CS214760B2 - Herbicide means and method of preparation of active substance thereof - Google Patents

Abstract

Substituted diphenyl ethers represented by the formula:- <IMAGE> wherein: A is oxygen or sulfur; X is hydrogen or halogen; Y is halogen or trifluoromethyl; Z is halogen, nitro, or cyano; R is hydrogen or C1-3 alkyl; R<1> is C1-3 alkylidene or monosubstituted C1-3 alkylidene, wherein the substituent is C1-4 alkyl; and R<2> is hydrogen, C1-10 alkyl, C1-10 alkoxy, C3-8 cycloalkyl, or an agronomically acceptable ionic species, are used to control weeds.

Description

A represents oxygen or sulfur,

X represents hydrogen or halogen,

Y is halogen or trifluoromethyl,

Z is halogen, nitro or cyano,

R is hydrogen or (C 1 -C 4) alkyl,

R 1 represents an alkylidene or a moiety substituted by 1 to 3 carbon atoms in which the substituent is an alkyl group containing 1 to 3 carbon atoms. 1-4 carbon atoms; and

R ² represents hydrogen or alkyl containing 1 · · to 10 'carbon atoms, cycloalkyl .obsahující 3-8 carbon atoms or agronomidky acceptable ionic species, and the carrier and / or adjuvant.

Examples of halogen atoms represented by X, Y and Z in the above formula are bromine, chlorine or fluorine, preferably bromine or chlorine. Examples of alkyl groups represented by R and R ² include the following representative groups: methyl, ethyl, n-propyl, isopropyl, η-butyl, isobutyl, tert-butyl, n-amyl, hexyl, Heptyl, octyl, isooctyl, nonyl, decyl and the like. Examples of R 1 alkylidene radicals include methylidene, ethylidene or propylidene. Suitable cycloalkyl groups R ² are cyclopentyl, cyclohexyl and cycloheptyl. · As. Examples of suitable agronomically ion species in the meaning of R ² may be mentioned alkali metals such as sodium, potassium or lithium, alkaline earth metals such as barium · calcium or ammonium, or alkylammonium or alkanolammonium · containing from 1 to 4 carbon atoms.

The compounds of formula I have:. herbicidal effect. Specific examples of the valuables falling within the scope of this general formula, which are preferably used in the compositions of the present invention include:

ethyl N- [5- (2 ', 4'-dichlorophenoxy) -2-nitrobenzoyl] glycinate, ethyl-N-sec-butyl-N- [5- (2,4'-dichlorophenoxy) -2-nitrobenzoyl] glycinate, isopropyl N- ^[i 5- (2 ', 4 ^{<-dichlorfenoxy)} -2-nitrobenzoyl] glycinate,

N- [5- (2 ', 4'-dichlorophenoxy) -2-nitrobenzoyl] glycine, ethyl N- [2 \ 4'-dichloro-phenoxy] -2-nitrobenzoyl] alanine, Ethyl-N- [(2 ^t , 4'-dichlorophenoxy) -2-nitrobenzoyl] alanine, ethyl-N- [2'-chloro-4'-trifluoromethyl lfenoxy] -2-nitro-benzoylglycinate, ethyl N- [(2 ^<-chloro-4'- trifluoromethylphenoxy) -2-niitrobenzoy 1] glycinate, propyl-N- [5- (2 ', 4 ^{<dichlorophenoxy)} -2, nitrate obenzoyl] glycine, N-amyl-N- [5- (2 \ 4 &apos; -dichlorophenoxy] -2-nitrobenzoyl] glycinate, ethyl N- [5- (2,4'-dichlorophenoxy) -2-nitrobenzoyl] -3-aminopropionate, isopropyl N- [5- (2 ', 4'- dichlorophenoxy) -2-nitrobenzoyl] glycinate,

^N [5- (2 ^{<-chloro-4'-trifluoromethylphenoxy}} -2-nitro obenzoyl] glycinate, isopropyl N- [5- (2'-chloro-4'-trifluoromethylphenoxy e-nitrobenzoyl] glycine, methyl N- [5- (2'-chloro-4'-trifluoromethyl) -2-nitrobenzoyl] glycinate, sec-butyl-N- [5- (2'-chloro-4'-trifluoromethylphenoxy) -2-nitrobenzoy 1] glycinate, ethyl N- [5- (2'-chloro-44rif luormethy lfenoxy) -2-nitro obenzoyl] alanine, ethyl-N- ^[5- (2 ^{<4-chloro <trifluoromethylphenoxy)} -2 nitrobenzoyl] -3-aminopropionate

Of the compounds exemplified, those which contain the trifluoromethyl group as Y in the general formula are particularly effective. Formula I.

Of course, within the scope of the invention are 1 herbicidal compositions comprising stereoisomers and optical isomers of the compounds of formula (I).

The present invention also relates to a process for the preparation of? The process according to the invention is characterized in that the correspondingly substituted benzoyl halide of the formula II

where

Hal is halogen and

X, Y and Z are as defined for Formula I, reacted with at least a stoichiometric amount of the respective substituted compound of Formula III

O

II

RHN — R ¹ —C — A — R ² (ΙΠ) where

R, R ¹ , A and R ² are as defined for formula (I).

The reaction is carried out by methods known in the art. The substituted benzoyl halides of the formula II and the compounds of the formula III can be obtained from commercial sources or can be prepared by known methods. Preferably, at least a siechiometric amount of substituted benzoyl halide is added with stirring to the substituted amino ester, preferably in the presence of an acid acceptor such as triethylamine, pyridine, N, N-dimethylaniline and the like. Since the reaction is exothermic, the benzoyl halide is added sequentially. If desired, the substituted benzoyl halide or compound of formula III, usually a substituted aminoester, or the like, may be dissolved in an inert solvent such as benzene, methylene chloride, chloroform, ethyl acetate, tetrahydrofuran or the like. Upon completion of the addition of the substituted benzoyl halide, the reaction mixture is brought to reflux and reflux is maintained until the desired degree of conversion is achieved. The reaction mixture was cooled to ambient temperature and washed successively with dilute mineral acid, dilute sodium hydroxide solution and water and allowing the phases to separate. The substituted diphenyl ether is isolated from the organic phase by any of the known methods, for example by evaporation, crystallization, vacuum drying and the like.

If desired, the substituted diphenyl ether obtained as product may optionally be further purified, for example by recrystallization.

The following Examples 1 to 9 illustrate the synthesis of certain specific substituted diphenyl ether compounds of the invention. The examples are illustrative only and do not limit the scope of the invention in any way.

Example 1

Ethyl N- [5- (2 ', 4'-dichlorophenoxy) -2-nitrobenzoyl] glycinate

A 100 ml flask equipped with a dropping funnel, a reflux condenser and a magnetic stir bar was charged with a solution of 1.03 g (0.0.1 mole) of glycine ethyl ester and 1.01 g (0.01 mole) of triethylamine in 25 ml of benzene. The solution was stirred at ambient temperature was added dropwise thereto к 3,450 g (0.01 mol) of 5- ⁽² ', ^{4'-dichlorophenyl} -XY) -2-hitrobenzoylchloridu in 25 ml benzene. The reaction mixture is heated due to the exothermic reaction. After the addition was complete, the mixture was stirred at room temperature for 2 hours, then heated to boiling, maintained at reflux for 2 hours, and then cooled to room temperature. The mixture was transferred to a separatory funnel and washed separately with 30 ml of 1 N hydrochloric acid, 30 ml of water, 30 ml of 1 N sodium hydroxide and 30 ml of water. The organic layer was dried over magnesium sulfate and concentrated in a rotary evaporator at 55 ^° C to a rusty solid containing ethyl N- [5- (2 ', 4'-dichlorophenoxy) -2-nitrobenzoyl] glycinate. The solid was recrystallized from a minimum amount of benzene: ligroin (30: 70 vol. / Vol.) To give a tan crystalline solid comprising ethyl N- [5- ⁽² ', 4'-dichlorophenoxy) -2-nitrobenzoyl Jglycinátem m.p. 1.10-112 ° C. The mass spectrum shows a molecular weight of 412 ^and with fragments at 412, 310 and 236th

Example 1 a d 2

Methyl N- [5- (2 ‘, 4‘-dichlorophenoxy) -2-nitrobenzo-yl] glycinate

A 100 ml three-necked flask equipped with a reflux condenser, a dropping funnel and a magnetic stir bar was charged with a solution of 0.89 g (0.01 mol) of glycine methyl ester and 1.0 g (0.01 mol of triethylamine in 30 ml of tetrahydrofuran). 3.45 g (0.01 mol) of 5- (2 &apos;, 4 ' -dichlorophenoxy) -2-nitrobenzoyl chloride in 20 ml of tetrahydrofuran are added dropwise thereto, followed by exothermic heat generation. The mixture was diluted with 50 ml of ethyl acetate and washed sequentially with 30 ml of 1 N hydrochloric acid, 30 ml of 1 N sodium hydroxide and 30 ml of ethyl acetate. The organic layer was separated, dried (MgSO 4) and concentrated in a rotary evaporator at 55 ° C to give a yellow syrup which crystallized on standing. The crystalline yellow material was recrystallized from a solution in benzene and ligro. tin (30: 70 v / v) to give a feathery brownish solid consisting of methyl N- [5- (2 ', 4'-dichlorophenoxy) -2-nitrobenzoyl] glycinate. Its melting point is 133-135 ° C. The mass spectrum shows a molecular weight of 398. 2.5 g of the obtained material corresponds to a yield of 63%.

Example 3

Sec-butyl-N- [5- (2 ', 4'-dichlorophenoxy) -2-nitrobenzoyl] glycinate

2.06 g (0.005 mol) of ethyl N- [5- (2 ', 4'-dichlorophenoxy) -2-nitrobenzoyl] glycinate (prepared according to Example 1) are placed in a 100 ml flask equipped with a reflux condenser and a magnetic stir bar. 0.4 g (0.01 mol) of sodium hydroxide in 20 ml of water is then added. The suspension was stirred and refluxed until all solids dissolved (about 50 minutes) and then an additional 10 minutes. The solution was cooled and 20 ml of 10% hydrochloric acid solution was added. A sticky solid is formed. The density is diluted with 50 mL of water and extracted twice with 50 mL of ethyl acetate. The extracts were combined, washed with water, and then dried over magnesium sulfate. The solvent was removed on a rotary evaporator at 55 ° C. A light brown syrup consisting of N- [5- (2 ‘, 4‘-dichlorophenoxy) -2-nitrobenzoyl] glycine is obtained, the mass spectrum of which has a molecular weight of 384 with fragments of 384 and 310.

A solution of 3.84 g of N- [5- (2 ', 4 ^{<-dichlorfenoxy)} -2-nitrobenzoyl] glycine (prepared as described above) and 0.35 g of phenolsulfonic acid in 50 ml of sec-butanol is added to 100 ml flask attached to a Dean-Stark master and equipped with a magnetic stirring bar. The solution is refluxed under stirring and the water is separated by azeotropic separation. After about 26 hours at reflux, the solution was cooled and the sec-butanol was removed on a rotary evaporator at 55 ° C. The residue is dissolved in 50 ml of methylene chloride and the solution is washed twice with 30 ml of 1 N sodium hydroxide and once with 30 ml of water. The organic layer was dried over magnesium sulfate and concentrated in a rotary evaporator at 55 ° C. A pale red oil is formed from which a crude product of sec-butyl N- [5- (2 ', 4'-dichlorophenoxy) -2-nitrobenzoyl glycinate crystallizes on standing. The crude product was recrystallized from a minimal amount of hot solvent mixture of ethyl acetate and ligroin (2.5: 75 by volume) 1a. to give a white solid consisting of sec-butyl-N- [5- (2 ', 4'-dichlorophenoxy) -2-nitrobenzoyl] glycinate having a molecular weight of 440 determined by mass spectrography (fragments at 440, 367 and 310).

214780

Example 4

I-Sopropyl-N- [5- (2 ', 4'-dichlorophenoxy) -2-nitrobenzoyl] glycinate

A solution of 3.84 g of N- [5- (2 ', 4'-dichlorophenoxy) ^{-2-nitrobenzene:} benzoyl] glycine (prepared as in Example 3) and 0.35 g of phenolsulfonic acid in 50 ml of isopropanol are introduced into a 100 ml flask equipped with Dean-Stark water separator, reflux condenser and magnetic stirrer. The solution is boiled and water is separated by azeotropes. After refluxing for 26 hours, the solution was cooled and the sec-butanol was evaporated in a rotary evaporator at -55 ° C. A sticky solid is formed as a residue. The solid is dissolved in 50 ml of ethyl acetate and the solution is washed with 30 ml of 1 N sodium hydroxide and then with 30 ml of water. The organic layer was dried over magnesium sulfate and concentrated in a rotary evaporator at 55 ° C. An off-white solid is obtained. This solid was recrystallized from the minimum amount of hot solvent mixture of ethyl acetate and ligroin (25:75 by volume) to give a white powder (3.1 g, 73 percent yield) of isopropyl-N- (5- ( 2 ', 4'-dichlorophenoxy] -2-nitrobenzoyl glycinate having a molecular weight of 426 as determined by mass spectrography (fragments at 426,367 -a-310), m.p. 99-100 ° C.

Example 1 a d 5

Ethyl N- [5 * (2‘-chloro-4‘-trifluoromethylphenoxy) -2-nitrobenzoyl] glycinate

The procedure described in Example 1 was repeated except that an equivalent amount of 5- (2'-chloro-4'-trifluoromethylphenoxy) -2-nitrobenzoyl chloride was used instead of -5- (2 ', 4'). (Dichlorophenoxy) -N-nitrobenzoyl chloride. Ethyl N- [5- (2'-chloro-4'-trifluoromethylphenoxy) -2-nitrobenzoyl] glycinate is obtained.

Pri puts

Ethyl N- [5- (2‘-chloro-4‘-trifluoromethylphenoxy) -2-nitrobenzoyl] alaninate

To a 100 ml three-necked flask equipped with a dropping funnel, a reflux condenser and a magnetic stir bar was added 1.4 g (0.012 mol) of ethyl alanine ester and 1.1 g (0.01 mol) of triethylamine in 80 ml of benzene. 3.79 g (0.01 mol) of 5- (2'-chloro-4'-trifluoromethylphenoxy) -2-nitrobenzoyl chloride in 20 ml are added dropwise with stirring at ambient temperature (about 20 DEG C.). benzene. The reaction is exothermic. After the addition was complete, the mixture was refluxed for 6 hours, cooled and transferred to a separatory funnel. It is then washed separately with 30 ml of 1N hydrochloric acid, 30 ml of water, 30 ml of 1N sodium hydroxide and 30 ml of water. The organic layer was dried with magnesium sulfate and concentrated in a rotary evaporator at 55 ° C. 3.8 g of pure yellow oil, ethyl N- [5- (2‘-chloro-4‘-trifluoromethylphenoxy) -2-nitro-benzoyl] -laninate, are obtained as a residue.

NMR (acetone, de)

7.1 to 8.3 Å (multiplet, 7H)

4.55 <5 (quartet, 1 H),

4.15 a (quartet, 2H),

1.25-δ (multiplet, 6H).

The yellow oil crystallizes on standing and the crystals have a melting point of 98-100 ° C.

Example 7

Ethyl N- [5- (2‘-chloro-4'-trifluoromethylphenoxy) -2-nitrobenzoyl] -3-aminopropionate

Into a 160 ml 3-necked flask equipped with a dropping funnel, a reflux condenser and a magnetic stir bar, was charged 1.4 g (0.012 mol) of ethyl beta-alanine and 1.1 g (0.01 mol) of triethylamine at 30 ° C. ml benzene. 3.79 g (0.01 moles) of 2‘-chloro-4‘-trifluoromethylphenoxy-2-nitrobenzoyl chloride in 20 ml of benzene are added dropwise to the solution while stirring at a temperature of about 20 DEG C. (about 20 DEG C.). The reaction is exothermic. After the addition was complete, the mixture was refluxed for 6 hours, cooled and transferred to a longer funnel. It is then washed separately with 30 ml of 1 N hydrochloric acid, 30 ml of water, 30 ml of 1 N sodium hydroxide and 30 ml of water. The organic layer was dried with magnesium sulfate and concentrated in a rotary evaporator at 55 degrees Celsius. As a residue, -3.7 g of a clear yellow oil consisting of ethyl N- [5- (2-chloro-4'-trifluoromethylphenoxy) -2-nitrobenzoyl] -3-aminopropionate is obtained.

NMR - (acetone, - to)

7.1 to 8.2 δ (multiplet, 7H)

4.0 (quartet, 2H),

4.56 ó (quartet, -ZH),

3.62 δ (triplet, 2H),

1.28 δ (-triplet, 3H).

Example 8

Sec-butyl-N- [5- (2'-chloro-4'-trifluoromethylphenoxy) -2-nitrobenzoyl] glycinate

The glycinate prepared according to Example 5 is hydrolyzed and esterified according to the method described in Example 3. There is obtained sec-butyl-N-η 5 - (2‘-chloro-4‘-trifluoromethylphenoxy) -2-nitrobenzoyl] glycinate.

Example 9

1-Sopropyl-N- [5- (2'-chloro-4'-trifluoromethylphenoxy) -2-nitrobenzoyl] glycinate

The glycinate prepared according to Example 5 is hydrolyzed and esterified with isopropyl alcohol according to the procedure of Example 3.

1- (3-isopropyl-N- (4-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoyl) glycinate.

The procedure for the synthesis of the compounds of the invention has been illustrated in more detail by the preceding examples. It will be understood, however, that any substance within the scope of the active ingredients of the compositions of the invention can be prepared by one skilled in the art by simply changing the starting materials and using the described or other suitable preparation methods.

It has been found that the compounds of the invention effectively suppress the growth of various unwanted plants, i.e., weed plants, when applied in a herbicidally effective plant. The amount is in an environment where weed plants are expected to grow before emergence or when applied to already emerged weed plants. By "herbicidally effective amount" is meant that amount of compound or mixture of compounds that is required to damage or destroy weeds to an extent that makes it impossible to heal plants after application. The amount of a particular compound or mixture of compounds applied to achieve a satisfactory herbicidal effect can vary over a wide range and depends on various factors such as the resistance of the particular weed species, the extent of weeds, climatic conditions, soil conditions, application method and the like. a dose of 0.22 to 11.21 kg / ha of compound or mixture of compounds is required. Of course, the activity of a particular compound against a particular type of weed can be readily determined by laboratory or field tests. These tests are carried out according to conventional methods.

The active compounds may be used as such or in the form of formulations containing also agronomically suitable auxiliaries, inert carriers, other herbicides or other commonly used agricultural chemicals, for example pesticides, stabilizers, safety enhancers, fertilizers and the like. forms of such compositions or even the compounds themselves are dusts, granules, wettable powders, solutions, suspensions, aerosols, emulsions, dispersions, etc. The content of the active compound or active compounds in the compositions also containing typical agronomically suitable substances can vary within wide limits from about 0.05 to about 95% by weight of the composition. Typically, such compositions comprise about 5 to about 75% by weight of the compound or; of the compounds of the invention.

The compounds of formula (I) are effective in controlling various broadleaf and grass weeds in pre-emergence or post-emergence application at a rate of less than 2.24 kg / ha, while not significantly damaging the crops such as corn, wheat, rice or soybean. Examples of weed plants which can be effectively controlled by the compounds of the present invention include: white mustard (Brassica kaber), gray grass (Setaria glaucaj, bloodwort (Digitaria · sanguinalis), Sesbania spp., Abutilon (Abutilon theophrasti), Sorghum halepense, Echinochloa crusgalli, Datura stramonium, Sida spinosa, Ipomoa purpurea and the like

Some of the compounds prepared according to Examples 1 to 9 were tested for herbicidal activity against certain weed species under controlled laboratory conditions in terms of light, temperature and humidity. Seeds of selected weeds are sown on test areas. In the case of pre-emergence tests, test areas are treated with the selected compound immediately after sowing. In the case of post-emergence tests, the areas are treated with the selected compound after two weeks of germination. The compounds are applied to the test areas as a solution spray. % of the compound in the solvent, in an amount corresponding to the desired degree of treatment. The weed growth status at the time of treatment is recorded. The toxic effect of the compounds is evaluated periodically after application. The test results are summarized in the following table. The table shows both the weed test species, the compound applied (indicated by the number of the examples according to which they were prepared), the rate of application (kg / ha) and the fact whether the application was carried out pre-emergence or post-emergence.

Weed plant

5.

Compound

6 7 7

Sorghum halepense

Datura stramoniumx

Brassica kaberx

Echinochloa crusgallix

Sesbania spp.x

Abutilon theophrastix

Ipomoa purpureax

Setaria glauca

Digitaria sanguinalis,

Sida spinosa

Xanthium grade application10

Type of treatment: pre pre-emergence (pre) post-emergence (post)

In all these tests, it was observed that all the different weed plants were either killed or damaged so that they did not recover within 20 to 24 days after application of the compounds.

x

X

X

X

X

X

X

X

X

X for

X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X 2 2 2 2 post over post for

The invention has been described in detail by way of examples of specific embodiments. However, it is not limited to these embodiments. The present invention is within the scope of the invention.

Claims (7)

A herbicidal composition, characterized in that:. comprises a herbicidally effective amount of a compound or mixture of compounds of formula I wherein And represents oxygen or sulfur, X is hydrogen or halogen; Y is halogen or trifluoromethyl, Z is halogen, nitro or cyano, R represents. hydrogen or (C1-C4) -alkyl, R1 represents an alkylidene or a monosubstituted alkylidene having 1 to 3 carbon atoms in which the substituent is an alkyl group containing 1 to 4 carbon atoms and R 2 is hydrogen or an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or an agronomically acceptable type of ion, and a carrier and / or adjuvant. 2. A herbicidal composition as claimed in claim 1, characterized in that it contains at least one compound of the formula I as active ingredient in which Y represents a trifluoromethyl group or chlorine and the other symbols have the meaning given in claim 1. 3. A herbicidal composition as claimed in claim 1, characterized in that it contains at least one compound of the formula I as active ingredient, in which R2 represents an alkyl group containing up to 4 carbon atoms and the other symbols have the meaning given in point 1. 4. A herbicidal composition according to claim 1, characterized in that it contains at least one compound of the formula I as active ingredient, in which R2 represents, as an agronomically suitable ionic species, an alkali metal, alkaline earth metal ion, ammonium, alkylaminium. or - alkanolammonium of up to 4 carbon atoms and the other symbols have the meaning given in point 1. 5 ·. The herbicidal composition according to claim 1, characterized in that it contains at least one compound of the general formula I as active ingredient, in which Z represents a nitro- or cyano group and the other symbols have the meanings given in point 1. above. 6. A herbicidal composition as claimed in claim 1, wherein the active ingredient of the formula I is ethyl N- [5- (2 ', 4'-dichlorophenoxy) -2-nitrobehzoyl] glycinate, ethyl N- [5- (Ζ-CΗΙΗΙΤΤ-Ι-ud -udrmethylphenoxy) -2-nitrobenzoyl] glycinate, N- [5- (2 ', 4'-dichlorophenoxy) -2-nitrobenzoyl] glycine, N- [ 5- (2'-dichloro-4'-trifluoromethylphenoxy) -2> nitrobenzoylglycine, isopropyl-N- [5- (2'-chloro-4'-trifluoromethylphenoxy) -2-nitrobenzoyl] glycinate, methyl-N- [ 5- (2'-chloro-4'-N-methylphenoxy) -2-nitrobenzoyl] glycinate, sec-butyl N- [5- (2'-chloro-4'-trifluoromethylphenoxy] -2-nitrobenzoyl] glycinate , ethyl N- [5- (2'-chloro-4'-trifluoromethylphenoxy) -2-nitrobenzoyl] 2 1 4 7 6 О alaninate or ethyl-N- [5- ^(2-t -chlDr 4 ^<- trifluoromethylphenoxy) -2-nitro-benzoyl] -3-aminopropionate. 7. A process for the preparation of compounds of formula (I) according to claim 1, wherein the correspondingly substituted benzoyl halide of formula (II): Hal is halogen and X, Y and Z are as defined for formula I reacted with at least a stoichiometric amount of an appropriately substituted compound of formula O II RHN — R ¹ —C — A — R ² (ΠΙ) where R, R ¹ , A and R ² are as defined for formula (I).