JPH06340643A - Oxazole or thiazole derivative, its production and herbicide - Google Patents

Abstract

PURPOSE:To produce a new oxazole or thiazole derivative exhibiting excellent herbicidal effect on weeds before or after sprouting at a low rate of application. CONSTITUTION:An oxazole or thiazole derivative of formula I {R<1> is halogen, NO2, alkyl, halosulfonyl or B-R<4> [B is O, S(O)n ((n) is 0-2) or NR<5> (R<5> is H, alkyl, alkenyl, alkynyl, cycloalkyl, etc.); R<4> is H, alkyl, alkenyl, alkynyl, cycloalkyl, phenoxyalkyl, phenylthioalkyl, etc.]; R<2> is OH, alkyl, haloalkyl, cycloalkyl, alkoxy, haloalkoxy, alkoxyalkyl or alkylthioalkyl; R<3> is H or halogen; A is O or S; X and Y are halogen, alkyl or haloalkyl}, e.g. 4-(4-chloro-2- fluoro-5-isopropoxyphenyl)-2-isopropyloxazole of formula II.

Description

Detailed Description of the Invention

[0001]

The present invention relates to the general formula (I)

[Chemical 6] [In the formula, R ¹ is a halogen atom, a nitro group, a (C1-6) alkyl group, a halosulfonyl group or -BR ⁴ (In the formula, B is O and S (O) n (wherein, n is 0 to 2). , Or NR
⁵ (In the formula, R ⁵ is a hydrogen atom, a (C1-6) alkyl group, a halo (C1-6) alkyl group, a (C2-6) alkenyl group, a halo (C2-6) alkenyl group, (C2-6) Alkynyl group, halo (C2-6) alkynyl group, cyclo (C
3-6) alkyl group, phenyl (C1-6) alkyl group, which may be the same or different, a halogen atom, (C1-
6) alkyl group, halo (C1-6) alkyl group, (C1
-6) alkoxy group, halo (C1-6) alkoxy group,
A phenyl (C1-6) alkyl group having at least one substituent selected from a (C1-6) alkylthio group or a halo (C1-6) alkylthio group on the phenyl ring;
6) represents a substituted aminosulfonyl group having one or more substituents selected from an alkylsulfonyl group, a halo (C1-6) alkylsulfonyl group, an aminosulfonyl group, or the same or different (C1-6) alkyl group. . And R ⁴ represents a hydrogen atom, a (C1-6) alkyl group, a halo (C1-6) alkyl group, a hydroxy (C1-6) alkyl group, a (C2-6) alkenyl group, a halo (C2-6).
Alkenyl group, (C2-6) alkynyl group, halo (C2
-6) alkynyl group, cyclo (C3-6) alkyl group,

Halocyclo (C3-6) alkyl group, (C
1-6) Alkoxy (C1-6) alkyl group, halo (C
1-6) Alkoxy (C1-6) alkyl group, (C1-
6) Alkoxy (C1-6) alkoxy (C1-6) alkyl group, halo (C1-6) alkoxy (C1-6) alkoxy (C1-6) alkyl group, (C1-6) alkylthio (C1-6) alkyl Group, halo (C1-6) alkylthio (C1-6) alkyl group, cyano (C1-6)
Alkyl group, (C1-6) alkylcarbonyloxy (C1-6) alkyl group, phenylcarbonyloxy (C1-6) alkyl group, phenoxy (C1-6) alkyl group, which may be the same or different, a halogen atom, ( C
1-6) alkyl group, halo (C1-6) alkyl group,
(C1-6) alkoxy group, halo (C1-6) alkoxy group, (C1-6) alkylthio group or halo (C1-
6) a substituted phenoxy (C1-6) alkyl group having one or more substituents selected from alkylthio groups on the phenyl ring, a phenylthio (C1-6) alkyl group,

Halogen atoms, which may be the same or different,
(C1-6) alkyl group, halo (C1-6) alkyl group, (C1-6) alkoxy group, halo (C1-6) alkoxy group, (C1-6) alkylthio group or halo (C1
-6) a substituted phenylthio (C1-6) alkyl group having one or more substituents selected from alkylthio groups on the phenyl ring, a phenyl (C1-6) alkyl group, which may be the same or different, a halogen atom, ( C1-6) alkyl group, halo (C1-6) alkyl group, (C1-6) alkoxy group, halo (C1-6) alkoxy group, (C1-6)
A substituted phenyl (C1-6) alkyl group having one or more substituents selected from an alkylthio group or a halo (C1-6) alkylthio group on the phenyl ring, and tri ((C1-6) alkyl which may be the same or different. ) Cyril (C1-
6) Alkyl group, which may be the same or different, di ((C1-
6) Alkoxy) phosphinyl (C1-6) alkyl group, (C1-6) alkylsulfonyl group, halo (C1-)
6) Alkylsulfonyl group, aminosulfonyl group, substituted aminosulfonyl group having one or more substituents selected from the same or different (C1-6) alkyl group, or-(CHR ⁶ ) m-CO-B ¹ -R ⁷ (In the formula, R ⁶ is a hydrogen atom or (C 1
-6) represents an alkyl group,

M is an integer of 0 to 5, B ¹ is O, S or
NR ⁵ (in the formula, R ⁵ is the same as above), and R ⁷ is a hydrogen atom, a (C1-6) alkyl group, a halo (C1-6) alkyl group, a (C2-6) alkenyl group, a halo ( C2-6) alkenyl group, (C2-6) alkynyl group, halo (C2-
6) Alkynyl group, (C1-6) alkoxy (C1-
6) Alkyl group, halo (C1-6) alkoxy (C1-
6) Alkyl group, cyclo (C3-6) alkyl group, cyano (C1-6) alkyl group, (C1-6) alkylthio (C1-6) alkyl group, halo (C1-6) alkylthio (C1-6) alkyl Group, (C1-6) alkoxy (C1-6) alkoxy (C1-6) alkyl group, tri ((C1-6) alkyl) silyl (C1-6) alkyl group, which may be the same or different, phenyl group, the same Or may be different, a halogen atom, a (C1-6) alkyl group,
One or more substituents selected from a halo (C1-6) alkyl group, a (C1-6) alkoxy group, a halo (C1-6) alkoxy group, a (C1-6) alkylthio group or a halo (C1-6) alkylthio group. A substituted phenyl group having a group,

Phenyl (C1-6) alkyl group or the same or different, halogen atom, (C1-6) alkyl group, halo (C1-6) alkyl group, (C1-6) alkoxy group, halo (C1 -6) Alkoxy group, (C1-
6) a substituted phenyl (C1-6) alkyl group having one or more substituents selected from an alkylthio group or a halo (C1-6) alkylthio group on the phenyl ring, and R ⁵ and R ⁷
May together be interrupted by an oxygen atom (C2-
6) It can also represent an alkylene group, and when B ¹ is O, R ⁷
Can also represent an alkali metal atom, a primary amine salt or a secondary amine salt. ), R ² is a hydroxyl group, (C1-
6) alkyl group, halo (C1-6) alkyl group, cyclo (C3-6) alkyl group, (C1-6) alkoxy group,
A halo (C1-6) alkoxy group, a (C1-6) alkoxy (C1-6) alkyl group or a (C1-6) alkylthio (C1-6) alkyl group, R ³ represents a hydrogen atom or a halogen atom, A represents O or S, and X and Y may be the same or different and each represents a halogen atom, a (C1-6) alkyl group or a halo (C1-6) alkyl group. ] It is related with the oxazole or thiazole derivative represented by these, its manufacturing method, and a herbicide.

[0006]

2. Description of the Prior Art Japanese Unexamined Patent Publication (Kokai) No. 2-250873 discloses an oxadiazol derivative and describes that it is useful as a herbicide. The oxazol or thiazole derivative of the present invention means a heterocycle. They differ in structure.

[0007]

DISCLOSURE OF THE INVENTION As a result of intensive studies by the present inventors to create a new herbicide, the oxazole or thiazole derivative represented by the general formula (I) of the present invention was identified. The present invention has been completed by discovering that it is a novel compound which has not been described in the literature and has excellent herbicidal activity at a low dose.

[0008]

Accordingly, the present invention relates to an oxazole or thiazole derivative represented by the general formula (I), a method for producing the same, and a herbicide containing the derivative as an active ingredient. . As the definition of each substituent of the oxazole or thiazole derivative represented by the general formula (I) of the present invention, a halogen atom represents a halogen atom such as a chlorine atom, a fluorine atom, a bromine atom or an iodine atom, For example, “(C1-6)” of each substituent represents a substituent having 1 to 6 carbon atoms, and (C1-6) alkyl is, for example, methyl, ethyl, n-propyl, i-propyl, n-. Butyl, i-butyl,
s-butyl, t-butyl, n-pentyl, n-hexyl, etc. represent alkyl having 1 to 6 carbon atoms, and (C1-6) alkoxy means methoxy, ethoxy, n-propoxy, i-propoxy, an alkoxy group having 1 to 6 carbon atoms such as n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentyloxy, and n-hexyloxy groups is shown, and (C1-
6) Alkylthio means methylthio, ethylthio, n-propylthio, i-propylthio, n-butylthio, i-butylthio, s-butylthio, t-butylthio, n-pentylthio, n
-A hexylthio group or other alkylthio having 1 to 6 carbon atoms, and a (C2-6) alkenyl group is a carbon atom having one double bond in the molecule such as ethenyl, propenyl, butenyl, pentenyl, and hexenyl. The alkenyl group of 2 to 6 and its isomers are represented by (C2-6) alkynyl group having 2 triple carbon atoms having one triple bond in the molecule such as ethynyl, propynyl, butynyl, pentynyl and hexynyl. 6 alkynyl groups are shown, and cyclo (C3
-6) The alkyl group is cyclopropyl, cyclobutyl,
Cyclopentyl, cyclohexyl group, etc., with 3 to 3 carbon atoms
Shows 6 alicyclic compounds, which may be the same as or different from "halo" and represents a group substituted with one or more halogen atoms, and may be the same as or different from a (C1-6) haloalkyl group. Having one or more halogen atoms (C1-
6) represents an alkyl group.

The oxazo group represented by the general formula (I) of the present invention
As a typical method for producing a thiol or thiazole derivative, the following production method can be exemplified. Manufacturing method 1.

[Chemical 7] [In the formula, R ^2-1 , R ³ , R ^4-1 , B ² , X, Y and A are the same as defined above. This reaction is carried out by reacting an oxazole or thiazole derivative represented by the general formula (I-1) with a compound represented by the general formula (II) in the presence of an inert solvent and in the presence or absence of a base. An oxazole or thiazole derivative represented by the general formula (I-2) can be produced by reacting with.

Any inert solvent can be used in this reaction as long as it does not significantly inhibit the progress of this reaction. For example, halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, benzene, toluene, xylene and the like. Aromatic hydrocarbons, esters such as ethyl acetate, nitriles such as acetonitrile and benzonitrile, chain ethers such as methyl cellosolve diethyl ether, cyclic ethers such as dioxane and tetrahydrofuran, sulfolane , Dimethylformamide, dimethyl sulfone, dimethyl sulfoxide, water, etc., and these inert solvents may be used alone or in combination. When using a mixed solvent of water and an organic solvent, a phase transfer catalyst such as triethylbenzylammonium chloride can be used together with a base.

As the base that can be used in this reaction, an inorganic base or an organic base can be used. Examples of the inorganic base include hydroxides of alkali metals or alkaline earth metals such as sodium, potassium, magnesium and calcium, Carbonates or alcoholates can be used, and as the organic base, for example, organic bases such as triethylamine and pyridine can be used. Since this reaction is an equimolar reaction, an equimolar amount of the oxazol or thiazole derivative represented by the general formula (I-1) and the compound represented by the general formula (II) may be used. It can also be used in excess.

The reaction temperature may be appropriately selected from the range of 0 ° C. to the boiling point range of the inert solvent used, preferably 10
C. to the boiling point range of the inert solvent used. The reaction time is not constant depending on the reaction scale and the reaction temperature, but may be appropriately selected from the range of several minutes to 48 hours. After completion of the reaction, the desired product is isolated from the reaction system containing the desired product by a conventional method, for example, solvent extraction or the like, and purified if necessary to obtain an oxazol represented by the general formula (I-2). -Or thiazole derivatives can be prepared.

[0013]

[Chemical 8]

[In the formula, R ^1-1 is a halogen atom, and (C 1-
6) an alkyl group or -OR ^4-2 (wherein R ^4-2 is (C1-6)
Indicates an alkyl group. R ^2-2 is a (C 1-6) alkyl group, a lower halo (C 1-6) alkyl group, a lower cyclo (C 1-6) alkyl group, a (C 1-6) alkoxy (C
1-6) alkyl group, (C1-6) alkylthio (C1
-6) represents an alkyl group, Z represents a halogen atom, X
And Y are the same as above. ]

Manufacturing method 2. General formula (III) + general formula (IV)
→ General formula (I-3) This reaction is carried out by reacting the compound represented by the general formula (III) with the compound represented by the general formula (IV). Can be prepared.
In this reaction, use of an inert solvent is not particularly required, but an inert solvent can also be used, and the reaction is preferably performed without a solvent. The compound represented by the general formula (IV) may be appropriately selected from the equimolar to excess molar range with respect to the compound represented by the general formula (III), and preferably the equimolar to 2-fold molar range. Is good. The reaction temperature may be 80 ° C. to 200 ° C., preferably around 150 ° C. The reaction time is not constant depending on the reaction temperature, reaction scale, etc., but may be appropriately selected from the range of several minutes to 48 hours.
After completion of the reaction, the oxazol derivative represented by the general formula (I-3) can be produced by isolating it from the reaction system containing the desired product by a conventional method and purifying it if necessary.

Manufacturing method 3. General formula (III) + general formula (V)
→ general formula (I-4) This reaction is carried out by reacting the compound represented by the general formula (III) with the compound represented by the general formula (V) in the presence of an inert solvent. ) The thiazole derivative represented by these can be manufactured. Any inert solvent that can be used in this reaction may be used as long as it does not significantly inhibit the progress of this reaction. For example, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, etc., aromatic solvents such as benzene, toluene, xylene, etc. Hydrocarbons, esters such as ethyl acetate,
Acetonitrile, nitriles such as benzonitrile, chain ethers such as methyl cellosolve diethyl ether, cyclic ethers such as dioxane and tetrahydrofuran, sulfolane, dimethylformamide, dimethyl sulfone,
Examples of the solvent include dimethyl sulfoxide and water. These inert solvents may be used alone or in combination.

The compound represented by the general formula (V) is represented by the general formula (II
It may be selected from an equimolar to excess molar range with respect to the compound represented by I), and preferably in an equimolar to 2-fold molar range. The reaction temperature may be room temperature to the boiling point range of the inert solvent used. The reaction time is not constant depending on the reaction temperature, reaction scale, etc., but may be appropriately selected from the range of several minutes to 48 hours. After completion of the reaction, the thiazole derivative represented by the general formula (I-4) can be produced by isolating it from the reaction system containing the desired product by a conventional method and purifying it if necessary.

Production Method 4 General Formula (III) + General Formula (IV)
→ general formula (I-4) This reaction is carried out by reacting the compound represented by the general formula (III), the compound represented by the general formula (IV) and the Lawesson's reagent in the presence of an inert solvent. The thiazole derivative represented by the general formula (I-4) can be produced. This reaction is performed in the same manner as in Production method 3, and the compound represented by the general formula (IV) and the Lawesson's reagent are selected from the equimolar to 3-fold molar range relative to the compound represented by the general formula (III). You can do it. After completion of the reaction, the thiazole derivative represented by the general formula (I-4) can be produced by isolating it from the reaction system containing the desired product by a conventional method and purifying it if necessary.

Manufacturing method 5.

[Chemical 9] (In the formula, R ^4-2 represents a (C1-6) alkyl group, M represents an alkali metal atom, and X, Y and Z are the same as above.)
By reacting the compound represented by the general formula (VI) with the compound represented by the general formula (VII) in the presence of an inert solvent, and then by reacting with an acid to hydrolyze and cyclize the compound represented by the general formula (I- Five)
The thiazole derivative represented by can be produced.
This reaction is based on J. Med. Chem. 1991, 34, 18
As an inert solvent which can be produced by the method described in 60-1866 and can be used in this reaction, for example, acetone, ethanol, acetonitrile, dimethylformamide, dimethylsulfoxide, water or the like can be used. As the compound represented by the general formula (VI), for example, sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate or the like can be used, and as the acid, for example, a mineral acid such as hydrochloric acid or sulfuric acid can be used. can do.

Manufacturing method 6.

[Chemical 10] (In the formula, R ^2-3 is a (C 1-6) alkyl group or (C 1-)
6) represents a haloalkyl group, wherein R ^4-2 , X, Y and Z are the same as defined above. ) By reacting a thiazole derivative represented by the general formula (I-5) with a compound represented by the general formula (VIII) in the presence or absence of an inert solvent and in the presence of a base, A thiazole derivative represented by the formula (I-6) can be produced. This reaction can be produced in the same manner as in Production method 1.

Manufacturing Method 7.

[Chemical 11] (In the formula, R ^3-1 represents a halogen atom, and R ¹ , R ² , X, Y and A are the same as above.) This reaction is represented by the general formula (I-7): oxazol or thiazo. The oxazole or thiazole derivative represented by the general formula (I-8) can be produced by halogenating the diol derivative in the presence of an inert solvent.

As the inert solvent which can be used in this reaction,
For example, halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, aromatic hydrocarbons such as benzene, toluene and xylene, methyl cellosolve and diethyl ether.
Chain or cyclic ethers such as tellurium, tetrahydrofuran and dioxane, organic acids such as acetic acid, sulfolane, dimethyl sulfoxide, N, N-dimethylformamide, acetonitrile, water and the like can be used, and an inert solvent thereof can be used. These may be used alone or in combination. Examples of the halogenating agent include chlorine, bromine, iodine,
Sulfuryl chloride, phosphorus pentachloride, phosphorus pentabromide and the like can be used. A catalytic amount of iron powder for the purpose of promoting this reaction,
Potassium iodide, iodine and the like can be used, and dehalogenating agents such as sodium acetate, potassium acetate, sodium hydrogencarbonate and potassium hydrogencarbonate can also be used.

Since this reaction is an equimolar reaction, it has the general formula (I-
The halogenating agent may be used in an equimolar amount to the oxazole or thiazole derivative represented by 7), but it may be used in a slight excess. The reaction temperature may be selected from the range of −10 ° C. to the boiling point range of the inert solvent used to carry out the reaction. The reaction time is not constant depending on the reaction scale, reaction temperature, etc., but may be selected from the range of several minutes to 48 hours.
After completion of the reaction, the oxazol or thiazole derivative represented by the general formula (I-8) can be produced by isolating the reaction mixture containing the desired product by a conventional method and purifying it if necessary. .

Manufacturing Method 8.

[Chemical 12] (In the formula, R ² , R ³ , X, Y and A are the same as above.) In this reaction, a compound represented by the general formula (IX) is subjected to a nitration reaction with a nitrating agent in the presence of an inert solvent. By the general formula (I-9)
An oxazole or thiazole derivative represented by can be produced. As the nitrating agent that can be used in this reaction, for example, concentrated nitric acid or a mixture of fuming nitric acid and concentrated sulfuric acid, acetyl nitrate produced by mixing concentrated nitric acid and acetic anhydride, and the like can be used. As the inert solvent that can be used in this reaction, a mineral acid such as sulfuric acid or hydrochloric acid can be used. Since this reaction is an equimolar reaction, the nitrating agent may be used in an equimolar amount to the compound represented by the general formula (IX), but may be used in excess.

The reaction temperature may be in the range of -10 ° C to 140 ° C, preferably -10 to 20 ° C. The reaction time is not constant depending on the reaction scale, reaction temperature, etc., but may be selected from the range of several minutes to 48 hours. After completion of the reaction, a compound of the general formula can be obtained by a conventional method from a reaction solution containing the desired product, for example, by pouring the reaction solution into ice water to collect precipitated crystals by filtration, or by isolating by operations such as solvent extraction, and purifying as necessary. The oxazole or thiazole derivative represented by (I-9) can be produced.

Manufacturing Method 9.

[Chemical 13] (In the formula, R ² , R ³ , X, Y, and A are the same as above.) In this reaction, the oxazole or thiazole derivative represented by the general formula (I-9) is reacted in the presence of an inert solvent. The oxazole or thiazole derivative represented by the general formula (I-10) can be produced by subjecting the compound to a reduction reaction with a reducing agent. Examples of the inert solvent that can be used in this reaction include alcohols such as methanol, ethanol and propanol, and diethyl ether.
Tellur, methyl cellosolve, dioxane, chain-like or cyclic ethers such as tetrahydrofuran, organic acids such as acetic acid,
Mineral acids such as hydrochloric acid, water and the like can be used, and these inert solvents can be used alone or in a mixture.

As the reducing agent which can be used in this reaction, for example, zinc, iron, tin, tin chloride or the like can be used under acidic conditions. Under neutral or basic conditions, zinc powder can be used under the same conditions as under acidic conditions. In the catalytic hydrogenation method, the reaction can be carried out under normal pressure or under pressure. For example, Raney-nickel, palladium carbon, palladium oxide, platinum, platinum black, platinum sulfide carbon, rhodium alumina, etc. are used. can do. When the reaction is carried out under acidic conditions, the reducing agent may be used in an equimolar to excess molar range with respect to the oxazole or thiazole derivative represented by the general formula (I-9). When used in a catalytic hydrogenation method such as Raney-Nickel, it is used in an amount of 5 to 20% by weight based on the weight of the oxazole or thiazole derivative represented by the general formula (I-9). %, When a noble metal catalyst such as platinum or palladium is used, it may be used in the range of 0.02 to 5% by weight.

The reaction temperature may be in the range of 0 ° C to 150 ° C, preferably 10 to 100 ° C. The reaction time is not constant depending on the reaction scale, reaction temperature, etc., but may be selected from the range of several minutes to 48 hours. After completion of the reaction, when the reaction is carried out under acidic conditions, the reaction solution containing the desired product is poured into ice water and isolated by a method such as solvent extraction to make it basic, or the reaction solution in the case of catalytic hydrogenation method. It can be isolated by filtering off the catalyst from the, and the filtrate is concentrated, and by performing purification or the like if necessary, the compound of the general formula (I-1
Oxazole or thiazole derivatives represented by 0) can be produced.

Manufacturing method 10.

[Chemical 14] (In the formula, R ² , R ³ , X, Y, Z and A are the same as above.) In this reaction, a compound represented by the general formula (IX) is reacted with a halosulfonylating agent in the presence of an inert solvent. By making the general formula
The oxazole or thiazole derivative represented by (I-11) can be produced. Examples of the inert solvent that can be used in this reaction include methylene chloride, chloroform, halogenated hydrocarbons such as carbon tetrachloride, aliphatic nitriles such as acetonitrile, methyl cellosolve, diethyl ether, dioxane, and tetrahydrofuran. Mineral acids such as chain or cyclic ethers and concentrated sulfuric acid can be used.

As the halosulfonylation, for example, chlorosulfonic acid or the like can be used, or in addition, sulfonation is performed with fuming sulfuric acid, and the resulting sulfonic acid is used as an alkali metal salt, and the alkali metal salt is phosphorus pentachloride. A method for producing an oxazol or thiazole derivative represented by the general formula (1-11) by chlorination with, etc., reacting fuming sulfuric acid, and then reacting with carbon tetrachloride to obtain the desired general formula (1 The method for producing an oxazole or thiazole derivative represented by -11) can be used. When using chlorosulfonic acid, the amount used may be selected from the range of equimolar to excess molar to the compound represented by the general formula (IX),
It is preferable to use an excess amount, and when fuming sulfuric acid is used, it may be used by selecting from a range of equimolar to excess molar, preferably used in excess molar, and carbon tetrachloride is also used in an equimolar to excess molar amount. It may be used by selecting from the range.

The reaction temperature may be in the range of 0 to 180 ° C, preferably 15 to 100 ° C. The reaction time is not constant depending on the reaction scale, reaction temperature, etc., but may be selected from the range of several minutes to 48 hours. After completion of the reaction, the reaction mixture containing the desired compound is subjected to a conventional method, for example, the reaction solution is poured into ice water, and isolated by a method such as solvent extraction, and purified as necessary to give the compound of the general formula (I-11). The oxazole or thiazole derivatives represented can be prepared.

Manufacturing Method 11.

[Chemical 15] (In the formula, R ² , R ³ , X, Y, Z and A are the same as above.) In this reaction, an oxazol or thiazole derivative represented by the general formula (I-11) is used as an inert solvent. The oxazole or thiazole derivative represented by the general formula (I-12) can be produced by the reduction reaction in the presence. This reduction reaction may be carried out in the presence of an inert solvent such as glacial acetic acid, and as the reducing agent used in this reaction, for example, zinc, tin, tin chloride or the like can be used. It may be used in an equimolar to excess molar amount with respect to the oxazole or thiazole derivative represented by the general formula (I-11), preferably 5
It is better to use more than twice the mole.

The reaction temperature may be in the range of 0 to 180 ° C, preferably 15 to 120 ° C. The reaction time is not constant depending on the reaction scale, reaction temperature, etc., but may be selected from the range of several minutes to 48 hours. After completion of the reaction, the reaction mixture containing the target compound is subjected to a conventional method, for example, the reaction solution is poured into ice water, and isolated by a method such as solvent extraction, and purified by the general formula (I-12) as necessary. The oxazole or thiazole derivatives represented can be prepared.

Manufacturing method 12.

[Chemical 16] (In the formula, R ² , R ³ , R ^4-2 , X, Y, Z and A are the same as the above.) The oxazole or thiazole derivative represented by the general formula (I-13) is inactive. By reacting with a dealkylating agent in the presence of a solvent, an oxazo group represented by the general formula (I-14)
Thiol or thiazole derivatives can be prepared. As the dealkylating agent used in this reaction, aluminum halide, boron trihalide, mineral acid and the like can be used. For example, aluminum halide such as aluminum chloride and aluminum bromide, boron trichloride, boron tribromide. ,
When using a boron trihalide such as boron triiodide,
Examples of the inert solvent include halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, benzene,
Aromatic hydrocarbons such as toluene and xylene can be used, and when mineral acids such as hydrobromic acid and hydroiodic acid are used, organic acids such as glacial acetic acid, water and the like mineral acids themselves. Can also be used as an inert solvent, and these inert solvents can be used alone or in a mixture.

When aluminum halide is used as the dealkylating agent, the amount used is in the range of catalytic amount to equimolar amount with respect to the oxazole or thiazole derivative represented by the general formula (I-13). When boron trihalide is used, it should be selected from the equimolar to 1.5-fold molar range and used after completion of the reaction to decompose the boron complex by adding water to the reaction solution. Good. When the mineral acid is used, it is preferable to use it in a large excess with respect to the oxazole or thiazole derivative represented by the general formula (I-13).

The reaction temperature may be selected from room temperature to the boiling point range of the inert solvent used. The reaction time is not constant depending on the reaction scale, reaction temperature, etc., but may be selected from the range of several minutes to 48 hours. After completion of the reaction, it is isolated by a conventional method from the reaction solution containing the desired product and, if necessary, purified or the like to produce an oxazole or thiazole derivative represented by the general formula (I-14). You can

Representative examples of the oxazole or thiazole derivative represented by the general formula (I) of the present invention are shown in Table 1 below, but the present invention is not limited thereto. General formula
(I)

[Chemical 17]

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

[Table 3]

[0041]

[Table 4]

[0042]

[Table 5]

[0043]

[Table 6]

[0044]

[Table 7]

[0045]

[Table 8]

[0046]

[Table 9] Note: In Table 1, "-c" or "c-" indicates an alicyclic compound, and "Ph" indicates a phenyl group. Physical properties of the compounds shown in Table 1 are shown in Table 2.

[0047]

[Table 10]

[0048]

[Table 11]

[0049]

[Table 12]

[0050]

[Table 13]

[0051]

[Table 14]

[0052]

[Table 15]

[0053]

[Table 16]

[0054]

[Table 17]

[0055]

[Table 18]

The oxazo group represented by the general formula (I) of the present invention
The compound represented by the general formula (III) when producing a thiol or thiazole derivative can be produced, for example, by the production method shown below.

[Chemical 18] (In the formula, R ^1-1 , X, Y and Z are the same as defined above, and Z ¹ represents a halogen atom.) The compound represented by the general formula (X) and the compound represented by the general formula (XI) The compound represented by the general formula (III) can be produced by subjecting and to a Friedel-Crafts reaction or halogenating the compound represented by the general formula (XII). Similarly, the compounds represented by the general formula (VI) and the general formula (IX) can be produced from the corresponding starting compounds by the above method and the method of the present invention.

[0057]

EXAMPLES Representative examples of the present invention will be illustrated below, but the present invention is not limited thereto. Example 1. 1-1. Preparation of 4- (4-chloro-2-fluoro-5-isopropoxyphenyl) -2-isopropyloxazole (Compound No 12).

[Chemical 19] 1-Bromo-2- (4-chloro-2-fluoro-5-isopropoxyphenyl) -2-ethanone 3.10 g (1
0.0 mmol) and 2.61 g of isobutyric acid amide (3
0.0 mmol) was heated at 150 ° C. to 160 ° C. for 5.5 hours. After completion of the reaction, the reaction solution containing the desired product was poured into ice water, extracted with ether, the extract was dried over magnesium sulfate, and the solvent was distilled off to obtain an oily product, which was purified by dry column chromatography. Thus, 2.44 g of the desired product was obtained. Yield 81.9% Physical properties ¹ H-NMR [CDCl ₃ / TMS, δ value (ppm)] 1.391 (12H, m), 3.153 (1H, m), 4.641 (1H, m), 7.157 (1H,
d), 7.616 (1H, d), 7.933 (1H, d).

1-2. Preparation of 4- (4-chloro-2-fluoro-5-isopropoxyphenyl) -2-methylthiazole (Compound No 38).

[Chemical 20] 1-Bromo-2- (4-chloro-2-fluoro-5-isopropoxyphenyl) -2-ethanone 0.93 g
(3.0 mmol) and thioacetamide 0.24 g
(3.2 mmol) was added to 15 ml of water and the mixture was refluxed at 4
The reaction was carried out over time. After completion of the reaction, the reaction solution containing the desired product was neutralized with an aqueous sodium hydroxide solution, extracted with dichloromethane, the extract was dried over magnesium sulfate, and the solvent was distilled off to obtain an oily product, which was subjected to dry column chromatography-
The desired product (0.75 g) was obtained by purification with. Yield 87.5% Physical properties nD1.5845 (20.0 ° C)

Example 2. Preparation of 4- (4-chloro-2-fluoro-5-methoxyphenyl) -2-hydroxythiazole (Compound No 34).

[Chemical 21] 1-Bromo-2- (4-chloro-2-fluoro-5-methoxyphenyl) -2-ethanone 1.13 g (4.01)
Limol) was dissolved in 30 ml of acetone, 0.41 g (4.21 mmol) of potassium thiocyanate was gradually added, and the reaction was carried out at room temperature for 2 hours. Then, the reaction solution was poured into ice water and extracted with ethyl acetate. The extract was dried over magnesium sulfate and then the solvent was distilled off to give crude crystals obtained with ethanol 3
0 ml and 1 N-hydrochloric acid 7 ml were added and the reaction was carried out for 10 hours under heating. Further, 1 N-hydrochloric acid 24 ml was added and the reaction was carried out for 11 hours. After completion of the reaction, the reaction solution is allowed to cool and the precipitated crystals are collected by filtration, washed with water and dried to give the desired product 0.62.
g was obtained. Yield 59.5% Physical properties ¹ H-NMR [DMSO-d ₆ / TMS, δ value (ppm)] 3.901 (3H, s), 6.799 (1H, t), 7.353 (1H, d), 7.569 (1H,
d).

Example 3. Preparation of 4- (4-chloro-2-fluoro-5-methoxyphenyl) -2-difluoromethoxythiazole (Compound No 36).

[Chemical formula 22] 0.62 g (2.39) 4- (4-chloro-2-fluoro-5-methoxyphenyl) -2-hydroxythiazole
Mmol) and 0.35 g (5.02 mmol) of potassium carbonate were added to 20 ml of dimethylformamide, and the reaction was carried out at 80 ° C. for 30 minutes while blowing Freon 22 gas into the reaction solution. After the reaction is completed, the reaction solution is poured into ice water,
After extraction with ethyl acetate, the extract was dried over magnesium sulfate, the solvent was distilled off, and the resulting oily product was purified by dry column chromatography to give 0.59 g of the desired product.
Got Yield 79.8% Physical properties ¹ H-NMR [CDCl ₃ / TMS, δ value (ppm)] 3.949 (3H, s), 7.194 (1H, d), 7.355 (1H, t), 7.363 (1H,
d), 7.582 (1H, d).

Example 4. 4-1. Preparation of 5-chloro-4- (4-chloro-2-fluoro-5-isopropoxyphenyl) -2-isopropyloxazole (Compound No 13).

[Chemical formula 23] 4- (4-chloro-2-fluoro-5-isopropoxyphenyl) -2-isopropyloxazole 1.20 g
(4.03 mmol) was dissolved in 30 ml of acetonitrile, 0.72 g (5.24 mmol) of sulfuryl chloride was added under ice cooling, and the reaction was carried out for 8 hours. After completion of the reaction, the reaction mixture containing the desired product is made basic by adding an aqueous sodium hydrogen carbonate solution, extracted with ethyl acetate, dried over anhydrous magnesium sulfate, and the solvent is distilled off to give the desired product 1.15.
g was obtained. Yield 81.9% Physical properties ¹ H-NMR [CDCl ₃ / TMS, δ value (ppm)] 1.370-1.400 (12H, m), 3.110 (1H, m), 4.540 (1H, m), 7.18
0 (1H, d), 7.191 (1H, d).

4-2. 5-chloro-4- (4-chloro-2-fluoro-5-isopropoxyphenyl) -2-
Production of methyl thiazole (Compound No 39).

[Chemical formula 24] 0.75 g of 4- (4-chloro-2-fluoro-5-isopropoxyphenyl) -2-methylthiazole (2.6
(2 mmol) was dissolved in 30 ml of carbon tetrachloride, 0.39 g (2.89 mmol) of sulfuryl chloride was added under ice-cooling, the reaction was carried out for 5 hours, and further 3 ml of dimethylformamide.
And 0.33 g of sodium hydrogen carbonate were added and the mixture was allowed to stand overnight. After completion of the reaction, dichloromethane is added to the reaction solution containing the desired product, the organic layer is separated, the extract is dried over magnesium sulfate, and the solvent is distilled off to obtain an oily product which is purified by dry column chromatography. The target object 0.4
8 g was obtained. Yield 57.1% Physical properties nD1.5810 (19.8 ° C)

4-3. Preparation of 5-bromo-4- (4-chloro-2-fluoro-5-methoxyphenyl) -2-difluoromethoxythiazole (Compound No 37).

[Chemical 25] 4- (4-chloro-2-fluoro-5-methoxyphenyl) -2-difluoromethoxythiazole 0.55 g
(1.78 mmol) was dissolved in 25 ml of dichloromethane, 0.31 g (1.96 mmol) of bromine was added dropwise under ice-cooling at 0 ° C or lower to carry out reaction for 1 hour, and further reacted at room temperature for 4 hours. I went. After completion of the reaction, the reaction solution containing the desired product was washed with an aqueous solution of sodium hydrogen carbonate and then with an aqueous solution of sodium thiosulfate, dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain 0.70 g of the desired product. Yield Quantitative physical properties ¹ H-NMR (CDCl ₃ / TMS, δ value (ppm)) 3.914 (3H, s), 7.009 (1H, d), 7.240 (1H, d), 7.262 (1H,
t).

Example 5. 5-chloro-4- (2,4-
Dichloro-5-nitrophenyl) -2-methylthiazo-
(Compound No 56).

[Chemical formula 26] 5-chloro-4- (2,4-dichlorophenyl) -2-
4.18 g (15 mmol) of methyl thiazole was dissolved in 23 ml of concentrated sulfuric acid, and mixed acid (60% nitric acid 3.94) was added to the solution.
g and 7.15 g of concentrated sulfuric acid) were added dropwise under ice cooling, and then the reaction was carried out at room temperature for 5 hours. After the reaction was completed, the reaction solution containing the target product was poured into ice water, extracted with ether, the extract was dried over magnesium sulfate, and the solvent was distilled off to obtain 4.79 g of the target product. Yield 98.7% Physical properties mp 69.0-70.6 ° C

Example 6. 4- (4-amino-2,4-
Dichlorophenyl) -5-chloro-2-methylthiazo-
(Compound No 57).

[Chemical 27] 5.35 g (13.4 mmol) of 5-chloro-4- (2,4-dichloro-5-nitrophenyl) -2-methylthiazole and 12.13 g (53.8 mmol) of stannous chloride were added to concentrated hydrochloric acid. In addition to 70 ml, the reaction was carried out at 70-80 ° C for 1 hour. After completion of the reaction, the reaction mixture containing the desired product was poured into ice water, made basic with an aqueous sodium hydroxide solution, extracted with ethyl acetate, the extract was dried over magnesium sulfate, and the solvent was distilled off to obtain an oily substance. The desired product 3.6 was obtained by purifying 4.10 g of the product by dry column chromatography.
9 g was obtained. Yield 93.5% Physical property mp102.2 ° C

Example 7. 5-chloro-4- (2,4-
Preparation of dichloro-5-chlorosulfonylphenyl) -2-methylthiazole (Compound No 52).

[Chemical 28] 5-chloro-4- (2,4-dichlorophenyl) -2-
1.48 ml of chlorosulfonic acid was added dropwise to 1.13 g (4.06 mmol) of methyl thiazole under ice cooling, and after completion of the addition, reaction was carried out at 100 ° C. for 5 hours. After completion of the reaction, the reaction solution containing the desired product was poured into ice water and extracted with ether,
The extract was dried over magnesium sulfate and the solvent was distilled off to obtain 1.03 g of the desired product. Yield 67.3% Physical properties mp 134.5 ° C

Example 8. 5-chloro-4- (2,4-
Preparation of dichloro-5-mercaptophenyl) -2-methylthiazole (Compound No 53).

[Chemical 29] 5-chloro-4- (2,4-dichloro-5-chlorosulfonylphenyl) -2-methylthiazole 0.79 g
(2.10 mmol) and 2.60 g of stannous chloride (1
(1.5 mmol) was added to 3 ml of concentrated hydrochloric acid to 70 ° C to 80 ° C.
The reaction was carried out at 0 ° C for 1 hour. After completion of the reaction, the reaction solution containing the target product was poured into ice water, extracted with ether, the extract was dried over magnesium sulfate, and the solvent was distilled off to obtain 0.58 g of the target product. Yield 89.1% Physical properties mp 54.7-55.2 ° C

Example 9. 9-1. Preparation of 5-bromo-4- (4-chloro-2-fluoro-5-hydroxyphenyl) -2-difluoromethoxythiazole (Compound No 33).

[Chemical 30] 0.70 g (1.78 mmol) of 5-bromo-4- (4-chloro-2-fluoro-5-methoxyphenyl) -2-difluoromethoxythiazole was dissolved in 10 ml of concentrated sulfuric acid, and 70 ° C to 75 ° C. The reaction was carried out for 8 hours. After completion of the reaction, the reaction solution containing the target product was poured into ice water, extracted with ether, the extract was dried over magnesium sulfate, and the solvent was distilled off to obtain 0.67 g of the target product. Yield Quantitative physical properties ¹ H-NMR (CDCl ₃ / TMS, δ value (ppm)) 5.430 (1H, s), 7.161 (1H, d), 7.191 (1H, d), 7.252 (1H,
t).

9-2. Preparation of 5-chloro-4- (4-chloro-2-fluoro-5-hydroxyphenyl) -2-isopropyloxazole (Compound No 4).

[Chemical 31] 5-chloro-4- (4-chloro-2-fluoro-5-isopropoxyphenyl) -2-isopropyloxazo-
1.15 g (3.46 mmol) of this solution was dissolved in concentrated sulfuric acid,
The reaction was carried out at room temperature for 1 hour. After completion of the reaction, the reaction solution containing the desired product was poured into ice water, extracted with ether, the extract was dried over magnesium sulfate, and the solvent was distilled off to obtain an oily product, which was purified by dry column chromatography. By doing so, 0.57 g of the desired product was obtained. Yield 56.8% Physical properties ¹ H-NMR [CDCl ₃ / TMS, δ value (ppm)] 1.369 (3H, s), 1.393 (3H, s), 3.107 (1H, m), 7.152 (1H,
d), 7.274 (1H, d).

Example 10. 10-1. 5-chloro-4- (4-chloro-2-fluoro-5- (2-propynyloxy) phenyl) -2-
Production of isopropyl oxazole (Compound No 23).

[Chemical 32] 0.30 g (1.03 mmol) of 5-chloro-4- (4-chloro-2-fluoro-5-hydroxyphenyl) -2-isopropyloxazole, potassium carbonate 0.1
2 g (0.87 mmol) and 0.2 propargyl bromide
0 g (1.72 mmol) was suspended in 20 ml of acetone and reacted under reflux for 3 hours. After completion of the reaction, the reaction solution containing the desired product is poured into ice water, extracted with ethyl acetate, the extract is dried over magnesium sulfate, and the solvent is distilled off to obtain an oily product, which is purified by dry column chromatography. As a result, 0.30 g of the desired product was obtained. Yield 88.4
% Physical properties nD1.5644 (24.0 ° C)

10-2. Preparation of 5-bromo-4- (4-chloro-2-fluoro-5-methoxycarbonylmethoxyphenyl) -2-difluoromethoxythiazole (Compound No 49).

[Chemical 33] 5-Bromo-4- (4-chloro-2-fluoro-5-hydroxyphenyl) -2-difluoromethoxythiazo-
0.67 g (1.78 mmol), potassium carbonate 0.
18 g (1.30 mmol) and methyl bromoacetate 0.1.
41 g (2.68 mmol) was suspended in 25 ml of acetone, and the reaction was carried out under reflux for 3 hours. After completion of the reaction, the reaction solution containing the desired product is poured into ice water, extracted with ethyl acetate, the extract is dried over magnesium sulfate, and the solvent is distilled off to obtain an oily product, which is purified by dry column chromatography. As a result, 0.74 g of the desired product was obtained. Yield 93.1% mp 65.5-66.7 ° C

The oxazo group represented by the general formula (I) of the present invention
Examples of herbicides containing a thiol or thiazole derivative as an active ingredient include, for example, Novier (common name for "Tainubie", first-year grass of grass family, highly damaging grass of paddy field), and Periwinkle (Cyperaceae 1).
Annual grass, paddy field damage), Pinus sylvestris (Cyperaceae perennial grass, occurring in wetlands, waterways, and paddy fields, typical perennial damage of paddy fields), Urikawa (Oldaceae, paddy fields, wetlands, and perennial damage occurring in ditches) , Firefly (Perennial perennial grass,
(Occurs in paddy fields, wetlands, ditches), oat (perennial grass, perennial land, wasteland, field), mugwort (perennial perennial grass, mountains, land), honey clover (1st grass, field, (Representatively damaging grasses in orchards), Rumex japonicus (Perennial perennial grass, occurring in fields, roadsides), Kogomegayatsu (Cyperaceae 1)
Annual grass, Aoyu (1st year grass family, vacant land, roadside, upland field), Ona fir (1st year family Asteraceae, harmful grass field), hibiscus (1st year mallow family, harmful field field), Josh Paddy fields such as Korean morning glory (convolvulaceae first-year grass, field harmful grass), Scutellaria baicalensis (Sesameaceae 1-2 year-old grass, field harmful grass), Yaemgra (Rubiaceae first year grass, field, arable land harmful grass) It is useful for weeding annual and perennial weeds that occur in fields, orchards, wetlands, etc.

The oxazo group represented by the general formula (I) of the present invention
A herbicide containing a thiol or thiazole derivative as an active ingredient shows an excellent herbicidal effect on weeds before and after emergence. After that (including the case where useful plants have already been planted like a garden), the weeds of the present invention can be effectively expressed with the characteristic physiological activity of the weeds of the present invention by treating the weeds from the initial stage to the growing stage.
However, the herbicide of the present invention should not be used only in such an embodiment.For example, the herbicide of the present invention can be used not only as a herbicide for paddy fields but also as a herbicide for general weeds. It can be used, for example, cuttings, fallow fields, ridges, farm roads, waterways,
It can also be used to control general weeds such as grasslands, cemeteries, parks, roads, playgrounds, vacant lots around buildings, cultivated land, track ends, and forests. In this case, it is economically most effective to treat the weeds by the first stage of development, but the treatment is not necessarily limited to this, and it is possible to control the weeds in the growing season.

The oxazo group represented by the general formula (I) of the present invention
When using a thiol or thiazole derivative as a herbicide,
In general, it is used by formulating into a convenient shape for use according to a conventional method for pesticide formulation. That is, the general formula of the present invention
The oxazole or thiazole derivative represented by (I) is
These are mixed with an appropriate inert carrier or, if necessary, an auxiliary agent in an appropriate ratio to dissolve, separate, suspend, mix, impregnate, adsorb or adhere to give an appropriate dosage form such as suspension. It may be used by formulating it as a turbid agent, emulsion, liquid, wettable powder, granule, powder, tablet, or the like.

The inert carrier that can be used in the present invention may be either solid or liquid, and examples of the material which can be a solid carrier include soybean flour, cereal flour, wood flour, bark flour, sawdust powder, Tobacco stem powder, walnut shell powder, bran, fibrin powder, residue after extraction of plant extracts, synthetic polymers such as ground synthetic resin, clays (eg kaolin, bentonite, acid clay, etc.), talcs (eg talc, pyrophyllide) Etc.), silicas (for example, diatomaceous earth, silica sand, mica, white carbon [hydrogenated finely divided silicon, synthetic highly dispersed silicic acid also referred to as hydrous silicic acid, and some products include calcium silicate as a main component]), activated carbon, Sulfur powder, pumice stone, calcined diatomaceous earth, crushed brick, fly ash, sand, calcium carbonate, inorganic mineral powder such as calcium phosphate, ammonium sulfate,
Examples thereof include chemical fertilizers such as ammonium phosphate, ammonium nitrate, urea, ammonium chloride, and compost, which are used alone or in the form of a mixture of two or more kinds.

The material which can be used as a liquid carrier is selected from those having solvent ability per se and those having no solvent ability but capable of dispersing the active ingredient compound with the aid of an auxiliary agent. The following carriers can be mentioned as typical examples, and these can be used alone or in the form of a mixture of two or more kinds, and for example, water, alcohols (for example, methanol, ethanol, isopropanol, butanol). -, Ethylene glycol, etc.), ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone,
Diisobutyl ketone, cyclohexanone, etc.), ethers (eg ethyl ether, dioxane, cellosolve,
Dipropyl ether, tetrahydrofuran etc.), aliphatic hydrocarbons (eg kerosene, mineral oil etc.), aromatic hydrocarbons (eg benzene, toluene, xylene, solvent naphtha, alkylnaphthalene etc.), halogenated hydrocarbons (eg dichloroethane) , Chloroform, carbon tetrachloride, etc.), esters (eg ethyl acetate, diisopropyl phthalate, dibutyl phthalate, dioctyl phthalate)
Etc.), amides (eg dimethylformamide, diethylformamide, dimethylacetamide etc.), nitrites (eg acetonitrile etc.), dimethylsulfoxides and the like.

As the other auxiliary agents, there may be mentioned the representative auxiliary agents exemplified below. These auxiliary agents are used depending on the purpose and may be used alone or in some cases in combination of two or more kinds of auxiliary agents. However, in some cases it is also possible to use no adjuvant at all. Surfactants are used for the purpose of emulsifying, dispersing, solubilizing and / or wetting the active ingredient compound, for example polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene higher fatty acid. Ester, polyoxyethylene resin acid ester, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, alkyl aryl sulfonate, naphthalene sulfonic acid condensate,
Examples thereof include surfactants such as lignin sulfonate and higher alcohol sulfate.

Further, for the purpose of stabilizing the dispersion of active ingredient compounds, adhering and / or binding, auxiliary agents exemplified below can be used, for example, casein, gelatin, starch,
Auxiliary agents such as methylcellulose, carboxymethylcellulose, gum arabic, polyvinyl alcohol, pine oil, bran oil, bentonite and lignin sulfonate can also be used. The following auxiliaries can also be used for improving the flowability of the solid product, for example waxes, stearates, alkyl phosphates and the like. As a deflocculant for a suspending product, an auxiliary agent such as a naphthalenesulfonic acid condensate or a condensed phosphate can be used. As the defoaming agent, for example, an auxiliary agent such as silicone oil may be used.

The compounding ratio of the active ingredient compound can be adjusted according to need. For example, 0.01 to 50% by weight in the case of powder or granules, and 0. 01 to 50% by weight is suitable. The herbicide containing the oxazol or thiazole derivative represented by the general formula (I) of the present invention as an active ingredient is used as it is in order to kill or suppress the growth of various weeds, or appropriately diluted with water or the like. Alternatively, an amount effective for killing or suppressing growth in the form of a suspension may be applied to the weed, or applied to foliage or soil at a place where the development or growth of the weed is not preferable.

The oxazo group represented by the general formula (I) of the present invention
The amount of the herbicide containing a thiol or thiazole derivative as an active ingredient is various factors such as purpose, target weeds, growth status of crops, tendency of weeds, weather, environmental conditions, dosage form,
It varies depending on the application method, application place, application time, etc., but is 0.1 g to 10 g per hectare as an active ingredient compound.
It may be appropriately selected from the range of kg according to the purpose. For the purpose of further controlling the weeds to be controlled, the herbicide containing the oxazol or thiazole derivative represented by the general formula (I) of the present invention as an active ingredient, for the purpose of expanding the suitable control period, or for reducing the dose. It is also possible to use it by mixing with other herbicides. Typical formulation examples and test examples of the present invention are shown below, but the present invention is not limited thereto. In the formulation examples, “part” means “part by weight”.

Formulation Example 1 Compound of the present invention 50 parts Xylene 40 parts Mixture of polyoxyethylene nonylphenyl ether and calcium alkylbenzene sulfonate 10 parts The above components are uniformly mixed and dissolved to obtain an emulsion. Formulation Example 2 Compound of the present invention 3 parts Cray powder 82 parts Diatomaceous earth powder 15 parts The above ingredients are uniformly mixed and pulverized to give a powder.

Formulation Example 3 Compound of the present invention 5 parts Mixed powder of bentonite and clay 90 parts Calcium lignin sulfonate 5 parts The above components are uniformly mixed and kneaded by adding an appropriate amount of water to granulate,
Dry to make granules. Formulation Example 4 Compound of the present invention 20 parts Kaolin and synthetic highly disperse silicic acid 75 parts Mixture of polyoxyethylene nonylphenyl ether and calcium alkylbenzene sulfonate 5 parts The above are uniformly mixed and pulverized to obtain a wettable powder.

Test Example 1 Herbicidal effect test on paddy field weeds after emergence: Soil was packed in a 1/1000 al pot to make paddy field,
The seeds of paddy field weeds Novier (EC), firefly (SJ), and soul stalks of Mizugaya-tsuri (CS) and Urikawa (SP) were adjusted to the one-leaf stage. This was treated with a predetermined amount of a drug solution containing a compound of the present invention (compounds listed in Table 1) as an active ingredient. 21 days after the treatment, the herbicidal effect was investigated, the herbicidal rate was calculated in comparison with the untreated, and the judgment was made according to the following criteria. At the same time, an investigation of phytotoxicity to rice was also conducted, and it was judged according to the following criteria.

Criteria for herbicidal activity. 5: 95% or higher herbicide rate. 4 ... 70% or more and less than 95% herbicidal rate. 3 ... 50% or more and less than 70% herbicidal rate. 2 ... 30% or more and less than 50% herbicidal rate. 1 ... 10% or more and less than 30% herbicidal rate. 0 ... less than 10% herbicide rate. Criteria for drug damage. 5: 90% or more and 100% herbicidal rate. 4 ... 80% or more and less than 90% herbicidal rate. 3 ... 50% or more and less than 80% herbicidal rate. 2 ... 30% or more and less than 50% herbicidal rate. 1 ... grazing rate of 1% or more and less than 30%. 0 ... 0% (no chemical damage). The results are shown in Table 3.

[0085]

[Table 19]

[0086]

[Table 20]

[0087]

[Table 21]

[0088]

[Table 22]

[0089]

[Table 23]

Test Example 2 Herbicidal effect on field weeds before emergence: A polyethylene vat having a length of 10 cm, a width of 20 cm and a height of 5 cm was filled with soil, and this was used as a weed (E) which is a field weed.
C), Ichibi (AT), Onami fir (XS), Yaemgra (GA), Scutellaria baicalensis (VP), and soybean and wheat seeds as field crops were sown and covered. A drug containing the compound of the present invention (compounds listed in Table 1) as an active ingredient was treated as a spray solution having a predetermined concentration. The herbicidal effect was investigated 14 days after the treatment, and the herbicidal rate was calculated and judged in the same manner as in Test Example 1. At the same time, phytotoxicity to soybean and wheat was investigated, and judgment was made according to Test Example 1. The results are shown in Table 4.

[0091]

[Table 24]

[0092]

[Table 25]

Test Example 3 Herbicidal effect on field weeds after emergence: A polyethylene vat having a length of 10 cm × width of 20 cm × height of 5 cm was filled with soil, and seeds of soybean and wheat were sown as the following harmful landweeds and upland crops. The soil was covered and grown to the following leaf stage, and a drug containing the compound of the present invention (compounds shown in Table 1) as an active ingredient was treated as a spray solution having a predetermined concentration. The herbicidal effect was investigated 14 days after the treatment, and the herbicidal rate was calculated and judged in the same manner as in Test Example 1. At the same time, phytotoxicity to soybean and wheat was investigated, and judgment was made according to Test Example 1.

Test weed species and their leaf stages and soybean and wheat leaf stages. Flies (EC) 2-leaf stage Betula (AT) 1-leaf stage Ona fir (XS) 1-leaf stage Yaemgra (GA) 2-leaf stage Oenidofuguri (VP) 1-leaf stage Wheat 2-leaf stage Soybean 1-leaf stage The results are shown in Table 5. .

[0095]

[Table 26]

[0096]

[Table 27]

[0097]

[Table 28]

[0098]

[Table 29]

[0099]

[Table 30]

[0100]

[Table 31]

Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication location A01N 55/00 C 9159-4H C07D 263/34 263/38 277/24 277/26 277/28 277/32 277 / 34 C07F 7/08 A

Claims (3)

[Claims] 1. A compound represented by the general formula (I): [In the formula, R ¹ is a halogen atom, a nitro group, a (C1-6) alkyl group, a halosulfonyl group or -BR ⁴ (In the formula, B is O and S (O) n (wherein, n is 0 to 2). , Or NR
⁵ (In the formula, R ⁵ is a hydrogen atom, a (C1-6) alkyl group, a halo (C1-6) alkyl group, a (C2-6) alkenyl group, a halo (C2-6) alkenyl group, (C2-6) Alkynyl group, halo (C2-6) alkynyl group, cyclo (C
3-6) alkyl group, (C1-6) alkylsulfonyl group, halo (C1-6) alkylsulfonyl group, phenyl (C1-6) alkyl group, which may be the same or different, 1
The above halogen atom, (C1-6) alkyl group, halo (C1-6) alkyl group, (C1-6) alkoxy group,
Phenyl (C1-6) having a substituent selected from a halo (C1-6) alkoxy group, a (C1-6) alkylthio group or a halo (C1-6) alkylthio group on the phenyl ring.
6) An alkyl group, an aminosulfonyl group, or a substituted aminosulfonyl group having one or more substituents selected from the same or different (C1-6) alkyl groups. )
The indicated, R ⁴ is a hydrogen atom, (C1-6) alkyl, halo (C1-6) alkyl, hydroxy (C1-6) alkyl, (C2-6) alkenyl group, halo (C2-6)
Alkenyl group, (C2-6) alkynyl group, halo (C2
-6) alkynyl group, cyclo (C3-6) alkyl group,
Halocyclo (C3-6) alkyl group, (C1-6) alkoxy (C1-6) alkyl group, halo (C1-6) alkoxy (C1-6) alkyl group, (C1-6) alkoxy (C1-6) alkoxy (C1-6) alkyl group, halo (C1-6) alkoxy (C1-6) alkoxy (C
1-6) alkyl group, (C1-6) alkylthio (C1
-6) alkyl group, halo (C1-6) alkylthio (C
1-6) alkyl group, cyano (C1-6) alkyl group,
(C1-6) alkylcarbonyloxy (C1-6) alkyl group, phenylcarbonyloxy (C1-6) alkyl group, phenoxy (C1-6) alkyl group, which may be the same or different, a halogen atom, (C1-6) ) Alkyl group, halo (C1-6) alkyl group, (C1-6) alkoxy group, halo (C1-6) alkoxy group, (C1-6)
A substituted phenoxy (C1-6) alkyl group having one or more substituents selected from an alkylthio group or a halo (C1-6) alkylthio group on the phenyl ring, a phenylthio (C1-6) alkyl group, the same or different Well, halogen atom, (C1-6) alkyl group, halo (C1-
6) Alkyl group, (C1-6) alkoxy group, halo (C
1-6) Alkoxy group, (C1-6) alkylthio group or substituted phenylthio (C1-6) alkyl group having at least one substituent selected from halo (C1-6) alkylthio group on the phenyl ring, phenyl ( C1-6) alkyl group, which may be the same or different, a halogen atom, (C1
-6) alkyl group, halo (C1-6) alkyl group, (C
1-6) alkoxy group, halo (C1-6) alkoxy group, (C1-6) alkylthio group or halo (C1-6)
A substituted phenyl (C1-6) alkyl group having one or more substituents selected from alkylthio groups on the phenyl ring,
Tri ((C1-6) alkyl) which may be the same or different
Silyl (C1-6) alkyl group, which may be the same or different, di ((C1-6) alkoxy) phosphinyl (C1-
6) alkyl group, (C1-6) alkylsulfonyl group,
A substituted aminosulfonyl group having one or more substituents selected from a halo (C1-6) alkylsulfonyl group, an aminosulfonyl group, and (C1-6) alkyl groups which may be the same or different, or-(CHR ⁶ ) m- CO-B ¹ -R ⁷ (In the formula, R ⁶ represents a hydrogen atom or a (C 1-6) alkyl group, m represents an integer of 0 to 5, B ¹ represents O, S or NR ⁵ (in the formula, R ⁵ is the same as the above.), And R ⁷ is a hydrogen atom, a (C1-6) alkyl group, a halo (C1-6) alkyl group, a (C2-6) alkenyl group, a halo (C2-6) alkenyl group. , (C2-6)
Alkynyl group, halo (C2-6) alkynyl group, (C1
-6) Alkoxy (C1-6) alkyl group, halo (C1
-6) Alkoxy (C1-6) alkyl group, cyclo (C
3-6) alkyl group, cyano (C1-6) alkyl group,
(C1-6) alkylthio (C1-6) alkyl group, halo (C1-6) alkylthio (C1-6) alkyl group,
(C1-6) Alkoxy (C1-6) Alkoxy (C1
-6) Alkyl group, which may be the same or different, ((C
1-6) alkyl) silyl (C1-6) alkyl group, phenyl group, which may be the same or different, a halogen atom,
(C1-6) alkyl group, halo (C1-6) alkyl group, (C1-6) alkoxy group, halo (C1-6) alkoxy group, (C1-6) alkylthio group or halo (C1
-6) a substituted phenyl group having one or more substituents selected from alkylthio groups, a phenyl (C1-6) alkyl group, which may be the same or different, a halogen atom, (C1
-6) alkyl group, halo (C1-6) alkyl group, (C
1-6) alkoxy group, halo (C1-6) alkoxy group, (C1-6) alkylthio group or halo (C1-6)
A substituted phenyl (C1-6) alkyl group having one or more substituents selected from an alkylthio group on the phenyl ring is shown, and R ⁵ and R ⁷ may be taken together and interrupted by an oxygen atom (C2- 6) It can also represent an alkylene group, where B ¹ is O
In the case of, R ⁷ can also represent an alkali metal atom, a primary amine salt or a secondary amine salt. ), R ² is a hydroxyl group,
(C1-6) alkyl group, halo (C1-6) alkyl group, cyclo (C1-6) alkyl group, (C1-6) alkoxy group, halo (C1-6) alkoxy group, (C1-
6) Alkoxy (C1-6) alkyl group or (C1-
6) represents an alkylthio (C1-6) alkyl group, R ³ represents a hydrogen atom or a halogen atom, A represents O or S, X and Y may be the same or different, and a halogen atom,
A (C1-6) alkyl group or a (C1-6) haloalkyl group is shown. ] The oxazole or thiazole derivative represented by these. 2. A compound represented by the general formula (I-1): [In the formula, B ² is O, S or NR ⁵ (in the formula, R ⁵ is a hydrogen atom,
(C1-6) alkyl group, halo (C1-6) alkyl group, (C2-6) alkenyl group, halo (C2-6) alkenyl group, (C2-6) alkynyl group, halo (C2-
6) an alkynyl group, a cyclo (C1-6) alkyl group,
(C1-6) Alkylsulfonyl group, halo (C1-6)
An alkylsulfonyl group, a phenyl (C1-6) alkyl group, which may be the same or different, and one or more halogen atoms,
(C1-6) alkyl group, halo (C1-6) alkyl group, (C1-6) alkoxy group, halo (C1-6) alkoxy group, (C1-6) alkylthio group or halo (C1
-6) Phenyl (C1-6) alkyl group having a substituent selected from alkylthio group on the phenyl ring, aminosulfonyl group, or may be the same or different (C1-6)
A substituted aminosulfonyl group having one or more substituents selected from alkyl groups is shown. ), And R ^2-1 is (C1-
6) alkyl group, (C1-6) halo (C1-6) alkyl group, cyclo (C3-6) alkyl group, (C1-6) alkoxy group, halo (C1-6) alkoxy group, (C1-
6) Alkoxy (C1-6) alkyl group, (C1-6)
An alkylthio (C1-6) alkyl group, R ³ represents a hydrogen atom or a halogen atom, A represents O or S, X
And Y may be the same or different, a halogen atom, (C1
-6) represents an alkyl group or a (C1-6) haloalkyl group. ] And an oxazole or thiazole derivative represented by the general formula (II): embedded image R ^4-1 -Z (II) [wherein R ^4-1 is a (C 1-6) alkyl group, halo (C1-
6) alkyl group, hydroxy (C1-6) alkyl group,
(C2-6) alkenyl group, halo (C2-6) alkenyl group, (C2-6) alkynyl group, halo (C2-6) alkynyl group, cyclo (C3-6) alkyl group, halocyclo (C3-6) alkyl. Group, (C1-6) alkoxy (C1-6) alkyl group, halo (C1-6) alkoxy (C1-6) alkyl group, (C1-6) alkoxy (C
1-6) Alkoxy (C1-6) alkyl group, halo (C
1-6) Alkoxy (C1-6) Alkoxy (C1-
6) alkyl group, (C1-6) alkylthio (C1-
6) Alkyl group, halo (C1-6) alkylthio (C1
-6) alkyl group, cyano (C1-6) alkyl group,
(C1-6) alkylcarbonyloxy (C1-6) alkyl group, phenylcarbonyloxy (C1-6) alkyl group, phenoxy (C1-6) alkyl group, which may be the same or different, a halogen atom, (C1-6) ) Alkyl group, halo (C1-6) alkyl group, (C1-6) alkoxy group, halo (C1-6) alkoxy group, (C1-6)
A substituted phenoxy (C1-6) alkyl group having one or more substituents selected from an alkylthio group or a halo (C1-6) alkylthio group on the phenyl ring, a phenylthio (C1-6) alkyl group, the same or different Well, halogen atom, (C1-6) alkyl group, halo (C1-
6) Alkyl group, (C1-6) alkoxy group, halo (C
1-6) Alkoxy group, (C1-6) alkylthio group or substituted phenylthio (C1-6) alkyl group having at least one substituent selected from halo (C1-6) alkylthio group on the phenyl ring, phenyl ( C1-6) alkyl group, which may be the same or different, a halogen atom, (C1
-6) alkyl group, lower halo (C1-6) alkyl group,
Lower (C1-6) alkoxy group, halo (C1-6) alkoxy group, (C1-6) alkylthio group or halo (C1
-6) Substituted phenyl (C1-6) alkyl group having one or more substituents selected from alkylthio group on the phenyl ring, and tri ((C1-6) alkyl) silyl (C1-6, which may be the same or different. ) Alkyl group, di ((C1-6) alkoxy) phosphinyl (C1-6) alkyl group, which may be the same or different, (C1-6) alkylsulfonyl group, halo (C1-6) alkylsulfonyl group, aminosulfonyl group , May be the same or different (C1-6)
A substituted aminosulfonyl group having one or more substituents selected from an alkyl group or-(CHR ⁶ ) m-CO-B ¹ -R ⁷ (wherein R ⁶
Represents a hydrogen atom or a (C1-6) alkyl group, and m is 0
Is an integer of 5 to 5, B ¹ is O, S or NR ⁵ (in the formula, R ⁵ is the same as the above), R ⁷ is a hydrogen atom, a (C1-6) alkyl group, halo (C1-6). ) Alkyl group, (C2-6) alkenyl group, halo (C2-6) alkenyl group, (C2-
6) alkynyl group, halo (C2-6) alkynyl group,
(C1-6) Alkoxy (C1-6) alkyl group, halo (C1-6) alkoxy (C1-6) alkyl group, cyclo (C3-6) alkyl group, cyano (C1-6) alkyl group, (C1- 6) Alkylthio (C1-6) alkyl group, halo (C1-6) alkylthio (C1-6) alkyl group, (C1-6) alkoxy (C1-6) alkoxy (C1-6) alkyl group, the same or different. May be tri ((C1-6) alkyl) silyl (C1-6) alkyl group, phenyl group, same or different, halogen atom, (C1-6) alkyl group, halo (C1-6) alkyl group, (C1-6) alkoxy group, halo (C1-6) alkoxy group, (C1-6) alkylthio group or halo (C
1-6) Substituted phenyl group having one or more substituents selected from alkylthio group, phenyl (C1-6) alkyl group or the same or different, halogen atom, (C
1-6) alkyl group, halo (C1-6) alkyl group,
(C1-6) alkoxy group, halo (C1-6) alkoxy group, (C1-6) alkylthio group or halo (C1-
6) represents a substituted phenyl (C1-6) alkyl group having one or more substituents selected from alkylthio groups on the phenyl ring, and R ⁵ and R ⁷ together may be interrupted by an oxygen atom ( It can also represent a C2-6) alkylene group. ) And Z represents a halogen atom. ] The compound of the general formula (I-2) characterized by reacting with a compound represented by [In the formula, R ^2-1 , R ³ , R ^4-1 , B ² , X, Y and A are the same as defined above. ] The manufacturing method of the oxazole or thiazole derivative represented by these. 3. A compound represented by the general formula (I): [In the formula, R ¹ is a halogen atom, a nitro group, a (C1-6) alkyl group, a halosulfonyl group or -BR ⁴ (In the formula, B is O and S (O) n (wherein, n is 0 to 2). , Or NR
⁵ (In the formula, R ⁵ is a hydrogen atom, a (C1-6) alkyl group, a halo (C1-6) alkyl group, a (C2-6) alkenyl group, a halo (C2-6) alkenyl group, (C2-6) Alkynyl group, halo (C2-6) alkynyl group, cyclo (C
3-6) alkyl group, phenyl (C1-6) alkyl group, which may be the same or different, a halogen atom, (C1-
6) alkyl group, halo (C1-6) alkyl group, (C1
-6) alkoxy group, halo (C1-6) alkoxy group,
A phenyl (C1-6) alkyl group having at least one substituent selected from a (C1-6) alkylthio group or a halo (C1-6) alkylthio group on the phenyl ring;
6) represents a substituted aminosulfonyl group having one or more substituents selected from an alkylsulfonyl group, a halo (C1-6) alkylsulfonyl group, an aminosulfonyl group, or the same or different (C1-6) alkyl group. . And R ⁴ represents a hydrogen atom, a (C1-6) alkyl group, a halo (C1-6) alkyl group, a hydroxy (C1-6) alkyl group, a (C2-6) alkenyl group, a halo (C2-6).
Alkenyl group, (C2-6) alkynyl group, halo (C2
-6) alkynyl group, cyclo (C3-6) alkyl group,
Halocyclo (C3-6) alkyl group, (C1-6) alkoxy (C1-6) alkyl group, halo (C1-6) alkoxy (C1-6) alkyl group, (C1-6) alkoxy (C1-6) alkoxy (C1-6) alkyl group, halo (C1-6) alkoxy (C1-6) alkoxy (C
1-6) alkyl group, (C1-6) alkylthio (C1
-6) alkyl group, halo (C1-6) alkylthio (C
1-6) alkyl group, cyano (C1-6) alkyl group,
(C1-6) alkylcarbonyloxy (C1-6) alkyl group, phenylcarbonyloxy (C1-6) alkyl group, phenoxy (C1-6) alkyl group, which may be the same or different, a halogen atom, (C1-6) ) Alkyl group, halo (C1-6) alkyl group, (C1-6) alkoxy group, halo (C1-6) alkoxy group, (C1-6)
A substituted phenoxy (C1-6) alkyl group having one or more substituents selected from an alkylthio group or a halo (C1-6) alkylthio group on the phenyl ring, a phenylthio (C1-6) alkyl group, the same or different Well, halogen atom, (C1-6) alkyl group, halo (C1-
6) Alkyl group, (C1-6) alkoxy group, halo (C
1-6) Alkoxy group, (C1-6) alkylthio group or substituted phenylthio (C1-6) alkyl group having at least one substituent selected from halo (C1-6) alkylthio group on the phenyl ring, phenyl ( C1-6) alkyl group, which may be the same or different, a halogen atom, (C1
-6) alkyl group, halo (C1-6) alkyl group, (C
1-6) alkoxy group, halo (C1-6) alkoxy group, (C1-6) alkylthio group or halo (C1-6)
A substituted phenyl (C1-6) alkyl group having one or more substituents selected from alkylthio groups on the phenyl ring,
Tri ((C1-6) alkyl) which may be the same or different
Silyl (C1-6) alkyl group, which may be the same or different, di ((C1-6) alkoxy) phosphinyl (C1-
6) alkyl group, (C1-6) alkylsulfonyl group,
A substituted aminosulfonyl group having one or more substituents selected from a halo (C1-6) alkylsulfonyl group, an aminosulfonyl group, and (C1-6) alkyl groups which may be the same or different, or-(CHR ⁶ ) m- CO-B ¹ -R ⁷ (In the formula, R ⁶ represents a hydrogen atom or a (C 1-6) alkyl group, m represents an integer of 0 to 5, B ¹ represents O, S or NR ⁵ (in the formula, R ⁵ is the same as the above.), And R ⁷ is a hydrogen atom, a (C1-6) alkyl group, a halo (C1-6) alkyl group, a (C2-6) alkenyl group, a halo (C2-6) alkenyl group. , (C2-6)
Alkynyl group, halo (C2-6) alkynyl group, (C1
-6) Alkoxy (C1-6) alkyl group, halo (C1
-6) Alkoxy (C1-6) alkyl group, cyclo (C
3-6) alkyl group, cyano (C1-6) alkyl group,
(C1-6) alkylthio (C1-6) alkyl group, halo (C1-6) alkylthio (C1-6) alkyl group,
(C1-6) Alkoxy (C1-6) Alkoxy (C1
-6) Alkyl group, which may be the same or different, ((C
1-6) alkyl) silyl (C1-6) alkyl group, phenyl group, which may be the same or different, a halogen atom,
(C1-6) alkyl group, halo (C1-6) alkyl group, (C1-6) alkoxy group, halo (C1-6) alkoxy group, (C1-6) alkylthio group or halo (C1
-6) a substituted phenyl group having one or more substituents selected from alkylthio groups, a phenyl (C1-6) alkyl group, which may be the same or different, a halogen atom, (C1
-6) alkyl group, halo (C1-6) alkyl group, (C
1-6) alkoxy group, halo (C1-6) alkoxy group, (C1-6) alkylthio group or halo (C1-6)
A substituted phenyl (C1-6) alkyl group having one or more substituents selected from an alkylthio group on the phenyl ring is shown, and R ⁵ and R ⁷ may be taken together and interrupted by an oxygen atom (C2- 6) It can also represent an alkylene group, where B ¹ is O
In the case of, R ⁷ can also represent an alkali metal atom, a primary amine salt or a secondary amine salt. ), R ² is a hydroxyl group,
(C1-6) alkyl group, halo (C1-6) alkyl group, cyclo (C3-6) alkyl group, (C1-6) alkoxy group, halo (C1-6) alkoxy group, (C1-
6) Alkoxy (C1-6) alkyl group or (C1-
6) represents an alkylthio (C1-6) alkyl group, R ³ represents a hydrogen atom or a halogen atom, A represents O or S, X and Y may be the same or different, and a halogen atom,
A (C1-6) alkyl group or a halo (C1-6) alkyl group is shown. ] The herbicide containing the oxazole or thiazole derivative represented by these as an active ingredient.