JPH1045724A - Production of n-sulfonylpyrimidinecarboxylic acid amide derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently obtain the subject compound useful as a herbicide by reacting a sulfonamide derivative with a pyrimidine-2-carboxylic acid phenyl ester derivative. SOLUTION: A 4,6-dialkoxypyrimidine-2-carboxylic acid phenyl ester derivative of formula I (R is an alkoxy; Y is a halogen, an alkyl, an alkoxy, etc.; (n) is 0, 1 or 2) is reacted with a sulfonamide derivative of the formula R<1> SO2 NH2 (R<1> is an alkyl, an alkenyl, an alkynyl, a cycloalkyl, an alkylamino, etc.) to give the objective compound of formula II. The compound of formula I is a new compound and is obtained by reacting a phenyloxalyl chloride with a dialkylpropanediimidate dihydrochloride. Consequently, the compound of formula II is simply obtained without using a condensation agent and raw materials requiring many processes in the production.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a process for producing an N-sulfonylpyrimidinecarboxylic acid amide derivative useful as a herbicide, and a 4,6-dialkoxypyrimidine-2-carboxylic acid phenyl ester useful as a raw material for the process. It relates to derivatives.

[0002]

2. Description of the Related Art N-sulfonyl nitrogen-containing 6-membered aromatic carboxylic acid amide derivatives or salts thereof, a description of a production method and a pesticide, and production of a compound represented by the general formula (VIII) As a method, a sulfonamide derivative represented by the general formula (VI) as shown in (Chemical Formula 5) and a carboxylic acid derivative represented by the following general formula (VII) are mixed with a suitable solvent in the presence of a suitable condensing agent. Among them, a production method for reacting in the presence of a base, if necessary, is known (W
O-9318012).

[0003]

Embedded image [Wherein R ² represents a (substituted) alkyl group, a (substituted) alkenyl group, an alkynyl group (substituted) cycloalkyl group, a (substituted)
Represents an alkylamino group or a (substituted) dialkylamino group, R ³ and R ⁴ are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a haloalkyl group, or a haloalkoxy group, and Z represents a methine group or Indicates a nitrogen atom. ]

[0004]

However, the above WO
The production method described in JP-A-9318012 is not industrially necessary because the production of the compound represented by the general formula (VII) requires a relatively long process, and a condensing agent must be used. It is hard to say that this is an advantageous method. An object of the present invention is to provide a method capable of producing an N-sulfonylpyrimidinecarboxylic acid amide derivative more efficiently.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies on a method for producing an N-sulfonylpyrimidinecarboxylic acid amide derivative in order to achieve the above object, and as a result, have found that a sulfonamide derivative and phenylpyrimidine-2-carboxylate are used. It has been found that the above-mentioned object can be achieved by reacting an ester derivative, and a pyrimidine-2-carboxylic acid phenyl ester derivative as a raw material thereof is reacted with a phenyloxalyl chloride derivative and dimethylpropanediimidate dihydrochloride. The present invention was found to be a novel compound which can be produced by the method of the present invention, and the present invention was completed.

That is, the present invention provides the following items (1) and (2).

(1) General formula (II)

[0008]

Embedded image [Wherein, R represents an alkoxy group, Y represents a halogen atom,
It represents an alkyl group, an alkoxy group, a cyano group, a nitro group or an alkoxycarbonyl group, and n represents 0, 1 or 2. ]

4,6-dialkoxypyrimidine-2-carboxylic acid phenyl ester derivative represented by the general formula (III)

[0010]

Embedded image [Wherein, R ¹ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkylamino group, Or an unsubstituted dialkylamino group or cyclic amino group. ]

Wherein the compound is reacted with a sulfonamide derivative represented by the following general formula (I):

[0012]

Embedded image [Wherein, R and R ¹ are as defined above. ]

A process for producing an N-sulfonylpyrimidinecarboxylic acid amide derivative represented by the formula:

(2) General formula (II)

[0015]

Embedded image [Wherein, R represents an alkoxy group, Y represents a halogen atom,
It represents an alkyl group, an alkoxy group, a cyano group, a nitro group or an alkoxycarbonyl group, and n represents 0, 1 or 2. ]

4,6-dialkoxypyrimidine-2-carboxylic acid phenyl ester derivative represented by the formula:

The terms used in the present specification are defined below. The halogen atom includes fluorine, chlorine, bromine and iodine atoms.

The alkyl group means a linear or branched alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, an n-hexyl group and an n-octyl group. And the like.

The haloalkyl groups may be the same or different
1 to 8 carbon atoms substituted with 10 to 10 halogen atoms
And includes, for example, a chloromethyl group, a difluoromethyl group, a trifluoromethyl group, a tetrafluoroethyl group and the like.

The alkenyl group means a linear or branched alkenyl group having 2 to 8 carbon atoms, for example, an allyl group, 1-
Butenyl, 2-butenyl, 2-pentenyl and the like.

The alkynyl group means a linear or branched alkynyl group having 2 to 8 carbon atoms, and includes, for example, a propargyl group, a 1-butynyl group and a 2-butynyl group.

The cycloalkyl group means a cycloalkyl group having 3 to 8 carbon atoms, and includes, for example, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group and the like.

The term "alkoxy group" means a (alkyl) -O- group in which the alkyl moiety has the above-mentioned meaning, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy group, tert-butoxy group, n-hexyloxy group,
n-octyloxy group and the like.

The alkylamino group is a (alkyl) -NH- group in which the alkyl moiety has the above-mentioned meaning, and includes, for example, a methylamino group, an ethylamino group, an isopropylamino group and the like.

The term "dialkylamino group" means a (alkyl) ₂ N-group in which the alkyl moiety has the above-mentioned meaning, and includes, for example, a dimethylamino group, a methylethylamino group and a diisopropylamino group.

The term "alkoxycarbonyl group" means a (alkoxy) -CO- group in which the alkoxy moiety has the above-mentioned meaning, and includes, for example, a methoxycarbonyl group, an ethoxycarbonyl group and an isopropoxycarbonyl group.

The cyclic amino group includes an aziridinyl group, an azetidinyl group, a pyrrolidinyl group, a piperidinyl group and the like.

The term "substituted" means that the compound is mono-substituted or poly-substituted by, for example, a halogen atom, an alkoxy group, a cyano group, an alkoxycarbonyl group, a haloalkyl group or the like.

[0029]

BEST MODE FOR CARRYING OUT THE INVENTION Next, typical examples of N-sulfonylpyrimidinecarboxylic acid amide derivatives represented by the general formula (I) produced by the method of the present invention are shown in Table 1 below.
Table 2 shows typical examples of the compound of the present invention represented by the general formula (II), but the present invention is not limited to these. The compound numbers will be referred to in the following description.

The compound represented by the general formula (I) has two types of geometric isomers, an entgegen (E) form and a tuzamen (Z) form, and can be produced by the method of the present invention. The compounds represented by) include any of these isomers and a mixture of these isomers in any ratio.

[0031]

[Table 1]

[0032]

[Table 2]

Next, the method of the present invention relating to the production of the N-sulfonylpyrimidinecarboxylic acid amide derivative represented by the general formula (I) will be described as Production Method 1.

<Production Method 1>

[0035]

Embedded image [Wherein, R, R ¹ , Y and n are as defined above. This method comprises converting an N-sulfonylpyrimidinecarboxylic acid amide derivative represented by the general formula (I) into a 4,6-dialkoxypyrimidine-2-carboxylic acid phenyl ester derivative represented by the general formula (II), It is produced by reacting a sulfonamide derivative represented by the formula (III) with a suitable solvent in the presence of a base.

The 4,6-dialkoxypyrimidine represented by the general formula (II) used as a raw material in this reaction:
Examples of 2-carboxylic acid phenyl ester derivatives include 4,6-dimethoxypyrimidine-2-carboxylic acid
Phenyl ester, 4,6-dimethoxypyrimidine-2
-Carboxylic acid 4-chlorophenyl ester, 4,6-
Dimethoxypyrimidine-2-carboxylic acid 4-methylphenyl ester, 4,6-dimethoxypyrimidine-2-
Carboxylic acid 4-methoxyphenyl ester, 4,6-
Dimethoxypyrimidine-2-carboxylic acid 2,4-dimethylphenyl ester, 4,6-dimethoxypyrimidine-2-carboxylic acid 2,6-dimethylphenyl ester, 4,6-dimethoxypyrimidine-2-carboxylic acid
2,6-dichlorophenyl ester, 4,6-dimethoxypyrimidine-2-carboxylic acid phenyl ester,
4,6-dimethoxypyrimidine-2-carboxylic acid 4-
Cyanophenyl ester, 4,6-dimethoxypyrimidine-2-carboxylic acid 4-nitrophenyl ester,
4,6-dimethoxypyrimidine-2-carboxylic acid 4-
Examples include methoxycarbonyl phenyl ester.

Examples of the sulfonamide derivative represented by the general formula (III) used as the other raw material in the reaction include, for example, Z-3-chloro-2-propenesulfonamide, E-2,3-dichloro- Examples thereof include 2-propenesulfonamide, Z-3-chloro-2-methyl-2-propenesulfonamide, 1-ethylpropylaminosulfonamide, propargylsulfonamide, cyclopropylmethylsulfonamide, and 3-chloropropanesulfonamide.

The amount of the raw material used is as follows: the sulfonamide derivative represented by the general formula (III) and the 4,6-dialkoxypyrimidine-2-carboxylic acid phenyl ester derivative represented by the general formula (II) are used. Used in the range of 0 to 1.3 equivalents.

Examples of the base used in this reaction include alkali metal hydrides such as sodium hydride, alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, and alkali metal hydroxides such as potassium carbonate, sodium carbonate and sodium hydrogen carbonate. Carbonates, and triethylamine,
Pyridine, 1,8-diazabicyclo- [5.4.0]-
Organic bases such as 7-undecene (DBU) and the like can be mentioned. The base is used in an amount of 0.01 to 10 equivalents, preferably 1.0 to 1.2 equivalents, based on the sulfonamide derivative represented by the general formula (III).

The solvent used in this reaction includes, for example, aprotic polar solvents including N, N-dimethylformamide (DMF), dimethylsulfoxide (DMSO) and the like; tetrahydrofuran (THF), diethyl ether, dioxane and the like. Ethers; halogenated hydrocarbons including dichloromethane, chloroform, etc .; ketones, including acetone, methyl isobutyl ketone; nitriles, including acetonitrile, propionitrile; aromatic, including toluene, benzene, xylene, etc. Group hydrocarbons and the like. The amount of the solvent used is in the range of 1 ml to 1000 ml, preferably 10 ml to 200 ml, per 1 g of the sulfonamide derivative represented by the general formula (III).

The reaction temperature is generally in the range of -50 ° C to the boiling point of the solvent, preferably in the range of 0 ° C to room temperature, and the reaction time is not particularly limited, but is usually 30 minutes to 24 hours.
Time range.

The 4,6-dialkoxypyrimidine-2-carboxylic acid phenyl ester derivative represented by the general formula (II) used as a raw material in the above-mentioned production method 1 is a novel compound and is produced according to the following production method 2. be able to.

<Production method 2>

[0044]

Embedded image [Wherein, R, Y and n are as defined above. ]

The 4,6-dialkoxypyrimidine-2-carboxylic acid phenyl ester derivative represented by the general formula (II) is represented by the formula (V) and the phenyloxalyl chloride derivative represented by the general formula (IV). To a dialkylpropanediimidate dihydrochloride in a suitable solvent in the presence of a base.

The phenyloxalyl chloride derivative represented by the general formula (IV) used in this reaction includes:
For example, phenyloxalyl chloride, 4-chlorophenyloxalyl chloride, 4-methylphenyloxalyl chloride, 4-methoxyphenyloxalyl chloride,
2,4-dichlorophenyloxalyl chloride, 2,4
-Dimethylphenyloxalyl chloride, 2,6-dimethylphenyloxalyl chloride, 4-cyanophenyloxalyl chloride, 4-nitrophenyloxalyl chloride, 4-methoxycarbonylphenyloxalyl chloride, and the like.

With respect to the dialkylpropanediimidate dihydrochloride represented by the formula (V), the phenyloxalyl chloride derivative represented by the general formula (IV) is 1.0 to 1.
Used in the range of 5 equivalents.

The phenyloxalyl chloride derivative represented by the general formula (IV) can be obtained, for example, from Chemische Berichite, Vol. 54B, Vol.
It can be synthesized according to the method described on page 13 (1921). The dialkylpropanediimidate dihydrochloride represented by the general formula (V) can be used, for example, in Journal of American Chemical Society (Journal of
American Chemical Society), vol. 71, p. 40 (1949).

Examples of the base used in this reaction include organic bases such as triethylamine, N, N-diisopropylethylamine and pyridine and carbonates such as sodium carbonate, sodium hydrogencarbonate and potassium carbonate. The amount of the base used is 3 to the dialkylpropanediimidate dihydrochloride represented by the general formula (V).
A range of ~ 5 equivalents is suitable.

The solvent used in this reaction includes, for example, aprotic polar solvents including N, N-dimethylformamide (DMF), dimethylsulfoxide (DMSO) and the like; tetrahydrofuran (THF), diethyl ether, dioxane and the like. Ethers; halogenated hydrocarbons including dichloromethane, chloroform, etc .; ketones, including acetone, methyl isobutyl ketone; nitriles, including acetonitrile, propionitrile; aromatic, including toluene, benzene, xylene, etc. Group hydrocarbons and the like. The amount of the solvent used is in the range of 1 ml to 1000 ml, preferably 10 ml to 100 ml, per 1 g of dialkylpropanediimidate dihydrochloride represented by the formula (V).

The reaction temperature is generally in the range of -50 ° C. to the boiling point of the solvent, and the reaction time is usually in the range of 30 minutes to 2 minutes.
Time range.

Among the sulfonamide derivatives represented by the general formula (III) used as a raw material in the production method 1, the compounds wherein R ¹ in the formula is a substituted or unsubstituted alkenyl group are described below. It can be manufactured according to the manufacturing method 3 described below.

<Production Method 3>

[0054]

Embedded image [In the formula, X ¹ represents a hydrogen atom, a halogen atom or an alkyl group, and X ² represents a halogen atom or an alkyl group. ]

As the 2-alkenylsulfonamide derivative represented by the general formula (X), a 2-alkenylsulfonyl chloride derivative represented by the general formula (IX) in which X ² and a chlorosulfonylmethyl group are in a cis configuration is suitably used. By reacting the 2-alkenylsulfonyl chloride derivative represented by the general formula (IX) with 1 to 10 equivalents of ammonia gas or aqueous ammonia at -50 ° C to the boiling point of the solvent in a suitable solvent. Obtainable.

As a solvent, tetrahydrofuran (TH
F) ethers including diethyl ether, dioxane, etc .; halogenated hydrocarbons including dichloromethane, chloroform, etc .; ketones including acetone, methyl isobutyl ketone, etc .; aromatics including toluene, benzene, xylene, etc. Examples include hydrocarbons and water. The amount of the solvent used is 2 represented by the general formula (IX).
-With respect to 1 g of the alkenylsulfonyl chloride derivative,
It is performed in the range of 1 ml to 1000 ml, preferably 5 ml.
ml to 100 ml.

The 2-alkenylsulfonyl chloride derivative represented by the general formula (IX) can be obtained by the following Method A or Method B.

(Method A)

[0059]

Embedded image [Wherein, X ¹ and X ² have the same meanings as described above, and X ⁴ represents a halogen atom. ]

2-alkenyl represented by the general formula (IX)
The sulfonyl chloride derivative is represented by X²And halogenomethyl
Group [Group —CH in General Formula (XI)] ₂-X ⁴] Is the cis configuration
An alkenyl halide derivative represented by the general formula (XI)
Reacts conductor with 1.0-1.5 equivalents of sodium sulfite
Alkenyl represented by the general formula (XII)
The sodium sulfonate derivative is replaced with 1 to 10 equivalents of pentachloride
Chlorination with chlorinating agents such as phosphorus and phosphorus oxychloride
You can get more.

The reaction between the alkenyl halide derivative represented by the general formula (XI) and sodium sulfite is usually performed in a solvent. Examples of the solvent include water. The amount of the solvent to be used is 1 ml to 1000 ml, preferably 5 ml to 100 ml, per 1 g of the alkenyl halide derivative represented by the general formula (XI).

The reaction temperature is generally in the range of 0 ° C. to the boiling point of the solvent, preferably 20 ° C. to 100 ° C., and the reaction time is generally in the range of 1 to 24 hours.

The chlorination reaction of the sodium alkenylsulfonate derivative represented by the general formula (XII) is usually performed in a solvent. As the solvent, for example, chloroform can be mentioned, but a chlorinating agent (for example, phosphorus oxychloride) can be used as the solvent, or the reaction can be carried out without a solvent. The amount of the solvent used is 1 ml to 1 g of the sodium alkenyl sulfonate derivative represented by the general formula (XII).
It is performed in the range of 1000 ml, preferably 5 ml to 1
00 ml.

The reaction temperature is generally in the range of 0 ° C. to the boiling point of the solvent, preferably 20 ° C. to 100 ° C., and the reaction time is usually in the range of 10 minutes to 10 hours.

(Method B)

[0066]

Embedded image [Wherein X ¹ and X ² have the same meanings as above. ]

2-alkenyl represented by the general formula (IX)
The sulfonyl chloride derivative is represented by X²And chlorosulfoni
A methyl group [the group —CH in the general formula (XIII); ₂-SO
₂Cl] is alkenylsulfonyl chloride having a cis configuration
Derivatives and trans-coordinated alkenylsulfonyl chlorides
Represented by the general formula (XIII), which is a mixture with
From alkenylsulfonyl chloride derivatives
Heats alkenylsulfonyl chlorides
It can be obtained by decomposing and removing.

Usually, this thermal decomposition is carried out by mixing the alkenylsulfonyl chloride derivative represented by the general formula (XIII), which is a mixture, generally at 100 ° C. to 200 ° C., preferably at 12 ° C.
The heating may be carried out in the range of 0 ° C to 170 ° C, and the reaction time is usually in the range of 30 minutes to 2 hours.

Next, specific examples of the 2-alkenylsulfonyl chloride derivative represented by the general formula (IX) and the 2-alkenylsulfonamide derivative represented by the general formula (X) are shown in (Table 3).

[0070]

[Table 3]

[0071]

Next, the present invention will be described in more detail with reference to production examples and reference examples, but the present invention is not limited to these examples.

Preparation Example 1 Preparation of N- (Z-3-chloro-2-propenylsulfonyl) -4,6-dimethoxypyrimidine-2-carboxylic acid amide (Compound No. I-1) Z-3-chloro-2- Propene sulfonamide 0.2
4 g (1.5 mmol), 4,6-dimethoxypyrimidine-2-carboxylic acid phenyl ester 0.40 g
(1.5 mmol) was dissolved in 30 ml of acetonitrile, 0.23 g (1.5 mmol) of 1,8-diazabicyclo- [5.4.0] -7-undecene (DBU) was added, and the mixture was reacted at room temperature overnight. I let it. The reaction solution was concentrated, and the residue was dissolved in water and ethyl acetate. The aqueous layer was made acidic with citric acid and extracted with ethyl acetate. The organic layer was washed with water and brine, dried over anhydrous magnesium sulfate, and concentrated. The obtained crystals are washed with isopropyl ether to give the desired N-
(Z-3-chloro-2-propenylsulfonyl) -4,
6-Dimethoxypyrimidine-2-carboxylic acid amide (0.41 g, mp 162-163 ° C., yield 84%) was obtained.

Production Example 2 N- (E-2,3-dichloro-
Production of 2-propenylsulfonyl) -4,6-dimethoxypyrimidine-2-carboxylic acid amide (Compound No. I-2) E-2,3-dichloro-2-propenylsulfonamide was prepared in the same manner as in Production Example 1. 29 g (1.5 mmol)
And 0.40 g (1.5 mmol) of 4,6-dimethoxypyrimidine-2-carboxylic acid phenyl ester and 1,
From 0.23 g (1.5 mmol) of 8-diazabicyclo [5.4.0] -7-undecene (DBU),
-(E-2,3-dichloro-2-propenylsulfonyl) -4,6-dimethoxypyrimidine-2-carboxylic acid amide (0.1 g, melting point 160-161 ° C, yield 20)
%).

Production Example 3 N- (2-methyl-3-chloro-2-propenylsulfonyl) -4,6-dimethoxypyrimidine-2-carboxylic acid amide (Compound No. I-3)
In the same manner as in Production Example 1, 2-methyl-3-chloro-2-
0.19 g (1.1 mmol) of propenylsulfonamide, 0.29 g (1.1 mmol) of 4,6-dimethoxypyrimidine-2-carboxylic acid phenyl ester and 1,8-diazabicyclo [5.4.0] -7 -Undecene (DBU) from 0.17 g (1.1 mmol) to N- (2-methyl-3-chloro-2-propenylsulfonyl) -4,6-dimethoxypyrimidine-2-carboxylic acid amide (0.24 g) 137-140 ° C, yield 6
3%).

Production Example 4 N- (1-ethylpropylaminosulfonyl) -4,6-dimethoxypyrimidine-2-
Production of carboxylic acid amide (Compound No. I-4) In the same manner as in Production Example 1, 48 mg (0.29 mmol) of 1-ethylpropylaminosulfonamide and 4-methylphenyl 4,6-dimethoxypyrimidine-2-carboxylate 80 mg (0.29 mmol) of ester and 1,8
-Diazabicyclo [5.4.0] -7-undecene (D
BU) from 44 mg (0.29 mmol) of the desired N-
(1-ethylpropylaminosulfonyl) -4,6-dimethoxypyrimidine-2-carboxylic acid amide (77 m
g, melting point 153-154 ° C, yield 80%).

Production Example 5 Production of N- (isopropylsulfonyl) -4,6-dimethoxypyrimidine-2-carboxylic acid amide (Compound No. I-5)
3 mg (0.27 mmol) and 4,6-dimethoxypyrimidine-2-carboxylic acid 4-chlorophenyl ester 80 mg (0.27 mmol) and 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) 41m
The desired N- (isopropylsulfonyl) -4,6-dimethoxypyrimidine-2-carboxylic acid amide (66 mg, melting point: 182-184 ° C, yield: 84%) was obtained from g (0.27 mmol).

Production Example 6 Phenyl ester of 4,6-dimethoxypyrimidine-2-carboxylic acid (Compound No. II)
Synthesis of -1) A suspension of 2.0 g (10 mmol) of dimethylpropanediimidate dihydrochloride in 50 ml of chloroform was added at 0 ° C.
And N, N-diisopropylethylamine 4.6 g (36
(Mmol) was added dropwise and stirred for 15 minutes. A solution of 2.0 g (11 mmol) of phenyloxalyl chloride in 20 ml of chloroform was added dropwise at 0 ° C, and the mixture was stirred at 0 ° C for 30 minutes. The reaction solution was poured into ice water, extracted with chloroform, dried over anhydrous magnesium sulfate, and concentrated. The obtained crystals were washed with diisopropyl ether (IPE) to obtain the desired phenyl ester of 4,6-dimethoxypyrimidine-2-carboxylic acid (1.3 g, melting point: 134 to 135 ° C, yield: 50%).

¹ H-NMR data (60 MHz, CDC
l ₃ solvent, [delta] value, ppm): 4.06 (6H, s) 6.22 (1H, s) 7.20~7.50 (5H, m)

Production Example 7 Synthesis of 4,6-dimethoxypyrimidine-2-carboxylic acid 4-chlorophenyl ester (Compound No. II-2) In the same manner as in Production Example 6, 10 g (46 mmol) of 4-chlorophenyloxalyl chloride was prepared. Dimethylpropanediimidate dihydrochloride 11.7 g (57.5 mmol)
And 27 g of N, N-diisopropylethylamine (0.
207 mol) to the desired 4,6-dimethoxypyrimidine-2-carboxylic acid 4-chlorophenyl ester (6.
1 g, melting point 130-132 ° C, yield 45%). ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value, ppm): 4.06 (6H, s) 6.23 (1H, s) 7.23 (2H, d) 7.40 (2H, d)

Production Example 8 Synthesis of 4,6-dimethoxypyrimidine-2-carboxylic acid 4-methylphenyl ester (Compound No. II-3) In the same manner as in Production Example 6, 5 g (25 mmol) of 4-methylphenyloxalyl chloride ), 6.3 g (31.5 mmol) of dimethylpropanediimidate dihydrochloride and 14.3 g of N, N-diisopropylethylamine (0.
11 mol) to the desired 4,6-dimethoxypyrimidine-
2-carboxylic acid 4-methylphenyl ester (3.0
g, melting point 89-90 ° C., yield 45%).

¹ H-NMR data (60 MHz, CDC
l ₃ solvent, [delta] value, ppm): 2.39 (3H, s) 4.07 (6H, s) 6.22 (1H, s) 7.15 (2H, d) 7.22 (2H, d)

Production Example 9 Synthesis of 4,6-dimethoxypyrimidine-2-carboxylic acid 4-methoxyphenyl ester (Compound No. II-5) In the same manner as in Production Example 6, 5 g of 4-methoxyphenyloxalyl chloride (23. 3 mmol), 5.9 g (29 mmol) of dimethylpropanediimidate dihydrochloride and 13.5 g of N, N-diisopropylethylamine
(0.104 mol) to give the desired 4,6-dimethoxypyrimidine-2-carboxylic acid 4-methoxyphenyl ester (2.7 g, melting point 96-98 ° C, yield 40%). ¹ H-NMR data (60 MHz, CDCl ₃ solvent, δ
Value, ppm): 3.82 (3H, s) 4.07 (6H, s) 6.21 (1H, s) 6.94 (2H, d) 7.20 (2H, d)

Reference Example 1 Synthesis of E-2,3-dichloro-2-propenesulfonamide (Compound No. III-7) 40 g (0.19 mol) of E-2,3-dichloro-2-propenesulfonyl chloride and dichloromethane 300
The mixture was placed in a three-necked flask, and in a dry ice-acetone bath, 0.82 mol of ammonia gas was blown in at -30 ° C for 30 minutes while stirring. The three-necked flask was taken out of the dry ice-acetone bath, and the stirring was further continued for 2 hours.
After the formed salt was filtered off, the filtrate was concentrated under reduced pressure. The resulting crystals were filtered off, washed with diisopropyl ether and dried to obtain the desired E-2,3-dichloro-2-propenesulfonamide (34.2 g, melting point 45-50 ° C, yield 95%). Was.

¹ H-NMR data (60 MHz, CDC
l ₃ solvent, [delta] value, ppm): 4.23 (2H, s) 6.30 (2H, b) 6.50 (1H, s)

Reference Example 2 Z-3-chloro-2-methyl-
2-propenesulfonamide (Compound No. III-8)
In the same manner as in Reference Example 1, Z-3-chloro-2-methyl-
7.9 g of 2-propenesulfonyl chloride (0.04
Mol) and 0.2 mol of ammonia gas
3-Chloro-2-methyl-2-propenesulfonamide (7.0 g, yield 97%) was obtained.

¹ H-NMR data (60 MHz, CDC
l ₃ solvent, [delta] value, ppm): 2.00 (3H, d) 4.07 (2H, s) 5.05 (2H, b) 6.20 (1H, q)

Reference Example 3 Synthesis of Z-3-chloro-2-propenesulfonamide (Compound No. III-6) 31.5 g of Z-3-chloro-2-propenesulfonyl chloride (0. 18 mol) and 0.822 mol of ammonia gas to give the desired Z-3-chloro-2-propenesulfonamide (24.3 g, melting point 73-76 ° C, yield 86.8%).

¹ H-NMR data (60 MHz, CDC
l ₃ solvent, [delta] value, ppm): 4.07 (2H, d) 5.00 (2H, bs) 6.00 (1H, q) 6.48 (1H, d)

Reference Example 4 E-2,3-dichloro-2-propenesulfonyl chloride (Compound No. III-2)
Synthesis of E-1,2,3-trichloropropene 43.7 g (0.
3 mol), 38 g (0.3 mol) of sodium sulfite and 200 ml of water were placed in an eggplant-shaped flask and stirred for 3 hours while heating under reflux. After confirming that the reaction solution was uniform, the mixture was concentrated under reduced pressure, and the crystal residue was dried to obtain E-2,3 as white crystals.
-Sodium dichloro-2-propenesulfonate was obtained quantitatively.

The above sodium salt was finely crushed, placed in an eggplant-shaped flask, and added with 62 g (0.3 mol) of phosphorus pentachloride and shaken at room temperature. After a while, hydrogen chloride was generated violently, generating heat and melting. The reaction was further stirred at room temperature for 2 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to produce POC.
was evaporated l _3, The residue was dissolved in dichloromethane 500 ml, washed with water and aqueous sodium bicarbonate solution and dried over anhydrous magnesium sulfate. After drying, the solvent was distilled off and the residue was distilled under reduced pressure to obtain the target E-2,3-dichloro-2-propenesulfonyl chloride (46 g, boiling point 132 ° C./20 mmHg, yield 73%).

Reference Example 5 Z-3-chloro-2-methyl-
2-propenesulfonyl chloride (Compound No. III-
Synthesis of 3) As in Reference Example 4, 25 g (0.21 mol) of 1,3-dichloro-2-methyl-propene (1: 1E, Z mixture), 26.5 g (0.21 mol) of sodium sulfite And 43.7 g (0.21 mol) of phosphorus pentachloride and 30
g of 3-chloro-2-methyl-2-propenesulfonyl chloride (1: 1E, Z mixture) was prepared, pyrolyzed at 150 ° C. for 1 hour in a nitrogen stream, and then distilled under reduced pressure to obtain the desired compound. Of Z-3-chloro-2-methyl-2-propenesulfonyl chloride (12 g, boiling point 134-140 ° C /
25 mmHg, 31% yield).

Reference Example 6 Synthesis of Z-3-chloro-2-propenesulfonyl chloride (Compound No. III-1) In the same manner as in Reference Example 4, 26 g (0.234 mol) of Z-1,3-dichloropropene were prepared. Sodium sulfite 2
9.5 g (0.234 mol) and 70 g of phosphorus pentachloride
(0.336 mol) using the desired Z-3-chloro-2
-Propenesulfonyl chloride (31.5 g, boiling point 1
22 ° C./35 mmHg, yield: 76.9%).

¹ H-NMR data (60 MHz, CDC
l ₃ solvent, [delta] value, ppm): 4.52 (2H, d) 6.00 (1H, q) 6.60 (1H, d)

[0094]

Industrial Applicability A method for easily and efficiently industrially producing an N-sulfonylpyrimidinecarboxylic acid amide derivative useful as a herbicide without using a condensing agent and a raw material requiring many steps in the production as in the past, and the production thereof. Provided are 4,6-dialkoxypyrimidine-2-carboxylic acid phenyl ester derivatives useful as raw materials for the method.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Nobuhide Wada 408-1, Shioda, Fukuda-cho, Iwata-gun, Shizuoka Prefecture Inside of K-I Research Institute Co., Ltd. 408 No. 1 Inside KI Research Institute, Inc.

Claims (2)

[Claims] 1. A compound of the general formula (II) [Wherein, R represents an alkoxy group, Y represents a halogen atom,
It represents an alkyl group, an alkoxy group, a cyano group, a nitro group or an alkoxycarbonyl group, and n represents 0, 1 or 2. 4,6-dialkoxypyrimidine-2 represented by the formula:
-Carboxylic acid phenyl ester derivative and a compound represented by the general formula (II)
I) [Wherein, R ¹ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkylamino group, Or an unsubstituted dialkylamino group or cyclic amino group. And a sulfonamide derivative represented by the following general formula (I): [Wherein, R and R ¹ are as defined above. The method for producing an N-sulfonylpyrimidinecarboxylic acid amide derivative represented by the formula: 2. A compound of the general formula (II) [Wherein, R represents an alkoxy group, Y represents a halogen atom,
It represents an alkyl group, an alkoxy group, a cyano group, a nitro group or an alkoxycarbonyl group, and n represents 0, 1 or 2. 4,6-dialkoxypyrimidine-2 represented by the formula:
-Carboxylic acid phenyl ester derivatives.