KR840001962B1 - Process for the preparation of cyclopropylaniline derivatives - Google Patents

Abstract

The title compds. [I; R = H or C1-4 alkyl; X,Y = halogen; n = 0, 1, 2; m = 0, 1, 2, 3, 4 were prepd. as plant growth regulators . Thus, 3-chloro-4-(2,2-dichlorcyclopropyl)acetophenone was oximated; a Beckmann rearrangement of the oxime product gave 3-chloro4-(2,2- dichlorocyclopropyl) aniline.

Description

[Name of invention]

Method for preparing cyclopropylaniline derivative

Detailed description of the invention

The present invention relates to a method for producing a novel cyclopropylaniline derivative represented by the following general formula (I).

Wherein R represents a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms, X and Y represent the same or different halogen atoms, respectively, and R ₁ represents a hydrogen atom or an alkyl group containing 1 to 6 carbon atoms N is an integer of 0, 1 or 2, and when n is greater than 1, various atoms X may be the same or different, m is an integer of 0, 1, 2, 3 or 4, and m is 1 If larger, several atoms Y may be the same or different.)

Several cyclopropylaniline derivatives have already been described in the literature. For example, 4- (2,2-dichlorocyclopropyl) -aniline used as a raw material for drug production is

However, there is no mention or suggestion in the literature that the above-mentioned compounds have activity on the regulation of plant growth.

The present invention relates to novel compounds represented by the above general formula (I) except for two compounds described in the above document, namely 4- (2,2-dichlorocyclopropyl) -aniline and 4-chloropropylaniline. will be.

Compounds according to general formula (I) may react with a suitable acid such as hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid to form salts. These salts and compositions containing these salts are also included within the scope of the present invention. Among the foregoing, hydrochloric acid addition salts of compounds according to general formula (I) are preferred.

The present invention particularly relates to cyclopropylaniline derivatives represented by the following general formula (II) and salts thereof (particularly hydrochloric acid addition salts).

(Wherein X ₁ represents a hydrogen atom or a halogen atom, X ₂ represents a halogen atom ₁

More specifically, the present invention provides a compound according to formula (II) or a composition containing at least one salt of the compound as an active ingredient and a novel compound according to formula (II) except for the above known compounds. And salts thereof.

Among the 4-cyclopropylaniline derivatives according to the general formula (II), preferably, the present invention is a compound in which (Y) p represents a halogen atom located at the third position on the benzene nucleus, as a salt and an active ingredient of these compounds, Or to a composition containing salts.

Compounds according to general formula (I) can be obtained from cyclopropylacetophenones represented by the following general formula (III) by a method characterized by being composed of several processes and all processes among the following processes.

(Wherein R, X, Y, m and n have the same meaning as defined in General Formula (I).)

Process a (Oxime Generation)

Reaction formula with hydroxyl amine salt and general formula (III) in the presence of sodium hydroxide

(Wherein X, Y, R, m and n have the same meaning as defined in formula (I), and Z represents a monovalent or divalent anion of a strong acid such as a chlorine anion or a sulfate anion.)

The reaction is preferably carried out by contacting an organic aqueous solution containing hydroxylamine hydrochloric acid addition salt and cyclopropylacetophenone with an aqueous sodium hydroxide solution at a temperature of about 60 to 100 ° C.

Process b (replacement reaction)

A process for converting cyclopropylacetophenoxime (IV) produced from process "a" to cyclopropylacetoanilide (V) by Beckmann Rearrangement according to the following scheme:

(Wherein R, X, Y, m and n are as defined in general formula (I).)

This conversion reaction is carried out under the conditions generally available for Beckman displacement reactions as described above (particularly Organic Reaction, II, Chapter 1). The conversion is preferably carried out with a strong strong acid such as sulfuric acid or a strong strong acid such as phosphoric acid at a temperature of from 100 to 150 ° C, preferably from 120 to 130 ° C.

Process c (hydrolysis)

A step of hydrolyzing cycloproafilsetanilide (V) produced from step "b" to cyclopropylacetaniline (VI) by the following reaction formula:

(Wherein R, X, Y, m and n are as defined in general formula (I).)

The hydrolysis reaction is carried out by diluting with water and then by brief heating of the reaction mixture resulting from process “b” at about 100 to 150 ° C., preferably about 130 ° C.

Process d (alkylation)

Alkylated cyclopropyl aniline (Ⅵ) produced in step "c" the general formula (Ⅰ) (R ₁ is

This alkylation reaction is similar to the method described in Organic Syntheses, Collective Volume IV, p.240 (preparation of N-methyl-p-chloroaniline and N-ethyl p-chloroaniline from p-chloroaniline). In the process, alkylorthoftmate represented by general formula (R ₁ -O) ₃ -CH (wherein R ₁ represents an alkyl group having 1 to 6 carbon atoms) is reacted with cyclopropyl aniline (VI).

However, R ₁ is as defined above, and X, Y, R, m and n are as defined in General Formula I.) Cyclopropylform anilide represented by General Formula I can be obtained and then subjected to hydrolysis. have.

The reaction of the alkylorthoformate and cyclopropylaniline is preferably carried out at a temperature of about 100 to 250 ° C. in the presence of an acid. The hydrolysis reaction of cyclopropyl anilide is carried out by heating the reaction mixture to reflux in the presence of acid.

The product from the reaction medium can be isolated by filtration, distillation or recrystallization of the solvent and then purified by conventional methods as necessary.

Continuously performing the processes a, b and c without performing the process d with reference to the above-described method ₁

The compounds according to general formula I can be converted to salts preferably by treatment with a suitable acid such as hydrochloric acid, sulfuric acid, nitric acid and the like.

General formula among these salts

Hydrochloric acid addition salts represented by the formula are particularly preferred since they are generally more soluble in water than the compounds of the general formula (I) to which they are derived. That is, these compounds of hydrochloric acid addition salt type are particularly preferable for the preparation of agrochemical compositions which can be diluted with water (the various substituents in the general formula VI have the same meanings as defined in the general formula I).

Starting materials used to carry out the process of the invention can be prepared from the process described below.

In general formula (III), cyclopropyl acetophenone which m is 0 can be manufactured by making acetyl chloride and cyclopropylbenzene react. Several of these cyclopropylacetophenones are described in the literature, in particular 4-cyclopropylacetophenone and 4- (2,2-dichlorocycl ""

In general formula (III), cyclopropyl acetophenone (III) whose m is not 0 may be prepared by reacting halogenated cyclopropylacetophenone (III) with a halogen on a phenyl nucleus in general formula (III). There is a number. This halogenation reaction can be carried out in anhydrous medium in an inert organic solvent in the presence of AlCl ₃ and FeCl ₃ in the presence of a Lewis acid type catalyst.

The present invention will be described in more detail with reference to the following Examples, which are not intended to limit the present invention. The structure of the compounds described above was either infrared spectrum or nuclear magnetic resonance spectrum (NMR) (NMR spectrum was performed at 60 MHz in DMSO using hexamethylenedisiloxane as internal standard.)

Example 1

Preparation of 4- (2,2-dichlorocyclopropyl) -3-chloroaniline (Compound No. 1)

To a suspension of aluminum chloride (167 g, 1.25 mol) in anhydrous dichloroethane (350 ml) was added dropwise acetyl chloride (98.1 g) at a temperature of 0 to 5 ° C., followed by 2,2-dichlorocyclopropylbenzene (187 g, 1.0 Mole) was added dropwise over 2 hours.

The mixture was stirred under cold water until gas evolution was completed, and the reaction mixture was added to 1 g of ice and 50 ml of concentrated hydrochloric acid after the temperature was brought to room temperature.

After stirring for 30 minutes, the organic layer was decanted, the aqueous layer was extracted with methylene chloride (3 × 100 ml), the combined organic layers were washed with water (200 ml), and then

2,2-dichlorocyclopropylbenzene, used as starting material, was prepared by the method described in "Tetrahedron Letters, 1969, p. 4569, and Chem. Ber, 108,2803-2808 (1975)".

A solution of 4- (2,2-dichlorocyclopropyl) -acetophenone (196.0g, 0.42mol) dissolved in anhydrous dichloroethane (75ml) in a solution of aluminum chloride (140g, 1.05mol) in anhydrous dichloroethane (75ml). Was added dropwise at a temperature of 0-5 ° C. The chlorine gas (33.0 g, 0.46 mol) was then dissolved in the mixture over 45 minutes while maintaining the temperature at 0-5 [deg.] C. The reaction mixture was then added to ice (700 g) and concentrated hydrochloric acid (25 ml) and the organic layer was decanted, washed with 10% sodium bicarbonate solution (2 x 100 ml), dried over sodium sulfate and evaporated. It was done.

The crude product was recrystallized twice from hexane to give 4- (2,2-dichlorocyclopropyl) -3-chloroacetophenone (53.0 g) having a melting point of 74 占 폚 (yield 48%).

Hydroxide of water (50 ml) in an aqueous alcohol solution (500 ml of ethanol + 100 ml of water) of hydroxylamine hydrochloride (46 g, 0.66 mol) with 4- (2,2-dichlorocyclopropyl) -3-chloroacetophenone (158.1 g) A sodium (26.4 g, 0.66 mol) solution was added dropwise over 15 minutes and refluxed.

After the addition, the reaction mixture was refluxed for 1 hour and the ethanol was evaporated in vacuo to precipitate. It was filtered off, washed with water and dried. In a mixture of hexane and chlorohexane

4- (2,2-dichlorocyclopropyl) -3-chloroacetophenoxime (58.2 g) was dissolved in concentrated sulfuric acid (55 ml) at a temperature of 10-15 ° C. The resulting viscous solution was added dropwise into concentrated sulfuric acid (18 ml) and heated to 120-125 ° C. to maintain the temperature at 120-130 ° C. without supplying heat externally.

After all the additions were heated to maintain this temperature for 10 minutes, the medium was cooled to about 60 ° C. and then water (73 ml) was added to reflux the mixture for 2 hours. It cooled simultaneously with stirring, and precipitated aniline sulfate. This was filtered off, washed with water and treated with 5N sodium hydroxide solution (70 ml) and methylene chloride (100 ml).

The ethylene chloride solution was washed with water and dried over anhydrous sodium sulfate. After distilling off the solvent, black oil (36.5g) is crystallized and then recrystallized in a mixed solvent of petroleum ether (90%) and cyclohexane (10%) to give a 4- (2,2) melting point of 66.5 ° C. -Dichlorocyclopropyl) -3-chloroaniline (23.0 g) was obtained. Yield (66.5%)

Example 2

Preparation of 4- (2,2-dichlorocyclopropyl) -aniline (Compound No. 2)

In Example 1 is the product of the acetylation process

EXAMPLES 3 AND 4

The following compounds were prepared by following the method described in Examples 1 and 2 using suitable starting materials.

4- (2,2-dichlorocyclopropyl) -3-bromoaniline (Compound No. 3) in light brown liquid, yield 13%,

4- (2,2-dibromocyclopropyl) -aniline (Compound No. 4) in a reddish brown liquid, yield 6.4%.

Example 5

Preparation of 4- (2,2-dichlorocyclopropyl) -3-chloro-N-methylaniline (Compound No. 5).

4- (2,2-dichlorocyclopropyl) -3-chloroaniline obtained in Example 1 was used as starting material. 4- (2,2-dichlorocyclopropyl) -3-chloroaniline (47.3 g, 0.2 mole), trough a 250 ml three-necked bottom flask with a vigrocolumn, usually a cooler and thermometer

=1.5878인 4-(2,2-디클로로시클로프로필)-3-클로로-N-메틸아닐린(20.7g)을 얻었다. 수율 71.6%This was added to a 250 ml round bottom flask with 10% hydrochloric acid (100 ml) and heated to reflux for 2 hours. After cooling to 10 ° C., the reaction mixture was neutralized with 10% potassium hydroxide solution. The product was extracted with ethyl ether and the extract was washed with water and dried over anhydrous sodium sulfate. Ethyl ether was evaporated off, and then separated by silica liquid chromatography.

4- (2,2-dichlorocyclopropyl) -3-chloro-N-methylaniline (20.7 g) with = 1.5878 was obtained. Yield 71.6%

Example 6

=1.57810인 4-(2,2-디클로로시클로프로필)-3-클로로-N-에틸아닐린(화합물 N0.6)이 얻어진다. 수율 63%.As a result of performing the method described in Example 5 using an appropriate starting material, the refractive index

4- (2,2-dichlorocyclopropyl) -3-chloro-N-ethylaniline (Compound N0.6) with = 1.57810 is obtained. Yield 63%.

Example 7

Preparation of 4- (2,2-dichlorocyclopropyl) -3-chloroaniline hydrochloride addition salt (Compound No. 7)

4- (2,2-dichlorocyclopropyl) -3-chloroaniline prepared in Example No. 1 was used as starting material.

4- (2,2-dichlorocycle in 250ml round bottom flask equipped with reflux cooler

[Examples 8 to 10]

The following compounds were obtained following the method shown in Example 7 using compounds No. 3, 2 and 5 as starting materials, respectively.

Compound No. 8: 4- (2,2-dichlorocyclopropyl) -3-bromoaniline hydrochloride addition salt (melting point, 214-215 degreeC)

Compound No. 9: 4- (2,2-dichlorocyclopropyl) -aniline hydrochloride addition salt (melting point, 250 degreeC or more)

Compound No.10: 4- (2,2-dichlorocyclopropyl) -3-chloro-N-methylaniline

In the experiments of Examples I to IV described below, the term solution refers to a hydrating or active ingredient containing 20% by weight of the active ingredient if the active ingredient is soluble in water or if the active ingredient is insoluble in water. Refers to an aqueous dispersion or emulsion obtained by diluting an emulsion containing about 200 g / l with water, respectively. These experiments were carried out in a greenhouse or outdoors by treating plant oils such as kidney beans and soybeans with a solution containing 0.1 g / l to 20 g / l of active ingredient to be tested. Next, the biological and morphological changes that the treated plants changed over time were observed and compared with the control plants treated under the same conditions with a solution containing no active ingredient.

Example I

Greenhouse Experiment on Contender Variation Kidney Bean (Phaseolus vulgaris)

An emulsion solution having the following composition was diluted with water to prepare a test active ingredient solution having a desired concentration.

Active ingredient to be tested. … … … … … … … … … … … … … … … … … … … … … 206 g

Electrodeposition and emulsifiers (ethylene oxide condensates / ethylene oxide 30 to 33 units and dode

Castor oil 4/1 mixture containing 20 g of sodium benzene sulfonate ... … … 102 g

Solvent (aromatic hydrocarbon obtained from petroleum fraction)... … … … … … … … … 692 g

Seeds of kidney beans were planted in a 9 × 9 × 9cm pot filled with agricultural soil, covered with 0.5cm thick soil, and stored in a greenhouse maintained at 70% relative humidity and room temperature to supply water by underground irrigation. .

Pre-prepared solution of kidney beans at a rate of about 500 meters per hectare, so that the dose of the active ingredient is 2 to 8 kg / hectare on the leaves at the time of the second round and last snow. Was sprayed.

Treatment ports were placed in ditches where water could be supplied by underground water and maintained for 35 days at room temperature and 70% relative humidity.

After 35 days, the average size of the plants treated with Compound No. 1 at a rate of 2 kg per hectare was half the size of the control group.

The average size of the plants treated with Compound No. 1 at a rate of 2 to 4 kg per hectare are respectively 80 to 40% of the control.

The average size of plants treated with 8 kg per hectarear with Compound No. 2, 5, 6, 7, 9, and 10 was 4 per hectare with Compound No. 2, 6, 7, 8, 9 and 10 Equivalent to 50% of the control as in the plants administered kg.

The average size of plants treated with 2 kg per hectarear with Compound Nos. 5, 6, 7 and 9 was equivalent to 75% of the control as in plants fed Compound No. 5 with 4 kg per hectare. .

Example II

Greenhouse Experiments on Amsoy 71 Variant Soybean (Glycine max) A solution prepared by diluting the same emulsion stock as in Example I was used.

Except for seeding soybean seed previously inoculated with risbium sowing one seed per pot in a 20 × 20 × 20 cm pot containing peat, sand and humus in equal proportions and water supplied from the surface. The pots were stored in the greenhouse as in I.

When the soybean plants reached the third leaf stage, that is, about 30 days after the start of the experiment, the plants were sprayed at a rate of 500 liter solution per hectare, as in Example I.

Treatment ports were then stored for 15 days in a greenhouse at room temperature and 70% relative humidity.

After about 15 days, the second branch index of plants treated with Compound No. 1 at a dose of 2 kg per hectarear increased on average by 50% compared to the control.

Example III

Field Experiments on Amsoy 71 Variant Soybean (Glycine max)

On May 15, soybean seeds previously treated with rizobium were sown in compartments of 12 m 2 each.

When soybean plants reached the third leaf stage, that is, about one month after the start of the experiment, the solution prepared by diluting the emulsion solution as in Example I to water at the target concentration was 3 l per compartment (2,500 l per hectare). These plants were sprayed.

Two experiments were performed on different compartments at each administration. After 3.5 months of treatment, the fruiting index (ie, the podding branching) and main stem and fruiting indexes

When 2 kg of the compound No. 1 active ingredient per hectarear was administered under the conditions mentioned above, the following result (value for 1 soybean plant) was obtained.

Example IV

Soybean seeds were sown at the end of July in 3 × 10m sections in two equilibrium rows 0.5m apart from each other, each 10m long, with Amsoy 71 variegated soybean (Glycine max).

A solution prepared by diluting the same emulsion solution as in Example I with water of the desired concentration was used.

When the soybean plants reached the sixth leaf stage on August 30, the plants in the first row were treated with a solution prepared in advance so that 1 kg per hectare were administered, and the plants in the second row were not treated as controls. The results are described below.

From the above results, if the compound is treated using No. 1 under the above conditions,

Further, from the above results, the compounds according to the present invention can be used for spraying all kinds of plants such as monocotyledonous plants (flowers and plants) or dicotyledonous plants such as large-scale farms and industrial farms, such as fruit trees, vegetables, ornamental plants, medicinal plants and spices plants. It can be clearly seen that there are remarkable characteristics such as an increase in yield, a large number of branches, and a smaller size to obtain more compact plants.

In the use of the compound according to the present invention, the compound is rarely used as such, and in addition to the active ingredient according to the present invention, it is used in the form of a composition composed of a carrier and / or a surfactant.

Generally these compositions are composed of 0.1 to 95% by weight of active ingredient, 0 to 99.9% by weight of carrier and / or 0 to 20% by weight of surfactant.

As used herein, the term "carrier" refers to an organic or inorganic, natural or synthetic material that is combined with an active ingredient to facilitate its use in plants, seeds or soil, or to facilitate transport or handling. As the carrier, solid carriers such as clay, natural or synthetic silicates, calcium carbonate, magnesium carbonate or calcium sulfate, or liquid carriers such as water, alcohols, ketones, ethers, esters, aromatic hydrocarbons, halogenated hydrocarbons or petroleum fractions can be used.

As the surfactant on the present specification, ionic or nonionic infiltration, dispersion or emulsifier can be used. Examples of these surfactants include condensates of ethylene oxide with fatty alcohols, fatty acids, fatty amides or amines or alkylphenols, fatty acid esters of sorbitol and sucrose oil.

In the composition according to the present invention, in addition to the active ingredients, carriers and surfactants, dispersants, peptizing agents, protective colloids, thickeners, adhesives, stabilizers, preservatives, corrosion inhibitors, dyes, metal ion sequestrants, which increase rainfall durability, Other additives, such as a foam inhibitor, an anti-caking agent, and an antifreeze agent, can be blended.

The composition according to the present invention can be removed with a hydrating agent, water soluble, powder, granule, liquid, emulsion emulsion or emulsifier, suspension stock or suspension and dispersant.

A hydrating agent is usually prepared in a powder form by mixing the active ingredient, solid carrier, infiltration and dispersant so as to contain 10 to 95% by weight of the active ingredient and 0.5 to 20% by weight of the surfactant. The premix is then ground in a mill or "airjet" mill, such as a pin disk mill with a powder separator, preferably using an active ingredient having a low melting point.

A few examples of the formulation of the hydrating agent composition according to the present invention are as follows (wherein percentages represent weight units).

Compound No. 1 25.0%

Alkyl-Sulfosuccinate (infiltrant) 2.0%

Alkali metal salt (dispersant) of naphthalene sulfonic acid condensate 7.0%

Kaolin Clay 66.0%

Compound No. 2 50.0%

Alkyl naphthalene sulfonate (infiltrant) 3.0%

Lignosulfonic acid alkali metal (dispersant) 10.0%

Kaolin Clay 37.0%

Compound No. 1 50.0%

Polyoxyethylenated Fat Alcohol 1.4%

Lignosulfonic acid alkali metal 10.0%

Fossil Silica 38.6%

Compound No. 1 50.0%

Sodium alkylnaphthalene sulfonate (infiltrant) 4.0%

Alkali metal salt (dispersant) of sulfonic acid condensate 3.0%

Kaolin Clay 20.0%

Fossil Clay 23.0%

Compound No. 1 60.0%

Polyoxyethylenated Alkylphenol 2.0%

Alkali metal salt (dispersant) of naphthalene sulfonic acid condensate 5.0%

Kaolin Clay 33.0%

The water-soluble powder is obtained by mixing 20 to 95% by weight of the active ingredient, 0 to 10% by weight of the anti-caking additive, 0 to 1% by weight of the wetting agent and the residual% of the water-soluble additive (mainly salt). Number

Active ingredient (Compound No. 1) 80.0%

Anion Infiltration Agent (Alkaliphthalenesulfonic Acid Alkali Metal) 0.5%

Anti-Static Silica 4.0%

Sodium sulfate (soluble additive) 15.5%

Powders can be prepared in the same way as for hydrating agents, but without surfactants, dispersants and protective colloids. In this case, when the active ingredient is liquid, a solid carrier is used to facilitate grinding and absorption and to impart fluidity.

Generally, granules and micro granules containing a low proportion of the active ingredient may be prepared in advance and impregnated, or may be prepared in large quantities by atomization or extrusion. In the latter case, binders and hygroscopic materials should be added to enable rapid breakdown of the granules and microgranules into the soil. These compositions are usually composed of 0.5 to 25% by weight of the active ingredient and 0 to 10% by weight of additives such as stabilizers, soluble control agents, binders and solvents.

The emulsion solution is prepared by dissolving the active ingredient in a solvent (generally an aromatic hydrocarbon), if necessary, in addition to a solvent, a co-solvent such as ketones, esters, ethers, or a mixed solvent such as a common solvent. These compositions combine 10 to 60% by weight of active ingredient with 2 to 20% by volume of emulsifier to mix the active ingredient with a solvent and emulsifier in a bat equipped with a stirrer and heating or cooling of the circulating fluid. It can manufacture by melt | dissolving in water.

Two formulation examples of the emulsion stock solution according to the present invention are described as follows.

Active ingredient (Compound No. 1) 200g

Alkyl sulfonate 20 g

80 g of oxyethylenated nonylphenol containing 9 units of ethylene oxide

Solvents (aromatic hydrocarbons from petroleum fraction)

1 liter (ie 667 g)

Active ingredient (Compound No. 1) 400g

24g sodium dodecylbenzenesulfonate

16 g of oxyethylenated nonylphenol containing 10 units of ethylene oxide

200 g of cyclohexanone

1 liter of solvent (aromatic hydrocarbon)

A fluid suspension suspension, which can be diluted with water and then sprayed, is prepared so that a stable flowable material is obtained in which no precipitation is produced. These compositions include 10 to 50% by weight of active ingredient, 0.5 to 15% by weight of surfactant, 0.5 to 10% by weight of protective colloid or precipitation inhibitor, 0 to 10% by weight of various additives such as antifoaming agent, thickening agent, stabilizer, adhesive and antifreeze agent % And a carrier (an organic liquid in which water or the active ingredient is insoluble or a mixture of both ingredients). The solid may be dissolved or the organic solid or inorganic dye may be dissolved in the carrier as an antifreeze agent for water.

These suspension stocks are prepared by dispersing the active ingredients crushed in advance in a liquid carrier such as water, vegetable oil or mineral oil, or an emulsion mixture of these two components, blending auxiliary additives such as a viscosity adjusting agent, a preservative and an antifreeze, and then storing the dispersion. It can manufacture by grind | pulverizing in a mill.

Aqueous dispersion and water obtained by diluting the hydrating agent or emulsion solution according to the present invention with water

The above-mentioned compositions are all applied by various methods such as spraying to the space of the plant, immersing seeds, plants, soil masses around the plants, roots or fruits, watering the soil, and injecting the plants. Can be used for plants.

That is, the present invention relates to a method of controlling plant growth (modulating the physiology of plants in various ways) by using at least one compound represented by the general formula (I) or salts of these compounds in plants. Dosage of the active ingredient may vary depending on various factors, such as the type of crop to be treated, growth stage, climatic conditions, and soil properties. The treatment operation according to the invention can be carried out by using 0.050 kg to 10 kg of the active ingredient in the crop per 1 hectare of a dose.

Claims (1)

In the presence of sodium hydroxide, the hydroxylamine salt is reacted with a compound of the following general formula (III), and the compound of the following general formula (IV) obtained at this time is converted to a compound of the following general formula (V) by a displacement reaction. A process for preparing a cyclopropylaniline derivative of the following general formula (VI), characterized in that the compound is hydrolyzed.

Wherein R represents a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms, X and Y represent the same or different halogen atoms, respectively, n is an integer of 0, 1 or 2, and n is greater than 1 In this case, various atoms X may be the same or different, m is an integer of 0, 1, 2, 3 or 4, and when m is larger than 1, various atoms Y may be the same or different.)

Wherein R, X, Y, m and n are as defined above.

Wherein R, X, Y, m and n are as defined above.