CS233443B1 - 2 * alkoxycarbonylmethylthio-3-alkylbenzothiazole salts and their preparation - Google Patents
2 * alkoxycarbonylmethylthio-3-alkylbenzothiazole salts and their preparation Download PDFInfo
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Abstract
Vynález rieši spSsob přípravy nových látok 2-alkoxykarbonylmetyltio-3-alkylbenzotiazoliových soli všeobecného vzorca I kde R znamená metoxy, etoxy, propoxy, izopropoxy, alyloxy; Ir znamená metyl, etyl, alyl, propyl, butyl, benzyl a X" znamená brom. Podstata spSsobu přípravy látok podTa vynálezu spočívá,v tom, že.deriváty 3-R-2- -benzotiazollntionu, kde K' znamená to istá ako vo vzorci I, reagujú s XCHgCOR, kde R a X znamená to istá, ako vo vzorci I v prostředí organických rozpúštadiel,ako sú nitrometán, nižšie alifatická ketony, tetrahydrofurán a acetonitril pri teplote 18 až 85 °C po dobu 2 až 96 hodin. Látky podTa vynálezu sú účinné ako stimulátory alebo inhibitory rastu rastlín.The invention solves a process for the preparation of new substances of 2-Alkoxycarbonylmethylthio-3-alkylbenzothiazolium salts of general formula I where R means methoxy, ethoxy, propoxy, isopropoxy, allyloxy; Ir means methyl, ethyl, allyl, propyl, butyl, benzyl and X" means bromine. The essence of the method of preparation of substances according to the invention is that the derivatives of 3-R-2-benzothiazolinthione, where K' means the same as in formula I, react with XCHgCOR, where R and X mean the same as in formula I, in the environment of organic solvents such as nitromethane, lower aliphatic ketones, tetrahydrofuran and acetonitrile at a temperature of 18 to 85° C. for 2 to 96 hours. The substances according to the invention are effective as plant growth stimulators or inhibitors.
Description
233443 2
Vynález se týká 2-alkoxykarbonylnetyltio-3-alkylbenzotiezóllových soli obecnéhovzorca Z N — R1 sch2cor kde K maněná netozy, etoxy, propozy, izopropoxy, alylozy; R* maněná netyl, otyl, alyl, propyl, butyl, benzyl a X" maněná brón a spdaob leh přípravy.
Syntéza benzotiazóliových aoll pri využití benzotiasolu a 2-alkylbensotiazolu, reap. 4- alebo 5-aUbstituovmého benaotlnzolu bola věnovaná pozornost v prácach (Sutoris V.,Halené J., Sekerka V.: ča. AO 223 426; Halené J., Sutoris V., Sekerka V.: PV 7434-82; Suto-rla V., Halené J., Sekerka V.: PV 688-82). Připravované beqzotlazóliové aoll preukázallatlnulačné účinky (Sutorla V., Sekerka V., Halené J.s 225 008) mtlnlkróbnu účinnost na O*baktérie skupiny Staphylococcua (Sutorla V., Poltínová P., Halené J.: PV 8540-82) a zvyšo-vanie obsahu cukru v rostlinách produkujúclch cukor (Sutorla V., Sekerka V., Helgaš J.,
Baj81 P.: PV 2928-82). Přípravě 2-alkyltlo-3-alkylkylbenzotlazóliovým soliam bola doteraz věnovaná pozornostv súvlslosti so étúdloa leh stálosti (Sexton W. A.: J. Chea. Soc. 1939) 470; Bradlov H. L.,Vanderwerf C.A.: J. Org. Chen. 16, 1 143 (1951); Bellenaon B., Haner F. H.: J. Chen. Soc.1939, 143) a étúdloa polohy jednotlivých alkylov. Bolo zlatěné, že pri reakci! 2-alkyl-tlobensotiazólov a alkylhalogenidon, ktorého alkylakupina je odlišná od alkylskupinyv alkyltlobenzotlazole, dochádza k vzájoanej výnene alkylových skupin a produkton syntézyje snes kvartémych solí (Fry D. J., Kendall J. D.: J. Chen. Soc. 1951, 1 716). Předpoklá-dá aa, že výnena alkylových skupin je zapříčiněná tvorbou prechodnej sulfóniovej zlúčeni-ny (Hoore C. Q., Wlght E. S.: J. Chen. Soc. 1952, 4 237). Keí sú alkylové skupiny rovnaké,získá aa jednotný produkt kvartér nej aoll. Štruktúme definovatelné 2-alkyltlo-3-alkyl-bensotiasóllové aoll ano připravili pOaobenín alkylhalogenidni na 3-alkyl-2-benzotiazolin-tlóny, ktoré aa dajú připravit zahrievanín 2-alkyltiobenzotiazolu za přítomnosti jódu.Preényk je závislý od povahy alkylu a reakčnej doby (Sexton *. A.: J. Chea. Soc. 1939, 470;Hoore C. O., Valght E. S.: J. Chen. Soc. 1952, 4 237). Vznik 3-aubatituovaných-2-tioxo-benzotlazollnových zlúčenín bol zlatěný pri Stúdiu Uichaelovej a Mannichovej reakcieu 2-nerkaptobenaotiazolu (Halasa A. F., Snith O. E. P.: J. Org. ,Chea. 36 , 636 /1971/) napr.s netylvlnylketónon, akrylonltroloa, vinylfenylketónon, 2- a 4-vinylpyrldínon atň. 2-Alko-zykarbonylnetyltlo-3-alkylbenzotiazóliové soli podlá vynálezu nie sú v literatúre doterazpopísané. Podobné étúdlu biologickej účinnosti nebola do súčaanej doby věnovaná pozornost.
Podstata apčaobu přípravy látok podlá vynálezu spočívá v ton, Že deriváty 3-r’-2--benzotlasolíntiónu vsorca XI
kde R1 maněná to iaté ako vo vzorci I, reagujú a XCHgCOR, kde R a X znanená to isté, akovo vzorci X v prostředí organických rozpúštadiel ako sú nltronetán, nižšie alifatickéketony, tetrahydrofurán a acetonltrll, pri teplota 18 až 85 °C po dobu 2 až 96 hodin. Uve-denú reakciu naznačuje naaledovná achána: (oCn, , xch,cor - (oCn?"’“:-+ kde R, r' a X' je hoře uvedené. Všeobecné postupy kvarternizácie 3-R^-2-benzotiasolíntiónu. 3 233443 Přikladl 0,02 molu 3-substituovaného-2-bensotiasollntiónu a 0,025 aolu prlsluSného esterubróaoctovej kyseliny sa rozpust! í 15 »1 nitroaetánu. ReakSná zaas za nechá ztát prl teplo-ta 18 až 23 °C 96 hodin. VyldSená kvartérna sol ea krystalizuje zo zazel tetrahydrofuránua metanolu (3:1) alebo ea preayje na flltri acetónoa. Příklad 2 0,02 aolu 3-substituovaného-2-bensotlazólintiónu a 0,025 aolu.prlsl. esteru bróaoctovejkyseliny sa rozpustí v 15 al nitroaetánu. ReakSná zaes sa zahrleva 2 hodiny na 65 až 70 ®C.Keá produkt po ochladení nevykryStallzuje, přidá sa 5 al éteru. Krystalický podlel ea pre-ayje na flltri acetónoa alebo krystalizuje zo zaesl tetrahydrofuránu a aetanolu (-3 : 1). Příklad 3 0,02 molu 3-substltuovaného-2-benzotlasollntlónu a 0,03 aolu príel. esteru bróaoctovejkyseliny sa rozpustí v 15 ml acetonu alebo tetrahydrofuránu. Reakčná zase sa zahrleva20 hodin na 65 až 70 °C. Po ochladení sa krystalický podlel preayje na flltri acetónoa. - Příklad 4 5,1 e (0,02 mol) 3-benzyl-2-bensotlazolintionu a 0,03 aolu prlsluSného esteru bróa-octovej kyseliny sa rozpustí v 25 ml nitroaetánu. ReakSná zaes sa zahrleva 96 hodin na80 až 85 °C. Vylúčená kvartérna sol sa krystalizuje zo zaesl tetrahydrofuránu a aetanolu(3:1). Výsledky eleaentámej analýzy podlá vynálezu a fyzikálno-chealcké konstanty synteti-zovaných zlúSenín sú uvedené v tabuXke 1. 2334*3 4 to
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Vysvětlivky: C 2-MetoxykarbonylBetyltio-3-aetylbenzotiazóliuBbroBld II 2~Etoxykarbonylmetyltio-3-Bétylbenxotiazóliuabroaid III *2-Fropoxykarbonylaetyltio-3~aetylbezotiasóliuabromid IV 2-Izopropoxykarbonylaetyltio-3-metylbenzotiasóliuBbroaid V 2-Alyloxykarbonylaetyltlo-3-aetylbensotiazóliuabroBld VI 2-MetoxykarbonylBetyltio-3-etylbensotlasóliuabroaid VII 2-Moxykarbonylmetyltlo-3-etylbensotiasóliuabroaid VIII 2-PropoxykarbonylBetyltlo-3-etylbenzotiasóliuBbroaid IX 2-Izopropoxykarbonylaetyltio-3-etylbenzotiazóliuabroBÍd X 2-Alyloxykarbonylaetyltio-3-etylbenzotiasóliuabroBld XI 2-Metoxy-karbonylaetyltio-3~propylbenzotlazóliumbroaid XII 2-£toxykarbonylaetyltio-3-pi*opylbenzotiasóliumbroald XIII 2-Propoxykarbonylaetyltlo-3-piOpylben«otiazóliuabroBÍd XIV 2-Isopropoxykarbonylaetyltlo-3-propylbensotiazóliuabroBÍd XV 2-Alyloxykarbonylaetyltlo-3-propylbenzotiazóliuabroaid XVI· 2-Metoxykarbonylaetyltio-3-alylbenzotiazóliuabroaid XVII 2-Etoxykarbonylaetyltio-3-alylbensotiazóliuabroaid XVIII 2-Metoxykarbonylmetyltio-3-butylbenzotlazÓliUBbroald XIX 2-£toxykarbonylaetyltlo-3-butylbenzotiazólluBbroald XX 2-Propoxykarbonylaetyltio-3-butylbenzotlazóliumbromid XXI 2-Alyloxykarbonylaetyltio-3-butylbenzotiazólluBbroaid XXII 2-Uetoxykarbonylaetýltlo-3-benzylbenxotlazóliuabraaid. XXIII 2-StoxykarbonylBetyltio-3-bensylbenzotiazóliuabroaid 'h-NMR apektrá boli naměřené na přístroji TESLA BS 487 A pri 80 MHz v deuterovanej trl-fluoroctovej kyselině, vndtorný Standard hexaaetyldiailoxán.
Naaerané 'h NMR chemické posuny 6-2-alkyltio-3-alkylbenzotiaxóliových solí syntetisováných podlá vynálezu m - aultiplet q - kvartet s - singlet p - kvintet d - dublet sex - sextet t - triplet h - septet I. 2-aetoxykarbonylaetyltio-3-aetylbensotiazóliuabroald: 7,2 až 7,9 (a, 4 H, ar.), 3,88 (s, 3 H, s Ň-CH,), 4,19 (s, 2 H, -S-CH2-), 4,80 (s, 3 H,-o-ch3). II. 2-etoxykarbonylaetyltio-3-aetylbenzotiazóliuabroaid: 7,2 až 7,9 (a, 4 H, ar.), 3,87 (s, 3 H, s í-CHj), 4,16 (s, 2 H, -S-CH2-), 4,01 (q, 2 H,-O-CHj-), 0,95 (t, 3 H, -CH3). III. 2-propoxykarbonylaetyltlp-3-aetylbenzotiasóliuabroBid: 7,2 až 7,9 (a, 4 H, ar.), 3,87 (s, 3 H, « í-CHj), 4,18 (s, 2 H, -S-CHg-), 3,93 (t, 2 H,-O-GH2-), 1,36 (sex, 2 H, -CH2-), 0,65 (t, 3 H, -CH3). IV. 2-izopropoxykarbonylaetyltio-3-aetylbenzotiasóliUBbroaid: 7,2 až 7,9 (a, 4 H, ar.), 3,86 (s, 3 H, ; í-CHj), 4,13 (s, 2 H, -S-CHg-), 4,85 (h, 1 H,-CH«), 0,96 (d, 6 H, -CHj). V. 2-alyloxykarbonylmetyltio-3-metylbeneotiazóliuabroBid: 7,2 až 7,9 (a, 4 H, ar.), 3,88 (s, 3 H, 5Í-CH3), 4,20 (s, 2 H, -S-CHj-), 4,43 (d, 2 H,-O-CH2-), 5,5 (a, 1 H, »CH-), 5,0 (a, 2 H, =CH2). 7 233443 VI. 2-aetoxykarbonylaetyltio-3-etylbenzotiasóliuabroald: 7,2 až 7,9 (a, 4 H, ar.), 4,38 (q, 2 H, -í-CHg-), 1,25 (t, 3 H, -CHj), 4,20 (·, 2 H, -S-CHg-), 3,56 (s, 3 H, -O-CH3). VII. 2-etoxykarbonylaetyltlo-3-etylbenzotiazóliuabroaid: 7,2 až 7,9 («, 4 H, ar.), 4,38 (q, 2 H, -Á-CH2-), 1,25 (t, 3 H, -C^), 4,2« (z, 2 B, -S-CH2-), 4,03 (q, 2 H, -OCHg-), 0,98 (t, 3 H, -CH3). . VIII. 2-propoxykarbonyIaetyltio-3-etylbenzotiazóliuabroaid: 7,2 až 7,9 (a, 4 H, ar.), 4,40 (q, 2 H, sí-CHg-), 1,25 (t, 3 H, -CH3>, 4,24 (a, 2 H, -S-CH2-), 3,94 (t, 2 H, -O-CH2-), 1,38 (sex, 2 H, -CHg-), 0,63 (t, 3 H, -CHj). IX. 2-izopropoxykarbonylaetyltio-3-etylbenzotlazóliuabroBÍd: 7,2 až 7,9 (a, R H, ar.), 4,38 (q, 2 H, »Í-CH2-), 1,23 (t, 3 H, -CBj), 4,15 (a, 2 H, -S-CH2-), 4,81 (h, 1 H, -CH»), 0,98 (d, 6 H, -CHj). X. 2-alyloxykarbonylaetyltio-3-etyIbenzotiazóliuabroald: 7,2 až 7,9 (a, 4 H, ar.), 4,43 (a, 4 H, sí-CH2-, -0-CH2-), 1,25 (t, 3 H, -CBj), 4,23 (a, 2 H,rS-CHg-), 5,5 (a, 1 Η, «CH-). XI. 2-aetoxykerbonylaetyltio-3-propylbenzotiazóliuabroaid: 7,2 až 7,9 (a, 4 H, ar.), 4,28 (t, 2 H, ;ft-CH2-), 1,70 (sex, 2 H, -CHjr)i 0,73 (t, 3 H, -CH3), 4,20 (S, 2 H, -S-CH2-), 3,59 (s, 3 H, -O-C^). XII. 2-etoxykarbonylaetyltio-3-propylbenzotiazóliuBbroaid:. 7,2 až 7,9 (a, 4 H, ar.), 4,29 (t, 2 H, aí-CHg-), 1,70 (sex, 2 H, -CH2-), 0,73 (t, 3 H, -CH3), 4,20 (s, 2 H, -S-CH2-), 4,02 (q, 2 H, -O-CHg-), 0,95 (t, 3 H, -0-CH3). XIII. 2-propoxykarbonylaetyltio-3-propylbenzótiazóliuabroaid: 7,2 až 7,9 (a, 4 H, ar.), 4,29 (t, 2 H, zí-CHg-), 1,70 (sex, 2 H, -CHg-), 0,70 (t, 6 H, -CH3), 3,93 (t, 2 H, -O-CH,,-), 1,36 (sex, 2 H, -CH2-). XIV. 2-lzopropoxykarbonylaetyltlo-3-propylbenžotiazóliuabroald: i_ 7,2 až 7,9 (a, 4 H, ar.), 4,28 (t, 2 H, afc-CHg-), 1,69 (sex, 2 H, -CHg-), 0,70 (t, 3 H, -Cl^), 4,16 (s, 2 H, -S-CH2-), 4,85 (h, 1 H, -O-CH=), 0,94 (d, 6 H, -CH3). XV. 2-alyloxykarbonylaetyltlo-3-propylbenzotiazóliuabroald: 7,2 až 7,9 (a, 4 H, ar.), 4,30 (t, 2 H, =Í-CH2-), 1,70 (sex, 2 H, -CHg-), 0,73 (t, 3 H, -CH-j), 4,23 (s, 2 H, -S-CH2-), 4,43 (d, 2 H, -O-CHg-), 5,5 (a, 1 H, =CH-), 5,0 (a, 2 H, =ch2). XVI. 2-aetoxykarbonylaetyltio-3-alylbenzotlazóliuabroaid: 7,2 až 7,9 (a, 4 H, ar), 5,0 (a, 4 H, =fc-CH2-, -CHg), 5,5 (a, 1 H, -CH-), 4,20 (a, 2 H,-S-CH2-), 3,56 (s, 3 H, -O-CH3). XVIII. 2-aetozykarbonylaetyItio-3-butylbenzotiazóliuabroaid: 7,2 až 7,9 (a, 4 H, ar.), 4,33 (t, 2 H, 5S-CH2-), 1,7 (a, 2 H, -CH2-), 1,2 (a, 2 H, -CH2'-),0,63 (t, 3 H, -CH3), 4,20 (s, 2 H, -S-CH2-), 3,56 (s, 3 H, -O-CHj). XIX. 2-etoxykarbonylaetyltio-3-butylbenzotiazóliuabroaid: 7,2 až 7,9 (a, 4 H, ar.), 4,31 (t, 2 H, sft-CHg-), 1,6 (a, 2 H, -CH2), 1,3 až 0,5 (a, SH,-CH2-, -CH3), 4,19 (s, .2 H, -S-CHg-), 4,02 (q, 2 H, -O-CH2-). XX. 2-propoxykarbonylaetyltio-3-butylbenzotiazóliuabroaid: 7,2 až 7,9 (a, 4 H, ar.), 4,35 (t, 2 H, zí-CH2-), 1,8 až 1,0 (a, 6 H, -CHg-), 0,63 (t, 6 H,-CB3), 4,26 (s, 2 H, -S-CH2-), 3,94 (t, 2 H, -O-CHg-). 233443 8 XXI. 2-alyloxykarbonylmetyltio-3-butylbenzotiazóliumbromld: 7,2 až 7,9 (m, 4 H, ar.), 4,33 (t, 2 H, »Í-CH2-), 1,6 (m, 2 H, -CH2-), 1,1 (m, 2 H, -CHg-),0,63 (t, 3 H, -CH-), 4,24 (a, 2 H, -S-CHj-), 4,43 (d, 2 H, -O-CHg-), 5,5 (·, 1 H, «CH-), 5,0 (a, 2 H, -0¾). XXII. 2-metoxykarbonylmetyltlo-3-benzylbenzotiazólluBbromid: 7,2 až 7,9 (a, 4 H, ar.), 5,52 (t, 2 H, -ft-CHg-), 4,25 (s, 2 H, -S-CHg-). XXIII. 2-etoxykarbonylmetyltlo-3-benzylbenzotiasóliumbromid: 7,2 až 7,9 (a, 4 H, ar.), 5,52 (t, 2 H, »t-CH2-), 4,25 (s, 2 H, -S-CHj-). Látky podlá vynálezu sú účinné ako stimulůtory alebo inhibitory rastu rastlín. Bašto-vé testy sa uskutečnili autorml aodifikovanou metodou na objekte vika siata. Příklad 4osvětluje spOsob testovania zlúčenín podlá vynálezu na stiaulačnú a inhiblčnú účinnost. Příklad 4
Seaená vlky slátej klíčili v Petrlho aiskách v termostate v tme pri 25 °Č. Klíčencepo 48-hodinovom raste sa exponovali v molárnych roztokoch 2-R-3-r'-substituovaných benzo-tiazóliových solí, kde B, B* a X~ podlá všeobecného vzorca je uvedená v I až XXIII, tabuT-ka 1 v koncentračnej Skále 10”’6 až 10-1 mol.dm-3. Po 24 hodinách inkubácle bol stanovenýprírastok predlžovacieho rastu koreňov. Pri každoa stanovení bol uskutečněný aj rastovýefekt v kontrolněj sérii, šířka pokusného a kontrolného súboru, ako aj signlfikantnosťaedal súborai boli stanovené bioaetricky.
Ako Standardy boli testované kyselina beta-indulyloctová (IAA), kyselina 2,4-dichlór-fenoxyoctová (2,4-D) a 2-chlóretyltrimetylamóniuachlorid (CCO). Výsledky stiaulačnéhoa inhiblčného účinku syntetizovaných zlúčenín podlá vynálezu sú uvedené v tabuXke 2.
Tabulka 2
Stiaulačný a inhibičný účinek syntetizovaných zlúčenín podlá vynálezu fiíslo R B1 X" Stiaulácia +Bua mol.dm“3 Inhibíci· -a - mol.dm' I II 00¾ OC2H5 0¾ CH3 , 1 Br Br 7.15 4,05 io-’1 10“7 10"13 III 0C3H7 ch3 Br 3,55 IV OC-jILy-i CH3 Br 5,50 10“9 . 10"13 v och2gh»ch3 ch3 Br ,0-7 5,15 VI VII 00¾ OCgH, c2h5 C2H5 Br Br 3,85 4,9 10-’3 VIII Ο°3Η7 .¾¾ Br 21,60 10“3 IX OCjtty-i C2H5 Br 2,00 10-5 1,50 10“13 10“’3 X och2ch-ch? c2h5 Br 4,30 XI 00¾ 5¾ Br XII °°2η5 c3«7 Br 1,55 10“7 XIII oe3H7 Br 2,55 10“9 10“H 10-13 XIV QC^-i C3“7 Br 3,80 XV och2ch«ch2 · *3*1 Br 1,20 XVI OCH. CH,GH-CH, Br 13,40 10-3
233443 2
The present invention relates to 2-alkoxycarbonylmethylthio-3-alkylbenzothiazole salts of the general formula ZN-R1 sch2cor2 wherein K is manganese, ethoxy, propyloxy, isopropoxy, allyl; R * manna not polished, otyl, allyl, propyl, butyl, benzyl and X "manna brone and spdaob leh preparations.
Synthesis of benzothiazolium aolls using benzotiasol and 2-alkylbenzothiazole, reap. 4- or 5-abitite benaotlnzol was paid attention in works (Sutoris V., Halené J., Sekerka V .: č. AO 223 426; Halené J., Sutoris V, Sekerka V .: PV 7434-82; rla V., Halene J., Sekerka V .: PV 688-82). The prepared beotzlazlazol aolls demonstrated the exudative effects (Sutorla V., Sekerka V., Halen Js 225 008) of the Strobhylococcus group of O * bacteria (Sutorla V., Poltinova P., Halene J .: PV 8540-82) and content enhancement sugar in sugar-producing plants (Sutorla V., Sekerka V., Helgaš J.,
Baj81 P .: PV 2928-82). The preparation of 2-alkylthio-3-alkylkylbenzotlazolium salts has hitherto been the focus of the study of stability and stability (Sexton WA: J. Chea. Soc. 1939) 470; Bradlov HL, Vanderwerf CA: J. Org. Chen. 16, 1143 (1951); Bellenaon B., Haner FH: J. Chen. Soc.1939, 143) and the individual alkyl positions. It was gold that in response! 2-alkyl-tlobensothiazole and an alkyl halide whose alkyl group is different from the alkyl group in the alkyllobenzotlazole exemplifies the alkyl groups and product synthesis of quaternary salts (Fry DJ, Kendall JD: J. Chen. Soc. 1951, 1716). It is believed that the exemption of alkyl groups is due to the formation of a transient sulfonium compound (Hoore CQ, Wl ES: J. Chen. Soc. 1952, 4 237). When the alkyl groups are the same, aa is a uniform product of quaternary aoll. Structured definable 2-alkylthio-3-alkylbenzothiazole aolls have prepared alkyl alkyl halides to 3-alkyl-2-benzothiazolinones, which can be prepared by heating 2-alkylthiobenzothiazole in the presence of iodine. The reaction is dependent on the nature of the alkyl and the reaction time (Sexton J. Chea Soc 1939, 470, Hoore CO, Valght ES, J. Chen, Soc., 1952, 4, 237). The formation of the 3-aubatitated-2-thioxo-benzotlazoline compounds was gold in the study of Uichael and Mannich reaction of 2-non-caprobobothothiazole (Halasa AF, Snith OEP: J. Org., Chea. 36, 636 (1971)) e.g. vinyl phenyl ketone, 2- and 4-vinylpyridine dinone. The 2-alkoxycarbonylmethylthio-3-alkylbenzothiazole salts of the present invention are not described in the literature. Similarly, the study of biological efficacy has not been addressed until now.
The principle and the preparation of the compounds according to the invention lies in the fact that the derivatives of 3-r-2-benzotlasolinothione have XI
wherein R 1 and m are as defined in formula I, and XCHgCOR, wherein R and X are the same, but formula X in an organic solvent environment such as nltronethane, lower aliphatic ketones, tetrahydrofuran and acetonitrile, at 18 to 85 ° C for 2 hours up to 96 hours. The aforementioned reaction is indicated by an algae agane: (oCn,, xch, cor - (oCn? "': - + where R, r', and X 'are as above. General quaternization procedures of 3-R 2 -2-benzothiasolinothione. EXAMPLE 1 0.02 mol of 3-substituted-2-benzothiazolithone and 0.025 mol of the appropriate ester-acetic acid are dissolved in 15 [mu] l of nitroaethane, and the reaction mixture is left to stand for 18 to 23 [deg.] C. for 96 hours. from tetrahydrofuran and methanol (3: 1) or elapsed on acetone, Example 2 0.02 aol of 3-substituted-2-benzothlazolintione and 0.025 aol of bromoacetic acid ester are dissolved in 15 [mu] l of nitroaethane. to 65 DEG-70 DEG C. After cooling, the product is added to 5 .mu.l of ether, crystallized according to acetonitrile or crystallized from tetrahydrofuran and aethanol (-3: 1). of substituted-2-benzotlasoltone and 0.03 of sol. the bromoacetic acid ester is dissolved in 15 ml of acetone or tetrahydrofuran. The reaction was again heated to 65-70 ° C for 20 hours. After cooling, the crystalline base was washed with acetone. Example 4 5.1 e (0.02 mol) of 3-benzyl-2-bensotlazolintione and 0.03 aol of the corresponding bromo-acetic ester are dissolved in 25 ml of nitroaethane. The reaction mixture was heated to 80-85 ° C for 96 hours. The precipitated quaternary salt was crystallized from tetrahydrofuran and aethanol (3: 1). The results of the eleaent analysis according to the invention and the physico-chewing constants of synthesized compounds are shown in Table 1.
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<M 8 233443
Legend: C-2 3-MetoxykarbonylBetyltio aetylbenzotiazóliuBbroBld II 2-ethoxycarbonylmethylthio-3-Bétylbenxotiazóliuabroaid III-2 * 3-Fropoxykarbonylaetyltio aetylbezotiasóliuabromid IV-2-Izopropoxykarbonylaetyltio metylbenzotiasóliuBbroaid-3 V-2 3-Alyloxykarbonylaetyltlo aetylbensotiazóliuabroBld VI-2 MetoxykarbonylBetyltio-3- VII-2 etylbensotlasóliuabroaid Moxykarbonylmetyltlo-3-etylbensotiasóliuabroaid 2 VIII-3-PropoxykarbonylBetyltlo etylbenzotiasóliuBbroaid IX-2 Izopropoxykarbonylaetyltio etylbenzotiazóliuabroBÍd-3 X-2 3-Alyloxykarbonylaetyltio etylbenzotiasóliuabroBld XI-2-Methoxy-3-karbonylaetyltio propylbenzotlazóliumbroaid XII 2- £ 3 toxykarbonylaetyltio -pi * opylbenzotiasóliumbroald Propoxykarbonylaetyltlo XIII-2-3-piOpylben «otiazóliuabroBÍd Isopropoxykarbonylaetyltlo XIV-2-3-2-propylbensotiazóliuabroBÍd Alyloxykarbonylaetyltlo XV-XVI propylbenzotiazóliuabroaid 3 · 2 3-Metoxykarbonylaetyltio alylbenzotiazóliuabroaid Etoxykarbonylaetyltio XVII-2-3-alylbensotiaz liuabroaid XVIII 2-methoxycarbonylmethylthio-3-butylbenzotlazÓliUBbroald 2- £ toxykarbonylaetyltlo XIX-XX butylbenzotiazólluBbroald 3-2-3-Propoxykarbonylaetyltio butylbenzotlazóliumbromid XXI-2-3-Alyloxykarbonylaetyltio butylbenzotiazólluBbroaid XXII-2-3-Uetoxykarbonylaetýltlo benzylbenxotlazóliuabraaid. XXIII 2-SteroxycarbonylBetylthio-3-bensylbenzothiazoluabroide The 1 H-NMR apectra were measured on a TESLA BS 487 A instrument at 80 MHz in deuterated trifluoroacetic acid, standard Standard hexaethyldiailoxane.
1 H NMR chemical shifts of 6-2-alkylthio-3-alkylbenzotiaxol salts synthesized according to the invention m - aultiplet q - quartet s - singlet p - quintet d - doublet sex - sextet t - triplet h - septet I. 2-aethoxycarbonylethylthio-3 -aetylbenzothiazoluabroald: 7.2-7.9 (a, 4H, ar.), 3.88 (s, 3H, sN-CH3), 4.19 (s, 2H, -S-CH2- ), 4.80 (s, 3H, -o-ch3). II. 2-ethoxycarbonylaethylthio-3-ethylbenzothiazoluabroaid: 7.2-7.9 (a, 4H, ar), 3.87 (s, 3H, ss-CH3), 4.16 (s, 2H, -) S-CH 2 -), 4.01 (q, 2 H, -O-CH 3 -), 0.95 (t, 3 H, -CH 3). III. 2-propoxycarbonylaethyl-prop-3-ethylbenzothiazoluabroBid: 7.2-7.9 (a, 4H, ar), 3.87 (s, 3H, N-CH3), 4.18 (s, 2H, -) S-CH 3 -, 3.93 (t, 2 H, -O-GH 2 -), 1.36 (sex, 2 H, -CH 2 -), 0.65 (t, 3 H, -CH 3). IV. 2-isopropoxycarbonylethylthio-3-ethylbenzothiazolubbroide: 7.2-7.9 (a, 4H, ar), 3.86 (s, 3H, 1H-CH3), 4.13 (s, 2H, -) S-CH 3 -, 4.85 (h, 1 H, -CH 3), 0.96 (d, 6 H, -CH 3). V. 2-Allyloxycarbonylmethylthio-3-methylbeneothiazoluabroBid: 7.2-7.9 (a, 4H, ar.), 3.88 (s, 3H, 5H-CH3), 4.20 (s, 2H, -S-CH3-, 4.43 (d, 2H, -O-CH2-), 5.5 (a, 1H, --CH-), 5.0 (a, 2H, = CH2). 7 233443 VI. 2-aethoxycarbonylaethylthio-3-ethylbenzothiazoluabroald: 7.2-7.9 (a, 4H, ar.), 4.38 (q, 2H, -H-CH2-), 1.25 (t, 3H, 4.20 (2 H, -S-CH 3 -), 3.56 (s, 3 H, -O-CH 3). VII. 2-ethoxycarbonylaethyltlo-3-ethylbenzothiazoluabroaid: 7.2-7.9 (1.4H, ar), 4.38 (q, 2H, -Á-CH2-), 1.25 (t, 3H, - (CH 2) 2 4.2 (z, 2 B, -S-CH 2 -), 4.03 (q, 2 H, -OCH 3 -), 0.98 (t, 3 H, -CH 3). . VIII. 2-propoxycarbonylethylthio-3-ethylbenzothiazoluabroaid: 7.2-7.9 (a, 4H, ar.), 4.40 (q, 2H, ss-CH3-), 1.25 (t, 3H, -). CH 3, 4.24 (a, 2 H, -S-CH 2 -), 3.94 (t, 2 H, -O-CH 2 -), 1.38 (sex, 2 H, -CH 2 -), 0 , 63 (t, 3 H, -CH 3), IX, 2-isopropoxycarbonylethylthio-3-ethylbenzothlazoliumabromide: 7.2-7.9 (a, RH, ar), 4.38 (q, 2 H, 2'- CH2-), 1.23 (t, 3H, -CBj), 4.15 (a, 2H, -S-CH2-), 4.81 (h, 1H, -CH2), 0.98 (d, 6H, -CH3) X. 2-Allyloxycarbonylethylthio-3-ethylbenzothiazoluabroald: 7.2-7.9 (a, 4H, ar.), 4.43 (a, 4H, ss-CH2- , -0-CH2-), 1.25 (t, 3H, -CBj), 4.23 (a, 2H, rS-CHg-), 5.5 (a, 1 1, «CH-). XI: 2-Aethoxycarbonylethylthio-3-propylbenzothiazoluabroaid: 7.2-7.9 (a, 4H, ar.), 4.28 (t, 2H,; ft-CH2-); H, -CH3R0.73 (t, 3H, -CH3), 4.20 (S, 2H, -S-CH2-), 3.59 (s, 3H, -OC3). 2-ethoxycarbonylaethylthio-3-propylbenzothiazolium bromide: 7.2-7.9 (a, 4H, ar), 4.29 (t, 2H, al-CH2-), 1.70 (sex, 2H) , -CH 2 -, 0.73 (t, 3 H, -CH 3), 4.20 (s, 2H, -S-CH 2 -), 4.02 (q , 2 H, -O-CH 3 -, 0.95 (t, 3 H, -O-CH 3). XIII. 2-propoxycarbonylaethylthio-3-propylbenzothiazoluabroaid: 7.2-7.9 (a, 4H, ar.), 4.29 (t, 2H, z-CH3-), 1.70 (sex, 2H, -) CH 3 -, 0.70 (t, 6 H, -CH 3), 3.93 (t, 2 H, -O-CH 2 -), 1.36 (sex, 2 H, -CH 2 -). XIV. 2-isopropoxycarbonylalkyl-3-propylbenzothiazoluabroald: 7.2-7.9 (a, 4H, ar.), 4.28 (t, 2H, afc-CH2-), 1.69 (sex, 2H, -CH 3 -, 0.70 (t, 3 H, -Cl 2), 4.16 (s, 2 H, -S-CH 2 -), 4.85 (h, 1 H, -O-CH =) , 0.94 (d, 6H, -CH 3). XV. 2-allyloxycarbonylactyl-3-propylbenzothiazoluabroald: 7.2-7.9 (a, 4H, ar.), 4.30 (t, 2H, .dbd.CH2 -), 1.70 (sex, 2H, -CH 3 -, 0.73 (t, 3 H, -CH 2 -), 4.23 (s, 2 H, -S-CH 2 -), 4.43 (d, 2 H, -O-CH 2 -) ), 5.5 (a, 1H, = CH-), 5.0 (a, 2H, = ch2). XVI. 2-Aethoxycarbonylaethylthio-3-allylbenzothlazoluabroaid: 7.2-7.9 (a, 4H, ar), 5.0 (a, 4H, = fc-CH2-, -CH8), 5.5 (a , 1 H, -CH-), 4.20 (a, 2H, -S-CH 2 -), 3.56 (s, 3 H, -O-CH 3). XVIII. 2-Aetozycarbonylethylthio-3-butylbenzothiazoluabroaid: 7.2-7.9 (a, 4H, ar), 4.33 (t, 2H, 5S-CH2-), 1.7 (a, 2H, - CH 2 -), 1.2 (a, 2 H, -CH 2 -), 0.63 (t, 3 H, -CH 3), 4.20 (s, 2 H, -S-CH 2 -), 3, 56 (s, 3H, -O-CH3). XIX. 2-ethoxycarbonylaethylthio-3-butylbenzothiazoluabroaid: 7.2-7.9 (a, 4H, ar.), 4.31 (t, 2H, ss-CH3-), 1.6 (a, 2H, -). CH 2), 1.3 to 0.5 (a, SH, -CH 2 -, -CH 3), 4.19 (s, 2 H, -S-CH 3 -), 4.02 (q, 2H, -) O-CH 2 -). XX. 2-propoxycarbonylethylthio-3-butylbenzothiazoluabroaid: 7.2-7.9 (a, 4H, ar.), 4.35 (t, 2H, zi-CH2-), 1.8-1.0 (a, 6 H, -CH 3 -, 0.63 (t, 6 H, -CB 3), 4.26 (s, 2 H, -S-CH 2 -), 3.94 (t, 2 H, -O-CH 3) -). 233443 8 XXI. 2-allyloxycarbonylmethylthio-3-butylbenzothiazolium bromide: 7.2-7.9 (m, 4H, ar.), 4.33 (t, 2H, H-CH2-), 1.6 (m, 2H, -CH 2 -, 1.1 (m, 2 H, -CH 2 -), 0.63 (t, 3 H, -CH-), 4.24 (a, 2 H, -S-CH 3 -), 4 , 43 (d, 2 H, -O-CH 3 -), 5.5 (1.1 H, CH -), 5.0 (a, 2 H, -0¾). XXII. 2-methoxycarbonylmethyl-3-benzylbenzothiazolobromide: 7.2-7.9 (a, 4H, ar.), 5.52 (t, 2H, -pht-CH2-), 4.25 (s, 2H, -S-CH 3 -). XXIII. 2-ethoxycarbonylmethyl-3-benzylbenzothiazolium bromide: 7.2-7.9 (a, 4H, ar.), 5.52 (t, 2H, t-CH2-), 4.25 (s, 2H, -S-CH 3 -). The compounds of the invention are effective as plant growth stimulators or inhibitors. The bastion tests were carried out by an authorized method on the object of the vetch. Example 4 illustrates a method for testing compounds of the invention for stialating and inhibitory activity. Example 4
Sowed wolf wolves sprouted in Petrl's aisaks in a thermostate in the dark at 25 ° C. Keying after 48-hour growth was exposed in molar solutions of 2-R-3-r'-substituted benzothiazolium salts, where B, B * and X ~ according to the general formula are given in I-XXIII, Table 1 in the Concentration Rock 10 ”6 to 10-1 mol.dm-3. After 24 hours of incubation, the increase in root extension growth was determined. In each determination, the growth effect in the control series was also performed, the width of the experimental and control sets, as well as the frequency of the analysis and bioassay were determined bioaetrically.
As standards, beta-indulylacetic acid (IAA), 2,4-dichloro-phenoxyacetic acid (2,4-D) and 2-chloroethyltrimethylammonium chloride (CCO) were tested. The results of the stialational inhibitory effect of the synthesized compounds of the invention are shown in Table 2.
Table 2
Stialating and inhibitory effect of the synthesized compounds according to the invention Number R B1 X "Stability + Bua mol.dm" 3 Inhibition · -a-mol.dm I II 00¾ OC2H5 0¾ CH3, 1 Br Br 7.15 4.05 io-1 10 ” 7 10 "13 III 0C3H7 ch3 Br 3.55 IV OC-JILY-i CH3 Br 5.50 10" 9. 10 "13 in och2gh» ch3 Br, 0-7 5.15 VI VII 00¾ OCgH, c2h5 C2H5 Br Br 3.85 4.9 10-'3 VIII Ο ° 3Η7 .¾¾ Br 21.60 10 ”3 IX OCjtty -i C2H5 Br 2.00 10-5 1.50 10 “13 10” '3 X och2ch-ch? c2h5 Br 4.30 XI 00¾ 5¾ Br XII °° 2η5 c3 «7 Br 1.55 10“ 7 XIII oe3H7 Br 2.55 10 “9 10” H 10-13 XIV QC ^ -i C3 “7 Br 3.80 XV och2ch« ch2 · * 3 * 1 Br 1.20 XVI OCH. CH, GH-CH, Br 13, 40 10-3
Claims (3)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS837216A CS233443B1 (en) | 1983-10-03 | 1983-10-03 | 2 * alkoxycarbonylmethylthio-3-alkylbenzothiazole salts and their preparation |
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| CS837216A CS233443B1 (en) | 1983-10-03 | 1983-10-03 | 2 * alkoxycarbonylmethylthio-3-alkylbenzothiazole salts and their preparation |
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| CS233443B1 true CS233443B1 (en) | 1985-03-14 |
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