JPH08259524A - Acid azide derivative and its production - Google Patents

Abstract

PURPOSE: To easily obtain in an industrially advantageous way an acid azide derivative useful as an intermediate for agrochemicals, medicines, etc., (e.g. herbicides) by reaction of a specific substituted benzoyl chloride derivative with an inorganic azide. CONSTITUTION: This derivative of formula I (Y is a halogen; R<4> is a lower alkyl) (pref. 5-acetyl-thio-4-chloro-2-fluorobenzoyl azide) is obtained by reaction of (A) a substituted benzoyl chloride derivative of formula II (e.g. 5- acetylthio-2,4-difluorobenzoyl chloride) with (B) an inorganic azide (pref. sodium azide) at the equivalent ratio B/A of pref. (0.95-1.05). The reaction is pref. conducted in a solvent such as acetone at -30 to 50 deg.C for 5min to 8h.

Description

Detailed Description of the Invention

[0001]

The present invention relates to the general formula [I]

[0002]

[Chemical 4]

[In the formula, Y represents a halogen atom, and R ⁴ represents a lower alkyl group. ] The present invention relates to a novel acid azide derivative and a method for producing the same. The novel acid azide derivative represented by the general formula [I] of the present invention is
Manufacturing intermediates for agricultural chemicals, for example, general formula [XIII] having excellent herbicidal activity

[0004]

Embedded image

[In the formula, Y represents a halogen atom, R ¹ represents —CHR ⁵ CO ₂ R ⁶ (wherein R ⁵ represents a hydrogen atom or a lower alkyl group, and R ⁶ represents a lower alkyl group). R ² represents a lower alkyl group, R ³ represents a lower alkoxy group, a lower alkenyloxy group, a lower alkynyloxy group, a lower alkoxyalkoxy group or a lower alkoxycarbonylalkoxy group. ] It is a compound useful as a production intermediate such as an N-acyl-N-phenyltetrahydrophthalamic acid derivative represented by

[0006]

2. Description of the Related Art Many acid azide derivatives have been known so far. However, the acid azide derivative represented by the general formula [I] has not been known so far and is a novel compound.

[0007]

DISCLOSURE OF THE INVENTION As a result of intensive studies, the present inventors have found that an acid azide derivative represented by the general formula [I] has an excellent herbicidal activity and an N-acyl-N represented by the general formula [XIII]. -It was found that the compound is useful as an intermediate for the production of a phenyltetrahydrophthalamic acid derivative, and further, the present inventors have found that the acid azide derivative represented by the general formula [I] having industrial significance is As a result of earnestly researching the novel production method, the acid azide derivative represented by the general formula [I] can be easily obtained by reacting the substituted benzoic acid chloride derivative represented by the general formula [II] with an inorganic azide. They have found that they can be manufactured and have completed the present invention.

That is, the present invention provides a compound represented by the general formula [I]:

[0009]

[Chemical 6]

[In the formula, Y represents a halogen atom, and R ⁴ represents a lower alkyl group. ] A novel acid azide derivative represented by the general formula [II]

[0011]

[Chemical 7]

[In the formula, Y represents a halogen atom and R ⁴ represents a lower alkyl group. ] The substituted benzoic acid chloride derivative shown by these and an inorganic azide are made to react, General formula [I]

[0013]

Embedded image

[In the formula, Y represents a halogen atom and R ⁴ represents a lower alkyl group. ] It is a manufacturing method of the novel acid azide derivative shown by these. Examples of the novel acid azide derivative represented by the general formula [I] which is a compound of the present invention include 5-acetylthio-2,4-difluorobenzoyl azide, 5-acetylthio-4-chloro-2-fluorobenzoyl azide, 5-acetylthio-4-bromo-2
-Fluorobenzoyl azide, 5-propionylthio-
2,4-difluorobenzoyl azide, 5-propionylthio-4-chloro-2-fluorobenzoyl azide,
5-propionylthio-4-bromo-2-fluorobenzoyl azide, 5-butyrylthio-2,4-difluorobenzoyl azide, 5-butyrylthio-4-chloro-2
-Fluorobenzoyl azide, 5-butyrylthio-4-
Bromo-2-fluorobenzoyl azide, 5-isobutyrylthio-2,4-difluorobenzoyl azide, 5-
Isobutyrylthio-4-chloro-2-fluorobenzoyl azide, 5-isobutyrylthio-4-bromo-2-fluorobenzoyl azide, 5-valerylthio-2,4-
Difluorobenzoyl azide, 5-valerylthio-4-
Chloro-2-fluorobenzoyl azide, 5-valerylthio-4-bromo-2-fluorobenzoyl azide, 5
-Isovalerylthio-2,4-difluorobenzoyl azide, 5-isovalerylthio-4-chloro-2-fluorobenzoyl azide, 5-isovalerylthio-4-bromo-2-fluorobenzoyl azide, 5-pivaloylthio-2,4-difluorobenzoyl azide , 5-pivaloylthio-4-chloro-2-fluorobenzoyl azide, 5-pivaloylthio-4-bromo-2-fluorobenzoyl azide, 5- (2-methylbutanoylthio)-
2,4-difluorobenzoyl azide, 5- (2-methylbutanoylthio) -4-chloro-2-fluorobenzoyl azide, 5- (2-methylbutanoylthio) -4-
Bromo-2-fluorobenzoyl azide, 5-hexanoylthio-2,4-difluorobenzoyl azide, 5-
Hexanoylthio-4-chloro-2-fluorobenzoyl azide, 5-hexanoylthio-4-bromo-2-fluorobenzoyl azide, 5- (2-methylpentanoylthio) -2,4-difluorobenzoyl azide, 5 −
(2-Methylpentanoylthio) -4-chloro-2-fluorobenzoyl azide, 5- (2-methylpentanoylthio) -4-bromo-2-fluorobenzoyl azide, 5- (3-methylpentanoylthio) -2,4-difluorobenzoyl azide, 5- (3-methylpentanoylthio) -4-chloro-2-fluorobenzoyl azide, 5- (3-methylpentanoylthio) -4-bromo-2-fluorobenzoyl azide 5- (4-methylpentanoylthio) -2,4-difluorobenzoyl azide, 5- (4-methylpentanoylthio) -4-chloro-2-fluorobenzoyl azide, 5- (4-methylpentanoylthio) ) -4-Bromo-2-fluorobenzoyl azide, 5- (2,2-dimethylbutanoylthio)-
2,4-difluorobenzoyl azide, 5- (2,2-
Dimethylbutanoylthio) -4-chloro-2-fluorobenzoylazide, 5- (2,2-dimethylbutanoylthio) -4-bromo-2-fluorobenzoylazide,
5- (2,3-Dimethylbutanoylthio) -2,4-difluorobenzoylazide, 5- (2,3-dimethylbutanoylthio) -4-chloro-2-fluorobenzoylazide, 5- (2,3 -Dimethylbutanoylthio) -4
-Bromo-2-fluorobenzoyl azide, 5- (3,
3-dimethylbutanoylthio) -2,4-difluorobenzoyl azide, 5- (3,3-dimethylbutanoylthio) -4-chloro-2-fluorobenzoyl azide, 5
-(3,3-Dimethylbutanoylthio) -4-bromo-
2-fluorobenzoyl azide, 5- (2-ethylbutanoylthio) -2,4-difluorobenzoyl azide,
5- (2-ethylbutanoylthio) -4-chloro-2-
Fluorobenzoyl azide, 5- (2-ethylbutanoylthio) -4-bromo-2-fluorobenzoyl azide, 5-heptanoylthio-2,4-difluorobenzoyl azide, 5-heptanoylthio-4-chloro-2-
Fluorobenzoyl azide, 5-heptanoylthio-4
-Bromo-2-fluorobenzoyl azide, 5- (2-
Methylhexanoylthio) -2,4-difluorobenzoylazide, 5- (2-methylhexanoylthio) -4
-Chloro-2-fluorobenzoyl azide, 5- (2-
Methylhexanoylthio) -4-bromo-2-fluorobenzoyl azide, 5- (3-methylhexanoylthio) -2,4-difluorobenzoyl azide, 5- (3
-Methylhexanoylthio) -4-chloro-2-fluorobenzoyl azide, 5- (3-methylhexanoylthio) -4-bromo-2-fluorobenzoyl azide, 5
-(4-methylhexanoylthio) -2,4-difluorobenzoyl azide, 5- (4-methylhexanoylthio) -4-chloro-2-fluorobenzoyl azide, 5
-(4-Methylhexanoylthio) -4-bromo-2-
Fluorobenzoyl azide, 5- (5-methylhexanoylthio) -2,4-difluorobenzoyl azide, 5
-(5-Methylhexanoylthio) -4-chloro-2-
Fluorobenzoyl azide, 5- (5-methylhexanoylthio) -4-bromo-2-fluorobenzoyl azide, 5- (2,2-dimethylpentanoylthio) -2,
4-difluorobenzoyl azide, 5- (2,2-dimethylpentanoylthio) -4-chloro-2-fluorobenzoyl azide, 5- (2,2-dimethylpentanoylthio) -4-bromo-2-fluorobenzoyl Azide,
5- (2,3-dimethylpentanoylthio) -2,4-
Difluorobenzoyl azide, 5- (2,3-dimethylpentanoylthio) -4-chloro-2-fluorobenzoyl azide, 5- (2,3-dimethylpentanoylthio) -4-bromo-2-fluorobenzoyl azide, 5
-(2,4-Dimethylpentanoylthio) -2,4-difluorobenzoyl azide, 5- (2,4-dimethylpentanoylthio) -4-chloro-2-fluorobenzoyl azide, 5- (2,4- Dimethylpentanoylthio)
-4-Bromo-2-fluorobenzoyl azide, 5-
(3,3-Dimethylpentanoylthio) -2,4-difluorobenzoyl azide, 5- (3,3-dimethylpentanoylthio) -4-chloro-2-fluorobenzoyl azide, 5- (3,3-dimethyl Pentanoylthio)-
4-Bromo-2-fluorobenzoyl azide, 5-
(3,4-Dimethylpentanoylthio) -2,4-difluorobenzoyl azide, 5- (3,4-dimethylpentanoylthio) -4-chloro-2-fluorobenzoyl azide, 5- (3,4-dimethyl Pentanoylthio)-
4-Bromo-2-fluorobenzoyl azide, 5-
(4,4-Dimethylpentanoylthio) -2,4-difluorobenzoyl azide, 5- (4,4-dimethylpentanoylthio) -4-chloro-2-fluorobenzoyl azide, 5- (4,4-dimethyl Pentanoylthio)-
4-Bromo-2-fluorobenzoyl azide, 5- (2
-Ethylpentanoylthio) -2,4-difluorobenzoylazide, 5- (2-ethylpentanoylthio)-
4-chloro-2-fluorobenzoyl azide, 5- (2
-Ethylpentanoylthio) -4-bromo-2-fluorobenzoyl azide, 5- (3-ethylpentanoylthio) -2,4-difluorobenzoyl azide, 5- (3
-Ethylpentanoylthio) -4-chloro-2-fluorobenzoyl azide, 5- (3-ethylpentanoylthio) -4-bromo-2-fluorobenzoyl azide, 5
-(2,2,3-trimethylpentanoylthio) -2,
4-difluorobenzoyl azide, 5- (2,2,3-
Trimethylpentanoylthio) -4-chloro-2-fluorobenzoyl azide, 5- (2,2,3-trimethylpentanoylthio) -4-bromo-2-fluorobenzoyl azide, 5- (2,3,3- Trimethylpentanoylthio) -2,4-difluorobenzoyl azide, 5-
(2,3,3-Trimethylpentanoylthio) -4-chloro-2-fluorobenzoyl azide, 5- (2,3,
3-Trimethylpentanoylthio) -4-bromo-2-
Examples thereof include fluorobenzoyl azide.

Next, the method for producing the acid azide derivative represented by the general formula [I] in the present invention will be described in detail.

[0016]

[Chemical 9]

[In the formula, Y represents a halogen atom, and R ⁴ represents a lower alkyl group. In the production method of the present invention, the substituted benzoic acid chloride derivative represented by the general formula [II] and the inorganic azide dissolved in water are mixed in a suitable solvent in the presence or absence of a suitable phase transfer catalyst. The acid azide derivative represented by the general formula [I], which is the compound of the present invention, can be easily produced by reacting for 5 minutes to 8 hours.

Examples of the substituted benzoic acid chloride derivative represented by the general formula [II] include 5-acetylthio-
2,4-difluorobenzoyl chloride, 5-acetylthio-4-chloro-2-fluorobenzoyl chloride,
5-acetylthio-4-bromo-2-fluorobenzoyl chloride, 5-propionylthio-2,4-difluorobenzoyl chloride, 5-propionylthio-4-chloro-2-fluorobenzoyl chloride, 5-propionylthio-4-bromo 2-Fluorobenzoyl chloride, 5-butyrylthio-2,4-difluorobenzoyl chloride, 5-butyrylthio-4-chloro-2-fluorobenzoyl chloride, 5-butyrylthio-4-bromo-2-fluorobenzoyl chloride, 5-isobutyrylthio -2,4-difluorobenzoyl chloride, 5-isobutyrylthio-4-chloro-2-fluorobenzoyl chloride, 5-isobutyrylthio-4-bromo-2-fluorobenzoyl chloride, 5-valerylthio-2,4
-Difluorobenzoyl chloride, 5-valerylthio-
4-chloro-2-fluorobenzoyl chloride, 5-valerylthio-4-bromo-2-fluorobenzoyl chloride, 5-isovalerylthio-2,4-difluorobenzoyl chloride, 5-isovalerylthio-4-chloro-
2-fluorobenzoyl chloride, 5-isovaleryl thio-4-bromo-2-fluorobenzoyl chloride, 5
-Pivaloylthio-2,4-difluorobenzoyl chloride, 5-pivaloylthio-4-chloro-2-fluorobenzoyl chloride, 5-pivaloylthio-4-bromo-2-fluorobenzoyl chloride, 5- (2-methylbutanoylthio)- 2,4-difluorobenzoyl chloride, 5- (2-methylbutanoylthio) -4-chloro-2-fluorobenzoyl chloride, 5- (2-methylbutanoylthio) -4-bromo-2-fluorobenzoyl chloride, 5-hexanoylthio-2,4-difluorobenzoyl chloride, 5-hexanoylthio-4-chloro-2-fluorobenzoyl chloride, 5-hexanoylthio-4-bromo-2-fluorobenzoyl chloride, 5- (2 -Methylpentanoylthio) -2,4-difluorobenzoi Chloride, 5- (2-methylpentanoylthio) -4-chloro-2-fluorobenzoyl chloride, 5- (2-methylpentanoylthio) -4-bromo-2-fluorobenzoyl chloride, 5- (3-methyl Pentanoylthio) -2,4-difluorobenzoyl chloride, 5- (3-methylpentanoylthio) -4
-Chloro-2-fluorobenzoyl chloride, 5- (3
-Methylpentanoylthio) -4-bromo-2-fluorobenzoyl chloride, 5- (4-methylpentanoylthio) -2,4-difluorobenzoyl chloride, 5-
(4-Methylpentanoylthio) -4-chloro-2-fluorobenzoyl chloride, 5- (4-methylpentanoylthio) -4-bromo-2-fluorobenzoyl chloride, 5- (2,2-dimethylbutanoi Lucio) -2,
4-difluorobenzoyl chloride, 5- (2,2-dimethylbutanoylthio) -4-chloro-2-fluorobenzoyl chloride, 5- (2,2-dimethylbutanoylthio) -4-bromo-2-fluorobenzoyl Chloride, 5- (2,3-dimethylbutanoylthio) -2,4
-Difluorobenzoyl chloride, 5- (2,3-dimethylbutanoylthio) -4-chloro-2-fluorobenzoyl chloride, 5- (2,3-dimethylbutanoylthio) -4-bromo-2-fluorobenzoyl chloride ,
5- (3,3-dimethylbutanoylthio) -2,4-difluorobenzoyl chloride, 5- (3,3-dimethylbutanoylthio) -4-chloro-2-fluorobenzoyl chloride, 5- (3,3 -Dimethylbutanoylthio)
-4-Bromo-2-fluorobenzoyl chloride, 5-
(2-Ethylbutanoylthio) -2,4-difluorobenzoyl chloride, 5- (2-ethylbutanoylthio)
-4-chloro-2-fluorobenzoyl chloride, 5-
(2-Ethylbutanoylthio) -4-bromo-2-fluorobenzoyl chloride, 5-heptanoylthio-2,
4-difluorobenzoyl chloride, 5-heptanoylthio-4-chloro-2-fluorobenzoyl chloride,
5-heptanoylthio-4-bromo-2-fluorobenzoyl chloride, 5- (2-methylhexanoylthio)
-2,4-difluorobenzoyl chloride, 5- (2-
Methylhexanoylthio) -4-chloro-2-fluorobenzoyl chloride, 5- (2-methylhexanoylthio) -4-bromo-2-fluorobenzoyl chloride,
5- (3-methylhexanoylthio) -2,4-difluorobenzoyl chloride, 5- (3-methylhexanoylthio) -4-chloro-2-fluorobenzoyl chloride, 5- (3-methylhexanoylthio) -4-Bromo-2-fluorobenzoyl chloride, 5- (4-methylhexanoylthio) -2,4-difluorobenzoyl chloride, 5- (4-methylhexanoylthio) -4-chloro-2-fluorobenzoyl chloride , 5- (4-methylhexanoylthio) -4-bromo-2-fluorobenzoyl chloride, 5- (5-methylhexanoylthio) -2,4-difluorobenzoyl chloride, 5-
(5-Methylhexanoylthio) -4-chloro-2-fluorobenzoyl chloride, 5- (5-methylhexanoylthio) -4-bromo-2-fluorobenzoyl chloride, 5- (2,2-dimethylpentanoyl) Lucio)-
2,4-difluorobenzoyl chloride, 5- (2,2
-Dimethylpentanoylthio) -4-chloro-2-fluorobenzoyl chloride, 5- (2,2-dimethylpentanoylthio) -4-bromo-2-fluorobenzoyl chloride, 5- (2,3-dimethylpentanoyl Lucio)
-2,4-difluorobenzoyl chloride, 5- (2,
3-dimethylpentanoylthio) -4-chloro-2-fluorobenzoyl chloride, 5- (2,3-dimethylpentanoylthio) -4-bromo-2-fluorobenzoyl chloride, 5- (2,4-dimethylpenta Noylthio) -2,4-difluorobenzoyl chloride, 5-
(2,4-Dimethylpentanoylthio) -4-chloro-
2-fluorobenzoyl chloride, 5- (2,4-dimethylpentanoylthio) -4-bromo-2-fluorobenzoyl chloride, 5- (3,3-dimethylpentanoylthio) -2,4-difluorobenzoyl chloride, 5
-(3,3-Dimethylpentanoylthio) -4-chloro-2-fluorobenzoyl chloride, 5- (3,3-dimethylpentanoylthio) -4-bromo-2-fluorobenzoyl chloride, 5- (3 4-dimethylpentanoylthio) -2,4-difluorobenzoyl chloride,
5- (3,4-dimethylpentanoylthio) -4-chloro-2-fluorobenzoyl chloride, 5- (3,4-
Dimethylpentanoylthio) -4-bromo-2-fluorobenzoyl chloride, 5- (4,4-dimethylpentanoylthio) -2,4-difluorobenzoyl chloride, 5- (4,4-dimethylpentanoylthio)- 4-
Chloro-2-fluorobenzoyl chloride, 5- (4,
4-dimethylpentanoylthio) -4-bromo-2-fluorobenzoyl chloride, 5- (2-ethylpentanoylthio) -2,4-difluorobenzoyl chloride,
5- (2-ethylpentanoylthio) -4-chloro-2
-Fluorobenzoyl chloride, 5- (2-ethylpentanoylthio) -4-bromo-2-fluorobenzoyl chloride, 5- (3-ethylpentanoylthio) -2,
4-difluorobenzoyl chloride, 5- (3-ethylpentanoylthio) -4-chloro-2-fluorobenzoyl chloride, 5- (3-ethylpentanoylthio)-
4-bromo-2-fluorobenzoyl chloride, 5-
(2,2,3-Trimethylpentanoylthio) -2,4
-Difluorobenzoyl chloride, 5- (2,2,3-
Trimethylpentanoylthio) -4-chloro-2-fluorobenzoyl chloride, 5- (2,2,3-trimethylpentanoylthio) -4-bromo-2-fluorobenzoyl chloride, 5- (2,3,3- Trimethylpentanoylthio) -2,4-difluorobenzoyl chloride, 5- (2,3,3-trimethylpentanoylthio)
-4-chloro-2-fluorobenzoyl chloride, 5-
(2,3,3-trimethylpentanoylthio) -4-bromo-2-fluorobenzoyl chloride and the like can be mentioned.

Examples of the inorganic azide include sodium azide and potassium azide. The inorganic azide is usually 0.8 per 1 equivalent of the substituted benzoic acid chloride derivative represented by the general formula [II].
Equivalent to 1.5 equivalent, preferably 0.9 equivalent to 1.2 equivalent, more preferably 0.95 equivalent to 1.05 equivalent is used. When the amount is less than this range, a large amount of unreacted substituted benzoic acid chloride derivative represented by the general formula [II] remains, which causes a decrease in yield and is economically disadvantageous. It is not preferable because the post-treatment step is burdened to remove the substituted benzoic acid chloride derivative represented by [II]. Further, even if used in excess of this range, there is almost no change in the yield of the desired acid azide derivative represented by the general formula [I], and a large amount of unreacted inorganic azide remains unreacted. However, this is not preferable because it is economically disadvantageous and a post-treatment step is required to remove unreacted inorganic azide.

As the solvent, for example, acetone,
Ketones such as methyl ethyl ketone and methyl isobutyl ketone, alcohols such as methanol, ethanol, propanol and butanol, ethers such as diethyl ether, dioxane, tetrahydrofuran (THF) and ethylene glycol dimethyl ether, organic acids such as acetic acid, propionic acid and butyric acid. , Halogenated hydrocarbons such as dichloroethane, carbon tetrachloride, chloroform, methylene chloride and chlorobenzene, and aromatic hydrocarbons such as benzene, toluene and xylene.

The reaction temperature is usually -50 ° C to 100 ° C,
Preferably -40 ° C to 70 ° C, more preferably -30
It is preferable to set the temperature to 50 ° C. When the temperature is lower than this range, the reaction does not proceed sufficiently, which causes a decrease in yield, which is economically disadvantageous, or the reaction rate is low and it takes a long time to complete the reaction. This may cause problems and is not preferable. Further, if the temperature is higher than this range, decomposition or the like may occur during the reaction, which causes a decrease in yield, which is economically disadvantageous, and a post-treatment step for removing decomposition products and the like. It is not preferable because it puts a load on.

In the production method of the present invention, after the reaction is completed,
To some extent, the reaction solution is concentrated or not concentrated, and then poured into water as it is, and the precipitated product is dried.
Alternatively, the organic layer is separated, washed with water and saturated saline,
The desired acid azide derivative represented by the general formula [I] can be obtained by drying and concentrating.

The general formula [II] which is the starting material for the above reaction

[0024]

[Chemical 10]

[In the formula, Y represents a halogen atom, and R ⁴ represents a lower alkyl group. ] The substituted benzoic acid chloride derivative represented by the following can be produced, for example, by the following route.

That is, according to the production method described in USP-3780027, the general formula [III]

[0027]

[Chemical 11]

[In the formula, Y represents a halogen atom. ] The general formula [IV] produced by reacting 2-fluoro-4-halobenzoic acid represented by

[0029]

[Chemical 12]

[In the formula, Y represents a halogen atom. ] 5-sulfonyl chloride-2-fluoro-4-halobenzoic acid represented by the following as a starting material, according to the method described in 1994 Patent Application No. 280938 already proposed by the present inventors, the general formula [V]

[0031]

[Chemical 13]

[In the formula, R ⁴ represents a lower alkyl group. ]
By reducing in the presence of a lower alkylcarboxylic acid represented by
I]

[0033]

Embedded image

[In the formula, Y represents a halogen atom, and R ⁴ represents a lower alkyl group. ] The substituted benzoic acid derivative shown by these is obtained, By chlorinating this, general formula [II]

[0035]

[Chemical 15]

[In the formula, Y represents a halogen atom, and R ⁴ represents a lower alkyl group. ] The substituted benzoic acid chloride derivative shown by these can be manufactured. The compound of the present invention represented by the general formula [I]

[0037]

Embedded image

[In the formula, Y represents a halogen atom and R ⁴ represents a lower alkyl group. ] The acid azide derivative represented by the following can be derived to an N-acyl-N-phenyltetrahydrophthalamic acid derivative having excellent herbicidal activity by the following route, for example.

That is, the general formula [I]

[0040]

[Chemical 17]

[In the formula, Y represents a halogen atom, and R ⁴ represents a lower alkyl group. ] The acid azide derivative shown by and general formula [VII]

[0042]

Embedded image

[In the formula, R ² represents a lower alkyl group. ]
By reacting with a carboxylic acid anhydride derivative represented by the following formula in the presence of an acid, if necessary.
I]

[0044]

[Chemical 19]

[In the formula, Y represents a halogen atom, and R ² represents a lower alkyl group. ] The imide derivative shown by this, and this and general formula [IX]

[0046]

Embedded image

[In the formula, Hal- represents a chlorine atom or a bromine atom, R ¹ represents -CHR ⁵ CO ₂ R ⁶ (provided that R ⁵ represents a hydrogen atom or a lower alkyl group, and R ⁶ represents a lower alkyl group. Represents.) Represents. ] By reacting with a halocarboxylic acid ester derivative represented by the formula [X]

[0048]

[Chemical 21]

[In the formula, Y represents a halogen atom, R ¹ represents —CHR ⁵ CO ₂ R ⁶ (wherein R ⁵ represents a hydrogen atom or a lower alkyl group, and R ⁶ represents a lower alkyl group). R ² represents a lower alkyl group. ] The anilide derivative represented by the following general formula [] is obtained by reacting it in the presence of a dehydrating chlorinating agent according to the method described in Japanese Patent Application No. 4205 of 1994 already proposed by the present inventors. X
I]

[0050]

[Chemical formula 22]

[In the formula, Y represents a halogen atom, R ¹ represents —CHR ⁵ CO ₂ R ⁶ (wherein R ⁵ represents a hydrogen atom or a lower alkyl group, and R ⁶ represents a lower alkyl group). R ² represents a lower alkyl group. ] The imidoyl chloride derivative shown by this and this and general formula [XII]

[0052]

[Chemical formula 23]

[In the formula, R ³ represents a lower alkoxy group, a lower alkenyloxy group, a lower alkynyloxy group, a lower alkoxyalkoxy group or a lower alkoxycarbonylalkoxy group. ] By reacting with a carboxylic acid derivative represented by the formula [XIII]

[0054]

[Chemical formula 24]

[In the formula, Y represents a halogen atom, R ¹ represents —CHR ⁵ CO ₂ R ⁶ (wherein R ⁵ represents a hydrogen atom or a lower alkyl group, and R ⁶ represents a lower alkyl group). R ² represents a lower alkyl group, R ³ represents a lower alkoxy group, a lower alkenyloxy group, a lower alkynyloxy group, a lower alkoxyalkoxy group or a lower alkoxycarbonylalkoxy group. ] N-acyl-N-phenyl tetrahydrophthalamic acid derivative shown by these can be derived.

N-represented by the above general formula [XIII]
The acyl-N-phenyltetrahydrophthalamic acid derivative has excellent herbicidal activity and is widely applicable to fields, paddy fields, fruit trees, meadows, lawns, forests, non-agricultural lands, etc. On the other hand, it is a compound showing high safety. Therefore, the acid azide derivative which is a novel compound represented by the general formula [I] of the present invention is an N-type compound represented by the general formula [XIII] which is a compound useful as a herbicide.
The compound is useful as an intermediate for the production of an acyl-N-phenyltetrahydrophthalamic acid derivative, and the production method of the present invention can easily produce the acid azide derivative represented by the general formula [I]. It is useful as a manufacturing method.

[0057]

The present invention will be specifically described below with reference to examples and reference examples. Reference Example 1 5-Sulfonyl chloride-4-chloro-2-fluorobenzoate
Production of acid (compound represented by general formula [IV]) 7.2 g of 4-chloro-2-fluorobenzoic acid under ice cooling
(41.4 mmol) was added to 25.0 g of chlorosulfate. Warm to room temperature, react for 30 minutes, then 120
The temperature was raised to ° C and the reaction was carried out for 4 hours. The reaction solution was cooled to room temperature, poured into ice water, and this was extracted twice with 100 ml of ethyl acetate. The extract was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to give a crude product.

The resulting crude product was recrystallized from n-hexane / ethyl acetate to give the desired 5-sulfonyl-4-chloride.
7.4 g of chloro-2-fluorobenzoic acid was obtained. Melting point = 149.0 ° C. to 150.0 ° C. ¹ H-NMR (CDCl ₃ , δ ppm) 7.54 (d, J = 9.7 Hz, 1 H), 8.85
(D, J = 13.0 Hz, 1H), 10.74 (bs,
1H) Reference Example 2 5-acetylthio-4-chloro-2-fluorobenzoic acid
(Compound represented by the general formula [VI]) 7.67 g (28.1 mmol ) of 5-sulfonyl chloride-4-chloro-2-fluorobenzoic acid, 2.20 g of red phosphorus
(70.2 mg atom) and 0.15 g iodine
(0.56 mmol) in 80 ml of acetic acid,
The reaction was performed at 0 ° C to 110 ° C for 3 hours. The reaction solution was cooled to room temperature, unreacted red phosphorus was filtered off, and the filtrate was concentrated,
The residue was poured into ice water, and this was extracted twice with 100 ml of ethyl acetate. The extract was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to give a crude product.

The obtained crude product was recrystallized from n-hexane / ethyl acetate to obtain 6.85 g of desired 5-acetylthio-4-chloro-2-fluorobenzoic acid. Melting point = 140.0 ° C. to 141.5 ° C. ¹ H-NMR (CDCl ₃ , δppm) 2.50 (s, 3H), 7.40 (d, J = 10.1H)
z, 1H), 8.19 (d, J = 7.9Hz, 1H),
11.29 (bs, 1H) Reference Example 3 5-Acetylthio-4-chloro-2-fluorobenzoi
Production of Lucuride (Compound of General Formula [II]) 5-Acetylthio-4-chloro-2-fluorobenzoic acid (6.63 g, 26.7 mmol) was added to thionyl chloride (15 m).
It was mixed in 1 and reacted under heating under reflux for 2 hours. After completion of the reaction, the mixture was cooled to room temperature, volatile components were distilled off, and the residue was n-
Recrystallization from hexane / toluene gave 6.55 g of the desired 5-acetylthio-4-chloro-2-fluorobenzoyl chloride.

Melting point = 66.0 ° C. to 67.0 ° C. ¹ H-NMR (CDCl ₃ , δppm) 2.52 (s, 3H), 7.43 (d, J = 10.1H)
z, 1H), 8.27 (d, J = 7.5 Hz, 1H) Example 1 5-acetylthio-4-chloro-2-fluorobenzoi
Preparation of luazide (compound of general formula [I]) 5.00 g (18.0 mmol ) of 5-acetylthio-4-chloro-2-fluorobenzoyl chloride was dissolved in 25 ml of acetone and cooled to -10 ° C. In this solution,
1.35 g of sodium azide dissolved in 3 ml of water (1
8.7 mmol) was added dropwise at 0 ° C, and after the addition was completed,
The reaction was carried out at 5 ° C for 10 minutes. After the reaction is complete, add 15
25 ml of water was added at a temperature below ℃, the precipitate formed was filtered off,
Washed with water. Dissolve the obtained precipitate in methylene chloride,
The extract was washed with water and saturated saline and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained crude product was recrystallized from n-hexane / ethyl acetate to give the desired 5-acetylthio-4-chloro-2-fluorobenzoyl azide 2.63.
g was obtained as colorless needle crystals.

Melting point = 82.0 ° C. to 83.5 ° C. (deco
mp. ) ¹ H-NMR (CDCl ₃ , δppm) 2.48 (s, 3H), 7.37 (d, J = 10.1H)
z, 1H), 8.09 (d, J = 7.5 Hz, 1H) Reference Example 4 N, N-diacetyl-5-acetylthio-4-chloro-
Preparation of 2-fluoroaniline (Compound of the general formula [VIII]
Compound) 1.00 g of 5-acetylthio-4-chloro-2-fluorobenzoyl azide was mixed in 3.0 ml of acetic anhydride,
After adding 1 drop of concentrated sulfuric acid at room temperature, the mixture was heated to 80 ° C. and reacted for 40 minutes under stirring. After cooling to room temperature, excess acetic anhydride was distilled off under reduced pressure, the residue was poured into cold water, and the mixture was extracted with ethyl acetate. The extract was washed with saturated aqueous sodium hydrogen carbonate solution, water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography with a developing solvent of n-hexane / ethyl acetate to give the desired N, N-diacetyl-5-acetylthio-4-chloro-2-fluoroaniline as a colorless oil. 0.86 g was obtained.

¹ H-NMR (CDCl ₃ , δppm) 2.35 (s, 6H), 2.47 (s, 3H), 7.3
7 (d, J = 7.9 Hz, 1H), 7.42 (d, J =
9.0 Hz, 1 H) Reference Example 5 N, N- dipropionyl -5-propionylthio-4-
Production of chloro-2-fluoroaniline (general formula [VII
Compound of I]) 1.00 g of 5-acetylthio-4-chloro-2-fluorobenzoyl azide is mixed with 3.5 ml of propionic anhydride, and 2 drops of concentrated sulfuric acid is added dropwise at room temperature, and then heated to 90 ° C. Then, the mixture was reacted for 3 hours with stirring. The mixture was cooled to room temperature, excess propionic anhydride was distilled off under reduced pressure, the residue was poured into cold water, and the mixture was extracted with ethyl acetate. The extract was washed with saturated aqueous sodium hydrogen carbonate solution, water and saturated brine, and dried over anhydrous magnesium sulfate. The solvent is distilled off, and the residue is n
-Purified by silica gel column chromatography with a developing solvent of hexane / ethyl acetate to give the desired N, N-dipropionyl-5-propionylthio-4- as a colorless oil.
0.95 g of chloro-2-fluoroaniline was obtained.

¹ H-NMR (CDCl ₃ , δppm) 1.14 (t, J = 7.0 Hz, 6H), 1.25
(T, J = 7.3 Hz, 3 H), 2.68 (q, J =
7.0 Hz, 4H) 2.73 (q, J = 7.3 Hz, 2
H), 7.35 (d, J = 7.9 Hz, 1H), 7.4
0 (d, J = 9.0 Hz, 1H) Reference Example 6 5-acetylamino-2-chloro-4-fluorophenyl
Production of methyl ruthioacetate (compound of general formula [X]) N, N-diacetyl-5-acetylthio-4-chloro-
A solution prepared by mixing 0.81 g of 2-fluoroaniline and 0.61 g of methyl bromoacetate in 10 ml of methanol and dissolving 0.33 g of potassium hydroxide in 2 ml of water was prepared at 15 ° C.
Dropwise at ~ 20 ° C. After completion of the dropping, the mixture was stirred at room temperature for 10 minutes, poured into cold water, and extracted with methylene chloride. The extract was washed with water and saturated saline and then dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was recrystallized from a mixed solvent of n-hexane / ethyl acetate to obtain 0.62 g of the target methyl 5-acetylamino-2-chloro-4-fluorophenylthioacetate.

Melting point = 125.0 ° C. to 126.5 ° C. ¹ H-NMR (CDCl ₃ , δppm) 2.10 (s, 3H), 3.34 (s, 1H), 3.6
5 (s, 3H), 3.89 (s, 2H), 7.56
(D, J = 7.55 Hz, 1H), 8.02 (d, J =
8.1 Hz, 1H) Reference Example 7 5-propionylamino-2-chloro-4-fluorophenyl
Production of methyl phenylthioacetate (compound of general formula [X]) N, N -dipropionyl- 5-propionylthio-4-
0.90 g of chloro-2-fluoroaniline and 0.61 g of methyl bromoacetate were mixed in 10 ml of methanol, and a solution of 0.33 g of potassium hydroxide in 2 ml of water was added dropwise at 15 ° C to 20 ° C. 1 at room temperature after dropping
After stirring for 0 minutes, it was poured into cold water and extracted with methylene chloride. The extract was washed with water and saturated saline and then dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was recrystallized from a mixed solvent of n-hexane / ethyl acetate to give the desired 5
0.52 g of methyl propionylamino-2-chloro-4-fluorophenylthioacetate was obtained.

Melting point = 104.5 ° C. to 105.0 ° C. ¹ H-NMR (CDCl ₃ , δppm) 1.24 (t, J = 7.4 Hz, 3 H), 2.44
(Q, J = 7.4 Hz, 2H), 3.68 (s, 2
H), 3.75 (s, 3H), 7.16 (d, J = 1)
0.3 Hz, 1 H), 7.32 to 7.56 (brs, 1
H), 8.53 (d, J = 8.1 Hz, 1H) Reference Example 8 2- (5 -Acetylamino -2-chloro-4-fluoro)
Preparation of methyl phenylthio) propionate (general formula
Compound of [X]) N, N-diacetyl-5-acetylthio-4-chloro-
0.81 g of 2-fluoroaniline and 0.66 g of methyl 2-bromopropionate were mixed in 10 ml of methanol, and a solution of 0.33 g of potassium hydroxide dissolved in 2 ml of water was added dropwise at 15 ° C to 20 ° C. After completion of dropping, the mixture was stirred at room temperature for 20 minutes, poured into cold water, and extracted with methylene chloride. The extract was washed with water and saturated saline and then dried over anhydrous magnesium sulfate. The solvent was distilled off, and the residue was n-
Recrystallization from a hexane / ethyl acetate mixed solvent gave 0.64 g of the target methyl 2- (5-acetylamino-2-chloro-4-fluorophenylthio) propionate.

Melting point = 80.5 ° C. to 81.0 ° C. ¹ H-NMR (CDCl ₃ , δppm) 1.26 (d, J = 7.0 Hz, 3 H), 2.22
(S, 3H), 3.71 (s, 3H), 3.85 (q,
J = 7.25 Hz, 1H), 7.26 (d, J = 11.1.
55 Hz, 1 H), 7.20 to 7.44 (brs, 1
H), 8.57 (d, J = 8.0 Hz, 1H) Reference Example 9 N- (4-chloro-2-fluoro-5-methoxycarbo)
Nylmethylthiophenyl) -acetimidoyl chloride
(Compound represented by the general formula [XI]) 10 g (34.3 mmol) of methyl 5-acetylamino-2-chloro-4-fluorophenylthioacetate and 7.14 g (34.3 mmol) of phosphorus pentachloride in 250 ml. It was suspended in benzene, heated to 60 ° C., and stirred for 1 hour.
After the reaction, the reaction solution was concentrated under reduced pressure to quantitatively obtain N- (4-chloro-2-fluoro-5-methoxycarbonylmethylthiophenyl) -acetimidoyl chloride as an oil.

Reference Example 10 N-acetyl-N- (4-chloro-2-fluoro-5-
Methoxycarbonylmethylthiophenyl) -3,4
Manufacture of 5,6-tetrahydrophthalamic acid methyl ester
Preparation ( Compound represented by the general formula [XIII]) N- (4-chloro-2-fluoro-5-methoxycarbonylmethylthiophenyl) -acetimidoyl chloride 10.6 g (34.3 mmol), 3,4,5, 6.95 g of 6-tetrahydrophthalamic acid monomethyl ester
(37.7 mmol) was dissolved in 50 ml of benzene, and 4.16 g of triethylamine dissolved in 10 ml of benzene.
(41.2 mmol) was added dropwise at 10 ° C or lower. After dropping, the mixture was stirred at 60 ° C. for 3 hours. After allowing to cool, it was washed with water and saturated saline and then dried over anhydrous magnesium sulfate. The solvent was concentrated to give crystals. Recrystallize from methanol,
5.09 g of N-acetyl-N- (4-chloro-2-fluoro-5-methoxycarbonylmethylthiophenyl)
-3,4,5,6-Tetrahydrophthalamic acid methyl ester was obtained.

[0068]

INDUSTRIAL APPLICABILITY The acid azide derivative represented by the general formula [I] of the present invention is a compound useful as a herbicide such as N-acyl-N-phenyltetrahydrophthalamic acid derivative which is useful as a herbicide. The compound is useful as a production intermediate, and the acid azide derivative represented by the general formula [I] can be easily produced by the production method of the present invention.

Claims (5)

[Claims] 1. A compound represented by the general formula [I]: [In the formula, Y represents a halogen atom, and R ⁴ represents a lower alkyl group. ] The novel acid azide derivative shown by these. 2. The novel acid azide derivative according to claim 1, wherein the acid azide derivative represented by the general formula [I] is 5-acetylthio-4-chloro-2-fluorobenzoyl azide. 3. A compound represented by the general formula [II]: [In the formula, Y represents a halogen atom, and R ⁴ represents a lower alkyl group. ] The substituted benzoic acid chloride derivative represented by the formula [I] [In the formula, Y represents a halogen atom, and R ⁴ represents a lower alkyl group. ] The manufacturing method of the novel acid azide derivative shown by these. 4. The process for producing a novel acid azide derivative according to claim 3, wherein the acid azide derivative represented by the general formula [I] is 5-acetylthio-4-chloro-2-fluorobenzoyl azide. 5. The method for producing a novel acid azide derivative according to claim 3 or 4, wherein the inorganic azide is sodium azide.