KR810001321B1 - Process for the preparation of 3-chloro-2,6-dinitro-n-(substituted phenyl)-4-(trifluoromethyl)benzenamines - Google Patents

Abstract

Title compds. (I; X = Cl, F, Br; m,p,s = 0,1; n =0,1,2; q.r = 0,1,2,3; total of the m, n, p. q, r and s is 1-3; position of trifluoromethyl group is 3 or 5), useful as bactericide, were prepd. by reaction of compd.(II) and compd.(III) in the presence of acid eliminating agent. Thus, sodium hydride 3.2 g was suspended in dimethyl formamide after washing with hexane. The suspension was cooled to -50oC and added in the 2-aminobenzotrifluoride 10.4 g and dimethylformamide 35ml soln. The mixt. was cooled to -30oC and added in the 2,4-dichloro-3,5-dinitrobenzotrifluoride 20 g and then left for 12 hr at room temp. to give compd.(I) (yield 8.8).

Description

Method for preparing 3-chloro-2,6-dinitro-N- (substitutedphenyl) -4- (trifluoromethyl) benzeneamine

The present invention relates to a method for preparing a new kind of substituted 2,6-dinitro-benzeneamine having a chlorine atom at the 3-position which is useful as a bactericide, and its sterilization composition and method of using the compound.

In the prior art, Barrow was published in U.S. Patent No. 3,950,377 (April 13, 1976) and claims 4-cyano or 4-trifluoromethyl-2,6-dinitrobenzeneamine derivatives in the claims are many variants of pests. And invertebrate pests. In addition, the patent claims that the compound and the disclosed composition are useful for controlling plant pathogens.

The compounds according to the invention are advantageous compared to the prior art because they show increased activity and reduced weakness and mammalian toxicity.

The present invention provides a method for preparing a new substituted 2,6-dinitro benzeneamine of the following formula (I).

은 각각 0,1,2 또는 3이고; m,n,p,q,r 및 S의 합계는 1 내지 3이고; n가 2일때 m,p,q 및 r는 모두 0, 트리플루오로메틸 그룹은 3 및 5위치에 있어야 하고; S가 1일 때 m 및 p는 양쪽다 o,n,q 및 r의 합계는 0이 아니어야 하고; q가 1일 때 m,n,r 및 S의 합계는 0이 아니어야 하고; 다음 구조식(Ⅱ)의 화합물을 산 제거제 존재하에 다음 구조식(Ⅲ)의 화합물과 반응시킴을 특징으로 한다.Wherein X is chloro, fluoro or bromo; m, p, and S are each 0 or 1; n is 0, 1 or 2; q and

Are 0, 1, 2 or 3, respectively; the sum of m, n, p, q, r and S is 1 to 3; when n is 2, m, p, q and r must all be 0 and the trifluoromethyl group must be in positions 3 and 5; M and p are both when S is 1, the sum of o, n, q and r must not be zero; when q is 1, the sum of m, n, r and S should not be zero; The compound of formula II is reacted with the compound of formula III in the presence of an acid scavenger.

The present invention also relates to a composition for controlling plant pathogens, comprising a sterilizing effective amount, an inert diluent and a surfactant of the compound of the above structural formula.

In addition, the present invention also relates to a method for controlling phytopathogens by spraying a cell culture site with a bactericidal effective amount of the compound of formula (I).

The preparation of a new compound of formula (I) having a chlorine atom at position 3 and a compound prepared from 2,4-dichloro-3,5-dinitrobenzotrifluoride of formula (II) is described in US Pat. No. 3,617,252. It is.

Compounds of formula (I) are prepared by reacting a compound of formula (II) with a compound of formula (III) in the presence of an acid scavenger. Suitable acid scavengers include strong bases such as sodium hydride sodium amide and potassium amide, tertiary amines such as triethylamine, triethanolamine and pyridine, inorganic bases such as carbonic acid, bicarbonate, calcium hydroxide and sodium. An excess of aniline of formula (III) is used as the acid scavenger. The reaction temperature of the mixture is used from 50 ℃ to reflux temperature.

The reaction is carried out under an inert organic solvent. Both protic and aprotic solvents are useful together. Amides such as lower alkanol benzene including ethanol and butanol and aromatic dimethylformaldehyde including xylene; Dimethyl sulfoxide is useful.

Certain conditions are preferred.

In one preferred process, the aniline of formula (III) is first combined with a base such as sodium hydride in a suitable solvent such as dimethylsulfoxide or dimethylformamide at a temperature of about-15 to 50 ° C. Other preferred bases include sodium amide and potassium amide. The mixture is allowed to warm to room temperature and again cooled to about 0--40 [deg.] C. and a solution of 2,4-dichloro-3,5-dinitrobenzotrifluorolide in an inert solvent such as dimethylformamide is added. The reaction mixture is stirred, warmed to room temperature overnight and diluted with ice water. Stirred for several hours to form a solid, collected by filtration and purified by recrystallization

In another preferred procedure, substituted aniline and 2,4-dichloro-3,5-dinitrobenzotrifluoride of formula (III) are mixed in a suitable solvent such as ethanol and refluxed for a time until the reaction is complete. Other solvents include propanol and butanol. Excess of substituted aniline can be used as an acid remover in the reaction. Other preferred acid removers include triethylamine, sodium carbonate and calcium carbonate. At the end of the heating point the reaction mixture is cooled and the solid separated off is collected, dried and recrystallized with a suitable solvent to give the required product.

In another preferred procedure, the substituted aniline is reacted with dimethylformamide in the presence of an acid scavenger such as anhydrous sodium carbonate. Excess of substituted aniline can be used as an acid remover, and calcium carbonate and triethylamine can also be used as an acid remover. At the end of the reaction time the reaction mixture is diluted with water, acidified with dilute acid and extracted with a suitable solvent such as methylene dichloride. The methylene chloride solution is dried, the solvent is evaporated and the residue is taken up with more methylenedichloride and chromatographed on a silica gel column. Fractions from the column are combined and concentrated in vacuo and the residue is recrystallized from a suitable solvent. The reaction may also be used with a solvent such as benzene or toluene, in which case the reaction mixture is preferably extracted with acid to remove unreacted aniline, the benzene or toluene solution is dried and the solvent is evaporated and the residue And chromatograph on a silica gel column.

Aniline intermediates are known in commercially available compounds or in the prior art.

The preparation of the new compounds of the present invention is further illustrated by the following examples.

Example 1

3-chloro-2,6-dinitro-4- (trifluoromethyl) -N-2- [2- (trifluoromethyl) phenyl] benzeneamine

3.2 g of sodium hydride (50%) is washed with hexane and the hexane is decanted off and transferred to 50 ml of dimethylformamide. The suspension is obtained by cooling to about −50 ° C. and adding it to a solution prepared from 10.4 g (0.065 moles) of 2-aminobenzotrifluoride and 35 ml of dimethylformamide. The resulting mixture is allowed to warm to room temperature, cooled to about −30 ° C. and added to 20 g of 2,4-dichloro-3,5-dinitrobenzotrifluoride and the resulting reaction mixture is allowed to warm to room temperature overnight. The reaction mixture is allowed to warm to room temperature overnight. The reaction mixture is poured into 4 liters of ice water and the aqueous mixture is stirred for about 2 hours. The mixture was filtered and the collected solid was recrystallized from a mixture of ethanol and water to obtain a product having a melting point of 135-137 ° C. 3-chloro-2,6-dinitro-4- (trifluoromethyl) -N- [2- (Trifluoromethyl) phenyl] benzeneamine. Yield 8.8

Calculated analysis of C ₁₄ H ₆ ClF ₆ N ₃ O ₄

The procedure below is the same as in Example 1 and the additive compound was prepared and separated. The compounds, along with the base starting materials and their weights used in the synthesis, are specified in the examples which follow.

Example 2

11.6 g of 3-chloro-N- (3,5-dichlorophenyl) -2,6-dinitro-4- (trifluoromethyl) benzeneamine having a melting point of 138-139 ° C. Weighed from 5-dichloro aniline and 20 g of 2,4-dichloro-3,5-dinitrobenzotrifluoride.

Calculated analysis of C ₁₃ H ₅ Cl ₃ F ₃ N ₃ O ₄

Example 3

7.7 g 2- of 5.3 g 3-chloro-2,6-dinitro-4- (trifluoromethyl) -N- [2- (cyano) phenyl benzeneamine having a melting point of 112-113 ° C. It is weighed from amino benzonitrile and 20 2,4-dichloro-3,5-dinitrobenzotrifluoride.

Calculated analysis of C ₁₄ H ₆ ClF ₃ N ₄ O ₄

Example 4

20 g of 2, 15.4 g of 3-chloro-2,6-dinitro-4- (trifluoromethyl) -N- (2,4,6-trichlorophenyl) benzeneamine having a melting point of 140-141 ° C. Is weighed from 4,6-trichloroaniline and 30 g of 2,4-dichloro-3,5-dinitrobenzotrifluoride.

Calculated analysis of C ₁₃ H ₄ Cl ₄ F ₃ N ₃ O ₄

Example 5

10.6 g (0.065 mol) of 5.0 g 3-chloro-N- (2,4-dichlorophenyl) -2,6-dinitro-4- (trifluoromethyl) benzeneamine having a melting point of 106-108 ° C It is weighed from 2,4-dichloroaniline and 20 g of 2,4-dichloro-3,5-dinitrobenzotrifluoride.

Calculated analysis of C ₁₃ H ₅ Cl ₃ F ₃ N ₃ O ₄

Example 6

10.6 g 2,5- of 4.35 g 3-chloro-N- (2,5-dichlorophenyl) -2,6-dinitro-4- (trifluoromethyl) benzeneamine having a melting point of 163-165 ° C. It is weighed from dichloroaniline and 20 g of 2,4-dichloro-3,5-dinitrobenzotrifluoride.

Calculated analysis of C ₁₃ H ₅ Cl ₃ F ₃ N ₃ O ₄

Example 7

10.6 g 2,6- of 12.2 g of 3-chloro-N- (2,6-dichlorophenyl) -2,6-dinitro-4- (trifluoromethyl) benzeneamine having a melting point of 151-152 ° C It is weighed from dichloroaniline and 20 g of 2,4-dichloro-2,5-dinitrobenzotrifluoride.

Calculated analysis of C ₁₃ H ₅ Cl ₃ F ₃ N ₃ O ₄

Example 8

2.5 g 3-chloro-N- (2,5-dibromophenyl) -2,6-dinitro-4- (trifluoromethyl) benzeneamine having a melting point of 176-177 ° C. Is weighed from 5-dibromoaniline and 20 g of 2,4-dichloro 3,5-dinitrobenzotrifluoride.

Calculated analysis of C ₁₃ H ₅ ClBr ₂ F ₃ N ₃ O ₄

Example 9

14.6 g of 3-chloro-N- (2,6-dibromophenyl) -2,6-dinitro-4- (trifluoromethyl) benzeneamine having a melting point of 164-165 ° C. Is weighed from 6-dibromoaniline and 20 g of 2,4-dichloro-3,5-dinitrobenzotrifluoride.

Calculated analysis of C ₁₃ H ₅ Br ₂ ClF ₃ N ₃ O ₄

Example 10

16.3 g 2,4 of 5.5 g 3-chloro-N- (2,4-dibromophenyl) -2,6-dinitro-4-trifluoromethyl) benzeneamine having a melting point of 122-123 ° C. Weighed from dibromoaniline and 20 g of 2,4-dichloro-3,5-dinitrobenzotrifluoride.

Calculated analysis of C ₁₃ H ₅ Br ₂ ClF ₃ N ₃ O ₄

Example 11

12.8 g of 2,6 g of 3-chloro-2,6-dinitro-N- (2,4,5-trichlorophenyl) -4- (trifluoromethyl) benzeneamine having a melting point of 144-145 ° C. Basis weight is from 4,5-trichloroaniline and 20 g of 2,4-dichloro-3,5-dinitrobenzotrifluoride.

Calculated analysis of C ₁₃ H ₄ Cl ₄ F ₃ N ₃ O ₄

Example 12

12.8 g of 3-chloro-2,6-dinitro-N- (3,4,5-trichlorophenyl) -4- (trifluoromethyl) benzeneamine having a melting point of 186 to 187 ° C. Is weighed from, 4,5-trichloroaniline and 20 g of 2,4-dichloro-3,5-dinitrobenzotrifluorolide.

Calculated analysis of C ₁₃ H ₄ Cl ₄ F ₃ N ₃ O ₄

Example 13

7.05 g of 3-chloro-2,6-dinitro-N- (2-dinitrophenyl) -4- (trifluoromethyl) benzeneamine having a melting point of 136 to 137 ° C. was substituted with 9 g of 2-nitroaniline and 20 g of Is weighed from 2,4-dichloro-3,5-dinitrobenzofluoride.

Calculated analysis of C ₁₃ H ₆ ClF ₃ N ₄ O ₆

Example 14

2.5 g 3-chloro-2,6-dinitro-N-yldi-4- (nitrotrifluoromethyl) benzeneamine having a melting point of 128-130 ° C. was charged with 15.25 g of chloronitroaniline and 50 g of 2,4- It is weighed from dichloro-3,5-dinitrobenzotrifluoride.

Calculated analysis of C ₁₃ H ₇ ClF ₃ N ₃ O ₄

Example 15

11.2 g of 2-chloro-4- of 3-chloro-N- (2-chloro-4-nitrophenyl) 2,6-dinitro-4- (trifluoromethyl) benzeneamine having a melting point of 141-142 ° C It is weighed from nitroaniline and 20 g, 2,4-dichloro-3,5-dinitrobenzotrifluoride.

Calculated analysis of C ₁₃ H ₅ Cl ₂ F ₃ N ₄ O ₆

Example 16

14.1 g 2- of 6.5 g N- (2-bromo-4-nitrophenyl) -3-chloro-2,6-dinitro-4- (trifluoromethyl) benzeneamine having 144-145 ° C. Basis weight from bromo-4-nitroaniline and 20 g of 2,4-dichloro-3.5-dinitrobenzotrifluoride.

Calculated analysis of C ₁₂ H ₅ BrClF ₃ N ₄ O ₆

Example 17

13.45 g of 5.98 g of 3-chloro-N- (2,6-dichloro-4-nitrophenyl) -2,6-dinitro-4- (trifluoromethyl) benzeneamine having a melting point of 176-177 ° C. Is weighed from 2,6-dichloro-4-nitroaniline and 20 g of 2,4-dichloro-3,5-dinitrobenzotrifluoride.

Calculated analysis of C ₁₃ H ₄ Cl ₃ F ₃ N ₄ O ₆

Example 18

6.8 g of 3-chloro-N- (2,4-difluorophenyl) -2,6-dinitro-4- (trifluoromethyl) benzeneamine having a melting point of 11-112 DEG C. It is weighed from 4-difluoroaniline and 20 g of 2,4-dichloro-3,5-dinitrobenzenetrifluoride.

Calculated analysis of C ₁₃ H ₅ ClF ₅ N ₃ O ₄

Example 19

3-chloro-N- (3,4-dichlorophenyl) -2,6-dinitro-4- (trufluoromethyl) benzeneamine

21.2 g (0.130 mole) of 3,4-dichloroaniline and 20 g (0.065 mole) of 2,4-dichloro-3,5-dinitrobenzotrifluoride are refluxed in 250 ml of ethanol for about 4 days. The reaction mixture is cooled and the solid separated by cooling is filtered and dried. The solid is recrystallized from ethanol to give 3-chloro-N- (3,4-dichlorophenyl) -2,6-dinitro-4- (trifluoromethyl) benzeneamine having a melting point of 152-153 ° C.

Calculated analysis of C ₁₃ H ₅ Cl ₃ F ₃ N ₃ O ₄

The following procedure followed the same procedure as in Example 19 and the additive compound was prepared and separated. The compounds, along with the base starting materials and their weights used in the synthesis, are specified in the examples which follow.

Example 20

12 g of 3-chloro-2,6-dinitro-N- (4-nitrophenyl) -4- (trifluoromethyl) benzeneamine having a melting point of 207-208 ° C. has 18 g of 4-nitroaniline and 20 g of 2 Was weighed from, 4-dichloro-3,5-dinitrobenzotrifluoride.

Calculated analysis of C ₁₃ H ₆ ClF ₃ N ₄ O ₆

Example 21

5 g of 3,4 was dissolved in 2.4 g of 3-chloro-1- (3,4-dibromophenyl) -2,6-dinitro-4- (trifluoromethyl) benzeneamine having a melting point of 166-167 ° C. -Balanced from dibromoaniline and 3 g of 2,4-dichloro-3,5-dinitrobenzofluoride.

Calculated analysis of C ₁₃ H ₅ Br ₂ ClF ₃ N ₃ O ₄

Example 22

8.25 g of 3-chloro-2,6-dinitro-4- (trifluoromethyl) -N- [4- (trifluoromethyl)] phenyl benzeneamine having a melting point of 154-155 ° C. is 12 g of 4- Weighed from aminobenzotrifluoride and 11.35 g of 2,4-dichloro-3,5-dinitrobenzotrifluoride.

Calculated analysis of C ₁₄ H ₆ ClF ₆ N ₃ O ₄

Example 23

8 g of 3-chloro-2,6-dinitro-4- (trifluoromethyl) -N- [3- (trifluoromethyl) phenyl] benzeneamine having a melting point of 159-160 ° C. has 12.0 g of 3- Obtained from aminobenzoyltrifluoride and 11.35 g of 2,4-dichloro-3,5-dinitrobenzotrifluoride.

Calculated analysis of C ₁₄ H ₆ ClF ₆ N ₃ O ₄

Example 24

13.0 g of 3-chloro-N- [4- (cyanomethyl) phenyl] -2,6-dinitro-4- (trifluoromethyl) benzeneamine having a melting point of 173 to 174 ° C is 13.2 g of 4- Basis weight was obtained from cyanomethylaniline and 15.25 g of 2,4-dichloro-3,5-dinitrobenzotrifluoride.

Calculated analysis of C ₁₅ H ₈ ClF ₃ N ₄ O ₄

Example 25

5.0 g of N- (2-bromo-4-methylphenyl) -3-chloro-2,6-dinitro-4- (trifluoromethyl) benzeneamine having a melting point of 119 to 120 ° C. is 9.3 g of 2- Weighed from bromo-4- (toluidine and 7.6 g of 2,4-dichloro-3,5-dinitrobenzotrifluoride).

Calculated analysis of C ₁₄ H ₈ BrClF ₃ N ₃ O ₄

Example 26

4.3 g of 3-chloro-N- (3-cyanophenyl) -2,6-dinitro-4- (trifluoromethyl) benzeneamine having a melting point of 147-149 ° C. was 4.72 g of 3-aminobenzonitrile. And 6.1 g of 2,4-dichloro-3,5-dinitrobenzotrifluoride.

Calculated analysis of C ₁₄ H ₆ ClF ₃ N ₄ O ₄

Example 27

3-chloro-N- (4-cyanophenyl) -2,6-dinitro-4- (trifluoromethyl) benzeneamine having a melting point of 179-181 ° C. is 2.36 g of 4-cyanoaniline and 3.0 g. From 2,4-dichloro-3,5-dinitrobenzotyltrifluoride.

Calculated analysis of C ₁₄ H ₆ ClF ₃ N ₃ O ₄

Example 28

16.45 g of 3-chloro-N- [4-chloro-3- (trifluoromethyl) -phenyl] -2,6-dinitro-4-) trifluoromethyl) benzeneamine having a melting point of 169-170 ° C. Silver was weighed from 25 g of 5-amino-2-chlorobenzotrifluoride and 19.5 g of 2,4-dichloro-3,5-dinitro-benzotrifluorotyl.

Calculated analysis of C ₁₄ H ₅ Cl ₂ F ₆ N ₃ O ₄

Example 29

3-chloro-2,6-dinitro-N- (3,5-dinitrophenyl) -4- (trifluoromethyl) benzeneamine

1.83 g (0.01 mole) of 3,5-dinitroaniline, 3.05 g (0.01 mole) of 2,4-dichloro-3,5-dinitrobenzotrifluoride, 0.53 g of sodium carbonate and 20 ml of dimethylformamide Heat about 4 hours in a steam bath. At the end of 2 hours an addition of sodium carbonate is added to the reaction mixture and heating is continued for 2 days. The reaction product mixture is poured into water, acidified with lean water-soluble acid and extracted with methylenedichloride. The methylene dichloride layer is dried, the desiccant is filtered off and the filtrate is concentrated in vacuo. The residue is taken up in methylene dichloride and chromatographed on silica gel. Fractions were combined and evaporated and the residue was recrystallized from ethanol to give 3-chloro-2,6-dinitro-N- (3,5-dinitrophenyl) -4- (trifluoromethyl) benzene having a melting point of 188-189 ° C. Obtain a product that is classified as an amine. Yield 0.65

Calculated analysis of C ₁₃ H ₅ ClF ₃ N ₅ O ₈

The next procedure was based on Example 29, where additional compounds were prepared and isolated. The compounds, along with the base starting materials and their weights used in the synthesis, are specified in the examples which follow.

Example 30

1.3 g of N- (2-bromo-4,6-dinitrophenyl) -3-chloro-2,6-dinitro-4- (trifluoromethyl) benzeneamine having a melting point of 144-146 ° C is 5.24 was weighed from g of 2-bromo-4,6-dinitroaniline and 6.10 g of 2,4-dichloro-3,5-dinitrobenzotrifluoride.

Calculated analysis of C ₁₃ H ₄ BrClF ₃ N ₅ O ₈

Example 31

N- [3,5-bis (trifluoromethyl) phenyl] -3-chloro-2,6-dinitro-4- (trotrifluoromethyl) benzeneamine

15.0 g (0.066 moles) of 3,5-bis (trifluoromethyl) aniline, 100 ml n-butanol, 20.g (0.066 moles) of 2,4-dichloro-3,5-dinitrobenzotrifluoride And 11 ml of triethylamine mixture are prepared in a 250 ml flask and the mixture is refluxed for about 48 hours. Allow the reaction mixture to cool and remove the solvent in vacuo. The residue is recrystallized by chromatography on a silica gel column using toluene as eluent. The fractions are concentrated in vacuo and the combined residues are recrystallized from ethanol. N- [3,5-bis (trifluoromethyl) -phenyl] -3-chloro-2,6-dinitro-4- (trifluoromethyl) -benzeneamine having a melting point of 156-158 ° C is obtained.

Yield 3.2

Calculated analysis of C ₁₅ H ₅ ClFgN ₃ O ₄

In order to use the novel plant sterilization method of the present invention, the above-mentioned compound is formulated into a new compound composed of one of the above-mentioned compounds as the active ingredient and the weight agent. Such new compositions are convenient for preparing the mixtures needed to spread to useful and desirable cell control zones.

Each active compound is formulated in a simple solution with a suitable solvent to be completely soluble at the required concentration. Such solvent systems include alcohols, acetone, aqueous alcohols and aqueous acetone, xylene, heavy aromatic naphtha and other organic solvents. These simple solutions can be adjusted with other fungicides or antifoaming agents, flavorings, coloring agents, emulsifying or dispersing agents, various surfactants, additions that increase or aid in the activity of the formulated compounds.

Compounds in which it is useful to present the form of the invention are formulated in several forms of preparations known to be skilled in agricultural or industrial drug art. These formulations include those such as compositions containing the active ingredient as a relatively large particle size granule, as a hydrating agent, as an emulsifiable concentrate, as components of other forms of formulations commonly used in the art. Such formulations include auxiliaries and extenders which are commonly used to facilitate the dispersion of the active ingredient for agricultural and industrial application of antiseptic poisons. These formulations contain 0.1% smaller or 90% or more by weight of the active ingredient.

Powder formulations are prepared by mixing the active ingredients in fine solids, used as dispersants and extenders for fungicides, which are applied to areas of required cell control. Typical solids used in the preparation of powdered active ingredients useful in the present invention include talc, kizegur, microclay, acidic clay or other common organic or inorganic solids. The particle size of the solid used in the preparation of the powdered formulation of the active ingredient has 50 microns or less. The active ingredient of the powder formulation is usually 0.5% to 90% by weight of the composition.

Granular preparations of the active ingredient are prepared as relatively coarse particles of inert solids such as sand, attapulgite, clay, gypsum, cornmeal, weathered biotite or other inorganic or organic solids, or by adsorbing or adsorbing a toxic agent. do. The active ingredients of these particulate preparations usually appear from 0.1% to 90% by weight of the composition.

Compounds in which the forms of the invention are useful are also formulated as hydrating powders. Hydrated powder formulations are solid compositions of matter which have absorbed or adsorbed the active ingredient to adsorbents such as microclays, talc, gypsum, weathered lime, wood flour, acidic clays and kigel-gurs. These formulations are preferably made from 0.5% to 90% of the active ingredient. These hydrating agent formulations usually contain small amounts of hydrating, dispersing or emulsifiers that are well dispersed in water or other liquid weight agents used to disperse the cell poison in the required cell control areas. Suitable hydration and / or dispersants include such as condensed arylsulfonic acids and their sodium salts, sodium lignin sulfate, sulfonate-oxide condensation mixtures, alkyl aral polyether alcohols, sulfonated nonionic mixtures, anionic wetting agents.

Suitable emulsifiers may be in the form of nonionics or ions, or mixtures thereof, and are condensation products of alkylene oxides of phenols with organic acids, polyoxyethylene derivatives of sorbitan esters, ether-alcohol complex salts, aralkyl sulfonates It includes such things as ionic agents.

Compounds useful in the form of the present invention are also formulated as emulsion concentrates. Emulsifiable concentrate formulations are homogeneous liquid or paste compositions containing the active ingredient in a composition which conveniently disperses the spread of the cell poison in the required cell control area in another liquid extender or water. Such emulsifiable concentrate formulations of the active ingredient may contain both liquid or solid emulsifiers and only the active ingredient together or other relatively non-volatile organic solvents such as isophorone, dioxane, bidirectional naphtha, xylene, or dimethylformamide. do.

Suitable emulsifiers used to prepare these emulsion concentrate compositions are immediately described in the above paragraphs. The active ingredient of such formulations usually consists of about 1% to 70% by weight of the cell poison composition.

Formulations of pesticides are well-developed and skilled techniques and therefore there will be no difficulty in the preparation of this new benzeneamine compound for use in the practical use of the present invention.

The following experimental procedure was used to demonstrate the bactericidal activity of the compound of formula (I).

[Experiment 1]

The use of the compounds of the present invention has been carried out in an on-line experiment to reduce the symptoms and severity of Staphylococcus aureus. Test compounds were formulated with a mixture of 500 ml of acetone, 500 ml of ethanol, and 2 ml of a solution prepared from 100 ml of Tween 20 and 70 mg of a compound (polyoxyethylene sorbitan from Tween 20 Chemical Division of ICI America, Wilmington, Delaware). Samples were diluted with 175 ml of deionized water containing one drop of Dow Corning antifoam C emulsion per 2 liters of water. (Dow Corning antifoam C is a silicone complex antifoaming agent made by Dow Corning, Midland, Michigan.) The final formulation contains 400 ppm of the test compound, 10,000 ppm of the organic solvent, and 1,000 ppm of Tween. This solution is diluted with deionized water to give a lower concentration of the specific test compound.

On the day of the test, the young broadleaf leaves are removed from the grapevines growing in the greenhouse. At the end of the wide plastic rug, place a leaf on the bottom of the plastic petri plate containing the white filter paper and place the leaf on the bottom of the petri plate. Tap the cotton ball around the tip of the leaf. Spray the test agent under the leaves at the required concentration and dry the leaves. As soon as the leaves are dried, they are inoculated by spraying a condiment suspension of Plasmopara Viticola using a Devilbiss nebulizer. Conidia suspension is prepared as follows. Conidia are obtained from recently infected leaf tissue stored in a room cooled to 5 ° C. The conidia are shaken off the surface of the solo leaf and suspended in deionized water to obtain an inoculation suspension.

After inoculation the plate is placed in a wet room. A 200-400 foot candle is supplied to cool with a white fluorescent lamp on a wet chamber, irradiated to the leaves for 14 hours and placed in a dark room for 10 hours at 68 ° F. The leaves observed disease symptoms and the results were obtained 7 days after treatment. A ratio scale of 1 to 5 is used as a result of sexuality, where 1 is equal to serious disease (or no treatment) 2 is normal disease, 3 is some disease, 4 is very mild and 5 is disease free (or 100% treatment) same.

The results of representative compounds tested of the invention are reported in Table 1. In Table 1, 1 indicates the test compound by Example number; Paragraph 2 is the spray rate per million (ppm); Clause 3 indicates disease treatment rates at the indicated ppm application rates.

TABLE 1

[Experiment 2]

Compounds were tested against Colletorichum laqenarium, an organic material that causes Oythrax aneurysm. The formulation of the test compound is as described in Test 1. Three cucumber seeds were sown in a plastic pot at 7.5 cm square. After 15 days of sowing, the test agent is sprayed onto all leaf surfaces and allowed to dry. Both plants were sprayed with only lean solvent-emulsifier solutions. After 24 hours the choletotrimerageumium conidia suspension in 0.1% polyoxyethylene sorbitan monolaurate was sprayed with a Dibilbis sprayer and the plant was placed in a 70 ° F. humidifier for 48 hours. After 18 days of sowing, the plants are returned to the greenhouse and the plants are left for about 7 to 9 days to observe the development of the disease condition, and the control is evaluated by comparison with the comparative plants. The same evaluation system values were used as those used in Test 1. The results are shown in Table 2.

[Experiment 3]

Evaluation of the effect of the compound according to the above structural formula on the organic substance causing rice blast, piricularia oryzae subspecies I, was carried out in a greenhouse in the following manner.

In a round plastic pot filled with a 50:50 mixture of sand and loam with a diameter of 6.2 cm, seedlings of Orija sativa L ¹ or ¹ rice are deeply planted and placed in a greenhouse. After 14 days from sowing, the test agent, the compound described in Test 1, is allowed to dry to spray on all leaf surfaces of the rice plants. Spray a single pot of rice plant surface as a comparison of lean solvent-emulsifier solution. On the leaves of every plant at 24 hours, the aqueous 0.1% polyoxyethylene sorbitan monolauret solution of Picdaria duck spp. After 17 days. About 22-24 days after sowing, the plants became ill and the results were recorded. The results are shown in Table 3 using the same ratio system from Test 1.

TABLE 2

TABLE 3

[Experiment 4]

Evaluation of the effect of the compound according to the above structural formula on the organic substance causing apple black rust, Venturia inaequalis, was carried out in a greenhouse in the following manner.

Four pre-germinated apple seeds, Malus Sylvestris strain (MacIntosh), are sown in plastic pots filled with 50:50 soil and sterile soil, 9.5 cm square. Cover the seeds with the same mixture. The preparation agent was sprayed onto all leaf surfaces of one pot of seedlings 21 days after sowing with seedlings 4-6 days old. One pot of seedlings was used for each test agent. Within 24 hours after spraying, all plants were inoculated with conidia suspension of the hospital and the plants were kept in a wet room at a temperature of 65 ° F. for 48 hours. The plants were transferred to the greenhouse on the 24th day of sowing and allowed to stand for 9 days to observe the trend of the condition, and the control was evaluated. The results are shown in Table 4 with the same values as the ratio system used in Test 1.

TABLE 4

[Experiment 5]

Evaluation of the compound effect by the above formula on the organic Helmin tho sporium sativum that causes Helmintosporium leaf spot disease was carried out in a greenhouse in the following manner.

The sterile greenhouse soil mixture and the upper layer of 6.25 cm diameter are sown seed of Triticum Asatum L 'monon' wheat in a round plastic pot covered with sato. When the seedlings grow 10 to 12.5 cm, the test agent is sprayed into one pot for each test agent 6 days after sowing. Into one pot for each test drug, 10 ml of each test drop is dropped into the soil. Two pots of wheat seedlings are sprayed with water containing a solvent-surfactant system and two pots are sprayed with water containing a solvent-surfactant system. These four pots are performed as a comparison. Test agents were prepared in the same manner as in test 1. All plants are left overnight at room temperature to allow for possible penetration of the drug into the plants. Within 24 hours all plants are inoculated with a Helmintosporium satibum spore suspension and placed for 48 hours at 70 ° C. in a wet room. After that, all the plants are transferred to the greenhouse for translation. After 4 days (13 days after sowing), the plants showed pathological symptoms. Treated plants were compared to untreated plants and the percentage of bacterial control was recorded. Cell control rates are the same as in test 1. The results are reported in Table 5 below.

TABLE 5

[Experiment 6]

Evaluation of the compound effect by the above formula on the organic material Verticillium alboatrum, which induces a fortisilum forgery of cotton, was carried out in a greenhouse in the following manner.

Fill a 227g paper cup with 150g of inoculated soil. Spray the test agent onto the soil and place the paper cup on the roller. After mixing, the soil is poured into round plastic pots of 6.25 cm diameter. Four 14-day-old cotton is planted in each pot and the roots covered with the remaining soil. Each test is to be treated without two drugs and the other one. All plants are placed in a greenhouse. Fake and cystic signs were observed 14 days after transplantation and results were recorded. The results are shown in Table 6 below. The ratio used the same thing as the previous test.

TABLE 6

[Experiment 7]

The evaluation of the effect of the compound by the above formula on the organic Botrytis Cierea, which causes the gray fungus Botrytis of grapes, was carried out in a greenhouse in the following manner.

Round grape fruit is sterilized for 5 minutes with 1: 5 solution of surface chlorine water (Chlorox) removed from the stem and rinsed three times with deionized water. This fruit is put into each of 12 pieces of 35 × 22 × 4 cm Pyrex plates. The fruit is suspended on the top of the bottom with a mesh. Finally, the fruit is burned with a Bunsen burner to injure and infect the surface. The grapefruit is sprayed with a test agent prepared in the same manner as described in Test 1. In addition, one grapefruit is sprayed with a lean solvent-emulsifier system. Within 24 hours all fruits are delivered by spraying 5 ml of condensation suspension per plate. Increase the humidity so that the disease is well infected and water is added to each plate containing berries. The Pyrex plate is closed with the same plate in the upper layer and the compartment between the two plates is closed with masking tape. All plates are incubated at 25 ° C. for 48 hours.

The symptoms were observed three days after the test drug spray and the results were recorded. The results are shown in Table 7 at the same rate as used in Test 1.

TABLE 7

The test results obtained in the above test show that the new compounds of the present invention have a degree of physiogenic cell in air and air.

Claims (1)

A process for preparing the compound of formula (I) characterized by reacting a compound of formula (II) with a compound of formula (III) in the presence of an acid scavenger.

Wherein X is chloro, fluoro or bromo, m, p and s are each 0 or 1, n is 0, 1 or 2, q and r are each 0, 1, 2 or 3, m, The sum of n, p, q, r and s is 1 to 3, and when n is 2, m, p, q, r, s and s should all be 0 and the trifluoromethyl group should be at positions 3 and 5 When s is 1, m and p are both 0, n, q and r should not have a sum of 0, and when q is 1, the sum of m, n, r and S should not be 0.