y | £ y | £ y | £ y | £ y | £ y | £ u | £ u | £ y | £ o |
| 0 | CM | o | CM | O | CM | o | CM | o | CM | o | CM | o | σ | CM | o | ^4 | CM | o | ||||
| Os Pí | *τΐ | *T | T | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| oo Pí | Ti | *r | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| r* PÍ | X | X | <7* | X | X | X | X | X | X | X | X | X | £ y | £ y | σι X y | σι X y | σι X y | σι X y | σι X y | £ y | £ y | £ u |
| Nr. | CM CM O «>1 4· | cn CM O xr | o Xt | ΙΛ CM O | £ o CM | CCM O CM ’Μ’ | 00 CM O CM xt | Os CM O CM | o m o Π •e | CA O | CM cn o Π M· | CA 3 Π | 3 o Π M* | v-> CA O CM Tf | s© CA O CM | r* CA O CM | 00 CA O | Os CA O CM | ••4 3 π | § ’Μ- | CA 5 •4· |
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0050/46142 β · • ·
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| 3 | Q | g | G | G | G | ^R O | G | G | G | G | G | G | G | G | G | G | G | G | »R O | G | G |
| u | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| £ O X □ | £ O X υ | £ 8 u | £ 8 Ϊ | m X 8 £ u | m X g z II O | d? g ¥ u | •Λ t ¥ O | Ir 0R ó l | £ ! | »R .¾ o l | g £ 8 Z II u | g l u ¥ υ | £ Ϊ δ | d? G 8* l | *n s z δ | WS X σ £ 8 i | ťM m X u o | CH £ u u | CH £ o | CM 5 << X X u u 1 1 o o u | |
| CM PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| g | m δ | g | g | m δ | tn δ | en δ | en X u | rs δ | g | g | rs δ | m δ | g | m δ | CO X Q | m δ | m X o | g | £ u | g | |
| m pí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| CM ^R Pí | £ u | £ o | £ Q | £ Q | £ u | £ u | £ u | £ u | g | £ o | £ υ | £ u | £ o | £ o | g | £ o | £ u | £ o | g | g | g |
| c | •R | CM | o | CM | o | •»4 | CM | o | CM | o | CM | o | CM | o | CM | o | |||||
| OS Pí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| oo fit | X | X | T| | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 41* | m X o | m X u | X u | cn X u | X o | £ u | £ υ | en X o | £ u | £ o | m X o | rs X u | m X u | £ u | £ Q | X u | δ | m X u | cn X o | g | «η X u |
| u z | i T | 3 CM | SO s CM | t 3 CM, | 00 3 CM | Ch 3 CM | S? o CN 4- | i/S O CM -T | CM <n o CM ’Τ | m IA o Π 4- | Š CM | WS O CM | Ό IA O Π 4 | ro CM τ|- | 00 IA O Π 4· | Os ΙΛ O CM | 8 o «Ί 4· | rR SO O CM | CN Ό O CN 4· | co Ό O Π | 3 R 4·' |
• ·
0050/46142 • ·
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| 3 | G | G | G | G | G | G | G | G | G | G | G | G | G |
| a | X | X | X | X | X | X | X | X | X | X | X | X | X |
| CM u a a u υ 1 1 o o | CM 5 ^tN X X u u 1 1 o o z o | n <n a a o o X a a o u 1 1 o o z' u | m <n X X u o X δ 8 1 1 o o u | m <·> a a o u X X X o u 1 1 o o Z O | g l | í | g l | WS X í | X G Ϊ | WS X ř δ | £ y a o | δ i u | |
| η | a | X | X | X | X | X | X | X | X | X | X | X | X |
| % | rs a u | § | δ | rs 5 | δ | δ | δ | δ | rs δ | δ | δ | rs δ | δ |
| m ^4 <x | X | X | X | X | X | X | X | X | X | X | X | X | X |
| CM Έϊ | a U | δ | X o | £ u | £ o | rs X u | £ u | £ o | δ | £ u | £ u | £ U | £ o |
| 0 | CM | o | CM | o | CM | o | CM | o | T | ||||
| O\ PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X |
| r* PÍ | rs X u | rs 5 | rs X u | M O | rs X u | rs X o | rs X u | £ u | rs X u | rs X u | £ u | rs X υ | £ o |
| ž | Ό SO O CM M· | 3 o | S o 4· | s φ | Ό O CM Φ | o r* o CM Φ | r* o CM φ | CM r> o CM -4· | cn t o «Ί 4· | -Φ | <n r~o ‘Ί 4· | O C— O CM φ· | ΓΓΟ CM Φ |
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| 5 | G | ^«4 O | G | G | G | G | G | G | G | G | G | G | «< υ | •m4 u | G | G | G | G | •Μ 0 | G | G | G |
| u | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| m | WS | |||||||||||||||||||||
| X | X | X | ||||||||||||||||||||
| vs | ws | «Λ | <ž | á | ||||||||||||||||||
| X | X | X | X n | X | X | |||||||||||||||||
| cs | rs | r ) | 0 | |||||||||||||||||||
| £ o | *n X ď | sn | | ws I | a? £ y | <s Z·* £ y | cs z** £ y | WS X s | WS X j | *n | 8 £ y 5 | 8 £ y | 8 i | rl | λ í I | f y | as £ Q | 8 z-s £ y i | & £ y. 3 | 8 z“> g 1 | |||
| é | 1 | íi o | X | £ υ | i o | u | o | á | u | X o | o | s | 'ď υ | t | δ | £ | X u | X 0 | ó | |||
| rs | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| pí | § | cn X u | f*S δ | § | cn X υ | £ o | £ u | cn δ | í | β | cn δ | § | § | § | í | í | g | í | cn δ | g | cn δ | cn δ |
| m * | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| cs PÍ | £ o | £ o | cn X υ | £ u | cn X o | cn X υ | £ u | £ u | £ o | £ o | £ o | £ G> | g | § | £ 0 | £ u | £ u | £ u | £ 0 | £ υ | £ o | |
| a | CS | o | CS | o | es | o | ^4 | rs | O | rs | o | ^4 | rs | 0 | rs | 0 | -4 | cs | ||||
| Os Pí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| oo Pí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| r- | cn X o | £ u | £ u | £ o | m X Q | £ u | f*S X o | £ o | cn δ | cn δ | m δ | £ o | cn δ | £ o | £ 0 | £ 0 | § | cn X u | cn X u | cn X Q | m δ | cn δ |
| ž | 00 ro <Ί | Os ro «Ί | S o 4· | 00 o rs xr | a 00 o es Φ | s o <Ί Φ | $ xr | 00 o rs Φ· | 3 o «Ί >r | 00 8 Φ | SJ 00 o rs φ· | 8 + | w Os O CS Φ | CM o* o Ί· | cn Os O est Φ | 3 0 CM e | <n Os 0 cs Φ | \O Os O rs Φ | rOs O rs Φ* | 8 o | 8 o n Μ- |
• · • · • «
0050/46142 • ·
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| >1 | u | G | G | G | G | G | G | G | G | G | G | G | G | G | G | G | ^A u | G | •A O | G | G | 0 |
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| £ 2 ca X 52 o | £ 1 u Ά u | £ £ CA X 52 u | o | o | o δ | o δ | o δ | CA X § Q | í o | § 5 | VS 8 5 | vs § X u | V» § X o | & o δ | £ <5 « | £ δ X Q | £ i | £ % i, | £ l | vs X g 5 O | f l | |
| rs | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| § | CA 5 | CA 5 | g | CA X υ | CA 5 | g | g | CA 5 | CA 5 | § | g | g | CA 5 | g | g | CA δ | g | CA X o | g | g | CA X t> | |
| CA PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| CN PÍ | £ u | £ u | £ u | g | £ u | g | £ o | £ o | g | £ u | £ υ | £ | £ u | £ o | £ υ | g | a o | £ o | £ Q | £ Q | g | £ υ |
| 0 | o | A | CM | © | CM | © | A | CM | o | CN | © | A | CM | o | CM | © | A | es | © | |||
| ©s PÍ | X | X | X | Ί1 | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 PÍ | X | X | a | X | X | g | g | CA δ | CA δ | CA X o | g | u | CA X u | £ u | g | CA δ | CA X u | CA X υ | CA X u | CA δ | CA X Q | 4? δ |
| r* Pí | CA « | £ u | CA X ϋ | CA X υ | CA X u | CA δ | cn X o | CA g | CA | CA X u | £ CJ | £ Q | CA X υ | £ υ | £ u | CA δ | £ u | CA X υ | CA X o | CA δ | £ u | CA X υ |
| u z | 8 <Ί Ν' | A O es | S CM Xt | m O 4· | 3 ^4 CM N* | O •A xt | 8 *A N· | š CM Ν' | 3 A <Ί N | 3 *A N | © •A *A CN Ν' | •A CN Ν' | CM A <Ί N* | cn A CN Ν’’ | «Μ «Α CN Xt | •A A Π N | © •A <N N* | r- A CM Ν’ | 00 Ν' | Os A CM Nr | «Α CN N | s CN Ν’ |
0050/46142
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| u | y | y | y | y | y | y | y | y | y | y | y | y | y | y | y | |
| X | X | X | X | X | X | X | a | a | X | X | X | X | X | X | X | |
| ks X g 5 y | Ui ©4 δ £ y | Vi ©4 s δ | ©4 O y | y X I 8 Z II U | g £ δ | 8 £ 1 | KS X ď £ 8 Ž | KS X tf £ 8 ? y | KS X σ £ 8 l | 43 rs X υ y | <N z“x rs X u u | 4J £ y | CN u e< ^d X X o a 1 1 o o zu | d X u «r ^d X X u u 1 1 o o v s o | d X u ^d X X o u 1 1 o o | |
| <s £ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| % | rs δ | rs 5 | § | § | rs X u | g | § | í | rs 5 | £ y | g | § | i? | § | § | £ y |
| rs ^4 PÍ | X | X | X | TJ | X | X | X | X | X | X | X | X | X | X | X | X |
| cm ^4 PÍ | £ y | £ y | £ y | £ u | rs X u | £ y | £ y | £ y | £ u | £ y | £ y | £ y | £ u | § | £ y | £ y |
| a | CM | o | CM | o | CM | o | CM | o | ^4 | <N | o | CM | ||||
| Os Pí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 Pí | £ y | rs X y | £ u | £ y | rs X u | rs X y | £ y | 5 | rs X y | £ u | rs δ | £ u | rs X o | β | rs X u | rs X y |
| íiH | n X u | X u | rs y | rs X u | rs X y | rs X y | £ y | rs X u | £ y | rs X u | rs X y | rs X y | rs X u | £ y | £ y | rs X y |
| Nr. | CM CM f4 CM Ν’ | m CM •4 CM Ν’ | ^4 CM Ν’ | trs CM CM N | S© CM ^4 CN N“ | r* CM Π Ν’ | 00 CM Ν’ | Os CM CM N | O rs CM Ν’ | rs CM Nr | CM rs ^4 CM Ν’ | n rs Π N | 3 π Ν’ | trs n CM Ν’ | Ό rs CM Ν’ | r* rs CM Ν’ |
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| a | □ | g | 0 | «*· υ | □ | G | G | G | G | G | G | G | «*4 Ο | G | G | G | G | |
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | ||
| rs rs | rs | rs | rs rs | |||||||||||||||
| δ 6 | X o | δ | δ δ | |||||||||||||||
| X 5 5 | > X u | X u | x„ X X o u | X | £ | £ | £ | CM | WS * | WS W rCM | CM £ | £ | ||||||
| I I | I | I | | | | X | £ | rs | K | X | y | 8 | 8 | 8 | 8 | 8 | δ | |||
| 1 1 o o | 1 o >> | O | o o -S X* | 'i | o | s> | í | í | f | X | 1 | X | X | i | 3 as | |||
| u | o | u | II O | δ | δ | o | U | o | ο | υ | υ | υ | Q | |||||
| zz* | 52 | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| ní | § | í | £ o | rs 5 | rs 5 | £ u | rs δ | δ | § | rs δ | § | rs δ | § | ί | § | £ Q | ||
| PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| CM ·Pí | § | £ o | £ U | § | £ o | § | £ U | £ υ | £ U | £ o | g | £ Q | ί | § | X υ | £ υ | £ u | |
| ň | o | CM | o | CM | O | ♦Η | CM | o | CM | ο | «Μ | CM | ο | |||||
| OS Pí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| 00 Pí | £ G> | £ U | rs X u | rs X o | rs X o | £ o | s | rs δ | rs 5 | s | rs δ | ί | £ ο | § | § | rs X u | ||
| r* Pí | £ u | £ o | £ o | £ υ | rs δ | ÍE G | X o | £ υ | rs X o | rs δ | rs X Q | δ | rs δ | £ υ | § | δ | rs δ | |
| ž’ | 00 r*s CM xř | Os m 4· | 3 <Ί xr | Xj* <Ί 4· | § •4· | <*s xT Π xr | 4 ^4 CM xř | WS ^r «Μ xr | 42146 | 4· | § Xt | π 4· | § χΤ | WS Π χΤ | CM ws •Μ <Ί ΧΤ | m W) CM 4·' | 4.2154 |
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| 3 | □ | G | G | G | 0 | G | G | G | 0 | G | G | u | υ | G | G | G | O | G | G | G | G | £ u |
| hJ | ►fl | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 45 £ £ o | WS X ř X o | WS i o | WS i u | 8 /—s δ Ϊ υ | WS 8 £ X u | WS z*s £ o X o | r> δ | n δ | δ | s I | CN rs § u | 45 cn X y o | sc SO £ 8 £ y, Ϊ o | WS X ž 8 £ y, *r X o | WS X sO * 8 £ u í X o | £ rs X y, u | cn X rs X y. o | í £ o | o | o | o δ | |
| CN & | X | X | TÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| í | í | § | rs δ | rs δ | rs δ | rs δ | í | § | § | í | § | § | í | rs δ | í | í | s | í | § | X | ||
| cn PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| CN PÍ | £ u | £ u | £ υ | £ o | rs X Q | £ q | £ u | £ o | š | £ u | í | £ o | £ u | í | ě | £ o | § | £ u | en δ | £ u | £ o | § |
| ca | CN | o | CN | o | CN | o | CN | o | CN | o | CM | o | CN | o | CN | o | ||||||
| OS »-< Pí | X | X | Tí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 Pí | £ u | £ Q | § | rs δ | £ u | § | g | rs X u | rs X υ | rs X u | δ | £ υ | cn δ | ě | δ | rs X u | rs X o | § | í | <? | £ υ | X_ |
| r* | £ u | £ u | ř7 | δ | rs X u | rs δ | m X o | rs X o | rs X u | § | rs X o | cn δ | £ Q | cn X O | rs X o | rs δ | £ o | £ υ | £ o | rs X O | £ u | X |
| Nr. | IA «A CN N* | s© A CN Ν’ | ΠΙΑ n M· | 00 ΙΑ CN | Os IA CN Ν’ | 8 CN N* | 3 CN Ν’ | cn s© CN Nr | >© CN Ν’ | 8 CN Ν’ | (A V© CN Nr | 8 CN Ν’ | \© »—i CN Ν’ | 8 CN Ν’ | qs >© CN Ν' | g π | r* *4 Ν’ | CN Γ* CN Ν’ | en p- CN Ν’ | —“4 CN Ν’ | IA r- CN Ν’ | Ό r— CN Ν' |
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| 3 | ťH X G> | cn X o | X G> | £ G) | cn X υ | £ o | m X G> | cn δ | cn X o | £ G> | g | cn δ | £ u | £ o | £ o | cn δ | cn δ | £ G) | cn δ | cn X G) | £ G) | £ u |
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| > | O δ | o II g> | X š G> | £ u | £ l G> | v-> fc 8 X G> | m fc 8 X G) | WS X 8 X G> | £ g G> | & 5 | & o 5 | £ i | £ 8 l | £ 8 G) | ws X g Ϊ | W> X í u | WS X § g | »4 l | g | *4 & o G) | s Ϊ G) £ l | 8 Ϊ 1 8 5 G> |
| CM fc | X | X | T | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| ^4 fc | X | <τ[ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| m ^4 p4 | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| CM Pí | £ o | s | £ G> | g | £ G> | £ G) | £ G) | £ G> | £ 5 | £ G> | £ o | £ G> | £ G> | g | £ Q | £ G) | g | £ u | £ u | £ υ | £ u | £ u |
| s | CM | o | CM | o | —4 | CM | o | CM | o | --4 | CM | o | »4 | CM | o | —4 | o | -4 | ||||
| Os * | X | 11 | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 fc | X | *TÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| rfc | X | TI | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| rr* CM MT | Π 4 | Os r* *4 CM | 8 «Μ | s CM | £3 00 CM Tf | oS —M Π M* | S Π 4 | m 00 ’Μ’ | s© 00 CM | ΓΟΟ 4M CM M* | 00 00 ^4 CM xt | Os OO CM *r | § | 44 Os CM | S w*4 CM | Sí «4 CM MŤ | ^4 CM M* | os CM | $ CM | Si <4 4 | oo Os CM |
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| 3 | cn a o | cn X υ | g | £ υ | cn X u | cn X υ | cn X o | £ υ | g | £ o | £ u | £ o |
| a | X | X | X | X | X | X | X | X | X. | X | X | |
| 8 X Ϊ | X CJ f l | «η X s 8 I | <Λ X s 8 l | CM X u υ | cn X y Q | Λ cn 3 y o | CN X u t/' ^cm X X u u 1 1 o o 'y' | CM 3 < X X υ u 1 1 o o | CM X u t/ ''“'CM X X υ u 1 1 o o N. -S o | m cn X X o u X X X u o 1 1 o o X. X' υ | <n cn X X υ υ X X X o u 1 1 o o u | |
| CM Pí | X | X | X | X | *T1 | X | X | X | X | X | X | X |
| % | X | X | X | X | X | X | X | X | X | X | X | X |
| m cd | X | X | X | X | T | X | X | X | X | X | X | X |
| CM Pí | £ o | £ u | £ u | £ u | £ o | £ o | £ u | £ u | g | £ o | £ u | g |
| 0 | CM | o | CM | o | CM | o | CM | o | ||||
| OS Pí | X | X | X | X | X | X | X | X | X | X | X | X |
| co Pí | X | X | X | X | X | X | X | X | X | X | X | X |
| r- OÍ | X | X | X | X | X | X | X | X | X | X | X | X |
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0050/46142
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| 3 | £ y | n 5 | £ y | m X u | en δ | £ y | £ y | m X y | £ y | f*Y X y | £ y | <*s X y | £ y | £ y | £ y | £ y | g | rY 8 | g | c*s X y | 8 | |
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| m PÍ | X | X | X | X | X | X | fTf | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| (H fc | £ y | £ y | £ y | £ u | £ y | £ y | g | g | £ y | £ y | £ y | g | £ y | g | g | g | g | £ y | g | g | g | |
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• ·
0050/46142 • · « · r' 159 -
| 3 | X y | rs X o | rs X y | rs X y | X y | rs X y | rs X y | X y | g | ď y | rs X y | rs X y | rs X y | rs 5 | X y | X y | m X y | X y | rs X y | rs X y | rs 5 | £ y |
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| J | l | 5 | Ϊ | δ | δ | 5 | i | ď y | X y | rs X y | o δ | o | O || | 8 X | 8 X | 8 X | 8 X | |||||
| δ | δ | δ | δ | δ | δ | O | δ | y | y | y | o | o | δ | y | y | y | y | y | ||||
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| *•4 fc | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| m fc | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| CM fc | g | X y | X y | x1 y | X y | X y | g | X y | X y | g | ď y | X y | X u | £ y | ď y | g | g | X y | x1 y | ď y | ď y | g |
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• * • · • ·
0050/46142 • · · ·
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| 3 | g | cn z u | £ u | £ o | z o | £ cj | £ o | £ o | z <J | m z o | £ o | m X cj | £ cj | z o | m X cj | m g | z u | m z CJ | m g | £ u | cn X CJ | f*1 z u |
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| rs X o | rs X u | rs X o | <n X o | rs 8 | rs X Q | £ u | rs X u | rs X o | rs X o | rs X ω | |
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| 0 | CN | o | CN | o | CN | o | ^4 | CN | o | ||
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| r* Pí | rs X u | rs X o | rs X <-) | rs X u | g | rs X υ | rs X u | rs X u | rs g | rs X o | £ Q |
| Z | v© r* <N xt | rr* CN CN N- | 00 r* CN CN xr | Os r* CN CN xf | 8 CN CN xř | 00 CN CN xr | <n 00 CN CN xf | m 00 CN CN xf | s CN CN xr | un 00 CN CN xř | X© 00 CN CN N* |
0050/46142
162
| z Q | x1 o | x1 o | rs X o | rs X u | Z Q | Z u | Z u | rs X o | rs X o | rs δ | rs X o | Z o | δ | c*> X Q | rs X o | £ u | δ | 3? O | rs X o | z? u | rs z u | |
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| cn | X | X | X | X | z | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| d | £ o | ď o | Z u | § | <? z o | í | Z o | £ o | z o | £ u | £ υ | 3? O | Z o | X o | £ u | £ u | s? o | ď u | § | z1 o | 4? s | š |
| ca | d | o | CM | o | CM | o | «4 | d | o | CM | o | CM | o | d | o | |||||||
| OS PÍ | *n | X | X | X | T | X | X | X | z | X | X | X | X | X | X | X | X | X | X | X | X | z |
| co 04 | X | X | X | X | T | X | X | X | z | X | X | X | X | X | X | X | X | X | X | X | X | X |
| d pí | X u | Z u | n X υ | § | «Π z υ | Z u | rs X υ | r*s X O | £ u | Π X u | rs X o | rs X o | z o | d? υ | rs X υ | n X υ | X o | rs X u | § | rs z υ | rs X u | rs o |
| u z | oo ÍM 4· | 3 d Π Φ* | Os 00 cm Π Φ· | £ d CM Φ | Os CM CM Φ* | s cm d Φ* | en Os CM CM Φ* | d CM Φ· | Ά Qs CM CM Φ | d d Φ· | d Os d d Φ | oo Os d d Φ· | Os Os d d Φ· | 8 | O en d Φ· | s m CM Φ* | 8 m d φ· | 3 cn d Φ· | 8 m CM Φ· | 8 m CM Φ· | o m Π Φ* | 8 m φ· |
• ·
0050/46142
| 3 | £ u | en X υ | cn X u | £ u | en X u | £ o | £ o | en X u | en X u | en X o | £ u | en X o | cn X υ | en X o | en 8 | en X u | £ g> | en 3 | en X Q | en X □ | £ u | £ o |
| a | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
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| CN % | a | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| cn PÍ | X | X | X | X | *e | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| CN PÍ | £ o | en X o | £ o | £ o | en X o | £ o | £ o | £ o | g | £ o | g | £ u | £ u | £ o | £ u | £ o | £ o | £ o | £ υ | £ u | £ u | g |
| ca | CN | o | CN | o | CN | O | CN | o | —4 | CN | o | »^4 | CN | o | CN | o | CN | o | ||||
| Os PÍ | T | X | X | T | *TÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 Pí | X | X | X | ΓΓ | T | X | X | X | X | en X u | en X u | en X u | en X u | en X Q | en X o | en X <J | cn X o | en X o | cn X o | en X o | en X o | en X o |
| r* r-< Pí | en X o | en X o | ř*S X u | en X u | en X u | en X u | cn X o | en X o | en X o | en X u | en 8 | cn X u | cn X G) | cn X o | cn X o | cn X o | en X o | en X u | en X u | en X υ | cn 8 | en 8 |
| 1U z | 3 cn CN Ν'* | o —4 cn CN Ν' | W«4 cn n | CN •—4 cn CN Ν’ | cn cn CN Ν' | 2 cn CN Ν' | on m CN Ν’ | vO cn CN Ν’ | t- cn CN Ν' | 00 cn CN Ν' | Os K cn Π Ν’ | 8 cn CN Ν’ | »-4 CN cn CN Ν’ | CN CN cn CN Ν’ | cn CN cn CN Ν' | 3 cn CN Ν' | wn CN cn CN Ν’ | VO CN cn CN Ν' | r* CN en CN Ν' | 00 CN cn CN Ν' | ©v CN cn CN Ν’ | O cn m CN Ν' |
0050/46142 • ·
| 3 | a u | tn X Q | m X Q | cn X u | rs X Q | m X υ | £ u | cn X Q | £ u | cn X o | fn X o | £ υ | cn X υ | fn X o | £ o | £ o | m X u | δ | § |
| A | a | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| § 5 υ | £ 8 l | •Λ X δ z δ | m X δ l | m X δ 5 u | u i δ | w § z δ | £ o o | až s 8 l | g Ϊ g 8 l | 5 X g l | K ž 8 l | tc | WS X σ X 8 o | CM cn X u o | £ υ | £ u | . CM o a a υ u 1 1 o o 'x ' u | Cí a u <r a a u u 1 1 o o υ | |
| CM | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| cn Pí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| ΓΜ Pí | X o | £ o | £ o | £ Q | £ u | £ u | £ o | £ u | £ u | δ | 5 | £ u | £ u | £ u | £ o | £ o | £ o | £ o | £ o |
| C3 | CM | o | CM | O | CM | o | 4—4 | CM | o | CM | o | CM | o | ||||||
| 01 Pí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 Pí | X u | «η X u | m 5 | cn X o | en X o | cn X u | m 8 | g | £ u | cn 5 | cn X o | cn X u | £ u | cn δ | £ Q | cn X u | cn X υ | £ u | en δ |
| r- ·-· Pí | cn X o | m X u | m X o | m o | m X u | cn X o | «η X Q | cn X o | £ o | cn o | £ o | £ o | £ o | cn X u | cn X u | cn X o | cn X o | £ o | £ Q |
| Ž | cn cn CM Φ | CM cn cn CM ΦΓ | cn cn m Π Φ | 3 m CM Φ | W) cn cn CM Φ | s© cn cn CM Φ | r*· cn m CM Φ* | 00 cn m Φ | 0S cn cn Π Φ | s cn CM Φ· | rH Φ* cn CM Φ | Φ cn CM Φ | cn Φ cn CM Φ | 3 cn CM Φ | Φ cn CM •Φ | $ cn CM Φ | rΦ cn CM Φ | 3 m CM Φ | Φ cn Φ |
0050/46142
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| 5 | σι X y | m X y | m X y | m 5 | £ o | £ u | m X y | £ y | σι X y | £ o | £ y | £ u | σι X y | £ y | m X u |
| .J | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
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| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| CA Pí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| CM PÍ | σι X o | £ o | £ u | £ y | £ o | g | £ y | £ y | g | g | £ y | £ y | £ y | £ u | £ y |
| 0 | CM | O | ^4 | CM | o | CM | o | CM | o | σ | CM | o | |||
| Os PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
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| t** Pí | X y | £ y | n X υ | f*l X o | X y | σι X y | m X y | σι X y | £ y | σι X y | σι X y | σι X y | £ u | £ y | σι y |
| Z | o Ά CA CM TT | »4 <A CA CM ’Μ’ | CM Ά CA CM | CA IA CA CM | 3 CA CM rř | *n CA CM Xt | SO <A CA CM M· | <A CA CM M | 00 m CA CM | ©s IA CA CM M | S CA CM | 5 CA CM | CM Ό CA CM **r | CA \© CA CM MŤ | 3 CA CM xr |
0050/46142
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| £ o | £ Q | PA a o | <a δ | pa a u | £ Q | g | g | m a o | £ υ | £ o | £ U | £ u | PA 5 | CA a u | £ o | g | £ u | PA a u | £ υ | £ o | CA a υ | |
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0050/46142
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0050/46142
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0050/46142
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| ž | Φ ΜΊ es Φ | Φ cm Φ | m Φ vn CS Φ | 5 rs Φ | tn Tf m rs Φ | $ WH rs | r- Φ Π | 00 Φ ΜΊ Π Φ | Os Φ <n rs | 8 m rs Φ | rs Φ | CS ΙΛ CS Φ | m ΙΛ Λ rs Φ | 3 0Ί CS Φ | m cs Φ | V© 1Λ m rs Φ | Γ— m rs Φ | 00 cs Φ | Os <r> cs Φ | 3 v-> rs Φ | rs Φ |
0050/46142
| G | G | G | G | G | G | G | G | G | G | G | G | G | |
| X | X | X | X | X | X | X | X | X | X | X | X | X | |
| CN 5 <r K X υ o 1 1 o o x. ' O | ÍN X u X X u u 1 1 o o o | cn cn X X u o X X X u u 1 1 o o | cn cn X X u o X X X u o 1 1 o o ''x s' o | cn cn X X u υ X X X u u 1 1 o o | rs δ g | rs 5 z ó | rs δ Q | vs § ? υ | l | £ o 5 | g υ | ||
| CN fc | X | X | X | X | X | X | X | X | X | X | X | X | X |
| pí | X | X | X | X | X | X | X | X | X | X | X | X | X |
| m Pí | £ Q | £ Q | rs 8 | £ u | £ u | g | g | g | £ u | £ Q | rs δ | £ υ | rs 5 |
| CN PÍ | £ υ | £ o | £ o | £ υ | £ o | £ o | g | £ o | £ υ | £ o | £ o | £ Q | g |
| 0 | CN | O | <4 | o | CM | o | CN | o | |||||
| Os Pí | g; | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 PÍ | £ u | £ u | £ u | rs X Q | rs δ | rs X o | m X Q | rs X Q | £ u | g | £ υ | rs X υ | rs δ |
| r* Pí | rs o | rs δ | rs δ | rs X Q | rs δ | £ o | g | rs X u | rs X o | rs X u | g | rs X u | £ u |
| u z | <n CN xf | cn \© tn CM xf | CN | sn \© wn CN xt | m CM xf | s© <n CN xf | <Λ CM xr | Ό <Λ CN xf | g u-> CN xf | fH r* CM xf | CM r<Λ 4· | cn r-* m CM xr | m |
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| G | G | G | G | G | G | G | G | G | G | G | G | G | G | G | 0 | G | G | G | G | G | ^-4 Q | |
| X | X | m | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| WS | WS | |||||||||||||||||||||
| X | X | X | ||||||||||||||||||||
| ws | WS | VS | Ό y. | <2 | <2 | |||||||||||||||||
| X | x | X | 33 | X | X | |||||||||||||||||
| CN | CN | o | o | rj | ||||||||||||||||||
| 4? X | ws i | WS X 1 | WS 1 | CN Z—K £ o z | CN ď z | CN z“s £ υ Z | ws X í? | £ 1 | WS X | 8 /*< § ¥ | 8 £ Q | 8 z“s í | CN £ | ri | 4? cn I 3 | CN ^cn X Ϊ | 45 £ | 8 z—s £ Q 5 | 8 £ | 8 z“·* £ y, 5 | ||
| δ | o | δ | £ o | £ o | £ o | £ o | o | u | £ o | £ υ | £ O | o | II o | δ | δ | δ | n u | δ | X u | o | δ | |
| cn £ | X | m | Ti | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| % | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| m PÍ | cn X u | X o | en δ | £ u | en 5 | en X o | en δ | en X u | en δ | en X u | £ o | § | £ Q | § | £ o | £ o | § | £ u | £ Q | cn δ | cn X Q | § |
| CN Pí | £ O | g | £ o | £ Q | £ υ | £ o | δ | £ o | £ o | en X u | £ υ | £ o | £ u | £ u | § | £ o | § | £ u | £ υ | £ u | £ Q | £ υ |
| a | CN | o | CN | o | CN | O | ^4 | CN | o | CN | o | CN | o | CN | O | CN | ||||||
| Qs PÍ | X | X | Ti | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| OO Pí | £ Q | cn X u | X (J | cn X u | £ o | en X o | en X o | en X u | en 35 □ | en X u | cn X o | cn X o | δ | en X u | £ u | en X u | δ” | en X υ | en X υ | en X Q | en δ | en δ |
| Π- PÍ | £ u | en X u | en X υ | cn X o | £ o | en X υ | en X o | en X u | £ υ | en δ | £ o | cn X υ | cn δ | en δ | cn X u | en X o | en X u | en X o | en X u | £ o | cn X u | cn X o |
| Ž | A Π· a CN N | \© r* IA CN N | rΠΙΑ CN N* | 00 ΠΙΑ CN N | Os ΠΙΑ CN N | 8 A CN Ν’ | 00 A CN Ν’ | CN 00 A Π N | m 00 A <Ί N | S A Π N | A 00 A CN N | 4.2586 | 4.2587 | s A CN N | 4.2589 | A CN N | o A CN N | CN Os A CN N | m Os A CN Ν’ | S A CN N* | A Os A CN N | \O O* A cn Ν’ |
0050/46142 • ·
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| s | y | y | y | y | y |
| X | X | X | X | X | |
| ť*S 1 £ y | m 1 m a y | m X £ cn X 9 y | o | o | |
| CH fc | X | X | X | X | X |
| fc | X | X | X | X | X |
| m | £ y | £ y | £ y | m X y | £ y |
| CH oá | § | £ y | m X y | £ y | £ y |
| 0 | o | CH | o | CH | |
| o\ pí | X | X | X | X | X |
| 00 fA | m X y | m X y | <n δ | X y | r*s X y |
| r* pí | X y | m X y | m X y | m X y | r*s X y |
| ž | £ m CH d· | Cg Os «Ί CH d· | Os Os ΜΊ CH d* | d· | 8 CH d· |
Tabulka 5: Sloučeniny formule
0050/46142
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| 3 | z | z | Z | X | Z | Z | CA 3 | CA Z o | m Z □ | CA Z o | CA δ | § | CA 3 | CA δ | CA Z u | CA 5 | CA δ | CA δ | CA 3 | CA Z o |
| z | z | Z | ÍT| | z | Z | z | z | z | z | Z | z | z | Z | z | z | Z | Z | z | z | |
| >· | ca 0 o | ca z 8 u | tn * 8 o | m * 8 o | & δ υ | £ δ o | z 8 u | CA Z 8 u | dc CM 8 υ | <A Z CM 8 o | £ O u | & g | CA Z 8 O | CA § u | v> i u | 8 O | £ 6 υ | £ ·«· o o | CA Z 8 u | z 8 O |
| <n 04 | iTi | z | z | z | z | z | z | z | z | z | z | z | z | z | z | z | z | z | z | |
| CM a | w | z | z | z | X | !Ti | z | z | z | z | z | z | z | z | z | z | z | z | z | z |
| δ | z | z | z | z | z | z | z | z | z | z | z | z | z | z | z | z | z | z | z | z |
| a | o | CM | o | CM | o | CM | o | CM | o | CM | o | CM | o | CM | o | CM | o | CM | o | CM |
| 0 Pí | z | Z | Z | Z | Z | z | Z | Z | z | Z | z | z | Z | Z | Z | z | Z | Z | Z | Z |
| CO PÍ | δ | cn z Q | ca o | <n z u | ca z o | ca z o | z | z | z | z | z | z | z | z | z | z | Z | z | CA Z u | z u |
| d PÍ | ca z u | CA Z o | z o | ca z o | cn z Q | CA Z o | z | z | z | z | z | z | z o | CA Z u | CA Z u | CA Z o | z u | CA Z υ | z υ | ΓΑ Z o |
| u z | cC in | 4· ví | t/n v> | \O ví | r~ ví | 00 r“4 ví | Os ví | o cm ví | CM ví | cm CM ví | en CM ví | 4· CM ví | V» CM ví | so CM ví | r* CM ví | oo CM ví | Os CM ví | o cn ví | cn ví | <N en •n |
0050/46142 • »
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| cn X o | CA X o | CA X o | CA 5 | G | G | G | G | G | □ | G | G | G | G | G | G | G | □ | G | ZZ u | |
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| K* CM 8 u | tž* g o | lz 04 O o | fc O | CA X 8 u | CA X 8 o | ΙΛ fc 8 u | ΙΛ fc 8 o | fc δ o | fc g | X 8 o | CA § o | ΙΛ X <M 8 o | X CM 8 o | fc O o | fc g | CA X 8 O | cn X 8 u | m X CM 8 u | V» fc 8 u | |
| cn fc | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| a | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| ^z fc | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| c | o | CM | o | CM | o | CM | o | CM | o | CM | o | CM | o | CM | o | CM | o | <s | o | CM |
| © fc | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| oo p! | cn X u | cn X u | CA X u | CA X u | X | X | X | X | X | X | X | X | X | X | X | X | cn X u | cn X Q | cn X o | cn X tj |
| czz PÍ | cn X o | CA X u | CA X o | cn X o | X | X | X | X | X | X | X u | g | CA X o | CA X υ | cn X o | cn X υ | cn X o | cn X O | cn X o | X u |
| u z | cn cn «ri | 4- cn m' | <r> cn «ri | Ό cn »n | rcn vn | oo cn <n | Os cn «ri | o «Λ | 4 iri | m «ri | cn l/í | 5 irí | •Λ iri | <D 4 <zi | Γ4 in | oo 4 «Λ | Os tT sri | O «Λ <n | «Λ «ri | <N n «r> |
0050/46142
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5.53 CHj CH3 η O η Η H ICOiPr
<Λ •ri • · • · • · • ·
183
Tabulka 6: Sloučeniny formule
| g | g | g | g | g | g | g | £ u | g | g | 1 CH3| | g | 1 CH31 | g | |
| 5 | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| > | 3 | 3 | 3 | δ | í δ | ^gi δ | VI 8 | f δ | £ B | 8 | £ δ δ | £ g δ | 3 | £ l |
| 2 fií | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| Pí | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| a | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| C3 | © | σ | <N | o | ·* | <4 | o | «4 | o | N | o | |||
| m oi | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| w o£ | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| r* Pí | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| * | 6 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 | o *d | vd | 4 | CA xd | 4· •4 >d |
·
0050/46142
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| cn X u | m X o | £ U | £ u | cn X o | cn X U | g | en 5 | en X U | £ o | cn X o | en X G> | £ o | en X G) | en X G> | £ G> | en X G) | cn X G) | |
| X | X | X | Π! | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| X | X g | VS X g g | vs X g ? u | 14 ©4 I II g> | ha fr. O z II u | |4 ! | g v X £ 8 Z δ | 8 8 G> | 8 a 8 ? u | VS X ž 8 | VS X ž 8 | X σ w 8 o | A £ 9 G> | CN £ y o | n X O o | CN υ X X o u 1 1 o o | CN 5 fí ^*CS X X o u 1 1 o o | |
| cn PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| CN —4 Pí | X | X | X | X | X | X | Ti | X | X | X | X | X | X | X | X | X | X | X |
| CN % | X | X | *T! | ,x | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| X | X | X | Ti | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| G | <N | o | CN | o | —4 | CN | o | CN | o | CN | o | CN | o | •^4 | ||||
| Os Pí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 —4 Pí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| r* 0$ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| ž | un vO | Ό *—4 O | r* —4 sO | 00 <5 | ©v •4 SO | o SO | CN v© | CN CN ní | cn n Ό | Ν’ CN VO | wn CN V© | V© CN <S | r*» CN vO | 00 CN © | Os CN V© | o cn v© | ^4 cn vO | CN cn v© |
* ·
0050/46142
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| A | £ Q | rs X u | £ u | rs X □ | δ | rs X u | rs X u | rs X u | rs X u | £ o | £ o | rs X u | £ o | £ o |
| S | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| >< | ΓΜ X υ <€ X X o u 1 1 o o o | rs rt X X o u X X X u u 1 1 o o | m Λ X X υ u X X X u o 1 1 o o υ | <n <n X X u o X X X u u 1 1 o o | rs 5 Ϊ | rs X ? | rs 1 υ | WS l | WS X f | ws X í | £ Q υ | £ y X o | δ υ | WS í X u |
| rs | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| CM | ffi | X | X | X | X | X | X | X | X | X | X | X | X | X |
| a | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| c | CM | o | CM | o | 4—4 | CM | o | CM | o | o | ||||
| Oj Ήί | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| OO eí | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| U z | m cn s© | Φ· m s© | WS m s© | V© m s© | rcn s© | 00 m v© | Os C*S S©' | o 4· SO | φ· S© | CM Φ* s© | cn Φ· s© | 4. | ΙΛ X | SO Φ; s© |
0050/46142
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| rs X o | X y | rs X o | X o | X y | X o | n X y | f*S X y | g | X y | X y | X y | X y | £ y | X y | rs X y | X y | g | rs X y | g | X y | rs X y | |
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| vs | vs | |||||||||||||||||||||
| fc | X | X | ||||||||||||||||||||
| vs | vs | vs | fc | fc | fc | |||||||||||||||||
| fc | fc | fc | X | X | X | rs X £ rs X | ||||||||||||||||
| vs I | vs X f | CM z“\ g | Λ ď fc | Xi X fc | vs I | VS X g | WS § | 8 ď % | 8 Ž fc z | 8 ď U Z | 4? | cm | 4? | X y, | g | CM cn X y, | 8 z\ g | 8 z** ď fc z | 8 z-s X | rs a | ||
| <? | l | 1 | 7 | 7 | 7 | z | rt | 2 | I | Λ | X y | u | y | |||||||||
| y | ři o | o | y | y | X o | y | y | X y | X y | X y | II y | δ | 11 y | II y | δ | y | w O | y | y | |||
| rs PÍ | X | X | a | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| CM Pí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| a | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| ~PÍ | Ti | TI | Tí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| G | CM | o | CM | © | w | CM | © | ^4 | CM | o | CM | o | CM | © | CM | o | ||||||
| Os PÍ | T* | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| oo «4 Pí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| c©á | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 14 | r* | 00 | O\ Xt s© | o vs v© | vs | CM WS | rs ws | 3 | WS vs | V© vs | r* vs | 00 vs | Os VS | s | v© | cm *© | rs sq | 3 | vs *© | £ | 3 | |
| z | >© | sO | 'O | *© | \6 | sO | SO | SO | Ό | Ό | so | S© | so | S© | s© | S© | v© | >© | *© | Ό |
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| J | £ υ | £ u | m X o | £ Q | £ o | m X u | rs X Q | e*» X Q | m z u | m X u | £ u | cn z o | £ u | m s | rs z u | Í*S z o | f*S z o | 3 | m z u | £ u | cn z o | rs X o |
| s | Ί1 | X | z | Z | z | X | X | X | z | X | X | z | z | X | z | z | z | Z | z | z | z | X |
| m X £ £ o | o | o | O | o II u | o ύ | O II O | es z 8 z o | cn § δ | cn X 8 X u | WS £ 8 X o | WS * 8 z o | WS * 8 X u | £ o z o | £ • *4 O z □ | £ δ z u | £ u | £ 8 % υ | £ υ | WS ¥ O | «η Ϊ | WS X g ? o | |
| Í*1 04 | X | X | z | z | z | X | X | z | Z | X | X | z | X | X | z | z | z | z | z | z | z | X |
| CH | X | X | z | z | z | X | X | z | z | X | X | z | z | z | z | z | z | z | z | z | z | X |
| a | X | X | z | z | z | z | X | z | X | X | X | z | X | z | z | z | z | z | z | z | z | X |
| * | X | X | z | z | z | z | X | z | X | X | X | z | X | z | z | z | z | z | z | z | z | X |
| G | CM | o | CM | o | •R | CM | o | CM | o | RR | CM | o | rR | CM | o | ^4 | <M | o | rR | CM | ||
| Ο» PÍ | m | X | z | Z | z | X | X | z | X | X | X | X | z | X | Z | z | z | Z | z | Z | Z | X |
| 00 •R X | X | X | z | z | X | X | X | z | X | X | X | z | X | z | z | z | z | z | z | Z | z | X |
| r* PÍ | X | X | z | z | £ u | m X o | m X u | <*» z o | cn X u | m X u | tn z u | cn X o | rs z o | 3 | cn z υ | rs z u | z υ | £ o | en z u | £ Q | <*> X υ | £ |
| ž | qs SO SO | o Γ*ζ s© | ^R e*· s© | CM t-ζ SO | c*s r* só | xř r* S© | Ά r* S© | S© r* © | rrS© | 00 r* s© | σ\ r* \© | o oo SO | 00 s© | CM 00 s© | m 00 so | 3 SO | <A 00 so | SO 00 s© | r* 00 S© | 00 00 s© | Os 00 SO | s SO |
• · • ·
0050/46142
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| £ υ | £ u | en X o | CA X o | CA X u | £ u | £ Q | £ o | £ u | £ u | CA X u | £ υ | CA X u | CA X u | CA X u | |
| 3 | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| u & f | ! | í | 8 v X o £ ! | 8 Ϊ £ 8 5 u | i g l | £ 8 l | X ď X u | US X ď £ i δ | £ 52 Q | Λ CA X 52 u | Λ! £ g | CM X <r X X U O 1 1 o o | CN 5 <4 ''“CN X X u u 1 1 o o | CN X u <r X X υ u 1 1 o o u | |
| CA oí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| CM v·* at | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| cm ní | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| a | o | A | CN | o | CN | o | CN | o | CN | © | A | CN | |||
| Os A Pí | ΓΤΪ | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| OO PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| r* Pí | £ Q | cn X υ | ca X u | CA u | CA X u | s | £ o | CA X <) | £ o | CA υ | £ υ | CA X u | CA X u | CA g | CA X o |
| ž | Os x© | CN Os χ© | ca Os x©‘ | 3 © | VA Os X© | Ό Os *© | rOs χ© | 00 Os x© | Os Os x© | 8 ©’ | © A © | CN O A X© | CA O X© | 3 © | VA O *© |
• · · • ·
0050/46142 • ·
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| m X y | en X U | m X υ | m X y | £ o | C*Y X o | m X y | CY X y | r*Y X y | CY X y | ΠΥ X y | X y | en X y | £ y | f*Y X y | í*l X y | ||||
| s | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | ||||
| <n | (H | ť*> | n | <n | f*) | ||||||||||||||
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0050/46142
| cn X o | £ u | £ Q | cn X υ | cn X u | cn X u | cn X υ | cn δ | cn δ | cn X y | £ υ | cn X o | cn X o | cn X o | cn X o | cn X u | cn X u | £ U | cn 5 | cn X υ | cn X y | cn X u | |
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| G | y | G | G | G | G | G | G | G | G | G | G | »H U | G | G | G | G | G | y | G | G | G | |
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| »1 | G | G | G | G | G | G | G | G | G | G | G |
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0050/46142 • · • ·
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| Ok «4 tÁ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
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| 1 | G | G | □ | G | G | G | G | G | •M4 υ | □ | G | G | G | G | —«4 G> | G | G | G | G | G | G | «Μ4 o |
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| z—k X fc | § fc | ra | ra | ra | X fc z | g z | X fc | £ fc | £ fc | £ o | I | 1 JP | 1 fp | £ o | rs X y | |||||||
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| T | CH- | z | z | % o | X | fcX | J1 | i | u | o | o | δ | II | II | X | X | ||||||
| CH | δ | δ | II G> | II u | δ | u | u | O | Q | Q | O | o | o | u | δ | u | υ | |||||
| rs | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| CM —4 CÁ | X | X | X | X | Tf | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| CM fc | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| fc | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| cs | CN | o | ——4 | CN | o | CN | o | CN | o | CN | o | ·—4 | CN | o | CN | o | ||||||
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| Nr. | 6.272 | j 6.273 | CN \o | 6.275 | 6.276 | 6.277 I | 6.278 | 6.279 | 6.280 | 6.281 | 6.282 | 16.283 | 6.284 ’ | 6.285 | 6.286 | 6.287 | 6.288 | 6.289 | 06Γ9 | ^4 0s \O | CN Ok <Ί kO | 6.293 |
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| A | G | G | G | G | G | G | G | 0 | G | G | G | G | G | G | G | G | G | ^4 u | G | G | G | G |
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| cn X 8 X o | WS t X o | WS £ 8 X o | WS t X o | & ·—« o X υ | £ δ δ | £ ·»· o X o | υ | £ 8 z II u | £ 8 u | WS z δ | WS X δ Ϊ | vs X g Ϊ | u« CL, δ o | Pw o l | l-r o g | 8 8 g | g g 8 z δ | g l 8 | WS X á § | ws X σ X 8 g | WS X ž 8 l | |
| cn ·—« | X | X | T | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| CM ož | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| CM ck | X | X | X | X | T | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| oá | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| cs | CM | o | CM | o | CM | o | CM | o | CM | o | CM | o | CM | o | CM | |||||||
| Ol *M Qá | X | ΓΓ | ΓΓΪ | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 aí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| r* | cn | cn X o | r» X o | £ u | m X u | cn δ | cn u | tn X u | cn X u | cn X υ | cn X u | cn X t> | cn X υ | cn X o | cn X o | cn X o | <n X o | cn X Q | cn X o | cn X υ | cn X Q | cn X o |
| Nr. | 3 CM s© | WS OS CM *© | SO Os CM s© | r* Os CM s© | 00 Os CM s© | Os Os CM v© | 8 cn s©* | o cn S© | CM O m S© | m o cn Ό’ | 3 cn s©‘ | W) o cn s© | SO O m so* | P— o cn s©' | 00 o cn s©* | os o en sO* | o ^4 cn s©‘ | cn s© | CM w4 cn s© | m cn s© | Φ cn s© | WS ••4 cn sO |
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| G | G | G | G | G | G | G | G | G | G | G | |
| X | X | X | X | X | X | X | X | X | X | X | |
| CM *rs X 9 G> | .« cn X o o | CM /*** cn X 9 o | ri X o c< X X u o 1 1 o o | CN 5 << X X u u 1 1 o o o | CÍ X o X X υ ό 1 1 o o o | cn m X X u u X X X o o 1 1 o o | cn cn X X O u X X X o u 1 1 o o u | m cn X X O u X X X u u 1 1 o o v. s u | X 9 l | ||
| cn X | X | X | X | X | *C | X | X | X | X | X | X |
| CM —M X | X | X | X | X | X | X | X | X | X | X | X |
| X | X | X | X | X | X | X | X | X | X | X | |
| Pí | X | X | X | X | X | X | X | X | X | X | X |
| G | CN | o | •4 | CN | o | —4 | <s | o | |||
| Ch Pá | X | X | X | X | X | X | X | X | X | X | X |
| 00 PÍ | X | X | X | š | X | X | X | X | X | X | X |
| £1* | en X υ | en X G) | en X G> | cn X υ | cn X G) | m X o | cn X G) | en 5 | cn X o | X G) | en X G) |
| á | Ό cn © | r* cn v© | 00 cn <© | ©v m v© | O CN m v© | CN cn V© | CN CN cn \O | cn CN cn v© | m so | un CN cn v© | Ό <S en *O |
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| G | G | G | G | G | G | G | G | G | G | G | G | G | 0 | G | 44 u | G | G | 44 u | G | G | G | |
| 2 | z | X | z | Z | Z | z | z | z | z | z | z | z | z | z | z | z | z | X | X | X | X | X |
| v> | v> | |||||||||||||||||||||
| z | X | X | ||||||||||||||||||||
| CM | CM | CM | ||||||||||||||||||||
| Q | Q | Q | ||||||||||||||||||||
| £ | £ | £ | z CM | X CM | X . r1 | PA Z y | ď | CM ď | z g* | 1 | j | O £ | O £ | O £ | 4? | |||||||
| £ | § | •n z £ | g | g | g | g | g | g | g, ? | y | Q | y, 5 | u w | y | 1 | |||||||
| £ u | % u | o | $ u | 8 u | z u | i u | x u | ύ υ | x u | o | ώ Q | z o | Z o | z o | o | z o | o | X u | δ | δ | II o | |
| η oí | X | X | z | X | z | z | z | z | z | z | z | X | z | X | z | z | X | X | X | X | X | X |
| CM | X | z | z | z | z | z | z | z | z | z | z | Z | z | X | X | z | X | X | X | X | X | X |
| Sn< | X | X | z | z | z | z | z | z | z | z | z | z | z | X | X | z | X | X | X | X | X | X |
| 4 θ' | X | X | z | z | z | z | z | z | z | z | z | z | z | X | X | X | X | X | X | X | X | X |
| c | d | o | d | o | d | o | d | o | d | o | d | © | d | © | «44 | d | ||||||
| 01 PÍ | X | X | z | z | z | z | z | z | z | z | z | z | z | X | X | z | z | X | X | X | X | X |
| 00 £ | X | X | z | z | z | z | z | z | z | z | z | z | z | X | X | z | X | X | X | X | X | X |
| r* Pá | pa X υ | pa z u | PA Z υ | řA Z u | CA Z u | CA Z o | m Z u | CA Z u | cn z υ | CA Z u | PA Z o | g | £ o | £ u | PA Z o | £ u | £ o | PA X o | CA X o | £ o | £ u | PA X u |
| ž | 6.327 | 6.328 | 6.329 | 6.330 | m A Ό | 6.332 | 6.333 | 6.334 | 6.335 | 6.336 | 6.337 | 6.338 | 6.339 1 | 6.340 | 6.341 | 6.342 | I 6.343 | 16.344 | I 6.345 | 6.346 | 6.347 | 6.348 |
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| δ | Q | δ | δ | δ | δ | δ | δ | δ | δ | δ | δ | δ | δ | δ | δ | δ | δ | δ | δ | δ | δ | |
| s | X | X | Ti | X | X | X | X | X | X | X | X | X | z | X | X | X | X | X | X | X | X | X |
| «Λ | m | |||||||||||||||||||||
| X | X | X | ||||||||||||||||||||
| Ό £ | y | |||||||||||||||||||||
| CM /*> | ►C Q | X o | cn | cn | ||||||||||||||||||
| u | ||||||||||||||||||||||
| CM z·** | CM | o | O | o | X | X | ||||||||||||||||
| δ | £ y. | £ o, | £ o | g | £ o | i | 1 | I | cn 3 | £ | cn X | VJ X ,7 | «Α fc | V) fc | fc | |||||||
| 5 | í | ? | cn X υ | £ o | £ ω | o II u | o || | o | 8 X | 8 X | 8 X | 0 X | 8 X | 8 X | 0 X | |||||||
| >* | δ | II u | δ | υ | u | o | u | u | u | o | o | o | o | δ | Q | Q | u | u | U | 0 | 0 | |
| cn fc | z | X | Tí | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| <M ot | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| TI | X | X | T | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| z fc | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| G | o | ^z | CM | o | CM | o | CM | o | fM | CM | o | CM | o | F4 | CM | 0 | zZ | CM | 0 | |||
| fc | X | X | z | Z | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| cn n | cn | cn X | cn X | cn X | £ | £ | £ | £ | £ | |||||||||||||
| z dá | T | X | TI | X | X | X | X | X | X | X | X | X | u | δ | υ | u | u | u | u | u | u | u |
| r* fc | cn X o | cn X u | cn z o | cn X o | cn X o | £ u | cn X o | X o | cn X o | cn X o | cn X o | cn X o | cn z u | cn X u | m X Q | cn X O | cn X o | cn X u | £ o | cn 8 | £ 0 | cn X 0 |
| á | © cn x© | 6.350 | 6.351 I | 6.352 | 6.353 | 6.354 | 6.355 | 6.356 | 16.357 I | 6.358 | 6.359 | 6.360 | 16.361 I | S cn V© | 6.363 | 6.364 | 6.365 | 6.366 | 6.367 | 16.368 | 6.369 | 6.370 |
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| G | G | G | G | G | G | G | G | G | G | u | G | G | G | G | G | G | G | o | G | G | |
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | |
| >* | £ O X o | £ • A O X o | £ 8 5 O | g l | £ 8 Ϊ | US X f | EC* g z II u | US X g z δ | U a. O Q | u ©4 o Ϊ | £ o l | G X 8 | £ 8 Z δ | 8 Ϊ 2 8 l | X ď u | US X σ £ 8 l | US X σ £ 8 z δ | Λί £ 52 υ | CM z-s cn | CN cn X u, o | CN u (4 <s X X u O 1 1 o o >s o |
| cn PÍ | X | X | ΓΓ! | X | X | X | X | X | X | X | X | X | X | X | X | X | X | χ | X | X | X |
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | χ | X | X | X | |
| CN | X | X | X | X | a | X | X | X | X | X | X | X | X | X | X | X | X | χ | X | X | X |
| X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | χ | X | X | X | |
| a | CN | o | CN | o | CN | o | *A | CN | o | w*4 | CN | o | CN | o | CN | O | |||||
| Os PŽ | X | X | •7* | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 •M PÍ | CA X o | CA X □ | CA X ω | £ o | cn X u | cn X u | £ u | cn X u | CA X o | cn X o | cn X o | cn X o | CA X Q | £ u | £ u | cn X u | cn X u | £ o | £ o | cn X υ | cn X υ |
| r- Pí | CA X o | CA X <0 | CA X o | CA X o | cn X o | cn X u | £ υ | CA X o | cn X u | £ u | cn X υ | CA X Q | CA X o | m o | cn X u | CA X o | £ u | cn X u | £ o | cn X u | cn X u |
| Nr. | ΓΓη X© | CN ΓΓη X© | cn r* cn X© | 3 cn X©’ | VA ΓΓη x© | X© r* cn X© | rr* cn x© | 00 ΓΓη x© | Os ΓΓη x© | O 00 cn x© | 00 m *© | CN 00 cn x© | cn 00 cn x©' | 3 cn x© | vs 00 cn X© | X© 00 cn X© | ΓΟΟ cn χ© | 00 00 cn X© | O 00 cn x© | o Oi cn xo | A Os cn xo |
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0050/46142
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| hJ | G | G | G | G | G | G | G | G | u | G | G | G |
| S | X | X | X | X | X | X | X | X | X | X | X | X |
| >- | CM X u c< '-cm δ δ 1 1 O o '-θ-' | CS o <f '—CM X X u o 1 1 o o | m m X X u o X X X o u 1 1 o o | cn <n X X o u X δ δ 1 1 o o X. s O | <n cn X x O O X X X o o 1 1 o o o | cn l | cn i | cn 1 | m 5 l | £ í | «Λ X i | £ υ X o |
| cn Pá | X | X | X | X | X | X | X | X | X | X | X | X |
| li* | X | X | X | X | X | X | X | X | X | X | X | X |
| CS ‘Sí | X | X | X | X | X | X | X | X | X | X | X | X |
| X | X | X | X | X | X | X | X | X | X | X | X | |
| a | rs | o | rs | o | rs | o | rs | o | ||||
| OS | X | X | X | X | X | X | X | X | X | X | X | X |
| 00 aí | X o | cn X o | cn X υ | cn X Q | £ u | cn X υ | cn g | £ u | cn δ | g | g | £ υ |
| r- | cn X u | cn X u | cn X Q | cn X o | g | £ o | £ υ | cn X o | cn δ | cn X ω | £ o | £ u |
| Nr. | es Os cn x© | cn Os cn x© | 3 n <5 | V) Os cn x© | X© Os cn x© | rOs cn x© | 00 Os cn so | Os Os cn x© | s Φ X© | i. | es 8 | m 8 o |
• ·
0050/46142
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| u | G | G | G | G | o | G | G | WR O | G | G | G | G | G | G | •R CJ | R4 CJ | G | G | G | G | G | G |
| S | X | X | X | X | X | X | X | X | X | X | z | z | z | z | z | z | z | z | z | z | z | z |
| 1 | £ o | vs X ď | vs X f | í | λ £ y z | £ y z | CM £ y z | VS 1 | VS X g | WS z g 1 | vs £ y | vs 8 £ y | vs X CH 8 £ CJ | rs í | λ í i | CN í | CN z*S rs z y | % y, z 8 £ y | Ví z s 8 £ □ | |||
| 1 o | íĚ O | i o | Z o | δ | z o | X o | X cj | X o | i CJ | CJ | i CJ | z CJ | i CJ | δ | Ir o | δ | S | δ | δ | o | z u | |
| rs PÍ | X | *TÍ | X | X | X | z | X | X | X | X | z | z | z | X | z | z | z | Z | z | z | z | z |
| 31* | X | X | X | X | X | z | X | X | X | X | z | z | z | X | z | z | z | z | z | z | X | z |
| CN Pí | X | X | X | X | X | z | X | X | X | X | z | z | z | X | z | z | z | z | z | z | X | z |
| X | X | X | X | X | z | X | X | X | X | z | z | z | X | z | z | z | z | z | z | X | z | |
| a | CN | o | CN | o | CN | o | CN | o | CN | o | CN | o | wR | CN | o | |||||||
| Os PÍ | X | X | X | X | X | z | X | X | X | X | z | z | z | X | z | z | z | Z | Z | z | X | z |
| 00 «R Pí | c*í X u | m X cj | rs X o | £ o | rs X u | rs X u | £ <j | £ u | rs X o | £ CJ | rs z u | z u | f*S X u | rs z (J | £ u | £ u | rs X u | £ CJ | rs z CJ | rs z u | rs X u | rs z u |
| r* Pí | X <j | m X o | cn X o | rs X cj | e*í X cj | «η X u | m X u | rs X o | cn X CJ | rs X CJ | c*> z o | rs z o | rs X <0 | rs z CJ | rs z o | rs z o | rs z CJ | cn Z CJ | rs z CJ | £ o | rs X u | cn z u |
| Nr. | 1 Ό | <A O Tf SO | Ό o 4- Ό | r** o X s© | 00 8 SO | Ch o 4- Ό | o 4 sO | Ν' SO | CN n O | m N; SO | 2 n SO | IA N. SO | S© 4; Ό | r* N so | 00 4 Ό | Os SO | o CN SO | (4 4; o | CN CN N, sO | cn CM N so | 3 n· so | IA CN N* SO |
0050/46142
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| G | G | G | G | G | G | G | |
| s | X | X | X | X | X | X | X |
| WS X g 8 £ Ϊ u | £ £ m X o s—z Q | £ X y. υ | cn X £ £ y Q | o | o | o | |
| cn | X | X | X | X | X | X | X |
| R*2 | X | X | X | X | X | X | X |
| a | X | X | X | X | X | X | X |
| a | X | X | X | X | X | X | X |
| β | CN | o | CN | o | CN | ||
| Ch pá | X | X | X | X | X | X | X |
| 00 Qá | cn X o | cn X u | £ o | cn X u | cn X o | en X o | en X u |
| PÍ | cn X o | rs X u | m X u | rs X o | cn X u | X o | rs X o |
| Nr. | Ό CN N v© | r· CN N s© | 00 CN N* Ό | Os CN N s© | o m N s© | m N s© | CN m Ν’ O |
···· ··· ···· • · · ···· · * · ·
207 • · · · · · · · · ··· ···· ·· ·· ·· ··
Tabulka 7: Sloučeniny formule
Zbytky R7 a R23 vytvářejí vazbu.
| Ή· | ÍP~ | R19 | n | Y | L | M | |
| 7.1 | H | H | H | 2 | coch3 | H | H |
| 72 | H | H | H | 2 | COC2H5 - | H | H |
| 73 | ch3 | H | H | 2 | coch3 | H | H |
| 7.4 | ch3 | H | H | 2 | COC2H5 | H | H |
| 73 | ch3 | ch3 | H | 2 | coch3 | H | H |
| 7.6 | ch3 | ch3 | H | 2 | COC2H5 | H | H |
| 7.7 | H | H | H | 2 | coch3 | H | ch3 |
| 7.8 | H | H | H | 2 | COC2H5 | H | ch3 |
| 7.9 | ch3 | H | H | 2 | coch3 | H | ch3 |
| 7.10 | ch3 | H | H | 2 | COC2H5 | H | ch3 |
| 7.11 | ch3 | ch3 | H | 2 | coch3 | H | ch3 |
| 7.12 | ch3 | ch3 | H | 2 | COC2H5 | H | ch3 |
| 7.13 | H | H | H | 2 | coch3 | H | a i |
| 7.14 | H | H | H | 2 | COC2H5 | H | a · |
| 7.15 | ch3 | H | H | 2 | coch3 | H | a , |
| 7.16 | ch3 | H | H | 2 | COC2H5 | H | a |
| 7.17 | ch3 | ch3 | H | 2 | coch3 | H | a |
| 7.18 | ch3 | ch3 | H | 2 | COC2H5 | H | a |
| 7.19 | H | H | H | 2 | coch3 | H - | ŇČh | |
| 720 | H | H | H | 2 | COC2H5 | H | NO2 |
| 721 | ch3 | H | H | 2 | coch3 | H | NO2 |
| 722 | ch3 | H | H | 2 | COC2H5 | H | N02 |
| 723 | ch3 | ch3 | H | 2 | coch3 | H | NO2 |
| 724 | ch3 | ch3 | H | 2 | COC2H5 | H | NO2 |
| 725 | H | H | H | 2 | coch3 | H | SO2CH3 |
| 726 | H | H | H | 2 | COC2H5 | H | SO2CH3 |
| 727 | ch3 | H | H | 2 | coch3 | H | SO2CH3 |
| 728 | ch3 | H | H | 2 | COQHí | H | SO2CH3 |
| 729 | ch3 | ch3 | H | 2 | coch3 | H | SO2CH3 |
| 730 | ch3 | ch3 | H | 2 | cocyij | H | SO2CH3 |
| 731 | H | H | H | 2 | COCH3 | ch3 | ch3 |
- 208 -
Tabulka 8: Sloučeniny formule
R19
| Nt. | R18 | R1* | n | Y | M | L | |
| 8.1 | H | H | H | 2 | coch3 | H | ch3 |
| 82 | H | H | H | 2 | COC2H5 | H | ch3 |
| 83 | ch3 | H | H | 2 | coch3 | H | ch3 |
| 8.4 | ch3 | H | H | 2 | COC2H5 | H | ch3 |
| 83 | ch3 | ch3 | H | 2 | COCH3 | H | ch3 |
| 8.6 | ch3 | ch3 | H | 2 | COC2H5 | H | CHa |
| 8.7 | H | H | H | 2 | coch3 | H | Cl |
| 8.8 | H | H | H | 2 | COC2H5 | H | a |
| 8.9 | ch3 | H | H | 2 | coch3 | H | Cl |
| 8.10 | ch3 | H | H | 2 | coc2h5 | H | a |
| 8.11 | ch3 | ch3 | H | 2 | coch3 | H | a |
| 8.12 | ch3 | ch3 | H | 2 | COC2H5 | H | a |
| ,8.13 | H | H | H | 2 | COCH3 | H | NO2 |
| 8.14 | H | H | H | 2 | COC2H5 | H | NO2 |
| ; 8.15 | ch3 | H | H | 2 | COCS3 | H | NO2 |
| 8.16 | ch3 | H | H | 2 | COC2H5 | H | NO2 |
| 8.17 | ch3 | ch3 | H | 2 | COCH3 | H | NO2 |
| 8.18 | ch3 | ch3 | H | 2 | COC2H5 | H | NO2 |
| 8.19 | H | H | H | 2 | COCH3 | H | SO2CH3 |
| 820 | H | H | H | 2 | COC2H5 | H | SO2CH3 |
| 821 | ch3 | H | H | 2 | COCH3 | H | SO2CH3 |
| i 822 | ch3 | H | H | 2 | COC2H5 | H | SO2CH3 |
| 823 | ch3 | ch3 | H | 2 | COCH3 | H | SO2CH3 |
| 824 | CHa | ch3 | H | 2 | COC2H5 | H | SO2CH3 |
| 825 | H | H . | H | 2 | COČHa | CH3 | CH3 |
| 826 | H | H | H | 2 | COCiHs | ch3 | ch3 |
| 827 | ch3 | H | H | 2 | COCH3 | ch3 | CHa |
| 828 | ch3 | H | H | 2 | COC2H5 | ch3 | CH3 |
| 829 | ch3 | <ZH3 | H | 2 | coch3 | ch3 | ch3 |
| 830 | ch3 | ch3 | H | 2 | COC2H5 | ch3 | ch3 |
| 831 | H | H | H | 2 | COCH3 | a | a |
| 832 | H | H | H | 2 | COC2H5 | a | a |
209
Tabulka 9: Sloučeniny formule
| Nr. | R15 | R16 | rI5- | n | X | Y | M | L |
| 9.1 | ch3 | ch3 | H | 2 | ch2 | c-o | H | CH3 |
| 92 | ch3 | ch3 | H | 0 | (CHzh | c-o | H | ch3 |
| 93 | ch3 | ch3 | H | 2 | (CHah | c-o | H | ch3 |
| 9.4 | ch3 | ch3 | H | 2 | ch2 | choch3 | H | ch3 |
| 9.5 | ch3 | ch3 | H | 0 | (CH2)2 | choch3 | H | ch3 |
| 9.6 | ch3 | ch3 | H | 2 | (CHzh | choch3 | H | ch3 |
| 9.7 | ch3 | ch3 | H | 2 | ch2 | CHOC2H5 | H | ch3 1 |
| 9.8 | ch3 | ch3 | H | 0 | (CHjh | CHOC2H5 | H | ch3 |
| 9.9 | ch3 | ch3 | H | 2 | (CHzh | CHOQHs | H | ch3 |
| 9.10 | ch3 | ch3 | H | 2 | ch2 | CHOiPr | H | ch3 |
| 9.11 | ch3 | ch3 | H | 0 | (CHíh | CHOiPr | H | ch3 |
| 9.12 | ch3 | ch3 | H | 2 | (012)2 | CHOiPr | H | ch3 |
| 9.13 | ch3 | ch3 | H | 2 | ch2 | c-noch3 | H | ch3 |
| 9.14 | ch3 | ch3 | H | 2 | (CH2)2 | c-noch3 | H | ch3 |
| 9.15 | ch3 | ch3 | H | 0 | (CHzh | c-noch3 | H | ch3 |
| 9.16 | ch3 | ch3 | H | 2 | ch2 | C-NOC2H5 | H | ch3 |
| 9.17 | ch3 | ch3 | H | 2 | (CHíh | ONOQHj | H | ch3 |
| 9.18 | ch3 | ch3 | H | 0 | (CHzh | ONOQHj | H | ch3 |
| 9.19 | ch3 | ch3 | H | 2 | ch2 | C-NOiPr | H | ch3 |
| 9.20 | ch3 | ch3 | H | 2 | (012)2 | C-NOiPr | H | ch3 |
| 9-21 | ch3 | ch3 | H | 0 | (Olih | C-NOiPr | H | ch3 |
| j 9.22 | ch3 | ch3 | H | 2 | ch2 | C-NOC^CH-CHa | H | ch3 ’ |
| 923 | ch3 | ch3 | H | 2 | (OÍ2)2 | O-NOCQzCH-CHa | H | ch3 |
| 924 | ch3 | ch3 | H | 0 | (012)2 | O-NOC^CH-CHa | H | ch3 |
| 925 | ch3 | ch3 | H | 2 | CH2 | C-NOCHzCsHí | H | ch3 i |
| 926 | ch3 | ch3 | H | 2 | mh | ONOCSAHj | H | ch3 i |
| 927 | ch3 | ch3 | H | 0 | (OÍ2)2 | O-NOCftCeHs | H | ch3 ! |
| 928 | ch3 | ch3 | H | 2 | ch2 | C(CH3h | H | CH3 |
| 929 | ch3 | ch3 | H | 2 | (CH2)2 | C(CH3)2 | H | ch3 |
| 930 | ch3 | ch3 | H | (CH2h | C(CH3)2 | H | ch3 |
0050/46142 • · · · ♦ ···· • · ···· · ·· • · · · * · · ··»» · • ···· · · · • · · · · · · · · · · · ·
210
| Nr. | R15 | R16 | R19 | n | X | Y | M | L |
| 9.31 5 | ch3 | ch3 | H | 2 | ch2 | / 0--CH^ c ch2 X0--CH2 | H | ch3 |
| ' 9.32 | ch3 | ch3 | H | 2 | (CH2)2 | /0— CH^ C ch2 ^0—ch2 | H | ch3 |
| 9.33 ) | ch3 | ch3 | H | 0 | (CH2)2 | /0--CH^ c ch2 ^0—ch2 | H | ch3 |
| 9.34 | ch3 | ch3 | H | 2 | ch2 | c/0-CH. CH3 'ο-οηΓ“3 | H | ch3 |
| 9.35 | ch3 | ch3 | H | 2 | (ch2)2 | /°-CVcH3 'o-chA0113 | H | ch3 |
| 9.36 | ch3 | ch3 | H | 0 | (CH2)2 | c/°-C^CH3 'o-chA®3 | H | ch3 |
| 9.37 | ch3 | ch3 | H | 2 | ch2 | ch-nhch3 | H | ch3 |
| 9.38 | ch3 | ch3 | H | 2 | (CH2)2 | ch-nhch3 | H | ch3 |
| 9.39 | ch3 | ch3 | H | 0 | (CH2)2 | ch-uhch3 | H | ch3 |
| 9.40 | ch3 | ch3 | H | 2 | ch2 | CH-NHC2H5 | H | CH3 1 |
| 9.41 | ch3 | ch3 | H | 2 | (CH2)2 | CIH4HC2H5 | H | ch3 1 |
| 9.42 | ch3 | ch3 | H | (CHzh | ch-nhc2h5 | H | CH3 1 | |
| 9.43 | ch3 | ch3 | H | 2 | ch2 | CH-N(CH3)2 | H | Oi3 f |
| 9.44 | ch3 | ch3 | H | 2 | (CHzh | CH-N(CH3)2 | H | CH3 1 |
| 9.45 | ch3 | ch3 | H | (CH2)2 | CH-N(CH3)2 | H | ch3 i | |
| 9.46 | ch3 | ch3 | H | 2 | ch2 | CH-NHOC2H5 | H | CH3 1 |
| 9.47 | ch3 | ch3 | H | 2 | (CH2)2 | CH44HOC2H5 | H | CH3 1 |
| 9.48 | ch3 | ch3 | H | (CH2)2 | CH-NHOC2H5 | H | CH3 1 | |
| 9.49 | ch3 | ch3 | H | 2 | ch2 | CH-N(CH3)OC2H5 | H | CH3 1 |
| 9.50 | ch3 | ch3 | 2 | (CH2)2 | CH-N(CH3)OC2H5 | H | ch3 i | |
| 9.51 | ch3 | ch3 | (CH2)2 | CH-N(CH3)OC2H5 | H | ch3 1 | ||
| 9.52 | ch3 | ch3 | H | 2 | ch2 | c=n-nh2 | H | ch3 I |
| 9.53 | ch3 | ch3 | H | 2 | (012)2 | ON-NH2 | H | ch3 I |
| 9.54 | ch3 | ch3 | 0 | (012)2 | C=N-NH2 | H | 013 1 | |
| 9.55 | ch3 | ch3 | 2 | ch2 | C=N-N(CH3)2 | H | ch3 i | |
| 9.56 | ch3 | ch3 | 2 | (CH2)2 | C=N-N(CH3)2 | H | CH3 1 | |
| 9.57 | ch3 | ch3 | (Ol2)2 | C=N-N(CH3)2 | H | ch3 1 | ||
| 9.58 | ch3 | ZH3 | l | ch2 | 3W4(CH3)OCH2Q$H5 | H | ch3 1 | |
| 9.59 | ch3 | ch3 | < | l | :ch2)2 | CH-N(CH3)OCH2QíH5 | H | ch3 I |
| 9.60 | zh3 | 2H3 | .Ol2)2 | ^-N(CH3)OCH2C6H5 | El | ch3 1 |
0050/46142 • 9 • ·
211 i
| Nr. | R15 | rí6 | R19 | n | X | Y | M | L |
| 9.61 | ch3 | ch3 | H | 2 | ch2 | C(CH3)-OCH3 | H | ch3 |
| 9.62 | ch3 | ch3 | H | 2 | (CH2)2 | C(CH3)~OCH3 | H | ch3 |
| 9.63 | ch3 | ch3 | H | 0 | (ch2)2 | C(CH3)-OCH3 | H | ch3 |
| 9.64 | ch3 | ch3 | H | 2 | ch2 | 0 | H | ch3 |
| 9.65 | ch3 | ch3 | H | 2 | (CH2)2 | 0 | H | ch3 |
| 9.66 | ch3 | ch3 | H | 0 | (CHzh | 0 | H | ch3 |
| 9.67 | ch3 | ch3 | Br | 2 | ch2 | choch3 | H | ch3 |
| 9.68 | ch3 | ch3 | Br | 2 | (CH2)2 | choch3 | H | ch3 |
| 9.69 | ch3 | ch3 | Br | 0 | (CH2)2 | choch3 | H | ch3 |
| 9.70 | ch3 | ch3 | Br | 2 | ch2 | choc2h5 | H | ch3 |
| 9.71 | ch3 | ch3 | Br | 2 | (CH2)2 | choc2h5 | H | ch3 |
| 9.72 | ch3 | ch3 | Br | 0 | (CH2h | choc2h5 | H | ch3 |
| 9.73 | ch3 | ch3 | Br | 2 | ch2 | CHOiPr | H | ch3 |
| 9.74 | ch3 | ch3 | Brr | 2 | (CH2)2 | CHOiPr | H | ch3 |
| 9.75 | ch3 | ch3 | Br | 0 | (CH2)2 | CHOiPr | H | ch3 |
| 9.76 | ch3 | ch3 | a | 2 | ch2 | choch3 | H | ch3 |
| 9.77 | ch3 | ch3 | a | 2 | (CH2)2 | choch3 | H | ch3 |
| 9.78 | ch3 | ch3 | Cl | 0 | (CH2)2 | choch3 | H | ch3 |
| 9.79 | ch3 | ch3 | a | 2 | ch2 | CHOC2H5 | H | ch3 |
| 9.80 | ch3 | ch3 | a | 2 | (CH2h | CHOC2H5 | H | ch3 |
| 9.81 | ch3 | ch3 | a | 0 | (CHzh | choc2h5 | H | ch3 |
| 9.82 | ch3 | ch3 | Cl | 2 | ch2 | CHOiPr | H | ch3 |
| 9.83 | ch3 | ch3 | Cl | 2 | (CHzh | CHOiPr | H | ch3 |
| 9.84 | ch3 | ch3 | Cl | 0 | (CH2h | CHOiPr | H | ch3 |
- 212 Tabulka 10: Sloučeniny formule
| 'Nr. | R17 | rTF“ | rU | n | Rii | Ri* | Y | L | M |
| 10.1 | H | H | H | 0 | H | H | 0=0 | H | ch3 |
| 102 | ch3 | H | H | 0 | H | H | OO | H | ch3 |
| 103 | ch3 | ch3 | H | 0 | H | H | oo | H | ch3 |
| 10.4 | H | H | H | 2 | H | H | oo | H | ch3 |
| 103 | ch3 | H | H | 2 | H | H | oo | H | ch3 |
| 10.6 | ch3 | ch3 | H | 2 | H | H | oo | H | ch3 |
| 10.7 | H | H | H | 0 | H | H | oo | H | a |
| 10.8 | ch3 | H | H | 0 | H | H | oo | H | a |
| 10.9 | ch3 | ch3 | H | 0 | H | H | oo | H | a |
| j 10.10 | H | H | H | 2 | H | H | oo | H | a |
| 10.11 | ch3 | H | H | 2 | H | H | oo | H | a |
| 10.12 | ch3 | ch3 | H | 2 | H | H | 0=0 | H | a |
| 10.13 | H | H | H | 0 | H | H | choch3 | H | ch3 |
| 10.14 | ch3 | H | H | 0 | H | H | choch3 | H | ch3 |
| 10.15 | ch3 | ch3 | H | 0 | H | H | choch3 | H | ch3 |
| 10.16 | H | H | H | 2 | H | H | choch3 | H | ch3 ΐ |
| 10.17 | ch3 | H | H | 2 | H | H | choch3 | H | ch3 i |
| 10.18 | ch3 | ch3 | H | 2 | H | H | choch3 | H | ch3 ; |
| 10.19 | H | H | H | 0 | H | H | choch3 | H | a 1 |
| 1020 | ch3 | H | H | 0 | H | H | choch3 | H | a |
| 1021 | ch3 | ch3 | H | 0 | H | H | choch3 | H | Cl |
| 1022 | H | H | H | 2 | H | H | CHOCH3 | H | a |
| 1023 | ch3 | H | H | 2 | H | H | CHOCH3 | H | a |
| 1024 | ch3 | ch3 | H | 2 | H | H | choch3 | H | a |
| 1025 | H | H | H | 0 | H | ch3 | 0=0 | H | ch3 |
| 1026 | ch3 | H | H | 0 | H | ch3 | 00 | H | ch3 |
| 1027 | ch3 | ch3 | H | H | ch3 | 00 | H | CH3 ; | |
| 1028 | H | H | H | 2 | H | ch3 | 00 | H | ch3 ' |
| 1029 | ch3 | H | H | 2 | H | ch3 | 00 | H | ch3 |
| 1030 | ch3 | ch3 | H | 2 | H | ch3 | 0=0 | H | ch3 |
| 1031 | H | H | H | H | ch3 | 00 | H | a | |
| 1032 | ch3 | H | H | H | ch3 | OQ | H | a |
213
Tabulka 11: Sloučeniny formule
| Nr. | ŘI7--------------- | n | X | Y | L | M |
| ,11.1 | 2-Ethylthiopropyl | 2 | ch2 | C-0 | H | CH3 |
| 113 | 2-Ethylthiopropyi | 0 | (CHzh | C-0 | H | ch3 |
| 113 | 2-Ethylthiopropyi | 2 | (CHjh | C-0 | H | ch3 |
| ilM | 2-Ethylthiopropyl | 2 | ch2 | CHOCH3 | H | ch3 |
| 113 | 2-Ethylthiopropyi | 0 | (CHzh | CHOCH3 | H | ch3 |
| 11.6 | 2-Ethylthiopropyl | 2 | (CHjh | CHOCH3 | H | ch3 |
| 11.7 | 2-Ethylthiopropyl | 2 | ch2 | CHOQH5 | H | ch3 |
| 11.8 | 2-Ethylthiopropyl | 0 | (CHah | CHOC2H5 | H | ch3 |
| 11.9 | 2-Ethylthiopropyl | 2 | (CHjh | CHOC2H5 | H | ch3 |
| 11.10 | 2-Ethylthiopropyi | 2 | ch2 | CHOiPr | H | ch3 |
| 11.11 | 2-Ethylthiopropyi | 0 | (CH2)2 | CHOiPr | H | CH3 |
| i 11.12 | 2-Ethylthiopropyl | 2 | (CHzh | CHOiPr | H | CH3 |
| 11.13 | 2-Ethylthiopropyl | 2 | ch2 | ONOCH3 | H | CH3 |
| 11.14 | 2-Ethylthiopropyi | 2 | (CHjh | C-NOCH3 | H | ch3 |
| : 11.15 | 2-Ethylthiopropyi | 0 | (CHjh | ONOCH3 | H | ch3 |
| j 11.16 | 2-Ethylthiopropyl | 2 | ch2 | C-NOC2H5 | H | ch3 |
| 11.17 | 2-Ethylthiopropyl | 2 | (CHjh | C-NOC2H5 | H | ch3 |
| 111.18 | 2-Ethylthiopropyl | 0 | (CHjh | ONOC2H5 | H | ch3 |
| ; 11.19 | 2-Ethylthiopropyl | 2 | ch2 | C-NOiPr | H | ch3 |
| i 1130 | 2-Ethylthiopropyi | 2 | (CHíh | C-NOiPr | H | ch3 |
| 1131 | 2-Ethylthiopropyl | 0 | (Ohh | C-NOiPr | H | ch3 |
| 1132 | 2-Ethylthiopropyi | 2 | ch2 | C-NOCH2CH-CHC1 | H | ch3 |
| 1133 | 2-Ethylthiopropyi | 2 | (CHah | ONOCH2CH-CHC1 | H | ch3 |
| 1134 | 2-Ethylthiopropyl | 0 | (CHjh | C-NOCH2CH-CHC1 | H | ch3 |
| 1135 | 2-Ethylthiopropyl | 2 | ch2 | C-N0CH2QHs | H | ch3 |
| 1136 | 2-Ethylthiopropyi | 2 | (CHih | ONOCH2QH5 | H | ch3 |
| 1137 | 2-Ethylthiopropyl | 0 | (CHjh | C-N0CH2C6Hs | H | ch3 |
| Π38 | 2-Ethylthiopropyl | 2 | ch2 | CÍCHsh | H | CH3 |
| 1139 | 2-Ethyhhiopropyi | 2 | (CHah | CíCHsh | H | ch3 |
| 1130 | 2-Ethylthiopropyi | 0 | (CHjh | CíCHjh · | H | ch3 |
| 1131 | 2-Ethylthiopropyl | 2 | ch2 | CH-NHCH3 | H | ch3 |
| 1132 | 2-Ethylthiopropyl | 2 | (CHzh | CH-NHCH3 | H | ch3 |
0050/46142
214
| Nr. | R17 | n | X | Y | L | M |
| 11.33 | 2—Ethylthiopropyl | 0 | (CH2)2 | CH-NHCH3 | H | ch3 |
| 1134 | 2-Ethylthiopropyl | 2 | ch2 | CH-NHC2H5 | H | ch3 |
| 5 11.35 | 2-Ethylthiopropyl | 2 | (CHzh | ch-nhc2h5 | H | ch3 |
| 1136 | 2-Ethylthiopropyl | 0 | (CH2)2 | ch-nhc2h5 | H | ch3 |
| 11.37 | 2-Ethylthiopropyl | 2 | ch2 | CH-N(CH3h | H | ch3 |
| 1138 | 2-Ethylthiopropyl | 2 | (CHzh | CH—N(CH3h | H | ch3 |
| 1139 | 2-Ethylthiopropyl | 0 | (CH2h | CH-N(CH3h | H | ch3 |
| ) 11.40 | 2-Ethylthiopropyl | 2 | ch2 | CH-NHOC2H5 | H | ch3 |
| 11.41 | 2-Ethylthiopropyl | 2 | (CH2h | CH-NHOCzHs | H | ch3 |
| 11.42 | 2-Ethylthiopropyl | 0 | (CHzh | CH-NHOC2H5 | H | ch3 |
| 11.43 | 2-Ethylthiqpropyl | 2 | CH2 | CH-N(CH3)OCzH5 | H | ch3 |
| 11.44 | 2-Ethylthiopropyl | 2 | (CHzh | CH-N(CH3)OCzH5 | H | ch3 |
| 11.45 | 2-Ethylthiopropyl | 0 | (CHzh | CH-N(CH3)OCzH5 | H | ch3 |
| 11.46 | 2-Ethylthiopropyl | 2 | CH2 | c=n-nh2 | H | ch3 |
| 11.47 | 2-Ethylthiopropyl | 2 | (CHzh | c=n-nh2 | H | ch3 |
| 11.48 | 2-Ethylthiopropyl | 0 | (CHzh | c=n-nh2 | H | ch3 |
| 11.49 | 2-Ethylthiopropyl | 2 | CH2 | C=N-N(CH3h | H | ch3 |
| 11.50 | 2-Ethylthiopropyl | 2 | (CHzh | C=N-N(CH3h | H | ch3 |
| 11.51 | 2-Ethylthiopropyl | 0 | (CHzh | C=N-N(CH3h | H | ch3 |
| 1132 | 2-Ethylthiopropyl | 2 | CHz | CH-N(CH3)OCHzC(5H5 | H | ch3 |
| 1133 | 2-Ethylthiqpropyl | 2 | (CHzh | CIPN(CH3)OCHzC6H5 | H | ch3 |
| 11.54 | 2-Ethylthiopropyl | 0 | (CHzh | CH-N(CH3XMCHzC6H5 | H | ch3 |
| 11.55 | 2-Ethylthiopropyl | 2 | CH2 | C(CH3>-OCH3 | H | ch3 |
| 11.56 | 2-Ethylthiopropyl | 2 | (CHzh | C(CH3)-OCH3 | H | ch3 |
| 1137 | 2-Ethylthiopropyl | (CHzh | C(CH3>-OCH3 | H | ch3 | |
| 1138 | 2-Ethylthiqpropyl | 2 | ch2 | 0 | H | ch3 |
| 1139 | 2-Ethylthiopropyl | 0 | (CHzh | 0 | H | ch3 |
| 11.60 | 2-Ethylthiopropyi | 2 | (CHzh | 0 | H | ch3 |
| 11.61 | Tetrahydropyranyl-3 | 2 | CH2 | c=o | H | ch3 |
| 11.62 | Tetrahydropyranyl-3 | 0 | (CHzh | c=o | ch3 | |
| 11.63 | Tetrahydropyranyl-3 | 2 | (CHzh | 00 | ch3 | |
| 11.64 | Tetrahydropyranyl-3 | 2 | CHz | choch3 | ch3 | |
| 11.65 | Tetrahydropyranyl-3 | 0 | (CHzh | choch3 | ch3 | |
| 11.66 | retrahydropyranyl-3 | 2 | (CHzh | choch3 | ch3 | |
| 11.67 | 'etrahydropyranyl-3 | 2 | CHz | CHOC2Hj | ch3 | |
| 11.68 | 'etrahydrqpyranyl-3 | (CHzh | choc2h5 | ch3 | ||
| 11.69 | retrahydropyranyl-3 | 2 | (CHzh | choc2h5 | ch3 | |
| 11.70 | 'etrahydropyranyl-3 | 2 | CHz | CHOiPr | ch3 | |
| 11.71 ' | 'etrahydropyranyl-3 | CHzh | CHOiPr | ch3 | ||
| 11.72 ' | retrahydropyranyl-3 í | CHzh | CHOiPr | ch3 | ||
| 11.73 ' | retrahydropyranyl-3 í | CH2 | >NOCH3 | CHj |
0050/46142
215 • · * · · · · • · · · • · · · · • · · ·
| Nr. | R17 | n | X | Y | L | M |
| 11.74 | Tetrahydropyranyl-3 | 2 | (CH2h | c=noch3 | H | ch3 |
| 11.75 | Tetrahydropyranyl-3 | 0 | (CHzh | c=noch3 | H | ch3 |
| 11.76 | Tetrahydropyranyl-3 | 2 | ch2 | c=noc2h5 | H | ch3 |
| 11.77 | Tetrahydropyranyl-3 | 2 | (CHzh | c=noc2h5 | H | ch3 |
| 11.78 | Tetrahydropyranyl-3 | 0 | (CH2)2 | c=noc2h5 | H | ch3 |
| 11.79 | Tetrahydropyranyl-3 | 2 | ch2 | C=NOiPr | H | ch3 |
| 11.80 | Tetrahydropyranyl-3 | 2 | (CH2)2 | C=NOiPr | H | ch3 |
| 11.81 | Tetrahydropyranyl-3 | 0 | (CHzh | C=NOiPr | H | ch3 |
| 11.82 | Tetrahydropyranyl-4 | 2 | ch2 | C=O | H | ch3 |
| 11.83 | Tetrahydropyranyl-4 | 0 | (CH2)2 | C=O | H | ch3 |
| 11.84 | Tetrahydropyranyl-4 | 2 | (CHzh | C=O | H | ch3 |
| 11.85 | Tetrahydropyranyl-4 | 2 | ch2 | choch3 | H | ch3 |
| 11.86 | Tetrahydropyranyl-4 | 0 | (CHzh | CHOCH3 | H | ch3 |
| 11.87 | Tetrahydropyranyl-4 | 2 | (CH2)2 | choch3 | H | ch3 |
| 11.88 | Tetrahydropyranyl-4 | 2 | ch2 | CHOCzHj | H | ch3 |
| 11.89 | Tetrahydropyranyl-4 | 0 | (CH2)2 | choc2h5 | H | ch3 |
| 11.90 | Tetrahydropyranyl-4 | 2 | (CHzh | choc2h5 | H | ch3 |
| 11.91 | Tetrahydropyranyl-4 | 2 | ch2 | CHOiPr | H | ch3 |
| 11.92 | Tetrahydropyranyl-4 | 0 | (CH2h | CHOiPr | H | ch3 |
| 11.93 | Tetrahydropyranyl-4 | 2 | (CHzh | CHOiPr | H | ch3 |
| 11.94 | Tetrahydropyranyl-4 | 2 | ch2 | C-NOCH3 | H | ch3 |
| 11.95 | Tetrahydropyranyl-4 | 2 | (CHzh | C=NOCH3 | H | ch3 |
| 11.96 | Tetrahydropyranyl-4 | 0 | (CHzh | c=noch3 | H | ch3 |
| 11.97 | Tetrahydropyranyl-4 | 2 | CH2 | C=NOC2H5 | H | ch3 |
| 11.98 | Tetrahydropyranyl-4 | 2 | (CHzh | c=noc2h5 | H | ch3 |
| 11.99 | Tetrahydropyranyl-4 | 0 | (CHzh | c=noc2h5 | H | ch3 |
| 11.100 | Tetrahydropyranyl-4 | 2 | ch2 | C=NOiPr | H | ch3 |
| 11.101 | Tetrahydropyranyl-4 | 2 | (CHzh | C=NOiPr | H | ch3 |
| 11.102 | Tetrahydropyranyl-4 | (CHzh | C=NOiPr | H | ch3 | |
| 11.103 | Tetrahydrothiopyranyl—3 | 2 | ch2 | C=O | H | ch3 |
| 11.104 | Tetrahydrothiopyranyl—3 | (CHzh | C=O | H | ch3 | |
| 11.105 | Tetrahydrothiopyranyl-3 | 2 | (CHzh | C=O | H | ch3 |
| 11.106 | Tetrahydrothiopyranyl—3 | 2 | ch2 | CHOCH3 | ch3 | |
| 11.107 | Tetrahydrothiopyranyl-3 | 0 | (CHzh | choch3 | ch3 | |
| 11.108 | Tetrahydrothiopyranyl-3 | 2 | (CHzh | choch3 | ch3 | |
| 11.109 | Tetrahydrothiopyranyl-3 | 2 | ch2 | CHOCzHj | ch3 | |
| 11.110 | retrahydrothiopyranyl-3 | i | (CHzh | choc2h5 | ch3 | |
| 11.111 | Tetrahydrothiopyranyl-3 | 2 | (CHzh | choc2h5 | ch3 | |
| 11.112 | retrahydrothiopyranyl-3 | 2 | CH2 | CHOiPr | ch3 | |
| 11.113 | retrahydrothiopyranyl-3 | (CHzh | CHOiPr | ch3 | ||
| 11.114 ' | retrahydrothiopyranyl-3 1 | l | (CHzh | CHOiPr | ch3 |
0050/46142
216 • · ·
| Nr. | Ř17 | n | X | Y | L | M |
| 11.115 | Tetrahydrothiopyranyl-3 | 2 | ch2 | c=noch3 | H | CH3 |
| 11.116 | Tetrahydrothiopyranyl-3 | 2 | (CH2)2 | c=noch3 | H | ch3 |
| 5 Π-117 | Tetrahydrothiopyranyl-3 | 0 | (CH2)2 | c=noch3 | H | ch3 |
| 11.118 | Tetrahydrothiopyranyl-3 | 2 | ch2 | onoc2h5 | H | ch3 |
| 11.119 | Tetrahydrothiopyranyl-3 | 2 | (CH2)2 | c=noc2h5 | H | ch3 |
| 11.120 | Tetrahydrothiopyranyl-3 | 0 | (CH2)2 | c=noc2h5 | H | ch3 |
| 11.121 | Tetrahydrothiopyranyl-3 | 2 | ch2 | ONOiPr | H | ch3 |
| ) 11.122 | Tetrahydrothiopyranyl-3 | 2 | (ch2)2 | ONOiPr | H | ch3 |
| 11.123 | Tetrahydrothiopyranyl-3 | 0 | (ch2)2 | ONOiPr | H | ch3 |
| 11.124 | 1-Methylthio-cyclopropyI | 2 | ch2 | OO | H | ch3 |
| 11.125 | 1-Methylthio-cyclopropy | 0 | (CH2)2 | oo | H | ch3 |
| 11.126 | 1-Methylthio-cyclopropy | 2 | (CH2)2 | oo | H | ch3 |
| 11.127 | 1-Methylthio-cyclopropy | 2 | ch2 | CHOCH3 | H | ch3 |
| 11.128 | 1-Methylthio-cyclopropy | 0 | (CH2)2 | CHOCH3 | H | ch3 |
| 11.129 | 1-Methylthio-cyclopropyl | 2 | (CH2)2 | CHOCH3 | H | ch3 |
| 11.130 | 1-Methylthio-cyclopropyl | 2 | ch2 | CHOC2H5 | H | ch3 |
| 11.131 | 1-Methylthio-cyclopropy | 0 | (CHzh | CHOC2H5 | H | ch3 |
| 11.132 | 1-Methylthio-cyclopropy | 2 | (CH2)2 | CHOC2H5 | H | ch3 |
| 11.133 | 1-Methylthio-cyclopropyl | 2 | ch2 | CHOiPr | H | ch3 |
| 11.134 | 1-Methylthio-cyclopropyl | 0 | (CH2)2 | CHOiPr | H | ch3 |
| 11.135 | 1-Methylthio-cyclopropyl | 2 | (CH2)2 | CHOiPr | H | ch3 |
| 11.136 | 1-Methylthio-cyclopropyl | 2 | ch2 | onoch3 | H | ch3 |
| 11.137 | 1-Methylthio-cyclopropyl | 2 | (CH2)2 | ONOCH3 | H | ch3 |
| 11.138 | -Methylthio-cyclopropyl | (CH2)2 | c=noch3 | H | ch3 | |
| 11.139 | 1-Methylthio-cyclopropyl | 2 | ch2 | ONOC2H5 | H | ch3 |
| 11.140 | 1-Methylthio-cyclopropyl | 2 | (CH2)2 | ONOC2H5 | H | ch3 |
| 11.141 | -Methylthio-cyclopropyl | 0 | (CH2)2 | ONOC2H5 | H | ch3 |
| 11.142 | -Methylthio-cyclopropyl | 2 | ch2 | ONOiPr | H | ch3 |
| 11.143 | 1-Methylthio-cyclopropyl | 2 | (CH2)2 | ONOiPr | H | ch3 |
| 11.144 | 1-Methylthio-cyclopropyl | 0 | (CH2)2 | ONOiPr | H | ch3 |
| 11.145 | >iinethoxy)methyl | 2 | ch2 | OO | H | ch3 |
| 11.146 | pimethoxy)methyl | 0 | (CH2)2 | OO | H | ch3 |
| 11.147 | Dimethoxy)methyl | 2 | (CH2)2 | OO | H | ch3 |
| 11.148 | Dimethoxy)njethyl | 2 | ch2 | CHOCH3 | H | ch3 |
| 11.149 | 5imethoxy)methyl | 1 | (GH2)2 | CHOCH3 | H | ch3 |
| 11.150 | )imethoxy)methyl | 2 | CH2)2 | CHOCH3 | H | ch3 |
| 11.151 | T>únethoxy)methyl | 2 | ch2 | CHOC2H5 | H | ch3 |
| 11.152 | Oimethoxy)methyl | :ch2)2 | CHOC2H5 | H | ch3 | |
| 11.153 | Dimethoxy)njethyl | :ch2)2 | CHOC2H5 | H | ch3 | |
| 11.154 | Dimethoxy)methyl | 2 | 3H2 | DHOiPr | rl | ch3 |
| 11.155 | Dimethoxy)methyl | CHih | :HOiPr | a | :ή3 |
0050/46142
217 c
c
| Nr. | ŘT7 | n | X | Y | L | M |
| 11.156 | (Dimethoxy)methyl | 2 | (CH2)2 | CHOiPr | H | CH3 |
| 11.157 | (Dimethoxy)methyl | 2 | ch2 | C=NOCH3 | H | ch3 |
| 11.158 | (Dimethoxy)methyl | 2 | (CH2)2 | c=noch3 | H | ch3 |
| 11.159 | (Dimethoxy)methyl | 0 | (CH2)2 | c=noch3 | H | ch3 |
| 11.160 | (Dimethoxy)methyl | 2 | ch2 | c=noc2h5 | H | ch3 |
| 11.161 | (Dimethoxy)niethyl | 2 | (CH2)2 | c=noc2h5 | IH | ch3 |
| 11.162 | (Dimethoxy)methyl | 0 | (CH2)2 | c=noc2h5 | H | ch3 |
| 11.163 | (Dimethoxy)methyl | 2 | ch2 | ONOiPr | H | ch3 |
| 11.164 | (Dimethoxy)methyl | 2 | (CH2)2 | C=NOiPr | H | ch3 |
| 11.165 | (Dimethoxy)methyl | 0 | (CH2)2 | C=NOiPr | H | ch3 |
• ·
- 218 Příklady provedení vynálezu
Příklady výroby
A) Výroba výchozích materiálů a meziproduktů
1. 3-Thio-2-methylbenzoová kyselina
100 g (0,66 mol) 3-amino-2-methylbenzoové kyseliny bylo smíseno s 270g ledu a 127 ml koncentrované kyseliny chlorovodíkové. Při teplotě 0 až 10°C byl potom přikapáván roztok 45,7 g (0,66 mol) dusitanu sodného ve 270 ml vody.
V jiné nádobě bylo rozpuštěno 84,2 g (0,79 mol) uhličitanu sodného a 106g (0,66 mol) methylxanthogenanu draselného ve 450 ml vody a získaný roztok byl zahřát na teplotu 60 až 70°C. Pak byl opatrně přikapáván roztok diazoniové soli a směs byla ještě 1 hodinu míchána. Potom bylo přidáno 106 g (2,65 mol) hydroxidu sodného ve 270 ml vody, tato reakční směs byla míchána další dvě hodiny, roztok byl okyselen kyselinou chlorovodíkovou a vzniklá sraženina byla odsáta. Pevný podíl byl promyt vodou a vysušen.
Výtěžek: 110 g (100% teorie) 3-thio-2-methylbenzoové kyseliny; b.t.: 155°C; 1H-NMR (d6-DMSO): δ [ppm] = 13,0 (1H,bs), 7,7 (2H,m), 7,3 (1 H,tr),
2,4 (3H,s). 2
2. Methylester kyseliny 3-thio-2-methylbenzoové
110 g (0,66 mol) 3-thio-2-methylbenzoové kyseliny bylo rozpuštěno v 1,6 I methanolu, který obsahoval 5 % kyseliny sírové a reakční směs byla zahřívána pod zpětným chladičem po dobu 5 hodin. Potom byl alkohol oddestilován, zbytek byl extrahován ethylacetárem, organická fáze byla promyta vodou a roztokem uhličitanu sodného, vysušena síranem sodným a bylo odpařeno rozpouštědlo.
Výtěžek: 104 g (87 % teorie) methylesteru 3-thio-2-methylbenzoové kyseliny; 1H-NMR (CDCI3): δ [ppm] = 7,6 (1H,d), 7,4 (1 H,d), 7,1 (1H,d), 3,9 (3H,s), 3,4(1H,s), 2,5 (3H,s).
* • ·
- 219
3. Methylester kyseliny 3-karboxyethylsulfonyl-2-methylbenzoové
g (0,38 mol) methylesteru 3-thio-2-methylbenzoové kyseliny bylo rozpuštěno ve 400 ml vody a zahříváno s 30,8 g (0,77 mol) hydroxidu sodného a 58,8 g (0,45 mol) brompropionové kyseliny za míchání po dobu 7 hodin pod zpětným chladičem. Po ochlazení byla vodná fáze promyta methyl-terc.-butyletherem. Potom byla vodná fáze okyselena 2N chlorovodíkovou kyselinou, vzniklá sraženina byla odsáta, promyta vodou a získaný produkt byl vysušen.
Výtěžek: 75,5 g (78 % teorie) methylesteru kyseliny 3-karboxyethylsulfonyl-
2-methylbenzoové; 1H-NMR (CDCI3): δ [ppm] = 7,66 (1H,d), 7,51 (1H,d)
7,20 (1 H,tr), 3,96 (3H,s), 3,18 (2H,tr), 2,70 (2H,tr), 2,63 (3H,s).
4, Methylester kyseliny 8-methylthiochroman-4-on-7-karboxylové
g (15,8 mmol) methylesteru kyseliny 3-karboxyethylsulfonyl-2methylbenzoové bylo mícháno při teplotě 70 °C po dobu 15 minut ve 40 g kyseliny polyfosforečné. Potom byl reakční roztok vlit do ledové vody a vzniklá sraženina byla odsáta. Produkt byl promyt vodou a vysušen v sušárně. Jako vedlejší produkt cyklizace může vznikat methylester kyseliny 8-methylthiochromen-4-on-7-karboxylové, který je možno oddělit pomocí chromatografie.
• ·
220
Výtěžek: 3,1 g (83 % teorie) methylesteru kyseliny 8-methylthiochroman-4on-7-karboxylové; 1H-NMR (CDCI3): δ [ppm] = 8,00 (1H,d), 7,30 (1 H,d), 3,94 (3H,s), 3,15 (2H,m), 2,98 (2H,m), 2,50 (3H,s);
Vedlejší produkt methylester kyseliny 8-methylthiochromen-4-on-7karboxylové: 1H-NMR (CDCI3): δ [ppm] = 8,4 (1 H,d), 7,9 (1 H.d), 7,8 (1 H.d), 7,0 (1H,d), 4,0(1H,s), 2,7 (3H,s).
5. Kyselina 8-methylthiochroman-4-on-7-karboxylová
41,1 g (0,17 mol) methylesteru kyseliny 8-methylthiochroman-4-on-7karboxylové bylo hydrolyzováno ve směsi 400 ml vody a methanolu s 10,3g (0,26 mol) NaOH při teplotě varu pod zpětným chladičem. Potom byl methanol oddestilován a zbytek byl zředěn vodou a okyselen 2N kyselinou chlorovodíkovou. Vysrážený produkt byl odsát, promyt vodou a vysušen.
Výtěžek: 34,4 g (89 % teorie) kyseliny 8-methylthiochroman-4-on-7karboxylové; b.t.: 243 až 246°C.
6. 8-Methyl-1,1 -dioxothiochroman-4-on-7-karboxylová kyselina
O
g (0,09 mol) 8-methylthiochroman-4-on-7-karboxylové kyseliny bylo rozpuštěno ve 100 ml kyseliny octové. K této směsi byl přidán wolframan sodný v množství na špičku laboratorní kopisti. Při teplotě 50 °C bylo potom přikapáno 24,9 g (0,22 mol) 30%ního roztoku hydroperoxidu. Reakční směs byla potom míchána ještě jednu hodinu a poté vlita do vody, vzniklá sraženina byla odsáta. Produkt byl po promytí vodou vysušen.
Výtěžek: 18,4 g (80 % teorie) 8-methyl-1,1-dioxothiochroman-4-on-7karboxylové kyseliny; b.t.: 224 až 225 °C.
221 • « · · ·
7. Methylester 4-hydroxy-8-methylthiochroman-7-karboxylové kyseliny
g (0,127 mol) methylesteru 8-methylthiochroman-4-on-7-karboxylové kyseliny bylo rozpuštěno ve směsi 120 ml methylenchloridu a 60 ml methanolu a roztok byl ochlazen na teplotu 0 až 5 °C. Potom bylo po částech přidáváno 2,4 g (0,064 mol) natriumborohydridu a reakční směs byla míchána ještě po dobu jedné hodiny. K roztoku bylo přidáno 200 ml 2N chlorovodíkové kyseliny, vznikly přitom dvě fáze. Organická fáze byla po oddělení vysušena a rozpouštědlo bylo oddestilováno. Získaný surový produkt byl použit bez dalšího čištění.
Výtěžek: 27,6 g (91 % teorie) methylesteru 4-hydroxy-8-methylthiochroman7-karboxylové kyseliny.
8. Methylester 4-ethoxy-8-methylthiochroman-7-karboxylové kyseliny
13,8 g (0,058 mol) methylesteru 4-hydroxy-8-methylthiochroman-7karboxylové kyseliny bylo zahříváno v 60 ml ethanolu s přídavkem 1 g kyseliny sírové po dobu 4 hodin na teplotu varu reakční směsi. Potom bylo rozpouštědlo oddestilováno a zbytek byl vyjmut do vody. Vodná fáze byla extrahována ethylacetátem. Organická fáze byla promyta roztokem hydrogenuhličitanu sodného, vysušena a odpařena. Produkt byl čištěn pomocí chromatografie.
Výtěžek: 10,1 g (60 % teorie) methylesteru 4-ethoxy-8-methylthiochroman7-karboxylové kyseliny; 1H-NMR (CDCI3): δ [ppm] = 7,44 (1H, d), 7,13 (1H,d), 4,40 (1H,m) 3,90 (3H,s), 3,60 (2H,m), 3,38 (1H,dtr), 2,90 (1H,m),
2,50 (3H,s)2,40 (1H,m), 1,98 (1H,m), 1,10 (3H.tr).
- 222Reakce pro přípravu methylesteru 4-methoxy-8-methylthiochroman-4-on-7karboxylové kyseliny a methylesteru 4-isopropoxy-8-methylthiochroman-on-7karboxylové kyseliny se provádí analogicky jako v dříve uvedeném předpisu, přičemž v případě methylesteru 4-methoxy-8-methylthiochroman-4-on-7karboxylové kyseliny je ethanol nahrazen methanolem a v případě methylesteru
4-isopropoxy-8-methylthiochroman--on-7-karboxylové kyseliny je ethanol nahrazen isopropanolem.
9. 4-Ethoxy-8-methylthiochroman-7-karboxylová kyselina
2,1 g hydroxidu sodného se rozpustí ve 20 ml vody. Při teplotě cca 20 °C se přikapává methylester 4-ethoxy-8-methylthiochroman-4-on-7karboxylové kyseliny rozpuštěný ve 20 ml methanolu. Reakční směs se zahřívá po dobu 2 hodin pod zpětným chladičem. Potom se oddestiluje rozpouštědlo a ke zbytku se přidá 2N kyselina chlorovodíková. Vodná fáze se extrahuje methylenchloridem. Organická fáze se vysuší a odpaří.
Výtěžek: 9,3 g (100 % teorie) 4-ethoxy-8-methylthiochroman-7-karboxylové kyseliny; b.t.: 89-98°C.
Hydrolýza příslušných esterů na 4-methoxy-8-methylthiochroman-7-karboxylovou kyselinu a 4-isopropoxy-8-methylthiochroman-7-karboxylovou kyselinu se provádí analogicky. Totéž platí i pro zmýdelnéní příslušných dále uvedených benzo[b]thiofenových derivátů.
10. 8-Methyl-4-ethoxy-1,1 -dioxothiochroman-7-karboxylová kyselina
8,4 g (0,033 mol) 4-ethoxy-8-methylthiochroman-7-karboxylové kyseliny se smísí se 60 ml kyseliny octové, k tomu se přidá na špičku laboratorní kopisti wolframan sodný. Při teplotě 50 °C se pomalu přikapává 7,9 g (0,07 mol) 30%ního roztoku hydroperoxidu a reakční směs se ještě 2 hodiny míchá, potom se vlije do vody a vodná fáze se extrahuje ethylacetátem. Organická fáze se promyje roztokem hydrogensiřičitanu, potom se vysuší a odpaří.
Výtěžek: 9,5 g (100 % teorie) 8-methyl-4-ethoxy-1,1-dioxothiochroman-7karboxylové kyseliny ; b.t.: 150 °C.
• ·
- 223 -
11. 8-Methylthiochroman-4-on-7-karboxyl-O-ethyloxim
Ke 20 ml methanolu se přidá 0,88 g (9 mmol) ethylhydroxylaminu, potom se přidá 0,62 g (4,5 mmol) uhličitanu draselného. Nakonec se přidají 2 g (9 mmol) 8-methylthiochroman-4-on-7-karboxylové kyseliny. Reakce probíhá za míchání po dobu 10 dnů při teplotě cca 20 °C. Reakční směs se potom zpracuje přídavkem vody a 2N chlorovodíkové kyseliny. Vzniklá sraženina se odsaje a vysuší.
Výtěžek: 2,2 g (92 % teorie) 8-methylthiochroman-4-on-7-karboxyl-Oethyloximu; b.t.: 166°C.
12. 8-Methyl-1,1 -dioxothiochroman-4-on-7-karboxyl-O-ethyloxim
3,0 g (0,011 mol) 8-methylthiochroman-4-on-7-karboxyl-0-ethyloximu se smísí spolu s wolframanem sodným v množství na špičku kopisti s 30 ml octové kyseliny. Při teplotě 50 °C se přikapává 2,8 g (0,024 mol) 30%ního roztoku hydroperoxidu. Po jednohodinovém míchání se reakční směs vlije do vody s ledem a vzniklá sraženina se odsaje. Získaný produkt se promyje vodou a vysuší.
Výtěžek: 2,5 g (74 % teorie) 8-methyl-1,1-dioxothiochroman-4-on-7karboxyl-O-ethyloximu; b.t. 198°C.
13. 8-Methyl-1-oxothiochroman-4-on-7-karboxylová kyselina
7,0 g (31,5 mmol) 8-methylthiochroman-4-on-7-karboxylové kyseliny bylo smíseno s wolframanem sodným v množství na špičku kopisti a se 70 ml octové kyseliny. Při teplotě 50 °C bylo přikapáno 3,6 g (31,5 mmol)
30%ního roztoku hydroperoxidu a reakční směs byla ještě 3 hodiny míchána, potom vlita do vody. Produkt byl extrahován ethylacetátem.
• · • ·
- 224 Organická fáze byla vysušena a rozpouštědlo bylo odpařeno. Produkt byl čištěn pomocí chromatografie.
Výtěžek: 5,4 g (72% teorie) 8-methyl-1 -oxothiochroman-4-on-7-karboxylové kyseliny; 1H-NMR (d6-DMSO): δ [ppm] = 8,0 (2H,m), 3,5 (3H,m) 2,8 (3H,s).
14. Methylester kyseliny 3-karboxymethylsulfanyl-2-methylbenzoové
K 1,6 g (0,068 mol) natriumhydridu ve 40 ml dimethylformamidu bylo přikapáno 12,4 g (0,068 mol) methylesteru kyseliny 3-thio-2-methylbenzoové v 80 ml dimethylformamidu a reakční směs byla míchána při teplotě 20 °C po dobu 60 minut.. Potom bylo přidáno 8 g (0,068 mol) chloroctové kyseliny a reakční směs byla míchána po dobu 4 hodin při teplotě cca 20 °C, potom byla vlita do ledové vody s ledem okyselené chlorovodíkovou kyselinou a promíchána.
Vzniklá sraženina byla odsáta, promyta vodou a vysušena.
Výtěžek: 14,6 g (89 % teorie) methylesteru kyseliny 3-karboxymethylsulfanyl-2-methylbenzoové; 1H-NMR ( de-DMSO) : δ [ppm] = 7,55 (1H,d), 7,45 (1 H,d), 7,21 (1 H,tr), 3,82 (2H,s), 2,50 (3H,s).
15. Methylester kyseliny 7-methyl-benzo[b]thiofen-3[2H]-on-6-karboxylové
14,3 g (0,06 mmol) methylesteru kyseliny 3-karboxymethylsulfanyl-2methylbenzoové bylo rozpuštěno v 300 ml methylenchloridu. Potom bylo přikapáno 13,1 g (0,11 mmol) thionylchloridu a směs byla 1 hodinu zahřívána pod zpětným chladičem. Pak bylo oddestilováno rozpouštědlo spolu s přebytečným thionylchloridem. Zbytek byl vyjmut do 100 ml methylenchloridu a bylo přidáno 31,8 g (0,24 mmol) chloridu hlinitého.
• · · · ··· ··· • · · · · · · · »·· • · ·· ·· ·· ···· • · ···· · · ······· · · ·· · « ··
- 225 Reakce byla prováděna za míchání po dobu 1 hodiny. Nakonec byla reakční směs vlita do vody s ledem a organická fáze byla oddělena. Po promytí a vysušení organické fáze bylo rozpouštědlo odpařeno. Získaný produkt byl bez dalšího čištění dále zpracován.
Výtěžek: 12,9 g (97 % teorie) methylesteru kyseliny 7-methylbenzo[b]thiofen-3[2H]-on-6-karboxylové; 1H-NMR (CDCI3): δ [ppm] = 7,65 (2H,m), 3,93 (3H,s), 3,88 (2H,s), 2,50 (3H,s).
16. Methylester kyseliny 7-methyl-3-hydroxybenzo[b]thiofen-[2H]-6-
12,8 g (0,058 mol) methylesteru kyseliny 7-methyl-benzo[b]thiofen-3[2H]on-6-karboxylové bylo rozpuštěno ve 120 ml methylenchloridu a 60 ml methánolu a tento roztok byl zchlazen na 0°C. Po částech byl přidáván 1,1g (0,029 mol) natriumborohydridu a směs byla míchána po dobu 3 hodin. Reakce byla přerušena přidáním vody. Vzniklé fáze byly oděleny a vodná fáze byla extrahována methylenchloridem. Spojené orgnanické fáze byly vysušeny. Rozpouštědlo bylo oddestilováno. Surový produkt byl dále zpracován.
Výtěžek: 13,2 g (100 % teorie) methylesteru kyseliny 7-methyl-3-hydroxybenzo[b]thiofen42H]-6-karboxylové; 1H-NMR (CDCI3): δ [ppm] =7,6 (2H,m),
5.3 (1H,m), 3,9 (3H,s), 3,7 (1H,m), 3,3 (1H,m) 2,4 (3H,s).
17. Methylester kyseliny 7-methyl-3-methoxybenzo[b]thiofen-[2H]-6-karboxylové
2.4 g (0,050 mol) NaH bylo rozpuštěno v 50 ml dimethylformamidu. Bylo prikapáno 13,2 g methylesteru kyseliny 7-methyl-3-hydroxy-benzo- [b]thiofen-[2H]-6-karboxylové rozpuštěného v 50 ml.. Reakční směs byla míchána ještě 2 hodiny při teplotě cca 20°C. Potom bylo přidáno 8,4 g
226 (0,059 mol) jodmethanu a směs byla míchána ještě 2 hodiny. Reakční směs byla vlita do vody s ledem a extrahována ethylácetátem. Organická fáze byla vysušena a zahuštěna. Produkt byl čištěn pomocí chromatografie.
Výtěžek: 3,5 g (25 % teorie) methylesteru kyseliny 7-methyl-3methoxybenzo[b]thiofen-[2H]-6-karboxylové; 1H-NMR (CDCI3).' δ [ppm] =
7,60 (1 H,d), 7,20 (1 H,d), 5,04 (1H,m), 3,90 (3H,s), 3,56 (1H,m), 3,40 (3H,s),
3,38 (1H,m), 2,50 (3H,s).
Příslušné benzothiofenové kyseliny se získají analogicky jako při dříve uvedeném zmýdelnění thiochromanonesterů.
Analogicky byly získány sloučeniny uvedené v následujících tabulkách:
- 227 Tabulka 12: Meziprodukty
| Nr. | T | n | X | Y | L | M | Phys. Daten |
| 12.1 | HO | 0 | (CHih | OO | H | H | Fp[°C]: 226-231 |
| 122 | HO | 2 | (CHjh | OO | H | H | Fp[°Q: 217-220 |
| 123 | HO | 0 | (CHíh | OO | H | ch3 | Fp [°C]: 243-246 |
| 12.4 | HO | 2 | (CHih | oo | H | ch3 | Fp [°CJ: 224-225 |
| 123 | HO | 0 | (CHjh | CHOCH3 | Ή | ch3 | Fjp [°C]: 117-118 |
| i 12.6 | HO | 2 | (CHjh | choch3 | H | ch3 | Fp [°CJ: 167-172 |
| í 12.7 | HO | 0 | (CH2h | CHOC2H5 | H | ch3 | Fp[°C]: 89-98 |
| 12.8 | HO | 2 | (CHih | CHOC2H5 | H | ch3 | Fp [°C]: 150 |
| 12.9 | HO | 0 | (CHjh | CHOiPropyl | H | ch3 | Fp[°C]: 138 |
| 12.10 | HO | 2 | (CHzh | CHOiPropyl | H | ch3 | Fp [°C]: 142 |
| 12.11 | HO | 0 | (CHzh | ONOC2H5 | H | ch3 | Fp[°Q:166 |
| 12.12 | HO | 2 | (CHzh | ONOC2H5 | H | ch3 | Fp[°Q:198 |
| 12.13 | HO | 0 | (CHzh | ONOCH2CH-CHCI | H | ch3 | Fp[°C]: 163 |
| 12.14 | HO | 2 | (CHjh | onoch2ch»chci | H | ch3 | FppQ:174 |
| 12.15 | HO | 0 | (CHih | ONOCH2CíH5 | H | ch3 | Fp[°C]: 178 |
| 12.16 | HO | 2 | (CHzh | ONO-tButyl | H | ch3 | Fjp [°Q: 217 |
| 12.17 | H3CO | 0 | (CHlh | C(CH3)2 | H | ch3 | Fp[°Q: 63-65 |
| 12.18 | HO | 2 | (CHjh | choch3 | H | a | Fp [°C]: 137-139 |
| 12.19 | HO | 2 | (CH2h | ONOC2H5 | H | a | Fp[°Q:205 |
| 1220 | HO | 0 | (CH2) | choch3 | H | ch3 | 300 MHz (d*-DMSO): 5[ppm]« 13.0 (IH, s), 735 (IH, d), 725 (IH, d), 5.10 (IH, s), 3.62 (IH, m), 3.42 (lH,m), 3.41 (3H,s), 2.42 (3H,s) |
| 1221 | HO | 2 | (CHz) | choch3 | H | ch3 | 1IL-NMR,300MHz (d^-DMSO): 8 (ppm]« 133 (1¾ bs), 8.10 (1¾ d), 7.60 (ΙΗ,άλ 5.18 (lH,m), 4.07(1¾ m), 3.75 (1¾ 3.40 (3¾ s), 2.70(3¾ z) |
| 1222 | HO | 2 | (CHih | 00 | H | a | ^H-NMRJOOMHz (dM)MSO):6[ppm]«142 (1¾ bs), 8.10 (1¾ ¢0,7.98(1¾ d), 4.13 (2¾ m), 3 JO (2¾ m) |
| 1223 | HO | (CHjh | OO | H | a | 1H-NMR,300MHz (dM)MSO): δ [ppm]a 13.9 (1¾ bs), 8.10 (1¾ (0,732(1¾ d), 3X1(2^), 2.90 (2¾ m) |
228
Tabulka 12a: Meziprodukty
L
| Nr. | T | n | Ř12“ | Ř13 | Ř22“ | Υ | L | M | Phys. Daten | |
| 12.45 | h3co | 0 | CH3 | ch3 | H | Η | ΟΟ | H | ch3 | ‘H-NMR, 270 MHz (CDCfc): δ [ppm] - 8.02,730,3.92,3.09, 2.50,133 |
| 1246 | h3co | 0 | H | ch3 | H | Η | ΟΟ | H | ch3 | FF(°Q:79 |
| 12.47 | h3co | 0 | CH3 | ch3 | H | Η | choch3 ¢1 | H | ch3 | ‘H-NMR, 270 MHz (CDCfe): δ [ppm] - 7.44,7.02,3.89,339, 333,328,230,248,121,0.88 |
| i 12.48 | h3co | 0 | H | H | ch3 | Η | ΟΟ | H | ch3 | Fjp[°Q:83 |
| 12.49 | h3co | 0 | H | H | ch3 | Η | choch3 | H | ch3 | ^-NMR, 270 MHz (CDC13): δ [ppm]-7.46,7.11,431,3.89, 3.65,337,248,244,1.64,144 |
| 1230 | HO | 0 | H | CH3 | Η | Η | choch3 | H | ch3 | Fp[°C]: 124 |
| 1231 | HO | 0 | ch3 | ch3 | Η | Η | choch3 | H | ch3 | Fp[°Q: 168 |
| 1232 | HO | 0 | H | H | ch3 | Η | choch3 | H | ch3 | Fp[°Q: 145 |
| 1233 | HO | 2 | H | CH3 | Η | Η | choch3 (tram) | H | ch3 | Fp[°C]:184 |
| 1234 | HO | 2 | ch3 | ch3 | Η | Η | CHOCH3 | H | ch3 | Fp[°C]: 161 |
| 1235 | HO | 2 | H | H | ch3 | Η | CHOCH3 | H | ch3 | Fp[°C]:182 |
Výroba konečných produktů
1. 2-(8-methyl-1,1 -dioxothiochroman-4-on-7-karbonyl)-1,3-cyklohexandion
O
θ) 17,4 g (0,0685 mol) kyseliny 8-methyl-1,1-dioxothiochroman-4-on-7karboxylové bylo rozpuštěno ve 170 ml toluenu, byla přidána 1 kapka dimethylfomnamidu a 8,96 g (0,0753 mol) thionylchloridu. Po čtyřhodinovém varu pod zpětným chladičem byla reakční směs odpařena. Reakční produkt byl použit pro další reakci.
• · · · · » r « · · · · · ·
229
Výtěžek: 18,6 g (99 % teorie) chloridu kyseliny 8-methyl-1,1-dioxoth iochroman-4-on-7-karboxylové;
b) 0,62 g (5,5 mmol) cyklohexan-1,3-dionu bylo smíseno s 0,56 g (5,5 mol) triethylaminu a 10 ml acetonitrilu. Ktéto směsi bylo přikapáno 1,5 g (5,5 mmol) chloridu kyseliny 8-methyl-1,1-dioxothiochroman-4-on-7karboxylové rozpuštěného ve 20 ml acetonitrilu.
Tato směs byla ještě jednu hodinu míchána pň teplotě cca 20 °C. Potom bylo přidáno 0,31 g (3,7 mmol) acetonkyanhydrinu a 2,8 g (22,5 mmol) triethylaminu. Po jednohodinovém míchání byla reakční směs vlita do 2N kyseliny chlorovodíkové a vodná fáze byla extrahována ethylacetátem. Organická fáze byla potom extrahována roztokem uhličitanu sodného a alkalická vodná fáze byla za chlazení okyselena. Vzniklá sraženina byla odsáta, promyta vodou a vysušena.
Výtěžek: 1,0 g (52 % teorie) 2-(8-methyl-1,1-dioxothiochroman-4-on-7karbonyl)-1,3-cyklohexandionu; b.t. 173 až 178°C.
2. 2-(8-methyl-1,1 -dioxothiochroman-4-on-7-karbonyl-O-ethyloxim)- cyklohexan-1,3-dion
1,0 g (3,4 mmol) O-ethyloxim-8-methyl-1,1-dioxothiochroman-4-on-7karboxylové kyseliny byl spolu s 0,39 g (3,5 mmol) cyklohexan-1,3-dionu smísen s 10 ml acetonitrilu, ktéto směsi bylo přidáno 0,75 g (3,6 mmol) dicyklokarbodiimidu (DCC) a tato směs byla míchána 2 hodiny. Potom bylo přidáno 0,1 ml acetonkyanhydrinu a 0,51 g (5,1 mmol) triethylaminu a směs byla míchána ještě dvě hodiny. Nakonec byla reakční směs rozmíchána v roztoku uhličitanu sodného. Směs byla extrahována ethylacetátem a
- 230 organická fáze byla odstraněna. Vodná fáze byla okyselena chlorovodíkovou kyselinou. Směs byla extrahována opět ethylácetátem, organická fáze byla vysušena a rozpouštědlo bylo oddestilováno. Produkt byl čištěn pomocí chromatografie.
Výtěžek: 600 mg (45 % teorie) 2-(8-methyl-1,1-dioxothiochroman-4-on-7karbonyl-O-ethyloxim)-cyklohexan-1,3-dionu; b.t.: 143°C.
3. 2-(8-methyl-4-ethoxy-1,1 -dioxothiochroman -7-karbonyl)-cyklohexan-1,3dion
a) K 8,8 g (0,031 mmol) 8-methyl-4-ethoxy-1,1 -dioxothiochroman -7karboxylové kyseliny rozpuštěné v 50 ml toluenu byly přidány 2 kapky dimethylformamidu a 4,4 g (0,04 mmol) thionylchloridu. Po čtyřhodinovém varu pod zpětným chladičem byla reakční směs zahuštěna.
Chlorid kyseliny byl přímo dále zpracován.
b) 0,56 g cyklohexan-1,3-dionu bylo smíseno s 0,47 d (6 mmol) pyridinu a 10 ml methylenchloridu. Ktéto směsi bylo přikapáno 1,5 g (5 mmol) chloridu kyseliny podle 3a) ve 20 ml methylenchloridu a tato směs byla míchána po dobu 1 hodiny. Tato reakční směs byla potom vlita do vody a získaný roztok byl okyselen kyselinou chlorovodíkovou, vodná fáze byla extrahována ethylácetátem, organická fáze byla vysušena a rozpouštědlo bylo oddestilováno.
Výtěžek: 1,88 g (99 % teorie) O-acylovaného produktu.
- 231 c) 1,3 g (3,4 mmol) produktu podle 3b) bylo rozpouštěno ve 20 ml acetonitrilu. Potom bylo přidáno 0,19 g (2,3 mmol) acetonkyanhydrinu a 1,7 g (17,2 mmol) triethylaminu a směs byla 2 hodiny míchána. Pak byla reakční směs vlita do 2N chlorovodíkové kyseliny a extrahována ethylacetátem. Organická fáze byla promyta roztokem uhličitanu sodného a odstraněna. Vodná alkalická fáze byla okyselena chlorovodíkovou kyselinou. Vzniklá sraženina byla odsáta a vysušena.
Výtěžek: 0,6 g (46 % teorie) 2-(8-methyl-4-ethoxy-1,1-dioxothiochroman -7karbonyl)-cyklohexan-1,3-dionu; 1H-NMR (CDCh): δ [ppm] = 17,5 (1H,s), 7,30 (1H,d), 7,18 (1 H.d), 4,47 (1H,m), 3,95-3,83 (1H,m), 3,70-3,50 (2H,m), 3,28 (1H,m), 2,81 (2H,tr), 2,71-2,50 (2H,m), 2,64 (3H,s), 2,43 (2H,tr), 2,05 (2H,m), 1,24 (3H.tr).
Analogickým způsobem byly získány i sloučeniny uvedené v následujících tabulkách:
• · • ·
- 232 Tabulka 13: Sloučeniny formule
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| X | X | X | X | X | X | X | X | X | X | X | |
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| s« | X | X | X | X | X | X | X | X | X | X | 1 S |
| X | X | X | X | X | X | X | X | X | X | X | |
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| n fií | X | X | X | X | X | X | X | X | X | X | X |
| c | CN | CN | CN | CN | o | o | e | CN | CN | CN | CN |
| o* aí | X | X | X | X | X | X | X | X | X | X | X |
| 00 «Μ až | X u | X | X | m δ | X | X | g | X | X | £ υ | X |
| r- Oí | δ | X u | X | CA X w | X | X u | £ u | X | g | 5 | X |
| £ | «Α CA | CA | cn cn | **e cn A | VA • cn | Ό • cn | m | 00 cn | Os cn •A | o rn | A A ' cn |
0050/46142
- 233 -
| Phys. Daten | Fp [°C]: 73 | NMR (CDC13), 300 MHz: δ [ppm] = 17.5 (IH, s), 7.30 (IH, d), 7.18 (IH, d), 4.47 (IH, m), 3.95-3.83 (IH, m), 3.70-3.50 (2H, m), 3.28 (IH, m), 2.81 (2H, tr), 2.71-2.50 (2H, m), 2.64 (3H, s), 2.43 (2H, tr), 2.05 (2H, m), 1.24(3H,tr) | CM 2 Ό U £ | NMR (CDCI3), 300 MHz: δ [ppm] = 17.5 (IH, s), 7.31 (IH, d), 7.18 (IH, d), 4.47 (IH, m), 3.96-3.82 (IH, m), 3.69-3.50 (2H, m), 3.28 (IH, m), 2.81 (2H, tr), 2.72-2.49 (2H, m), 2.68 (2H, s), 2.60 (3H, s), 2.31 (2H, s), 1.24 (3H, tr), 1.11 (6H, s) | Fp[°C]: 80-83 | Fp [°C]: 144-146 | Fp [°C]: 85 | NMR (CDCI3), 300 MHz: δ [ppm] = 17.25 (IH, s), 8.14 (lH,d),7.33 (IH, d), 3.90-3.57 (IH, m), 3.39-3.26 (IH, m), 2.99-2.79 (3H, m), 3.63 (3H, m), 2.44 (2H, tr), 2.13-2.03 (2H,m) |
| S | £ u | £ o | £ 0 | £ 0 | £ o | £ u | £ 0 | £ |
| X | X | X | X | X | X | X | X | |
| £ 8 δ | X § X 0 | X § X u | CHOC2H5 | CHOiPropyl | CHOiPropyl | CHOiPropyl | o | |
| % | X | X | X | X | X | X | X | X |
| * | X | X | X | X | X | X | X | X |
| cn PÍ | X | X | X | X | X | X | X | X |
| CM PÍ | X | X | X | X | X | X | X | X |
| s | CM | CM | CM | CM | CM | CM | CM | |
| 0* PÍ | X | X | X | X | X | X | X | X |
| 00 PÍ | X | X | X | m X Q | δ | X | X | X |
| c— | cn X o | X | cn X 0 | cn δ | £ o | X | cn X 0 | X |
| z | 13.12 | 13.13 | 13.14 | 13.15 | 13.16 | 13.17 j | 13.18 | 13.19 |
0050/46142
234
| Phys. Daten | NMR (CDC13), 300 MHz: δ [ppm] = 17.25 (lH,s), 8.14 (lH,d),7.33 (1H, d), 3.87 (1H, m), 3.69-3.58 (1H, m), 3.28 (1H, m), 2.96-2.79 (2H, m), 2.62 (3H, s), 2.57-2.44 (2H, m), 2.40-2.13 (2H,m), 1.15 (3H, d) | NMR (CDCI3), 300 MHz: δ [ppm] 17.30 (1H, m), 8.13 (1H, d), 7.34 (1H, d), 3.82 (1H, m), 3.64 (1H, m), 3.40-3.25 (1H, m), 2.91 (1H, m), 2.70 (2H, s), 2.64 (3H, s), 2.31 (2H, s), 1.15 (6H.s) | os N· rR r—» O ,O , | ch s© o | t/S r* O 0. | ws o* u p , £ | Fp [°C]: 192 | | os N rR u p . | Fp [°C]: 126 | 00 os 0 p , £ | rR Os O p , £” | NMR (d6—DMSO), 300 MHz: δ [ppm] - 8.05 (1H, d), 7.69 (1H, d), 4.18 (2H, m), 3.31 (2H, m), 2.62 (4H, m), 1.96 (2H, m) | 8 σ 2_, ,ο. Ix> | Fp [°C]: 104 |
| S | £ u | £ o | £ u | £ Q | £ o | £ υ | £ 0 | £ 0 | £ u | £ Q | £ Q | O | U | □ |
| u | z | X | X | X | X | X | X | X | X | X | X | X | X | X |
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| Bá | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| rs cd | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
| n PÍ | X | X | X | X | X | X | X | X | X | X | X | X | X | X |
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0050/46142 • ·
- 235 -
| Phys. Daten | Os O o , CU b | © 00 o £· | s Os O ,o , r°* | © © O 2_. £* | CM Os o o . £* | Fp [°CJ: 107 | | ‘H-NMRtCDCh), 250 MHz: δ [ppm] = 16.8,8.20,7.32, 4.33,3.37, 2.82,2.45,2.08,1.35 | Os Os u o , £* | 09 a © Os u ,ο , | CN 00 I Os Γ** O .o , & Um | Γ*· CA © CA u 2_. £* | 00 ^4 u o , £ | o O o , í£* | Ζ“ζ\ 05 a © Os u 2(£ | 00 G 2-. £ | s b’ O , | © oo b' o , | 5 ^4 b' 2_. o. n. | 3 ^4 b o , £* | © w4 b' O . íř | 00 Os u s_. ,o. u< |
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• · · ·
- 236 • · · ·
CM
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Dálen
Tabulka 15: Sloučeniny formule
| | te g CL S ta | s | 8 2 r* *4 | 00 9s 44 |
| s | <*» X y | X y | rs δ |
| X | X | X | |
| 0=0 | 8 | ! § | |
| rs OÍ | X | X | X |
| rj cd | X | X | X |
| cs | o | o | o |
| σ» Od | X | X | X |
| 00 ftí | X | X | rs δ |
| £ Od | X | J? δ | rs X y |
| ž‘ | tri | 3 | trs |
_____________Fp[°C]
1-Methyhhio-cyclopropyl 0 (CHjJž 0=0 H CH3 151-153
1-Methyhhio-cyclopropyl 2 (CH^ CM) H CIh 133-135
238
Sloučeniny I a jejich zemědělsky využitelné soli jsou vhodné jako herbicidy, a to jak ve formě směsí isomerů, tak i ve formě čistých isomerů. Herbicidní přípravky obsahující I potlačují velmi dobře růst rostlin na plochách nepoužívaných pro pěstování kulturních rostlin zejména při vysokých používaných dávkách. V kulturách jako je pšenice, rýže, kukuřice, sója a bavlna působí tyto látky proti plevelům a nežádoucím trávám bez poškozování kulturních rostlin. Tento efekt se uplatňuje především při nízkých používaných dávkách .
Vzhledem k mnohostrannému způsobu použití je možno sloučeniny I resp. prostředky které je obsahují používat i při pěstování řady dalších kulturních rostlin pro potlačování růstu nežádoucích plevelů. Tyto látky je možno použít např. pro následující kultury:
Allium cepa, Ananas co^mosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec, altissima, Beta vulgaris spec, rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoisensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Manihot esculenta, Medicago sativa, Musa spec., Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec., Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Ribes sylestre, Ricinus communis, Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (S.vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera, Zea mays.
Kromě toho je možno sloučeniny I používat i v kulturách, které jsou vyšlechtěny včetně genově-technických metod tak, že snášejí účinky herbicidů.
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- 239 Sloučeniny I resp. herbicidní prostředky které je obsahují je možno používat např. ve formě postřikových vodných roztoků, prášků, suspenzí, a rovněž ve formě vysokoprocentních vodných, olejových nebo jiných suspenzí nebo disperzí, emulzí, past, poprašovacích prostředků, posypových prostředků nebo granulátů které je možno postřikovat, rozstřikovat ve formě mlhy, rozprašovat, rozsypávat nebo rozlévat. Způsoby aplikace se řídí podle účelu použití; tyto způsoby by však měly v každém případě umožňovat co nejjemnější rozptýlení účinné látky podle tohoto vynálezu.
Jako inertní přísady přicházejí v úvahu frakce minerálních olejů se středním až vysokým bodem varu, jako je petrolej nebo motorová nafta, dále dehtové oleje a rovněž oleje rostlinného nebo živočišného původu, alifatické, cyklické a aromatické uhlovodíky, např. parafin, tetrahydronaftalen, alkylnaftaleny nebo jejich deriváty, alkylbenzeny nebo jejich deriváty, methanol, ethanol, propanol, butanol, cyklohexanol, cyklohexanon nebo silně polární rozpouštědla, jako je Nmethylpyrrolidon nebo voda.
Vodné aplikační formy je možno připravovat přídavkem vody z koncentrovaných emulzí, suspenzí, past, smáčitelných prášků nebo granulátů dispergovatelných ve vodě. Pro přípravu emulzí, past nebo olejových disperzí je možno používat substráty jako takové nebo rozpuštěné v oleji nebo v rozpouštědle, které se potom homogenizují ve vodě s použitím smáčecích, adhezivních, dispergačních nebo emulgačních prostředků. Koncentráty vhodné k ředění vodou je možno připravovat i z účinné látky, smáčecích, adhezivních, dispergačních nebo emulgačních prostředků a případně i rozpouštědel nebo oleje.
Jako látky zvyšující účinek (adjuvancia) je možno používat soli alkalických kovů, kovů alkalických zemin nebo amonné soli aromatických sulfonových kyselin, jako např. lignin-, fenyl-, naftyl- a dibutylnaftylsulfonových kyselin, a dále mastných kyselin, alkyl- a arylsulfonáty, alkyl-, laurylethersulfáty a sulfáty alifatických alkoholů s dlouhým řetězcem, jakož i soli sulfatovaných hexa-, hepta- a oktadekanolú a glykoletherů alifatických alkoholů s dlouhým řetězcem, kondenzační produkty sulfonovaného naftalenu a jeho derivátů s formaldehydem, kondenzační produkty naftalenu resp. naftalensulfonových kyselin s fenolem a formaldehydem, polyoxyethylenoktylfenolethery, ethoxylované isooktyl-, oktyl240 ” ··· ···· «· ·· «· nebo nonylfenoly, alkylfenyl-, tribiitylfenylpoíyglykolethery, alkylarylpolyetheralkoholy, isotridecylalkohol, kondenzáty alifatických alkoholů s dlouhým řetězcem s ethylenoxidem, ethoxylovaný ricinový olej, polyoxyethylenallkylethery nebo polyoxypropylenalkylethery, laurylalakoholpolyglykoletheracetáty, sorbitové estery, lignin-sulfitové výluhy nebo methylcelulóza.
Práškovité, posypové nebo rozprašovací prostředky je možno vyrábět míšením nebo společným rozemíláním aktivních látek s pevnými nosiči.
Granuláty, např. obalované, impregnované a homogenní granuláty je možno vyrábět vázáním účinné látky na pevné nosiče. Jako pevné nosiče se používají minerální hlinky jako jsou křemeliny, silikagely, silikáty, mastek, kaolin, vápenec, vápno, křída, bolus, spraš, jíl, dolomit, diatomická hlinka, sírany vápenatý a hořečnatý, oxid hořečnatý, mleté plasty, hnojivá jako jsou síran amonný, fosforečnan amonný, dusičnan amonný, močovina a rostlinné produkty jako je obilná moučka, moučka ze stromové kůry, moučka ze dřeva nebo z ořechových slupek, práškovitá celulóza nebo jiné pevné nosiče.
Koncentrace účinných látek I v přípravcích upravených pro použití se může ve značné širokém rozmezí měnit. Použité receptury obsahují zpravidla 0,001 až 98 hmotn. %, zejména 0,01 až 95 hmotn. % minimálně jedné účinné složky. Tyto účinné látky mají přitom čistotu 90 až 100 %, přednostně 95 až 100 % (podle NMR-spekter).
Sloučeniny I podle tohoto vynálezu mohou být použity např. v následujících recepturách:
I. 20 hmotn. dílů sloučeniny č.13.1 bylo rozpuštěno ve směsi skládající se z 80 hmotn. dílů alkylbenzenu, 10 hmotn.dílů adičního produktu 8 až 10 molů ethylenoxidu na 1 mol N-monoethanolamidu kyseliny olejové, 5 hmotn. dílů vápenaté soli dodecylbenzensulfonové kyseliny a 5^ hmotn. dílů adičního produktu 40 molů ethylenoxidu na 1 mol ricinového oleje. Vlitím a jemným rozptýlením tohoto roztoku do 100000 hmotn. dílů vody se získá vodná disperze, která obsahuje 0,02 hmotn.% účinné látky.
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II. 20 hmotn. dílů sloučeniny č.13.3 bylo rozpuštěno ve směsi skládající se ze 40 hmotn. dílů cyklohexanonu, 30 hmotn.dílů isobutanolu, 20 hmotn.dílú adičního produktu 40 molů isooktylfenolu a 10 hmotn.dílú adičního produktu 40 molů ethylenoxidu na 1 mol ricinového oleje. Vlitím a jemným rozptýlením tohoto roztoku do 100000 hmotn. dílů vody se získá vodná disperze, která obsahuje 0,02 hmotn.% účinné látky.
III. 20 hmotn. dílů účinné látky č.13.8 bylo rozpuštěno ve směsi skládající se ze 25 hmotn. dílů cyklohexanonu, 65 hmotn.dílú frakce minerálního oleje s bodem varu 210 až 80°C a 10 hmotn.dílú adičního produktu 40 molů ethylenoxidu na 1 mol ricinového oleje. Vlitím a jemným rozptýlením tohoto roztoku do 100000 hmotn. dílů vody se získá vodná disperze, která obsahuje 0,02 hmotn.% účinné látky.
IV. 20 hmotn.dílú účinné látky č.13.9 bylo dobře promíseno se 3 hmotn.díly sodné soli diisobutylnaftalen-a-sulfonové kyseliny, 17 hmotn.díly sodné soli ligninsulfonové kyseliny ze sulfitových výluhů a 60 hmotn.díly práškovitého silikagelu a tato směs byla rozemleta v kladivovém mlýnu. Jemným rozptýlením této směsi do 20000 hmotn. dílů vody se získá postřik, který obsahuje 0,1 hmotn.% účinné látky.
V. 3 hmotn.díly účinné látky č. 13.5 byly smíseny s 97 hmotn.díly jemného kaolinu. Získá se tak poprašovací prostředek, který obsahuje 3 hmotn.% účinné látky.
VI. 20 hmotn.dílú účinné látky č. 13.15 bylo důkladně promíseno se 2 hmotn.díly vápenaté soli dodecylbenzensulfonové kyseliny, 8 hmotn.díly polyglykoletheru s alifatickými alkoholy s dlouhým uhlíkatým řetězcem, 2 hmotn. díly sodné soli kondenzátu fenol-močovina-formaldehyd a s 68 hmotn.díly parafinického minerálního oleje. Tímto způsobem se získá stabilní olejová disperze.
VII. 1 hmotn. díl účinné látky č. 13.16 byl rozpuštěn ve směsi, skládající se ze 70 hmotn.dílú cyklohexanonu, 20 hmotn.dílú ethoxylovaného isooktylfenolu a 10 hmotn.dílú ethoxylovaného ricinového oleje. Byl tak získán stabilní emulzní koncentrát.
Vlil. 1 hmotn.díl účinné látky č.13.17 byl rozpouštěn ve směsi, skládající se z 80 hmotn.dílú cyklohexanonu a 20 hmotn.dílú preparátu Wettol ® EM 31 (=neionogenní emulgátor na bázi ethoxylovaného ricinového oleje). Byl tak získán stabilní emulzní koncentrát.
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·«««··· ·♦ ·· ··
Aplikaci účinné látky I resp. herbicidních prostředků je možno provádět před výsadbou nebo po vzejití rostlin. Jestliže některé rostliny snášejí některé účinné látky hůře, je třeba používat takové způsoby aplikace, při nichž je herbicidní prostředek rozptylován promocí rozstřikovacích zařízení tak, aby listy těchto citlivých kulturních rostlin nebyly zasaženy, nýbrž aby se účinná látka dostala na listy nežádoucích plevelů rostoucích níže nebo na nezakrytou plochu půdy (postdirected, lay-by).
Použitá dávka účinné látky se pohybuje v závislosti na účelu použití herbicidních přípravků, roční době, cílových rostlinách a stadiu růstu od 0,001 do 3,0, přednostně 0,01 až 1,0 kg aktivní složky (a.S.) na hektar.
Pro rozšíření spektra účinnosti a pro dosažení synergických efektů je možno benzoylderiváty I mísit s četnými zástupci jiných skupin herbicidních nebo růstových látek a tyto látky aplikovat společně. Tak např. je možno jako druhou složku směsi používat 1,2,4-thiadiazoly, 1,3,4-thiadiazoly, amidy, aminofosforečnou kyselinu a její deriváty, aminotraizoly, anilidy, aryloxy/heteroaryloxyalkanové kyseliny a jejich deriváty, benzoovou kyselinu a její deriváty, benzothiadiazinony, 2-(hetaroyl/aroyl)-1,3-cyklohexandiony, heteroarylarylketony, benzylisoxazolidinon, meta-CF3-fenylderiváty, karbamáty, chinolinkarboxylové kyseliny a jejich deriváty, chloracetanilid, deriváty cyklohexan-1,3dionu, diaziny, dichlorpropionovou kyselinu a její deriváty, dihydrobenzofuran, dihydrofuran-3-on, dinitroanilin, dinitrofenol, difenylether, dipyridyl, halogenkarboxylové kyseliny a jejich deriváty, močoviny, 3-fenyluracil, imidazol, imidazolinon, N-fenyl-3,4,5,6-tetrahydroftalimid, oxadiazoly, oxirany, fenoly, estery aryloxy- a heteroaryloxyfenoxypropionových kyselin, fenyloctovou kyselinu a její deriváty, 2-fenylpropionovou kyselinu a její deriváty, pyrazoly, fenylpyrazoly, pyridazin, pyridinkarboxylové kyseliny a jejich deriváty, pyrimidylethery, sulfonamidy, sulfonylmočoviny, triaziny, triazinony, triazolkarboxamidy a uráčily.
Kromě toho může být někdy zapotřebí přidávat sloučeniny I samotné nebo v kombinaci s jinými herbicidy do dalších prostředků pro ochranu rostlin a tyto prostředky potom aplikovat společné, např. s prostředky pro ochranu proti škůdcům nebo proti fytopatogenním plísním resp. bakteriím. Důležitá je i mísitelnost s roztoky minerálních solí, které se přidávají při nedostatku živin a stopových prvků. Je možno přidávat i oleje a olejové koncentráty, které nejsou fytotoxické.
• · • · • · _ _ · ·«»······
/. 4 J β< ···· · ······· ·· ·· ·*
Příklady použití
Herbicidní účinky benzoylderivátů formule I je možno prokázat pokusy provedenými ve skleníku:
Jako nádoby pro kultivaci byly použity plastové květináče se substrátem, kterým byla písčitá zem s cca 3 % humusu. Semena testovacích rostlin byla vysévána odděleně podle druhů.
Při použití herbicidů před vzejitím rostlin byly účinné látky suspendované nebo emulgované ve vodě aplikovány ihned po výsevu pomocí trysek s jemným rozprašováním. Kultivační nádoby byly jemé zality, aby se podpořilo klíčení a růst, a potom byly zakryty průhlednými plastovými víky, dokud rostliny nevzešly. Tyto kryty měly příznivý vliv na rovnoměrné klíčení testovacích rostlin, pokud nebyly poškozovány působením účinných látek.
Pro sledování ošetření rostlin pro jejich vzejití byly zkušební rostliny v závislosti na jejich růstové formě nejprve vypěstovány do výšky 3 až 15 cm a teprve potom byly ošetřeny účinnými látkami suspendovanými nebo emulgovanými ve vodě. Tyto zkušební rostliny byly proto buď vysety přímo a pěstovány ve stejných kultivačních nádobách, nebo byly nejprvne pěstovány oddělené jako sazenice a několik dnů před ošetřením byly přesazeny do zkušebních kultivačních nádob.
Použitá dávka pro tuto dodatečnou úpravu byla 0,5 nebo 0,25 kg účinné substance na 1 ha.
Tyto rostliny byly podle jednotlivých druhů udržovány na teplotě 10 až 25 °C resp. 20 až 35°C. Zkušební doba byla 2 až 4 týdny. V průběhu této doby byly rostliny ošetřeny a byla vyhodnocena jejich reakce na jednotlivá ošetření.
Hodnocení bylo prováděno podle stupnice od 0 do 100. Přitom hodnocení 100 znamenalo žádný vzrůst rostlin resp. úplné zničení alespoň nadzemních částí rostlin a 0 znamenala žádné poškození nebo normální průběh růstu.
Druhy rostlin pěstovaných při pokusech ve skleníku byly následující:
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| Latinský název | Německý název | Anglický název | český název |
| Chenopodium album (CHEAL) | WeiBer GánsefuB | lambsquarters (goosefoot) | merlík |
| Ipomoea subspecies (IPOSS) | Prunkwindearten | morningglory | povíjnice |
| Sinapis alba (SINAL) | WeiBer Senf | white mustard | hořčice bílá |
| Solanum nigrům (SOLNÍ) | Schwarzer Nachtschatten | black nightshade | lilek černý |
| Triticum aestivum (TRZAS) | Sommerweizen | summer wheat | pšenice jarní |
| Zea mays (ZEAMX) | Mais | Indián com | kukuřice |
Tabulka 17
Herbicidní aktivita pň ošetření vzrostlých rostlin ve skleníku
| Příkl.č. | 13.3 | |
| Použitá dávka (kg/ha akt.subst.) | 0.5 | 0,25 |
| Zkušební rostlina | Poškození v % | |
| TRZAS | 0 | 0 |
| CHEAL | 95 | 95 |
| SINAL | 95 | 95 |
| SOLNÍ | 100 | 95 |
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Tabulka 18
Herbicidní aktivita při při ošetření vzrostlých rostlin ve skleníku
| Příkl.č. | 13.13 | |
| Použitá dávka (kg/ha akt.subst.) | 0.5 | 0,25 |
| Zkušební rostlina | Poškození v % | |
| TRZAS | 10 | 0 |
| CHEAL | 95 | 95 |
| IPOSS | 100 | 100 |
| SOLNÍ | 100 | 100 |
JUDr. Ivan KOREČEK
Advokátní a patentová kancelář 160 00 Praha 6. Na baště sv. Jiří 9 P.O. BOX 275, 160 41 Praha 6
Česká republika • ·
Claims (13)
- PATENTOVÉ NÁROKY1. Benzoylderiváty formule I, kde jednotlivé substituenty mají následující význam:
L,M vodík, C1-C6-alkyl, C2-C6-alkenyl, C2-C6 -alkinyl, C1-C4 -alkoxyl, přičemž tyto skupiny mohou být případně substituovány jedním až pěti halogenovými atomy nebo C1-C4-alkoxyly; halogen, kyanoskupina, nitroskupina, skupina -(A)m-S(O)nR1 nebo skupina -(A)m-CO-R2; Y skupina skládající se z C=O, C=N-R3, CR7-NR5R6, CR7OR8, CR10R11, CR7SR8; 1,3-dioxanyl nebo 1,3-dioxolanyl substituovaný vodíkem nebo C1-C4 -alkylem; heteroatom ze skupiny kyslík, síra a dusík; X skládá se z řetězce (-CR12R13-), (-CR12R13-CR21R22-), (-CR12=R13-), (-CR12R13-CR12=R13-); NR23 vazba mezi X a Y může být nasycená nebo nenasycená;A 0, NR14; m nula nebo jedna; n R1 R2 R3 nula, jedna nebo dvě; C1-C4 alkyl, C1-C4 haloalkyl nebo NR14; C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxyl nebo NR14; vodík, -NR9R4; C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxyl, C1-C6 haloalkoxyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkinyl; • · • ·- 247 - ** ········♦···· případně substituovaný fenyl, přičemž těmito substituenty mohou být C1-C4 alkyl, C1-C4 alkoxyl, C1-C4 haloalkoxyl, C1-C4 haloalkyl, halogen, kyanoskupina, nitroskupina; případně substituovaný benzyl, přičemž těmito substituenty mohou být C1-C4 alkyl, C1-C4 alkoxyl, C1-C4 haloalkoxyl, C1-C4 haloalkyl, halogen, kyanoskupina, nitroskupina;případně substituovaná benzoyloxyskupina, přičemž těmito substituenty mohou být C1-C4 alkyl, C1-C4 alkoxyl, C1-C4 haloalkoxyl, C1-C4 haloalkyl, halogen, kyanoskupina, nitroskupina;R4 vodík, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 alkinyl,C=O-NR14;případné substituovaný fenyl, přičemž těmito substituenty mohou být C1-C4 alkyl, C1-C4 alkoxyl, C1-C4 haloalkoxyl, C1-C4 haloalkyl, halogen, kyanoskupina, nitroskupina;případně substituovaný benzyl, přičemž těmito substituenty mohou být C1-C4 alkyl, C1-C4 alkoxyl, C1-C4 haloalkoxyl, C1-C4 haloalkyl, halogen, kyanoskupina, nitroskupina;R9 vodík, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 alkinyl,C=O-NR14;případně substituovaný fenyl, přičemž těmito substituenty mohou být C1-C4 alkyl, C1-C4 alkoxyl, C1-C4 haloalkoxyl, C1-C4 haloalkyl, halogen, kyanoskupina, nitroskupina;případně substituovaný benzyl, přičemž těmito substituenty mohou být C1-C4 alkyl, C1-C4 alkoxyl, C1-C4 haloalkoxyl, C1-C4 haloalkyl, halogen, kyanoskupina, nitroskupina;R5, R6 nezávisle na sobě vodík, C1-C6 alkyl, C2-C6 alkenyl, C1-C4 haloalkyl, C2-C6 haloalkenyl, C1-C6 alkoxyl, C1-C6 haloalkoxyl;případně substituovaný fenyl, přičemž těmito substituenty mohou býtC1-C4 alkyl, C1-C4 alkoxyl, C1-C4 haloalkoxyl, C1-C4 haloalkyl, halogen, kyanoskupina, nitroskupina;- 248 -případné substituovaný benzyl, přičemž těmito substituenty mohou být C1-C4 alkyl, C1-C4 alkoxyl, C1-C4 haloalkoxyl, C1-C4 haloalkyl, halogen, kyanoskupina, nitroskupina; R7 vodík, C1-C6 alkyl, C1-C4 alkoxyl, C1-C4 haloalkyl, C1-C4 haloalkoxyl; případně substituovaný fenyl, přičemž jako substituenty mohou být jeden až tři halogeny, C1-C4 alkyl, C1-C4 alkoxyl, C1-C4 haloalkoxyl, nitroskupina; vazbu mohou tvořit R7 a R21 nebo R7 a R23 nebo R7a R12; R8 vodík, C1-C6 alkyl, C1-C4 halogenalkyl, případně substituovaný fenyl, přičemž těmito substituenty mohou být C1-C4 alkyl, C1-C4 alkoxyl, C1-C4 haloalkoxyl, C1-C4 haloalkyl, halogen, kyanoskupina, nitroskupina; případné substituovaný benzyl, přičemž těmito substituenty mohou být C1-C4 alkyl, C1-C4 alkoxyl, C1-C4 haloalkoxyl, C1-C4 haloalkyl, halogen, kyanoskupina, nitroskupina; R10,R11 nezávisle na sobě vodík, C1-C^6 alkyl; případné substituovaný fenyl, přičemž těmito substituenty mohou být jeden až tři halogeny, C1-C4 alkyl, C1-C4 alkoxyl, C1-C4 haloalkoxyl, nitroskupina; vazbu mohou tvořit R10 a R12 nebo R10 a R23 nebo R10a R21; r12,r13 nezávisle na sobě vodík, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxyl, C1-C6 haloalkoxyl; případně substituovaný fenyl, přičemž jako substituenty mohou být C1-C4 alkyl, C1-C4 alkoxyl, C1-C4 haloalkoxyl, C1-C4 haloalkyl, halogen, kyanoskupina, nitroskupina; R14 C1-C4 alkyl; R21 vodík, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxyl, C1-C6 haloalkoxyl; případně substituovaný fenyl, přičemž jako substituenty mohou být C1-C4 alkyl, C1-C4 alkoxyl, C1-C4 haloalkoxyl, C1-C4 haloalkyl, halogen, kyanoskupina, nitroskupina; ·« · · · * · • · · · ·- 249 - :······· ··R22 vodík, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxyl, C1-C6 haloalkoxyl; případně substituovaný fenyl, přičemž jako substituenty mohou být C1-C4 alkyl, C1-C4 alkoxyl, C1-C4 haloalkoxyl, C1-C4 haloalkyl, halogen, kyanoskupina, nitroskupina; R23 vodík, C1-C6 alkyl, C2-C6 alkenyl, C1-C6 alkoxyl; případné fenyl nebo benzyl substituovaný C1-C4 alkylem, C1-C4 alkoxylem, C1-C4 haloalkoxylem, C1-C4 haloalkylem, halogenem, kyanoskupinou nitroskupinou; Q v poloze 2 vázaný cyklohexan-1,3-dionový kruh formule II kdeR16, R18 a R20 představují vodík nebo alkyl C1-C4,R19 představuje vodík, C1-C4 alkyl nebo skupinu -COOR14;R17 představuje vodík, C1 až C4 alkyl, C3-C4 cykloalkyl, přičemž tyto skupiny mohou případně nést jeden až tři z následujících substituentů: halogen C1-C4 alkylthio nebo C1-C4 alkoxyl, neboR17 představuje tetrahydropyranyl-3, tetrahydropyranyl-4 nebo tetrahydrothiopyranyl-3, nebo • ·- 250 - : :• · · · · · ·R17 a R20 vytvářejí vzájemnou vazbu nebo tvoří tří- až šestičlenný karbocyklický kruh, přičemž v případě, že Y = 0=0, není X rovno NR23, jakož i zemědělsky využitelné soli. - 2. Benzoylderiváty formule la, kde L znamená vodík, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkinyl, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 halogenalkyl, C1-C4 halogenalkoxy, C1-C4 halogenalkylthio, C1-C4 alkylsulfonyl, halogen, nitroskupinu nebo kyanoskupinu a M znamená vodík, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkinyl, 01-04 alkoxy, 0104 alkylthio, C1-C4 halogenalkyl, C1-C4 halogenalkoxy, C1-C4 halogenalkoxy, 01-04 halogenalkylthio, 01-04 alkylsulfonyl, halogen, nitroskupinu nebo kyanoskupinu a Q, X, n a Y mají význam uvedený v nároku 1, přičemž v případě, že Y = 0=0 , není X rovno NR23.
- 3. Benzoylderiváty formule Ib kde L znamená C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkinyl, C1-C4 alkoxy, 01-04 halogenalkyl, 01-04 halogenalkoxy, halogen, nitroskupinu nebo kyanoskupinu aM znamená vodík, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkinyl, C1-C4 alkoxy, 01• · • » ··- 251 • · ·· • · · • · · • · · ·· • ·· • ·· ·C4 halogenalkyl, C1-C4 halogenalkoxy, halogen, nitroskupinu nebo kyanoskupinu a Q, X, n a Y mají význam uvedený v nároku 1, přičemž v případě, že Y = C=O , není X rovno NR23.
- 4. Benzoylderiváty formule I podle patentového nároku 1, kde substituenty L resp. M znamenají vodík, methyl, methoxyl, chlor, kyanoskupoinu, nitrosksupinu, trifluormethyl.
- 5. Benzoylderiváty formule Ic, kde L znamená vodík, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkinyl, C1-C4 alkoxy, C1-C4 halogenalkyl, C1-C4 halogenalkoxy, halogen, nitroskupinu nebo kyanoskupinu a M znamená vodík, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkinyl, C1C4 alkoxy, C1-C4 halogenalkyl, C1-C4 halogenalkoxy, halogen, nitroskupinu nebo kyanoskupinu a Q, X, n a Y a dále R22, R21, R12 a R13 mají význam uvedený v nároku 1.
- 6. Benzoylderiváty formule Id,Id kde L znamená vodík, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkinyl, C1-C4 alkoxy,C1-C4 halogenalkyl, C1-C4 halogenalkoxy, halogen, nitroskupinu nebo- 252 • ···· kyanoskupinu a M znamená vodík, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkinyl, CICÁ alkoxy, C1-C4 halogenalkyl, C1-C4 halogenalkoxy, halogen, nitroskupinu nebo kyanoskupinu a Q, X, n a Y a dále R12 a R13 mají význam uvedený v patentovém nároku 1.
- 7. Benzoylderiváty formule Ie,Ie kde L znamená vodík, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkinyl, C1-C4 alkoxy, C1-C4 halogenalkyl, C1-C4 halogenalkoxy, halogen, nitroskupinu nebo kyanoskupinu a M znamená vodík, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkinyl, CICÁ alkoxy, C1-C4 halogenalkyl, C1-C4 halogenalkoxy, halogen, nitroskupinu nebo kyanoskupinu a Q, X, n a Y a dále R12 a R13 mají význam uvedený v patentovém nároku 1.
- 8. Benzoylderiváty formule I podle nároku 1, kde n je jedna nebo dvě a Y znamená CR7-OR8, přičemž R7 a R8 mají význam uvedený v nároku 1.
- 9. Postup výroby sloučeniny formule I podle patentového nároku 1, vyznačující se tím, že příslušné výchozí látky formule II253 se acylují chloridem kyseliny formule lila nebo kyselinou lllb, přičemž L, Μ, X, n a Y mají význam podle patentového nároku 1, a tento acylovaný produkt se přeměňuje za přítomnosti katalyzátoru na sloučeniny I.
- 10. Herbicidní prostředky obsahující minimálně jeden benzoylderivát formule I podle patentového nároku I a běžné inertní přísady.
- 11. Postup pro potlačování nežádoucího růstu rostlin vyznačující se tím, že se na rostliny nebo jejich okolní prostředí působí herbicidně účinným množstvím benzoylderivátu formule 1 podle patentového nároku 1.
- 12. Benzoylderiváty formule III c kde T, L, Μ, X, n a Y mají následující význam:T chlor, OH nebo C1-C4 alkoxy;L vodík, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkinyl, C1-C4 alkoxy, C1-C4 halogenalkyl, C1-C4 halogenalkoxy, C1-C4-alkylthio, C1-C4 halogenthioalkyl, C1-C4 alkylsulfonyl, halogen, nitroskupina nebo kyanoskupina;• · • · · · • ·JUDr. Ivan KOREČEKAdvokátní a patentová kancelář 160 00 Praha 6, Na baště sv. Jiří 9 P.O. BOX 275, 160 41 Praha 6Česká republika .- >55 -12. Benzoylderiváty formule III cIIIc kde T, L, Μ, X, n a Y mají následující význam:T chlor, OH nebo C1-C4 alkoxy;L vodík, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkinyl, C1-C4 alkoxy, C1-C4 halogenalkyl, C1-C4 halogenalkoxy, C1 -C4-alkylthio, C1-C4 halogenthioalkyl, C1-C4 alkylsulfonyl, halogen, nitroskupina nebo kyanoskupina;M C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkinyl, C1-C4 alkoxy, C1-C4 halogenalkyl, C1-C4 halogenalkoxy, C1-C4-alkylthio, C1-C4 halogenthioalkyl, C1-C4 alkylsulfonyl, halogen, nitroskupina nebo kyanoskupina;X, Y, n podle patentového nároku 1, kromě případu, kdy X = (-CH2CH2-) nebo (_CH2“) a Y = C=O nebo kyslík, takže potom L a M nemohou představovat současně vodík a jestliže je Y = C=O, nemůže X odpovídat NR23
- 13. Benzoylderiváty formule llldL15Γ- * kde T, L, Μ, X, n a Υ mají následující význam:T chlor, OH nebo C1-C4 alkoxy;L C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkinyl, C1-C4 alkoxy, C1-C4 halogenalkyl, C1-C4 halogenalkoxy, C1-C4-alkylthio, C1-C4 halogenthioalkyl, C1-C4 alkylsulfonyl, halogen, nitroskupina nebo kyanoskupina;M vodík, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkinyl, C1-C4 alkoxy, C1-C4 halogenalkyl, C1-C4 halogenalkoxy, C1-C4-alkylthio, C1-C4 halogenthioalkyl, C1-C4 alkylsulfonyl, halogen, nitroskupina nebo kyanoskupina;X, Y, n podle patentového nároku 1, přičemž v případě, že je Y = C=O, nemůže X odpovídat NR23.KOREČEK ntová kancelář baště sv. Jiří 9 41 Praha 6JUDr. IvanAdvokátní a pa 160 00 Praha 6.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19532311A DE19532311A1 (de) | 1995-09-01 | 1995-09-01 | Benzoylderivate |
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| US (1) | US6054414A (cs) |
| EP (1) | EP0847394A1 (cs) |
| JP (2) | JP3027196B2 (cs) |
| KR (1) | KR100446200B1 (cs) |
| CN (1) | CN1100052C (cs) |
| AR (1) | AR003688A1 (cs) |
| AU (1) | AU717015B2 (cs) |
| BG (1) | BG102297A (cs) |
| BR (1) | BR9610208A (cs) |
| CA (1) | CA2227934A1 (cs) |
| CZ (1) | CZ60198A3 (cs) |
| DE (1) | DE19532311A1 (cs) |
| EA (1) | EA001202B1 (cs) |
| GE (1) | GEP20012443B (cs) |
| HU (1) | HUP9802430A3 (cs) |
| IL (1) | IL123165A (cs) |
| MX (1) | MX9801292A (cs) |
| NZ (1) | NZ316942A (cs) |
| PL (1) | PL325204A1 (cs) |
| SK (1) | SK24398A3 (cs) |
| TW (1) | TW334430B (cs) |
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| ZA (1) | ZA967313B (cs) |
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| WO1998040366A1 (de) * | 1997-03-10 | 1998-09-17 | Basf Aktiengesellschaft | Saccharin-5-carbonyl-cyclohexan-1,3,5-trionderivate, deren herstellung und deren verwendung als herbizide |
| GB9807779D0 (en) | 1998-04-09 | 1998-06-10 | Ciba Geigy Ag | Organic compounds |
| IL139276A0 (en) * | 1998-04-30 | 2001-11-25 | Basf Ag | Cyclohexenondioxthio chromanoyl derivatives |
| US6756343B1 (en) | 1998-10-06 | 2004-06-29 | Idemitsu Kosan Co., Ltd. | Triketone derivatives and herbicide |
| EP1144401A3 (de) * | 1998-12-15 | 2002-09-11 | Basf Aktiengesellschaft | Thiochromanoylcyclohexenon-derivate |
| EP1177179A1 (de) * | 1999-05-07 | 2002-02-06 | Basf Aktiengesellschaft | Benzoheterocyclylcyclohexenone und ihre verwendung als herbizide |
| AU5210900A (en) * | 1999-05-07 | 2000-11-21 | Basf Aktiengesellschaft | Cyclohexenone dioxothiochromanoyl derivatives |
| AR023255A1 (es) * | 1999-05-13 | 2002-09-04 | Idemitsu Kosan Co | Compuestos azoles y composiciones herbicidas que los contienen |
| JP2001002508A (ja) * | 1999-06-23 | 2001-01-09 | Idemitsu Kosan Co Ltd | 水稲用除草剤 |
| DE19929259A1 (de) * | 1999-06-25 | 2000-12-28 | Basf Ag | Cyclohexanon-Derivate von bicyclischen Benzoesäuren |
| AU2001241117A1 (en) * | 2000-04-04 | 2001-10-15 | Idemitsu Kosan Co. Ltd. | Fused-benzoyl derivatives and herbicide compositions containing the same |
| AR032779A1 (es) * | 2000-12-11 | 2003-11-26 | Basf Ag | Derivados de ciclohexenona de benzazolonas, acidos benzazolonacarboxilicos, agentes que contienen por lo menos un derivado de ciclohexenona, procedimiento para combatir el crecimiento indeseado de plantas y uso de dichos derivados como herbicidas |
| KR20030064864A (ko) * | 2000-12-21 | 2003-08-02 | 이데미쓰 고산 가부시키가이샤 | 벤조티오펜 유도체 및 이를 함유하는 제초제 조성물 |
| DE10215723A1 (de) * | 2002-04-10 | 2003-10-30 | Bayer Cropscience Gmbh | 3-Keto oder 3-Oximether substituierte Benzoylcyclohexandione |
| JP5844827B2 (ja) | 2011-03-15 | 2016-01-20 | バイエル・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングBayer Intellectual Property GmbH | N−(1,2,5−オキサジアゾール−3−イル)−、n−(テトラゾール−5−イル)−およびn−(トリアゾール−5−イル)ビシクロアリールカルボキサミド類およびそれらの除草剤としての使用 |
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| US3758522A (en) * | 1970-06-18 | 1973-09-11 | Leo Pharm Prod Ltd | Certain sulfamylbenzoic acids, esters thereof, and pharmaceutically acceptable salts thereof |
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| GB1432660A (en) * | 1973-10-30 | 1976-04-22 | Science Union & Cie | Piperazine derivatives processes for their preparation and and pharamacueitcal compositions containing them |
| DK139578A (da) * | 1978-03-29 | 1979-09-30 | Retroflame International | Brandhaemmende midler |
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| PH21446A (en) * | 1983-09-16 | 1987-10-20 | Stauffer Chemical Co | Certain 2-(2-substituted benzoyl)-1,3-cyclohexanediones |
| EP0137963B1 (en) * | 1983-09-16 | 1988-09-28 | Stauffer Chemical Company | Certain 2-(2-substituted benzoyl)-1,3-cyclohexanediones |
| LU85544A1 (fr) * | 1984-09-19 | 1986-04-03 | Cird | Derives heterocycliques aromatiques,leur procede de preparation et leur application dans les domaines therapeutique et cosmetique |
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| HU206242B (en) * | 1988-04-18 | 1992-10-28 | Sandoz Ag | Herbicidal compositions comprising substituted benzoyl bicyclodione derivatives as active ingredient |
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| AU626881B2 (en) * | 1988-07-14 | 1992-08-13 | F. Hoffmann-La Roche Ag | Benzofused heterocyclics used as pharmaceuticals |
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| AU675680B2 (en) * | 1992-10-14 | 1997-02-13 | Merck & Co., Inc. | Fibrinogen receptor antagonists |
| WO1994008988A1 (fr) * | 1992-10-15 | 1994-04-28 | Idemitsu Kosan Co., Ltd. | Derive de cyclohexanedione |
| DE4427995A1 (de) * | 1994-08-08 | 1996-02-15 | Basf Ag | Saccharinderivate |
| AU6777896A (en) * | 1995-08-25 | 1997-03-19 | E.I. Du Pont De Nemours And Company | Bicyclic herbicides |
| JP3052862U (ja) | 1998-04-01 | 1998-10-09 | サン.フレックス株式会社 | トルマリン効果を上げ得る板材製品被覆構造体 |
-
1995
- 1995-09-01 DE DE19532311A patent/DE19532311A1/de not_active Withdrawn
-
1996
- 1996-08-27 TW TW085110391A patent/TW334430B/zh not_active IP Right Cessation
- 1996-08-29 IL IL12316596A patent/IL123165A/en not_active IP Right Cessation
- 1996-08-29 CZ CZ98601A patent/CZ60198A3/cs unknown
- 1996-08-29 SK SK243-98A patent/SK24398A3/sk unknown
- 1996-08-29 NZ NZ316942A patent/NZ316942A/xx unknown
- 1996-08-29 GE GEAP19964208A patent/GEP20012443B/en unknown
- 1996-08-29 ZA ZA9607313A patent/ZA967313B/xx unknown
- 1996-08-29 PL PL96325204A patent/PL325204A1/xx unknown
- 1996-08-29 HU HU9802430A patent/HUP9802430A3/hu unknown
- 1996-08-29 KR KR10-1998-0701569A patent/KR100446200B1/ko not_active Expired - Fee Related
- 1996-08-29 WO PCT/EP1996/003800 patent/WO1997009324A1/de not_active Ceased
- 1996-08-29 CN CN96196604A patent/CN1100052C/zh not_active Expired - Fee Related
- 1996-08-29 BR BR9610208A patent/BR9610208A/pt unknown
- 1996-08-29 JP JP9510836A patent/JP3027196B2/ja not_active Expired - Fee Related
- 1996-08-29 US US09/029,680 patent/US6054414A/en not_active Expired - Fee Related
- 1996-08-29 MX MX9801292A patent/MX9801292A/es unknown
- 1996-08-29 AU AU69297/96A patent/AU717015B2/en not_active Ceased
- 1996-08-29 CA CA002227934A patent/CA2227934A1/en not_active Abandoned
- 1996-08-29 EP EP96930128A patent/EP0847394A1/de not_active Withdrawn
- 1996-08-29 EA EA199800233A patent/EA001202B1/ru not_active IP Right Cessation
- 1996-08-30 AR ARP960104187A patent/AR003688A1/es not_active Application Discontinuation
-
1998
- 1998-03-05 BG BG102297A patent/BG102297A/xx unknown
-
1999
- 1999-03-23 JP JP11120316A patent/JP2000026458A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CN1100052C (zh) | 2003-01-29 |
| SK24398A3 (en) | 1999-01-11 |
| JPH10510846A (ja) | 1998-10-20 |
| CA2227934A1 (en) | 1997-03-13 |
| TW334430B (en) | 1998-06-21 |
| KR19990044329A (ko) | 1999-06-25 |
| EA001202B1 (ru) | 2000-12-25 |
| EP0847394A1 (de) | 1998-06-17 |
| EA199800233A1 (ru) | 1998-10-29 |
| CN1194641A (zh) | 1998-09-30 |
| HUP9802430A3 (en) | 2002-01-28 |
| ZA967313B (en) | 1998-03-02 |
| IL123165A (en) | 2001-08-08 |
| US6054414A (en) | 2000-04-25 |
| AR003688A1 (es) | 1998-09-09 |
| JP3027196B2 (ja) | 2000-03-27 |
| WO1997009324A1 (de) | 1997-03-13 |
| PL325204A1 (en) | 1998-07-06 |
| KR100446200B1 (ko) | 2005-08-05 |
| DE19532311A1 (de) | 1997-03-06 |
| MX9801292A (es) | 1998-05-31 |
| IL123165A0 (en) | 1998-09-24 |
| AU6929796A (en) | 1997-03-27 |
| HUP9802430A2 (hu) | 1999-02-01 |
| GEP20012443B (en) | 2001-05-25 |
| AU717015B2 (en) | 2000-03-16 |
| NZ316942A (en) | 2000-01-28 |
| BR9610208A (pt) | 1999-02-02 |
| JP2000026458A (ja) | 2000-01-25 |
| BG102297A (en) | 1998-12-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PD00 | Pending as of 2000-06-30 in czech republic |