CS266991B1 - 3- (2-R-vinyl) -2-benzothiazolinones; - Google Patents
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Abstract
Podstatou riešenia sú nové látky, 3- -(2-R-vinyl)-2-benzotiazolinónov, vzorca I, kde R znamená fenyl, 2-nitrofenyl, 3-nitrofenyl, 4-nitrofenyl, 2-chlórfenyl, 4- -ohlórfenyl, 3,4-dichlórfenyl, 2-metoxyfenyl, 4-metoxyfenyl, 2,4-dimetoxyfenyl, 4-dimetylamínofenyl, 4-acetamidofenyl, 3,4-metylidéndioxyfenyl, 2-furyl, 3-pyridyl, 5- (4-metylfenyl)-2-furyl, ktoré může nájst uplatnenie ako regulátory rastu rastlín v oblasti stimulačnej alebo inhibičnej a ako nové východiskové zlúčeniny pre dalšie chemické reakcie. Uvedené látky možno připravit reakciou (2-oxo-3-benzotiazolinylmetyl)trifenylfosfóniumhalogenidu s RCHO, kde R je uvedené vyššie v prostředí organických rozpúštadiel ako sú bezvodý metylalkohol, etylalkohol a tetrahydrofurán za přítomnosti trietylaminu, metylátu sodného, alebo etylátu sodného pri teplote 64 až 80 °C po dobu 3 až 5 h.The essence of the solution are new substances, 3--(2-R-vinyl)-2-benzothiazolinones, formula I, where R means phenyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, 2-chlorophenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 2-methoxyphenyl, 4-methoxyphenyl, 2,4-dimethoxyphenyl, 4-dimethylaminophenyl, 4-acetamidophenyl, 3,4-methylidenedioxyphenyl, 2-furyl, 3-pyridyl, 5-(4-methylphenyl)-2-furyl, which can find application as plant growth regulators in the stimulating or inhibiting field and as new starting compounds for further chemical reactions. The mentioned substances can be prepared by reacting (2-oxo-3-benzothiazolinylmethyl)triphenylphosphonium halide with RCHO, where R is mentioned above in an environment of organic solvents such as anhydrous methyl alcohol, ethyl alcohol and tetrahydrofuran in the presence of triethylamine, sodium methylate or sodium ethylate at a temperature of 64 to 80 °C for 3 to 5 h.
Description
2 CS 266 991 B1
(I)
Vynález sa týká 3- (2-R-vinyl)-2-benzotiazolinónov obecného v?orca I.
N-CH—CH—R kde R znamená fenyl, 2-nitrofenyl, 3-nitrofenyl, 4-nitrofenyl, 2-chlórfenyl, 4-chlórfenyl, 3,4-dichlórfenyl, 2-metoxyfeny1, 4-metoxyfenyl, 2,4-dimetoxyfenyl, 4-dimetylamínofenyl, 4-acetamidofenyl, 3,4 metylidéndloxyfenyl, 2-furyl, 2-pyridyl, 5-(4-metylfenyl)-2-furyla spósobu ich přípravy. 2 oblasti derivátov benzotiazolu, podlá literárnej dokumentácie sú 3-substituované-2--benzotiazolinónynajúfiinnejšie v oblasti regulácie rastu rastlín (D’Amico J. J.: USA pat. 4 371 388 (1983); Chem. Abstr. 99, 22 454 (1983); D'Amico J. J.: USA pat. 4 187 097 (1977);
Eur. pat. 2 613 (1979); Chem. Abstr. 92, 419 332 (1983); Ueda I.: Jap. Pat. 92 956 (1979); *
Chem. Abstr. 92, 94 383 (1983); Sutoris V., Mikulášek S., Sekerka V., Konefiný V.: CS pat. 252 502 (1987); Varkonda š., Hýblová O., Sutoris V., Konefiný V., Mikulášek S.: CS pat. AO fi. 235 845.
Ofiinnosť bola zistená tiež v oblasti fungicídnej (Jap. pat. 9 040 546 (1977); ZSSRpat. 713 523 (1978); NSR pat. 2 846 980 (1978); D'Amico J. J.: Eur. pat. 7 772 (1980); Chem.Abstr. 93, 150 241 (1983) a tiež ako herbicid (Sohler E., Seidler L., Váňo J., šplháfiek R.,Fedor E.: CS pat. 172 118 (1974)).
Je známe, že okrem prirodzených regulátorov rastu sa rozvíja využitie rĎznych syntetic-kých látok. Uplatňujú sa predovšetkým tie, u ktorých postafiuje dávka v rozsahu niekolkýchgramov na ha, nie sú závislé od klimatických podmienok a nevyvolávajú negativné důsledky,ako sú napr. nežiaduce reziduá.
Teraz sa zistilo, že zlúfieniny typu 3-(2-R-vinyl)-2-benzotiazolínov, kde R znamenáto isté ako vo vzorci I, majú rastovoregulafiný úfiinok podlá vynálezu. 3-(2-R-vinyl)-2-benzotiazolíny podlá vynálezu nie sú v literatúre doteraz popísané.
Podstata spósobu přípravy látok podlá vynálezu spofiíva v tom, že (2-oxo-3-benzotiazolinyl-metyl)trifenylfosfóniumhalogenid vzorca II
(II) kde X- znamená chlór, bróm, jód, reaguje s aromatickými aldehydmi v prostředí bezvodýchorganických rozpúštadiel ako sú metanol, etanol, tetrahydrofurán, za přítomnosti trietylaminu,metylátu sodného alebo etylátu sodného pri teplote 64 až 80 °C, po dobu tri až pSť hodin.Uvedenú reakciu naznafiuje nasledovná schéma:
+ R-C .0
kde X~ je horeuvedené a R znamená to isté ako vo vzorci I.
Postupy přípravy 3-(2-R-finyl)-2-benzotiazolinónov Příklad 1 3-(2-fenylvinyl)-2-benzotiazolinón CS 266 991 B1 3
Po rozpuštění 4,6 g (0,01 mol) (2-oxo-3-benzotiazolinylmetyl)trifenylfosfóniumohloridu 3 v 30 cm bezvodého metanolu, přidá sa 1 g (0,01 mol) trietylamínu a za miešania sa prikvapká1,06 g (0,01 mol) benzaldehydu v 10 až 15 cm3 metanolu. Reakčná zmes sa 5 h zahrieva nateplotu varu. Po oohladení sa přidá 10 až 20 ci? vody a reakčná zmes sa nechá oez noc staf.Izolovaný krystalický podřel krystalizovaný z etanolu. T. t. 91 až 92,5 °C, výtažok 30 8.
Pre C^H^jNOS, m.h. 253,32 vypočítané % C = 71,15, 8 H = 4,43, 8 N = 5,53, % S = 12,64.
Zistené % C = 71,16, 8 H = 4,43, 8 N = 5,62, % S = 12,71. Příklad 2 3- (2- (2-nitrofenyl)vinyl)-2-benzotiazolinčn 3 K 30 cm bezvodého metanolu sa přidá 0,23 g (0,01 mol) sodíka a 4,6 (0,01 mol) (2-oxo--3-benzotiazolinylmetyl)trifenylfosóniumchloridu. Za miešania sa prikvapká roztok 1,5 g(0,01 mol) 2-nitrobenzaldehydu v 15 cm3 bezvodého metanolu. Reakčná zmes sa 3 h zahrievana teplotu varu. Po ochladení žitá krystalická látka sa krystalizuje z acetonu. Kryštalizáciasa urýchli přidáním 20 cm3 vody. T. t. 157 až 160 °C, výtažok 46 8.
Pre C15H10N2O3S, m.h. 298,32, vypočítané % C = 60,39, 8 H = 3,37, 8 N = 9,39, 8 S = 10,71.
Zistené % C = 60,15, % H = 3,25, 8 N = 9,15, % S = 10,53. Příklad 3 3- (2- (2-chlórfenyl)vinyl)-2-benzotiazolinón 5,5 g (0,01 mol) (2-oxo-3-benzotiazolinylmetyl)trifenylfosfóniumjodidu, 1 g (0,01 mol) trietylamínu, 2,1 g (0,01 mol) 2-chlórbenzaldehydu a 20 cm3 bezvodého tetrahydrofuránu sa3 mieša 4 h pri teplote varu reakčnej zmesi. Po přidaní 20 cm vody sa reakčná zmes chladí.Izolovaný pevný podiel sa krystalizuje z etanolu. T. t. 89 až 91 °C, výtažok 23 8.
Pre C15H10C1NOS, m.h. 287,77, vypočítané % C = 62,62, 8 H = 3,50, 8 N = 4,86, % S = 11,14
Zistené % C = 62,70, 8 H = 3,32, 8 N = 4,66, % S = 11,20. Příklad 4 2- (2-(4-betoxyfenyl)vinyl)-2-benzotiazolinón K 20 cm3 bezvodého etanolu sa přidá 0,23 g (0,01 mol) sodíka, 5 g (0,01 mol) (2-oxo-3--benzotiazolinylmetyl)trifenylfosfóniumbromidu a 2 g (0,015 mol) 4-metoxybenzaldehydu. Reakčnázmes sa zahrieva 4 h na teplotu varu. Přidá sa 20 cm3 vody a 48 h chladením v chladničkevznikne krystalický podiel, ktorý sa krystalizuje z etanolu. T. t. 78 až 80 °C, výtažok 32 8.
Pre Ο.,Η,,ΝΟ.ε, m.h. 283,35, vypočítané 8 C = 67,83, 8 H = 4,62, 8 N = 4,94, 8 S = 11,31.1 b i J z
Zistené 8 C = 67,70, 8 H = 4,50, 8 N = 4,80, % S = 11,16. Příklad 5 3- (2-(4-dimetylaminofenyl)vinyl)-2-benzotiazolinón K 15 cm3 bezvodého metanolu sa přidá 0,23 g (0,01 mol) sodíka, 5,0 g (0,01 mol) (2-ΟΧΟ-3- -benzotiazolinylmetyl)trifenylfosfóniumbromidu sa postupné přidá 2,34 (0,015 mol) 4-dimetyl-3 aminobenzaldehydu v 10 cm metanolu. K reakčnej zmesi po 5 h zahrievania na teplotu varusa přidá voda do mierneho zákalu. Chladením vzniknutá pevná látka sa kryŠtalizuje z etanolu. T. t. 144 až 146 °C, výtažok 34 8. CS 266 991 B1
Pre C17H16N2OS, ra.h. 296,39, vypočítané %C = 68,88, % H=5,77, % N=9,45, % S = 10,81.Zistené % C = 68,73, % H =» 5,41, % N = 9,55, % S = 10,77. Příklad 6 3-(2-pyridylvinyl)-2-benzotiazolinón 4,6 g (0,01 mol) (2-oxo-3-benzotiazolinylmetyl)trifenylfosfóniumchloridu sa rozpustí
O v 30 cm bezvodého metanolu, přidá sa 1 g (0,01 mol) trietylamínu a za miešania sa prikvapká3 1,07 g (0,01 mol) pyridinkarbaldehydu v 10 cm bezvodého metanolu. Zmes sa 4 h zahrievana teplotu varu. Po ochladení sa izoluje kryštalická látka o t. t. 137 až 140 °C, výťažok 44 i
Pre C^^H^qN^OS, m.h. 254,31, vypočítané % C = 66,12, % H = 3,96, % N = 11,01, % S = 12,60.Zistené % C = 66,27, % H = 3,94, ΐ N = 10,98, % S = 12,50. Výsledky elementárnej analýzy syntetizovaných zlúčenín podlá vynálezu sa uvedenév tabulke 1.
Tabulka 1
Charakterizácia syntetizovaných zlúčenín
Zlúčenina R Sumárny vzorec M.h. Vypočítané/Zistené Výťažok % T % c % H % N %,s I C6H5 C15H11NOS 253,32 71,15 4,43 5,53 12,64 30 91 71,16 4,43 5,62 12,71 II 2-n02C6H4 C15H10N2°3S 298,32 60,39 60,15 3,37 3,25 9,39 9,15 10,71 10,53 46 157 III 3-NO2C6H4 C15H10N2O3S 298,32 60,39 60,58 3,37 3,33 9,39 9,16 10,71 10,54 37 192 IV 4-no2c6h4 c15h10n2o2s 298,32 60,39 60,30 3,37 3,32 9,39 9,20 10,71 10,50 67 209 v 2-ClCgH4 C15H10C1NOS 287,77 62,62 3,50 4,86 11,14 23 89 62,70 3,32 4,66 11,20 VI 4-ClCgH4 C15H10C1NOS 287,77 62,62 3,50 4,86 11,14 • 49 · 132 62,35 3,66 4,72 10,96 VII 3,4-Cl2CgH3 C15HgCl2NOS 322,21 55,91 55,64 2,81 2,64 4,34 4,32 9,95 9,83 57 220 VIII 2-och3c6h4 c16h13no2s 283,35 67,83 68,00 4,62 4,59 4,94 4,99 11,31 11,38 50 65 IX 4-och3c6h4 c16h13no2s 283,35 67,83 67,70 4,62 4,50 4,94 4,80 11,31 11,16 32 78 X 2,4-(OCH3)2- C17H15NO3SC6H3 313,37 65,17 4,82 4,47 10,23 26 65 65,10 4,87 4,37 10,23 XI á-Hici^- α17Η16Ν2ο3 C6H4 296,39 68,88 5,77 9,45 10,81 34 144 68,73 5,41 9,55 10,77 XII 4-CH3CONHCgH4 ci7Hi4N2°2S 310,37 65,8065,92 . 4,54 4,48 9,02 8,94 10,30 10,28 68 225 XIII 3,4-O2CH2CgH4 C16HuNO3S 297,33 64,64 64,41 3,72 3,96 4,71 4,45 10,78 10,50 26 107 XIV 2-Fu3 C13HgNO2S 243,28 64,17 3,72 5,57 13,18 34 79 64,60 3,70 5,79 13,20 XV 3-Pyra C14H1qN2OS 254,31 66,12 3,96 11,01 12,60 44 137 66,27 3,94 10,98 12,50 XVI C6H5CH=CH C17H13NOS 279,36 73,07 4,69 5,01 11,47 50 164 73,45 4,73 5,02 11,47 XVII C20H15NO2S 333,42 72,05 4,53 4,20 9,61 45 143 71,82 4,56 4,20 9,56 . t.
°C až 92,5 až 160 až 195 až 212 až 91 až 135 až 223 až 67,5 až 80 až 68 až 146 až 228 až 109 až 82 až 140 až 167 až 145 askratky: Pyr - pyridylFu - furyl CS 266 991 B1 5
Infračervené spektrá 3-(2-R-vinyl)-benzotiazolínov, kde R znamená to isté ako vo vzorciI sa namerali v roztokoch tetrachlórmetánu a trichlórmetánu v oblasti 1 800 až 1 600 cm-1na mriežkovom spektrofotometr! Perkin-Elmer 567 pri laboratorněj teplote. Použili sa NaClkyvety hrůbky 0,1, 1,0 a 5,0 mm. Koncentrácia meraných roztokov sa volila tak, aby maximálnaabsorbancia bola 70 %-ná až 75 %-ná. Polohy pásov boli stanovené ako arytmetické priemetyz troch meraní s presnosťou +0,5 cm 1. Kalibrácia vlnočtovej stupnice spektrofotometra sakontrolovala s použitím referenčných spektier vodnej páry a indénu.
Vlnočty IC spektier syntetizovaných zlúčenín podlá vynálezu sú uvedené v tabulke 2.
Tabulka 2
Hodnoty IČ spektier syntetizovaných zlúčenín podlá vynálezu
Zlúčenina CHCl^ CCl^ i? (c=o) J (C=C) 1? (C=O) ?(C=C) I 1 684,5 1 644,0 1 700,5 1 645,0 II 1 687,5 1 645,0 1 701,0 1 646,0 III 1 686,5 1 645,5 1 699,5 - IV 1 688,5 1 644,5 1 704,5 1 644,0 v 1 685,0 1 643,0 1 703,0 1 643,0 VI 1 684,5 1 645,0 1 702,0 1 647,0 VII 1 678,0 1 646,0 1 705,0 1 648,0 VIII 1 681,0 1 642,0 1 700,0 1 641,5 IX 1 682,5 1 648,0 1 699,0 1 649,0 X 1 679,0 1 639,0 1 679,0 1 642,0 XI 1 678,5 1 644,0 1 697,0 - XII 1 681,5 1 647,5 1 701,0 - XIV 1 683,5 1 652,5 1 698,0 1 650,0 XV 1 688,5 1,644,5 1 702,0 1 644,0 XVI 1 683,5 1 639,0 1 697,0 1 639,0 XVII 1 681,5 1 650,0 1 695,0 1 650,5 Látky podlá vynálezu sú účinné ako regulátory rastu rastlín. Rastové testy boli zameranéna prolongačný rast primárných koreňov u Vicia Sativa L., cv. Solarka, ktorý je jednýmz dóležitých ukazatelov fyziologických, prejavov rastlín. Rastové testy sa uskutočnili antró-novou modifikovanou metodou. Příklad 7 osvětluje spdsob testovania zlúčenín podlá vynálezuna reguláciu rastu. Příklad 7
Semená Vicia Sativa L., cv. Solarka klíčili na Petriho miskách v termostate, v trnepri 25 °C. Klíčenci po 48 ,h raste sa exponovali v molárnych roztokoch 3-(2-R-vinyl)-2--benzotiazolinónich, kde R je uvedené vo vzorci I. Testovanie sa uskutočnilo v koncentračnějškále 10-3 až ÍCT13 mol l-1 a po 24 h inkubácii bol stanovený prírastok predlžovacieho rastukoreňov. Po každom stanovení bol uskutočnený aj rastový efekt v kontrolnej sérii. Šířkasúbormi boli stanovené biometricky. Výsledky regulácie rastu syntetizovaných zlúčenín podlávynálezu sú uvedené v tabulke 3. 6 CS 266 991 B1
Tabulka 3
Rastovoregulačný účinok syntetizovaných zlúčenín
Vicia sativa L., cv. Solarka
Stimulácla_· _Inhibicia
Zlúčenina 2\l/mm % C/(mol dm 3) - Δΐ/mm % I 1,56 4,95 10-5 6,83 21,69 II 10,83 32,43 III 1,79 6,86 10-7 6,64 25,47 IV 12,47 48,83 v 1, 87 7,15 10-13 16, 13 61,73 VI 3,64 12,89 10’5 5,49 19,46 -7 VII 3,36 10,81 10 4,06 14,81 VIII 1,26 4,52 ÍO-9 9,94 35,67 IX 3,33 10,53 10-11 6,40 20,26 X 5,67 20,67 10~7 3,77 13,75 XI 1,59 5,70 10-7 8,01 24,66 XII 3,81 13,29 10-7 2,88 10,05 XIII 2,14 6,70 10-11 5,07 15,88 XIV 1,87 6,23 10-5 13,53 45,10 -9 XVI 1,20 4,01 10 3 6,07 20,33 IAA 3,10 12,99 10-12 18,55 77,78 2,4-D 4,49 20,00 ÍO-9 23,30 94,15 ccc 3,85 11,23 C/(mol dm-J) 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 -3 -3 -3 -3 -3 -3 -3 -3 -3 -3 -3 -3 -3 -3 -6 -5 -3 IAA: beta-indolyloctová kyseliny 2,4-D: 2,4-dichlórfenoxyoctová kyselina CC: 2-chlóretyltrimetylamóniumchlorid
Rastové testy boli uskutočnené aj na Triticum aestivum L.. Příklad 9 osvětluje spůsobtestovania zlúčenín podlá vynálezu pa reguláciu rastu. Příklade
Zrno pšenice bolo napučené po dobu dvoch až troch h v destilovanej vodě pri laboratórnejteplote a naklíčenie prebiehalo v tme pri teplote 25 °C. Po vyklíčení koleoptil na 20 až25 mm z každej koleoptily bol vyseknutý 3 mm dlhý segment asi 2 mm pod povrchom. Koleoptilovésegmenty boli dané na 2 h do destilovanej vody a potom umiestnené po 10 do testovaných roz-tokov, obsahujúcich 2 % sacharózy. Inkubácia prebiehala za trepania, aby sa predišlo zakrý-veniu segmentov. Po 24 h inkubácii pri 25 °C bolo merané predlženie kleoptil pomocou zváčšovacieho fotografického prístroja. Rozdiely boli vyjádřené v % ku kontrole a preukaznosť bola vypočítaná t-testom. Celý pokus bol robený pri červenom svetle. Roztoky boli riedené v kon--3 -13 -1 centračnej stupnici 10 až 10 mol 1 , kontrola bola robená v 2 %-nej sacharoze. Biotest je citlivý nielen na auxínové látky, ale aj na inhibičné látky, ktoré predlžovanie segmentovbrzdia. Výsledky regulácie rastu syntetizovaných zlúčenín podlá vynálezu sú uvedené v tabulke 4.
Tabulka 4
Rastovoregulačný účinok syntetizovaných zlúčenín CS 266 991 B1 7
Tabulka 4 pokračovanie
Triticium aestivura L.
Stimulácia
Zlúčenina -— Δ1/mm % C/(mol dm-3)
I 0,50 II 0,17 III 0,61 IV 1,10 v 0,25 VI 0,17 VII 0,29 VIII IX 0,19 X XI XII 0, 29 XIII 0,49 XIV 0,35 XVI 0,62 IAA 5,93 2,4-D 2, 56 CCC 9,20 10'7 3,13 10-11 11,23 10-5 20,25 10-7 5,16 10"9 -ς 3,03 10 5, 99 10"7 —4 3,92 10 5,16 10-4 -7 9, 02 10 -5 7,23 10 12,80 ÍO-4 100,33 io-5 51, 09 10-5
Inhibícia - Δΐ/nun % C/(mol dm-3) 1.69 31,13 10-31,35 24,87 10-31,83 33,71 10-31,85 34, 07 10"31, 06 21,91 10-31,45 25,85 10-31,01 20,87 10-31,78 31,73 10-30,59 31,73 10-31,61 28,70 10-32,38 42,43 10-3 1.70 30,31 ÍO-31,81 33, 34 10-31,40 28,93 ÍO-30,64 13,85 ÍO-32,77 46,72 10-32,01 40,12 10~31,75 32,35 10-3
Ako Standardy bolí testované u Vioia Sativa L., cv. Solarka a u Triticum aestivum L. IAA: beta-indolyloctová kyselina, 2,4-D: 2,4-dichlórfenoxyoctová kyselina, CCC: 2-chlór-etyltrimetylamóniumchlorid.
Bolo zistené, že syntetizované zlúčeniny podlá vynálezu pósobením na semená Vicia Sativa-3 -13 -1 L., cv. Solarka v koncentrácii 10 až 10 mol 1 spósobili rozličný rastový efekt. V sti-mulácii rastu sú zlúčeniny 3-(2-(4-chlórfenyl)vinyl)-2-benzotiazolinón, 3-(2-(3,4-dichlór-fenyl)vinyl)-2-benzotiazolinón, 3-(2-(4-metoxyfeny1)vinyl)-2-benzotiazolinón, 3-(2-(2,4--dimetoxyfenyl)vinyl)-2-benzotiazolinón a 3-(2-(4-acidamidofenyl) vinyl)-2-benzotiazolinónpodlá vynálezu porovnatelné so štandardom beta-indolyloctovou kyselinou. Standardu 2,4-di-chlórfenoxyoctovej kyselině dá sa porovnat 3-(2-(2,4-dimetoxyfenyl)vinyl)-2-benzotiazolinón.Inhibičná účinnost v porovnáni s 2-chlóretyltrimetylamóniumchloridu bola u syntetizovanýchzlúčenin podlá vynálezu vyššia okrem 3-(2-(4-acetamidofenyl)vinyl)-2-benzotiazolinócu. Ne-dosiahli však inhibičné účinky v nižších koncentráciach.
Bolo zistené, že syntetizované zlúčeniny podlá vynálezu sú róznou mierou účinné ajna Triticum aestivum L.. Preukazná účinnost bola zistená u 3-(2-(3-nitrofenyl)vinyl)-2--benzotiazolinónu, 3-(2-(4-nitrofenyl)finyl)-2-benzotiazolinónu a u 3-(2-styrylvinyl)-2--benzotiazolinónu. Zistená inhibičná účinnost je porovnatelná zo všetkými štandardami.
Vysvětlivky: I 3- (2-fenylvinyl)-2-benzotiazolinónII 3- (2-(2-nitrofenyl)vinyl)-2-benzotiazolinón III 3-(2-(3-nitrofenyl)vinyl)-2-benzotiazolinónIV 3-(2-(4-nitrofenyl)vinyl)-2-benzotiazolinón V 3-(2-chlórfeny1)vinyl)-2-benzotiazolinónVI 3- (2- (4-chlórfenyl)vinyl)-2-benzotiazolinón VII 3-(2-(3,4-dichlórfeny1)vinyl)-2-benzotiazolinónVIII 3-(2-(2-metoxyfenyl)vinyl)-2-benzotiazolinón
2 CS 266 991 B1
(AND)
The invention relates to 3- (2-R-vinyl) -2-benzothiazolinones of the general formula I.
N-CH-CH-R wherein R is phenyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, 2-chlorophenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 2-methoxyphenyl, 4-methoxyphenyl, 2,4- dimethoxyphenyl, 4-dimethylaminophenyl, 4-acetamidophenyl, 3,4-methylidenedloxyphenyl, 2-furyl, 2-pyridyl, 5- (4-methylphenyl) -2-furyl, for their preparation. 2 regions of benzothiazole derivatives, according to the literature, are 3-substituted-2-benzothiazolinones most useful in the regulation of plant growth (D'Amico JJ: U.S. Pat. No. 4,371,388 (1983); Chem. Abstr. 99, 22,454 (1983)); D'Amico JJ: U.S. Pat. No. 4,187,097 (1977);
Eur. pat. 2,613 (1979); Chem. Abstr. 92, 419,332 (1983); Ueda I .: Jap. Pat. 92,956 (1979); *
Chem. Abstr. 92, 94, 383 (1983); Sutoris V., Mikulášek S., Sekerka V., Konefiný V .: CS Pat. 252, 502 (1987); Varkonda š., Hýblová O., Sutoris V, Konefiný V., Mikulášek S .: CS pat. AO fi. 235 845.
Also, fungicidal activity has been reported (Jap. Pat. 9,040,546 (1977); USSR Pat. 713,523 (1978); German Pat. No. 2,846,980 (1978); D'Amico JJ: Eur. Pat. 7 772 (1980)). 93, 150, 241 (1983) and also as a herbicide (Sohler, E., Seidler, L., J. J., climber R., Fedor, E., et al., 172, 118 (1974)).
It is known that, in addition to natural growth regulators, the use of various synthetic substances is being developed. In particular, those in which the dose in the range of a fewgrams per ha is applied, are not dependent on climatic conditions and do not produce negative consequences, such as undesirable residues.
It has now been found that 3- (2-R-vinyl) -2-benzothiazoline-type compounds wherein R is the same as in Formula I have a growth-regulating effect of the invention. The 3- (2-R-vinyl) -2-benzothiazolines of the present invention are not described in the literature.
The principle of the method of preparing the compounds of the invention is that (2-oxo-3-benzothiazolinylmethyl) triphenylphosphonium halide of formula II
(II) wherein X- is chloro, bromo, iodo, reacts with aromatic aldehydes in an anhydrous organic solvent environment such as methanol, ethanol, tetrahydrofuran, in the presence of triethylamine, sodium methylate or sodium ethylate at 64 to 80 ° C for three to three years The following diagram shows the above reaction:
+ RC .0
wherein X ~ is as above and R is the same as in Formula I.
Preparation of 3- (2-R-vinyl) -2-benzothiazolinones Example 1 3- (2-Phenylvinyl) -2-benzothiazolinone CS 266 991 B1 3
After dissolution of 4.6 g (0.01 mol) of (2-oxo-3-benzothiazolinylmethyl) triphenylphosphonium chloride 3 in 30 cm @ 3 of anhydrous methanol, add 1 g (0.01 mol) of triethylamine and add 1.06 g (0%) with stirring. (01 mol) of benzaldehyde in 10-15 cm 3 of methanol. The reaction mixture was heated to reflux for 5 h. After cooling, 10 to 20? water and the reaction mixture was allowed to stand overnight. The crystalline support isolated from ethanol was isolated. Mp 91-92.5 ° C, yield 30.8.
For C = HH ^ jNOS, m / z 253.32 calculated% C = 71.15, δ H = 4.43, 8 N = 5.53,% S = 12.64.
% C = 71.16, 8H = 4.43, 8N = 5.62,% S = 12.71. Example 2 3- (2- (2-Nitrophenyl) vinyl) -2-benzothiazoline 3 To 30 cm 3 of anhydrous methanol is added 0.23 g (0.01 mol) of sodium and 4.6 (0.01 mol) (2 - oxo-3-benzothiazolinylmethyl) triphenylphosphonium chloride. While stirring, a solution of 1.5 g (0.01 mol) of 2-nitrobenzaldehyde in 15 cm 3 of anhydrous methanol is added dropwise. The reaction mixture was refluxed for 3 h. After cooling, the precipitated crystalline material is crystallized from acetone. The crystallization is accelerated by the addition of 20 cm 3 of water. Mp 157-160 ° C, 46% yield.
For C 15 H 10 N 2 O 3 S, mh 298.32, calculated% C = 60.39, δ H = 3.37, δ N = 9.39, δ S = 10.71.
% C = 60.15,% H = 3.25, 8 N = 9.15,% S = 10.53. Example 3 3- (2- (2-chlorophenyl) vinyl) -2-benzothiazolinone 5.5 g (0.01 mol) of (2-oxo-3-benzothiazolinylmethyl) triphenylphosphonium iodide, 1 g (0.01 mol) of triethylamine, 2 1 g (0.01 mol) of 2-chlorobenzaldehyde and 20 cm3 of anhydrous tetrahydrofuran are stirred for 4 hours at the boiling point of the reaction mixture. After the addition of 20 cm of water, the reaction mixture was cooled. The isolated solid was crystallized from ethanol. Mp 89-91 ° C, yield 23.8.
For C15H10ClNOS, mh 287.77, calculated% C = 62.62, 8H = 3.50, 8N = 4.86,% S = 11.14
Found% C = 62.70, δ H = 3.32, δ N = 4.66,% S = 11.20. Example 4 2- (2- (4-bethoxyphenyl) vinyl) -2-benzothiazolinone 0.23 g (0.01 mol) of sodium, 5 g (0.01 mol) (2-oxo) was added to 20 cm 3 of anhydrous ethanol. 3-benzothiazolinylmethyl) triphenylphosphonium bromide and 2 g (0.015 mol) of 4-methoxybenzaldehyde. The reaction mixture is refluxed for 4 hours. Water (20 cc) was added and the crystalline fraction was crystallized by cooling in a refrigerator for 48 h, which crystallized from ethanol. Mp 78-80 ° C, yield 32.8.
For Ο., Η ,, ε, mh 283.35, calculated 8 C = 67.83, 8 H = 4.62, 8 N = 4.94, 8 S = 11.31.1 bi J z
Δ C = 67.70, δ H = 4.50, 8 N = 4.80,% S = 11.16. Example 5 3- (2- (4-Dimethylaminophenyl) vinyl) -2-benzothiazolinone To 15 cm 3 of anhydrous methanol was added 0.23 g (0.01 mol) of sodium, 5.0 g (0.01 mol) (2- Β-3- benzothiazolinylmethyl) triphenylphosphonium bromide is added in succession to 2.34 (0.015 mol) of 4-dimethyl-3-aminobenzaldehyde in 10 cm @ 3 of methanol. Water is added to the reaction mixture after heating for 5 hours at a boiling point to a slight turbidity. Cooling the solid formed is crystallized from ethanol. Mp 144-146 ° C, yield 34 8. CS 266 991 B1
For C17H16N2OS, ra.h. 296.39, calculated% C = 68.88,% H = 5.77,% N = 9.45,% S = 10.81. Found% C = 68.73,% H = »5.41,% N = 9.55,% S = 10.77. Example 6 3- (2-Pyridylvinyl) -2-benzothiazolinone 4.6 g (0.01 mol) of (2-oxo-3-benzothiazolinylmethyl) triphenylphosphonium chloride are dissolved
O in 30 cm @ 3 of anhydrous methanol, add 1 g (0.01 mol) of triethylamine and add 1.07 g (0.01 mol) of pyridinecarbaldehyde in 10 cm @ 3 of anhydrous methanol dropwise with stirring. The mixture was refluxed for 4 h. After cooling, the crystalline substance was isolated with mp 137-140 ° C, yield 44%
% C = 66.12,% H = 3.96,% N = 11.01,% S = 12.60.% C = 66 found. 27,% H = 3.94, N = 10.98,% S = 12.50. The results of the elemental analysis of the synthesized compounds of the invention are shown in Table 1.
Table 1
Characterization of synthesized compounds
Compound R Compound Formula Mh Calculated / Found Yield% T% c% H% N%, with I C6H5 C15H11NOS 253.32 71.15 4.43 5.53 12.64 30 91 71.16 4.43 5.62 12 , 71 II 2-n02C6H4 C15H10N2O3S 298.32 60.39 60.15 3.37 3.25 9.39 9.15 10.71 10.53 46 157 III 3-NO2C6H4 C15H10N2O3S 298.32 60.39 60 , 58 3.37 3.33 9.39 9.16 10.71 10.54 37 192 IV 4-no2c6h4 c15h10n2o2s 298.32 60.39 60.30 3.37 3.32 9.39 9.20 10, 71 10.50 67 209 in 2-ClCgH4 C15H10ClNOS 287.77 62.62 3.50 4.86 11.14 23 89 62.70 3.32 4.66 11.20 VI 4-ClCgH4 C15H10ClNOS 287.77 62, 62 3.50 4.86 11.14 • 49 · 132 62.35 3.66 4.72 10.96 VII 3.4-Cl2CgH3 C15HgCl2NOS 322.21 55.91 55.64 2.81 2.64 4, 34 4.32 9.95 9.83 57 220 VIII 2-och3c6h4 c16h13no2s 283.35 67.83 68.00 4.62 4.59 4.94 4.99 11.31 11.38 50 65 IX 4-och3c6h4 c16h13no2s 283.35 67.83 67.70 4.62 4.50 4.94 4.80 11.31 11.16 32 78 X 2.4- (OCH3) 2- C17H15NO3SC6H3 313.37 65.17 4.82 4.47 10.23 26 65 65.10 4.87 4.37 10.23 XI á-Hici ^ - α17Η16Ν2ο3 C6H4 296.39 68.88 5.77 9.45 10.81 34 144 68.73 5, 41 9, 55 10.77 XII 4-CH 3 CONHC 8 H 4 C 17 H 14 N 2 O 2 S 310.37 65.8065.92. 4.54 4.48 9.02 8.94 10.30 10.28 68 225 XIII 3.4-O2CH2CgH4 C16HuNO3S 297.33 64.64 64.41 3.72 3.96 4.71 4.45 10, 78 10.50 26 107 XIV 2-Fu3 C13HgNO2S 243.28 64.17 3.72 5.57 13.18 34 79 64.60 3.70 5.79 13.20 XV 3-Pyra C14H1qN2OS 254.31 66, 12 3.96 11.01 12.60 44 137 66.27 3.94 10.98 12.50 XVI C6H5CH = CH C17H13NOS 279.36 73.07 4.69 5.01 11.47 50 164 73.45 4 , 73 5.02 11.47 XVII C20H15NO2S 333.42 72.05 4.53 4.20 9.61 45 143 71.82 4.56 4.20 9.56. t.
From C to 92.5 to 160 to 195 to 212 to 91 to 135 to 223 to 67.5 to 80 to 68 to 146 to 228 to 109 to 82 to 140 to 167 to 145 ascretes: PyridylFu-furyl CS 266 991 B1 5
Infrared spectra of 3- (2-R-vinyl) -benzothiazolines, where R is the same as in Formula I, were measured in carbon tetrachloride and trichloromethane solutions in the 1800 to 1600 cm -1 area with a spectrophotometer! Perkin-Elmer 567 at room temperature. NaClkyvets of 0.1, 1.0 and 5.0 mm were used. The concentration of the solutions to be measured was chosen such that the maximum absorbance was 70% to 75%. The belt positions were determined as arymetry of three measurements with an accuracy of +0.5 cm 1. The spectrophotometer calibration of the wavelet scale was checked using reference spectra of water vapor and indene.
The IC spectra of the synthesized compounds of the invention are shown in Table 2.
Table 2
IR spectra of the synthesized compounds of the invention
Compound CHCl 3 CCl 3? (c = o) J (C = C) 1? (C = O)? (C = C) I 1,684.5 1,644.0 1,700.5 1,645.0 II 1,687.5 1,645.0 1,701.0 1,646.0 III 1,686.5 1,645.5 1,699.5 - IV 1,688.5 1,644.5 1,704.5 1,644.0 at 1,685.0 1,643.0 1,703.0 1,643.0 VI 1,644.5 1,645 , 1 1,702.0 1,647.0 VII 1,678.0 1,646.0 1,705.0 1,648.0 VIII 1,681.0 1,642.0 1,700.0 1,641.5 IX 1,682.5 1 648.0 1,699.0 1,649.0 X 1,679.0 1,639.0 1,679.0 1,642.0 XI 1,678.5 1,644.0 1,697.0 - XII 1,681.5 1,647, 5 1 701.0 - XIV 1 683.5 1 652.5 1 698.0 1 650.0 XV 1 688.5 1.644.5 1 702.0 1 644.0 XVI 1 683.5 1 639.0 1 697 , 1 1,639.0 XVII 1,681.5 1,650.0 1,695.0 1,650.5 The compounds of the invention are effective as plant growth regulators. Growth tests were focused on prolonged growth of primary roots in Vicia Sativa L., cv. Solarka, which is one of the important indicators of physiological, plant manifestations. Growth assays were performed by an anthracene modified method. Example 7 illustrates the method of testing compounds according to the invention for regulating growth. Example 7
Seeds of Vicia Sativa L., cv. Solarka germinated on Petri dishes in a thermostate, at 25 ° C. Germs after 48 h growth were exposed in molar solutions of 3- (2-R-vinyl) -2-benzothiazolinones, where R is shown in formula I. Testing was carried out at a concentration of 10-3 to 1313 moles of l-1 and after The 24 h incubation period was determined to be an increase in extension growth. A growth effect in the control series was also performed after each assay. The widths were determined biometrically. The results of the regulation of the growth of synthesized compounds of the invention are shown in Table 3. 6 CS 266 991 B1
Table 3
The growth-regulating effect of synthesized compounds
Vicia sativa L., cv. Solarka
Stimulation of inhibition
Compound 2 L / mm% C / (mol dm 3) - Δΐ / mm% I 1.56 4.95 10-5 6.83 21.69 II 10.83 32.43 III 1.79 6.86 10 -7 6.64 25.47 IV 12.47 48.83 v 1, 87 7.15 10-13 16, 13 61.73 VI 3.64 12.89 10'5 5.49 19.46 -7 VII 3.36 10.81 10 4.06 14.81 VIII 1.26 4.52 IO-9 9.94 35.67 IX 3.33 10.53 10-11 6.40 20.26 X 5.67 20 , 67 10 ~ 7 3.77 13.75 XI 1.59 5.70 10-7 8.01 24.66 XII 3.81 13.29 10-7 2.88 10.05 XIII 2.14 6.70 10-11 5.07 15.88 XIV 1.87 6.23 10-5 13.53 45.10 -9 XVI 1.20 4.01 10 3 6.07 20.33 IAA 3.10 12.99 10 -12 18.55 77.78 2.4-D 4.49 20.00 OO-9 23.30 94.15 ccc 3.85 11.23 C / (mol dm-J) 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 -3 -3 -3 -3 -3 -3 -3 -3 -3 -3 -3 -3 -3 -6 -5 -3 IAA: beta-indolylacetic 2,4-D: 2,4-dichlorophenoxyacetic acid CC: 2-chloroethyltrimethylammonium chloride
Growth assays were also performed on Triticum aestivum L. Example 9 illustrates the testing of the compounds of the invention and the growth regulation. Example
Wheat grain was swelled for two to three hours in distilled water at room temperature and germination was in the dark at 25 ° C. After germination of the coleoptiles to 20-25 mm from each coleopthilis, a 3 mm long segment was cut about 2 mm below the surface. Koleoptilse segments were given for 2 h in distilled water and then placed 10 times in test solutions containing 2% sucrose. Incubation was carried out with shaking to avoid segmenting. After 24 h incubation at 25 ° C the elongation extension was measured using a retractable camera. Differences were expressed in% to control and evidence was calculated by t-test. The whole experiment was done in red light. The solutions were diluted in a central scale of 10 to 10 mol 1, control was performed in 2% sucrose. The bioassay is sensitive not only to auxin substances, but also to inhibitory substances that prolong segment braking. The results of the regulation of the growth of the synthesized compounds of the invention are shown in Table 4.
Table 4
Growth-regulating effect of synthesized compounds CS 266 991 B1 7
Table 4 continued
Triticium aestivura L.
Stimulation
Compound-1 / mm% C / (mol dm-3)
I 0.50 II 0.17 III 0.61 IV 1.10 in 0.25 VI 0.17 VII 0.29 VIII IX 0.19 X XI XII 0, 29 XIII 0.49 XIV 0.35 XVI 0, 62 IAA 5.93 2.4-D 2, 56 CCC 9.20 10'7 3.13 10-11 11.23 10-5 20.25 10-7 5.16 10 "9-in 3.03 10 5, 99 10 "7 —4 3.92 10 5.16 10-4 -7 9, 02 10 -5 7.23 10 12.80 IO-4 100.33 io-5 51, 09 10-5
Inhibition - Δΐ / nun% C / (mol dm-3) 1.69 31.13 10-31.35 24.87 10-31.83 33.71 10-31.85 34, 07 10 "31, 06 21.91 10-31,45 25,85 10-31,01 20,87 10-31,78 31,73 10-30,59 31,73 10-31,61 28,70 10-32,38 42,43 10- 3 1.70 30.31 IO-31.81 33, 34 10-31.40 28.93 IO-30.64 13.85 IO-32.77 46.72 10-32.01 40.12 10 ~ 31.75 32.35 10-3
As Standards, Vioia Sativa L., cv. Solarka and Triticum aestivum L. IAA: beta-indolylacetic acid, 2,4-D: 2,4-dichlorophenoxyacetic acid, CCC: 2-chloroethyltrimethylammonium chloride.
It has been found that the synthesized compounds of the present invention are treated with seeds of Vicia Sativa-3 -13-1 L., cv. Solarka at a concentration of 10 to 10 mol 1 caused a different growth effect. In the growth stimulation, 3- (2- (4-chlorophenyl) vinyl) -2-benzothiazolinone, 3- (2- (3,4-dichlorophenyl) vinyl) -2-benzothiazolinone, 3- (2- (4-methoxyphenyl) vinyl) -2-benzothiazolinone, 3- (2- (2,4-dimethoxyphenyl) vinyl) -2-benzothiazolinone and 3- (2- (4-acidamidophenyl) vinyl) -2-benzothiazolinone according to the invention comparable with a beta-indolylacetic acid standard. The 2,4-dichlorophenoxyacetic acid standard can be compared to 3- (2- (2,4-dimethoxyphenyl) vinyl) -2-benzothiazolinone. The inhibitory activity compared to 2-chloroethyltrimethylammonium chloride was higher for the synthesized compounds of the invention except for 3- (2). - (4-acetamidophenyl) vinyl) -2-benzothiazolinone. However, they did not achieve inhibitory effects at lower concentrations.
The synthesized compounds of the present invention have been found to be a potent measure of Triticum aestivum L. Evidence was found for 3- (2- (3-nitrophenyl) vinyl) -2-benzothiazolinone, 3- (2- (4-nitrophenyl) vinyl) -2-benzothiazolinone and 3- (2-styrylvinyl) -2-benzothiazolinone. The observed inhibitory activity is comparable to all standards.
Legend: I 3- (2-Phenylvinyl) -2-benzothiazolinone III 3- (2- (2-nitrophenyl) vinyl) -2-benzothiazolinone III 3- (2- (3-nitrophenyl) vinyl) -2-benzothiazolinone III 3- ( 3- (2- (4-chlorophenyl) vinyl) -2-benzothiazolinone VII 3- (2- (4-chlorophenyl) vinyl) -2-benzothiazolinone-3- (2- (4-nitrophenyl) vinyl) -2-benzothiazolinone; 3,4-Dichlorophenyl) vinyl) -2-benzothiazolinone VIII 3- (2- (2-methoxyphenyl) vinyl) -2-benzothiazolinone
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