JP2000103776A - New nitroisourea derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject inexpensive new compound as an intermediate for producing various guanidine derivatives having insecticidal activity. SOLUTION: This new compound is represented by formula I (R1 is a 1-4C alkyl or benzyl; R2 is a 1-4C alkyl; R3 is H or a 1-4C alkyl), e.g. 1,3-dimethyl-2- nitroisourea. The compound of formula I is obtained by reaction between a compound of formula II (e.g. 1-methyl-2-nitroisourea), a compound of formula III and a salt thereof (e.g. methylamine hydrochloride) in the equivalent ratio of the compound of formula III to the compound of formula II of pref. 1 to 1.1 in a solvent such as water pref. at pH 1.0-9.0 pref. at 0-100 deg.C for 0.1-5 h.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel nitroisourea derivative, a method for producing the same, and a method for producing a nitroguanidine derivative having insecticidal activity using the nitroisourea derivative.

[0002]

2. Description of the Related Art Nitroguanidine derivatives having insecticidal activity and methods for producing them are disclosed in JP-A-2-288860, JP-A-3-157308, JP-A-7-179448 and the like. However, for example, Japanese Unexamined Patent Publication No.
As represented by 448 and the like, the production method has a drawback in that there are many exchange reactions between an isothiourea derivative and an amine, so that mercaptans having a bad smell are eliminated as a by-product. As an alternative to this, JP-A-Hei 1
Nos. 0 to 120666 show that the insecticidal activity represented by the formula (B) (Formula 9) can be obtained by reacting the isourea compound represented by the formula (A) (Formula 8) or a salt thereof with an amine or a salt thereof. A method for producing a guanidine derivative having the same is disclosed.

[0003]

Embedded image [Wherein, R ¹ represents an optionally substituted hydrocarbon group;
² represents hydrogen or an optionally substituted hydrocarbon group;
Represents an optionally substituted heterocyclic group, and X represents an electron withdrawing group.

[0004]

Embedded image [Wherein, R ³ represents an amino group which may be substituted,
R ² , Q and X represent the above-mentioned meanings]

However, according to this method, an expensive isourea compound represented by the formula (A) must be used as an intermediate in order to produce a guadinine derivative represented by the formula (B) having insecticidal activity. There was an inconvenience of not having to.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel nitroisourea derivative which overcomes the above-mentioned disadvantages of the prior art and is important as an intermediate for the production of a guadinine derivative having insecticidal activity. It is in. That is,
An object of the present invention is to provide a novel nitroisourea derivative which is inexpensive and is useful as an intermediate for the production of various guadinine derivatives having insecticidal activity. An object of the present invention is to provide a production method that does not produce a nitroguanidine derivative and a method for producing a nitroguanidine derivative having insecticidal activity using the nitroisourea derivative.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, as important intermediates for producing nitroguanidine derivatives having insecticidal activity,
A nitroisourea derivative different from the isourea compound represented by the formula (A) described in JP-A-10-120666 is found, and by using the nitroisourea derivative, various insecticidal activities can be easily obtained. The present inventors have found that a nitroguanidine derivative can be produced, and have completed the present invention.

That is, one aspect of the present invention is to provide a compound represented by the formula (1)
0)

Embedded image [Wherein, R ₁ represents an alkyl group having 1 to 4 carbon atoms or a benzyl group, R ₂ represents an alkyl group having 1 to 4 carbon atoms,
R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms].

Another aspect of the present invention is to provide a compound represented by the following formula (2):
1)

Embedded image [Wherein R ₁ has the same meaning as described above] and a nitroisourea represented by the formula (3):

[0010]

Embedded image Wherein R ₂ and R ₃ have the same meanings as described above, and a salt thereof at pH 7.0 to 9.0 with the amine represented by the formula (1). To produce a nitroisourea derivative.

Further, one of the present invention is the above formula (1)
And a nitroisourea derivative represented by the formula (4)
3)

Embedded image [In the formula, R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Q represents at least one nitrogen atom, oxygen atom and one sulfur atom, and halogen atom Represents a 5- or 6-membered heterocyclic ring which may be substituted with an amine derivative represented by the formula (5):

[0012]

Embedded image [Wherein, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and Q have the same meanings as described above].

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
In the present invention, the alkyl group having 1 to 4 carbon atoms of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ is a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, A butyl group,
A t-butyl group and the like can be exemplified. Examples of the 5- or 6-membered heterocyclic group which contains at least one nitrogen atom, oxygen atom and sulfur atom and which may be substituted with a halogen atom include a pyridyl group, a pyridazyl group, a pyrimidyl group and a pyrazolyl group. , Imidazolyl, furanyl, tetrahydrofuranyl, isoxazolyl, oxazolyl, thienyl, tetrahydrothienyl, thiazolyl, isothiazolyl and the like.
In the present invention, R ₁ and R ₂ each independently have 1 to 4 carbon atoms.
Is preferred, R ₃ is preferably a hydrogen atom, and R ₄ , R ₅ and R ₆ are preferably hydrogen atoms. Among them, Q is 2-chloro-, because of its excellent insecticidal activity.
5-thiazolyl group, 2-chloro-5-pyridinyl group, 3
-Preferably a tetrahydrofuranyl group.

The compound of the present invention represented by the formula (1) is a novel compound, and can be produced by the method described in the reaction formula (1).

[0015]

Embedded image [Wherein, R ₁ , R ₂ and R ₃ represent the same meaning as described above]

In the reaction formula (1), the compound represented by the formula (2) and the known amines represented by the formula (3) and salts thereof are brought to pH 7.0 from 9.0 in a solvent. The nitroisourea derivative represented by the formula (1) can be produced by adjusting the pH, preferably from 7.0 to 8.0, for the reaction. If the pH is lower than 7.0, the reaction hardly proceeds, and if the pH exceeds 9.0, the target product cannot be obtained.

The acids which form salts with the amines represented by the formula (3) include mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid; sulfonic acids such as methanesulfonic acid and p-toluenesulfonic acid; acetic acid; Examples thereof include carboxylic acids such as acids.

Solvents used in the reaction represented by the reaction formula (1) include water, alcohols such as methanol and ethanol, dimethylformamide (DMF), dimethylsulfoxide (DMSO), 1,3-dimethyl-2- Examples include aprotic polar solvents such as imidazolidinone (DMI), ethers such as tetrahydrofuran (THF) and dioxane, nitriles such as acetonitrile and propionitrile, and ketones such as acetone.

PH in the reaction represented by the reaction formula (1)
The adjustment of the combination of acids represented by mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and bases represented by alkali metal hydroxides such as sodium hydroxide and potassium hydroxide,
Also, a buffer represented by a general buffer such as sodium borate-hydrochloric acid or a special buffer such as Tris-hydrochloric acid buffer or triethanolamine-hydrochloric acid buffer can be used.
The amount of the amines represented by the formula (3) and salts thereof to be used is preferably 1 to 2 equivalents, more preferably 1 to 1.1 equivalents, to the compound represented by the formula (2).

In the reaction formula (1), the compound represented by the formula (2) is a known compound. Tr
av. Chim. Pays-Bas, 1962, 81
, P. 69, by nitration of 1-methylisourea sulfate.

The reaction temperature and reaction time of the above reaction can be varied over a wide range. Generally, the reaction temperature is preferably from -20 to 200C, more preferably from 0 to 10C.
The reaction time at 0 ° C is preferably 0.01 to 50 hours, more preferably 0.1 to 15 hours. Nitroisourea derivative represented by formula (1), when R ₃ is a hydrogen atom,
As shown in the following formula (Formula 16), the tautomers may exist in any ratio. This isomer as well as mixtures thereof are encompassed by the present invention.

[0022]

Embedded image

From the nitroisourea derivative represented by the formula (1) thus produced, the following reaction formula (2)
By the chemical formula 17, the nitroguanidine derivative having the insecticidal activity represented by the formula (5) can be produced.

[0024]

Embedded image [Wherein, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and Q have the same meanings as above]

In the reaction formula (2), the nitroisourea derivative represented by the formula (1) is reacted with an amine represented by the formula (4) or a salt thereof in a solvent in the absence or presence of a base. By doing so, a nitroguanidine derivative having insecticidal activity represented by the formula (5) can be produced.

Examples of the base used in the reaction represented by the reaction formula (2) include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, and alkaline earth metals such as magnesium hydroxide and calcium hydroxide. Hydroxides, sodium hydride, alkali metal hydrides such as potassium hydride, sodium methoxide, alkali metal alcoholates such as sodium ethoxide, alkali metal oxides such as sodium oxide, potassium carbonate, Alkali metal carbonates such as sodium carbonate, alkali metal phosphates such as tripotassium phosphate, trisodium phosphate, dipotassium hydrogen phosphate and disodium hydrogen phosphate, alkalis such as sodium acetate and potassium acetate Metal acetates, pyridine, 4- (dimethylamino) pyridine, triethylamine, dia Vicinal Crow emissions decene (DBU) organic bases such like.

Solvents used in the reaction represented by the reaction formula (2) include water, alcohols such as methanol, ethanol, propanol and butanol, dichloromethane,
Halogenated hydrocarbons such as chloroform, aromatic hydrocarbons such as benzene, toluene and xylene, dimethylformamide (DMF), dimethylacetamide (DM
A), aprotic polar solvents such as dimethylsulfoxide (DMSO), 1,3-dimethyl-2-imidazolidinone (DMI), 1-methyl-2-pyrrolidone (NMP), ethyl ether, isopropyl ether, 1, 2-
Dimethoxyethane (DME), tetrahydrofuran (T
HF), ethers such as dioxane, acetonitrile,
Examples thereof include nitriles such as propionitrile and ketones such as acetone and isopropyl ketone. Of these, water and alcohols are particularly preferred.

The amount of the amines represented by the formula (4) is preferably 1 to 2 equivalents, more preferably 1 to 1.2 equivalents, based on the nitroisourea derivative represented by the formula (1).
Is equivalent. The reaction temperature and the reaction time of the reaction represented by the reaction formula (2) can be changed in a wide range. Generally, the reaction temperature is preferably from -20C to 200C, more preferably from 0 to 100C, and the reaction time is from 0.01 to 50C.
The time is preferred, more preferably 0.1 to 15 hours.

In the reaction formula (2), the amines represented by the formula (4) are known compounds, for example, DE 37271
26A, JP-A-5-286936, JP-A-7-1794
48, EP446913A, JP-A-4-21674 and the like. In the reaction formula (2),
Examples of the acids that form salts with the amines represented by the formula (4) include mineral acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; sulfonic acids such as methanesulfonic acid and p-toluenesulfonic acid;
Examples thereof include carboxylic acids such as propionic acid. The nitroguandinine derivative represented by the formula (5) thus obtained exhibits excellent insecticidal activity.

[0030]

EXAMPLES Next, the contents of the present invention will be specifically described with reference to examples and reference examples, but the present invention is not limited to these examples. Example 1 Production of 1,3-dimethyl-2-nitroisourea (Compound 1-1) 15 g of water was added to 1.5 g of 1-methyl-2-nitroisourea.
and suspended therein.
9 g were added (pH = 3.3). PH 8 in aqueous suspension
1% aqueous solution of sodium hydroxide was added slowly at room temperature to keep the temperature at. After stirring at room temperature for 3 hours while maintaining the pH of the suspension aqueous solution at 8, a hydrochloric acid aqueous solution (4M) was added,
Subsequently, it was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure.
The obtained oil was purified by silica gel column chromatography (2: 1 hexane / ethyl acetate), and then recrystallized (ethyl acetate-hexane) to obtain 1.0 g of the title compound as colorless crystals. . _{^{1 H-NMR (CDCl 3,}} ppm): 3.02 (3H, d, J = 4.9Hz), 3.97 (3H, s), 9.
10 (1H, s)

Example 2 Production of 1,3-dimethyl-2-nitroisourea (Compound 1-1) 1.0 g of 1-methyl-2-nitroisourea was dissolved in a tris (hydroxymethyl) aminomethane-hydrochloric acid buffer solution ( Tris-HCl buffer solution, 1.0M, pH = 7.5) 1
0 ml, and add thereto 0.6 ml of methylamine hydrochloride.
g was added at room temperature. After stirring for 3 hours, an aqueous hydrochloric acid solution (4M) was added, followed by extraction with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained oil was purified by silica gel column chromatography (2: 1 hexane / ethyl acetate) and then recrystallized (ethyl acetate-hexane) to give 0.8 g of the title compound as colorless crystals. .

Comparative Example 1 1.0 g of 1-methyl-2-nitroisourea was added to 10 m of water.
l, to which 0.6 g of methylamine hydrochloride was added (pH = 3.3). A 1% aqueous sodium hydroxide solution was slowly added to the aqueous suspension at room temperature so as to maintain the pH at 6.5. The suspension was stirred at room temperature while keeping the pH of the aqueous solution at 6.5, but the reaction did not proceed at all.

COMPARATIVE EXAMPLE 2 1.0 g of 1-methyl-2-nitroisourea was added to 10 m of water.
l, and 0.6 g of methylamine hydrochloride was added (pH = 3.3). A 1% aqueous sodium hydroxide solution was slowly added to the aqueous suspension at room temperature so as to maintain the pH at 6.9. The suspension was stirred at room temperature while maintaining the pH of the aqueous solution at 6.9, but the reaction did not proceed at all, and the title compound was not obtained.

Comparative Example 3 1.0 g of 1-methyl-2-nitroisourea was added to 10 m of water.
l, and 0.6 g of methylamine hydrochloride was added (pH = 3.3). A 1% aqueous sodium hydroxide solution was slowly added to the aqueous suspension at room temperature so that the pH was maintained at 9.1. The suspension was stirred at room temperature for 3 hours while maintaining the pH of the aqueous suspension at 9.1. After the reaction solution was extracted with dichloromethane, the organic layer was dried over anhydrous magnesium sulfate.
The oily substance obtained by concentrating the organic layer under reduced pressure was subjected to silica gel column chromatography (2: 1 hexane / ethyl acetate).
After recrystallization (ethyl acetate-hexane), the target compound was not obtained, and 0.9 g of 1-methyl-2-nitroguanidine was obtained as colorless crystals.

The compounds which can be produced in the same manner as in Examples 1 and 2 are shown in Table 1 below. In Table 1, Me
Is a methyl group, Et is an ethyl group, n-Pr is an n-propyl group, i-Pr is an isopropyl group, n-Bu is an n-butyl group, and Bn
Represents a benzyl group.

[0036]

[Table 1]

Example 3 Preparation of 1-[(2-chloro-5-pyridyl) methyl] -3-methyl-2-nitroguanidine (compound 2-1) 1,3-dimethyl-2-nitroisourea To a solution of 0 g of methanol in 10 ml, 1.28 g of [(2-chloro-5-pyridyl) methyl] amine was added, and the mixture was stirred at room temperature for 5 hours. The reaction solution was concentrated under reduced pressure, and the obtained oil was purified by silica gel column chromatography (ethyl acetate) and then recrystallized (methanol-ether) to obtain 1.40 g of the title compound as colorless crystals. _{^{1 H-NMR (CDCl 3,}} ppm): 2.83 (3H, br-s), 4.42 (2H, br-s), 7.48
(1H, d, J = 8.1Hz), 7.78 (1H, dd, J = 2.2Hz, 8.1Hz), 7.92 (1H, b
rs), 8.35 (1H, d, J = 2.2Hz), 9.14 (1H, br-s)

Example 4 Preparation of 1-[(2-chloro-5-thiazolyl) methyl] -3-methyl-2-nitroguanidine (compound 2-2) 1,3-dimethyl-2-nitroisourea 1.3 g of [(2-chloro-5-thiazolyl) methyl] amine was added to a solution of 0 g of methanol in 10 ml, and the mixture was stirred at room temperature for 4 hours. The reaction solution was concentrated under reduced pressure, and the obtained oil was purified by silica gel column chromatography (ethyl acetate) and then recrystallized (methanol-ether) to obtain 1.11 g of the title compound as pale yellow crystals. _{^{1 H-NMR (CDCl 3,}} ppm): 2.80 (3H, s), 4.49 (2H, br-s), 7.58 (1
H, s), 7.93 (1H, br-s), 9.13 (1H, br-s)

Example 5 1-methyl-2-nitro-3-
Production of [(3-tetrahydrofuryl) methyl] guanidine [(3-Tetrahydrofuryl)] was added to a solution of 1.0 g of 1,3-dimethyl-2-nitroisourea in 10 ml of methanol.
0.91 g of [methyl] amine was added, and the mixture was stirred at room temperature for 3 hours. The reaction solution was concentrated under reduced pressure, and the obtained oil was purified by silica gel column chromatography (ethyl acetate) and then recrystallized (methanol-ether) to obtain 1.44 g of the title compound as colorless crystals. _{^{1 H-NMR (CDCl 3,}} ppm): 1.62-1.71 (1H, m), 2.05-2.16 (1H, m),
2.58-2.67 (1H, m), 2.97 (3H, d, J = 5.3Hz), 3.36 (2H, br-t),
3.62-3.66 (1H, m), 3.71-3.84 (2H, m), 3.89-3.95 (1H, m), 6.
04 (1H, br-s), 9.35 (1H, br-s)

Example 6 Preparation of 1-[(2-chloro-5-pyridyl) methyl] -3-methyl-2-nitroguanidine (Compound 2-1) 1,3-Dimethyl-2-nitroisourea 0 g was suspended in 10 ml of water, and [(2-chloro-5-pyridyl) methyl] amine (1.28 g) was added thereto, followed by stirring at room temperature for 3 hours. The reaction solution was diluted with water and extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the resulting oil was purified by silica gel column chromatography (ethyl acetate) and recrystallization (methanol-ether) to give the title compound 1.2.
3 g were obtained as colorless crystals.

Example 7 Preparation of 1-[(2-chloro-5-thiazolyl) methyl] -3-methyl-2-nitroguanidine (compound 2-2) 1,3-dimethyl-2-nitroisourea 0 g was suspended in 10 ml of water, and 1.32 g of [(2-chloro-5-thiazolyl) methyl] amine was added thereto.
Stirred for hours. The reaction solution was diluted with water and extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the resulting oil was purified by silica gel column chromatography (ethyl acetate) and recrystallization (methanol-ether) to give the title compound 0.9.
5 g were obtained as pale yellow crystals.

Example 8 1-methyl-2-nitro-3-
Production of [(3-tetrahydrofuryl) methyl] guanidine (compound 2-3) 1.0 g of 1,3-dimethyl-2-nitroisourea was suspended in 10 ml of water, and [(3-tetrahydrofuryl) methyl] amine was suspended. 0.91 g was added, and the mixture was stirred at room temperature for 4 hours. The reaction solution was diluted with water and extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the obtained oil was purified by silica gel column chromatography (ethyl acetate) and recrystallized (methanol-ether) to give 1.24 g of the title compound as a colorless product As crystals. The compounds which can be produced in the same manner as in Examples 3 to 8 are shown in Table 2 (Tables 2, 3, and 4).
In Table 2, Me represents a methyl group, Et represents an ethyl group, and n-
Pr is an n-propyl group, i-Pr is an isopropyl group, n-Bu is
It represents an n-butyl group.

[0043]

[Table 2]

[0044]

[Table 3]

[0045]

[Table 4]

[0046]

The compound of the present invention represented by the formula (1) is a novel compound, and furthermore, by reacting the compound with various amines represented by the formula (4), mercaptan having a bad smell is removed. Various nitroguanidine derivatives having insecticidal activity can be easily produced without growing. Therefore, the compound of the present invention represented by the formula (1) can be applied as an important intermediate for producing a nitroguanidine derivative having insecticidal activity.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Tsuyoshi Oura 1144 Togo, Togo, Mobara-shi, Chiba Mitsui Chemicals, Inc. (72) Inventor Kenji Odaka 1144, Togo, Togo, Mobara-shi, Chiba Mitsui Chemicals, Inc.

Claims (11)

[Claims] (1) Formula (1) (Formula 1) [Wherein, R ₁ represents an alkyl group having 1 to 4 carbon atoms or a benzyl group, R ₂ represents an alkyl group having 1 to 4 carbon atoms,
R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms]. 2. The nitroisourea according to claim 1, wherein R ₁ and R ₂ are each independently an alkyl group having 1 to 4 carbon atoms, and R ₃ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Derivatives. 3. The nitroisourea derivative according to claim 2, wherein R ₃ is a hydrogen atom. 4. A compound of the formula (2) Wherein R ₁ represents an alkyl group or a benzyl group having 1 to 4 carbon atoms, and a nitroisourea represented by the formula (3): [Wherein, R ₂ represents an alkyl group having 1 to 4 carbon atoms, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms] and a salt thereof with a pH of 7. 0 to 9.
Formula (1) characterized in that the reaction is carried out at 0. [R ₁ , R ₂ and R ₃ represent the same meaning as above]. 5. The nitroisourea according to claim 4, wherein R ₁ and R ₂ are each independently an alkyl group having 1 to 4 carbon atoms, and R ₃ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. A method for producing a derivative. 6. The method for producing a nitroisourea derivative according to claim 5, wherein R ₃ is a hydrogen atom. 7. A compound of the formula (1) [Wherein, R ₁ represents an alkyl group having 1 to 4 carbon atoms or a benzyl group, R ₂ represents an alkyl group having 1 to 4 carbon atoms,
R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms] and a nitroisourea derivative represented by the formula (4): [In the formula, R ₄ , R ₅ and R ₆ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Q represents at least one nitrogen atom, oxygen atom and one sulfur atom, and halogen atom Represents a 5- or 6-membered heterocyclic ring which may be substituted with an amine derivative represented by the formula (5): [Wherein, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and Q represent the same meaning as described above]. 8. R ₁ and R ₂ are an alkyl group having 1 to 4 carbon atoms, R ₃ , R ₄ , R ₅ and R ₆ are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Q is The method for producing a nitroguanidine derivative according to claim 7, which is a pyridyl group optionally substituted with a halogen atom, a thiazolyl group optionally substituted with a halogen atom, or a tetrahydrofuryl group. 9. R ₁ and R ₂ are methyl groups, and R ₃ ,
9. The method for producing a nitroguanidine derivative according to claim 8, wherein R ₄ , R ₅ and R ₆ are a hydrogen atom, and Q is a pyridyl group optionally substituted with a halogen atom. 10. R ₁ and R ₂ are methyl groups,
9. The method for producing a nitroguanidine derivative according to claim 8, wherein R ₃ , R ₄ , R ₅ and R ₆ are a hydrogen atom, and Q is a thiazolyl group optionally substituted with a halogen atom. 11. R ₁ and R ₂ are methyl groups,
9. The method for producing a nitroguanidine derivative according to claim 8, wherein R ₃ , R ₄ , R ₅ and R ₆ are hydrogen atoms and Q is a tetrahydrofuryl group.