JPH11236381A - Production of nitroguanidine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable the production of the subject compound without passing hydrolysis in a simple new process by reacting a specific nitroiminohexahydrotriazine derivative with ammonia, a primary amine or a secondary amine, or one of the salts of these compounds. SOLUTION: (A) A compound of formula I (A is a hydrocarbon ring, H or the like; R1 is a 1-10C acyclic or cyclic alkyl; R2 is H, a 1-6C alkyl or the like) is made to react with (B) ammonia, a primary amine or a secondary amine, or one of the salts of the compounds to obtain the objective compound of formula II. An preferable example of the compound B is an aliphatic cyclic amine. The compound B is preferably used in such an amount that it is >=0.1 equivalent based on the compound A when the compound B is a salt, and it is >=2 equivalents based on the compound A when the compound B is other than salts. The reaction is usually carried out in a solvent. The solvent is preferably an alcohol, the reaction temperature is preferably 30-120 deg.C, and the reaction time is preferably 1-24 hr.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel method for producing nitroguanidines. The method of the present invention is very useful for producing a compound used as an agricultural chemical (particularly an insecticide) or an intermediate thereof.

[0002]

2. Description of the Related Art It is well known that certain nitroguanidines are useful as pesticides (especially insecticides) or their intermediates (JP-A-2-288860, JP-A-3-109374, JP-A-3-157308, JP-A-7-179448, etc.).

The following is known as a method for producing disubstituted nitroguanidine.

A method of obtaining a 1,3,5-trisubstituted 2-nitroiminohexahydro-1,3,5-triazine by hydrolysis in the presence of an acid (JP-A-3-291267, JP-A-3-291267) No. 4-330049).

[0005]

Embedded image Method via certain isothiourea (Japanese Unexamined Patent Publication No.
No. 9173).

[0006]

Embedded image Methods via certain dithiocarbamic acid derivatives (JP-A-4-120054, JP-A-4-7415)
No. 8).

[0007]

Embedded image A method via 1,2-disubstituted-3-nitroisothioureas (JP-A-2-88860).

[0008]

Embedded image A method of directly alkylating monosubstituted nitroguanidine (Japanese Patent Application No. 8-158146).

[0009]

Embedded image

[0010]

SUMMARY OF THE INVENTION As described above,
Although only a few methods are known for producing disubstituted nitroguanidine from 5-trisubstituted-2-nitroiminohexahydrotriazine as a raw material, the method is a hydrolysis reaction with acids.

On the other hand, it is well known that nitroguanidine derivatives have high water solubility. In general, the water solubility of nitroguanidines tends to be higher under acidic conditions than under neutral conditions. Therefore, if water or acid is present in the reaction system, the crystallization yield and the extraction rate are reduced during the isolation operation, and the operation tends to be complicated.

When neutralization is performed to suppress this, triazines are regenerated by a reverse reaction, which further complicates the operation.

An object of the present invention is to provide a simple production method which can replace the above-mentioned hydrolysis method.

[0014]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, have found that 1,3,5-trisubstituted
In the process of searching for a method other than the hydrolysis of 2-nitroiminohexahydrotriazine, the mechanism is different from that of acid hydrolysis, and does not require an acid and does not require water.
The inventors have found a method of reacting with ammonia, a primary or secondary amine or a salt thereof, and have completed the present invention.

That is, the present invention relates to formula (1)

[0016]

Embedded image (Wherein A is an optionally substituted aromatic or non-aromatic hydrocarbon ring, an optionally substituted aromatic or non-aromatic heterocycle, a hydrogen atom, an optionally substituted alkyl group Alkenyl or alkynyl, R ₁
Represents an optionally substituted chain or cyclic alkyl group having 1 to 10 carbon atoms, and R ₂ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an alkenyl group or an alkynyl group. Show. Wherein the compound of formula (2) is reacted with ammonia, a primary or secondary amine or a salt thereof.

[0017]

Embedded image (Wherein, A and R ₂ have the above-mentioned meanings).

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Typical examples of the substituent A of the compound of the formula (1) used in the present invention include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and a t-butyl group. Group, pentyl group, hexyl group, vinyl group, allyl group, propargyl group, benzyl group, methoxymethyl group, methylthiomethyl group, trifluoromethyl group, phenyl group, 3-nitrophenyl group, 3-cyanophenyl group, 3- Chlorophenyl group, 3-trifluoromethylphenyl group, cyclopentyl group, cyclohexyl group, 2-pyridyl group, 3-pyridyl group, 2-chloro-5
-Pyridyl group, 2-methyl-5-pyridyl group, 2-methoxy-5-pyridyl group, 5-thiazolyl group, 2-chloro-5-thiazolyl group, 2-methyl-5-thiazolyl group,
2-chloro-5-pyrimidyl group, 2-chloro-5-oxazolyl group, 2-methyl-5-oxazolyl group, 2-furyl group, 3-furyl group, 2-tetrahydrofuryl group, 3
-Tetrahydrofuryl group, 2-methyl-4-tetrahydrofuryl group, 2-ethyl-4-tetrahydrofuryl group,
2-isopropyltetrahydrofuryl group, 2-t-butyl-4-tetrahydrofuryl group, 2,2-dimethyl-4
-Tetrahydrofuryl group and the like.

Typical examples of R ₁ include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl,
Pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, benzyl and the like.

Typical examples of R ₂ include a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n
-Butyl group, sec-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, cyclopentyl group,
Examples include a cyclohexyl group, an allyl group, a propargyl group, a methoxymethyl group, and a methylthiomethyl group.

Typical examples of the primary or secondary amine used in the present invention include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, t-butylamine, pentyl Amine, hexylamine, heptylamine, octylamine, cyclohexylamine, benzylamine, allylamine, propargylamine, aniline, phenylenediamine, toluidine,
Xylidine, ethylenediamine, trimethylenediamine, dimethylamine, diethylamine, benzylmethylamine, N-methylethylenediamine, N, N'-dimethylethylenediamine, N-methylaniline, pyrrolidine, piperidine, piperazine, N-methylpiperazine,
Morpholine, thiomorpholine, ethanolamine, diethanolamine, methoxyethylamine, amino acid esters such as methyl aminoacetate, hydrazine, N-methylhydrazine, N, N-dimethylhydrazine, N, N'-dimethylhydrazine, hydroxylamine, methoxyamine, benzyl Oxyamine and the like can be mentioned. The compound to be reacted with the compound represented by the formula (1) is preferably ammonia or an aliphatic amine, and particularly preferably an aliphatic cyclic amine.

The primary or secondary amine may be a reactant obtained by modifying a carrier insoluble in a solvent with a primary or secondary amino group. Typical examples are given below.

Examples of the carrier include a polymer compound and glass beads. Specific examples of the monomer forming the polymer compound carrier include styrene, divinylbenzene, aromatic vinyl compounds such as vinylpyridine, acrylates, methacrylates, acrylonitrile, acrylates such as acrylamide, Examples include phenols such as phenol, cyclic compounds such as ethylene oxide and ethylene imine, and vinyl alcohol.
As the polymer compound carrier, those obtained by polymerizing these alone or as a mixture can be used. Specific examples include polystyrene resin, acrylate resin, methacrylate resin, phenol resin, divinylbenzene resin, and divinylbenzene-styrene copolymer resin.

Specific examples of the primary or secondary amino group modified on these polymer compound carriers or glass beads include an amino group, a methylamino group, an ethylamino group, a propylamino group, a benzylamino group, -Aminoethylamino group, 3-aminopropylamino group, piperidino group, hydrazino group and the like. An appropriate spacer may be introduced between these functional groups and the carrier.

Specific examples of the reactant obtained by modifying a carrier insoluble in a solvent with a primary or secondary amino group include an anion exchange resin having an amino group. For example, Bayer's Levatit OC1059, Levatit OC10
65, Levatit R258-K, Levatit E82 / 8
1. Diaion WA20, Diaion WA21, Diaion CR20, Sepabeads FP-H manufactured by Mitsubishi Chemical Corporation
A13, Sepabeads FP-BA13, Sepabeads FP-
ZA13, Amberlight IRA6 manufactured by Rohm & Haas
E, aminopropyl-CPG manufactured by CPG, aminocellulofine manufactured by Chisso, and the like.

Ammonia or amine can also be used in the form of a salt. Specific examples of acids that form salts with these amines include mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and carbonic acid, formic acid,
Organic carboxylic acids such as acetic acid, and organic sulfonic acids such as methanesulfonic acid and toluenesulfonic acid. These salts can be used either anhydrous or hydrated.

The amount of ammonia or amine used is preferably at least 1 equivalent, more preferably at least 2 equivalents, based on the compound represented by the formula (1). In the case of salts, it is preferably at least 0.01 equivalent, more preferably at least 0.1 equivalent, based on the compound represented by the formula (1).

Although the reaction can be carried out without solvent,
Usually diluted with a solvent. Examples of the solvent include ethers such as tetrahydrofuran and dioxane, halogenated hydrocarbons such as dichloromethane and dichloroethane, ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile, N, N-dimethylformamide, and 1,3-dimethyl-2. -Imidazolidinone, dimethyl sulfoxide,
Aprotic polar solvents such as N-methylpyrrolidone; and alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol and ethylene glycol. Preferred are halogenated hydrocarbons such as dichloromethane and alcohols, and particularly preferred are alcohols. These solvents can be used as a mixture in any ratio. Water can be mixed with these.

The reaction temperature is preferably 10 ° C. or higher, particularly preferably 30 to 120 ° C. The reaction time is generally from 0.1 hour to 7 days, preferably from 1 to 24 days.
Time.

The reaction can be carried out either at normal pressure or under pressure.

The treatment after the reaction can be carried out according to a conventional method. For example, if necessary, salts may be removed by filtration or the like, and then cooled or a poor solvent may be added, and crystallization may be taken out. If necessary, after removing salts by filtration or the like, the reaction solution can be removed by concentration. Purification such as washing with water, treatment with activated carbon, and recrystallization can be carried out as required to obtain a high-purity product.

The compounds having a nitroimino group of the formulas (1) and (2) can exist as isomers (syn- and anti-isomers) or as tautomers. When A is a tetrahydrofuran ring or the like in the formulas (1) and (2), an asymmetric carbon exists, and it may exist as an optically active isomer, a racemate, or a mixture at an arbitrary ratio. All such isomers and tautomers, and mixtures thereof, are included within the scope of the present invention.

The method of the present invention has the following advantages over the conventional hydrolysis method. 1. In the method by hydrolysis, crystallization or purification is not easy due to the presence of water or acid in the reaction system, and contamination of inorganic salts due to neutralization is recognized, and complicated operations such as silica gel purification are required. Met. According to the method of the present invention, these complicated operations are not required. 2. In the neutralization of an acid, if the acidity is strong, the solubility of nitroguanidines in the aqueous layer increases, resulting in a decrease in extraction rate and crystallization yield. In addition, when the alkali metal becomes nearly alkaline or neutral due to the neutralization, the triazine as a raw material is regenerated, which results in a decrease in yield and purity. Therefore, it is necessary to strictly control the pH at the time of neutralization, which is very complicated industrially. The method of the present invention eliminates the need for pH management.

The above item 1 can be confirmed by (Comparative Example 1 / Example 1) and (Comparative Example 2 / Example 3) in the following examples, and the item 2 can be confirmed by (Comparative Example 3 / Example 10). .

[0035]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples. The pretreatment in Examples 11 to 15 means that a commercially available agent is washed with methanol and then washed with a reaction solvent.

The analysis conditions by high performance liquid chromatography (hereinafter abbreviated as HPLC) are as follows.

Column: L-column (Chemical Inspection Association) Eluent: methanol / water or acetonitrile / water Temperature: 40 ° C. Flow rate: 1 ml / min Detector: UV 210 or 254 or 278 nm Example 11 1- (2- Chloro-5-pyridyl) methyl-3,5-dimethyl-2-nitroiminohexahydrotriazine 5 g
To the mixture were added 20 g of methanol and 4.90 g of n-butylamine, and the mixture was refluxed for 6 hours. The reaction mixture was analyzed by HPLC and found to contain 3.96 g of 1- (2-chloro-5-pyridyl) methyl-3-methyl-2-nitroguanidine.
Yield 97.1%. The reaction was concentrated to half volume and cooled to produce crystals. The crystals were isolated by filtration and confirmed to have the desired structure. Table 1 shows the physical property values.

Example 2 25 g of ethanol and 3.73 of pyrrolidine were added to 5 g of 1- (2-chloro-5-thiazolyl) methyl-3-methyl-5-benzyl-2-nitroiminohexahydrotriazine.
g was added and stirred at 60 ° C. for 8 hours. HPLC the reaction solution
Analysis showed that 1- (2-chloro-5-thiazolyl) methyl-3-methyl-2-nitroguanidine 3.2
Contained 1 g. Yield 97.9%. Concentrate the reaction,
Water and ethyl acetate were added to carry out liquid separation, and the organic layer was dried under reduced pressure and isolated, and it was confirmed that the desired structure was obtained. Table 1 shows the physical property values.

Example 3 1- (3-tetrahydrofuryl) methyl-3-methyl-
5 g of 5-isopropyl-2-nitroiminohexahydrotriazine and 25 g of isobutanol and morpholine4.
58 g was added and the mixture was stirred at 100 ° C. for 4 hours. H
Analysis by PLC showed 1- (3-tetrahydrofuryl) methyl-3-methyl-2-nitroguanidine 3.3.
Contained 3 g. Yield 94.0%. Cool the reaction solution,
The resulting crystals were collected by filtration to confirm the structure. Table 1 shows the physical property values.

Example 4 1- (2-methyl-4-tetrahydrofuryl) methyl-
30 g of isopropanol and 1.58 g of ethylenediamine were added to 5 g of 3-methyl-5-ethyl-2-nitroiminohexahydrotriazine, and the mixture was stirred at 70 ° C. When the reaction solution was analyzed by HPLC, 1- (2-methyl-4
-Tetrahydrofuryl) methyl-3-methyl-2-nitroguanidine. Yield 93.2
%. The reaction solution is concentrated, and the mixture is concentrated on a silica gel column (ethyl acetate /
(Acetone) to confirm the structure. Table 1 shows the physical property values.

Example 5 1- (2-Tetrahydrofuryl) methyl-3-allyl-
20 g of ethylene glycol and 1.54 g of hydrazine monohydrate were added to 5 g of 5-t-butyl-2-nitroiminohexahydrotriazine, and the mixture was stirred at 50 ° C. for 12 hours.
The reaction solution was analyzed by HPLC and found to contain 3.33 g of 1- (2-tetrahydrofuryl) methyl-3-allyl-2-nitroguanidine. Yield 94.9%. Table 1 shows the physical property values.

Example 6 An autoclave was charged with 5 g of 1- (3-tetrahydrofuryl) methyl-3-methyl-5-cyclohexyl-2-nitroiminohexahydrotriazine, 25 g of methanol and 4.77 g of a 40% methylamine / methanol solution. At 60 ° C. for 6 hours. The reaction mixture was analyzed by HPLC to find 1- (3-tetrahydrofuryl) methyl-
It contained 2.98 g of 3-methyl-2-nitroguanidine. Yield 95.9%. Table 1 shows the physical property values.

Example 7 1- (3-tetrahydrofuryl) methyl-3-methyl-
To 5 g of 5-ethyl-2-nitroiminohexahydrotriazine, 15 g of methanol, 5 g of water and piperazine
06 g was added, and the mixture was stirred at 60 ° C. for 5 hours. Reaction solution is HP
Analysis by LC showed 1- (2-tetrahydrofuryl) methyl-3-methyl-2-nitroguanidine 3.4.
4 g. Yield 92.3%. Table 1 shows the physical property values.

Example 8 1- (2-Chloro-5-pyridyl) methyl-3,5-dimethyl-2-nitroiminohexahydrotriazine 15
150 g of dichloromethane and 13.1 g of morpholine
And pressurized to 1 MPa with nitrogen in an autoclave. When reacted at 90 ° C. for 4 hours, the reaction pressure was about 1.
It was 4 MPa. The reaction mixture was analyzed by HPLC and found to contain 12.05 g of 1- (2-chloro-5-pyridyl) methyl-3-methyl-2-nitroguanidine. Yield 98.5%. The reaction was concentrated to half volume and cooled to produce crystals. The crystals were isolated by filtration and confirmed to have the desired structure. Table 1 shows the physical property values.

Example 9 To 15 g of 1- (2-chloro-5-thiazolyl) methyl-3-methyl-5-benzyl-2-nitroiminohexahydrotriazine was added 150 g of dichloromethane and 6.01 g of ethanolamine, and the mixture was placed in an autoclave. The pressure was increased to 1.0 MPa with nitrogen. When the reaction was performed at 80 ° C. for 8 hours, the reaction pressure was about 1.2 MPa. Reaction solution is HP
Analysis by LC showed that 1- (2-chloro-5-thiazolyl) methyl-3-methyl-2-nitroguanidine 1
1.31 g. 92.0% yield. Approximately 50 g of saturated saline was added to the reaction solution, and the mixture was separated. The organic layer was dried under reduced pressure and isolated to confirm that it had the desired structure. Table 1 shows the physical property values.

Example 10 1- (3-tetrahydrofuryl) methyl-3-methyl-
15 g of 5-isopropyl-2-nitroiminohexahydrotriazine was charged with 150 g of dichloromethane, and about 1 g of ammonia gas was absorbed in an autoclave. When the pressure was increased to 1.0 MPa with nitrogen and the reaction was performed at 90 ° C. for 4 hours, the reaction pressure was about 1.3 MPa. H
Analysis by PLC showed 1- (3-tetrahydrofuryl) methyl-3-methyl-2-nitroguanidine.
00g. Yield 94.1%. Approximately 30 g of sodium sulfate acidified with sulfuric acid was added to the reaction solution to decompose it, and the aqueous layer was extracted again with dichloromethane. The organic layer was concentrated under reduced pressure, crystallized by adding ethyl acetate, and collected by filtration to confirm the structure. 83% isolated yield. Table 1 shows the physical property values.

Example 11 1- (2-Chloro-5-pyridyl) methyl-3,5-dimethyl-2-nitroiminohexahydrotriazine 5 g
To the mixture were added 20 g of methanol and 12 g of Bayer's pre-treated Levatit OC1059, and the mixture was refluxed for 6 hours. The reactants were filtered and washed with methanol. The filtrate was analyzed by HPLC to find 1- (2-chloro-5-pyridyl) methyl-3-methyl-2-nitroguanidine.
Contained 79 g. Yield 92.9%. The reaction was concentrated to half volume and cooled to produce crystals. The crystals were isolated by filtration and the structure was confirmed. Table 1 shows the physical property values.

Example 12 1- (2-Chloro-5-thiazolyl) methyl-3-methyl-5-benzyl-2-nitroiminohexahydrotriazine 5 g of ethanol and 25 g of pre-treated Diaion manufactured by Mitsubishi Chemical Corporation Add WA20 11g and add 60 ℃
For 8 hours. The reactants were filtered and washed with ethanol. When the filtrate was analyzed by HPLC, 1- (2-
Chloro-5-thiazolyl) methyl-3-methyl-2-nitroguanidine. Yield 90.0
%. The reaction solution was concentrated, and water and ethyl acetate were added to separate the solution.
The organic layer was isolated by drying under reduced pressure to confirm the structure. Table 1 shows the physical property values.

Example 13 1- (3-tetrahydrofuryl) methyl-3-methyl-
To 5 g of 5-isopropyl-2-nitroiminohexahydrotriazine were added 25 g of isobutanol and 15 g of pretreated Bayer Levatit OC1065, and the mixture was stirred at 70 ° C. for 4 hours. The reactants were filtered and washed with isobutanol. When the filtrate was analyzed by HPLC,
1- (3-tetrahydrofuryl) methyl-3-methyl-
It contained 3.37 g of 2-nitroguanidine. Yield 9
5.1%. The reaction solution was cooled, and the resulting crystals were collected by filtration to confirm the structure. Table 1 shows the physical property values.

Example 14 1- (2-Methyl-4-tetrahydrofuryl) methyl-
5 g of 3-methyl-5-ethyl-2-nitroiminohexahydrotriazine was heated and dissolved in 30 g of isopropanol, and pre-treated DIAION WA21 manufactured by Mitsubishi Chemical Corporation.
The solution was passed through a column packed with 20 g at 70 ° C. When the reaction solution and the washing solution of the column were combined and analyzed by HPLC, they contained 3.72 g of 1- (2-methyl-4-tetrahydrofuryl) methyl-3-methyl-2-nitroguanidine. Yield 92.2%. The reaction solution was concentrated and purified by a silica gel column (ethyl acetate / acetone) to confirm the structure. Table 1 shows the physical property values.

Example 15 1- (2-Tetrahydrofuryl) methyl-3-allyl-
40 g of Sepabeads FP-BA13 manufactured by Mitsubishi Chemical Co., Ltd. obtained by pretreating a solution of 20 g of ethylene glycol in 5 g of 5-t-butyl-2-nitroiminohexahydrotriazine.
Was charged into a test tube filled with and shaken at 50 ° C. for 12 hours. The reactants were filtered and washed with methanol. When the filtrate was analyzed by HPLC, 1- (2-tetrahydrofuryl) methyl-3-allyl-2-nitroguanidine was obtained.
09 g. Yield 88.1%. Table 1 shows the physical property values.

Example 16 1- (3-tetrahydrofuryl) methyl-3-methyl-
To 5 g of 5-cyclohexyl-2-nitroiminohexahydrotriazine were added 25 g of methanol and 14 g of Leytit R258-K manufactured by Bayer AG in a commercial form, and reacted at 60 ° C. for 5 hours. The reactants were filtered and washed with methanol. The filtrate was analyzed by HPLC to find 1-
(3-tetrahydrofuryl) methyl-3-methyl-2-
It contained 2.84 g of nitroguanidine. Yield 91.
4%. Table 1 shows the physical property values.

Example 17 1- (3-tetrahydrofuryl) methyl-3-methyl-
To 5 g of 5-ethyl-2-nitroiminohexahydrotriazine was added 25 g of methanol and 14 g of aminopropyl-CPG manufactured by CPG in a commercial form.
Allowed to react for hours. The reactants were filtered and washed with methanol. The filtrate was analyzed by HPLC and found to contain 3.50 g of 1- (3-tetrahydrofuryl) methyl-3-methyl-2-nitroguanidine. Yield 93.9%. Table 1 shows the physical property values.

Example 18 1- (2-chloro-5-pyridyl) methyl-3,5-dimethyl-2-nitroiminohexahydrotriazine 5 g
20 g of isobutanol and 2.21 of ammonium sulfate
g was added and stirred at 100 ° C. for 4 hours. The reaction solution was filtered, and the filtrate was analyzed by HPLC. As a result, it was found that the solution contained 3.90 g of 1- (2-chloro-5-pyridyl) methyl-3-methyl-2-nitroguanidine. 95.6% yield. The reaction was concentrated to half volume and cooled to produce crystals. The crystals were isolated by filtration and confirmed to have the desired structure.
Table 1 shows the physical property values.

Example 19 To 5 g of 1- (2-chloro-5-thiazolyl) methyl-3-methyl-5-benzyl-2-nitroiminohexahydrotriazine was added 25 g of ethanol and 1.52 g of ammonium acetate, and the mixture was refluxed for 4 hours. did. HPLC the reaction solution
As a result of analysis, 1- (2-chloro-5-thiazolyl) methyl-3-methyl-2-nitroguanidine 3.9 was obtained.
7 g. Yield 96.9%. Concentrate the reaction,
Water and ethyl acetate were added to carry out liquid separation, and the organic layer was dried under reduced pressure and isolated, and it was confirmed that the desired structure was obtained. Table 1 shows the physical property values.

Example 20 1- (3-tetrahydrofuryl) methyl-3-methyl-
25 g of methanol and 0.94 g of ammonium chloride were added to 5 g of 5-isopropyl-2-nitroiminohexahydrotriazine, and the mixture was refluxed for 4 hours. Filter the reaction,
The filtrate was analyzed by HPLC and found to contain 3.47 g of 1- (3-tetrahydrofuryl) methyl-3-methyl-2-nitroguanidine. Yield 97.9%. The reaction solution was cooled, and the resulting crystals were collected by filtration to confirm the structure. Table 1 shows the physical property values.

Example 21 1- (2-methyl-4-tetrahydrofuryl) methyl-
30 g of n-butanol and 2.32 g of ammonium sulfate were added to 5 g of 3-methyl-5-ethyl-2-nitroiminohexahydrotriazine, and the mixture was stirred at 110 ° C. for 5 hours. When the reaction solution was analyzed by HPLC, 1- (2-methyl-4-tetrahydrofuryl) methyl-3-methyl-
It contained 3.69 g of 2-nitroguanidine. Yield 9
7.4%. The reaction solution was concentrated and purified by a silica gel column (ethyl acetate / acetone) to confirm the structure. Table 1 shows the physical property values.

Example 22 1- (2-tetrahydrofuryl) methyl-3-allyl-
5 g of 5-t-butyl-2-nitroiminohexahydrotriazine, 20 g of ethanol and ammonium phosphate 2.
14 g was added and the mixture was refluxed for 5 hours. When the reaction liquid was analyzed by HPLC, it contained 3.30 g of 1- (2-tetrahydrofuryl) methyl-3-allyl-2-nitroguanidine. Yield 95.9%. Table 1 shows the physical property values.

Example 23 An autoclave was charged with 5 g of 1- (3-tetrahydrofuryl) methyl-3-methyl-5-cyclohexyl-2-nitroiminohexahydrotriazine, 25 g of methanol and 1.48 g of ammonium carbonate.
Allowed to react for hours. The reaction pressure was 0.2 MPa. The reaction mixture was analyzed by HPLC and found to contain 2.99 g of 1- (3-tetrahydrofuryl) methyl-3-methyl-2-nitroguanidine. 96.2% yield. Table 1 shows the physical property values.

Example 24 1- (3-Tetrahydrofuryl) methyl-3-methyl-
20 g of methanol and 2.77 g of diammonium hydrogen phosphate were added to 5 g of 5-ethyl-2-nitroiminohexahydrotriazine, and the mixture was stirred at 60 ° C. for 5 hours. When the reaction solution was analyzed by HPLC, 1- (2-tetrahydrofuryl) methyl-3-methyl-2-nitroguanidine was obtained.
Contained 53 g. Yield 94.7%. Table 1 shows the physical property values.

Example 25 1- (2-chloro-5-pyridyl) methyl-3,5-dimethyl-2-nitroiminohexahydrotriazine 5 g
20 g of isobutanol and 2.2 of methylamine hydrochloride
6 g was added and the mixture was stirred at 100 ° C. for 4 hours. The insolubles were removed by filtration, and the filtrate was analyzed by HPLC, and found to contain 3.81 g of 1- (2-chloro-5-pyridyl) methyl-3-methyl-2-nitroguanidine. Yield 93.4%. The filtrate was concentrated in half and cooled to produce crystals. The crystals were isolated by filtration and the structure was confirmed. Table 1 shows the physical property values.

Example 26 To 1 g of 1- (2-chloro-5-thiazolyl) methyl-3-methyl-5-benzyl-2-nitroiminohexahydrotriazine was added 25 g of n-butanol and 2.23 g of morpholine sulfate. Refluxed for 4 hours. The insolubles were separated by filtration, and the filtrate was analyzed by HPLC. As a result, it was found that 3.73 g of 1- (2-chloro-5-thiazolyl) methyl-3-methyl-2-nitroguanidine was contained. 91.1% yield.
The filtrate was concentrated, water and ethyl acetate were added thereto, and the mixture was separated. The organic layer was dried under reduced pressure and isolated to confirm the structure. Table 1 shows the physical property values.

Example 27 1- (3-tetrahydrofuryl) methyl-3-methyl-
25 g of isobutanol and 1.40 g of methylamine sulfate were added to 5 g of 5-isopropyl-2-nitroiminohexahydrotriazine, and the mixture was refluxed for 4 hours. The insolubles were removed by filtration, and the filtrate was analyzed by HPLC. As a result, it was found that the filtrate contained 3.33 g of 1- (3-tetrahydrofuryl) methyl-3-methyl-2-nitroguanidine. Yield 94.0%. The filtrate was cooled, and the resulting crystals were collected by filtration to confirm the structure. Table 1 shows the physical property values.

Example 28 1- (2-Methyl-4-tetrahydrofuryl) methyl-
30 g of n-butanol and 4.98 g of pyrrolidine hydrochloride were added to 5 g of 3-methyl-5-ethyl-2-nitroiminohexahydrotriazine, and the mixture was stirred at 110 ° C for 5 hours. The insolubles were removed by filtration, and the filtrate was analyzed by HPLC. As a result, it was found that the filtrate contained 3.47 g of 1- (2-methyl-4-tetrahydrofuryl) methyl-3-methyl-2-nitroguanidine. Yield 91.6%. The filtrate was concentrated and purified with a silica gel column (ethyl acetate / acetone) to confirm the structure. Table 1 shows the physical property values.

Comparative Example 1 1- (2-chloro-5-pyridyl) methyl-3,5-dimethyl-2-nitroiminohexahydrotriazine
90 ml of ethanol and 5.5 ml of 6M hydrochloric acid were added to 5 g, and the mixture was heated under reflux for 30 minutes. Since the solution was acidified by hydrochloric acid, no crystals were formed even when the reaction solution was cooled.

Comparative Example 2 1- (3-tetrahydrofuryl) methyl-3,5-dimethyl-2-nitroiminohexahydrotriazine 18 g
To the mixture was added 340 g of dichloromethane, 155 g of 7% hydrochloric acid was added, and the mixture was refluxed for 4 hours. After cooling, 33 g of common salt was added and the mixture was separated, and the aqueous layer was extracted four times with 50 g of dichloromethane. The extraction rate was 83%. The organic layers were combined, concentrated under reduced pressure, and crystallized by adding ethyl acetate to obtain 9.24 g of 1- (3-tetrahydrofuryl) methyl-3-methyl-2-nitroguanidine. Isolation yield 66.4%.

Comparative Example 3 1- (3-tetrahydrofuryl) methyl-3-methyl-
140 g of dichloromethane was added to 20 g of 5-isopropyl-2-nitroiminohexahydrotriazine, and 13%
106 g of sulfuric acid was added, and the mixture was heated under reflux for 8 hours. The reaction yield was 98%. After cooling, the pH was adjusted to 6.5 with a 45% sodium hydroxide solution. After adjustment, 1- (3-tetrahydrofuryl) methyl-3-methyl-5-isopropyl-2
-Nitroiminohexahydrotriazine increased by 9%. The layers were separated, and the aqueous layer was re-extracted with 140 g of dichloromethane. The organic layers were combined, concentrated under reduced pressure, and crystallized by adding ethyl acetate to give 1- (3-tetrahydrofuryl) methyl-3-.
10.3 g of methyl-2-nitroguanidine were obtained. 73% isolated yield.

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

As described above, according to the method of the present invention, substituted nitroguanidines useful as pesticides (especially insecticides) or intermediates thereof can be carried out without hydrolysis, and acid and No need for complicated operations derived from water,
The desired product can be obtained in a high yield by a simple method, and is particularly excellent as a production method.

 ──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. 9-258968 (32) Priority date Heisei 9 (1997) September 24 (33) Priority claim country Japan (JP) (31) Priority Claim No. Hei 9-347934 (32) Priority date Hei 9 (1997) December 17, (33) Priority country Japan (JP) (72) Inventor Mitsuhiko Miyamoto 30 Asamuta-cho, Omuta-shi, Fukuoka Mitsui Chemical Co., Ltd.

Claims (7)

[Claims] (1) Formula (1) (Wherein A is an optionally substituted aromatic or non-aromatic hydrocarbon ring, an optionally substituted aromatic or non-aromatic heterocycle, a hydrogen atom, an optionally substituted alkyl group Alkenyl or alkynyl, R ₁
Represents an optionally substituted chain or cyclic alkyl group having 1 to 10 carbon atoms, and R ₂ represents a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an alkenyl group or an alkynyl group. Show. Wherein the compound of formula (2) is reacted with ammonia, a primary or secondary amine, or a salt thereof. (Wherein, A and R ₂ have the same meanings as described above). 2. The method according to claim 1, wherein the reaction is carried out in a non-aqueous system. 3. The method according to claim 1, wherein the compound of the formula (1) is reacted with ammonia. 4. The method according to claim 1, wherein the compound of the formula (1) is reacted with an aliphatic amine. 5. The method according to claim 1, wherein the compound of the formula (1) is reacted with an ammonium salt or an amine salt. 6. In the formulas (1) and (2), A is an optionally substituted pyridyl group, thiazolyl group, oxazolyl group or tetrahydrofuryl group.
The described method. 7. In the above formulas (1) and (2), A is a 2-chloro-5-pyridyl group, a 2-chloro-5-thiazolyl group, a 2-tetrahydrofuryl group, or a 3-tetrahydrofuryl group. The method of claim 1.