CS269044B1

CS269044B1 - 2- (Chloroacetylamino) -6-substituted benzothiazoles and their preparation

Info

Publication number: CS269044B1
Application number: CS888092A
Authority: CS
Inventors: Maria Rndr Csc Henselova; Anna Doc Rndr Csc Gvozdjakova; Stefan Rndr Csc Varkonda; Vaclav Rndr Csc Konecny; Maria Rndr Pohankova; Ester Rndr Ticha; Alzbeta Dobrovodska
Original assignee: Henselova Maria; Gvozdjakova Anna; Varkonda Stefan; Konecny Vaclav; Maria Rndr Pohankova; Ticha Ester; Alzbeta Dobrovodska
Priority date: 1988-12-08
Filing date: 1988-12-08
Publication date: 1990-04-11
Also published as: CS809288A1

Abstract

Riešenia sa týká 2-chláracetylaeino-6-wetyl(alebo metoxy) benzotiazolov a spósobu ich přípravy reakciou 2-amino-6-metyl (alebo matoxy) benzotlazolu s chlóracetylchloridom v prostředí organického riedidla, pri teplote od 10 °C do teploty varu reakčnaj zmesi, počas 2 až 5 h. Uvedené zlúčeniny je možné použit ako regulátory rastu rastlín a fungicidyThe solution relates to 2-chloroacetyl-6-methyl (or methoxy) benzothiazoles and a method for their preparation by reacting 2-amino-6-methyl (or methoxy) benzothiazole with chloroacetyl chloride in an organic diluent, at a temperature from 10 °C to the boiling point of the reaction mixture, for 2 to 5 h. The above compounds can be used as plant growth regulators and fungicides.

Description

EN 269 044 B1 1

The present invention relates to 2- (chloroethylamino) -6-substituted benzothiazoles of the general formula I; c-nh-C 0-c 2 (c) wherein R is methyl or methoxy and the process for their preparation. 2- (Chloroacetylamino) -6-substituted benzothiazoles of general formula I It is possible to use it as growth regulators and fungicides.

Benzothiazole derivatives represent a large group of beterocyclic compounds with very diverse use. 3-Substituted benzothiazolium salts are known as active agents for controlling plant growth and increasing carbohydrate content in plants producing it (CS 237 706, CS 250 876) and also for improving the technological parameters of agricultural crops (CS 239 411). N-substituted oxobenzothiazolines and oxobenzoxazolines are known as plant growth promoters (US 4 149 871, US 4 227 915). Some 2-alkylthyl-3-alkylbenzothiazolium salts are known as stimulants or inhibitors of rasturastin (CS 239 422), 2-styryl-3-substituted benzothiazolium salts described as growth regulators, fungicides and bactericides and 3-aryloxyacetyl-2-benzothiazolines as herbicides and plant growth regulators (PV 2 979-87, CS 263 377).

New-2- (chloroacetylamino) -6-substituted benzothiazoles of formula X have now been found, wherein R is as defined above and prepared by reacting the 2-amino-6-substituted benzothiazole of formula n.

where R is as defined above, with chloroacetyl chloride in an organic diluent, at a temperature of from 10 ° C to the boiling point of the reaction mixture, for 2 to 5 hours. 2-Chloroethylamino-6-substituted benzothiazoles of the formula I can be used as growth enhancers , significantly affecting the elongation growth and overall biomass formation of the plants and as fungicides of the plant-important diseases causing pathogens such as Alternaria sp., Fusariuro nivale, Botritys cinerea, Tilletia foetida, and the like.

For this purpose, solutions, emulsions, powders, or other application forms known in the art, for example by mixing the active ingredient with excipients, diluents, diluents or the like, can be formulated into solutions, emulsions, and the like. The content of the compound of formula I according to the invention in such dosage forms can range from 0.01 to 95% by weight. 2 CS 269 044 Bl

The following examples illustrate, but do not limit the invention. Example 1

OK a solution of 0.05 mol of 2-amino-6-methylbenzothiazole in 50 cm of anhydrous vinegar and added dropwise with 0.06 mol of chloroacetyl chloride, the reaction mixture was allowed to stand for 3 h, at 20 to 25 ° C, the precipitate formed was collected crystallized from acetic alcohol (2: 1) to give 2- (chloroacetylamino) -6-methylbenzothiazole (compound A) with a melting point of 203 ° C to 205 ° C in a 75% yield.

Elemental analysis for C ^ QHgNN2SOClCl, MW 240.69:

H, 3.75; H, 11.63; N, 13.32; C, 49.38; H, 3.51; H, 11.49; 2 To a solution of 0.05 mol of 2-amino-6-methoxybenzothiazole in 50 cm of anhydrous toluene was added dropwise 0.05 mol of chloroacetyl chloride, the reaction mixture was not left to stand for 3 h at 55-60 ° C and worked up. as in Example 1. 2- (Chloroacetyl) -6-methoxybenzothiazole (Compound B) was obtained with a melting point of 241-242 ° C in 78% yield.

H, 3.53; N, 10.91; N, 12.49; C, 47.53; H, 3.39; % N, 12.38% S Example 3

Buckwheat seeds (Fagopyrum vulgare L.) were sent to experimental vessels filled with hypotonic sand to rows of 25 seeds per pot and did not breed into the Stage of Seeds, Ptom negotiated on the same count (20 pieces) per pot and at the stage of primary right leaf differentiation, the plants of Example 1 (Compound A) were applied to the plants in the form of graded concentration solutions of 25 to 500 mg of active ingredient, 1 at 7 ml to 700 cm, and kept in a greenhouse at 26-28. ° C with additional 8,000 lux with 12-hour photoperiod. After 14 days, the effect of the test compound was evaluated based on the major stem stem increment from the point of application to the terminal point. By comparing the incremental growth of treated and untreated plants, a stimulatory effect was found and expressed in% control. The data summarized in Tables 1 are the average of four replicates and confirm the significant stimulatory effect of Compound A on the terminal growth of buckwheat plants. CS 269 044 B1 3

Table 1

Test compound Concentration g. l "1 Average X, mm Length% Stems K w - 264.0 100.0 25 275.0 104.2 50 293.0 111.0 Compound A 75 297.0 112.5 100 313.0 118.6 500 299.6 113.5 Example 4

Alone spring barley of the Favorit variety was left out? 24 hrs. Of the compound of Example 1 (Compound A) in a graded concentration. 10 seeds were placed on petri dishes with 5 ml of distilled water equipped with a filter paper ring and the dishes were placed in a thermostat at 26 ° C + ° C and a relative air humidity of 85-90%. After 8 days, lengthwise incremental and coleopthilic metric were evaluated. Comparison of the length increments of treated and untreated plants revealed the percentage stimulatory effect of the test compound compared to control, the data summarized in Table 2 being the average of four replicates and confirming the significant effect of Compound A on barley plant growth growth.

Table 2

Average Length Test Compound Koleopticum Root Concentration mg. l “1 £, mm% κ 3 ?, mm% K 122.5 100.0 140.0 100.0 0.01 149.6 122.1 151.1 107.9 Compound A 0.1 128.4 104 , 8 155.0 110.7 1.0 108.1 88.2 142.1 101.5 10.0 97.5 79.6 119.4 85.3 EN 269 044 Bl Example 5

The spring barley seeds of the Favorit variety were left for 24 hours in a solution of the compound of Example 1 (Compound A) of the dehumidified concentration in the range of 0.01 to 10 mg of active ingredient. 1 µl, then 24 hours at room temperature, poured into test vessels filled with sandy-clay foil, 20 seeds per flask and regular grout were then kept in the greenhouse at 26-28 ° C for 16 days, the test compound being evaluated on the basis of the total biomass increment of the treated and untreated plants, which was converted to the average weight of one plant from a total of 100 plants.

By comparing the average biomass weight of treated and untreated growths, the percent stimulatory effect was calculated. The data in Table 3 illustrates the stimulatory effect of Compound A on the growth of total plant biomass biomass.

Table 3

Test Compound Concentrate. I "1 Average X Plant Weight, mg% K 0.01 0.1 241.6 307.7 266.7 100.0 127.4 110.4 Compound A lo 255.6 105.8 10.0 247.1 102, 3 Example 6 oa) Measured after 9 cm of nutrient agar medium to which was added 1 cm of solutions of the test compounds of Example 1 (Compound A) and Substrate 2 (Compound B) in staggered portions and after mixing, the homogenates were poured onto Petri dishes. a 10 mm diameter inoculum obtained from a growing colony of the appropriate micromycota-Alternariasp., Botrytis cinerea, Fusarium nivale, The plates were placed in a thermostat and maintained at the optimum growth rate of the individual pathogens.

Claims

B) 100 mg of Compound A and Compound B were added to samples of 100 g of sterilized sieved soil, and Compound B and the mixture were homogenised and the graded concentration of test compounds was added by adding pure soil. These mixtures were filled with Petri dishes, the surface leveled and moistened. An aqueous suspension of Xilletia foetida chlamydospores (1.5 cm @ 3 flask) in a laboratory sprayer was inoculated on the wet surface. Incubation was thermostated at the optimum temperature for pathogen growth. Growth of fungal colonies was monitored continuously in both procedures (6a, 6b) and evaluated metric. Based on the growth curves, the fungicidal activity of the test compounds was evaluated and a minimum inhibitory concentration of 33 cia-MIC (in micrograms of active ingredient per cm) was evaluated. Table 4 shows the fungicidal effect of the test compounds on the modelic chromocytes. Table 4: Alternaria sp. Botrytis l Fusarium nivale Tilletia foetida cinerea Compound A 50 - <MIC 100 <, MIC> 100 MIC> 100 31.6 <MIC <100 Compound B MIC <50 MIC J> 100 MIC> 100 31.6 <MIC <100 SUBSTANCE A 2- (chloroacetylamino) -6-substituted benzothiazoles of formula I.

wherein R is methyl or methoxy.

2, Preparation of 2- (chloroacetylamino) -6-substituted benzothiazoles according to claim 1, characterized in that it is a 2-amino-6-substituted benzothiazole of general formula II. C-NH "(II) wherein R is as defined above, is treated with chloroacetyl chloride in an organic diluent, at a temperature of from 10 ° C to the boiling point of the reaction mixture, for a period of from 2 to 5 hours.