JPH0248571A - Novel 1, 2, 4-oxadiazole derivative useful as selective herbicide - Google Patents

Abstract

NEW MATERIAL: A compd. of formula I (wherein X is Cl, F or methyl; Y is Cl or F; n is 1-3; R is a 1-7C alkyl, allyl, pyridyl or thienyl, (substd.) pyrrolyl, cinnamyl, NH₂, piperidino, phenylsulfonyl, 4,5-pyrroledion-2-yl, 2,3-epoxypropyl, (substd.) benzyl, (substd.) alkylcarbamoyloxy, (substd.) phenyl, etc.].

EXAMPLE: 3-N-propyl-5[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadiazole.

USE: A selective herbicide with low toxicity, high selectivity and strong activity to weeds.

PROCESS: E.g. a compd. of formula II and acyl chloride of formula III are reacted with each other to obtain the compd. of the formula I.

COPYRIGHT: (C)1990,JPO

Description

[Detailed description of the invention] [Industrial application field]

The present invention provides novel 1,2.4 having excellent herbicidal activity.
-Regarding an oxadiazole, a method for producing the same, and a herbicidal composition containing the same.

[Conventional technology]

Conventionally, in order to suppress weeds in rice fields and fields, 2゜4-D, 2
, 4.5-T, MCPA, and MCF'B have been applied to post-emergence foliar treatments.

[Problems to be solved by the invention]

However, phenoxy-type herbicides are known to be toxic to rice and crops depending on the time of treatment and climatic conditions. There has been a great need for the development of new forms of herbicides that have herbicidal effects against. New forms of herbicides are needed that have a high degree of selectivity between crops and weeds and have the highest activity against weeds.

[Means to solve the problem]

Under these circumstances, the present inventors have carried out extensive research in order to develop herbicides that are low in toxicity to rice and agricultural crops and have a high degree of selectivity between crops and weeds. As a result, 1 represented by the following general formula (I),
It has been found that 2.4-oxadiazole derivatives have low toxicity, high selectivity and strong activity against weeds. The object of the invention is therefore to be able to be produced industrially,
A 1,2,4-oxadiazole derivative (I) capable of suppressing annual and perennial weeds in field soils while having a high degree of selectivity between crops and weeds, and a new form containing the same The objective is to provide herbicides for The 1,2,4-oxadiazole derivative of the present invention is represented by the following general formula (I). (In the formula, X represents chlorine, fluorine atom or methyl group, Y represents chlorine or fluorine atom, n is an integer from 1 to 3, and R represents 03-7 alkyl group; allyl group; pyridyl group; thienyl group) ; Pyrrolyl group, which may be substituted; Cinnamyl group; Amino group; Piperidino group; Phenylsulfonyl group; 4,5-viroldion-2-yl group; 2,3-epoxyprobyl group; Unsubstituted or azido, alkoxy C1-3 hydroxyalkyl group substituted with; bromine atom,
Benzyl group substituted with chlorine atom, fluorine atom, Cl-2 alkyl, nitro, amino, acetylamino, thioethoxycarbonylamino, diethylcarbamyl, methylenedioxy or trifluoromethyl; phenoxy substituted with chlorine or fluorine atom Methyl group; bromine atom, chlorine atom, fluorine atom, acetyloxy, haloacetyloxy, optionally substituted Cl-2 alkylcarbamoyloxy, optionally substituted phenoxybenzoyloxy, methylsulfonyloxy, unsubstituted Phenoxyacetyloxy, ethyloxalyloxy,
C1-3 alkylamino, fluorophenylamino, phthalimide, optionally substituted phenylsulfonylamino, pyrrolidinoyl, thiophenoxy, ethyldithiophosphonyloxy, phenylsulfonyl, diethylthiocarbamyloxy, aminocarbamyl, ethoxycarbonyl, cyclo Methyl group substituted with hexenyl, thienyl or optionally substituted pyridyloxy; Phenyl group unsubstituted or substituted with chlorine atom, fluorine atom, methoxy, fluoromethyl; C2-3 alkoxy group: unsubstituted or a phenoxy group monosubstituted with a chlorine atom, a fluorine atom, a C2 alkoxy or an alkyloxycarbonyl-substituted C2 alkoxy; an unsubstituted or C5 alkyl, acetyl, a C5-2 alkoxycarbonyl, a Cl-2 alkylcarbamyl group or a phenylsulfonyl group Amino group substituted with; Bromine atom or chlorine atom; Cl-a alkylamino, Cl-2 alkoxy, amino, azido, phenylamino, halophenylamino, acetylamino, methylsulfonylamino, C1-4 alkyl, benzyl, phenyl , carbonyl group substituted with allylamino or optionally substituted pyridylamino; oxime group substituted with Ct-4 alkyl or phenyl; substituted with Cl-2 alkoxy, amino, hydroxyamino, ethylphosphonyl or chlorine atom The compound of the general formula (I) of the present invention can be produced, for example, by any of the following methods. (Margin below) (1) First method (II) (III) (I) (wherein, X represents a chlorine atom or a methyl group, Y represents a chlorine atom, and n is an integer of 1 or 3. R is a C3-7 alkyl group; a substituted benzyl group; a halomethyl group; a substituted phenoxymethyl group; a substituted phenyl group;
2-3 alkoxy group or substituted phenoxy group; represents an ester group or ester methyl group) That is, the compound (I) of the present invention is produced by reacting the compound (II) with the acyl chloride of the compound (III). It can be done. The above reaction is carried out in the presence of a catalyst at reflux temperature for 1 to 5 hours. In this reaction, various solvents such as acetone, alcohol, dioxane, etc. can be used. Examples of the catalyst include dimethylamine, trimethylamine, trifluoroboron ether, and sodium methoxide. (2) Second method (wherein, , is an oxygen or sulfur atom. When Z is a nitrogen atom, R and R2 are each c+
-g is an alkyl group, a hydrogen atom, a substituted phenyl group, an allylsulfonyl group or a cyclic acyl group, and when Z is an oxygen or sulfur atom, R is a phenyl group or a substituted carbonyl group) The above reaction is carried out at reflux temperature in the presence of a base. Various solvents that can be used in this reaction include:
Examples include acetone, dioxane, toluene, or xylene, tetrahydrofuran, and acetonitrile. Examples of the base include pyridine, triethylamine, potassium carbonate, and sodium hydroxide. (3) Third method Indicates a chlorine atom, and n is an integer of 1 or 3. Each R1 and R2 are the same or different, a hydrogen atom, C1-
The above reaction (representing an alkyl group, an acyl group, a sulfonyl group, an unsubstituted or substituted phenyl group, an amino group or a methoxy group) is carried out in a room in an organic solvent for 30 minutes to 1 hour. Solvents include alcohols such as methanol, ethanol and isopropanol, acetone,
Acetonitrile, tetrahydrofuran, etc. can be used. (4) Fourth method Ω (In the formula, X is a chlorine atom or a methyl group, Y is (In the formula, X
and Y represents a chlorine atom, R is a C9-4 alkyl group,
The above reaction is carried out in an organic solvent at about -78'C for 1 to 2 hours. Tetrahydrofuran, diethyl ether can be used as a solvent. (5) The fifth method represents an alkyl group or a phenyl group, and R2 is a hydrogen atom or a C
2-3 alkyl group) The above reaction is carried out at reflux temperature in the presence of an organic solvent. As the solvent, alcohols such as methanol, ethanol and isopropanol, acetone, acetonitrile, tetrahydrofuran, etc. may be used. (6) Sixth method (wherein X and Y represent a chlorine atom, and R6 represents an unsubstituted or methoxy-substituted Cl-3 furkyl group) The above reaction is carried out at reflux temperature in the presence of an organic solvent. carried out. Isopropyl alcohol can be used as a solvent. (7) Seventh method (wherein X and Y are chlorine atoms, Z is nitrogen or oxygen atom. When Z is nitrogen atom, R7 and R2
are each a hydrogen atom or a C1-2 alkyl group,
(When Z is an oxygen atom, R is a C9-3 alkyl group) The above reaction process was carried out at reflux temperature for 1 hour in the presence of an organic solvent, and then incubated for 15 minutes at room temperature. . As solvents, alcohols such as methanol, ethanol and propatool can be used to prepare carbamate groups. However, in order to produce urea groups, the reaction has to be carried out in the presence of dioxane as solvent at reflux temperature for 1 to 4 hours. (8) Eighth method (wherein X and Y are chlorine atoms, and R represents a Cl-2 alkyl group) The above reaction process is carried out at room temperature for 3 to 4 hours in the presence of an organic solvent. Ru. Alcohols such as methanol or ethanol can be used as solvents. (9) Ninth method H (In the formula, X and Y represent a chlorine atom, R1 represents a C1-2 alkyl group, and R2 represents a hydrogen atom or a hydroxyl group) It is carried out for 24 hours under. Alcohols such as methanol or ethanol can be used as solvents. After completion of the reaction, the final product can be separated and/or purified by conventional methods, if necessary. For example, after washing the reaction mixture with water, the solvent is distilled and the residue is purified by column chromatography to obtain compound (I) in high yield.

【Example】

The present invention will be further explained by the following specific examples, but the present invention is not limited thereto. Example 1 3-n-propyl-5[(2,4-dichlorophenoxy)methyl]-1,2,4-oxadiazole (compound 1
): 1.02g butyramidoxime, 2.40g 2,4
-dichlorophenoxyacetyl chloride and 0.14
g of trifluoroboron ether was added to 50 l of toluene. This mixture was heated at reflux for 6 hours. After the reaction was completed, the mixture was washed with 100a+1 water, the toluene was distilled, and the residue was dissolved in a mixed solvent (benzene: ether = 4:
Purify by column chromatography using 1),
1 g of the desired product was obtained (yield: 69.7%). Example 2 3-allyl-5-[(2-chloro-4-fluorophenoxy)methyl]-1,2°4-oxadiazole (compound 145) 0.71 g of 2-chloro-4-fluorophenol, 0 .77 g of 3-allyl-5-chloromethyl-1,2,4-oxadiazole and 0.83 g of potassium carbonate were added to 20 ml of acetone. After the reaction is complete,
After filtering the precipitate from the mixture, the acetone was removed by distillation, and the residue was purified by column chromatography to obtain 1.05 g of the desired product (benzene:hexane = 1:1) (yield: 80. 8%). Example 3 3-diethylcarbamyl-5-[(2゜4-dichlorophenoxy)methyl]-1゜2.4-oxadiazole (
Compound 99) 1.58 g of 3-ethoxycarbonyl-5
-[(2,4-dichlorophenoxy)methylgo 1.2
．． 4-oxadiazole and 0.73 g diethylamine were added to 3011 methanol. The mixture was stirred at room temperature for 1 hour. The precipitate was filtered from the reaction mixture and washed with 50ml of methanol. The white solid was dried to obtain 1.46 g of the desired product (yield: 84.9
%). Example 4 3-Ethylcarbonyl-5-[(2,4-dichlorophenoxy)methyl]-1°2.4-oxadiazole (Compound 112): 0.95 g of 3-ethoxycarbonyl-5-[( 2,
4-dichlorophenoxy)methylgol 1.2.4-oxadiazole was added to 30ml of tetrahydrofuran. After cooling the mixture to -78°C, add 3 liters of
of ethylmagnesium bromide (2M solution) was added dropwise. The mixture was stirred for 1 hour at -78°C, then
% cold HCI solution. The product was extracted with ether, concentrated, and purified by column chromatography (hexane: ethyl acetate = 4:1) to obtain 0.75 g of the desired product (yield: 83.
0%). Example 5 3-(α-hydroxyiminopropyl)-5-[(2,
4-dichlorophenoxy)methyl]-1,2,4-oxadiazole (compound 119): 0.9 g of 3-ethylcarbonyl-5-((2,4-dichlorophenoxy)methyl)-1,2,4-oxadiazole diazole and 0.21 g of hydroxyamine hydrochloric acid in 10 m
1 of methanol. This mixture was heated at reflux for 4 hours. After evaporating the methanol, water was added to the residue. This aqueous solution was extracted with ethyl acetate. After evaporating the ethyl acetate, the residue was purified by column chromatography (benzene:ether = 1:1) to obtain a 0.
Yield: 85°0%) to obtain 80g of desired product. Example 6 3-(1-hydroxybutyl)-5-[(2,4-dichlorophenoxy)methylgo 1.2.
4-Oxadiazole (Compound 138): 0.316 g of 3-propylcarbonyl-5-[(2,
4-dichlorophenoxy)methylgol 1.2.4-oxadiazole and 0.20 g of aluminum isopropoxide were added to 10 ml of isopropanol. The mixture was heated at reflux for 48 hours. After evaporating the isopropanol, water was added to the residue. This aqueous solution was extracted with ethyl acetate. After evaporating ethyl acetate, the residue was purified by column chromatography (hexane: ethyl acetate = 3:2) to obtain 0.17 g of the desired product (yield: 54.0%).
). Example 7 3-N,N-dimethylureido-5-[(2,4-dichlorophenoxy)methylgo 1.2.
4-Oxadiazole (compound 80): 1.57 g of 3-azidocarbonyl-5-[(2,4
-dichlorophenoxy)methylgol 1.2.4-oxadiazole was added to 20 ml of dioxane. After the mixture was refluxed for 1 hour, 0.30 g of dimethylamine was added with bubbling and the mixture was stirred at room temperature for 1 hour.
Stirred for 5 hours. The precipitate was filtered from the mixture and washed with dioxane. The precipitate was dried to obtain 0.9 g of the desired product (yield: 55.0%). Example 8 3-(iminomethoxymethyl)-5-[(2,4-dichlorophenoxy)methyl]-1,2,
4-Oxadiazole (Compound 125): 2.17 g of 3-(trichloromethyl)-5-[(2,
4-dichlorophenoxy)methyl]-1,2,4-oxadiazole was added to 50 al of methanol. After adding an excess of ammonia gas with bubbling at 0° C., the mixture was stirred at room temperature for 4 hours. After methanol was evaporated, water was added to the residue. This aqueous solution was extracted with ethyl acetate. After evaporating the ethyl acetate, the shallow solution was subjected to column chromatography (
Purification with hexane:ethyl acetate) gave 0.92 g of the desired product (yield: 50.9%). Example 9 3-iminoaminomethyl-5-[(2°4-dichlorophenoxy)methyl]-1°2.4-oxydiazole
(Compound 128): 0.62 g of 3-iminomethoxymethyl-5-[(2,
4-dichlorophenoxy)methyl]-1,2,4-oxadiazole was added to 20a+1 methanol. After adding excess ammonia gas with bubbling at O'C, the mixture was stirred at room temperature for 24 hours. A white precipitate was filtered from the reaction mixture and washed with methanol. The white precipitate was dried to obtain 0.54 g of desired product (yield: 94.4%). Typical compounds produced by a method similar to the above example are shown in Table 1 below, along with their physical properties. Although the compounds of the present invention can be used as herbicides as they are, they are usually used in the form of wetting agents, powders, emulsion concentrates, suspension concentrates, or granules. Such preparations may be used as they are, or may be used after being diluted with water. When liquid formulations are applied, solvents such as water, alcohols, ethers, acetones, esters, amides or petroleum ethers may be used. Further, as solid excipients, inorganic powders such as magnesium lime, gypsum, calcium carbonate, silica, alumina, zeolite, clay minerals, and resin powders may be used. The dosage of the compound (I) of the present invention as an active ingredient can be changed as appropriate depending on the form of the preparation, processing method, time, and climatic conditions. However, the dosage is usually 0.25-4k
It is preferable to set it within the range of g/ha. Even when the compound of the present invention is used alone for treatment, it has sufficient effects. However, if the treatment is performed in combination with one or more other compounds having herbicidal activity, it is possible not only to reduce the amount of the active ingredient, but also to extend or improve the herbicidal range. Representative examples of herbicides that can be used with the compounds of the invention include amide-type herbicides such as, for example, monalid, propanil, solan, dibenamide, fluoridoamine, mefluidine, benzamisol, butacura and aracra; trifluralin. , penfluralin, profluralin,
Dinitroaniline-type herbicides such as isoproparin, benzimenthaline and ethanfluralin; urea-type herbicides such as butrone, monolinuron, parafluron, tetrafluron, linuron, sulfocyazole, butiuron, chlorosulfuron and sulfometron-methyl; Chlorobufam, Parpan, Sialate, Fenmedizifam,
Carbamate-type herbicides such as butylate, triallate, bentiocarb and methylbencarb; oxyfluorophen, acifluorofrunethyl, lactofen,
Mention may be made of diphenyl ether type herbicides such as formesafen and fluoronitrophen; and diazine type herbicides such as oxacyacin and imazakim.

[Manufacturing example]

Some examples of formulations are shown below. Formulation Example 1 (Milk concentrate) 130 parts of the compound of the present invention, 60 parts of m-xylene and a surfactant mixture (polyoxyethylene alkyl allyl ether and sodium alkyl allyl sulfate) 1
0 parts were uniformly mixed and stirred to obtain a milky concentrate. Formulation Example 2 (Wetting agent) 410 parts of the compound of the present invention, 85 parts of white carbon, and 5 parts of a surfactant mixture (polyoxyethylene alkyl and allyl ether sulfate and polyoxyethylene alkyl and allyl ether) were mixed and ground. A wetting agent was obtained. Formulation Example 3 (Granules) 1003 parts of the compound of the present invention, 60 parts of bentonite, 35 parts of talc, 0.5 parts of sodium dodecylbenzenesulfonate, 0.5 parts of sodium metasilicate, and 1.5 parts of sodium tripolyphosphate. The mixture was mixed, an appropriate amount of water was added, and the mixture was kneaded. The mixture was granulated using an extrusion granulator and dried in a conventional manner to obtain granules.

[Example of exam]

Test Example 1 Weed control test against weeds in rice fields Soil from a rice field was placed in a 140 cm2 plastic pot, and then water was added to the pot. Rice seedlings (variety: Tongjin) at the 2.5-leaf stage were planted, and rice weed seeds were sown. Two days after implantation, the compounds of the invention were applied in predetermined amounts in the form of a moist powder. During the test period, the inside of the pot was kept flooded with water at a height of 2C11 above the soil surface. The herbicidal effect on weeds and the toxicity on rice were investigated 20 days after application of the compounds of the present invention. The results are shown in Table 2, and the herbicidal efficacy test criteria are shown in Table 3. (blank below) *Test plant abbreviation y Plant name (genus and species name) RYSA CHOR CPJU YPDI YPSE NEKE 0OVA AGPY BR,s Rice (Oryza 5ativa L,) Echinochloa crus-galliP,
BEAUV, var, oryzicola 0HW
I) Scirpus jumvoifrd TOCB
Cyperus difformis L, Cyperus 5erotinus ROTTB,
) Aneilea + a keisak HASSK, )
Monochoria vaginalis PRE
SL,) Urikawa (Sagittaria pygmaea MIQ,)
Mixture of seeds of caterpillar dicots, such as privets, trumpeters, and kikashigusa.

【Effect of the invention】

As described above, the new type of herbicide containing the compound (I) of the present invention has a high degree of selectivity between crops and weeds, and has strong activity against weeds. Applicant Korea Chemical Research Institute Numerical general technology No effect, no drug damage, no total heat control, almost killed. Excellent control, complete effect, complete annihilation, complete annihilation

Claims (11)

[Claims] (1) General formula (I) ▲Mathematical formula, chemical formula, table, etc.▼ (In the formula, X represents chlorine, fluorine atom or methyl group, Y represents chlorine or fluorine atom, and n is an integer from 1 to 3 Yes, R is C_3_-_7 alkyl group; allyl group; pyridyl group; thienyl group; optionally substituted pyrrolyl group; cinnamyl group; amino group; piperidino group; phenylsulfonyl group; 4,5-pyrroledione-2- yl group; 2,3-epoxypropyl group; unsubstituted or azide, alkoxy-substituted C_1_-_3 hydroxyalkyl group; bromine atom, chlorine atom, fluorine atom, C_1_-_2 alkyl, nitro, amino, acetylamino, Benzyl group substituted with thioethoxycarbonylamino, diethylcarbamyl, methylenedioxy or trifluoromethyl; phenoxymethyl group substituted with chlorine or fluorine atom; bromine atom, chlorine atom, fluorine atom, acetyloxy, haloacetyloxy , optionally substituted C_1_-_2 alkylcarbamoyloxy, optionally substituted phenoxybenzoyloxy, methylsulfonyloxy, optionally substituted phenoxyacetyloxy, ethyloxalyloxy, C_1_-_3 alkylamino, fluoro Phenylamino, phthalimide, optionally substituted phenylsulfonylamino, pyrrolidinoyl, thiophenoxy, ethyldithiophosphonyloxy, phenylsulfonyl, diethylthiocarbamyloxy, aminocarbamyl, ethoxycarbonyl, cyclohexenyl, thienyl or substituted Methyl group optionally substituted with pyridyloxy; phenyl group unsubstituted or substituted with chlorine atom, fluorine atom, methoxy, fluoromethyl; C_2_-_3 alkoxy group; unsubstituted or chlorine atom,
Fluorine atom, C_2 alkoxy or alkyloxycarbonyl substituted C_2 alkoxy-substituted phenoxy group; unsubstituted or C_5 alkyl, acetyl, C_1_-_2 alkoxycarbonyl, C_1_-_2 alkylcarbamyl group or phenylsulfonyl group-substituted amino Group; Bromine atom or chlorine atom; C_1_-_4 alkylamino, C_1_-_2 alkoxy, amino, azido, phenylamino, halophenylamino, acetylamino, methylsulfonylamino, C_1_-_4 alkyl, benzyl, phenyl, allylamino or substituted carbonyl group optionally substituted with pyridylamino; C_1_-_4 oxime group substituted with alkyl or phenyl; C_1_-_2 represents an imino group substituted with alkoxy, amino, hydroxyamino, ethylphosphonyl or chlorine atom ) A 1,2,4-oxadiazole derivative represented by: (2) Formula (I) according to claim 1 one or more of the compounds as active ingredients A herbicide composition containing: (3) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R is propyl; isopropyl; tertiary butyl; allyl; cyclohexenylmethyl; bromine atom, chlorine atom, fluorine atom, C_1_-_2 Benzyl group substituted with alkyl, nitro, amino, acetylamino, thioethoxycarbonylamino, diethylcarbamyl or dimethoxy group; Methyl group substituted with bromine, chlorine or fluorine atom; Phenoxymethyl substituted with chlorine or fluorine atom A phenyl group substituted with a chlorine atom, a fluorine atom, a methoxy group, a fluoromethyl group; a C_2_-_3 alkoxy group; a phenoxy group, or a chlorine atom, a fluorine atom, a C_2 alkoxy group, an ethoxycarbonyl group, or an ethoxycarbonylmethyl group (represents a substituted phenoxy group) and general formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X represents a chlorine atom or a methyl group, and Y represents a chlorine atom. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X, Y, n and R are as described above) A method for producing a compound represented by: (4) General formula (IV) MZ-R_1 (R_2) (wherein M represents a hydrogen or sodium atom, Z represents a nitrogen, oxygen or sulfur atom, and when Z is a nitrogen atom, R_1 and R_2 are the same or different, and C_1_-_2 alkyl group; fluorophenyl group; hydrogen atom; methylsulfonyl; unsubstituted or chlorine-substituted allylsulfonyl group; C_4 cyclic monoacyl group; or C_8 bicyclic diacyl group and when Z is oxygen or sulfur atom, R_1 is a phenyl group; substituted with methyl, C_1_-_2 alkylamino, halomethyl, nitrophenoxyphenyl, methylsulfonyl, ethoxycarbonyl, phenoxymethyl or diethylthiophosphonyl group (represents a carbonyl group) and the general formula (I-C) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X represents a chlorine atom or a methyl group, and Y represents a chlorine atom. , n is an integer of 1 or 3) General formula (I-B) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Z is nitrogen, oxygen or Represents a sulfur atom, R_1 and R_2 are C_1_-_2 alkyl group; fluorophenyl group; hydrogen atom; methylsulfonyl; unsubstituted or chlorine-substituted allylsulfonyl; C_4 cyclic monoacyl group; C_
8 Bicyclic diacyl group; phenyl group; methyl, C_1_-
_2 represents a carbonyl group substituted with alkylamino, halomethyl, nitrophenoxyphenyl, methylsulfonyl, ethoxycarbonyl, phenoxymethyl or diethylthiophosphonyl group, X, Y and n are as described above) Production method. (5) General formula (V) HNR_1R_2 (In the formula, R_1 and R_2 are each the same or different and are a hydrogen atom; C_1_-_4 alkyl group; an acetyl group;
Methylsulfonyl group; phenyl group unsubstituted or substituted with a chlorine or fluorine atom; indicates an amino group or a methoxy group (wherein, X represents a chlorine atom or a methyl group, Y represents a chlorine atom, and n is an integer of 1 or 3) ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1, R_2, X, Y, and n are as described above.) A method for producing a compound represented by the following. (6) General formula (VI) R-MgX (wherein, R represents a C_1_-_4 alkyl group; phenyl group or benzyl group, and X represents a chlorine atom). ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X and Y represent chlorine atoms, and n is an integer of 1) General formula (I - F) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X, Y, n, and R are as described above.) A method for producing a compound represented by the following. (7) General formula (VII) R_2ONH_2・HCl (In the formula, R_2 represents a hydrogen atom or a C_2_-_3 alkyl group) A compound represented by the general formula (I -F) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 represents a C_1_-_4 alkyl group or a phenyl group, X and Y represent a chlorine atom, and n is an integer of 1.) -G) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1, R_2, X, Y, and n are as described above.) A method for producing a compound represented by the following. (8) General formula (VIII) A compound represented by Al(i-PrO)_3 is represented by the general formula (I-F) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X and Y represent chlorine atoms, n is an integer of 1, and R_1 represents a C_1_-_3 alkyl group or a C_1_-_3 alkyl group substituted with a methoxy group. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X, Y, n, and R_1 are as described above.) A method for producing a compound represented by the following. (9) General formula (IX) HZ-R_1(R_2) (wherein, Z represents a nitrogen or oxygen atom, R_1 and R_2 represent a C_1_-_2 alkyl group or a hydrogen atom, and Z is a nitrogen atom time, R_1 and R_
2 are the same or different and represent a methyl group or a hydrogen atom, and when Z is an oxygen atom, R_1 represents a C_1_-_2 alkyl group) A compound represented by the general formula (I - J) ▲ Numerical formula, chemical formula , tables, etc. ▼ (In the formula, X and Y represent chlorine atoms, and n is an integer of 1) A general formula (I - I) characterized by reacting with a compound represented by There are chemical formulas, tables, etc. ▼ (In the formula, X, Y, Z, and n are as described above.) A method for producing a compound represented by the following. (10) Formula (X) Ammonia represented by NH_3 is expressed by the general formula (I −L)▲mathematical formula,
There are chemical formulas, tables, etc. ▼ (In the formula, X and Y represent chlorine atoms, and n is an integer of 1) A general formula characterized by reacting the compound represented by the following in the presence of methanol or ethanol. (I -K) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R represents a C_1_-_2 alkyl group, X, Y
and n are as described above) A method for producing a compound represented by: (11) A compound represented by the general formula (X I ) NH_2R_1 (in the formula, R_1 represents a hydrogen atom or a hydroxy group) is expressed by the general formula (I -K) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (in the formula , R represents a C_1_-_2 alkyl group, X and Y represent a chlorine atom, and n is an integer of 1) General formula (I -M) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R, R_1, X, Y, and n are as described above.) A method for producing a compound represented by the following.