SU373916A1 - Microbicide - Google Patents

Description

one:

The invention relates to new anti-adhesive compositions and active compounds for them.

The proposed antimicrobial compositions include at least one of the N-phenylcarbamate compounds of formula I as an active ingredient.

// - W-C-0-C-Rj // II I

OK.

where RI and Ra are each hydrogen or lower alkyl, for example methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, greg-butyl,

Cs is a cyano, carboxyl or group

/ Rs COOR or CON (

Re

wherein R4 is lower alkyl (e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, treg-bougyl);

&

Rs and Re-hydrogen or lower alkyl (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, Guoog-butyl); X and X each represents a Hib

with the proviso that RI and Ra are both hydrogen or one and the same or different lower alkyl, when Ra is cyano, and that Ri and R2 are each lower alkyl when Ra is carboxyl or a group of the formula COOR4, where R is as defined above.

Listed zipperes

Helminthosporium sigmoidium), parasites

industrial products (for example, Aspergillus niger).

Thus, N-phenylcarbamate compounds can be used as agricultural chemicals to prevent or inhibit plant diseases.

.3 caused by pathogenic fungi and bacteria. They can also be used as industrial chemicals to prevent or inhibit the deterioration of industrial products. The N-phenylcarbamates of formula I, in which Cs is carboxyl, can be used in the form of alkali metal salts as well as in the form of free acids. With this use, N-phenylcarbamates (I) can be used as such, but usually a suitable carrier is added to them to give them ordinary formulations such as dust, wettable powder, spray oil, aerosol, tablets, emulsifiable concentrate, pills or granules. In addition to the N-phenylcarbamide, these antimicrobial agents contain one or more fungicides, for example, blasticide alcohol, pentachlorobenzaloxime, 2,6-dichloro-4-nitroaniline, ethylene bis (dithiocarbamate) zinc, dimethylthiocarbamate zinc, ethylenebis (dithiocarbamate) manganese, bis (dimethylthiocarbamoyl) disulfide, 2, 4, 5, 5, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 3, 5, 5, 5, 5, 5, 5, 5, 5, 5, 5, and , 3-d ichloro-1,4-naphthoquinone, tetrachloro-p-benzoquino, p-dimethylaminobenzene diazonium sulphonate, 2- (1-methylgentyl) -4,6-dinitrophenyl crotonate-2-heptadelylimidazoline-acetate, 2,7-dichloro-6- (o- chloranilino) -z - triazine, dodecylguanidine - acetate, cyclic 5,5-dithiocarbonate 6-methyl-2,3-quinoxalinedithiol, N - trichloromethylthio - 4 cyclohexen-1, 2-dicarboximide, N- (1,1,2,2-tetrachloroethylthio) -4-cyclohexene - 1,2-dicarboximide, H- (3,5-dichlorophenyl) -maleimnd, N (3,5-dichlorophenyl) - succinimide, N - (3,5 - dichlorophenyl) - itaconimide, 3- (3 , 5 - dichlorophenyl) -5,5-dimethyloxazolidine-2,4-dione, 2,3-dihydro- 5-carboxanilido-6-methn-1,4,4-dioxide, 2,3-dihydro-5-carboxanilido-6-methyl1, 4-oxazine, 1- (Mn-butylcarbamoyl) -2-methoxycarbonylaminobenzimidazole, O , O-diethylS-benzylthiophosphate, O-ethyl-5.5-diphenyldithiophosphate, 0-butyl-5-benzyl-5-ethyl-dithiophosphate, O-ethyl-0-phenyl - (2,4,5-trichlorophenyl) phosphate, 0, O-dimethyl-O- (3-methyl-4-nitrophenyl) -thiophosphate, S-1,2-bis- (ethoxycarbonyl) ethyl-0,0-dimethyldithiophosphate, O, O-dimethylS- (N-methylcarbamoylmethyl) -dithiophosphate , O, O-diethyl-O- (2-isopropyl-6 - methyl-4 - pyrimidyl) -thiophosphate, 3,4-dimethylphenyl - N - methylcarbamate, iron methylaronate, 2 op4, 6-bis- (ethylamino) -s-triazine, 2,4-dichlorophenoxyacetic acid and its salts and esters, 2-methyl-4-chlorophenoxyacetic acid and its salts and esters, 2,4-dichlorophenyl-4-nitrophenyl ether sodium pentachlorophenol t, N-3,4 dichlorophenylpropionamide, 3- (3,4-dichlorophenyl) -1,1-dimethylurea, a, a, (x-trifluoro-2,6, 4 intro-S, Y-di -n-nropyl- / g-toluidine, 2-chloro, 6-diethyl - N - (methoxymethyl) - acetamide, 1-naphthril-M-methylcarbamate, methyl-N- (3,4-dilorphen) -carbamate, 4-chlorobenzyl- S, M - diethylnocarbamate, N, N-diallyl-2-chloroacetmide, ethyl-p- (2,4-dichlorophenoxy) -acrylate, cyclohexyl-p- (2,4-dichlorophen xi) - acrylate, n others. Antimicrobial compositions can also contain one or more substances known as active insecticides, acaricides nematocides, herbicides, fertilizers, soil conditioners, soil disinfectants, or plant growth regulators. The typical antimicrobial compositions according to the invention are shown below. Dusts obtained by dispersing at least one of the N-phenylcarbamate compounds (I) as the active ingredient at a concentration of 0.1-50% by weight in an inert carrier (for example, talc, diatomaceous earth, wood flour, clay). Wetted holes obtained by dispersing, at least one of the N-phenylcarbamate compounds (I) as an active ingredient in a concentration of 0.1-80% by weight in an inert adsorbing carrier (for example, diatomaceous earth) with wetting and / or dispersing an agent such as an alkali metal sulfate with a long aliphatic chain, a partially neutralized sulfuric acid derivative of an oil or natural glyceride, or a condensation product of alkylene oxide with an organic acid. Emulsifiable concentrates obtained by dispersing at least one of the N-phenylcarbamate compounds (I) as an active ingredient in a concentration of 0.1-50% by weight in an organic solvent (for example, dimethyl sulfoxide, with the addition of an emulsifier, an example of an alkali metal sulfate salt a long aliphatic chain, a partially neutralized sulfuric acid derivative of petroleum oil or natural glyceride or a condensation product of alkylene oxide with an organic acid. Compositions of N-fenylcarbamate compounds (I) is obtained by a method commonly used in the preparation of microbicidal granules, dusts and aerosols I. Preparation of antimicrobial compositions (parts and percentages are expressed by weight) A. Dust. 2 parts N-phenylcarbamate compound (I: K, SPZ; 2 n-CsNt, Cs COOC2H5; X), and 98 parts of the clay are ground and mixed well, but a dust containing 2% of the active ingredient. Dust can be used as such. B. Wettable powder. 50 parts of the N-phenylcarbamate compound (I: Ri R2 H; R3 CN; ), 5 parts of wetting agent (alkyl benzene sulfonate) and 45 parts of diatomaceous earth are crushed and mixed well, obtaining a wettable powder containing 50% of the active ingredient. The wettable powder is diluted with water before use.

B. Emulsifiable concentrate. 10 parts of N-feiylcarbamate compound (I: Ri X), 80 parts of dimethyl sulphoxide and 10 parts of emulsifier (nolnoxethylenephenylphepoloEOGO ether) are well mixed to form an emulsifiable concentrate containing 10% of the active ingredient. The emulsifiable concentrate is diluted with water before use.

G. Granules. 5 parts N-phenylcarbamate compound (I: Ri R2 CH3;

), 93.5 parts of β-clays and 1.5 parts of binding agent (polyvinyl alcohol) are milled and well mixed. The mixture is kneaded with water and granulated to obtain granules containing 5% of the active ingredient. Granules can be used as such.

D. Comprehensive Dust. 2 parts of N-fennl-carbamate compound (I: Rg COOCaHs; X X Bg), 1.5 hours. O-n-butyl5-ethnl-5-benzyldithiol phosphate and 96.5 parts of clay are crushed and mixed well to obtain dust, containing 3.5% active ingredient. Dust is used as such.

E. Complex wettable powder; 15 parts N-phenylcarbamate compound

T a b l II c a I

 Compound for comparison.

(I: R, Kz C: S, X), 20 cpentachlorononitrobenzene, 15 parts N- (1,1,2,2-tetrachloroethylthio) -4-1; iclohexene - 1,2 - dicarboxyimide, 45 parts diatomaceous earth and 5 parts of the wetting agent (alkyl benzene sulfonate) is milled and carefully biased to obtain a wettable powder containing 50% of the active ingredients. The wettable powder is diluted with water before use.

P. Test the antimicrobial activity of N-phenylcarbamate compounds (I).

Example 1. Dust containing the required concentration of 3 / cg / a of the tested compounds was applied to rice plants grown on the field and reaching the stage of three or four leaves. After one day, the plants were sprayed to inoculate Pyricularia oryzae spore suspension. Ten days after that, the number of lesions was counted. Results of Compound Comparison.

eight

ds in table. 1, from which it is clear that N-phenylcarbamate compounds and (I) have stronger anti-fungal activity than known agents, and when used together with known anti-fungal agents, give a clear synergistic effect.

Example 2. Dust containing the desired concentration of the test compound was used on rice plants grown in plants with a diameter of 9 cm and grown to the four-leaf stage, in an amount of 100 mg per tray when using a spray bottle. After one day, the plants were sprayed to infect the Cochliobolus miyabeanus spore suspension. Three days later, the number of lesions was counted. The results are given in Table. 2, from which it can be seen that the N-phenylcarbamate compounds (I) have a stronger anti-fungal activity than the known agents,

table 2

Example 3. Dust containing a certain concentration of the test compound was used on rice plants grown to a height of 50-GO cm in Wagner's pot size 1/500 and in an amount of 3 kg per 10 when using a spray bottle. One day later, the disc of the pellicularia sasakii mycelium was grafted onto the leaves. The damage status of the sheet was observed after 5 days thereafter, and the degree of damage was calculated according to the following equation.

/ indicator of the number of degree of HIV v infection of the stems} XJQQ

defeat

total number

Chine stems

Compound for comparison.

 Compound for comparison.

ten

where the infection rate is determined by the following indicators:

Infection Rate Infection State

0No plots per sheet

1Sumble spot slightly

2Porage area of less than 3 cm

The results are given in Table. 3, from which it is clear that L-feiyl carbamate compounds (I) possess stronger antifungal activity than the known antifungal agents, and when used together with known antifungal agents, they give a synergistic effect.

Table 3

Table

Example 4. A wettable powder containing a certain concentration of the test compound was used on rice plants grown to a height of 50-60 cm in Wagner pots of 1/5000 a size in an amount of 3 kg pa 10 a when using a spray bottle. One day later, the disk-shaped micelle Pellicularia sasakii settled on the leaves. The condition of leaf infestation was observed 5 days thereafter, and the extent of the damage was calculated according to the following equation. The degree of damage (scored factor X number of stems) is the total number of stems X 3 where the infection rate was determined according to the following scale:

Infection state

Indicator

zaralteni

ABOUT

No damaged areas on the leaves

1 Damage partial

2Infected areas less than 3 cm in size

3Infected areas of at least 3 cm

The results are given in Table. 4, from which it is clear that N-phenylcarbamates (I) possess stronger antifungal activity than the known antifungal agents, and when used together with known antifungal agents, give a synergistic effect.

Compound

N-Phenylcarbamate (I: R, N-Phenylcarbamate (I: Ri..j;) N-Phenylcarbamate (I: R, .j; Ra COOCaHj; X) N-Phenylcarbamate (I: R, CH3; Ra n-CzH ;; R3 COOCjH5;

Y -Y:

N-Phenylcarbamate (I: Ri.H; R.CONHa;

)

N-Phenylcarbamate (I: R, R3 CONH2:) N-Phenylcarbamate (I: R, H; R3 CONH2;

) N-Phenyl-carbamate (I: Ri.H; (CH3) 2;

X) N-Phenylcarbamate (I: Ri CH3; Ra "-C3H ,; R3 COOC2H5;

X)

+

1- (N-H-Butyl carbamoyl) -2-methoxycarbonyl laminobenzium midazol +

6-Methyl-2,3-hnnoksalinditnol cyclic S, S-dithiocarbonate

s-Cyanoethnl-N- (2,5-dnichlorophenyl) -carbonate l- (Nn-Butylcarbamoyl) -2-mgtoxicarobenilaminobenzymidazole

a-Carbamoylethyl-M- (3,4-dichlorophenyl) -carbamate 6-Methyl-2,3-quinoxalindithiol cyclic S, S-dithiocarbonate a-Kapbamoylethyl-N-phenylcarbamate

Untreated

 Compound for comparison

12

where the infection rate was determined on the 20 following scale:

Infection rate

Area of infection

Missing

1 small

3Medium

5th century

The results are given in Table. 5, from which it can be seen that the N-phenylcarbamate compounds (I) have a stronger anti-fungal activity than the known anti-fungal agents, and when used together with known anti-microbial agents give a clear synergistic effect.

Table 5

Damage rate

10.3 15.6 13.8 20.4

6.8

7.3 6.0

4.3

53.6 38.4

50.6

25.6 50.6 64.9 Example 5. A wettable powder containing the test compound was diluted with water to a certain concentration and applied to seedlings of pumpkin grown in pots with a diameter of 12 cm before the three or four leaves stage, in an amount of 7 ml mix on the pot. One day later, the plants were sprayed to inoculate Sphaerotheca fuliginea spore suspension. After 10 days, the state of infection was observed on the top four leaves and the degree of damage was calculated by the infection area according to the following equation / indicator-number {infection of leaves j h / 1r, l, Degree:; 1UU, damage Example 6. In each pot with a diameter of 9 cm, field soil and soil (10 ml) infected with Pellicularia filamentosa were poured dispersed on the surface. The test compound in the form of an emulsifiable concentrate was diluted with water, providing a concentration of 500 parts per million, and the diluted mixture was poured into pots in an amount of 15 ml per pot. Two hours later, they sowed 10 cucumbers there. After five days, the infection status of the germinated seedlings was observed, and the percentage of yield was calculated according to the following equation.

Compounds

N-Phenylcarbamate (, - Kz C1HG;) K-Phenylcarbamate (I: K, X) N-Phenylcarbamate (I; X) N-Phenylcarbamate (I: R, Kz COOC2H5;)

N-Phenylcarbamate (I: R, CH3; Rj H-C3H ,; R3 COOCaH5;)

N-Phenylcarbamate (I: R, I) N-Phenylcarbamate () N-Phenylcarbamate (I: Rj R3 CONH2; X) N-Phenylcarbamate (I: R, H; Rs CONHa; Br) N-Phenylcarbamate (I: Ri H ; R3 CONH2; Br)

N-Phenylcarbamate (I: Ri H; (CH3) j;)

N-Phenylcarbamate (I: R ,,; R3 CONHC3H ,;

X)

a-Kapbamoyletlll-N-phenylkarbamamat a-Kapbamoil-N- (3,4-dichlorophenyl) -karabamata Pentachloronitrobenzene Untreated (uninoculated) Untreated (inoculated)

 Compound dL Comparisons Example 7. When determined in accordance with the agar dilution method, N-phenylcarbamate compounds (I) gave minimal inhibitory concentrations, as

Compound

N-Phenylcarbamate () N-Phenylcarbamate {I: R,)

N-Phenylcarbamate (1: I, CH3; Rj H-C3H ,; R3 COOC2H5;)

Table 6

Percent

harvest - .. --1

89.4 92.3 83.2 99.0 74.8

88.6 90.4 98.6 93.4 90.2 91.4

93,8

ABOUT

43.2 83.4 100 O

Minimum inhibitory concentration

hours for 1 million

2000 2000 5000) 14 Percent yield Number of healthy seedlings in treated pots Number of seedlings in untreated pots 6, from which it is seen that the N-phenylcarbamate compounds (I) have a stronger anti-fungal activity than the known anti-fungal agents. shown in Table. 7, against Aspergillus niger LTCC No. 9642, which caused serious damage to industrial products, Table

IS subject matter

Use as a microbicide of N-feiilcarbamate of General formula I

sT.S & ie

le

COOR, go

R:

NH-C-O-C-Ro II 1 O R,

where RI and R2 are Hydrogen or lower alkyl, for example methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, Greg-butyl;

Cs - cyano, carboxyl il and the group of the formula

where 4 is lower alkyl (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, Greg-butyl);

Rs and Re are hydrogen or lower alkyl (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, "zobutyl, greg-butyl);

X and X are halogen, with the proviso that Ri and Rj are both hydrogen atoms or lower alkyl radicals when R.-j is recognized, and that RI and R2 each represent lower alkyl when Ra is carboxyl or a group of the formula COOR4, where R4 is a pointer value.