KR820001600B1 - Process for the preparation of n-benzl halo acetamide derivative - Google Patents

Abstract

Fortyseven title compds. (I; R1 = C4-7 tert-alkyl; X = halo; R2 = Me, Et; R2,R3 = Me, Et; R2R3 = C2-5 alkylene; Y,Z=H, halo, Me, MeO) useful as herbicides, were prepd. by reaction of haloacetic acid(II) or their reactive derivs. and benzyl amine(III). Thus, the mixt. of 100 ml toluene, 9 g III (Y,Z = Me; R2,R3 = H) and 5.8 g pyridine was reacted with 11. 3g α-tert-butyl acetyl acetyl chloride for 3hr to give 15.8 g I(R1 = tert-Bu; X= Cl; R2,R3 = H; Y,Z = Me)(m.p., 159-160≰C).

Description

Method for preparing N-benzylhalo acetamide derivative

The present invention relates to a process for the preparation of N-benzylhalo acetamide derivatives and their use. More specifically, the present invention relates to a herbicidal composition comprising an N-benzylhalo acetamide derivative and the aforementioned derivatives and a method for preparing the same.

The aforementioned N-benzylhalo acetamide derivatives can be represented by the following general formula.

[Formula I]

Wherein R ₁ is a C ₄ -C ₇ tertiary alkyl group, X is a halogen atom, R ₂ is a methyl group or an ethyl group, R ₃ is a methyl group or an ethyl group, or when R ₂ and R ₃ are taken together, C _2- C ₅ alkylene group, and Y and Z may be the same or different, respectively, hydrogen atom, halogen atom, methyl group or methoxy group.

The term halogen atom as used above generically means chlorine, cancelled, fluorine and oxo.

As a result of extensive research, it was found that N-benzylhalo acetamide derivative (I) has strong herbicidal activity against various weeds. For example, rice and weeds such as Echinochloa Crus-galli, Digitaria sanguinalis, Setaria viridis, the following yearly and perennial weeds, Cyperus esculentus, Cyperus difformis, Cyperus rotundus, Scirpus Hotarui, Inflorescence, Eleocharis acicularis, Bangdong and Eleo charis Kuroguwai Weeds such as weeds, amaranthus retroflexus, amaranthus and weeds, dentiferous weeds such as the Chenopodium album, Ladysthumb (Polygonum persicaria) and Curlydock (Rumex japonicus) Polygonaceae such as)), Pontedeiraceae such as the water scabbard, Hyunsamaceae such as the Liternia pyxidaria, and Sagittaria pygmaea. Taraxacum officin Weeds such as asters, and oxalidasea, such as oxalis corniculata, can be markedly inhibited or eradicated by leaves or soil treatment before or after germination. Therefore, the herbicidal action is effective in suppressing or eradicating not only field weeds but also faucet weeds.

Advantageously, the N-benzylhalo acetamide derivative (I) is suitable for various crops such as rice, soybean, cotton, corn, peanut, sunflower, rapeseed, potato and many such as lettuce, cabbage, tomato, cucumber and carrot. No harm is done to the vegetables.

Therefore, N-benzylhalo acetamide derivative (I) is useful as a herbicide that can be used in crops, vegetables and rice. In addition, the aforementioned derivatives are also useful as herbicides for use in orchards, grasses, ranches, tea gardens, mulberry fields, rubber plantations, forests, and the like.

Japanese Unexamined Patent Publication (Unexamined) No. 8828/1973 discloses pivalic acid amide derivatives which are slightly similar to N-benzylhalo acet derivative (I) in chemical structure and have herbicidal action.

However, the herbicidal action of N-benzylhalo acetamide derivative (I) is generally superior to that of the pivalic acid amide derivative. N-benzylhalo acetamide derivatives (I) show extremely high herbicidal activity without any detriment to the crops against fresh and perennial weeds compared to pivalic acid amide derivatives. Furthermore, N-benzylhalo acetamide derivative (I) is very unique in its high potency in suppressing or eradicating Cyperaceae weeds. N-benzylhalo acetamide derivative (I) has the general formula:

[Formula II]

Or halo acetic acid, or its reactive derivative, wherein R ₁ and X are as defined above, respectively,

[Formula III]

It can be prepared by reacting with a benzyl amine compound (where R ₂ , R ₃ Y and Z are as defined above, respectively).

Haloacetic acid (II) or its reactive derivatives are synthesized, for example, by the method disclosed in J.AM. Chem. Soc., 71,3929 (1933).

In the reaction described above, halo acetic acid (II) or its reactive derivative and the benzylamine compound (III) described above may be used in an equivalent ratio of 0.4 to 1.5: 1, preferably 0.5 to 1.1: 1.

The reaction may be carried out in the presence or absence of an inert solvent. Examples of inert solvents include hydrocarbons (e.g. benzene, toluene, xylene), halogenated hydrocarbons (e.g. chlorobenzene, methylene chloride, chloroform, tetra chloride), ethers (e.g. diisopropyl ether, tetra hydrofuran, dioxane) , Alcohols (eg methanol, ethanol, isopropanol), ketones (eg acetone, methyl ethyl ketone, methyl isobutyl ketone), esters (eg ethyl acetate), nitrile (eg acetonitrile), dimethyl sulfoxide, dimethyl Formamide, water and the like.

Particularly suitable among these is benzene. The reaction may be carried out extensively from the boiling point of the solvent to the boiling point of the solvent, preferably at 0 ° C. If necessary, cooling and heating may be performed.

As the haloacetic acid (II) or a reactive derivative thereof, free acid, acid anhydride, acid chloride, acid bromide, acid ester and the like may be used. Depending on the type of reactive derivative, a condensing agent, a dehydrating agent, an acid remover or a catalyst may be used for the reaction. In the case of free acids, dicyclohexyl carbodiimide, phosphorus pentachloride, thionyl chloride, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, triethylamine, pyridine, quinoline, isoquinolime, N, N Dimethylaniline, N-methylmorpholine, etc. may be examples of reaction aids. In the case of acid chlorides or acid bromide, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, triethylamine, pyridinequinoline, isoquinoline, N, N-dimethylaniline, N, N-diethylaniline, N-methyl Morpholine, sodium acetate, and the like, preferably triethylamine may be used as the reaction aid. When using a reaction aid, the amount is preferably from catalyst amount to 1.5 equivalents, preferably from 0.9 to 1.1 equivalents, for the material to be removed from the released compound as a result of the reaction.

The recovery of the reaction product from the reaction mixture may be carried out essentially by conventional methods. For example, the reaction mixture is filtered and / or washed with water and subsequently distilled to remove the solvent to obtain a reaction product, such as N-benzylhalo acetamide derivative (I).

If desired, the reaction product described above may be purified by conventional methods such as recrystallization essentially from a suitable solvent such as benzene, toluene, n-hexane, methanol, ethanol, chloroform or methylisobutyl ketone.

The N-benzylhaloacetamide derivative (I) prepared in this way has an asymmetric carbon atom, and therefore, there is an optical property, and the N-benzylhaloacetamide derivative (I) is used in the present invention. It is useful as a herbicide.

Practical embodiments relating to the preparation of the N-benzyl haloacetamide derivative (I) are described in detail in the following examples.

Example 1

Toluene (100 ml), α, α-dimethyl benzyl amine (9 g) and pyridine (5.8 g) were injected into a 200 ml drift neck flask containing α-tert-tert-butyl acetyl chloride (11.3). g) was added dropwise while stirring at room temperature. Stirring was added dropwise over 3 hours. The reaction mixture was washed with water to remove pyridine hydrochloride. The toluene layer was dried over anhydrous sodium sulfate, and the solvent was filtered off under reduced pressure. The obtained residue was recrystallized from ethanol to obtain 15.8 g of N- (α, α-dimethylbenzyl) -α-chloro-tert-butyl acetamide. Melting point 159-160 ℃

Elemental Analysis:

This theory: C, 67.28%, H, 8.28%, N, 5.23%, C1,13.24%.

Found: C, 67.35%, H, 8.40%, N, 5.11%, C1,13.37%.

Example 2

1) Inject a benzene (100 ml), α-α-dimethylbenzylamine (9 g) and triethylamine (7.4 g) into a 200 ml double neck flask and add α-bromo-tert-butylacetyl chloride (14.5 g). ) Was added dropwise while stirring at room temperature.

Stirring was continued for 3 hours. The reaction mixture was washed with water to remove triethylamine hydrochloride. The benzene layer was dried over anhydrous sodium sulfate, and then the solvent was filtered off under reduced pressure. The resulting residue was recrystallized from ethanol to give 15.3 g of N- (α, α-dimethylbenzyl-α-bromo-tert-butylacetamide.melting point 182-183 ° C.

Elemental Analysis:

This launch: C, 57.70%, H, 7.10%, N, 4.49%, Br, 25.59%.

Found: C, 57.87%, H, 7.20%, N, 4.59%, Br, 25.56%.

2) Methyl isobutyl ketone (150 ml), α, α-dimethylbenzylamine (33.8 g) and triethylamine (27.8 g) were injected into a 500 ml drift four-neck flask, where α-bromo-tert- Butyl acetbromide (64.5 g) was added dropwise while stirring at room temperature. Stirring was continued for 3 hours. When the reaction was completed, water (200 ml) was added to the stock, and the reaction mixture was gradually heated to remove methyl isobutyl ketone, followed by cooling to room temperature. The precipitated crystals were filtered off, washed with water, dried and recrystallized with ethanol to obtain N- (α, α-dimethylbenzyl) -α-bromo-tert-butyl acetamide (61.5 g).

3) α-bromo-tert-butyl acetic acid (9.8 g) and benzene (50 ml) were injected into a 200 ml drift four-neck flask, where pyridine (50 ml) and α, α-dimethyl benzylamine (6.9 g) were added. Add dropwise while stirring at room temperature. And here again dicyclohexyl carbodiimide (10.8 g) was added and the reaction continued at 60-70 ° C. for 6 hours and then cooled. The solvent was filtered off under reduced pressure, and the residue was extracted with hot benzene. The benzene extract was concentrated by filtration, and the residue was recrystallized from ethanol to obtain N- (α, α-dimethylbenzyl) -α-bromo-tert-butyl acetamide (10.8 g).

Example 3

Benzene (100 ml), α, α-dimethylbenzyl amine (9 g) and triethyl amine (7.4 g) were charged into a 200 ml drift four-neck flask, where α-bromo-tert-amyl was added while stirring at room temperature. Acetyl chloride (15.5 g) was added dropwise. Stirring was continued for 3 hours. After the reaction was completed, the reaction mixture was washed with water to remove triethylamine hydrochloride. The benzene layer was dried over anhydrous sodium sulfate, and then the solvent was filtered off under reduced pressure.

The residue was recrystallized from ethanol to give 15.8 N- (α, α-dimethylbenzyl) -α-bromo-tert-amylacetamide. Melting point 136-137 ° C.

Elemental Analysis:

This launch: C, 58.90%, H, 7,41%, N, 4.29%, Br, 24.49%.

Found: C, 58.88%, H, 7.65%, N, 4.28%, Br, 24.44%.

Example 4

Benzene (150 ml), α, α, 2-trimethylbenzylamine (7.5 g) and triethylamine (6 g) were charged in a 200 ml drift four neck flask, containing α-bromo-tert-butylacetyl chloride (10.2). g) was added dropwise while stirring at room temperature. Stirring was continued for 3 hours. After the reaction was completed, the reaction mixture was washed with water to remove triethylamine hydrochloride. The benzene layer was dried over anhydrous sodium sulfate, and the solvent was filtered off under reduced pressure.

The residue was recrystallized from ethanol to give 13.8 g of N- (α, α, 2-trimethylbenzyl) -α bromo-tert butyl acetamide. Melting Point, 166.5 ℃ -168 ℃

Elemental Analysis:

This launch: C, 58.90%, H, 7.41%, N, 4.29%, Br, 24.49%.

Found: C, 59.16%, H, 7.43%, N, 4.33%, Br, 24.50%.

Example 5

Benzene (100 ml), 1-phenylcyclopropylamine (8.9 g) and triamine (7.4 g) were charged into a 200 ml drift four neck flask, containing α-bromo-tert-butyl acetyl chloride (14.5 g). Add dropwise while stirring at room temperature. Stirring was continued for 3 hours. When the reaction was completed, the reaction mixture was washed with water to remove triethylamine hydrochloride. The benzene layer was dried over anhydrous sodium sulfate, and the solvent was filtered off under reduced pressure.

The obtained residue was recrystallized from ethanol to obtain 14.8 g of N- (1-phenyl cyclopropyl) -α-bromo-tert-butyl acetamide. Melting point 161-162.5 ℃

Elemental Analysis:

This theory: C, 58.07%, H, 6.50%, N, 4.51%, Br, 25.76%.

Found: C, 58.24%, H, 6.73%, N, 4.50%, Br, 25.74%.

Other N-benzylhaloacetamide derivatives (I) can be prepared in the same manner as described above, a particular example of which will be indicated in the first table. However, it does not mean to limit the scope of the present invention.

In practical use of the N-benzyl halo acetamide derivative (I), it may be used as granules, powders, crude powders, hydrating agents, emulsifying thickeners, dispersing agents, homemade handmade or oily suspensions.

In the various formulations described above, a solid or liquid carrier is used. Examples of solid carriers are mineral powders (e.g. kaolin, bentonite, clay, monrolillonite, talc, silica, mica, vermiculite, gypsum, calcium carbonate, apatite). Vegetable powders (e.g. soy flour, flour, wood flour, tobacco powder, starch, crystalline cellulose), high molecular weight compounds (e.g., petroleum resins, polyvinyl chloride, dammargum, ketone resins), alumina, waxes and similar compounds to be.

Examples of liquid carriers include kerosene, alcohol (e.g., methanol, ethanol, ethylene glycol, benzyl alcohol), aromatic hydrocarbons (e.g. toluene, benzene, xylene, methylnaphthalene), halogenated hydrocarbons (e.g., chloroform, carbon tetrachloride, monochlorobenzene) , Ethers (e.g. dioxane, tetrahydrofuran), ketones (e.g. acetone, methyl ethyl ketone, cyclohexanone, isophorone), esters (e.g. ethyl acetate, butyl acetate, ethylene glycol acetate), acid amides (e.g. , Dimethyl formamide), nitrile (eg acetonitrile), ether alcohols (eg ethylene glycol ethyl ether), water and similar compounds.

Surfactants used in emulsification, dispersion or diffusion are nonionic, anionic, cationic and amphoteric active agents. Examples of the surface active agent include polyoxy ethylene alkyl ether, polyoxy ethylene alkylaryl ether, polyoxy ethylene fatty acid ester, sorbitan fatty acid ester, polyoxy ethylene sorbitan fatty acid ester, oxyethylene-oxypropylene polymer, polyoxy ethylene alkyl phosphate, fat Acid salts, alkyl sulfates, alkyl sulfonic acids, alkylarylsulfonic acids, alkyl phosphates, polyoxy ethylene alkyl sulfates, quaternary ammonium salts and similar compounds.

However, the surfactant is of course not limited to the above-mentioned compounds. And if necessary, gelatin, casein, sodium alginate, starch, agar, polyvinyl alcohol or similar compounds and the like can be used as an adjuvant.

In preparing the herbicide composition, the content of N-benzyl halo acetamide derivative (I) is usually 0.05 to 95% by weight, preferably 3 to 50% by weight.

Practical examples of herbicide compositions according to the invention will be indicated in the following several examples, in parts and percentages expressed by weight.

Preparation Example 1

50 parts of Compound No. 1, 2.5 parts of dodecyl benzenesulfonate, 2.5 parts of lignin sulfonate and 45 parts of diatomaceous earth are mixed well during powdering to obtain a wetting agent.

Preparation Example 2

30 parts of compound No. 4, 10 parts of emulsifier ("Sorpol-SM-100" manufactured by Toho Chemical Co., Ltd.) and 60 parts of xylene are mixed well to obtain an emulsion concentrate.

Preparation Example 3

5 parts compound No. 37, 1 part white carbon, 5 parts lignin sulfonate and 89 parts clay are mixed well during powdering.

The mixture is of course well cleared, granulated and dried to obtain granules.

Preparation Example 4

30 parts Compound 20, 1 part isopropyl phosphate, 66 parts clay and 30 parts talc mix well during powdering. The mixture is opened with water, granulated and dried to obtain granules.

Preparation Example 5

40 parts bentonite, 5 parts lignin sulfonate and 55 parts clay are mixed well during powdering. The mixture is opened with water, granulated and dried to obtain granules having no active ingredient. The granules are obtained by infiltrating 5 parts of compound No. 7 into the granules.

Preparation Example 6

Granules are obtained by infiltrating 90 parts of 16-48 mesh bentonite with 5 parts of Compound No. 23.

The N-benzyl haloacetamide derivative (I) may be used together to improve the herbicidal action of other herbicides. And in some cases, a synergistic effect can be expected. Herbicides that can be mixed include phenoxy, such as 2,4-dichloro phenoxy acetic acid, 2-methyl-4-chloro phenoxy acetic acid and 2-methyl-4-chloro phenoxybutyric acid (including esters and salts thereof). Herbicides; Benzoic acid herbicides such as 3,6-dichloro-2-methoxy benzoic acid and 2,5-dichloro-3-amino benzoic acid; 2,4-dichloro phenyl-4'-nitro phenyl ether, 2,4,6-trichloro phenyl-4'-nitrophenyl ether, 2-chloro-4-trifluoromethyl phenyl-3'-ethoxy-4 'Nitrophenylteer, 2,4-dichlorophenyl-4'-nitro-3'methoxyphenyl ether, 2,4-dichlorophenyl-3'-methoxy carbonyl-4'-nitro phenylether sodium, 5- Diphenyl ether herbicides such as (2′-chloro-4′-trifluoro methylphenoxy) -2-nitro benzoate; 2-chloro-4,6-bisethylamino-1,3,5-triazine, 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine, 2-methylthio- 4,6-bisethyl amino-1,3,5-triazine, 2-methylthio-4,6-bisisopropylamino-1,3,5-triazine and 4-amino-6-tert-butyl Triazine herbicides such as 3-methyl thio-1,2,4-triazine-5-one; 3- (3,4-dichloro phenyl) -1,1-dimethylurea, 3- (3,4-dichlororophenyl) -1-methoxy-1-methylurea, 1, (2,2-dimethyl benzyl Urea herbicides such as) -3-p-tolylurea and 1- (2,2-dimethylbenzyl) -3-methyl-3-phenylurea; Carbamate herbicides such as isopropyl-N- (3-chlorophenyl) carbamate and methyl-N- (3,4-dichlorophenyl) carbamate; S-ethyl-N, N-dipropylthiol carbamate, S- (4-chlorozenzyl) -N, N-diethylthiol carbamate, S-ethyl-N, N-hexamethylene thiolcarbamate Thiolcarbamate herbicides such as S-2,3-dichloroallyl-N, N-diisopropyl thiol carbamate and S-ethyl-N, N-dibutyl thiolcarbamate; 3,4-chloropropionanilide, N-methoxymethyl-2,6-diethyl-α-chloroacet anilide, 2-chloro-2 ', 6'-diethyl-N-butoxy methylacet anilide, 2- Acid anhydride herbicides such as chloro-2 ′, 6′-diethyl-N- (n-propoxyethyl (acetanilide and N-chloro acetyl-N- (2,6-diethylphenyl) glycineethyl ester); Uracil herbicides such as 5-bromo-3-second-butyl-6-methyluracil and 3-cyclohexyl-5,6-trimethylene uracil; N- (phosphonomethyl) glycine, 0-ethyl-0- (2-nitro-5-methylphenyl) -N-tert-butyl phosphoramido thioate, S- (2-methyl-1-piperidylcarbonyl-methyl) o, o-da-n-propyl dithio Phosphorus herbicides such as phosphate and S- (2-methyl-1-piperidylcarbonylmethyl), 0,0-diphenyldiriophosphate; α, α, α-trifluoro-2,6-di Toluidine herbicides such as nitro-N, N-dipropyl-p-toluidine; trichloro acetic acid, 2,2- Herbicides of aliphatic compounds, such as chloro propionic acid and 2,2,3,3-tetrafluoro propionic acid; 5-tert-butyl-3- (2,4-dichloro-5-isopropoxyphenyl) -1 , 3,4-oxadiazolin-2-one; 3-isopropyl-1H-2,1,3-benzothiadiazine (4) -3H-one-2,2-dioxide; 2,6-dichlorobenzo Nitrile; α- (β-nathoxy) propionanilide; 4 ′-(phenylsulfonyl)-(1,1-trifluoromethylsulfono) -0-toluidine; 4- (2,4-dichlorobenzoyl)- 1,3-dimethylpyrazol-5-yl-p-toluene-sulfate, Np-chloro benzyloxyphenyl-Δ'-tetra hydro phthalimide and similar compounds, however, herbicides, of course, It does not stop.

The herbicides of the present invention can be used as fungicides, pyrethrin-type insecticides, plant growth regulators, fertilizers and the like.

When the N-benzyl haloacetamite derivative (I) is used as a herbicide, it can be used in a wide range of amounts. The amount is typically about 0.1 to 1 kg per hectare, preferably about 0.25 to 5 kg.

Any test showing herbicidal efficacy of the N-benzyl haloacetamide derivative (I) will be indicated in the following examples where% is by weight.

Example 1

A paddy soil was filled with a bagny pot having a diameter of 14 cm to create paddy conditions. The three-leaf growing rice seedlings are transplanted into the tactical pots, and the seeds of blood (Echinochloa-cruss-galli) and Scirpus Hotarui, and the slender lavender ripples over winter (Eleocharis) aciculaiis) eyes were sown. Each test compound of the required amount was reagentd under immersion. 25 days after the reagent, the herbicide and phytotoxicity of the test compound were examined for the transplanted and sown plants, and spontaneously sprinkled with water wolves (Momochoria Vaginalis). The results are shown in Table 2.

In the reagent, the hydrating agent containing the required amount of the test compound was diluted with water, and the reagent was reacted at a rate of 10 ml in one port by the pipette method. The herbicidal action was evaluated by numbers classified 0 to 5.

As for the assessment of phytotoxicity, the three factors (ie plant height, number of shoots and total weight (dry weight)) were examined. The ratio of the treated area to the untreated area was calculated for the three elements. Phytotoxicity was assessed based on the lowest of the three ratios, classified into the following 0-5 ratings.

TABLE 2

Example 11

Seeds of weeds such as tubers of Digitaria Sanguinalis, Amaranthus retroflexus and Cyperus rotundus, and seeds of crops such as beans and cotton were sown in 10 cm pots and covered with soil. Separately, each required amount of test compound was combined with the emulsion concentrate and diluted with water. The diluted chemical solution was reagentd with a manual nebulizer and the soil thus treated was mixed and placed at a depth of 2 cm from the surface of the soil in the pot. Each of the aforementioned weeds and crops were grown in a greenhouse. Thus, 20 days after the reagent, herbicidal activity and phytotoxicity of the test compound were examined. The test results are shown in Table 3. Herbicides were evaluated by dividing them into numbers ranging from 0 to 5. Phytotoxicity to crops is expressed in the same standard as the standard for herbicidal action.

TABLE 3

Note: 1) A compound disclosed in Japanese Unexamined Patent Publication (Unexamined) No. 8828/1973.

2) compounds disclosed in US Pat. No. 3,498,781.

3) A compound as disclosed in US Chem. Soc 55,4209 (1933).

4) compounds disclosed in US Pat. No. 2,864,679.

5) A compound disclosed in Japanese Unexamined Patent Publication (Unexamined) No. 5005/1979.

6) Compound disclosed in Japanese Unexamined Patent Publication (Unexamined) No. 50051/1979.

Claims (1)

N-benzylhaloacetamide derivatives represented by formula (I) characterized by reacting a haloacetic acid represented by formula (II) or a reactive derivative thereof with a benzylamine compound represented by formula (III) Manufacturing method.

(In the above formula, R ₁ represents a C ₄ to C ₇ dml tertiary alkyl group, X represents a halogen atom, R ₂ represents a methyl group or ethyl group, R 3 represents a methyl group or ethyl group, or R 3 represents an alkylene group of C 2 to C 5, And when Y and R ₂ and R ₃ together represent an alkylene group of C _{2 ~} C ₅ , and Y and Z may be the same or different, each hydrogen atom, halogen atom, methyl group or methoxy group)