DK146536B - Fremgangsmaade til fremstilling af pyrido(3,4-e)-as-triaziner eller salte heraf - Google Patents
Fremgangsmaade til fremstilling af pyrido(3,4-e)-as-triaziner eller salte heraf Download PDFInfo
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- DK146536B DK146536B DK379972A DK379972A DK146536B DK 146536 B DK146536 B DK 146536B DK 379972 A DK379972 A DK 379972A DK 379972 A DK379972 A DK 379972A DK 146536 B DK146536 B DK 146536B
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- DK
- Denmark
- Prior art keywords
- pyrido
- nitro
- general formula
- triazines
- mixture
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 8
- HWMWVURSDQRNDO-UHFFFAOYSA-N (3-nitropyridin-4-yl)hydrazine Chemical compound NNC1=CC=NC=C1[N+]([O-])=O HWMWVURSDQRNDO-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- 150000002905 orthoesters Chemical class 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000000203 mixture Substances 0.000 description 14
- -1 N- (3-nitro-4-pyridylamino) -imino ether compound Chemical class 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- ODUCDPQEXGNKDN-UHFFFAOYSA-N nitroxyl Chemical class O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RYAFSYUBWRLFHS-UHFFFAOYSA-N 3-methylpyrido[3,4-e][1,2,4]triazine Chemical compound C1=CN=CC2=NC(C)=NN=C21 RYAFSYUBWRLFHS-UHFFFAOYSA-N 0.000 description 2
- SNAMXDPWMHPIQG-UHFFFAOYSA-N 3-phenylpyrido[3,4-e][1,2,4]triazine Chemical compound C1=CC=CC=C1C1=NN=C(C=CN=C2)C2=N1 SNAMXDPWMHPIQG-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000006476 reductive cyclization reaction Methods 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003918 triazines Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NDQXKKFRNOPRDW-UHFFFAOYSA-N 1,1,1-triethoxyethane Chemical compound CCOC(C)(OCC)OCC NDQXKKFRNOPRDW-UHFFFAOYSA-N 0.000 description 1
- FGWYWKIOMUZSQF-UHFFFAOYSA-N 1,1,1-triethoxypropane Chemical compound CCOC(CC)(OCC)OCC FGWYWKIOMUZSQF-UHFFFAOYSA-N 0.000 description 1
- HLTDBMHJSBSAOM-UHFFFAOYSA-N 2-nitropyridine Chemical class [O-][N+](=O)C1=CC=CC=N1 HLTDBMHJSBSAOM-UHFFFAOYSA-N 0.000 description 1
- QVAJPNZUNGKQOO-UHFFFAOYSA-N 3-nitro-N-[3-[3-[(3-nitropyridin-4-yl)hydrazinylidene]propoxy]propylideneamino]pyridin-4-amine Chemical compound [N+](=O)([O-])C=1C=NC=CC=1NN=CCCOCCC=NNC1=C(C=NC=C1)[N+](=O)[O-] QVAJPNZUNGKQOO-UHFFFAOYSA-N 0.000 description 1
- QLILRKBRWXALIE-UHFFFAOYSA-N 3-nitropyridine Chemical compound [O-][N+](=O)C1=CC=CN=C1 QLILRKBRWXALIE-UHFFFAOYSA-N 0.000 description 1
- JOTRPRKONYTVBV-UHFFFAOYSA-N 4-chloro-3-nitropyridine Chemical compound [O-][N+](=O)C1=CN=CC=C1Cl JOTRPRKONYTVBV-UHFFFAOYSA-N 0.000 description 1
- XMRMLOKLNLMWBY-UHFFFAOYSA-N Cl.Cl.C(C)C=1NNC2=C(N1)C=NC=C2 Chemical compound Cl.Cl.C(C)C=1NNC2=C(N1)C=NC=C2 XMRMLOKLNLMWBY-UHFFFAOYSA-N 0.000 description 1
- VAOQZVHKRSKXEM-UHFFFAOYSA-N Cl.Cl.CC=1NNC2=C(N1)C=NC=C2 Chemical compound Cl.Cl.CC=1NNC2=C(N1)C=NC=C2 VAOQZVHKRSKXEM-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ZQDXEVWNBNDLPI-UHFFFAOYSA-N pyrido[3,4-e][1,2,4]triazine Chemical compound N1=CN=C2C=NC=CC2=N1 ZQDXEVWNBNDLPI-UHFFFAOYSA-N 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- BQFPCTXLBRVFJL-UHFFFAOYSA-N triethoxymethylbenzene Chemical compound CCOC(OCC)(OCC)C1=CC=CC=C1 BQFPCTXLBRVFJL-UHFFFAOYSA-N 0.000 description 1
- GKASDNZWUGIAMG-UHFFFAOYSA-N triethyl orthoformate Chemical compound CCOC(OCC)OCC GKASDNZWUGIAMG-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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 ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/76—Nitrogen atoms to which a second hetero atom is attached
- C07D213/77—Hydrazine radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Pyridine Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
<19) DANMARK (W) \K D. /
§<12) FREMLÆGGELSESSKRIFT on 146536 B
DIREKTORATET FOR PATENT- OG VAREMÆRKEVÆSENET
(21) Patentansøgning nr.: 3799/72 (51) Int.CI.3: C 07 D 471/04 (22) Indleverlngsdag: 01 aug 1972 (41) Aim. tilgængelig: 03 feb 1973 (44) Fremlagt: 31 okt 1983 (86) International ansøgning nr.: - (30) Prioritet: 02 aug 1971 HU EE 1933 (71) Ansøger: 1EGYT GYOGYSZERVEGYESZETI GYAR; Budapest X, HU.
(72) Opfinder: Zoltan 1Budai; HU, Pal 1Benko; HU, Laszlo ‘Pallos; HU, Andras ‘Messmer; HU, Andras 1Gelle-ri; HU, Daniel 1Berenyi; HU.
(74) Fuldmægtig: Ingeniørfirmaet Budde, Schou & Co (54) Fremgangsmåde til fremstilling af pyri-do(3,4-e)-as-triaziner eller salte heraf
Opfindelsen angår en særlig fremgangsmåde til fremstilling af pyrido/^,4-e/r-as-triaziner med den almene formel (i) . ί3Χ?Λ.
D R
9 9 eller af dihydro-pyrido[3,4-e]-as-triaziner med den almene formel (IV)
D
r m 2 146536 Ιοί I ίχν) begge i form af frie baser eller salte heraf. I ovenstående formler betyder R hydrogen, en alkylgruppe med 1-6 carbonatomer eller en phenylgruppe. Ovenstående forbindelser er kendte stoffer med anti-mikrobiel virkning.
Ifølge en kendt fremgangsmåde kan 3-alkyl-pyridoZ5,4-e7-as-tria-ziner fremstilles ved at bringe 4-chlor-3-nitro-pyridin til reaktion med en acylhydrazin, katalytisk reducere de opnåede 4-acylhydrazino--3-nitro-pyridiner og underkaste de opnåede mellemprodukter ringslutning (fransk patentskrift nr. 1.449*778). Ved gentagelse af ovenstående syntese blev 3-raethyl-pyrido/3,4-e7-as-triazin imidlertid kun opnået i et udbytte på 15$, og dette råprodukt indeholdt store mængder forureninger. Et rent produkt kunne kun opnås efter flere omkrystallisationstrin. Ifølge en anden kendt fremgangsmåde fremstilles pyrido/3,^“§/”-as -triazin og dets 3-methyl-derivat ved en firetrins-syntese (reduktion, acylering, ringslutning og oxidation), idet der gås ud fra 4-hydrazino-3-nitro-pyridin (J. Heterocycl. Chem. 8 (1971) P· 47).
Til grund for den foreliggende opfindelse ligger den erkendelse, at forbindelserne med de almene formler (IV) og (i) kan fremstilles i høje udbytter og høj renhedsgrad, når deres syntese udføres via iminoether-derivater med den almene formel (III)
R
„NH-N=C-OCEL
r'V
r (in) hvori R har den ovenfor angivne betydning. Iminoether-derivaterne, der er hidtil ukendte forbindelser, kan fremstilles i høje udbytter og er yderst tilbøjelige til reduktiv ringslutning. Under dannelsen af iminoether-forbindelserne forekommer ingen bireaktioner, der fører til biprodukter af hydrazidin-typen, og når nitrogruppen i iminoether--derivaterne reduceres, reagerer den dannede aminogruppe samtidig med iminoether-gruppen, og der dannes ringsluttede produkter med den almene formel (IV).
3 146536 I overensstemmelse hermed er fremgangsmåden ifølge opfindelsen ejendommelig ved, at 4-hydrazino-3-nitro-pyridin bringes til reaktion med en orthoester med den almene formel (II) R - C(OC2H5)3 (II) hvori R har den ovenfor angivne betydning, den opnåede N-(3-nitro--4-pyridylamino)-iminoether-forbindelse med den almene formel (III) underkastes reduktion og ringslutning i nærværelse af en katalysator, og den opnåede dihydro-pyrido[3,4-e]-as-triazin med den almene formel (IV) om ønsket oxideres til den tilsvarende aromatiske forbindelse med den almene formel (I), fortrinsvis med luftens oxygen, og/eller forbindelserne med de almene formler (I) eller (IV) om ønsket omdannes til deres salte.
Dihydroforbindelserne med den almene formel (IV) er almindeligvis yderst følsomme over for oxidation; som følge heraf omdannes de til de tilsvarende aromatiske forbindelser, når blot den ved den reduktive ringslutning opnåede reaktionsblanding inddampes i nærværelse af luft. På grund af denne kendsgerning fraskilles dihydroforbindelserne med den almene formel (IV) fortrinsvis ved filtrering af reaktionsblandingen under en indifferent gasatmosfære, som er fri for oxygen, og filtratet behandles med saltsyre, da dihydro--pyridoj/5,4-e7-as-triaziner kan stabiliseres i form af deres salte.
Udgangsstofferne med den almene formel (II) kan fremstilles ved kendte metoder (jf. f.eks. Aliphatic Orthoester, Reinhold, N.Y., 1943; Chem. Rev. 4^ (1949), p. 463).
Den vigtigste fordel ved fremgangsmåden ifølge opfindelsen I forhold til den kendte teknik ligger i den kendsgerning, at de aromatiske . forbindelser med den almene formel (i) kan fremstilles i en totrins-synte-se i et totaludbytte på 60-70% og i høj renhedsgrad. Det skal nævnes, at de aromatiske forbindelser ifølge de kendte fremgangsmåder kun kan opnås i et maksimalt udbytte på 30-j55$, og de indeholder stadig store mængder af forureninger.
Fremgangsmåden ifølge opfindelsen belyses nærmere ved nedenstående eksempler.
4 146536
Eksempel 1
Pyrido[ 3,4-e]-as-triazin.
En blanding af 18,5 g (0,12 mol) 4-hydrazino-3-nitro--pyridin, 300 ml ethyl-orthoformiat og 0,1 g p-toluensulfonsyre omrøres og opvarmes ved tilbagesvaling i 3 timer. Blandingen køles med isvand, og den udskilte orangerøde udfældning frafil-treres. Der fås 20,4 g (81,0%) N-(3-nitro-4-pyridylamino)-form-imino-ethylether, smeltepunkt 108-109°C.
Analyse:
Beregnet for CgH^gN^O^ (210,2): C = 45,70%, H = 4,76%, N = 26,65%
Fundet: C = 45,41%, H = 7,78%, N = 26,45%
En blanding af 21,02 g (0,1 mol) N-(3-nitro-4-pyridyl--amino)-formimino-ethylether, 800 ml ethanol og 1,5 g palladium--på-carboii-katalysator omrystes under hydrogenatmosfære, indtil den beregnede mængde hydrogen er absorberet. Katalysatoren frafil-treres, og opløsningen inddampes i vakuum til ca. 1/20 af dens oprindelige rumfang ved en temperatur, som ikke overstiger 50°C.
Den udskilte udfældning frafiltreres og omkrystalliseres fra heptan.
Der fås 11,2 g (85%) pyrido[5,4-e]-as-triazin, smeltepunkt 91°C (under sønderdeling).
Analyse:
Beregnet for CgH^N^ (132,13): C = 54,51%, H = 3,05%, N = 42,45%
Fundet: C = 54,60%, H = 3,10%, N = 42,45%
Eksempel 2 3-Phenyl-pyrido[3,4-e]-as-triazin.
En blanding af 15,4 g (0,1 mol) 4-hydrazino-3-nitro--pyridin, 50 ml ethyl-orthobenzoat og en lille mængde p-toluen-sulfonsyre omrøres og koges, og det ved reaktionen dannede ethanol afdestilleres. Derefter afdampes størstedelen af ortho-esteren, og remanensen tritureres i benzin. De faste stoffer omkrystalliseres fra methanol. Der fås 25,5 g (89%) N-(3-nitro--4-pyridylamino)-benzimino-ethylether, smeltepunkt 109-110°C.
5 148538
Analyse:
Beregnet for ci4Hi4N4°3 (286,29): C = 58,70%, H = 4,93%, N = 19,55%
Fundet: C = 58,80%, H = 4,99%, N = 19,60%
En blanding af 28,62 g (0,1 mol) N-(3-nitro--4-pyridylamino)-benzimino-ethylether, 1300 ml ethanol og 1,5 g palladium-på-carbon hydrogeneres, indtil den beregnede mængde hydrogen er absorberet. Katalysatoren fjernes ved filtrering, og filtratet inddampes i vakuum. Remanensen omkrystalliseres fra ethanol til dannelse af røde glansfulde krystallameller. Der fås 18,3 g (88%) 3-phenyl-pyrido[3,4-e]-as-triazin, smeltepunkt 127-127,5°C.
Analyse:
Beregnet for C^2HgN4 (208,23): C = 69,20%, H = 3,87%, N = 26,85%
Fundet: C = 69,14%, H = 3,86%, N = 26,99%.
Eksempel 3 3-Methyl-pyrido[3,4-e]-as-triazin.
En blanding af 55 g (0,357 mol) 4-hydrazino-3-nitro--pyridin, 0,1 g p-toluensulfonsyre og 472 g triethyl-orthoacetat omrøres og koges i 2 timer. Blandingen afkøles, og den udskilte orangerøde udfældning frafiltreres og tørres. Der fås 67,65 g (84,3%) N-(3-nitro-4-pyridylamino)—acetimino-ethylether. Det opnåede produkt omkrystalliseres fra en 1,5-dobbelt mængde benzen til dannelse af et stof, som smelter ved 120-122°C.
Analyse:
Beregnet for C9Hi2N4°3 (224'2); C = ‘48,20%, H = 5,38%, N = 24,90%
Fundet: C = 47,90%, H = 5,40%, N = 24,78%
En blanding af 3,36 g (15 mmol) N-(3-nitro-4-pyridyl-amino)-acetimino-ethylether, 400 ml ethanol og 0,5 g palladium--på-carbon-hydrogeneres, indtil den teoretiske mængde hydrogen er absorberet. Katalysatoren fjernes ved filtrering, og filtratet hældes i saltsyreholdig isopropanol. Filtreringen udføres under indifferent gasatmosfære, som er fri for oxygen. Den opnåede opløsning inddampes til ca. 1/20 af dens oprindelige rumfang, den udskilte udfældning frafiltreres og omkrystalliseres fra en blanding af ethanol og isopropanol. På denne måde fås 2,32 g (70%) 3-methyl--1,2-dihydro-pyrido[3,4-e]-as-triazin-dihydrochlorid, smeltepunkt 220-221°C.
6 146536
Analyse:
Beregnet for (221,10) : C = 38,05%, H = 4,56%, Cl = 32,10%, N = 25,35%
Fundet: C = 38,00%, H = 4,50%, Cl = 32,54%, N = 25,45% 2,21 g (0,01 mol) 3-methyl-1,2-dihydro-pyrido[3,4-eJ--as-triazin-dihydrochlorid opløses i 30 ml vand, og der sættes hertil en opløsning af 6,6 g (0,02 mol) kaliumferricyanid i 25 ml vand. Den resulterende blanding gøres alkalisk med kaliumhydroxidopløsning, og blandingen omrøres i 0,5 timer. Blandingen ekstraheres med ether, og etherlaget afdampes. Der fås 1,31 g (90%) 3-methyl--pyrido[3,4-e]-as-triazin, smeltepunkt 112-113°C (efter omkrystallisation fra benzen).
Analyse:
Beregnet for C^HgN^ (146,16)J
C = 57,60%, H « 4,14%, N = 38,35%
Fundet: C = 57,06%, H = 4,47%, N = 37,98%.
Eksempel 4 3-Ethyl-l,2-dihydro-pyrido[3,4-e]-as-triazin-dihydro-chlorid._______
En blanding af 7,7 g (0,05 mol) 4-hydrazino-3-nitro--pyridin, 0,1 ml ethanolisk saltsyre og 25 ml triethyl-orthopropionat koges i 3 timer. Det ved reaktionen dannede ethanol fjernes ved afdampning, og remanensen afkøles. Den udskilte udfældning frafil-treres og tritureres med ether. Der fås 3 g (25%) N-(3-nitro-4--pyridylamino)-propionimino-ethylether, smeltepunkt 98-100°C.
Analyse:
Beregnet for cioHl4N4°3 (238'2): C = 50,40%, H = 5,92%, N = 23,52%
Fundet: C = 50,46%, H = 6,00%, N = 23,42%.
En blanding af 1,8 g (7,55 mmol) N-(3-nitro-4--pyridylamino)-propionimino-ethylether, 250 ml ethanol og 0,5 g palladium-på-carbon-katalysator omrystes under hydrogenatmosfære, indtil den beregnede mængde hydrogen er absorberet. Katalysatoren fjernes ved filtrering, og filtratet inddampes under nitrogenatmosfære. Remanensen blandes med ethanolisk saltsyre til dannelse af et 146536 7 lysebrunt krystallinsk produkt. Der fås 0,85 g (47,8%) af den i overskriften nævnte forbindelse, smeltepunkt 253-254°C (efter omkrystallisation fra methanol).
Analyse:
Beregnet for CgH12Cl2N4 (235,13): C = 40,80%, H = 5,14%, Cl = 30,25%, N = 23,85%
Fundet: C = 40,60%, H = 5,05%, Cl = 30,72%, N = 23,34%.
Claims (1)
- 8 U6S36 Patentkrav. Fremgangsmåde til fremstilling af pyrido/^,4-e7-as-triaziner med den almene formel (I) (ϊ) eller af dihydro-pyrido[3,4-e]-as-triaziner med den almene formel (IV) CsIa., i hvilke formler R betyder hydrogen, en alkylgruppe med 1-6 carbonatomer eller en phenylgruppe, begge i form af frie baser eller salte heraf, kendetegnet ved, at 4-hydrazino-3-nitro-pyridin bringes til reaktion med en orthoester med den almene formel (II) r-c(oc2h5)5 (II) hvori R har den ovenfor angivne betydning, den opnåede N-(3-nitro-4--pyridylamino)-iminoether.-forbindelse med den almene formel (III) R nh-n=c-oc2h5 ΓοΎ (m) ^N02
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HUEE001933 HU164031B (da) | 1971-08-02 | 1971-08-02 | |
| HUEE001933 | 1971-08-02 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DK146536B true DK146536B (da) | 1983-10-31 |
| DK146536C DK146536C (da) | 1984-04-09 |
Family
ID=10995378
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK379972A DK146536C (da) | 1971-08-02 | 1972-08-01 | Fremgangsmaade til fremstilling af pyrido(3,4-e)-as-triaziner eller salte heraf |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5523834B2 (da) |
| AT (1) | AT313910B (da) |
| DE (1) | DE2237073C2 (da) |
| DK (1) | DK146536C (da) |
| HU (1) | HU164031B (da) |
| NL (1) | NL178691C (da) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HU165677B (da) * | 1972-05-05 | 1974-10-28 |
-
1971
- 1971-08-02 HU HUEE001933 patent/HU164031B/hu unknown
-
1972
- 1972-07-28 AT AT656372A patent/AT313910B/de not_active IP Right Cessation
- 1972-07-28 DE DE19722237073 patent/DE2237073C2/de not_active Expired
- 1972-07-31 NL NL7210506A patent/NL178691C/xx not_active IP Right Cessation
- 1972-07-31 JP JP7601572A patent/JPS5523834B2/ja not_active Expired
- 1972-08-01 DK DK379972A patent/DK146536C/da not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| AT313910B (de) | 1974-03-11 |
| NL178691C (nl) | 1986-05-01 |
| DK146536C (da) | 1984-04-09 |
| DE2237073A1 (de) | 1973-02-15 |
| JPS4828499A (da) | 1973-04-14 |
| HU164031B (da) | 1973-12-28 |
| NL7210506A (da) | 1973-02-06 |
| JPS5523834B2 (da) | 1980-06-25 |
| DE2237073C2 (de) | 1983-03-10 |
| NL178691B (nl) | 1985-12-02 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PBP | Patent lapsed |