CS231229B1 - Processing method of 3-r-y-r1-substituted benzothiazel salts - Google Patents

Processing method of 3-r-y-r1-substituted benzothiazel salts Download PDF

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CS231229B1
CS231229B1 CS743482A CS743482A CS231229B1 CS 231229 B1 CS231229 B1 CS 231229B1 CS 743482 A CS743482 A CS 743482A CS 743482 A CS743482 A CS 743482A CS 231229 B1 CS231229 B1 CS 231229B1
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bromide
wed
substituted
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methyl
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Jan Halgas
Viktor Sutoris
Vladimir Sekerka
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Jan Halgas
Viktor Sutoris
Vladimir Sekerka
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Vynález sa týká 3-R-Y-r’-substituovaných benzotiazóliových soli obecného vzorce IThe invention relates to 3-R-Y-r '-substituted benzothiazolium salts of formula I

/1/ kde R znamená metyl, alyl, propargyl, metoxykarbonylmetyl, etoxykarbonylmetyl, propoxykarbonylmetyl, alyloxykarbonylmetyl, benzyl, 2-metylbenzyl, 3-metylbenzyl, 4-metylbenzyl, 2-chlór benzyl, 3-chlórbenzyl, 4-chlárbenzyl, 2-nitrobenzyl, 3-nitrobenzyl, 4-nitrobenzyl, 3-briabenzyl, 4-brómbenzyl, 3-fluórbenzyl, 4-fluórbenzy1, 4-metoxybensyl, 4-kyanobenzyl, 4-eulfamoylbenzyl; R* 1 znamená 4-H, 4-metyl, 4-chlór, 6-H, 6-metyl, 6-chlórj X znamená bromidový, jódidový, metosulfátový anlon a Y znamená 4, 6 a spSsebu ich přípravy.(1) wherein R represents methyl, allyl, propargyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, allyloxycarbonylmethyl, benzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2-chlorobenzyl, 3-chlorobenzyl, 2-chlorobenzyl, 4-chlorobenzyl 3-nitrobenzyl, 4-nitrobenzyl, 3-briabenzyl, 4-bromobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 4-methoxybensyl, 4-cyanobenzyl, 4-eulfamoylbenzyl; R 1 is 4-H, 4-methyl, 4-chloro, 6-H, 6-methyl, 6-chloro X is bromide, iodide, metosulfate anonone and Y is 4,6 and their preparation.

Do súčasnej doby bola nejvačSia pozornost věnovaná syntéze rSznych 2-alkylbenzotiezóliových solí. Niektoré kvartérne soli benzotiazólu nesubstituované v poloze 2 sú tiež dávno známe, ale ich biologickým vlastnostiam nebola prakticky věnované žiadna pozornost. Zásadné literárně odkazy z chemickej oblasti benzotiazólu boli citované v AO autorů Suteriae V., Halgaše J., Sekerky V. 6. 223426 2-R-3-R^-substituované benzotiazólové soli a spfisob ich přípravy a čialej v Ss. autorskom osvedSeniu S. 231212.To date, most attention has been devoted to the synthesis of various 2-alkylbenzothiazolium salts. Some quaternary benzothiazole salts unsubstituted at the 2-position have also been known for a long time, but their biological properties have been virtually ignored. Essential literary references in the chemical field of benzothiazole have been cited in the AO of Suteriae V., Halgaša J., Sekerky V. 6. 223426 2-R-3-R 1 -substituted benzothiazole salts and methods for their preparation and starting in Ss. certificate p. 231212.

Chemické vlastnosti benzotiazólu nasvedčujú tomu, že tiazóliový kruh v podstatě nemá aromatický charakter. Elektrofilné substitučné reakcie prebiehajú na benzénovom jadre /Hunter R. F.: J. Chem. Soc. 1926, 537J 1930, 125; 1935, 1975/, predovšetkým v polohe 6.The chemical properties of the benzothiazole indicate that the thiazolium ring is substantially non-aromatic in nature. Electrophilic substitution reactions take place on the benzene nucleus / Hunter R. F .: J. Chem. Soc. 1926, 537, 1930, 125; 1935, 1975], particularly at position 6.

Aj v případe 2-fenylbenzotiazólu idú elektrofilné substitúcie do tej istej polohy a nie na fenylovú skupinu /Rivier H., Zeltner J.: Helv. Chim. Acta 20, 691 (1937)/. Stádium prenosov elektronových efektov substituentov z benzénového jadra na reakčné centrum v polohe 2 ukázalo, že efekty sa prenášajú takmer výlučné cez dusíkový atóm heterooyklu a nie cez atóm síry /Bartoli G., Todesco P.E.: Tetrahedron 32, 399 (1976); Sawhney S. N., Boykin D. W.: J. Org. Chem. 44, 1136 (1979)/. Pri vysokých teplotách sa benzotiazól halogenuje do polohy 2 a jedná sa pravděpodobně o radikálový priebeh reakcie /Jansen L., Wibaut J. P.: Rec. Trav. Chim. Pays-Bas 56, 699 (1937)/.Also in the case of 2-phenylbenzothiazole, the electrophilic substitutions go to the same position and not to the phenyl group. Rivier H., Zeltner J .: Helv. Chim. Acta 20, 691 (1937)]. The phase transfer of the electron effect of the substituents from the benzene nucleus to the reaction center at position 2 showed that the effects are transmitted almost exclusively through the heterooyl nitrogen atom and not through the sulfur atom / Bartoli G., Todesco P.E .: Tetrahedron 32, 399 (1976); Sawhney, S. N., Boykin, D. W., J. Org. Chem. 44, 1136 (1979)]. At high temperatures, the benzothiazole is halogenated to the 2-position and is likely to be a radical reaction / Jansen L., Wibaut J.P .: Rec. Trav. Chim. Pays-Bas 56, 699 (1937)].

Pfisobením minerálnych kyselin na benzotiazól .vznikajú soli, silné bázy spfisobujú štiepanie tiazólového kruhu, ktoré je podporované prítomnosťou elektrónakceptórnyoh skupin na benzénovom jadre /Bartoli G., Ciminale F., Todesco P. E.: J. Chem. Soc. Perkin Trans.By the addition of mineral acids to the benzothiazole, salts are formed, and the strong bases cause cleavage of the thiazole ring, which is supported by the presence of electron acceptor groups on the benzene nucleus. Bartoli, G., Ciminale, F., and Todesco, P.E. Soc. Perkin Trans.

1975, 1472/. 6-substituované 2-benzotiazólaminy, východiskové látky pre přípravu 6-substi tuovaných benzotiazólov sa připravili tiokyanáciou příslušných p-substituovaných anilínov. /Brewster R. Q., Danis F. B.: J. Am. Chem. Soc. 58, 1364 (1936)/ a podobné 4-substituované 2-benzotiazólamíny z o-substituovaných anilínov převedením na tiomočoviny a ich oyklizáciou pfisobením brómu /Dalgliesh C. E., Mann F. G.: J. Chem. Soc. 1945, 893/.1975, 1472]. 6-substituted 2-benzothiazol amines, starting materials for the preparation of 6-substituted benzothiazoles, were prepared by thiocyanation of the corresponding β-substituted anilines. / Brewster R. Q., Danis F. B .: J. Am. Chem. Soc. 58, 1364 (1936)] and similar 4-substituted 2-benzothiazol amines from o-substituted anilines by conversion to thioureas and their bromination by cyclization (Dalgliesh C. E., Mann F. G., J. Chem. Soc. 1945, 893.

Na dezamináciu bola aplikovaná metoda /Cadogan J. 1. G., Molina G. A.: J. Chem. Soc. Perkin I, 1973, 541/, ktoré po diazotácii niektorých aromatických alebo heterocyklických amínov pentylnitritom v bezvodom tetrahydrofuráne poskytuje deriváty s vodíkom naviazaným na mieste pfivodnej aminoskupiny. Podl’a literatúry 3-R-Y-R -substituované benzotiazóliové soli všeobecného vzorca I nie sú doteraz známe.The method of Cadogan J. 1 G., Molina G. A., J. Chem. Soc. Perkin I, 1973, 541), which, after diazotization of some aromatic or heterocyclic amines with pentylnitrite in anhydrous tetrahydrofuran, provides derivatives with hydrogen bonded in place of the natural amino group. According to the literature, the 3-R-Y-R-substituted benzothiazolium salts of the formula I are not yet known.

i Podstata spfisobu přípravy 3-R-Y-r’ substituovaných benzotiazóliových soli pedl’a vynálezu spočívá v tom, že 4-r’ alebo 6-r’ benzotiazól, kde r’ znamená to isté ako vo vzorci I, reaguje s zlúčeninou obecného vzorca RX, kde R a X znamená to isté ako vo vzorci I, v prostředí organických rozpúštadiel, ako sú dimetylformamid, dimetylsulfoxid, acetonitril, nižšije alifatické ketony a alkoholy pri teplote 50 až 100 °C po dobu 5 až 30 hodin.The process for preparing the 3-RY-r 'substituted benzothiazolium salts of the present invention is characterized in that the 4-r' or 6-r 'benzothiazole, wherein r' is the same as in formula I, reacts with a compound of formula RX wherein R and X are the same as in Formula I in an environment of organic solvents such as dimethylformamide, dimethylsulfoxide, acetonitrile, lower aliphatic ketones and alcohols at 50 to 100 ° C for 5 to 30 hours.

Uvedenú reakciu naznačuje schéma:This reaction is indicated by the scheme:

kde R, r’ a X má horeuvedený význam.where R, r 'and X are as defined above.

Příklad 1 mól substituovaného 2-aminobenzotiazólu sa rozpustil v 500 ml bezvodého tetrahydrofuránu a roztok sa prikvapkal do vriacej zmesi 186 g /1,6 mólu/ pentylnitrilu a 1 000 al bezvodého tetrahydrofuránu počas 1,5 hodiny. Zmes sa zohrievala na reflux áalších 6 hodin. Rozpúšladlo sa oddestilovalo a tmavý zvyšok sa premyl vodou. Organická vrstva sa oddělila, vodná sa extrahovala 200 ml benzénu. Benzénový extrakt sa přidal k organickej vrstvě a táto zmes sa destilovala pri zníženom tlaku. Po oddestilování rozpúšťadla a 1-pentanolu sa zachytával produkt. Destilát sa ešte raz predestiloval pri zníženom tlaku cez 20 cm vpichovanú kolonu. Chlórderiváty sa prekryštalizovali zo zriedeného etanolu.Example 1 mole of substituted 2-aminobenzothiazole was dissolved in 500 ml of anhydrous tetrahydrofuran and the solution was added dropwise to a boiling mixture of 186 g (1.6 mol / pentylnitrile) and 1000 l of anhydrous tetrahydrofuran over 1.5 hours. The mixture was heated at reflux for an additional 6 hours. The solvent was distilled off and the dark residue was washed with water. The organic layer was separated, the aqueous was extracted with 200 mL of benzene. The benzene extract was added to the organic layer and this mixture was distilled under reduced pressure. After distilling off the solvent and 1-pentanol, the product was collected. The distillate was distilled once more under reduced pressure through a 20 cm needled column. The chloro derivatives were recrystallized from dilute ethanol.

Příklad 2Example 2

Příprava 3-metyl-4-chlórbenzotiazóliumjodidu /1/Preparation of 3-methyl-4-chlorobenzothiazolium iodide (1)

Do sklenenej ampule sa vleje roztok 4,27 g /0,025 mol/ 4-chlórbenzotiazólu v 5 ml acetonu. Trubice se ochladí v zmesi l’adu a soli a naváži sa do nej 4,26 g /0,03 mol/ metyljodidu. Obsah trubice sa premieša a ochladí v zmesi C02 a acetonu s teplotou asi -80 °C. Potom sa vopred zúžený otvor zataví a trv.bica sa nechá ohriat na laboratórnu teplotu, vloží sa do vodného kúpela a pomaly sa zahrieva na teplotu 55 °C. Pri tejto teplote sa zahrieva 10 hodin. Potom sa znova ochladí a po otvorení sa kryštalická kvartérna sol odsaje, premyje bezvodým acetónom a prekryštalizuje z bezvodého tetrahydrofurénu s 1' až 2 % metanolu.A solution of 4.27 g (0.025 mol) of 4-chlorobenzothiazole in 5 ml of acetone is poured into a glass vial. The tubes were cooled in an ice / salt mixture and weighed 4.26 g (0.03 mol) of methyl iodide. The contents of the tube were mixed and cooled in a mixture of CO 2 and acetone at a temperature of about -80 ° C. The pre-tapered orifice is then sealed and the tube allowed to warm to room temperature, placed in a water bath and slowly warmed to 55 ° C. It is heated at this temperature for 10 hours. It is then recooled and, after opening, the crystalline quaternary salt is suctioned off, washed with anhydrous acetone and recrystallized from anhydrous tetrahydrofuran with 1 'to 2% methanol.

Příklad 3Example 3

Příprava 3-metyl-4-metylbenzotiazóliummetosulfátu /111/Preparation of 3-methyl-4-methylbenzothiazolium methosulfate (111)

14.9 g /0,1 mol/ 4-metylbenzotiazólu, 12,6 g /0,1 mol/dimetylsulfátu zreaguje státim pri laboratórnej teplote po dobu 20 hodin. Kryštalizácia sa uskutočnila zo zmesi metanolu a tetrahydrofuránu (1:3)·14.9 g (0.1 mol) of 4-methylbenzothiazole, 12.6 g (0.1 mol) of dimethyl sulfate are reacted by standing at room temperature for 20 hours. Crystallization was carried out from a mixture of methanol and tetrahydrofuran (1: 3).

Přikládáattaches

Příprava 3-izopropoxykarbonylmetyl-6-chlórbenzotiazólium bromidu /XVII/Preparation of 3-isopropoxycarbonylmethyl-6-chlorobenzothiazolium bromide (XVII)

16.9 g /0,1 mol/ 6-chlórbenzotiazólu, 27,1 g /0,15 mol/ izopropylesteru kyseliny brómoctovej sa mieša s 10 ml dimetylformamldu a 5 ml acetonu. Reakčná zmes sa zohrieva 6 až 12 hodin pri 50 až 70 °C. Po ochladení sa do reakčnej zmesi přidá 10 až 20 ml éteru alebo petrol éteru. Krystalický podiel sa krystalizuje zo zmesi metanol a éter /1:3/.16.9 g (0.1 mol) of 6-chlorobenzothiazole, 27.1 g (0.15 mol) of isopropyl bromoacetate are mixed with 10 ml of dimethylformamide and 5 ml of acetone. The reaction mixture is heated at 50 to 70 ° C for 6-12 hours. After cooling, 10-20 ml of ether or petroleum ether are added to the reaction mixture. The crystalline fraction was crystallized from methanol / ether (1: 3).

Výsledky elementárnej analýzy a fyzikálno-chemické konštanty syntetizovaných zlúčenín I až LVI sú uvedené v tabuíke 1.The results of elemental analysis and physicochemical constants of synthesized compounds I-LVI are shown in Table 1.

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Vysvětlivky:Explanation:

I 3~Metyl-4-chlórbenzotiazóliuffljo<3id13-Methyl-4-chlorobenzothiazolium sulfide <3id

II 3-Metyl-4-chlorbenzotiazóliummetosulfátII 3-Methyl-4-chlorobenzothiazolium methosulfate

III 3-Metyl-4-metylbenzotiazóliumsietO8UlfátIII 3-Methyl-4-methylbenzothiazoliumsulfonate

IV 3~Jíetyl-6-chlórbenzot,iszóliumbromidIV 3-Ethyl-6-chlorobenzot, isolium bromide

V 3-Metyl-6-chlórbenzotiazóliumjodidV 3-Methyl-6-chlorobenzothiazolium iodide

VI 3-Metyl-6-metylbenzotiazóliumbromidVI 3-Methyl-6-methylbenzothiazolium bromide

VII 3-Metyl~6-metylbenzotiazólium jodidVII 3-Methyl-6-methylbenzothiazolium iodide

VIII 3-Propargyl-4-metylbenzotiazóliumbromidVIII 3-Propargyl-4-methylbenzothiazolium bromide

IX 3-Propargyl--6-metylbenzotiazóliumbroniidIX 3-Propargyl-6-methylbenzothiazolium bromide

X 3~Propargyl-6~chlórbenzotiazólIunibroniidX3-Propargyl-6-chlorobenzothiazolunibroniide

XI 3-Alyl-6-chlór-bsnzotiazóliumbromidXI 3-Allyl-6-chloro-benzothiazolium bromide

XII 3-Metoxykarbonylmetyl-£-metylbenzotiazollumbroaid íIII 3~Metoxykarbonylmetyl~6-chlórbenzotiazóltumbromidXII 3-Methoxycarbonylmethyl-.beta.-methylbenzothiazolium bromide III 3-Methoxycarbonylmethyl-6-chlorobenzothiazolium bromide

XIV 3-Etoxykarbonylmetyl~6-metylbenzotiazóliumbromidXIV 3-Ethoxycarbonylmethyl-6-methylbenzothiazolium bromide

XV 3-Propoxykarbonylaietyl-6-metylbenzotiazoliumbro)iiidXV 3-Propoxycarbonylaiethyl-6-methylbenzothiazolium bromide

XVI 3-Propoxykarbanylmetyl-6-chlórbenzotiazóliumbromidXVI 3-Propoxycarbanylmethyl-6-chlorobenzothiazolium bromide

XVII 3-Izopropoxykarbonylmetyl-6-metylbenzotiazóliUB!broiiiidXVII 3-Isopropoxycarbonylmethyl-6-methylbenzothiazolium bromide

XVIII 3-Izopropoxykarbonylmetyl-6-chlórbenzotiazóliumbroaiidXVIII 3-Isopropoxycarbonylmethyl-6-chlorobenzothiazolium bromide

XIX 3-Alyloxykarbonylmetyl-6-chlórbenzotiazoliumbromidXIX 3-Allyloxycarbonylmethyl-6-chlorobenzothiazolium bromide

XX 3-/2-Metylbenzyl/benzotiazóliumbroiaidXX 3- (2-Methylbenzyl) benzothiazolium bromide

XXI 3/3”Metylbenzyl/benzotlazólíumbromidXXI 3/3 ”Methylbenzyl / benzotlazolium bromide

XXII 3-/4-Metylbenzyl/benzotiazóliumbroniidXXII 3- (4-Methylbenzyl) benzothiazolium bromide

XXIII 3-/2-Chlórbenzyl/benzotiazóliumbrom.idXXIII 3- (2-Chlorobenzyl) benzothiazolium bromide

XXIV 3-/3-Chlórbenzyl/benzot.iazóliunibromidXXIV 3- (3-Chlorobenzyl) benzothiazolium bromide

XXV 3-/4-Chlórbenzyl/benzotiazóliumbromidXXV 3- (4-Chlorobenzyl) benzothiazolium bromide

XXVI 3-/3-Nitrobenzyl/benzotiazóliumbromidXXVI 3- (3-Nitrobenzyl) benzothiazolium bromide

XXVIÍ 3-/3-Brómbenzyl/benzotiazóliumbroniidXXVIII 3- (3-Bromobenzyl) benzothiazolium bromide

XXVIII 3-/4-Brómbenzyl/benzotiazóliumbromidXXVIII 3- (4-Bromobenzyl) benzothiazolium bromide

XXIX 3-/3-Fluorbenzyl/benzotiazól.iumbi'on!ÍdXXIX 3- (3-Fluorobenzyl) -benzothiazolium-biodone

XXX 3-/4-Fluorbenzyl/benzotiazóliumbromidXXX 3- (4-Fluorobenzyl) benzothiazolium bromide

XXXI 3-/4-Metoxybenzyl/benzotiazóliumbroniidXXXI 3- (4-Methoxybenzyl) benzothiazolium bromide

XXXII 3-/4-Kyanobenzyl/benzotiazóliumbromidXXXII 3- (4-Cyanobenzyl) benzothiazolium bromide

XXXIII 3-/1-Naftylmetyl/benzotiazóliumbromidXXXIII 3- (1-Naphthylmethyl) benzothiazolium bromide

XXXIV 3-/2-Naftylmetyl/benzotiazóliumbromidXXXIV 3- (2-Naphthylmethyl) benzothiazolium bromide

XXXV 3-/4-Sulfamoylbenzyl/benzotiazóliumbromidXXXV 3- (4-Sulfamoylbenzyl) benzothiazolium bromide

XXXVI 3-/4-MeEyloxybenzyl/benzotiazóliumbroniidXXXVI 3- (4-Methyloxybenzyl) benzothiazolium bromide

XXXVII 3-Benzyl-6-metylbenzotiazóliumjodidXXXVII 3-Benzyl-6-methylbenzothiazolium iodide

XXXVIII 3~/2-Metylbenzyl/-6-metylbenzotiazóliumbromidXXXVIII 3- (2-Methylbenzyl) -6-methylbenzothiazolium bromide

XXXIX 3-/3-Metylbenzyl/-6-metylbenzotiazóliumbromidXXXIX 3- (3-Methylbenzyl) -6-methylbenzothiazolium bromide

XL 3-/4-Metylbenzyl/-6-metylbenzotiazóliumbromidXL 3- (4-Methylbenzyl) -6-methylbenzothiazolium bromide

XLI 3-/2-Chlórbenzyl/-6-metylbenzotiazóliumbromidXLI 3- (2-Chlorobenzyl) -6-methylbenzothiazolium bromide

XLII 3-/3-Chlórbenzyl/-6-metylbenzotiazóliumbromidXLII 3- (3-Chlorobenzyl) -6-methylbenzothiazolium bromide

XLIII 3-/4-Chlórbenzyl/-6-metylbenzotiazóliumbromidXLIII 3- (4-Chlorobenzyl) -6-methylbenzothiazolium bromide

XLIV 3-/2-Niti'obenzyl/-6-metylberiZotiazóliumbro(nidXLIV 3- (2-Nitrobenzyl) -6-methylbenzothiazolium bromide (nid

XLV 3-/3-Nitrobenzyl/-6.-iíetýlbenzatiazóliuinl»i,eeiáXLV 3/3-Nitrobenzyl / -6.-iíetýlbenzatiazóliuinl »i, EEIA

XLVI 3-/4-KitrobenzyI/-6-metylbenzotiazóliumbromidXLVI 3- (4-Kitrobenzyl) -6-methylbenzothiazolium bromide

XLVII 3-/3-Brómbenzyl/-6-metylbenzotiazóliumbromidXLVII 3- (3-Bromobenzyl) -6-methylbenzothiazolium bromide

XLVIII 3-/4-Brómbenzyl/-6-metylbenzotiazóliumbromidXLVIII 3- (4-Bromobenzyl) -6-methylbenzothiazolium bromide

XLIX 3-/3-Fluorbenzyl/-6-ffletylbenzotiazóliumbromidXLIX 3- (3-Fluorobenzyl) -6-phenylbenzothiazolium bromide

L 3-/4-Fluorbenzy3./-6-metylbenzotiazóliumbromidL 3- (4-Fluorobenzyl) -6-methylbenzothiazolium bromide

LI 3-/4-Metoxybenzyl/-6-metylbenzotiazóliumbromidLI 3- (4-Methoxybenzyl) -6-methylbenzothiazolium bromide

Lil 3-/4-Kyanobenzyl/-6~metylbenzotiazóliumbromidLil 3- (4-Cyanobenzyl) -6-methylbenzothiazolium bromide

Lili 3-/1~Naftylmetyl/-6-metylbenzotiazóliumbromid :31229Lili 3- (1-Naphthylmethyl) -6-methylbenzothiazolium bromide: 31229

LIV 3“/2-Naftylmetyl/-6-metylbenzotiazóliumbromid LV 3-/4-Sulf amoylbenzyl/-6-nietylbřínzotiazóliumbromidLIV 3 '(2-Naphthylmethyl) -6-methylbenzothiazolium bromide LV 3- (4-Sulfamoylbenzyl) -6-methylbenzothiazolium bromide

LVI 3-/4-Mezyloxybenzyl/~6-metylbenzotiazóliumbromidLVI 3- (4-Mesyloxybenzyl) -6-methylbenzothiazolium bromide

Látky podl’a vynálezu sú účinné ako stimulátory a inhibitory rastu rastlín. Kastové testy sa realizovali autormi modifikovanou metodou na modelovom objekte Vika siata. Tento model bol vybraný .pře vysokú homogenitu v klíčivosti semien a raste klíčencov. Příklad 5 bližšie osvětluje spfisob testovania zlúčenín podTa vynálezu na stimulačnú a Inhiblčnú účinnost.The compounds of the invention are effective as plant growth promoters and inhibitors. Caste tests were performed by the authors modified method on the model object Vika siata. This model was selected for high homogeneity in seed germination and germination growth. Example 5 illustrates in more detail how to test compounds for stimulatory and inhibitory activity.

Příklad 5Example 5

Semená Viky siatej klíčili v Petriho miskách v termostate v tme, pri 25 °C. Klíčence po 48 hodinóvom raste sa exponovali v molárnych roztokoch 3-R-4-R1 - a 3-R-6-R1 _ substituovaných benzotiazóliových solí, kde R, R1 a X“ podTa všeobecného vzorca je uvedené v I až LVI, tabuTka 1, v koncentračnej škále 10_1“ až 10~1 M. Po 24 hodinách inkubácií bol stanovený prírastok predlžovacieho rastu koreňov. Pri každom stanovení bol uskutočnený aj rastový efekt v kontrolnej sérii. Sirka pokusného a kontrolného súboru, ako aj signifikantnost medzi súbormi, boli stanovené biometricky.Seeds of Vetch were germinated in petri dishes in a thermostate in the dark at 25 ° C. Germs after 48 hours of growth were exposed in molar solutions of 3-R-4-R 1 - and 3-R-6-R 1 -substituted benzothiazolium salts, wherein R, R 1 and X "as shown in I to LVI , Table III 1, in the concentration range of 10 _1 "and 10 ~ 1 M. After 24 hours of incubation was determined by addition of the extension of root growth. For each assay, a growth effect was also performed in the control series. The width of the test and control sets as well as the significance between sets were determined biometrically.

Ako Standardy boli testované kyselina beta-indolyloctové /IAA/, kyselina 2,4-dichlórfenoxyoctová /2,4-D/ a 2-chlóre.tyltrimetylamóniumchlorid /GCC/. Výsledky stimulačného a inhibičného účinku váčšiny syntetizovaných zlúčenín podTa vynálezu sú uvedené v tabuTke 2.Beta-indolylacetic acid (IAA), 2,4-dichlorophenoxyacetic acid (2,4-D) and 2-chloro-trimethyl-ammonium chloride (GCC) were tested as standards. The results of the stimulatory and inhibitory effect of most of the synthesized compounds of the invention are shown in Table 2.

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Claims (2)

1. 3-R-Y-R1-substituované benzotiazóliové soli všeobecného vzorce I r1+oT^€ ch x'(+i /1/ kde R znamená metyl, alyl, propargyl, metoxykarbonylmetyl, etoxykarbonylmetyl, propoxykarbonylmetyl, alyloxykarbonylmetyl, benzyl, 2-metylbenzyl, 3-metylbenzyl, 4-metylbenpyl,1. 3-substituted 1-RYR benzotiazóliové salts of Formula I, R @ 1 + ^ oT € ch x '(i + / 1 / wherein R is methyl, allyl, propargyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, allyloxycarbonylmethyl, benzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2- chlórbenzyl, 3-chlórbenzyl, 4-chlórbenzyl, 2-nitrobenzyl, 3-nitrobenzyl, 4-nitrobenzyl,2-chlorobenzyl, 3-chlorobenzyl, 4-chlorobenzyl, 2-nitrobenzyl, 3-nitrobenzyl, 4-nitrobenzyl, 3- brómbenzyl, 4-brómbenzyl, 3-fluórbenzyl, 4-fluorbenzyl, 4-metoxykenzyl, 4-kyanobenzyl,3-bromobenzyl, 4-bromobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 4-methoxycenzyl, 4-cyanobenzyl, 4- sulfoamoylbenzyl, R1 znamená 4-H, 4-metyl, 4-chlór, 6-H, 6-ehlór, 6-metyl; a X* znamená brómidový, jodidový, metosulfátový anion a Ϊ znamená 4,6.Sulfoamoylbenzyl 4, R 1 is 4-H, 4-methyl, 4-chloro, 6-H, 6-chloro, 6-methyl; and X * is a bromide, iodide, metosulfate anion and Ϊ is 4.6. 2. Sp6sob pripravy látok všeobecného vzorca I podTa bodu 1 vyznačujúci sa tým, že 4-R1 alebo 6-R1 - benzotiazól, kde R1 znamená to isté ako vo vzorci I, reaguje s zlúčeninou všeobecného vzorca RX, kde R a X znamená to isté ako vo vzorci I, v prostředí organických rozpúštadiel, ako sú dimetylformamid, dimetylsulfonid, aoetonitril, nižšie alifatické ketony a alkoholy, pri teplote 50 až 100 °C, po dobu 5 až 30 hodin.2. Sp6sob preparation of compounds of formula I to be cut down to claim 1 characterized in that the 4-R 1 -R 6, or 1 - benzothiazole, wherein R 1 is the same as in formula I, is reacted with a compound of the formula RX, wherein R and X it is the same as in formula I, in an organic solvent environment such as dimethylformamide, dimethylsulfonide, aoetonitrile, lower aliphatic ketones and alcohols, at a temperature of 50 to 100 ° C, for 5 to 30 hours.
CS743482A 1982-10-20 1982-10-20 Processing method of 3-r-y-r1-substituted benzothiazel salts CS231229B1 (en)

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