RU1512075C - Ethers on the base of 1-oxymethyl-1,2,4-triazol possessing fungicide and bactericide activity - Google Patents

Abstract

The invention relates to derivatives of 1M triazole, in particular N-1,2,4-triazolylmethyl bfir. acetic acid, N - (- MeTOKCH-l, 2,4, triazolyl-2, 2,2-trichloroethyl) acetam-: DU (or formamide) having fungicide. gicidal and bactericidal activity. The purpose of the invention is to expand the spectrum of action of the fungicides indicated and their activity. The synthesis is carried out from 1-hydroxymethyl-1,2,4-triazole and the corresponding chloro-derivatives in benzene. Yield,%: mp, s; gross f-la: a) 78; 51-52; b) 79; 16.9-170; c) 81; 133-136; ,. The new substances are active against the bacteria Hanthomonas malvaccarum and Pseudomo -, nas lachrimano, i.e. bacteriosis of cucumbers, on green plants of the causative agents of spatter, dusty head, diseases of cotton (gummosis). Fungicidal activity of new substances is 1.5-2 times higher than analogue preparations, 5 tablets. e 9 s

Description

The invention relates to new chemical compounds of the general formula I

N ROCHjlI I

with

N

 eHCO HCOliJHCH-

SNZSOSH1SN

tci

SS1z

having fungicidal and bactericidal activity.

The purpose of the invention is to expand the spectrum of action of fungicides on the basis of 1,2,4-triazole and increase their activity in comparison with the structural analogue, bayleton.

Primers illustrate the synthesis of target compounds.

Example 1, .l-N-l, 2j4-Tiazolylmethyl ester of. Acetic acid (1, a).

To a mixture of 4.95 g (0.05 mol) of 1-hydroxymethyltriazole, 5 g of triethylamine in 100 ml of benzene, 3.9 g (0.05 mol) of acetyl chloride are added dropwise. Stir the reaction mixture at komsd

3

315

unTiioii templrtur 7. h, then nsh-rep.. 3 h on guyd sing bank. It cools, the sunflower salt is filtered and the trap lamine is removed, and the solvent is removed from the filtrate. The remaining oil is distilled in vacuo to give 5.5 g (78%) of 1-N-1,2,4-triazolylmethyl ester-acetic acid with a boiling point of 108-109 ° / 7 mm. When standing, the product crystallizes. Mp. 51-52 C, IR spectrum 1740 cm- ())

Found,%: C u2.71; And 5.00; 29.86.

Calculated,%: С А2.55, Н 4.96; K 29.78.

The substance is soluble in acetone, alcohol, in ode,

Example 2. H- (1-methoxy-1, 2, 4-triaeolyl-2, 2, 2-trichloroethyl) acetamide (1,6).

To a mixture of 1.46 g (0.015 mol) of 1-ok snmethyl-, 2, A-triazole, 1, A8 g of triethylamine in 50 ml of benzene, a solution of 3.4 g (0.015 mol) of N is slowly added with stirring - (1,2,2,2-tetrachloroethyl) acetamide in benzene. After completion of the addition of reagents, the reaction mixture was heated in a water bath for 10 hours. Cool, filter out the precipitate. Rinse it several times with water, dry and get 3.4 g (79%) of N- (1-meth OXI-, 2,4-triazolyl-2,2,2-trichloroethyl) acetates, c (1, 6). Mp 169-170 ° C. Colorless crystals soluble in acetone, alcohol, ire soluble in water.

IR: 1690 (), 3430 cm (N-H).

Hai toe-Ho,%: C 28.95; H 2.98; N, 19.18; C1 37.35.

C, H-, N, 0,, Cl3.

Calculated,%: C 29.21; H 3.13; N19.47; C1 37.04.

Example 3. N- (1-methoxy-1,2,4-triazolyl-2,2,2-tetrachloroethyl) forms d (1, c).

It is similarly treated with the use of ;-(, 2,2,2-tetrachlorostyl) formamide. Yield 81%. Colorless crystals soluble in acetone, worse in alcohol, poorly in water.

Mp 135-136 ° C. NK spectrum: | 695 (), 3430 cm- (N-H).

Found,%: C 26.60; H 2.38; N, 20.10; C1 38.56,

,.

Calculated,%: C 2G5.32; And 2.53; N 20, .7; G4 38.93.

Tests of proparatope 1 a-p on micelles of the fungus Rhizcctonia solani l on bacteria x Papillonaria; malv. and Pseudomonas Iftcfi.

The preparations were dissolved in acetone and in molten glucose-potato agar under sterile conditions. 18-20 hours after the medium was poured into Petri dishes, the agar plate was inoculated with pieces of mycelium (three replicates). After an appropriate incubation in a thermostat at 25-26 ° C, the diameter of the colonies was measured in comparison with the control (inoculation of test objects without drug administration). Tests of the preparations were carried out at a concentration of 0.003%. X-lonium growth inhibition was calculated using the Abbot formula

T

P) 1 Ps

P

00,

where P VC is the diameter of the colonies in the control; PD - the diameter of the colonies in the experiment.

The test results are presented in table 1.

Test Connection | HERI as soil fungicides.

In order to study soil fungicides according to the plant-host scheme, the pathogen and the medium used the modified method of HSPA in green cucumber plants. For this, 100 g of non-sterile soil, 2 parts of turf, 1 part of peat, G part of sand were taken. The preparation was applied to the soil mixture at the rate of 200 kg / ha for the active ingredient. After 3 days, 10 seeds of cucumbers were sown to a depth of 1-1.5 cm. When germination appeared, seed germination was determined. A dazomet at the same rate of consumption was taken as a standard. The repetition of the experience is fourfold. After 10 days in the summer or 2-3 weeks (in the winter period), in these variants the seedling death was determined. Fungicidal activity (root rot suppression) was determined by the number of dead seedlings and mycological analysis of plants. The test results are presented in Table 2. .. ;

Test compounds against bacterium rhiza of cucumbers.

i The following procedure was used to study preparations for bactericidal activity.

5

Plants in phase. A-6 leaves per

24 h of inoculation were placed in a humid chamber to better open stomata. Then, after the moisture has dried, the plants are treated with aqueous suspensions of compounds 1, a-c at a concentration of 0.05%, and control plants with water. After the preparation has dried on the plants, they are sprayed with a suspension of bacteria. Spraying is carried out under low pressure from the underside of the sheet. After bacterial inoculation, the plants are placed in a humid chamber for 14 hours. Then they are transferred to a greenhouse with a 12-hour light period and a temperature of 22-24 ° C. Accounting for the development of the disease is carried out on the 7th day after, after inoculation on a pibal scale. The studied compounds showed high bactericidal activity against cucumber bacteriosis at the level of the standard, and compound 1.6 was higher than the standard

The test results are presented in table.3.

Testing compounds as dressing agents for barley seeds against a complex of mold and dusty crust pathogens.

The activity of the compounds against a complex of mold pathogens of seeds was studied in laboratory conditions, against dusty smut barley - in the field ..

Weighed portions of the seeds were placed in flasks, a suspension of preparations was added thereto, and shaken for 5 min. Norm, consumption, preparations 2 g / kg, water consumption 5 ml / kg standards - granozan, baytan. The seeds thus treated were laid out on moistened filter paper in Petri dishes and kept at a temperature of 22- for 5 days. Further, the percentages were shown for germinating: seeds affected by mold pathogens, and the size of the seedlings was measured. At; determination of the activity of the preparations: against the dusty head infected with dusty smut, barley seeds were etched with the preparations and sown in the soil. The size of the divisions is 1 m, the repeat is 5-fold. Registration of lesions: plants of a smut smut were carried out after flowering of an ear.

The test results are presented in table.4.

Thus, compounds 1, a-b have activity against complex5

20756

CA pathogens plsmppottil CPMJTK And dusty gopovni barley.

Testing compounds n to a group of seed dressers for cotton seeds against a complex of pathogens: 17 forestry seeds and gummosis.

The seed dressing method is the same as for seed dressing.

JQ bar. The consumption rate of the drug is 7 g / kg, water consumption is 20 ml / kg. Standard trichlorophenol t of copper (TCFM).

The activity of the preparations against mold causative agents was studied by 15 methods of spreading the etched seeds onto moistened filter paper in Petri dishes, the seeds were kept for 5-6 days at a temperature of 24-26 ° С, and then the percentage was determined

20 damage to the seed by mold pathogens. The activity of preparations against gummosis was determined by the method of negative zones of a nutrient-agarized medium infected with

25 bacterium Hanthomonas malv. (gammosis pathogen), pickled cotton seeds were laid out. From the formation of negative zones around the etched seeds, the active was determined; g.

0. The value of drugs ..

The test results are presented in table.5.

Compounds 1a-b have activity against a complex of mold and cotton gummosis pathogens

 at the standard level.

Thus, the obtained derivatives of α-oximeths1-1,2,4-triazole (1, a-c) are more active than the standard. -Bayleton, in the fight against root rot and bacteriosis, and can be used as soil fungicides and protectants seed n.

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Formula of the invention

Esters based on 1-hydroxymethst-1,2,4-triazole, of the general formula

1

DOSNg T. I

2K

5еД "СНзСО-, HCONHCH-,

SNzSOBNSN

s: s1.

SS1z

possessing fungicidal and bactericidal activity.

 I5I20758

Table 1

table 2

twenty

.Table 3

Tests of Compounds Against Cucumber Bacteriosis on Green XB Solution Pathogen Paeudomonae lach rimans.

Table 4

.THCFM (ea-alon) j

151207510

Table 5

4 22

92 68

3- O