JPH1121274A - Benzoylcyclohexanedione derivative and herbicide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the new subject compound capable of being industrially and advantageously synthesized, having sure effects with a lower dose, highly safe and useful as herbicides good in selectivity with crops. SOLUTION: This benzoylcyclohexanedione derivative is a compound expressed by the formula (R<1> and R<2> are each H, a halogen, a 1-6C alkyl, etc.; R<3> is H or a 1-6C alkyl; R<4> is hydroxy, a 1-6C alkyl, etc.; R<5> to R<10> are each cyano, formyl, etc.), e.g. 2-(2,4-dichloro-3-ethoxyiminomethyl)benzoyl-1,3- cyclohexanedione. The compound of the formula is obtained by reacting a 3-acyl compound, etc., with an amino compound in the presence of a catalyst (e.g.; an inorganic acid, etc., such as hydrochloric acid, sulfuric acid, etc.), by using a solvent (e.g.; methylene chloride, chloroform, etc.), hydrolyzing the obtained compound with an alkali such as NaOH, etc., an acid such as sulfuric acid, etc., then reacting by using an inorganic halogen compound such as thionyl chloride, etc., reacting a dione compound with the reaction product in the presence of a base and transforming the obtained product in the presence of a cyano compound, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a benzoyl group
The present invention relates to a benzoylcyclohexanedione derivative substituted with an iminoalkyl group or the like and a herbicide.

[0002]

2. Description of the Related Art It has been reported that a 2-benzoylcyclohexane-1,3-dione compound similar to the compound of the present invention has herbicidal activity as disclosed in JP-A-3-255047 and JP-A-6-55047.
271562 and WO94 / 04524. However, a compound in which the 3-position of a benzoyl group is substituted with an iminoalkyl group or the like, such as the compound of the present invention, is not known.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a herbicide which can be synthesized industrially advantageously, is effective at a lower dose, has high safety, and has high selectivity to crops. It is.

[0004]

According to the present invention, there is provided a compound represented by the general formula [1]:

[0005]

Embedded image

[Wherein R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, a C _1-6 alkyl group,
Represents a _1-6 alkoxy group, a C _1-6 haloalkyl group, a C _1-6 haloalkoxy group, a C _1-6 alkylthio group, a C _1-6 alkylsulfinyl group or a C _1-6 alkylsulfonyl group. R ³ represents a hydrogen atom or a C _1-6 alkyl group.
R ⁴ is a hydroxy group, C _1-6 alkyl group, C _1-6 haloalkyl group, C _2-6 alkenyl group, C _2-6 haloalkenyl group, C _2-6 alkynyl group, C _2-6 haloalkynyl group ,
C _3-8 cycloalkyl group, C _1-6 alkoxy group, C _1-6
Alkoxy C _1-4 alkyl group, C _1-6 haloalkoxy group, C _3-8 cycloalkyl group, C _2-6 alkenyloxy group, C _2-6 haloalkenyloxy group, C _2-6 alkynyloxy group, C _2-6 haloalkynyloxy group, C
_1-6 alkylamino group, phenyl group which may be substituted, benzyl group which may be substituted, phenyloxy group which may be substituted, benzyloxy group which may be substituted or Represents a good phenylamino group.

R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰
Are each independently a hydrogen atom, a cyano group, a formyl group, a halogen atom, a C _1-6 alkyl group, a C _1-6 haloalkyl group, a C _1-6 alkoxy group, a C _1-6 haloalkoxy group, a C _{1 -6} alkylthio group, C _1-6 alkylsulfinyl group, C _1-6 alkylsulfonyl group, C _1-6 alkylthio C _1-4 alkyl group, C _1-6 alkylsulfinyl C
_1-4 alkyl group, C _1-6 alkylsulfonyl C _1-4 alkyl group, C _1-6 alkoxy C _1-4 alkyl group, C _1-6 alkylcarbonyloxy C _1-4 alkyl group, hydroxy C _1-6 Alkyl group, di C _1-6 alkoxy C _1-4 alkyl group, C _1-6 alkoxycarbonyl group, hydroxyimino C _1-6 alkyl group, C _1-6 alkoxyimino C _1-4 alkyl group, C _2-6 Alkenyloxyimino C _1-4 alkyl group, C _2-6 alkynyloxyimino C _1-4 alkyl group,
C _1-6 haloalkoxyimino C _1-4 alkyl group, C _2-6
Haloalkenyloxyimino C _1-4 alkyl group, C _2-6
Haloalkynyloxy imino C _1-4 alkyl groups, optionally substituted phenyl group, optionally substituted phenylthio C _1-4 alkyl group, optionally substituted phenylsulfonyl C _1-4 alkyl group, a substituted Phenylsulfonyl C _1-4 alkyl group which may be substituted, and phenyl C _1-4 alkyloxy C _1-4 alkyl group which may be substituted. (R ⁵ and R ⁶ ), (R ⁷ and R ⁸ ) or (R ⁹ and R ¹⁰ ) may together form an oxo or C _2-4 alkylene chain. ⁶ and R ⁸ may together form a methylene or C _2-4 alkylene chain. Or a salt thereof, and a herbicide containing the compound.

In R ¹ and R ² , halogen atoms include fluorine, chlorine and bromine atoms, and C _1-6 alkyl groups include methyl, ethyl, propyl, and the like.
Isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group and the like; C _1-6 alkoxy group includes methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, t-butoxy group; But C _1-6
Examples of the haloalkyl group include fluoromethyl group, 1-fluoroethyl group, 2-fluoroethyl group, difluoromethyl group, trifluoromethyl group, difluorochloromethyl group, fluorochloromethyl group, trichloromethyl group, tribromomethyl group, and toluene. Examples of a C _1-6 haloalkoxy group include a trifluoromethoxy group, a 1,1,2,2-tetrafluoroethoxy group, a trichloromethoxy group, and a difluoromethoxy group. _{As a 1-6} alkylthio group,
Examples of the methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group and the like, and examples of the C _1-6 alkylsulfinyl group include methylsulfinyl group, ethylsulfinyl group, propylsulfinyl group, isopropylsulfinyl group, butylsulfinyl group and the like. C
_{Examples of the 1-6} alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, and a butylsulfonyl group.

In R ³ , examples of the C _1-6 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group and a t-butyl group.

The C _1-6 alkyl group for R ⁴ includes:
Examples of the methyl group, ethyl group, propyl group, isopropyl group, butyl group, s-butyl group and t-butyl group include C _1-6 haloalkyl groups such as fluoromethyl group, 1-fluoroethyl group and 2-fluoroethyl group. group, difluoromethyl group, trifluoromethyl group, difluoromethyl chloromethyl group, fluoromethyl chloromethyl group, trichloromethyl group, tribromomethyl group, trifluoroethyl group, etc. pentafluoroethyl group, examples of the C _2-6 alkenyl group , a vinyl group, 1-propenyl group, allyl group, crotyl group, a butadienyl group, and examples of the C _2-6 haloalkenyl group, 1-chloro vinyl, 2-chlorovinyl group, 3-chloroallyl group, 2-Kurorokurochiru Groups such as ethynyl, 1-propynyl, and C _2-6 alkynyl;
A 2-propynyl group and the like as a C _2-6 haloalkynyl group, a 2-chloroethynyl group, a 2-bromoethynyl group,
3-chloro-2-propynyl group, 3,3,3-trifluoro-1-propynyl group and the like, and C _3-8 cycloalkyl groups include cyclopropyl group, cyclopentyl group,
Cyclohexyl group, as the C _1-6 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, etc. t- butoxy group, C _1-6
Examples of the alkoxy C _1-4 alkyl group include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, an isopropoxymethyl group, a butoxymethyl group, a t-butoxymethyl group, a methoxymethyl group, an ethoxyethyl group, a propoxyethyl group, Propoxyethyl group, butoxyethyl group, t-butoxyethyl group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, isopropoxypropyl group, butoxypropyl group, etc., and C _1-6 haloalkoxy group is trifluoromethoxy Group, 1,
Examples thereof include a 1,2,2-tetrafluoroethoxy group, a trichloromethoxy group, and a difluoromethoxy group.

The C _3-8 cycloalkyloxy group includes cyclopropyloxy group, cyclopentyloxy group, cyclohexyloxy group and the like, and the C _2-6 alkenyloxy group includes vinyloxy group, 1-propenyloxy group, Allyloxy group, crotyloxy group, butadienyloxy group and the like, and C _2-6 haloalkenyloxy group include 1-chlorovinyloxy group, 2-chlorovinyloxy group, 3-chloroallyloxy group, 2-chlorochloro A C _2-6 alkynyloxy group such as a tyloxy group; an ethynyloxy group, a 1-propynyloxy group,
Examples of the C _2-6 haloalkynyloxy group include a 2-chloroethynyloxy group, a 2-bromoethynyloxy group, a 3-chloro-2-propynyloxy group, and a 3,3,3-trifluoro- group. Examples of the C _1-6 alkylamino group include a 1-propynyloxy group and the like, and examples thereof include a mono or di C _1-6 alkylamino group such as a methylamino group, an ethylamino group, a dimethylamino group, and a diethylamino group.

In R ⁴ , a phenyl group which may be substituted, a benzyl group which may be substituted, a phenyloxy group which may be substituted, a benzyloxy group which may be substituted or Examples of the substituent on the phenylamino group which may be a halogen atom,
_Examples thereof include a C _1-4 alkyl group, a C _1-4 alkoxy group, a C _1-4 haloalkyl group and a C _1-4 alkoxy group.
Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom. Examples of the C _1-4 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a t-butyl group. _{Examples of the} C _1-4 alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group and a t-butoxy group.
_1-4 haloalkyl groups include fluoromethyl group, 1-
Fluoroethyl group, 2-fluoroethyl group, difluoromethyl group, trifluoromethyl group, difluorochloromethyl group, fluorochloromethyl group, trichloromethyl group, tribromomethyl group, trifluoroethyl group, pentafluoroethyl group, etc. _{Examples of the} C _1-4 haloalkoxy group include a trifluoromethoxy group, a 1,1,2,2-tetrafluoroethoxy group, a trichloromethoxy group, a difluoromethoxy group, and the like.

In R ^{5 to} R ¹⁰ , a halogen atom is a fluorine atom, a chlorine atom, a bromine atom or the like, and a C _1-6 alkyl group is a methyl group, an ethyl group, a propyl group,
Isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group and the like; C _1-6 alkoxy group includes methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, t-butoxy group; But C _1-6
Haloalkyl groups include fluoromethyl, 1-fluoroethyl, 2-fluoroethyl, difluoromethyl, trifluoromethyl, difluorochloromethyl, fluorochloromethyl, trichloromethyl, tribromomethyl, tribromomethyl, Examples of a C _1-6 haloalkoxy group include a trifluoromethoxy group, a 1,1,2,2-tetrafluoroethoxy group, a trichloromethoxy group, and a difluoromethoxy group. _{As a 1-6} alkylthio group,
Examples of the methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group and the like, and examples of the C _1-6 alkylsulfinyl group include methylsulfinyl group, ethylsulfinyl group, propylsulfinyl group, isopropylsulfinyl group, butylsulfinyl group and the like. C
_{Examples of the 1-6} alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, and a butylsulfonyl group.
The _1-6 alkylthio C _1-4 alkyl group, methylthiomethyl group, methylthioethyl group, ethylthiomethyl group, propyl thio methyl group, isopropylthio methyl group, and butyl thio methyl group, C _1-6 alkylsulfinyl C the, the methylsulfinyl methyl group, methylsulfinyl ethyl group, ethylsulfinyl methyl, propyl sulfinyl methyl, isopropyl-sulfinyl methyl group, C _1-6 alkylsulfonyl C _1-4 alkyl group _1-4 alkyl group, Methylsulfonylmethyl, methylsulfonylethyl, ethylsulfonylmethyl, propylsulfonylmethyl, isopropylsulfonylmethyl, etc. are C _1-6 alkoxy C
_{Examples of the 1-4} alkyl group include a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, a propoxymethyl group, an isopropoxymethyl group, and a butoxymethyl group.

In R ^{5 to} R ¹⁰ , the C _1-6 alkylcarbonyloxy C _1-4 alkyl group includes an acetoxymethyl group, an acetoxyethyl group, a propionyloxymethyl group, an isobutyryloxymethyl group, and the like. _{Examples of the 1-6} alkyl group include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group. Examples of the diC _1-6 alkoxy C _1-4 alkyl group include a dimethoxymethyl group, a dimethoxyethyl group, and a dimethoxyethyl group. An ethoxymethyl group, a dipropoxymethyl group, a dibutoxymethyl group, a di-t-butoxymethyl group and the like are exemplified by a C _1-6 alkoxycarbonyl group such as a methoxycarbonyl group,
Ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, the hydroxyimino C _1-6 alkyl group, a hydroxyiminomethyl group, hydroxyimino ethyl, hydroxyimino-propyl, etc. hydroxyimino-butyl group, C _{1- As the 6} alkoxyimino C _1-4 alkyl group, a methoxyiminomethyl group,
A methoxyiminoethyl group, an ethoxyiminomethyl group, a propoxyiminomethyl group, a butoxyiminomethyl group and the like, and examples of the C _2-6 alkenyloxyimino C _1-4 alkyl group include a vinyloxyiminomethyl group, a vinyloxyiminoethyl group, 1-propenyloxyiminomethyl group,
The crotyloxyiminomethyl group, allyloxyiminomethyl group and the like, and the C _2-6 alkynyloxyimino C _1-4 alkyl group include an ethynyloxyiminomethyl group, an ethynyloxyiminoethyl group, a propargyloxyiminomethyl group and the like. , C _1-6 haloalkoxy imino C _1-4
Examples of the alkyl group include a fluoromethyliminomethyl group,
Examples of a trifluoromethyliminomethyl group, a difluorochloromethyliminomethyl group, a trichloromethyliminomethyl group, and a C _2-6 haloalkenyloxyimino C _1-4 alkyl group include a 1-chlorovinyloxyiminomethyl group, A chlorovinyloxyiminomethyl group, a 3-chloroallyloxyiminomethyl group or the like is a C _2-6 haloalkynyloxyimino C _1-4 alkyl group,
Chloroethynyloxyiminomethyl group, 3-chloro-2
-Propynyloxyiminomethyl group and the like.

In R ^{5 to} R ¹⁰ , optionally substituted phenyl groups include halogen atoms such as fluorine, chlorine and bromine, methyl, ethyl, propyl, isopropyl, butyl, isobutyl and the like. Group, a C _1-4 alkyl group such as t-butyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, t
A C _1-4 alkoxy group such as _-butoxy group, a fluoromethyl group, a 1-fluoroethyl group, a 2-fluoroethyl group,
C _1-4 haloalkyl groups such as difluoromethyl group, trifluoromethyl group, difluorochloromethyl group, fluorochloromethyl group, trichloromethyl group, tribromomethyl group, trifluoroethyl group, trifluoromethoxy group, 1,1, C _1-4 such as 2,2-tetrafluoroethoxy group, trichloromethoxy group, difluoromethoxy group, etc.
Examples of the phenylthio C _1-4 alkyl group which may be substituted with a phenyl group which may be substituted with a haloalkoxy group include halogen atoms such as a fluorine atom, a chlorine atom and a bromine atom, a methyl group and an ethyl group , Propyl group,
C _1-4 alkyl groups such as isopropyl group, butyl group, isobutyl group, t-butyl group, methoxy group, ethoxy group,
C _1-4 alkoxy groups such as propoxy group, isopropoxy group, butoxy group, t-butoxy group, fluoromethyl group, 1-fluoroethyl group, 2-fluoroethyl group, difluoromethyl group, trifluoromethyl group, difluorochloro C _1-4 haloalkyl groups such as methyl group, fluorochloromethyl group, trichloromethyl group, tribromomethyl group, trifluoroethyl group, trifluoromethoxy group, 1,1,2,2-tetrafluoroethoxy group, trichloromethoxy C _1-4 such as a group or a difluoromethoxy group
Examples of the optionally substituted phenylsulfinyl C _1-4 alkyl group such as a phenylthiomethyl group, a phenylthioethyl group and a phenylthiopropyl group which may be substituted with a haloalkoxy group include a fluorine atom and a chlorine atom. , A bromine atom, a halogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a C _1-4 alkyl group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group. C _1-4 alkoxy groups such as a group, butoxy group, t-butoxy group,
Such as fluoromethyl, 1-fluoroethyl, 2-fluoroethyl, difluoromethyl, trifluoromethyl, difluorochloromethyl, fluorochloromethyl, trichloromethyl, tribromomethyl, and trifluoroethyl Phenyl which may be substituted with a C _1-4 haloalkoxy group such as a C _1-4 haloalkyl group, trifluoromethoxy group, 1,1,2,2-tetrafluoroethoxy group, trichloromethoxy group, difluoromethoxy group and the like. Examples of the optionally substituted phenylsulfonyl C _1-4 alkyl group such as a sulfinylmethyl group, a phenylsulfinylethyl group, a phenylsulfinylpropyl group, and a phenylsulfinylbutyl group include halogen atoms such as a fluorine atom, a chlorine atom, and a bromine atom. , Methyl group, ethyl group, pro Group, an isopropyl group, a butyl group, an isobutyl group, C _1-4 alkyl group such as t- butyl group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, C _1-like t- butoxy ₄ alkoxy group, fluoromethyl group, 1-fluoroethyl group, 2-fluoroethyl group, difluoromethyl group, trifluoromethyl group, difluoromethyl chloromethyl group, fluoromethyl chloromethyl group, trichloromethyl group, tribromomethyl group, a trifluoromethyl Substituted with a C _1-4 haloalkyl group such as an ethyl group, a C _1-4 haloalkoxy group such as a trifluoromethoxy group, a 1,1,2,2-tetrafluoroethoxy group, a trichloromethoxy group, and a difluoromethoxy group. Phenylsulfonylmethyl group, phenylsulfonylethyl group, phenylsulfonylp Propyl group, a phenylsulfonyl butyl group. Examples of the substituted phenyl C _1-4 optionally alkyloxy C _1-4 alkyl group, a fluorine atom, a chlorine atom, a halogen atom, a methyl group such as a bromine atom, an ethyl group , propyl group, isopropyl group, butyl group, isobutyl group, C _1-4 alkyl group such as t-butyl group, a methoxy group, an ethoxy group, a propoxy group, C ₁ such as isopropoxy, butoxy, t-butoxy group _-4 alkoxy group, fluoromethyl group, 1-
C _1-4 haloalkyl groups such as fluoroethyl group, 2-fluoroethyl group, difluoromethyl group, trifluoromethyl group, difluorochloromethyl group, fluorochloromethyl group, trichloromethyl group, tribromomethyl group and trifluoroethyl group , Trifluoromethoxy group, 1,
A phenylmethoxymethyl group, a phenylmethoxyethyl group, a phenylethoxymethyl group, which may be substituted with a C _1-4 haloalkoxy group such as a 1,2,2-tetrafluoroethoxy group, a trichloromethoxy group, a difluoromethoxy group, Examples include a phenylpropoxymethyl group, a phenylisopropoxymethyl group, and a phenylbutoxymethyl group.

Further, in R ^{5 to} R ¹⁰ , examples of the C _2-4 alkylene chain include ethylene, trimethylene and tetramethylene.

Some of the compounds of the present invention and the intermediate compounds described below have a substituent having 1 to 6 (C _1-6 ) or 2 to 6 (C _2-6 ) carbon atoms. Preferably, the carbon number is 1-4 (C _1-4 ) or 2-4 (C _2-4 ), respectively. The same applies to the following.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the present invention can be produced by the following method. Production method (i)

[0019]

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(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ represent the same meaning as described above, Q represents a lower alkyl group, and X represents a halogen atom. )

That is, compound (5) or compound (6) obtained via compound (4) is reacted with compound (3) using 3-acyl or 3-formylbenzoate (2) as a starting material. After obtaining the intermediates (7a) and (7b), the target product (1) is obtained.

The compound (4) is prepared by using the compound (2) and the compound (8) in an amount of 1 mol or one of each in excess. Synth. , I, 80 (194)
It can be produced by the method described in 1). Solvents used in the reaction include halogenated hydrocarbons such as methylene chloride and chloroform; aromatic hydrocarbons such as benzene and toluene; alcohols such as methanol and ethanol; ethers such as diethyl ether and tetrahydrofuran (THF). And the like. The reaction mixture is stirred at −10 ° C. to the reflux temperature of the solvent until the reaction is completed. In addition, the use of a catalyst can shorten the reaction time. Examples of the catalyst include inorganic salts such as hydrochloric acid and sulfuric acid, zinc chloride, and titanium tetrachloride. A Lewis acid such as p-toluenesulfonic acid can be used. Furthermore, in order to remove generated water, it is possible to use molecular sieves, KOH, or the like, or to reflux using Dean Stark. In the formula (4), R
After obtaining a compound in which ⁴ is a hydroxy group, a compound in which R ⁴ is an alkoxy group can be produced by reacting the compound with an alkyl halide or the like.

Compound (5) is obtained by converting compound (4) to NaOH
It can be produced by hydrolysis using an alkali such as, or an acid such as sulfuric acid.

The compound (6) can be produced by a general synthetic chemistry method using the compound (5) with an inorganic halide such as thionyl chloride and phosphorus pentachloride.

Compound (7a) and compound (7b) are
The compound (6) and the compound (3) can be obtained by reacting each of the compounds (1) in an amount of 1 mol or one of them in excess in the presence of 1 mol or an excess of a base.

The base used in this reaction is KO
Alkali metal hydroxides such as H and NaOH; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; alkaline earth metal carbonates such as calcium carbonate And tertiary amines such as triethylamine and diisopropylethylamine, organic bases such as pyridine, sodium phosphate and the like.

As the solvent, water, methylene chloride,
Chloroform, toluene, ethyl acetate, dimethylformamide (DMF), THF, dimethoxyethane (DM
E), acetonitrile and the like are used.

The reaction mixture is stirred from 0 ° C. to the boiling point of the solvent until the reaction is completed. The reaction can also be performed in a two-phase system using a phase transfer catalyst such as a quaternary ammonium salt.

Further, the compounds (7a) and (7b)
Can also be obtained by reacting compound (5) with compound (3) in the presence of a dehydrating condensing agent such as dicyclohexylcarbodiimide (DCC). DCC
Solvents used in the reaction with, for example, methylene chloride, chloroform, toluene, ethyl acetate, DM
F, THF, DME, acetonitrile, t-amyl alcohol and the like. The reaction mixture is stirred in a temperature range from -10 ° C to the boiling point of the solvent until the reaction is completed, and the reaction mixture is processed in a conventional manner.

The compounds (7a) and (7b) can be used as a mixture for the next rearrangement reaction as it is. The rearrangement reaction is performed in the presence of a cyano compound and a mild base. That is, the compounds (7a) and (7b
1) with 1 to 4 mol of base, preferably 1 to 2 mol
Moles of base and from 0.01 mole to 1.0 mole, preferably
The compound (1) is obtained by reacting 0.05 to 0.2 mol of a cyanide compound.

As the base, the above-mentioned base, ie, KO
Alkali metal hydroxides such as H and NaOH; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; alkaline earth metal carbonates such as calcium carbonate And tertiary amines such as triethylamine and diisopropylethylamine, organic bases such as pyridine, and sodium phosphate.

Examples of the cyan compound include potassium cyanide, sodium cyanide, acetone cyanohydrin, hydrogen cyanide, and a polymer holding potassium cyanide. It is preferable to add a small amount of a phase transfer catalyst such as crown ether to the reaction system because the reaction is completed in a shorter time. Reaction temperature is 80 ° C
It is carried out at lower temperatures, preferably from room temperature to 40 ° C.
Solvents used are benzene, toluene, acetonitrile, 1,2-dichloroethane, methylene chloride, chloroform, ethyl acetate, DMF, methyl isobutyl ketone,
THF, DME, and the like.

This rearrangement reaction can also be carried out in an inert solvent in the presence of a base such as potassium carbonate, sodium carbonate, triethylamine, pyridine and the like. The amount of the base used is based on Compounds (7a) and (7b).
The solvent is 0.5 to 2.0 mol, and THF, dioxane, t-amyl alcohol, t-butyl alcohol and the like are used as the solvent. The reaction temperature is preferably from room temperature to the boiling point of the solvent used.

Further, the compound (1) can be obtained by using a base together with a dehydrating condensing agent such as DCC without isolating the compounds (7a) and (7b). As the base used, potassium carbonate, sodium carbonate, triethylamine, pyridine and the like are used, and the amount of the base used is 0.5 to 2.0 with respect to the compound (3).
Is a mole. Examples of the solvent include THF, dioxane, t-amyl alcohol, and t-butyl alcohol, and the reaction temperature is preferably from room temperature to the boiling point of the solvent used.

Production method (ii)

[0036]

Embedded image

(Where R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , Q, and X have the same meaning as described above. )

That is, a compound (9) or a compound (10) is obtained from a 3-acyl or 3-formylbenzoic acid ester (2) as a starting material, and the compound (3) is reacted with the compound (9). Intermediate (11a) and / or
Alternatively, (11b) is manufactured. Then, the intermediate (11)
The compound (8) is reacted with a) and / or (11b) to obtain an intermediate (12a) and / or (12b), and the desired product (1) is obtained by a rearrangement reaction.

Compound (9) is obtained by converting compound (2) to NaOH
It can be produced by a general synthetic chemistry method using an alkali such as alkali or an acid such as sulfuric acid.

Compound (10) can be produced by a general synthetic chemical method using compound (9) with an inorganic halogenating agent such as thionyl chloride and phosphorus pentachloride.

Compounds (11a) and (11b) can be prepared by reacting compound (10) with compound (3) in the same manner as described in production method (i), or by reacting compound (9) with compound ( 3) in the presence of a dehydrating condensing agent.

Compounds (12a) and (12b) can be produced from compounds (11a) and (11b) and compound (8) in the same manner as in production method (i).

Further, the compounds (12a) and (12b) produced by the above method may be rearranged in the presence of a base or a base in the presence of a base with the cyanide compound described in the production method (i), Compound (1) can be produced.

Production method (iii)

[0045]

Embedded image

(Where R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , Q, and X have the same meaning as described above. M represents a lower alkyl group, and two Ms may be combined to form a ring. )

That is, 3-acyl or 3-formylbenzoic acid ester (2) is converted to acetal compound (13)
To give compound (14), which is then reacted with compound (3) to produce compound (15a) and / or (15b). Then, the obtained intermediate (15a) and / or (15b) is converted to a compound (16) by a rearrangement reaction, and a compound (17) is obtained by deprotection. The object (1) is obtained.

The compound (13) is prepared by using the compound (2) and an alcohol such as methanol, ethanol and ethylene glycol, or an orthoester such as methyl orthoformate in an amount of 1 mol or one of them in excess. Org. Synth. , III, 644 (195)
It can be produced by a general synthetic chemical technique such as the method described in 5).

Compound (14) is obtained by converting compound (13) to Na
It can be produced by a general synthetic chemistry method using an alkali such as OH.

Compounds (15a) and (15b) can be produced from compound (14) and compound (3) in the same manner as in the method of reacting in the presence of a dehydrating condensing agent such as DCC described in production method (i). can do.

The compound (16) can be produced from the compounds (15a) and (15b) in the same manner as in the production method (i) in the presence of a base or in the presence of a base. it can.

Compound (17) can be produced from compound (16) by a general synthetic chemistry method using an acid or the like.

Compound (17) produced by the above method
Can be produced by using the compound (2) and the compound (8) described in the production method (i) in the same manner as in the method for producing the compound (4).

Production method (iv) In addition, of compound (1) obtained as described above, compound (1a) is used as a starting material, and the compound for the purpose of converting a substituent on a cyclohexane ring is obtained by the following method. (1
b) and (1c) can also be produced.

[0055]

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(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ have the same meaning as described above. )

That is, compound (1a) is reacted with a halogenating agent such as phenyltrimethylammonium tribromide or Meldrum's acid dibromide in an appropriate solvent at an appropriate temperature from 0 ° C. to the boiling point of the solvent, preferably from room temperature to 50 ° C.
By reacting for several hours to several tens of hours, a halogenated trione compound (1b) can be produced. Examples of the solvent used for the reaction include methylene chloride,
Benzene, ethyl acetate, THF, acetonitrile, DM
E and so on. Next, a nucleophilic reagent (nucleop) is added to the halogenated trione form (1b) in the presence of a base.
and the desired compound (1)
c) can be produced.

Production method (v)

[0059]

Embedded image

(Where R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ have the same meaning as described above. R ¹¹ is lower alkyl which may be branched,
Means aralkyl or acetyl. Z is a leaving group, and represents a halogen atom, an alkylsulfonate group, an arylsulfonate group, or the like. )

Compound (1e) is prepared by reacting compound (1d) with a hydrohalic acid such as hydrochloric acid or hydrobromic acid, trifluoroacetic acid, boron tribromide, etc., hydrogenolysis or alkali hydrolysis. And, if necessary, by subsequent hydrolysis.

Further, compound (1e) can be converted to a halogenated, alkylsulfonated or allyl compound by a conventional method.
The compound (1f) can be obtained by conversion to rusulfonate. The compound (1g) is produced by reacting this compound (1f) in a solvent in the presence of an equimolar or more base at -20 ° C to the boiling point of the solvent used, preferably at room temperature to 100 ° C for 30 minutes to several tens of hours. can do. The base used is an alkali metal hydroxide such as KOH or NaOH, an alkaline earth metal hydroxide, diisopropylethylamine, triethylamine,
Pyridine, 1,8-diazabicyclo [5.4.0] unde-7-cene (DBU), t-BuOK, triton B,
Sodium carbonate, sodium phosphate and the like. As the solvent, water, alcohol, methylene chloride, benzene, toluene, ethyl acetate, DM
F, THF, DME, acetonitrile and the like are used.

Production method (vi)

[0064]

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(Where R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ have the same meaning as described above. R ¹² and R ¹³ represent a lower alkyl group;
¹⁴ is a hydrogen atom, a C _1-6 alkyl group, a C _2-6 alkenyl group, a C _2-6 alkynyl group, a C _1-6 haloalkyl group,
_2-6 haloalkenyl group, a C _2-6 haloalkynyl group, m is 0, 1, 2 or 3, preferably 0 or 1. )

Compound (1h) is compound (1)
It can be produced by a known method from a compound in which R ⁸ is — (CH ₂ ) _m —CH (OR ¹² ) (OR ¹³ ). Next, the compound (1h), in an inert solvent, equimolar or more formula: and H compound represented by ₂ NOR ^14, to the boiling point of the solvent used -20 ° C., preferably 100 ° C. from room temperature
And reacting for 30 minutes to several tens of hours to produce compound (1i). The reaction is completed in a shorter time by adding a small amount of an acid catalyst such as sulfuric acid. Examples of the solvent used include water, alcohol, methylene chloride, benzene, toluene, ethyl acetate, DMF, THF, DME, acetonitrile and the like, alone or as a mixture.

(Preparation of Raw Materials) Benzoic acids, which are important intermediates of the compound of the present invention, can be prepared as follows.

[0068]

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(In the formula, R ¹ , R ² , R ³ and Q have the same meanings as described above.) That is, the 3-formyl compound (2a) is reacted with hydroxylamine or a hydroxylamine salt to give a hydroxyimino compound. After obtaining (4a), a chlorinating agent such as chlorine is reacted to obtain imidoyl chloride (4b). Next, G represented by R ³ MgY (R ³ represents a C _1-6 alkyl group and Y represents a halogen atom).
The reaction of the alkylated product (4
c) and further, in the presence of a suitable base, R'Y '
(R ′ represents a lower alkyl group, and Y ′ represents a halogen atom or the like.) The compound (4d) is obtained by reacting an alkyl halide represented by the formula (4).

Incidentally, among the compounds (4), those in which R ⁴ is an alkoxy group include, for example, Tetrahedro
n, Letters. , 34 , 5117 (1993) and the following method.

The aldehyde (2a) and the ketone (2), which are important synthetic intermediates for producing the compound of the present invention, can be produced as follows.

[0072]

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(In the formula, R ¹ , R ² , R ³ and Q have the same meanings as described above, and W represents a halogen atom.)

That is, a known method such as halogen such as chlorine or bromine or a halogenating agent such as N-bromosuccinimide (NBS) or N-chlorosuccinimide (NCS) is converted from the toluene derivative (2b) by light or light. The reaction is carried out in the presence of a radical reaction initiator such as benzoyl peroxide to obtain a benzyl halide derivative (2c). Am. Chem.
Soc. , 71, 1767 (1949) to produce the aldehyde compound (2a). That is, an aldehyde compound (2a) can be produced by reacting an alkali metal salt of a nitroalkane such as 2-nitropropane with an alcohol solvent such as methanol or ethanol at a temperature between 0 ° C. and the boiling point of the solvent. it can.

Next, the ketone compound (2) can be converted from the aldehyde compound (2a) by using, for example, Org. Synth. , II
I, 200 (1955), the alcohol form (2d) was obtained by the method according to the Grignard reaction,
It can be produced by a known method such as an oxidation reaction of es reagent, manganese dioxide or the like.

Further, the benzoic acids represented by the compound (2g) are reacted with the mercaptan represented by R ″ SH in the presence of a base on the 4─Cl form represented by the compound (2e), 4-SR ′ represented by compound (2f)
After being made into a body, it can be manufactured by oxidation. When SO ₂ R ′ is substituted at a position other than the 4-position, it can be converted in the same manner from the chloro form at the corresponding position.

[0077]

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(Wherein, R ¹ and R ³ have the same meanings as described above, and R ″ represents a lower alkyl group.)

The base used in this reaction includes alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, metal alkoxides such as sodium methoxide and sodium ethoxide, carbonates such as sodium carbonate and potassium carbonate, and hydrogen. Hydrides such as sodium iodide, triethylamine, diisopropylethylamine, DBU,
An organic base such as pyridine can be exemplified. Examples of the solvent used in the reaction include alcohols such as methanol and ethanol, ethers such as THF and DME, amides such as DMF, N, N-dimethylacetamide, DMSO, acetonitrile, benzene, toluene, and xylene. And the like.

In the next oxidation reaction, water, an organic acid such as acetic acid,
In an inert solvent such as a halogenated hydrocarbon such as methylene chloride, chloroform and carbon tetrachloride, a peracid such as hydrogen peroxide, peracetic acid, perbenzoic acid, m-chloroperbenzoic acid, sodium hypochlorite, etc. This is performed using an oxidizing agent such as hypochlorous acid such as potassium chlorite. The reaction proceeds smoothly in a temperature range from room temperature to the boiling point of the solvent.

The cyclic dione represented by the general formula (3) is
It can be manufactured according to a known method.

When the compound (1) contains a free hydroxyl group, a salt thereof, in particular, an agriculturally and horticulturally acceptable salt, enamine or an analog thereof,
Acylate, sulfonate, carbamate, ether,
Thioethers, sulfoxides or sulfones can be derived. Suitable agriculturally and horticulturally acceptable salts include salts of alkali metals such as sodium, potassium and lithium, salts of alkaline earth metals such as magnesium and calcium, copper, and the like.
Examples include salts of transition metals such as manganese and zinc, and salts such as ammonium.

Examples of ammonium salts include those of the formula: N ⁺ R
aRbRcRd (wherein Ra, Rb, Rc and Rd
Are each independently a hydrogen atom and, optionally,
A C _1-10 alkyl group substituted by a hydroxy group or the like). Ra, Rb, Rc
When R and Rd are optionally substituted alkyl groups, they preferably contain from 1 to 4 carbon atoms.

A suitable enamine or analog thereof is OH
Each of the moieties is represented by the formula: -NReRf, wherein Re and Rf are each independently a hydrogen atom or an optionally substituted alkyl or aryl group, e.g., having 1-6 carbon atoms, e.g., phenyl; Group), a halogen atom, S (O) gRh (where Rh is, for example, an alkyl or aryl group optionally having 1 to 6 carbon atoms and optionally substituted, such as a phenyl group, Is 0-2
Represents ). Suitable acylate, ether or carbamate derivatives are those wherein the OH moiety is of the formula: -OCORi, -ORj or -OR, respectively.
OCONRkR1 (where Ri and Rj are the same as above R
h represents the same meaning, and Rk and Rl represent the same meaning as Re described above. ). These derivatives can be manufactured by a conventional method.

The compound (1) of the present invention may exist in an optically active form, and may exist in a number of tautomeric forms as shown below. All such forms are within the scope of the present invention.

[0086]

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In the present invention, after completion of the reaction, the desired product can be obtained by performing ordinary post-treatment. The structure of the compound of the present invention was determined from IR, NMR, MS and the like.

[0088]

BEST MODE FOR CARRYING OUT THE INVENTION

(Herbicide) The compound of the present invention has a high herbicidal activity in any of soil treatment and foliage treatment under field cultivation conditions, and is effective for various field weeds such as crabgrass, cyperacea, ibis, and wildflower, and is useful for corn, wheat, soybean. , Cotton and other crops.

The compounds of the present invention also include compounds exhibiting a plant growth regulating effect such as a growth inhibitory effect on useful plants such as crops, ornamental plants and fruit trees.

The compounds of the present invention have excellent herbicidal activity against various kinds of paddy weeds such as nobies, stag beetles, omodaka and firefly of paddy weeds, and also include compounds showing selectivity to rice. Furthermore, the compound of the present invention can also be applied to the control of weeds in orchards, lawns, track ends, vacant lots and the like. The compounds of the present invention also include those having a plant growth regulating action, a bactericidal activity, an insecticidal / miticidal activity.

The herbicide of the present invention contains one or more of the compounds of the present invention as an active ingredient. When the compound of the present invention is actually applied, it can be used in a pure form without adding other components, and can be in the form of a general pesticide for use as a pesticide, that is, wettable powder, granule, powder ,emulsion,
It can be used in the form of a water solvent, a suspending agent, a flowable or the like. When solid additives are used as additives and carriers, plant powders such as soybean flour and flour, diatomaceous earth,
Mineral fine powders such as apatite, gypsum, talc, bentonite, pyrophyllite, and clay, and organic and inorganic compounds such as sodium benzoate, urea, and sodium sulfate are used. For liquid dosage forms, petroleum fractions such as kerosene, xylene and solvent naphtha, cyclohexane,
Cyclohexanone, DMF, DMSO, alcohol, acetone, trichloroethylene, methyl isobutyl ketone, mineral oil, vegetable oil, water, etc. are used as solvents. In order to take a uniform and stable form in these formulations,
If necessary, a surfactant can be added. Examples of the surfactant include, but are not particularly limited to, alkyl phenyl ether to which polyoxyethylene is added, alkyl ether to which polyoxyethylene is added, higher fatty acid ester to which polyoxyethylene is added, and sorbitan to which polyoxyethylene is added. Nonionic surfactants such as higher fatty acid esters, tristyryl phenyl ether added with polyoxyethylene, sulfates of alkyl phenyl ethers added with polyoxyethylene, alkyl benzene sulfonates, sulfates of higher alcohols, alkyls Examples thereof include sulfates, alkylnaphthalene sulfonates, polycarboxylates, lignin sulfonates, formaldehyde condensates of alkylnaphthalene sulfonates, and copolymers of isobutylene-maleic anhydride.

The active ingredient concentration in the herbicide of the present invention varies depending on the form of the preparation described above. For example, in the case of a wettable powder, it is 5 to 90% by weight (hereinafter simply referred to as%). Write)), preferably 10 to 85%: 3 to 70%, preferably 5 to 60% in emulsion: 0.01 to 50%, preferably 0.05% in granules ~
A concentration of 40% is used.

The wettable powder and emulsion thus obtained are diluted to a predetermined concentration with water to form a suspension or an emulsion.
The granules are sprayed or mixed before or after germination of the weeds. In actually applying the herbicide of the present invention, an appropriate amount of 0.1 g or more of the active ingredient per hectare is applied.

The herbicide of the present invention can be used by mixing with known fungicides, insecticides, acaricides, herbicides, plant growth regulators, fertilizers and the like. In particular, it is possible to reduce the amount of the drug used by mixing and using the herbicide. In addition to not only saving labor, but also higher effects can be expected due to the synergistic action of the mixed drug. In that case, a combination with a plurality of known herbicides is also possible.

Suitable agents to be used in combination with the herbicide of the present invention include anilide herbicides such as diflufenican and propanil, chloroacetanilide herbicides such as arachlor and pretilachlor, and 2,4-D, 2,4.
-An aryloxyalkanoic acid herbicide such as DB; an aryloxyphenoxyalkanoic acid herbicide such as diclohop-methyl and fenoxaprop-ethyl; an arylcarboxylic acid herbicide such as dicamba and pyrithiobac; imidazo such as imazaquin and imazethapyr; Linone herbicides, urea herbicides such as diuron and isoproturon, carbamate herbicides such as chlorprofam and fenmedipham, thiocarbamate herbicides such as thiobencarb and EPTC, and dinitroaniline herbicides such as trifluralin and pendimethalin. Diphenyl ether herbicides, such as, ashifluorfen and fomesafen;
Sulfonylurea herbicides such as bensulfuron-methyl and nicosulfuron; triazinone herbicides such as metribuzin and metamitrone; triazine herbicides such as atrazine and cyanazine; triazopyrimidine herbicides such as flumeturum; and nitriles such as bromoxynil and diclobenil. -Based herbicides, phosphate-based herbicides such as glyphosate and glyphosinate, quaternary ammonium salt-based herbicides such as paraquat and difenzoquat, full microlac-
Cyclic imide herbicides such as pentyl and fluthiacet-methyl, and others such as isoxaben, etofumesate, oxadiazon, quinclorac, chromazone, sulcotrione, simmethillin, dithiopyr, pyrazolate, pyridate, flupoxam, bentazone, benflusate, and also cetoxydim, tralkoxydim. And cyclohexanedione-based herbicides. Vegetable oils and oil concentrates can also be added to these combinations.

[0096]

The compounds of the present invention will be described in more detail with reference to Examples and Reference Examples.

Example 1 2- (2,4-dichloro-3-ethoxyiminomethyl)
Production of benzoyl-1,3-cyclohexanedione (Compound No. 1-1)

[0098]

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In 5 ml of methylene chloride, 0.50 g of 2,4-dichloro-3-ethoxyiminobenzoyl chloride was added.
0.21 g of cyclohexane-1,3-dione was dissolved, and 0.23 g of triethylamine was added dropwise under ice water. 1 at room temperature
After stirring for an hour, the reaction solution was washed with 1N hydrochloric acid and then with a saturated saline solution, and then dried over anhydrous magnesium sulfate. After the solvent was distilled off under reduced pressure, the residue was dissolved in 5 ml of acetonitrile, and 0.04 g of acetone cyanohydrin and 0.3 of triethylamine were dissolved.
3 g was added at room temperature, followed by stirring for 3 hours. 1N hydrochloric acid was added to the reaction solution, and the mixture was extracted with ethyl acetate. The residue obtained by concentrating the solvent under reduced pressure was purified by silica gel column chromatography to obtain 0.31 g of the desired compound as an oil. n _D ²⁴ 1.5807

Example 2 Preparation of 2- (2-chloro-4-methanesulfonyl-3-methoxyiminomethyl) benzoyl-1,3-cyclohexanedione (Compound No. 1-2)

[0101]

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2-chloro-4-methanesulfonyl-3-
3.7 g of dimethoxymethyl benzoic acid was dissolved in 60 ml of ethyl acetate, 2.7 g of DCC and 1.5 g of cyclohexane-1,3-dione were added under ice-cooling, and the mixture was stirred at room temperature overnight. After the precipitated insoluble matter was filtered off, the filtrate was concentrated under reduced pressure, and the obtained residue was dissolved in 35 ml of acetonitrile, 0.31 g of acetone cyanohydrin and 2.4 g of triethylamine were added, and the mixture was stirred at room temperature overnight. 1 in the reaction mixture
After adding normal hydrochloric acid and extracting with methylene chloride, the organic layer was washed with saturated saline. The solvent was distilled off, and the resulting crystals were washed with methanol to obtain 2.5 g of 2- (2-chloro-4-methanesulfonyl-3-dimethoxymethyl) benzoyl-1,3-cyclohexanedione. mp. 191-19
4 ℃

2.3 g of 2- (2-chloro-4-methanesulfonyl-3-dimethoxymethyl) benzoyl-1,3-cyclohexanedione was dissolved in 40 ml of acetone, and 3 ml of hydrochloric acid was added at room temperature. After the mixture was heated to reflux for 1 hour, the solvent was distilled off under reduced pressure. The precipitated crystals were washed with ethanol, and then washed with 2- (2-chloro-4-methanesulfonyl-).
1.6 g of 3-formyl) benzoyl-1,3-cyclohexanedione were obtained. mp. 161-164 ° C

0.30 g of 2- (2-chloro-4-methanesulfonyl-3-formyl) benzoyl-1,3-cyclohexanedione was dissolved in 5 ml of methanol, and 0.04 g of methoxyamine was added at room temperature. Stirred. The crystals obtained by distilling off the solvent were washed with methanol to obtain 0.18 g of the desired compound. mp. 173-176
° C

Next, Production Examples of important intermediates of the compound of the present invention are shown below as Reference Examples. Reference Example 1 Production of methyl 2,4-dichloro-3-formylbenzoate

[0106]

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To 100 ml of methanol was added 26.61 g of a 28% methanol solution of sodium methylate.
Below 29 ° C, 12.29 g of 2-nitropropane were added dropwise.
Then, after adding 41.16 g of methyl 3-bromomethyl-2,4-dichlorobenzoate, the mixture was heated under reflux for 30 minutes. After cooling, the reaction solution was concentrated under reduced pressure, the residue was dissolved in 1000 ml of ethyl acetate, and washed with a 1% aqueous sodium hydroxide solution under ice-cooling. The organic layer was washed with water and then with a saturated saline solution and dried over anhydrous magnesium sulfate. The solvent was concentrated under reduced pressure, and the resulting crystals were washed with benzene and then with n-hexane to give the desired product methyl 2,4-dichloro-
22.00 g of 3-formylbenzoate as crystals were obtained. mp. 103-104 ° C

Reference Example 2 Production of 2,4-dichloro-3-formylbenzoic acid

[0109]

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1.04 g of methyl 2,4-dichloro-3-formylbenzoate was dissolved in 5 ml of ethanol.
10 ml of a normal aqueous sodium hydroxide solution was added, and the mixture was stirred at room temperature for 17 hours. The reaction solution was poured into 40 ml of ice water, acidified with concentrated hydrochloric acid, and the precipitated crystals were filtered and dried to obtain 0.75 g of the desired product 2,4-dichloro-3-formylbenzoic acid as crystals. mp. 188-190 ° C

Reference Example 3 Production of methyl 3-acetyl-2,4-dichlorobenzoate

[0112]

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Dissolve 2.47 g of methyl 2,4-dichloro-3-formylbenzoate in 20 ml of dry THF,
At -70 ° C, 4 ml of a methylmagnesium bromide-diethyl ether solution (3.0 mol / l) was slowly added dropwise. After the completion of the dropwise addition, the cooling bath was removed, and the mixture was stirred for 1 hour while the temperature was raised naturally. The reaction mixture was poured into ice water, acidified with diluted hydrochloric acid, and extracted with diethyl ether. Organic layer, water,
After washing with saturated saline, it was dried over anhydrous magnesium sulfate. The solvent was concentrated under reduced pressure to give methyl 2,4-dichloro-
2.42 g of 3- (1-hydroxyethyl) benzoate was obtained as an oil. Next, methyl 2,4-dichloro-3- (1-hydroxyethyl) benzoate 2.42
g was dissolved in 10 ml of benzene, 4 g of manganese dioxide was added, and the mixture was heated under reflux for 1 hour.
Was added and heated under reflux for 1 hour. The reaction solution was cooled to room temperature, and insolubles were separated by filtration. From the filtrate, the solvent was distilled off under reduced pressure to obtain 1.75 g of the target product, methyl 3-acetyl-2,4-dichlorobenzoate. n _D ²³ 1.5495

Reference Example 4 Production of methyl 2,4-dichloro-3- (1-ethoxyiminoethyl) benzoate

[0115]

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1.7 g (6.9 mmol) of methyl 3-acetyl-2,4-dichlorobenzoate was added to 20 m of benzene.
After adding 4.1 g (69 mmol) of ethoxyamine, 0.78 g (4.1 mmol) of titanium tetrachloride was added at 0 ° C. The mixture was stirred overnight at room temperature, washed with 1N hydrochloric acid and then with a saturated saline solution, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified using silica gel column chromatography,
2,4-dichloro-3- (1-ethoxyiminoethyl)
0.42 g of benzoate was obtained. ¹ H-NMR (δ ppm, CDCl ₃ ): 1.33 (3H, t), 2.15
(3H, s), 3.92 (3H, s), 4.23 (2H, q), 7.40 (1H, d), 7.73 (1H, d)

Reference Example 5 2,4-dichloro-3- (1-ethoxyiminoethyl)
Manufacture of benzoic acid

[0118]

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0.42 g (1.5 mmol) of methyl 2,4-dichloro-3- (1-ethoxyiminoethyl) benzoate was dissolved in 5 ml of methanol, 2 ml of a 10% aqueous NaOH solution was added, and the mixture was stirred at room temperature for 1 hour. . The reaction mixture was acidified by adding 1N hydrochloric acid, and the precipitated crystals were filtered,
Drying yielded 0.35 g of the desired product. ¹ H-NMR (δ ppm, CDCl ₃ ): 1.35 (3H, t), 2.18
(3H, s), 4.26 (2H, q), 7.45 (1H, d), 7.92 (1H, d)

Reference Example 6 2,4-Dichloro-3- (1-ethoxyiminoethyl)
Manufacture of benzoyl chloride

[0121]

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0.35 g (1.27 mmol) of 2,4-dichloro-3- (1-ethoxyiminoethyl) benzoic acid was dissolved in 10 ml of benzene, and thionyl chloride was dissolved in 0.2 ml of benzene.
23 g (1.91 mmol) and 1 drop of pyridine were added, and the mixture was heated under reflux for 1 hour. After cooling, the solvent was distilled off under reduced pressure to give 2,4.
0.37 g of -dichloro-3- (1-ethoxyiminoethyl) benzoyl chloride was obtained.

Reference Example 7 Production of methyl 2-chloro-4-methanesulfonyl-3-dimethoxymethylbenzoate

[0124]

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Methyl 2-chloro-4-methanesulfonyl-3-formylbenzoate 3.0 g (11 mmol)
Was dissolved in 50 ml of methanol, 0.5 g of concentrated sulfuric acid was added, and the mixture was heated under reflux for 8 hours. The solvent was concentrated under reduced pressure, the residue was dissolved in benzene, washed with 3% aqueous sodium hydrogen carbonate and then with saturated saline, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 3.0 g of the desired product. ¹ H-NMR (δ ppm, CDCl ₃ ): 3.24 (3H, s), 3.
54 (6H, s), 3.98 (3H, s), 6.28 (1H, s), 7.70 (1H, d), 8.19 (1H,
d)

Reference Example 8 Production of 2-chloro-4-methanesulfonyl-3-dimethoxymethylbenzoic acid

[0127]

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Methyl 2-chloro-4-methanesulfonyl-3-dimethoxymethylbenzoate (3.0 g, 9.3 mmol) was dissolved in methanol (30 ml), 10% aqueous sodium hydroxide solution (20 ml) was added, and the mixture was stirred at room temperature for 1 hour. . The reaction mixture was acidified by adding 1N hydrochloric acid, and the precipitated crystals were filtered, washed with water and dried to obtain 2.5 g of the desired product.
¹ H-NMR (δ ppm, CDCl ₃ ): 2.99 (3H, s),
3.56 (6H, s), 6.29 (1H, s), 7.89 (1H, d), 8.24 (1H, d)

Representative examples of the compounds of the present invention, including the compounds obtained in the above Examples, are shown in Tables 1 and 2. Table ¹ shows the ¹ H-NMR data in the table.

[0130]

[Table 1001]

[0131]

[Table 1002]

[0132]

[Table 1003]

[0133]

[Table 1004]

[0134]

[Table 1005]

[0135]

[Table 1006]

[0136]

[Table 1007]

[0137]

[Table 1008]

[0138]

[Table 1009]

[0139]

[Table 1010]

[0140]

[Table 1011]

[0141]

[Table 1012]

[0142]

[Table 1013]

[0143]

[Table 1014]

[0144]

[Table 2001]

[0145]

[Table 2002]

[0146]

[Table 2003]

[0147]

[Table 2004]

[0148]

[Table 2005]

[0149]

[Table 2006]

[0150]

[Table 2007]

[0151]

[Table 2008]

[0152]

[Table 2009]

[0153]

[Table 2010]

[0154]

[Table 2011]

[0155]

[Table 2012]

[0156]

[Table 2013]

[0157]

[Table 2014]

[0158]

[Table 2015]

[0159]

[Table 2016]

[0160]

[Table 2017]

[0161]

[Table 2018]

[0162]

[Table 2019]

[0163]

[Table 2020]

[0164]

[Table 2021]

[0165]

[Table 2022]

[0166]

[Table 3]

(Herbicide) Next, formulation examples of the herbicide of the present invention will be described a little, but the active ingredient compound, additives and addition ratios are not limited to the present example but can be changed in a wide range. is there. Parts in Formulation Examples represent parts by weight.

Example 3 Wetting agent 20 parts of the compound of the present invention 20 parts White carbon 20 parts Diatomaceous earth 52 parts Sodium alkyl sulfate 8 parts The above components were uniformly mixed and finely pulverized to obtain a wettable powder having an active ingredient of 20%. .

Example 4 Emulsion 20 parts of the compound of the present invention 55 parts of xylene 15 parts of dimethylformamide 10 parts of polyoxyethylene phenyl ether The above were mixed and dissolved to obtain an emulsion having an active ingredient of 20%.

Example 5 Granules Compound of the present invention 5 parts Talc 40 parts Clay 38 parts Bentonite 10 parts Sodium alkyl sulfate 7 parts After uniformly mixing and finely pulverizing, the diameter is 0.5 to 1.0 m.
m was granulated to obtain granules having an active ingredient of 5%.

[0171]

Next, test examples relating to the effect of the herbicide of the present invention will be described. The herbicidal effect was investigated according to the following criteria and expressed as a weed kill index.

Survey criteria Weed kill rate Weed kill index 0% 0 20-29% 240-49% 460-69% 680-89% 8 100% 10 Also, 1, 3, 5, 7, 9 The numerical values represent intermediate values between 0 and 2, 2 and 4, 4 and 6, 6 and 8, and 8 and 10, respectively.

[0173]

(Equation 1)

Test Example 1 Foliage spraying treatment A 200 cm ² pot was filled with soil, and the surface layer was filled with strawberry,
Various seeds of Brassica napus, Meishishiba, Aquinoenokorogosa and Maize were sowed, lightly covered with soil and grown in a greenhouse.
Example 4 when each plant grew to a plant height of 5 to 25 cm
The water dilution of the emulsion represented by the formula (1) was sprayed onto the foliage with a small sprayer in an amount equivalent to 1000 l / ha so that the active ingredient had a predetermined dose. Three weeks later, the phytotoxicity of the crop and the herbicidal effect of the weeds were investigated in accordance with the above-mentioned criteria, and the results are shown in Table 4.

[0175]

[Table 4]

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 317/24 C07C 317/24 317/32 317/32 317/44 317/44 323/45 323/45 323/63 323/63 (72) Inventor Masami Furuguchi 345 Takada, Odawara-shi, Kanagawa Japan Soda Co., Ltd.Odawara Research Laboratory Co., Ltd. Inventor Akihiro Takahashi 345 Takada, Odawara-shi, Kanagawa Nippon Soda Co., Ltd.

Claims (2)

[Claims] 1. A compound of the general formula [1] [Wherein, R ¹ and R ² each independently represent a hydrogen atom,
Halogen atom, C _1-6 alkyl group, C _1-6 alkoxy group, C _1-6 haloalkyl group, C _1-6 haloalkoxy group,
Represents a C _1-6 alkylthio group, a C _1-6 alkylsulfinyl group or a C _1-6 alkylsulfonyl group. R ³ represents a hydrogen atom or a C _1-6 alkyl group. R ⁴ represents a hydroxy group, a C _1-6 alkyl group, a C _1-6 haloalkyl group,
_2-6 alkenyl group, C _2-6 haloalkenyl group, C _2-6 alkynyl group, C _2-6 haloalkynyl group, C _3-8 cycloalkyl group, C _1-6 alkoxy group, C _1-6 alkoxy C
_1-4 alkyl group, C _1-6 haloalkoxy group, C _3-8 cycloalkyloxy group, C _2-6 alkenyloxy group, C
_2-6 haloalkenyloxy group, C _2-6 alkynyloxy group, C _2-6 haloalkynyloxy group, C _1-6 alkylamino group, optionally substituted phenyl group, optionally substituted benzyl group , A phenyloxy group which may be substituted, a benzyloxy group which may be substituted or a phenylamino group which may be substituted.
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a cyano group, a formyl group, a halogen atom, a C _1-6 alkyl group, a C _1-6 haloalkyl group, C
_1-6 alkoxy group, C _1-6 haloalkoxy group, C _1-6 alkylthio group, C _1-6 alkylsulfinyl group, C _1-6
Alkylsulfonyl group, C _1-6 alkylthio C _1-4 alkyl group, C _1-6 alkylsulfinyl C _1-4 alkyl group, C _1-6 alkylsulfonyl C _1-4 alkyl group, C
_C1-6 alkoxy C _1-4 alkyl group, C _1-6 alkylcarbonyloxy C _1-4 alkyl group, a hydroxy C _1-6 alkyl group, di C _1-6 alkoxy C _1-4 alkyl group, C _1-6
Alkoxycarbonyl group, hydroxyimino C _1-6 alkyl group, C _1-6 alkoxyimino C _1-4 alkyl group, C
_2-6 alkenyloxyimino C _1-4 alkyl group, C _2-6
Alkynyloxyimino C _1-4 alkyl group, C _1-6 haloalkoxyimino C _1-4 alkyl group, C _2-6 haloalkenyloxyimino C _1-4 alkyl group, C _2-6 haloalkynyloxyimino C _{1- 4} alkyl group, optionally substituted phenyl group, optionally substituted phenylthio C
_1-4 alkyl group, optionally substituted phenylsulfonyl C _1-4 alkyl group, optionally substituted phenylsulfonyl C _1-4 alkyl group or optionally substituted phenyl C _1-4 alkyloxy, Represents a C _1-4 alkyl group. (R ⁵ and R ⁶ ), (R ⁷ and R ⁸ ) or (R ⁹ and R ¹⁰ ) together form oxo or C
_2-4 may form an alkylene chain of further R ⁶
And R ⁸ may together form a methylene or C _2-4 alkylene chain. Or a salt thereof. 2. A compound of the general formula [1] (Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ ,
R ⁸ , R ⁹ and R ¹⁰ have the same meaning as described above. Or a salt thereof, as an active ingredient.