JPH09227504A - N-phenyltetrahydrophthalamic acid derivative, its production and herbicide containing the same as active ingredient - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new N-phenyltetrahydrophthalamic acid derivative which has excellent herbicidal activity and is broadly applicable to crop fields, paddy fields, orchards, in addition, uncultivated fields and is useful as a herbicide with high safety to crop plants. SOLUTION: This phthalamic acid derivative is represented by formula I (X and Y are each a halogen; R<1> is a lower alkylthio; R<2> is a lower alkyl; R<3> is a lower alkoxy), typically methyl N-acetyl-N-[4-chloro-2-fluoro-5-(1-methyl- propargylthio)phenyl]-3,4,5,6-tetrahydro-phthalamate. The compound of formula I is prepared to a herbicide in the form of a wettable powder, granules or an emulsion. The compound of formula II is prepared by reaction of a imiyl chloride derivative with a carboxylic acid of formula III in the presence of an acid acceptor or with an alkali metal salt of carboxylic acid of formula IV. Further, a compound of formula II is obtained by dehydrochlorination reaction of an aniline derivative.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a herbicide, more specifically a novel compound represented by the general formula [I]

[0002]

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(Wherein X and Y independently represent a halogen atom, R ¹ represents a lower alkylthio group, a lower alkenylthio group, a lower alkynylthio group, R ² represents a lower alkyl group, a halogenated lower alkyl group, It represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted pyridyl group or a substituted or unsubstituted thienyl group, and R ³ represents a lower alkoxy group, a lower alkenyloxy group, a lower alkynyloxy group or a lower alkoxyalkoxy group. )
N-phenyltetrahydrophthalamic acid derivative represented by the following, a method for producing the same, a herbicide containing the same as an active ingredient, and a general intermediate [II] which is an intermediate for the production.

[0004]

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(Wherein X and Y independently represent a halogen atom, R ¹ represents a lower alkylthio group, a lower alkenylthio group, a lower alkynylthio group, R ² represents a lower alkyl group, a halogenated lower alkyl group, And a substituted or unsubstituted phenyl group, a substituted or unsubstituted pyridyl group or a substituted or unsubstituted thienyl group.) And a method for producing the same. INDUSTRIAL APPLICABILITY The N-phenyltetrahydrophthalamic acid derivative of the present invention has excellent herbicidal activity and is useful as a herbicide that can be widely applied to fields, paddy fields, orchards, meadows, lawns, forests or non-agricultural lands. It is also highly safe for crops.

[0006]

The herbicidal activity of tetrahydrophthalamic acid derivatives has long been well known,
For example, N- (4'-chlorophenyl) -3,4,5,6-tetrahydrophthalamic acid methyl ester disclosed in JP-A-48-44425 is known.

However, the conventional herbicidal activity of tetrahydrophthalamic acid derivatives is not always sufficient, or the herbicidal spectrum against weeds is greatly limited,
In addition, the selectivity between crops and weeds is not sufficient, and there is a problem with crop safety.

The present invention solves the above-mentioned conventional problems, has a novel herbicidal activity, and is highly safe for crops, a method for producing the same, and a novel compound as an active ingredient. It is an object of the present invention to provide a herbicide contained therein, a production intermediate thereof, and a production method thereof.

[0009]

The inventors of the present invention have found that a novel tetrahydrophthalamic acid derivative having a specific acyl substituent on the amide nitrogen atom has extremely excellent herbicidal activity, selectivity and herbicidal spectrum. Has already been proposed [USP / 5,292,922]. Based on this, as a result of further intensive studies, the following invention was completed.

That is, the first aspect of the present invention is to formula [I]

[0011]

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(Wherein X and Y independently represent a halogen atom, R ¹ represents a lower alkylthio group, a lower alkenylthio group, a lower alkynylthio group, R ² represents a lower alkyl group, a halogenated lower alkyl group, It represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted pyridyl group or a substituted or unsubstituted thienyl group, and R ³ represents a lower alkoxy group, a lower alkenyloxy group, a lower alkynyloxy group or a lower alkoxyalkoxy group. )
Is an N-phenyltetrahydrophthalamic acid derivative represented by

The second aspect of the present invention is to formula [I]

[0014]

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(Wherein X and Y independently represent a halogen atom, R ¹ represents a lower alkylthio group, a lower alkenylthio group, a lower alkynylthio group, R ² represents a lower alkyl group, a halogenated lower alkyl group, It represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted pyridyl group or a substituted or unsubstituted thienyl group, and R ³ represents a lower alkoxy group, a lower alkenyloxy group, a lower alkynyloxy group or a lower alkoxyalkoxy group. )
It is a herbicide characterized by containing the N-phenyl tetrahydrophthalamic acid derivative shown by these as an active ingredient.

The third aspect of the present invention is to formula [II]

[0017]

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(Wherein X and Y independently represent a halogen atom, R ¹ represents a lower alkylthio group, a lower alkenylthio group, a lower alkynylthio group, R ² represents a lower alkyl group, a halogenated lower alkyl group, And a substituted or unsubstituted phenyl group, a substituted or unsubstituted pyridyl group or a substituted or unsubstituted thienyl group), and a general formula [III]

[0019]

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(Wherein R ³ represents a lower alkoxy group, a lower alkenyloxy group, a lower alkynyloxy group or a lower alkoxyalkoxy group) and the carboxylic acids are reacted in the presence of a deoxidizing agent. Characteristic general formula [I]

[0021]

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(Wherein, X and Y independently represent a halogen atom, R ¹ represents a lower alkylthio group, a lower alkenylthio group, a lower alkynylthio group, R ² represents a lower alkyl group, a halogenated lower alkyl group, It represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted pyridyl group or a substituted or unsubstituted thienyl group, and R ³ represents a lower alkoxy group, a lower alkenyloxy group, a lower alkynyloxy group or a lower alkoxyalkoxy group. )
Is a method for producing an N-phenyltetrahydrophthalamic acid derivative represented by

The fourth aspect of the present invention is to formula [II]

[0024]

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(Wherein X and Y independently represent a halogen atom, R ¹ represents a lower alkylthio group, a lower alkenylthio group, a lower alkynylthio group, R ² represents a lower alkyl group, a halogenated lower alkyl group, And a substituted or unsubstituted phenyl group, a substituted or unsubstituted pyridyl group or a substituted or unsubstituted thienyl group.), And an imidoyl chloride derivative represented by the general formula [IV]

[0026]

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(Wherein R ³ represents a lower alkoxy group, a lower alkenyloxy group, a lower alkynyloxy group or a lower alkoxyalkoxy group, and M represents an alkali metal), and an alkali metal salt of a carboxylic acid. General formula [I] characterized by reacting

[0028]

[Chemical 21]

(Wherein X and Y independently represent a halogen atom, R ¹ represents a lower alkylthio group, a lower alkenylthio group, a lower alkynylthio group, R ² represents a lower alkyl group, a halogenated lower alkyl group, It represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted pyridyl group or a substituted or unsubstituted thienyl group, and R ³ represents a lower alkoxy group, a lower alkenyloxy group, a lower alkynyloxy group or a lower alkoxyalkoxy group. )
Is a method for producing an N-phenyltetrahydrophthalamic acid derivative represented by

The fifth aspect of the present invention is to formula [II]

[0031]

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(Wherein X and Y independently represent a halogen atom, R ¹ represents a lower alkylthio group, a lower alkenylthio group, a lower alkynylthio group, R ² represents a lower alkyl group, a halogenated lower alkyl group, It represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted pyridyl group, or a substituted or unsubstituted thienyl group.).

Further, the sixth aspect of the present invention is the general formula [V]

[0034]

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(Wherein, X and Y independently represent a halogen atom, R ¹ represents a lower alkylthio group, a lower alkenylthio group, a lower alkynylthio group, R ² represents a lower alkyl group, a halogenated lower alkyl group, A substituted or unsubstituted phenyl group, a substituted or unsubstituted pyridyl group, or a substituted or unsubstituted thienyl group) is reacted in the presence of a dehydrating chlorinating agent. [II]

[0036]

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(Wherein, X and Y independently represent a halogen atom, R ¹ represents a lower alkylthio group, a lower alkenylthio group, a lower alkynylthio group, R ² represents a lower alkyl group, a halogenated lower alkyl group, It represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted pyridyl group or a substituted or unsubstituted thienyl group.).

The compound of the present invention, N-phenyltetra
As a specific example of the hydrophthalamic acid derivative [I]
Is, for example, N-acetyl-N- (4-chloro-2-phenyl).
Luoro-5-methylthiophenyl) -3,4,5,6-
Tetrahydrophthalamic acid methyl ester, N-acetyl
Le-N- (4-chloro-2-fluoro-5-methylthio
Phenyl) -3,4,5,6-tetrahydrophthalamine
Acid ethyl ester, N-acetyl-N- (4-chloro-
2-Fluoro-5-methylthiophenyl) -3,4
5,6-Tetrahydrophthalamic acid allyl ester, N
-Acetyl-N- (4-chloro-2-fluoro-5-me
Tylthiophenyl) -3,4,5,6-tetrahydrof
Taramic acid propargyl ester, N-acetyl-N-
(4-chloro-2-fluoro-5-methylthiophene
) -3,4,5,6-Tetrahydrophthalamic acid meth
Xymethyl ester, N-acetyl-N- (4-chloro
-2-Fluoro-5-methylthiophenyl) -3,4
5,6-Tetrahydrophthalamic acid ethoxymethyl ester
Ter, N- (2-chloroacetyl) -N- (4-chloro
-2-Fluoro-5-methylthiophenyl) -3,4
5,6-Tetrahydrophthalamic acid methyl ester, N
-(2-chloroacetyl) -N- (4-chloro-2-phenyl)
Luoro-5-methylthiophenyl) -3,4,5,6-
Tetrahydrophthalamic acid ethyl ester, N- (2-
Chloroacetyl) -N- (4-chloro-2-fluoro-
5-methylthiophenyl) -3,4,5,6-tetrahi
Drophthalamic acid allyl ester, N- (2-chloroacetic acid
Cetyl) -N- (4-chloro-2-fluoro-5-methyl
Ruthiophenyl) -3,4,5,6-tetrahydrophthal
Laminic acid propargyl ester, N- (2-chloroacetate
Tyl) -N- (4-chloro-2-fluoro-5-methyl
Thiophenyl) -3,4,5,6-tetrahydrophthala
Mic acid methoxymethyl ester, N- (2-chloroacetate
Tyl) -N- (4-chloro-2-fluoro-5-methyl
Thiophenyl) -3,4,5,6-tetrahydrophthala
Mic acid ethoxymethyl ester, N-benzoyl-N-
(4-chloro-2-fluoro-5-methylthiophene
) -3,4,5,6-Tetrahydrophthalamic acid methyl ester
Ester, N-benzoyl-N- (4-chloro-2-
Fluoro-5-methylthiophenyl) -3,4,5,6
-Tetrahydrophthalamic acid ethyl ester, N-ben
Zoyl-N- (4-chloro-2-fluoro-5-methyl
Thiophenyl) -3,4,5,6-tetrahydrophthala
Mic acid allyl ester, N-benzoyl-N- (4-qua
Loro-2-fluoro-5-methylthiophenyl) -3,
Propargyl 4,5,6-tetrahydrophthalamic acid
Stell, N-benzoyl-N- (4-chloro-2-fur
Oro-5-methylthiophenyl) -3,4,5,6-te
Trahydrophthalamic acid methoxymethyl ester, N-
Benzoyl-N- (4-chloro-2-fluoro-5-me
Tylthiophenyl) -3,4,5,6-tetrahydrof
Taramic acid ethoxymethyl ester, N- (4-chloro
-2-Fluoro-5-methylthiophenyl) -N-nico
Tinyl-3,4,5,6-tetrahydrophthalamic acid
Chill ester, N- (4-chloro-2-fluoro-5-
Methylthiophenyl) -N-nicotinyl-3,4,5,5
6-Tetrahydrophthalamic acid ethyl ester, N-
(4-chloro-2-fluoro-5-methylthiophene
R) -N-nicotinyl-3,4,5,6-tetrahydro
Phthalamic acid allyl ester, N- (4-chloro-2-
Fluoro-5-methylthiophenyl) -N-nicotinyl
-3,4,5,6-Tetrahydrophthalamic acid propal
Gilester, N- (4-chloro-2-fluoro-5-
Methylthiophenyl) -N-nicotinyl-3,4,5,5
6-Tetrahydrophthalamic acid methoxymethyl ester
L, N- (4-chloro-2-fluoro-5-methylthio
Phenyl) -N-nicotinyl-3,4,5,6-tetra
Hydrophthalamic acid ethoxymethyl ester, N- (4
-Chloro-2-fluoro-5-methylthiophenyl)-
N- (3-thiophenecarboxy) -3,4,5,6-
Tetrahydrophthalamic acid methyl ester, N- (4-
Chloro-2-fluoro-5-methylthiophenyl) -N
-(3-Thiophenecarboxy) -3,4,5,6-te
Trahydrophthalamic acid ethyl ester, N- (4-qua
Rolo-2-fluoro-5-methylthiophenyl) -N-
(3-Thiophenecarboxy) -3,4,5,6-teto
Lahydrophthalamic acid allyl ester, N- (4-chloro
Rho-2-fluoro-5-methylthiophenyl) -N-
(3-Thiophenecarboxy) -3,4,5,6-teto
Lahydrophthalamic acid propargyl ester, N- (4
-Chloro-2-fluoro-5-methylthiophenyl)-
N- (3-thiophenecarboxy) -3,4,5,6-
Tetrahydrophthalamic acid methoxymethyl ester, N
-(4-chloro-2-fluoro-5-methylthiophene
) -N- (3-thiophenecarboxy) -3,4
5,6-Tetrahydrophthalamic acid ethoxymethyl ester
Ter, N-acetyl-N- (4-chloro-2-fluoro
-5-ethylthiophenyl) -3,4,5,6-tetra
Hydrophthalamic acid methyl ester, N-acetyl-N
-(4-chloro-2-fluoro-5-ethylthiophene
Ethyl) -3,4,5,6-tetrahydrophthalamic acid
Ester, N-acetyl-N- (4-chloro-2-phenyl)
Luoro-5-ethylthiophenyl) -3,4,5,6-
Tetrahydrophthalamic acid allyl ester, N-acetyl
Le-N- (4-chloro-2-fluoro-5-ethylthio
Phenyl) -3,4,5,6-tetrahydrophthalamine
Acid propargyl ester, N-acetyl-N- (4-qua
Loro-2-fluoro-5-ethylthiophenyl) -3,
Methoxymethyl 4,5,6-tetrahydrophthalamate
Ester, N-acetyl-N- (4-chloro-2-fur
Oro-5-ethylthiophenyl) -3,4,5,6-te
Trahydrophthalamic acid ethoxymethyl ester, N-
(2-chloroacetyl) -N- (4-chloro-2-full
Oro-5-ethylthiophenyl) -3,4,5,6-te
Trahydrophthalamic acid methyl ester, N- (2-
Loloacetyl) -N- (4-chloro-2-fluoro-5
-Ethylthiophenyl) -3,4,5,6-tetrahydr
Loftalamic acid ethyl ester, N- (2-chloroacetate
Chill) -N- (4-chloro-2-fluoro-5-ethyl
Thiophenyl) -3,4,5,6-tetrahydrophthala
Mic acid allyl ester, N- (2-chloroacetyl)-
N- (4-chloro-2-fluoro-5-ethylthiophene
Nyl) -3,4,5,6-tetrahydrophthalamic acid
Lopargyl ester, N- (2-chloroacetyl) -N
-(4-chloro-2-fluoro-5-ethylthiophene
) -3,4,5,6-Tetrahydrophthalamic acid meth
Xymethyl ester, N- (2-chloroacetyl) -N
-(4-chloro-2-fluoro-5-ethylthiophene
) -3,4,5,6-Tetrahydrophthalamic acid eth
Xymethyl ester, N-benzoyl-N- (4-chloro
2--2-fluoro-5-ethylthiophenyl) -3,
Methyl 4,5,6-tetrahydrophthalamic acid ester
, N-benzoyl-N- (4-chloro-2-fluoro
-5-ethylthiophenyl) -3,4,5,6-tetra
Hydrophthalamic acid ethyl ester, N-benzoyl-
N- (4-chloro-2-fluoro-5-ethylthiophene
Nyl) -3,4,5,6-tetrahydrophthalamic acid
Ryl ester, N-benzoyl-N- (4-chloro-2
-Fluoro-5-ethylthiophenyl) -3,4,5,
6-tetrahydrophthalamic acid propargyl ester,
N-benzoyl-N- (4-chloro-2-fluoro-5
-Ethylthiophenyl) -3,4,5,6-tetrahydr
Loftalamic acid methoxymethyl ester, N-benzoi
Le-N- (4-chloro-2-fluoro-5-ethylthio
Phenyl) -3,4,5,6-tetrahydrophthalamine
Acid ethoxymethyl ester, N- (4-chloro-2-phenyl)
Luoro-5-ethylthiophenyl) -N-nicotinyl-
Methyl ethene 3,4,5,6-tetrahydrophthalamate
Tell, N- (4-chloro-2-fluoro-5-ethylthio
Ophenyl) -N-nicotinyl-3,4,5,6-teto
Lahydrophthalamic acid ethyl ester, N- (4-chloro
R-2-fluoro-5-ethylthiophenyl) -N-ni
Cotinyl-3,4,5,6-tetrahydrophthalamic acid
Allyl ester, N- (4-chloro-2-fluoro-5
-Ethylthiophenyl) -N-nicotinyl-3,4,
5,6-Tetrahydrophthalamic acid propargyl ester
L, N- (4-chloro-2-fluoro-5-ethylthio
Phenyl) -N-nicotinyl-3,4,5,6-tetra
Hydrophthalamic acid methoxymethyl ester, N- (4
-Chloro-2-fluoro-5-ethylthiophenyl)-
N-nicotinyl-3,4,5,6-tetrahydrophthala
Mic acid ethoxymethyl ester, N- (4-chloro-2
-Fluoro-5-ethylthiophenyl) -N- (3-thi
Offencarboxy) -3,4,5,6-tetrahydro
Phthalamic acid methyl ester, N- (4-chloro-2-
Fluoro-5-ethylthiophenyl) -N- (3-thio
Fencarboxy) -3,4,5,6-tetrahydrof
Taramic acid ethyl ester, N- (4-chloro-2-phenyl)
Luoro-5-ethylthiophenyl) -N- (3-thiof)
Encarboxy) -3,4,5,6-tetrahydrophthal
Lamic acid allyl ester, N- (4-chloro-2-fur
Oro-5-ethylthiophenyl) -N- (3-thiophene
Carboxy) -3,4,5,6-tetrahydrophthala
Minic acid propargyl ester, N- (4-chloro-2-
Fluoro-5-ethylthiophenyl) -N- (3-thio
Fencarboxy) -3,4,5,6-tetrahydrof
Taramic acid methoxymethyl ester, N- (4-chloro
-2-Fluoro-5-ethylthiophenyl) -N- (3
-Thiophenecarboxy) -3,4,5,6-tetrahi
Drophthalamic acid ethoxymethyl ester, N-acetyl
Le-N- (4-chloro-2-fluoro-5-allylthio
Phenyl) -3,4,5,6-tetrahydrophthalamine
Acid methyl ester, N-acetyl-N- (4-chloro-
2-Fluoro-5-allylthiophenyl) -3,4
5,6-Tetrahydrophthalamic acid ethyl ester, N
-Acetyl-N- (4-chloro-2-fluoro-5-a
Rylthiophenyl) -3,4,5,6-tetrahydrof
Talamic acid allyl ester, N-acetyl-N- (4-
Chloro-2-fluoro-5-allylthiophenyl)-
3,4,5,6-Tetrahydrophthalamic acid propargy
Ester, N-acetyl-N- (4-chloro-2-phenyl)
Luoro-5-allylthiophenyl) -3,4,5,6-
Tetrahydrophthalamic acid methoxymethyl ester, N
-Acetyl-N- (4-chloro-2-fluoro-5-a
Rylthiophenyl) -3,4,5,6-tetrahydrof
Taramic acid ethoxymethyl ester, N- (2-chloro
Acetyl) -N- (4-chloro-2-fluoro-5-a
Rylthiophenyl) -3,4,5,6-tetrahydrof
Taramic acid methyl ester, N- (2-chloroacetyl
) -N- (4-chloro-2-fluoro-5-allylthio)
Ophenyl) -3,4,5,6-tetrahydrophthalami
Acid ethyl ester, N- (2-chloroacetyl) -N
-(4-chloro-2-fluoro-5-allylthiophene
) -3,4,5,6-Tetrahydrophthalamic acid ant
Ester, N- (2-chloroacetyl) -N- (4-
Chloro-2-fluoro-5-allylthiophenyl)-
3,4,5,6-Tetrahydrophthalamic acid propargy
Ester, N- (2-chloroacetyl) -N- (4-
Chloro-2-fluoro-5-allylthiophenyl)-
Methoxyme 3,4,5,6-tetrahydrophthalamic acid
Chill ester, N- (2-chloroacetyl) -N- (4
-Chloro-2-fluoro-5-allylthiophenyl)-
Ethoxyme 3,4,5,6-tetrahydrophthalamic acid
Tyl ester, N-benzoyl-N- (4-chloro-2
-Fluoro-5-allylthiophenyl) -3,4,5,
6-Tetrahydrophthalamic acid methyl ester, N-be
Nzoyl-N- (4-chloro-2-fluoro-5-ari
Ruthiophenyl) -3,4,5,6-tetrahydrophthal
Lamic acid ethyl ester, N-benzoyl-N- (4-
Chloro-2-fluoro-5-allylthiophenyl)-
Allyl 3,3,4,5,6-tetrahydrophthalamic acid
Ter, N-benzoyl-N- (4-chloro-2-fluor
Lo-5-allylthiophenyl) -3,4,5,6-teto
Lahydrophthalamic acid propargyl ester, N-ben
Zoyl-N- (4-chloro-2-fluoro-5-allyl
Thiophenyl) -3,4,5,6-tetrahydrophthala
Mic acid methoxymethyl ester, N-benzoyl-N-
(4-chloro-2-fluoro-5-allylthiophene
) -3,4,5,6-Tetrahydrophthalamic acid eth
Xymethyl ester, N- (4-chloro-2-fluoro
-5-allylthiophenyl) -N-nicotinyl-3,
Methyl 4,5,6-tetrahydrophthalamic acid ester
L, N- (4-chloro-2-fluoro-5-allylthio
Phenyl) -N-nicotinyl-3,4,5,6-tetra
Hydrophthalamic acid ethyl ester, N- (4-chloro
-2-Fluoro-5-allylthiophenyl) -N-nico
Tinyl-3,4,5,6-tetrahydrophthalamic acid
Ryl ester, N- (4-chloro-2-fluoro-5-
Allylthiophenyl) -N-nicotinyl-3,4,5,5
6-tetrahydrophthalamic acid propargyl ester,
N- (4-chloro-2-fluoro-5-allylthiophene
Nyl) -N-nicotinyl-3,4,5,6-tetrahydr
Loftalamic acid methoxymethyl ester, N- (4-qua
Rolo-2-fluoro-5-allylthiophenyl) -N-
Nicotinyl-3,4,5,6-tetrahydrophthalamine
Acid ethoxymethyl ester, N- (4-chloro-2-phenyl)
Luoro-5-allylthiophenyl) -N- (3-thiof)
Encarboxy) -3,4,5,6-tetrahydrophthal
Lamic acid methyl ester, N- (4-chloro-2-fur
Oro-5-allylthiophenyl) -N- (3-thiophene
Carboxy) -3,4,5,6-tetrahydrophthala
Minic acid ethyl ester, N- (4-chloro-2-fluor
Lo-5-allylthiophenyl) -N- (3-thiophene
Carboxy) -3,4,5,6-tetrahydrophthalamide
Acid allyl ester, N- (4-chloro-2-fluoro
-5-allylthiophenyl) -N- (3-thiophena)
Ruboxi) -3,4,5,6-tetrahydrophthalamine
Acid propargyl ester, N- (4-chloro-2-fur
Oro-5-allylthiophenyl) -N- (3-thiophene
Carboxy) -3,4,5,6-tetrahydrophthala
Mic acid methoxymethyl ester, N- (4-chloro-2
-Fluoro-5-allylthiophenyl) -N- (3-thi
Offencarboxy) -3,4,5,6-tetrahydro
Phthalamic acid ethoxymethyl ester, N-acetyl-
N- (4-chloro-2-fluoro-5-propargylchi
Ophenyl) -3,4,5,6-tetrahydrophthalami
Acid methyl ester, N-acetyl-N- (4-chloro
-2-Fluoro-5-propargylthiophenyl)-
Ethyl 3,4,5,6-tetrahydrophthalamate
Ter, N-acetyl-N- (4-chloro-2-fluoro
-5-propargylthiophenyl) -3,4,5,6-
Tetrahydrophthalamic acid allyl ester, N-acetyl
Le-N- (4-chloro-2-fluoro-5-propargy
Ruthiophenyl) -3,4,5,6-tetrahydrophthal
Laminic acid propargyl ester, N-acetyl-N-
(4-chloro-2-fluoro-5-propargyl thiof
Phenyl) -3,4,5,6-tetrahydrophthalamic acid
Methoxymethyl ester, N-acetyl-N- (4-
Lolo-2-fluoro-5-propargylthiophenyl)
-3,4,5,6-Tetrahydrophthalamic acid ethoxy
Methyl ester, N- (2-chloroacetyl) -N-
(4-chloro-2-fluoro-5-propargyl thiof
Phenyl) -3,4,5,6-tetrahydrophthalamic acid
Methyl ester, N- (2-chloroacetyl) -N-
(4-chloro-2-fluoro-5-propargyl thiof
Phenyl) -3,4,5,6-tetrahydrophthalamic acid
Ethyl ester, N- (2-chloroacetyl) -N-
(4-chloro-2-fluoro-5-propargyl thiof
Phenyl) -3,4,5,6-tetrahydrophthalamic acid
Allyl ester, N- (2-chloroacetyl) -N-
(4-chloro-2-fluoro-5-propargyl thiof
Phenyl) -3,4,5,6-tetrahydrophthalamic acid
Propargyl ester, N- (2-chloroacetyl)-
N- (4-chloro-2-fluoro-5-propargylchi
Ophenyl) -3,4,5,6-tetrahydrophthalami
Acid methoxymethyl ester, N- (2-chloroacetyl
) -N- (4-chloro-2-fluoro-5-propal
Gilthiophenyl) -3,4,5,6-tetrahydrof
Taramic acid ethoxymethyl ester, N-benzoyl-
N- (4-chloro-2-fluoro-5-propargylchi
Ophenyl) -3,4,5,6-tetrahydrophthalami
Acid methyl ester, N-benzoyl-N- (4-chloro
Rho-2-fluoro-5-propargylthiophenyl)-
Ethyl 3,4,5,6-tetrahydrophthalamate
Ter, N-benzoyl-N- (4-chloro-2-fluor
Lo-5-propargylthiophenyl) -3,4,5,6
-Tetrahydrophthalamic acid allyl ester, N-ben
Zoyl-N- (4-chloro-2-fluoro-5-propa
Rugylthiophenyl) -3,4,5,6-tetrahydro
Phthalamic acid propargyl ester, N-benzoyl-
N- (4-chloro-2-fluoro-5-propargylchi
Ophenyl) -3,4,5,6-tetrahydrophthalami
Acid methoxymethyl ester, N-benzoyl-N-
(4-chloro-2-fluoro-5-propargyl thiof
Phenyl) -3,4,5,6-tetrahydrophthalamic acid
Ethoxymethyl ester, N- (4-chloro-2-fur
Oro-5-propargylthiophenyl) -N-nicotini
Methyl ru-3,4,5,6-tetrahydrophthalamate
Ester, N- (4-chloro-2-fluoro-5-pro
Pargylthiophenyl) -N-nicotinyl-3,4
5,6-Tetrahydrophthalamic acid ethyl ester, N
-(4-chloro-2-fluoro-5-propargylthio
Phenyl) -N-nicotinyl-3,4,5,6-tetra
Hydrophthalamic acid allyl ester, N- (4-chloro
-2-Fluoro-5-propargylthiophenyl) -N
-Nicotinyl-3,4,5,6-tetrahydrophthalamide
Acid propargyl ester, N- (4-chloro-2-phenyl)
Luoro-5-propargylthiophenyl) -N-nicoti
Nyl-3,4,5,6-tetrahydrophthalamic acid meth
Xymethyl ester, N- (4-chloro-2-fluoro
-5-propargylthiophenyl) -N-nicotinyl-
Ethoxyme 3,4,5,6-tetrahydrophthalamic acid
Chill ester, N- (4-chloro-2-fluoro-5-
Propargylthiophenyl) -N- (3-thiophena)
Ruboxi) -3,4,5,6-tetrahydrophthalamine
Acid methyl ester, N- (4-chloro-2-fluoro-
5-propargylthiophenyl) -N- (3-thiophene
Carboxy) -3,4,5,6-tetrahydrophthala
Minic acid ethyl ester, N- (4-chloro-2-fluor
Ro-5-propargylthiophenyl) -N- (3-thio
Fencarboxy) -3,4,5,6-tetrahydrof
Thallamic acid allyl ester, N- (4-chloro-2-phenyl)
Luoro-5-propargylthiophenyl) -N- (3-
Thiophenecarboxy) -3,4,5,6-tetrahydr
Loftalamic acid propargyl ester, N- (4-chloro
Rho-2-fluoro-5-propargylthiophenyl)-
N- (3-thiophenecarboxy) -3,4,5,6-
Tetrahydrophthalamic acid methoxymethyl ester, N
-(4-chloro-2-fluoro-5-propargylthio
Phenyl) -N- (3-thiophenecarboxy) -3,
Ethoxymethyl 4,5,6-tetrahydrophthalamate
Ester, N-acetyl-N- [4-chloro-2-fur
Oro-5- (1-methylpropargylthio) phenyl]
Methyl ether of -3,4,5,6-tetrahydrophthalamic acid
Stell, N-acetyl-N- [4-chloro-2-fluor
Lo-5- (1-methylpropargylthio) phenyl]-
Ethyl 3,4,5,6-tetrahydrophthalamate
Tell, N-acetyl-N- [4-chloro-2-fluoro
-5- (1-Methylpropargylthio) phenyl]-
Allyl 3,3,4,5,6-tetrahydrophthalamic acid
Tell, N-acetyl-N- [4-chloro-2-fluoro
-5- (1-Methylpropargylthio) phenyl]-
3,4,5,6-Tetrahydrophthalamic acid propargy
Ester, N-acetyl-N- [4-chloro-2-phenyl
Luoro-5- (1-methylpropargylthio) pheny
]]-3,4,5,6-Tetrahydrophthalamic acid meth
Xymethyl ester, N-acetyl-N- [4-chloro
-2-Fluoro-5- (1-methylpropargylthio)
Phenyl] -3,4,5,6-tetrahydrophthalamine
Acid ethoxymethyl ester, N- (2-chloroacetyl
) -N- [4-chloro-2-fluoro-5- (1-me
Cylpropargylthio) phenyl] -3,4,5,6-
Tetrahydrophthalamic acid methyl ester, N- (2-
Chloroacetyl) -N- [4-chloro-2-fluoro-
5- (1-methylpropargylthio) phenyl] -3,
Ethyl 4,5,6-tetrahydrophthalamate
L, N- (2-chloroacetyl) -N- [4-chloro-
2-Fluoro-5- (1-methylpropargylthio) fur
[Ethenyl] -3,4,5,6-tetrahydrophthalamic acid
Allyl ester, N- (2-chloroacetyl) -N-
[4-chloro-2-fluoro-5- (1-methylpropa
Rugylthio) phenyl] -3,4,5,6-tetrahydr
Loftalamic acid propargyl ester, N- (2-chloro
L-acetyl) -N- [4-chloro-2-fluoro-5-
(1-Methylpropargylthio) phenyl] -3,4
Methoxymethyl 5,6-tetrahydrophthalamic acid
Ter, N- (2-chloroacetyl) -N- [4-chloro
-2-Fluoro-5- (1-methylpropargylthio)
Phenyl] -3,4,5,6-tetrahydrophthalamine
Acid ethoxymethyl ester, N-benzoyl-N- [4
-Chloro-2-fluoro-5- (1-methylpropargy
Luthio) phenyl] -3,4,5,6-tetrahydrof
Taramic acid methyl ester, N-benzoyl-N- [4
-Chloro-2-fluoro-5- (1-methylpropargy
Luthio) phenyl] -3,4,5,6-tetrahydrof
Taramic acid ethyl ester, N-benzoyl-N- [4
-Chloro-2-fluoro-5- (1-methylpropargy
Luthio) phenyl] -3,4,5,6-tetrahydrof
Thallamic acid allyl ester, N-benzoyl-N- [4
-Chloro-2-fluoro-5- (1-methylpropargy
Luthio) phenyl] -3,4,5,6-tetrahydrof
Taramic acid propargyl ester, N-benzoyl-N
-[4-chloro-2-fluoro-5- (1-methylpro
Pargylthio) phenyl] -3,4,5,6-tetrahi
Drophthalamic acid methoxymethyl ester, N-benzo
Il-N- [4-chloro-2-fluoro-5- (1-me
Cylpropargylthio) phenyl] -3,4,5,6-
Tetrahydrophthalamic acid ethoxymethyl ester, N
-[4-chloro-2-fluoro-5- (1-methylpro
Pargylthio) phenyl] -N-nicotinyl-3,4
5,6-Tetrahydrophthalamic acid methyl ester, N
-[4-chloro-2-fluoro-5- (1-methylpro
Pargylthio) phenyl] -N-nicotinyl-3,4
5,6-Tetrahydrophthalamic acid ethyl ester, N
-[4-chloro-2-fluoro-5- (1-methylpro
Pargylthio) phenyl] -N-nicotinyl-3,4
5,6-Tetrahydrophthalamic acid allyl ester, N
-[4-chloro-2-fluoro-5- (1-methylpro
Pargylthio) phenyl] -N-nicotinyl-3,4
5,6-Tetrahydrophthalamic acid propargyl ester
N- [4-chloro-2-fluoro-5- (1-methyl
Lupropargylthio) phenyl] -N-nicotinyl-
Methoxyme 3,4,5,6-tetrahydrophthalamic acid
Chill ester, N- [4-chloro-2-fluoro-5-
(1-Methylpropargylthio) phenyl] -N-nico
Tinyl-3,4,5,6-tetrahydrophthalamic acid
Toxymethyl ester, N- [4-chloro-2-fluor
Lo-5- (1-methylpropargylthio) phenyl]-
N- (3-thiophenecarboxy) -3,4,5,6-
Tetrahydrophthalamic acid methyl ester, N- [4-
Chloro-2-fluoro-5- (1-methylpropargyl
Thio) phenyl] -N- (3-thiophenecarboxy)
-3,4,5,6-Tetrahydrophthalamic acid ethyl ester
Stell, N- [4-chloro-2-fluoro-5- (1-
Methylpropargylthio) phenyl] -N- (3-thio
Fencarboxy) -3,4,5,6-tetrahydrof
Thallamic acid allyl ester, N- [4-chloro-2-phenyl]
Luoro-5- (1-methylpropargylthio) pheny
] -N- (3-Thiophenecarboxy) -3,4
5,6-Tetrahydrophthalamic acid propargyl ester
N- [4-chloro-2-fluoro-5- (1-methyl
Lupropargylthio) phenyl] -N- (3-thiophene
Carboxy) -3,4,5,6-tetrahydrophthala
Mic acid methoxymethyl ester, N- [4-chloro-2
-Fluoro-5- (1-methylpropargylthio) fe
Nyl] -N- (3-thiophenecarboxy) -3,4
5,6-Tetrahydrophthalamic acid ethoxymethyl ester
Tell can be mentioned.

The N-phenyltetrahydrophthalamic acid derivative [I] which is the compound of the present invention is represented by, for example, the imidoyl chloride derivative represented by the general formula [II] and the general formula [III] as shown in the following formula. It can be produced by reacting with a carboxylic acid.

[0040]

Embedded image

(Wherein X and Y independently represent a halogen atom, R ¹ represents a lower alkylthio group, a lower alkenylthio group, a lower alkynylthio group, R ² represents a lower alkyl group, a halogenated lower alkyl group, It represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted pyridyl group or a substituted or unsubstituted thienyl group, and R ³ represents a lower alkoxy group, a lower alkenyloxy group, a lower alkynyloxy group or a lower alkoxyalkoxy group. The reaction is carried out without a solvent or in a suitable solvent, for example, in a solvent such as benzene, toluene, xylene, methylene chloride, chloroform, ethyl acetate, dioxane, tetrahydrofuran, diethyl ether, N, N-dimethylformamide, dimethyl sulfoxide and the like. A suitable deoxidizer such as triethylamine, It can be suitably carried out by adding an organic base such as pyridine or an inorganic base such as potassium hydroxide or sodium hydroxide.

Since the above-mentioned reaction in the present invention is an equimolar reaction, it is preferable that the ratio of the carboxylic acid [III] to the imidoyl chloride derivative [II] is about 1 time, usually 0.8. The molar ratio is appropriately 1.2 to 1.2 times, and more preferably 0.9 to 1.1 times. When it is less than this range, a large amount of the imidoyl chloride derivative [II] added excessively remains unreacted, and when it is more than this range, the carboxylic acid [III] excessively added remains unreacted. Since a large amount remains, the reaction cannot be performed efficiently, which is economically disadvantageous, and the burden on the purification step increases because the unreacted raw material is removed or recovered, which is not preferable.

The addition amount of the deoxidizing agent in the above reaction of the present invention may be 1 time mol or more with respect to the imidoyl chloride derivative [II], but usually 1 time mol to 3 times mol. It is suitable to be 1 mol to 2 mol. When the amount is less than this range, the reaction does not proceed sufficiently and causes a decrease in yield, which is not preferable. Further, addition of more than this range does not change the reaction so much, it is only economically disadvantageous, and the burden on the purification step for removing the excess deoxidizing agent increases, which is not preferable. .

The reaction temperature is not particularly limited, but usually-
20 ° C to 200 ° C is suitable, and more preferably 20 ° C.
C to 70C. At a temperature lower than this range, a sufficient reaction rate cannot be obtained, the reaction time becomes very long, and the reaction may not be performed efficiently, which is not preferable. Further, at a temperature higher than this range, decomposition or the like may occur, which causes a decrease in yield, and the burden on the purification step for removing the decomposed product increases, which is not preferable.

The N-phenyltetrahydrophthalamic acid derivative [I] which is a compound of the present invention is represented by the imidoyl chloride derivative represented by the general formula [II] and the general formula [IV] as shown in the following formula. It can also be produced by reacting with an alkali metal salt of a carboxylic acid.

[0046]

Embedded image

(Wherein X and Y independently represent a halogen atom, R ¹ represents a lower alkylthio group, a lower alkenylthio group, a lower alkynylthio group, R ² represents a lower alkyl group, a halogenated lower alkyl group, It represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted pyridyl group or a substituted or unsubstituted thienyl group, and R ³ represents a lower alkoxy group, a lower alkenyloxy group, a lower alkynyloxy group or a lower alkoxyalkoxy group. The reaction is carried out without solvent or in a suitable solvent, for example, benzene, toluene, xylene, methylene chloride, chloroform, ethyl acetate, dioxane, tetrahydrofuran, diethyl ether, N, N-dimethylformamide, dimethyl sulfoxide, water and the like. In a solvent, adding a phase transfer catalyst if necessary It can be more suitably performed.

Since this reaction is an equimolar reaction, it is preferable that the ratio of the alkali metal salt [IV] of the carboxylic acid to the imidoyl chloride derivative [II] is about 1 time mol, usually 0.8. The molar ratio is appropriately 1.2 to 1.2 times, and more preferably 0.9 to 1.1 times. If it is less than this range, a large amount of the imidoyl chloride derivative [II] added excessively remains unreacted, and if it is more than this range, the alkali metal salt [IV] of excessively added carboxylic acid is A large amount remains unreacted, and the reaction cannot be performed efficiently, which is economically disadvantageous. Further, unreacted imidoyl chloride derivative [II] or unreacted carboxylic acid alkali metal salt [IV] ] Is not preferable because the burden on the purification step increases due to the removal or recovery of

Examples of the phase transfer catalyst used in this reaction include crown ethers such as 18-crown-6-ether, polyethers such as polyethylene glycol, quaternary phosphonium salts such as tetraphenylphosphonium chloride, and tetraether. Examples thereof include quaternary ammonium salts such as butylammonium bromide and tetrabutylammonium hydrogen sulfate.

The amount of the phase transfer catalyst used is not particularly limited and may be appropriately adjusted according to the desired reaction rate, but is usually 0.0 with respect to the imidoyl chloride derivative [II].
1 mol% to 20 mol% is suitable, and more preferably,
It is 0.1 mol% to 10 mol%. If it is less than this range, a sufficient reaction rate cannot be obtained, the reaction time becomes very long, and the reaction may not be carried out efficiently, which is not preferable. In addition, addition of more than this range does not change the reaction so much and is economically disadvantageous, which is not preferable.

The reaction temperature is not particularly limited, but is usually 0.
℃ ~ 200 ℃ is suitable, more preferably 0 ℃ ~ 1
00 ° C. At a temperature lower than this range, a sufficient reaction rate cannot be obtained, the reaction time becomes very long, and the reaction may not be performed efficiently, which is not preferable. Further, at a temperature higher than this range, decomposition or the like may occur, which causes a decrease in yield, and the burden on the purification step for removing the decomposed product increases, which is not preferable.

The imidoyl chloride derivative [II] required as a starting material for obtaining the N-phenyltetrahydrophthalamic acid derivative [I] of the present invention is, for example, a compound represented by the general formula [V]

[0053]

Embedded image

(Wherein X and Y independently represent a halogen atom, R ¹ represents a lower alkylthio group, a lower alkenylthio group, a lower alkynylthio group, R ² represents a lower alkyl group, a halogenated lower alkyl group, An anilide derivative represented by a substituted or unsubstituted phenyl group, a substituted or unsubstituted pyridyl group or a substituted or unsubstituted thienyl group can be produced as a starting material.

The reaction can be carried out using a dehydrating chlorinating agent in the presence or absence of a reaction solvent according to the following reaction formula.

[0056]

Embedded image

(Wherein X and Y independently represent a halogen atom, R ¹ represents a lower alkylthio group, a lower alkenylthio group, a lower alkynylthio group, R ² represents a lower alkyl group, a halogenated lower alkyl group, It represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted pyridyl group or a substituted or unsubstituted thienyl group.) Preferred examples of the dehydration chlorinating agent used in the reaction include:
Examples thereof include phosphorus pentachloride, phosphorus trichloride-chlorine, thionyl chloride, arylsulfonyl chloride, phosgene, triphenylphosphine-carbon tetrachloride, and polymer-supported triphenylphosphine-carbon tetrachloride.

The amount of the dehydrating chlorinating agent to be used is usually 1 equivalent to 10 equivalents based on the anilide derivative [V].
More preferably, it is 1 equivalent to 2 equivalents. If the amount is less than this range, the reaction may not proceed sufficiently and may cause a decrease in yield, which is not preferable. Further, even if added in excess of this range, the reaction does not change so much, it is only economically disadvantageous, and the burden on the purification step for removing the excess dehydrating chlorinating agent increases, so it is preferable. Absent.

Preferred examples of the solvent used in the reaction include halogenated hydrocarbons such as dichloroethane, carbon tetrachloride, chloroform and methylene chloride, aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, and acetonitrile. And a polar solvent such as dimethyl sulfoxide.

The reaction temperature is not particularly limited, but is usually 0.
℃ ~ 120 ℃ is suitable, more preferably room temperature ~ 1
00 ° C. At a temperature lower than this range, a sufficient reaction rate cannot be obtained, the reaction time becomes very long, and the reaction may not be performed efficiently, which is not preferable. Further, at a temperature higher than this range, decomposition or the like may occur, which causes a decrease in yield, and the burden on the purification step for removing the decomposed product increases, which is not preferable.

[0061]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be specifically described below with reference to Examples and Reference Examples.

[0062]

EXAMPLES Reference Example 1 5-Acetylamino-2-chloro-4-fluoro- (1
-Methylpropargyl) thiophenol production (general formula
Compound of [V]) 5-Acetylamino-2-chloro-4-fluoro-thiophenol 5.6 g (27.5 mmol), potassium carbonate 1.9 g (13.7 mmol), N, N-dimethylformamide (DMF). Mix 40 ml and add DMF to it
4.45 g (30.0 mmol) of methanesulfonic acid (1-methylpropargyl) ester dissolved in 15 ml was added dropwise at room temperature. After completion of dropping, the mixture was reacted at room temperature for 3 hours, DMF was distilled off under reduced pressure, the residue was dissolved in 100 ml of ethyl acetate, and this was washed with water and saturated saline.
After drying over anhydrous magnesium sulfate, ethyl acetate was distilled off under reduced pressure to obtain a crude target product. Recrystallization from ethyl acetate / n-hexane was carried out to obtain 5.2 g of the target 5-acetylamino-2-chloro-4-fluoro- (1-methylpropargyl) thiophenol.

Melting point = 85.0 to 86.0 ° C. Reference Example 2 N- [4-chloro-2-fluoro-5- (1-methylprop
Production of lopargylthio) phenyl] nicotinamide
Compound of general formula [V] ) 4.39 g (19.1 mm) of 4-chloro-2-fluoro-5- (1-methylpropargylthio) aniline under ice cooling
ol), 5.5 ml of triethylamine (39.5 mmo
l) and 70 ml of 1,2-dichloroethane (EDC) were mixed, and 3.5 g of nicotinic acid chloride hydrochloride (1 g)
9.7 mmol) was added in small portions. After completion of the addition, the mixture was reacted at room temperature for 5 hours and then washed with water and saturated saline. After drying over anhydrous magnesium sulfate, ED under reduced pressure
C was distilled off to obtain a crude target product. Recrystallization from ethyl acetate / n-hexane was performed to obtain the desired N- [4-chloro-2-
3.2 g of fluoro-5- (1-methylpropargylthio) phenyl] nicotinamide was obtained.

Melting point = 126.0-128.0 ° C. Example 1 N- [4-chloro-2-fluoro-5- (1-methylprobe
Lopargylthio) phenyl] -acetimidoyl chloride
Preparation of compound (compound of general formula [II]) 5-acetylamino-2-chloro-4-fluoro- (1
-Methylpropargyl) thiophenol 1.50 g
(5.52 mmol) and 1.15 g of phosphorus pentachloride (5.5
2 mmol) was suspended in 20 ml of toluene, heated to 60 ° C., and stirred for 1 hour. After completion of the reaction, the reaction solution was concentrated under reduced pressure and quantitatively N- [4-chloro-2-fluoro-5-
(1-Methylpropargylthio) phenyl] -acetimidoyl chloride was obtained.

¹ H-NMR (CDCl ₃ , δppm) 1.56 (d, J = 7.0 Hz, 3H), 2.33
(D, J = 2.2 Hz, 1H), 2.62 (s, 3
H), 3.99 (dq, J = 7.0, 2.2 Hz, 1
H), 7.17 (d, J = 7.9 Hz, 1H), 7.2
3 (d, J = 9.7 Hz, 1 H) Example 2 N- [4-chloro-2-fluoro-5- (1-methylprobe
Lopargylthio) phenyl] nicotinoylimidoylk
Production of Lolid (Compound of General Formula [II]) N- [4-chloro-2-fluoro-5- (1-methylpropargylthio) phenyl] nicotinamide 1.30 g
(3.88 mmol) and 0.81 g of phosphorus pentachloride (3.8
9 mmol) was suspended in 30 ml of toluene, heated to 70 ° C., and stirred for 2 hours and 30 minutes. After completion of the reaction, the reaction solution was poured into 50 ml of ice water and stirred well, 1.5 ml of triethylamine was added, and the mixture was stirred again well. 50 ml of ethyl acetate was added, the layers were separated, and the organic layer was washed with water and saturated brine. After drying over anhydrous magnesium sulfate, the organic solvent was distilled off under reduced pressure to quantitatively obtain N- [4-chloro-2-fluoro-5- (1-methylpropargylthio) phenyl] nicotinoylimidoyl chloride. It was

¹ H-NMR (CDCl ₃ , δppm) 1.59 (d, J = 7.0 Hz, 3H), 2.34
(D, J = 2.2 Hz, 1H), 4.03 (dq, J =
7.0, 2.2 Hz, 1H), 6.6 to 6.8 (m, 3
H), 7.1-7.7 (m, 3H) Example 3 N-acetyl-N- [4-chloro-2-fluoro-5-
(1-Methylpropargylthio) phenyl] -3,4
Manufacture of 5,6-tetrahydrophthalamic acid methyl ester
Production ( Compound of General Formula [I], Compound No. 1) N- [4-chloro-2-fluoro-5- (1-methylpropargylthio) phenyl] -acetimidoyl chloride 1.60 g (5.52 mmol) And 3, 4, 5, 6-
Tetrahydrophthalamic acid monomethyl ester 1.02
g (5.54 mmol) was dissolved in 30 ml of toluene,
1.2 ml of triethylamine dissolved in 5 ml of toluene
(8.6 mmol) was added dropwise at room temperature. After dropping, 7
The reaction was carried out at 0 ° C for 1.5 hours. After cooling to room temperature, it was washed with water and saturated saline. After drying over anhydrous magnesium sulfate, the organic solvent was distilled off under reduced pressure to obtain a crude target product. Recrystallization from methanol was performed to obtain 1.0 g of N-acetyl-N- [4-chloro-2-fluoro-5- (1-
Methylpropargylthio) phenyl] -3,4,5,6
-Tetrahydrophthalamic acid methyl ester was obtained.

Melting point = 120.0-122.0 ° C. ¹ H-NMR (CDCl ₃ , δppm) 1.58 (d, J = 7.0 Hz, 3 H), 1.4-1.
8 (m, 4H), 2.19 (s, 3H), 2.2-2.
4 (m, 5H), 3.74 (s, 3H), 3.9-4.
2 (m, 1H), 7.33 (d, J = 8.8Hz, 1
H), 7.76 (d, J = 7.7 Hz, 1H) Example 4 N- [4-chloro-2-fluoro-5- (1-methylprobe
Lopargylthio) phenyl] -N-nicotinyl-3,
4,5,6-Tetrahydrophthalamic acid methyl ester
(Compound of general formula [I], compound No. 2) N- [4-chloro-2-fluoro-5- (1-methylpropargylthio) phenyl] nicotinoylimidoyl chloride 1.31 g (3.70 mmol) ) And 3,4,5,
0.83 g (3.73 mmol) of 6-tetrahydrophthalamic acid monomethyl ester / potassium salt was mixed in 10 ml of N, N-dimethylformamide and reacted at 80 ° C. for 3 hours. After cooling to room temperature, the reaction solution was concentrated under reduced pressure, the residue was dissolved in 50 ml of ethyl acetate, and washed with water and saturated saline. After drying over anhydrous magnesium sulfate, the organic solvent was distilled off under reduced pressure to obtain a crude target product. Purified by silica gel column chromatography, 0.
60 g of N- [4-chloro-2-fluoro-5- (1-
Methylpropargylthio) phenyl] -N-nicotinyl-3,4,5,6-tetrahydrophthalamic acid methyl ester was obtained.

Melting point = 101.0 to 102.0 ° C. ¹ H-NMR (CDCl ₃ , δppm) 1.58 (d, J = 7.0 Hz, 3 H), 1.6 to 1.
9 (m, 4H), 2.2 to 2.6 (m, 4H), 2.4
9 (d, J = 2.2 Hz, 1H), 3.74 (s, 3
H), 3.9 to 4.1 (m, 1H), 7.09 (d, J
= 9.2 Hz, 1H), 7.0-7.2 (m, 1H),
7.89 (bd, J = 7.9 Hz, 1H), 8.08
(D, J = 7.9 Hz, 1H), 8.4 to 8.8 (m,
2H) The herbicide of the present invention containing an N-phenyltetrahydrophthalamic acid derivative [I] which is a compound of the present invention as an active ingredient is a variety of weeds which are problematic in the treatment of flooded soil in paddy fields, for example, Nobie. It has an excellent herbicidal activity against grass weeds, broad-leaved weeds such as Azena, Aegina, Oenothera and Mizohakobe, Cyperaceae weeds such as Tadagayatsui and Firefly, and weeds such as konjac, and both foliar treatment and soil treatment of field. Various weeds that are also problematic in, for example, mustard, blue sky, chickweed,
Shiroza, Onami fir, Malaba morning glory, Yaemgra, purslane, velvetleaf, horned nematode, Ebisugusa,
Broad-leaved weeds such as Inouzuki, Anodontid, Polygonum, Violet, etc. However, it has excellent herbicidal activity, and the herbicide of the present invention shows almost no harmful phytotoxicity against major crops such as rice, wheat, corn and soybean.

Therefore, the herbicide of the present invention can be used in fields, paddy fields,
It can be widely used for orchards, meadows, lawns, forests or non-agricultural land. The herbicide of the present invention contains the above-mentioned compound of the present invention, N-phenyltetrahydrophthalamic acid derivative [I], as an active ingredient, and is an agricultural chemical auxiliary generally used in this field, that is, an inert solid carrier. , A liquid carrier and an emulsifying dispersant may be used to form an arbitrary dosage form such as a wettable powder, an emulsion, a granule, a powder and a flowable agent. Examples of these inert carriers include talc, clay, bentonite, kaolin, diatomaceous earth, calcium carbonate, wood flour, starch, gum arabic, water, alcohol, kerosene, benzene, xylene, n-hexane, acetone, Examples thereof include N, N-dimethylformamide, glycol ether, N-methylpyrrolidone and the like.

In addition, a formulation auxiliary agent such as a spreading agent,
A diluent, a surfactant, a solvent and the like can be appropriately added. The amount of the compound of the present invention, N-phenyltetrahydrophthalamic acid derivative [I], used as a herbicide can be appropriately selected depending on the method, purpose, time, and weed generation state, but it is usually an active ingredient. Is preferably 0.5 g to 300 g per hectare. If it is less than 0.5 g, a sufficient herbicidal effect cannot be obtained, which is not preferable. Further, even if it is used in an amount of more than 300 g, the herbicidal effect does not change so much, it is economically disadvantageous, and it may cause chemical damage, which is not preferable. Particularly preferably, it is 1 g to 300 g per hectare.

In addition to herbicides containing the compound of the present invention, N-phenyltetrahydrophthalamic acid derivative [I], other types of herbicides, plant growth regulators, fungicides, insecticides and other pesticides and fertilizers can be used. It is also possible to mix and use a soil improver and the like.

Next, examples of the herbicide of the present invention will be given.
The compounds, carriers, auxiliaries and proportions used are not limited to those in this example. The composition ratios of the components in the present examples indicate parts by weight.

Example 5 (Wettable powder) Compound No. 1 10 parts Sodium lignin sulfonate 1.5 parts Polyoxyethylene alkylaryl ether 1.5 parts Clay 87 parts These components were mixed until uniform and pulverized to obtain a wettable powder.

Example 6 (Wettable powder) Compound No. 2 10 parts Sodium lignin sulfonate 1.5 parts Polyoxyethylene alkylaryl ether 1.5 parts Clay 87 parts These components were mixed until uniform and ground to obtain a wettable powder.

Example 7 (Granule) Compound No. 1 7 parts Bentonite 30 parts Sodium alkyl sulfate 2 parts Clay 61 parts These components were mixed until uniform, kneaded, and granulated by a usual granulation method to obtain granules.

Example 8 (Granule) Compound No. 2 7 parts Bentonite 30 parts Sodium alkyl sulfate 2 parts Clay 61 parts These components were mixed until uniform, kneaded, and granulated by an ordinary granulation method to obtain granules.

Example 9 (Emulsion) Compound No. 1 5 parts N-methylpyrrolidone 44 parts Solpol 7065 43 parts (Toho Chemical Industry Co., Ltd. product) Solpol 355 8 parts (Toho Chemical Industry Co., Ltd. product) These components were mixed to obtain an emulsion. .

Example 10 (Emulsion) Compound No. 25 parts N-methylpyrrolidone 44 parts Solpol 7065 43 parts (product of Toho Chemical Industry Co., Ltd.) Solpol 355 8 parts (product of Toho Chemical Industry Co., Ltd.) These ingredients were mixed until uniform to obtain an emulsion. .

Next, N, which is a compound of the present invention, was tested by a test example.
-The herbicidal effect of the phenyltetrahydrophthalamic acid derivative [I] will be described. Test Example 1 (Flooded Soil Treatment) A pot of 1/15500 are was filled with paddy soil (clay loam soil), and various kinds of weed seeds of Novier, broadleaf weed, firefly and cyperus edulis were uniformly mixed and sown on the surface. Two
Paddy rice seedlings at the ~ 3 leaf stage were transplanted to a depth of 2 cm and submerged to a depth of 3 cm. Three days later, at the beginning of the development of Novier, a predetermined amount of the wettable powder diluent of each compound obtained in Example 5 or Example 6 was dropped on the water surface. Thereafter, the plants were grown in a glass room, and 4 weeks after the treatment, the herbicidal effect and the phytotoxicity of rice were evaluated. The results are shown in Table 1. In addition, the numerical values in the table show phytotoxicity to paddy rice and herbicidal effect, and are specifically as follows.

5: Complete death 4: Major harm 3: Medium harm 2: Minor harm 1: Minor harm 0: Harmless (normal growth) Test Example 2 (foliar treatment) Grown by soil cultivation in a pot of 1/15500 are. The wettable powder diluent of each compound obtained in Example 5 or Example 6 was spray-treated at the seedling stage (2 to 3 leaf stage) of each plant of rice, edible millet, Japanese radish, Amaranthus communis and Cercis chinensis. Thereafter, the plants were grown in a glass room, and four weeks after the treatment, the herbicidal effect was evaluated. The results are shown in Table 2. In addition,
The herbicidal effect was evaluated in the same manner as in Test Example 1.

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[Table 1]

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[Table 2]

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Industrial Applicability The N-phenyltetrahydrophthalamic acid derivative, which is a novel compound of the present invention, has excellent herbicidal activity, and is used for upland fields, paddy fields, orchards, pastures, lawns, forests or non-arable land. It provides a herbicide that can be widely applied to, and is highly safe for crops.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takeo Furumata 2805 Imafuku Nakadai, Kawagoe City, Saitama Central Glass Co., Ltd.

Claims (11)

[Claims] 1. A compound of the general formula [I] (In the formula, X and Y independently represent a halogen atom, R ¹ represents a lower alkylthio group, a lower alkenylthio group, a lower alkynylthio group, and R ² represents a lower alkyl group, a halogenated lower alkyl group, a substituted or non-substituted one. Represents a substituted phenyl group, a substituted or unsubstituted pyridyl group or a substituted or unsubstituted thienyl group, and R ³ represents a lower alkoxy group, a lower alkenyloxy group, a lower alkynyloxy group or a lower alkoxyalkoxy group). N-
Phenyltetrahydrophthalamic acid derivative. 2. A compound of the general formula [I] (In the formula, X and Y independently represent a halogen atom, R ¹ represents a lower alkylthio group, a lower alkenylthio group, a lower alkynylthio group, and R ² represents a lower alkyl group, a halogenated lower alkyl group, a substituted or non-substituted one. Represents a substituted phenyl group, a substituted or unsubstituted pyridyl group or a substituted or unsubstituted thienyl group, and R ³ represents a lower alkoxy group, a lower alkenyloxy group, a lower alkynyloxy group or a lower alkoxyalkoxy group). N-
A herbicide containing a phenyltetrahydrophthalamic acid derivative as an active ingredient. 3. The herbicide according to claim 2, which is formulated as a wettable powder containing an inert carrier. 4. The herbicide according to claim 2, which is formulated as a granule containing an inert carrier. 5. The herbicide according to claim 2, which is formulated as an emulsion containing an inert carrier. 6. The N-phenyltetrahydrophthalamic acid derivative is N-acetyl-N- [4-chloro-2-fluoro-5- (1-methylpropargylthio) phenyl]-.
The herbicide according to any one of claims 2 to 5, which is 3,4,5,6-tetrahydrophthalamic acid methyl ester. 7. The N-phenyltetrahydrophthalamic acid derivative is N- [4-chloro-2-fluoro-5- (1-
Methylpropargylthio) phenyl] -N-nicotinyl-3,4,5,6-tetrahydrophthalamic acid methyl ester, the herbicide according to any one of claims 2 to 5. 8. A compound represented by the general formula [II]: (In the formula, X and Y independently represent a halogen atom, R ¹ represents a lower alkylthio group, a lower alkenylthio group, a lower alkynylthio group, and R ² represents a lower alkyl group, a halogenated lower alkyl group, a substituted or non-substituted one. A substituted phenyl group, a substituted or unsubstituted pyridyl group, or a substituted or unsubstituted thienyl group), and a general formula [III] (Wherein R ³ represents a lower alkoxy group, a lower alkenyloxy group, a lower alkynyloxy group or a lower alkoxyalkoxy group) and is reacted in the presence of a deoxidizing agent. General formula [I] (In the formula, X and Y independently represent a halogen atom, R ¹ represents a lower alkylthio group, a lower alkenylthio group, a lower alkynylthio group, and R ² represents a lower alkyl group, a halogenated lower alkyl group, a substituted or non-substituted one. Represents a substituted phenyl group, a substituted or unsubstituted pyridyl group or a substituted or unsubstituted thienyl group, and R ³ represents a lower alkoxy group, a lower alkenyloxy group, a lower alkynyloxy group or a lower alkoxyalkoxy group). N-
Process for producing phenyltetrahydrophthalamic acid derivative. 9. A compound represented by the general formula [II]: (In the formula, X and Y independently represent a halogen atom, R ¹ represents a lower alkylthio group, a lower alkenylthio group, a lower alkynylthio group, and R ² represents a lower alkyl group, a halogenated lower alkyl group, a substituted or non-substituted one. And a substituted or unsubstituted phenyl group, a substituted or unsubstituted pyridyl group or a substituted or unsubstituted thienyl group.), And an imidoyl chloride derivative represented by the general formula [IV]: (Wherein R ³ represents a lower alkoxy group, a lower alkenyloxy group, a lower alkynyloxy group or a lower alkoxyalkoxy group, and M represents an alkali metal), and reacts with an alkali metal salt of a carboxylic acid. The general formula [I] is characterized by: (In the formula, X and Y independently represent a halogen atom, R ¹ represents a lower alkylthio group, a lower alkenylthio group, a lower alkynylthio group, and R ² represents a lower alkyl group, a halogenated lower alkyl group, a substituted or non-substituted one. Represents a substituted phenyl group, a substituted or unsubstituted pyridyl group or a substituted or unsubstituted thienyl group, and R ³ represents a lower alkoxy group, a lower alkenyloxy group, a lower alkynyloxy group or a lower alkoxyalkoxy group). N-
Process for producing phenyltetrahydrophthalamic acid derivative. 10. A compound represented by the general formula [II]: (In the formula, X and Y independently represent a halogen atom, R ¹ represents a lower alkylthio group, a lower alkenylthio group, a lower alkynylthio group, and R ² represents a lower alkyl group, a halogenated lower alkyl group, a substituted or non-substituted one. And a substituted or unsubstituted pyridyl group or a substituted or unsubstituted thienyl group.). 11. A compound represented by the general formula [V]: (In the formula, X and Y independently represent a halogen atom, R ¹ represents a lower alkylthio group, a lower alkenylthio group, a lower alkynylthio group, and R ² represents a lower alkyl group, a halogenated lower alkyl group, a substituted or non-substituted one. A substituted phenyl group, a substituted or unsubstituted pyridyl group or a substituted or unsubstituted thienyl group) is reacted in the presence of a dehydrating chlorinating agent [II]. [Chemical 11] (In the formula, X and Y independently represent a halogen atom, R ¹ represents a lower alkylthio group, a lower alkenylthio group, a lower alkynylthio group, and R ² represents a lower alkyl group, a halogenated lower alkyl group, a substituted or non-substituted one. A substituted phenyl group, a substituted or unsubstituted pyridyl group, or a substituted or unsubstituted thienyl group.).