JPH07291970A - Pyrazole derivative and herbicide using the same - Google Patents

Abstract

PURPOSE:To obtain a novel derivative which has high selectivity for paddy rice plant and can control over a wide variety of weeds in rice paddies, particularly annular Cyperus micro-iria such as umbrella plant and annular broad leaf weeds such as tooth cup. CONSTITUTION:A derivative of the formula I [R<1> is a 1-4C alkyl; R<2> is H, a 1-4C alkyl; Q is H, arylsulfonyl; R<3> is the formula II (n is 0-2)] and a salt thereof, for example, 4-methoxyimino-8-(1-ethyl-5-hydroxypyrazol-4-yl) carbonylthiochroman-1,1-dioxide. The compound is obtained, for example, by reaction of a compound of the formula IV with a compound of the formula V in the presence of a dehydrating agent such as N,N-dicyclohexylcarbodiimide to provide a compound of the formula VI followed by rearrangement of the product.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a pyrazole derivative and a herbicide using the same.

[0002]

2. Description of the Related Art Herbicides are extremely important agents for labor saving of weed control work and improvement of productivity of agricultural and horticultural crops. Therefore, research and development of herbicides have been actively conducted for many years, and a wide variety of agents are currently available. Has been put to practical use. But,
Even today, there is a demand for the development of a new drug having more excellent herbicidal properties, in particular, a drug capable of controlling only the target weeds at a low dose without causing phytotoxicity on cultivated crops.

Further, along with paddy rice, various weeds in paddy fields, such as annual grass weeds such as Nobie, annual cyperaceous weeds such as pearl oysters, annual broad-leaved weeds such as eels, yellow cypresses, urinary cucumbers, hirshiros, swordfish, cyperus japonicus, cyperus cylindrica. , Kurogwai,
It is known that perennial weeds such as Japanese sardines and celery grow, and it is extremely important for rice production that these weeds should be effectively weeded with a small amount of spraying without damaging the rice plants due to environmental problems. is there.

By the way, it is already known that a pyrazole derivative having a thiochroman ring has herbicidal activity,
International publication WO93 / 180 by the same applicant as this application
In the publication No. 31, for example, the formula

[Chemical 4] The compound represented by

This is also described in International Publication WO94 / 1431 by the same applicant as the present application, for example, the formula

[Chemical 5] The compound represented by

[0006]

The thiochroman ring-containing pyrazole derivatives described in these patent publications have high selectivity for cultivated crops and can control both grass and broad-leaved weeds at low doses. It has the advantage of.

[0007] However, it is desirable that a wide variety of pyrazole derivatives used as herbicides exist, and they show high selectivity particularly to rice, and a wide range of paddy field weeds, especially annual cyperaceae weeds such as cyperus communis The advent of new pyrazole derivatives capable of controlling broad-leaved weeds and herbicides using the same have been desired.

Therefore, an object of the present invention is to provide a novel pyrazole derivative which exhibits high selectivity for paddy rice and is capable of controlling a wide range of paddy field weeds, in particular, annual Cyperaceae weeds such as Cyperus japonicus, and annual broad-leaved weeds such as Cyperaceae. To provide a herbicide.

[0009]

The pyrazole derivative of the present invention which achieves the above object has a general formula

[Chemical 6] [Wherein R ¹ is a C ₁ -C ₄ alkyl group, R ² is hydrogen or a C ₁ -C ₄ alkyl group, Q is hydrogen or an arylsulfonyl group, and R ³ is a general formula.

[Chemical 7] (Wherein R ⁴ is hydrogen, a C ₁ -C ₄ alkyl group or an alkynylalkyl group, and n is an integer of 0 to 2)]. .

The herbicide of the present invention which achieves the above object is characterized by containing the pyrazole derivative represented by the above general formula (I) and / or a salt thereof as an essential component.

First, the novel pyrazole derivative of the present invention will be described.

The novel pyrazole derivative of the present invention has the general formula

[Chemical 8] Is a compound represented by.

In the formula (I), R ¹ is a C ₁ -C ₄ alkyl group, that is, a methyl group, an ethyl group, an n-propyl group,
A propyl group such as i-propyl group and a butyl group such as n-butyl group. The propyl group and the butyl group may be linear or branched as described above. Preferably R ¹ is a methyl group or an ethyl group.

R ² is hydrogen or a C ₁ -C ₄ alkyl group, and as the C ₁ -C ₄ alkyl group, the same linear or branched alkyl groups as those exemplified above for R ¹ , that is, a methyl group, an ethyl group , Propyl groups such as n-propyl group and i-propyl group, and butyl groups such as n-butyl group. Preferably R ² is hydrogen or a methyl group.

Q is hydrogen or an arylsulfonyl group.

The above arylsulfonyl group has the general formula

[Chemical 9] Those represented by are preferred.

X in the general formula (II) is hydrogen, a halogen atom or a C ₁ -C ₄ alkyl group. Examples of the halogen include fluorine, chlorine, bromine and iodine, and C ₁
As the C ₄ -alkyl group, the same linear or branched alkyl groups as those exemplified in the above R ¹ , that is, propyl groups such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, etc. Butyl group.

Particularly preferred X is hydrogen, methyl group, chlorine,
It is fluorine.

Further, m representing the number of X in the general formula (II) is 0.
Is an integer of 2 and particularly preferably m is 1 or 2.

As mentioned above, Q is hydrogen or an arylsulfonyl group (for example, an arylsulfonyl group represented by the general formula (II)), and preferably Q is hydrogen or a phenylsulfonyl group (in the general formula (II), X = H), 4-toluenesulfonyl group _{(X = 4-CH 3,} m = 1), 2- toluenesulfonyl group _{(X = 2-CH 3,} m = 1), 2,
4- xylene sulfonyl group _{(X = 2-CH 3,} 4-CH
₃ , m = 2), 2-chlorobenzenesulfonyl group (X =
2-Cl, m = 1), 4-chlorobenzenesulfonyl group (X = 4-Cl, m = 1), 2,4-dichlorobenzenesulfonyl group (X = 2-Cl, 4-Cl, m = 2),
2,5-dichlorobenzenesulfonyl group (X = 2-C
1, 5-Cl, m = 2), 4-fluorobenzenesulfonyl group (X = 4-F, m = 1), 3,4-difluorobenzenesulfonyl group (X = 3-F, 4-F, m = 2).

R ³ is a general formula

[Chemical 10] Is a group represented by.

R ⁴ in the general formulas (IIIb) and (IIIc) is hydrogen, a C ₁ -C ₄ alkyl group or an alkynylalkyl group.

As the C ₁ -C ₄ alkyl group, a linear or branched alkyl group similar to those exemplified for R ¹ above, that is, a methyl group, an ethyl group, an n-propyl group,
Examples thereof include propyl groups such as i-propyl group and butyl groups such as n-butyl group, and examples of the alkynylalkyl group include propargyl group.

Preferred R ⁴ is hydrogen, methyl group, ethyl group or propargyl group.

The general formulas (IIIa), (IIIb) and (IIIc)
N in the above is an integer of 0 to 2.

The constituent elements R ¹ , R ² , R ³ and Q in the general formula (I) showing the pyrazole derivative of the present invention have been described above. The preferred specific examples of the pyrazole derivative of the present invention are shown in Table 1. Tables 2 and 3 are as follows.

[0027]

[Table 1]

[0028]

[Table 2]

[0029]

[Table 3]

A pyrazole derivative in which Q is hydrogen in the general formula (I), that is, a general formula

[Chemical 11] The pyrazole derivative represented by the formula (1) may have a structure represented by the general formula (Ia2) or the general formula (Ia3) as shown in the following formula due to tautomerism. However, the pyrazole derivative of the present invention has all of these structures. The compound of the above is included.

[Chemical 12]

Further, the pyrazole derivative represented by the general formula (Ia1) is an acidic substance and can be easily converted into a salt by treating with a base, and this salt is also included in the pyrazole derivative of the present invention. is there.

The base is not particularly limited as long as it is known, but examples thereof include organic bases such as amines and anilines, and inorganic bases such as sodium salts and potassium salts.

Examples of amines include alkylamines, dialkylamines and trialkylamines. Alkyl group is typically C ₁ -C ₄ alkyl group. Examples of the anilines include aniline, alkylaniline, dialkylaniline and the like. Substituted alkyl groups are usually C _1-
It is a C ₄ alkyl group.

As the sodium salt, sodium hydroxide,
The potassium salt is a salt obtained by using sodium carbonate and the like, and the potassium salt is a salt obtained by using potassium hydroxide, potassium carbonate and the like.

In the general formula (I), R ³ is the general formula (III
a pyrazole derivative represented by b), that is, a general formula

[Chemical 13] The pyrazole derivative represented by the formula (1) has geometrical isomers represented by the general formula (Ib1) and the general formula (Ib2) based on the alkoxyimino group as shown in the following formula. Or a mixture of these.

[Chemical 14]

In the general formula (I), R ³ is the general formula (III
a pyrazole derivative represented by c), that is, a general formula

[Chemical 15] The pyrazole derivative represented by has an asymmetric carbon atom and various isomers represented by the following formulas. The pyrazole derivative of the present invention has the general formula (Ic1) and the general formula (Ic2).
It includes all isomers including the isomers represented by and mixtures thereof.

[Chemical 16]

The herbicide of the present invention contains the novel pyrazole derivative of the present invention represented by the formula (I) and / or its salt as an essential component, and these compounds are liquid carriers such as a solvent or It can be used by mixing it with a solid carrier such as a fine powder of a mineral substance and formulating it in the form of a wettable powder, an emulsion, a powder, a granule or the like. A surfactant may be added in order to impart emulsifying property, dispersibility, spreadability and the like during formulation.

When the herbicide of the present invention is used in the form of a wettable powder, it is usually 10 to 55% by weight of the pyrazole derivative and / or its salt of the present invention, 40 to 88% by weight of a solid carrier, and 2 to 5 of a surfactant. The composition may be prepared by blending it in the proportion of% by weight and used. When used in the form of an emulsion, it is usually prepared by mixing 20 to 50% by weight of the pyrazole derivative of the present invention and / or a salt thereof, 35 to 75% by weight of a solvent and 5 to 15% by weight of a surfactant. Good.

On the other hand, when it is used in the form of a powder, it is usually a pyrazole derivative of the present invention and / or its salt 1-15.
% By weight, 80-97% by weight of solid carrier and 2 to surfactant
It may be prepared by blending at a ratio of 5% by weight. Further, when used in the form of granules, the pyrazole derivative of the present invention and / or its salt is contained in an amount of 1 to 15% by weight, and a solid carrier 80 to 9
It may be prepared by mixing 7% by weight and 2 to 5% by weight of a surfactant. Here, a fine powder of a mineral substance is used as a solid carrier, and as the fine powder of a mineral substance, for example, diatomaceous earth, oxides such as slaked lime, phosphates such as apatite,
Examples thereof include sulfate such as gypsum, talc, pyroferrite, clay, kaolin, bentonite, acid clay, white carbon, quartz powder, and silicate such as silica powder.

An organic solvent is used as the solvent. Specifically, aromatic hydrocarbons such as benzene, toluene and xylene, chlorinated hydrocarbons such as o-chlorotoluene, trichloroethane and trichloroethylene, cyclohexanol and amyl alcohol, Alcohols such as ethylene glycol, isophorone, cyclohexanone, ketones such as cyclohexenyl-cyclohexanone, butyl cellosolve, ethers such as diethyl ether and methyl ethyl ether, esters such as isopropyl acetate, benzyl acetate and methyl phthalate, amides such as dimethylformamide or the like. Can be mentioned.

Further, as the surfactant, any of anionic type, nonionic type, cationic type and zwitterionic type (amino acid, betaine etc.) can be used.

The herbicidal agent of the present invention can contain other herbicidal active ingredients, if necessary, together with the pyrazole derivative represented by the general formula (I) and / or its salt as an active ingredient. As such other herbicidal active ingredients, conventionally known herbicides, for example, phenoxy type, diphenyl ether type, triazine type, urea type, carbamate type, thiol carbamate type, acid anilide type, pyrazole type, phosphoric acid type, sulfonylurea type. , Oxadiazone-based compounds, and the like, which can be appropriately selected and used from these herbicides.

Further, the herbicide of the present invention can be mixed with insecticides, fungicides, plant growth regulators, fertilizers, etc., if necessary.

Next, the method for producing the pyrazole derivative of the present invention will be described. To facilitate the understanding, the reaction formula is shown in FIG.

In step 1, the compound represented by the general formula (IV) is treated with N, N-dicyclohexylcarbodiimide (hereinafter referred to as DC).
C) in the presence of a dehydrating agent such as C) to obtain a compound represented by the general formula (VI), and then the compound (VI) is rearranged to obtain the desired compound. A pyrazole derivative represented by the general formula (I _H ) is obtained. The ester compound represented by the general formula (VI) formed as an intermediate at this time can be isolated, but can also be directly used for the rearrangement reaction without isolation.

As the dehydrating agent used in the condensation reaction of the compound (IV) and the compound (V), 1,1 in addition to the above-mentioned DCC
-Carbonyldiimidazole (hereinafter referred to as CDI), 1
-(3-Dimethylaminopropyl) -3-ethylcarbodiimide (hereinafter referred to as EDC) can be used.
The solvent used is not particularly limited as long as it is an inert solvent for the reaction, but when the reaction is carried out without isolating the compound (VI), acetonitrile, tertiary amyl alcohol and the like are preferable. When compound (VI) is isolated, halogenated hydrocarbon solvents such as methylene chloride, acetonitrile, tertiary amyl alcohol and the like are preferable. The reaction temperature is not particularly limited as long as it is in the range of 0 ° C to the boiling point of the solvent, but usually room temperature is preferable. The reaction time of the condensation reaction between the compound (IV) and the compound (V) is in the range of 1 to 48 hours, but usually 2 to
It takes about 3 hours.

The rearrangement reaction can be achieved by using a base when the reaction is carried out without isolating the compound (VI). Examples of the base include sodium carbon, potassium carbonate, triethylamine, pyridine and the like, and it is preferable to use 1 to 2 equivalents of the base with respect to the compound (VI). The reaction temperature is not particularly limited as long as it is in the range of 0 ° C to the boiling point of the solvent, but is usually preferably 80 to 90 ° C. The rearrangement reaction is accomplished in the range of 1 to 72 hours, usually 8
It will be completed in about 40 hours.

When the rearrangement reaction is carried out after the compound (VI) is isolated, it can be achieved by reacting the compound (VI) with a cyanide ion in the presence of a base. Examples of the base used at this time include sodium carbonate, potassium carbonate, triethylamine, pyridine and the like, and it is preferable to use 1 to 2 equivalents of the base with respect to the compound (VI). Also,
Examples of cyanide that releases cyanide ions include alkali metal cyanide and cyanohydrin compounds such as acetocyanohydrin, and it is preferable to use cyanide in an amount of 0.05 to 0.5 molar equivalent with respect to compound (VI). The reaction temperature is not particularly limited as long as it is in the range of 0 ° C to the boiling point of the solvent, but usually room temperature is preferable. 1 rearrangement reaction
It is achieved within a range of up to 72 hours, but is usually completed within about 8 to 40 hours.

In step 2, the compound (I _H ) was added with Q ′.
By reacting with Hal, the desired general formula (I
A compound represented by Q ′) is obtained, which is a compound (I _H ).
On the other hand, it is preferable to use Q'Hal in a molar ratio of 1: 1 to 1: 3.

In this reaction, it is preferable to use a base such as sodium carbonate, potassium carbonate, tritylamine or pyridine in an equivalent amount or more with respect to the compound (I _H ).

The reaction temperature is preferably in the range of room temperature to the boiling point of the solvent used. As the solvent used,
Examples thereof include aromatic hydrocarbon solvents such as benzene and toluene, ether solvents such as diethyl ether, and halogenated hydrocarbon solvents such as methylene chloride and chloroform. It is also possible to carry out in a two-phase system solvent of these solvents and water. In this case, preferable results can be obtained by adding a phase transfer catalyst such as benzyltriethylammonium chloride to the reaction system.

The pyrazole derivative represented by the formula (V) used as a reaction reagent in the above method can be produced, for example, by the method described in JP-A-61-257974.

In the compound of the formula (IV) used as a starting material in the step 1, the compound in which R ³ is a group represented by the general formula (IIIa) is

[Chemical 17] The compound (IVa) is produced by the reaction represented by the following formula.

[Chemical 18]

First, thiosalicylic acid (XI) and acrylic acid (XII) are reacted to obtain an addition compound (XIII),
By ring closure, a sulfide compound (n = 0) of the general formula (IVa1), which is one embodiment of the desired compound of the general formula (IVa), is obtained.

The solvent used in this reaction is 1,1,
A halogenated hydrocarbon solvent such as 2,2-tetrachloroethane can be used. The reaction proceeds smoothly by using a base catalyst such as triethylamine.

Next, the sulfide compound represented by the general formula (IVa1) is oxidized with an oxidizing agent to give the compound represented by the general formula (IVa2), which is another embodiment of the target compound of the general formula (IVa). A sulfoxide compound (n = 1) or sulfone compound (n = 2) is obtained.

Although various kinds of oxidizing agents can be used, hydrogen peroxide is particularly preferable. Various solvents may be used, but acetic acid is particularly preferable. In the case of producing a sulfoxide compound (n = 1), 1 equivalent of an oxidizing agent may be used to react at 0 ° C. to 30 ° C. In the case of producing a sulfone compound (n = 2),
The reaction may be performed at 50 to 100 ° C. by using 2 equivalents or more of an oxidizing agent.

Further, in the compound of the formula (IV) used as the starting material in the above step 1, R ³ is represented by the general formula (IIIb)
The compound represented by

[Chemical 19] This compound (IVb) is produced by the reaction shown in the following formula.

[Chemical 20]

First, the sulfide compound of the general formula (IVa1) obtained as described above is treated with an alkoxyamine (VII
By reacting with (I), the desired general formula (IVb)
A sulfide compound (n = 0) of the general formula (IVb1), which is one embodiment of the compound of

This reaction is carried out at 0 ° C. in water or an organic solvent (eg ethanol, methanol, acetic acid) in the presence of an acid catalyst (eg hydrochloric acid) or a base catalyst (eg pyridine, aniline, sodium hydroxide, sodium carbonate). ~ Is carried out at the reflux temperature of the solvent (water or organic solvent). As an example, it is preferably carried out in ethanol in the presence of pyridine at a reflux temperature. In this reaction, alkoxyamine (VIII) was added to the starting compound (IVa1) in an amount of 1.5
It is preferable to use ˜5.0 times mole, 1.0 to 2.0
It is particularly preferable to use a double mole.

Next, the sulfide compound (n = 0) represented by the general formula (IVb1) is oxidized with an oxidizing agent to give a compound represented by the general formula (IVb), which is another embodiment of the general formula (IVb). A sulfoxide compound (n = 1) or sulfone compound represented by (IVb2) is obtained.

Although various kinds of oxidizing agents can be used, hydrogen peroxide is particularly preferable. Various solvents may be used, but acetic acid is particularly preferable. When a compound (sulfoxide) in which n is 1 is produced, 1 equivalent of an oxidizing agent may be used and the reaction may be performed at room temperature.
When a compound (sulfone) in which n is 2 is used, it is sufficient to use 2 equivalents or more of an oxidant and react at 50 to 100 ° C.

In the compound of the formula (IV) used as the starting material in the above step 1, R ³ is a compound represented by the general formula (IIIc)
The compound represented by

[Chemical 21] This compound (IVc) is produced by the method represented by the following formula.

[Chemical formula 22]

First, the compound of the general formula (IVa1) is reduced to obtain the alcohol (IX) of the general formula (IX). The reaction temperature is usually -20 ° C to 50 ° C. Various reducing agents may be used, and one example is sodium borohydride.

Next, the alcohol of the general formula (IX) and the alcohol R ⁴ OH are dehydrated and condensed to obtain the ether compound of the general formula (X). As the solvent, aromatic hydrocarbon solvents such as benzene, toluene and xylene,
A halogenated hydrocarbon solvent such as 1,2-dichloroethane or carbon tetrachloride can be used. Alcohol R ⁴ OH
Can also be used in excess as the solvent. As a catalyst
The reaction proceeds smoothly by using a catalyst such as sulfuric acid, aromatic sulfonic acid and aromatic sulfonic acid halide, boron trifluoride and aluminum chloride. The temperature is usually 60 ℃
Is the boiling temperature of the solvent, preferably the reflux temperature of the solvent or alcohol R ⁴ OH used.

Then, the compound of the general formula (X) is hydrolyzed to obtain a sulfide compound (n = 0) of the general formula (IVc1), which is one embodiment of the desired compound of the general formula (IVc). . This hydrolysis is achieved by using an alkali metal hydroxide. Examples of the alkali metal hydroxide used at this time include sodium hydroxide and potassium hydroxide, and sodium hydroxide is preferable. A mixed solvent of water and an organic solvent is used as the solvent, and examples of the organic solvent include alcohols such as methanol and ethanol.

Next, the sulfide compound (n = 0) represented by the general formula (IVc1) is oxidized with an oxidizing agent to give a compound represented by the general formula (IVc), which is another embodiment of the target compound of the general formula (IVc). The sulfoxide compound (n = 1) or sulfone compound (n = 2) represented by (VIc2) is obtained.

Although various kinds of oxidizing agents can be used, hydrogen peroxide is particularly preferable. Various solvents may be used, but acetic acid is particularly preferable. To obtain a compound (sulfoxide) in which n is 1, 1
The reaction may be carried out at 0 to 30 ° C in an equivalent amount, and when a compound (sulfone) in which n is 2 is used, the reaction may be carried out at 50 to 100 ° C using 2 equivalents or more of an oxidizing agent.

[0069]

EXAMPLES For convenience of description, first, the production examples of the starting materials used when producing the compound (I) of the present invention will be described as reference examples, and then the production examples of the compound (I) of the present invention will be described. Finally, a test example of the compound (I) of the present invention as a herbicide will be described as a herbicide example.

Reference Example 1 [Production Example of Starting Material (IVa1)] Thiochroman-4-one-8-carboxylic acid (VIIa1) was produced by the reaction shown in the following formula.

[Chemical formula 23]

(1) thiosalicylic acid (XI) 9.8 g (6
4 mmol) and acrylic acid (XII) 4.6 g (64 mmo)
l), 1,1,2,2-tetrachloroethane (50 ml),
The mixture was heated under reflux in a mixed solution of 0.2 ml of triethylamine. After 2 hours, the mixture was cooled to room temperature and the resulting solid was collected by filtration. 13.7 g (yield 95%) of β- (2-carboxylbenzenethio) -propionic acid (XIII) was obtained. ¹ HNMR (CDCl ₃ , ppm): δ2.4-2.8
(2H, m), 3.0-3.4 (2H, m), 7.1-
7.6 (2H, m), 7.8-8.1 (2H, m)

(2) To 128 g of polyphosphoric acid, 13.68 g (60.47 mmol) of β- (2-carboxylbenzenethio) -propionic acid (XIII) obtained in the above (1) was added, and after sufficiently stirring, about 80 Heated to ° C. After the reaction, the mixture was cooled on an ice bath and ice water was poured. The resulting solid was collected by filtration, washed with water and dried. 12.6 g (yield 100%) of 8-carboxylthiochroman-4-one (IVa1) was obtained. ¹ HNMR (CDCl ₃ , ppm): δ 2.8-3.0
(2H, m), 3.1-3.3 (2H, m), 7.32
(1H, t, J = 7.8Hz), 8.24 (2H, d
d, J = 1.8 and 7.7 Hz)

Reference Example 2 [Production Example of Starting Materials (IVb1, IVb2)] 4-methoxyiminothiochroman-8-carboxylic acid (IV
b1) and its 1,1-dioxide (IVb2) were prepared by the following reactions.

[Chemical formula 24]

(1) 5,0 g (24 of 8-carboxyl-thiochroman-4-one (IVa1) obtained in Reference Example 1 (2)
mmol) and o-methylhydroxylamine (VIII) hydrochloride (4.0 g, 23 mmol) in ethanol (15 m).
The mixture was heated under reflux in a mixed solvent of 1 and 7.8 ml of pyridine for 2 hours. After distilling off the solvent under reduced pressure, 100 ml of 5% hydrochloric acid was added,
The resulting solid was collected by filtration, dissolved in saturated aqueous sodium hydrogen carbonate solution, and washed with ethyl acetate. 5% Hydrochloric acid was added to the aqueous layer, and the resulting precipitate was collected by filtration, washed with water, and dried under reduced pressure. 4-methoxyiminothiochroman-8-carboxylic acid (IVb1) (4.0 g, yield 71%) was obtained. ¹ HNMR (CDCl ₃ , ppm): δ 2.8-3.2
(4H, m), 3.9 (3H, s), 7.2 (1H,
t), 7.9-8.2 (2H, m)

(2) 3.0 g of 4-methoxyiminothiochroman-8-carboxylic acid (IVb1) obtained in (1) above (1
3 mmol) of 30% hydrogen peroxide 4.3 g (38 mm
Ol) and acetic acid in 5 ml at 80 ° C. for 3 hours. Ethyl acetate was added to the reaction product, which was cooled to room temperature, 2% aqueous sodium hydrogen sulfite solution was added, the mixture was extracted with methylene chloride, washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off to give 1.9 g of 4-methoxyiminothiochroman-8-carboxylic acid-1,1-dioxide (IVb2) (yield 81
%)Obtained. ¹ HNMR (acetone-d ₆ , ppm): δ3.2-
3.6 (4H, m), 4.01 (3H, s), 7.7-
7.8 (2H, d), 8.17 (1H, t)

Reference Example 3 [Production Example of Starting Materials (IVc1, IVc2)] 4-Methoxythiochroman-8-carboxylic acid (IVc1) and its 1,1-dioxide (IVc2) were produced by the following reaction.

[Chemical 25]

(1) Thiochroman-4-one-8-carboxylic acid (IVa1) (7.00 g, 33.7 mmol) was added with 30 ml of methanol. 2.55 g of sodium borohydride (6
7.3 mmol) was added slowly. After reacting for 2 hours with ice cooling, it was reacted for 3 hours at room temperature. Then, the reaction mixture was put into 5% hydrochloric acid, and the precipitated white crystals were collected by filtration and dried under reduced pressure. 5.24 g (yield 74%) of 4-hydroxythiochroman-8-carboxylic acid (XI) was obtained. ¹ HNMR (CDCl ₃ , ppm): δ2.1-2.3
(2H, m), 2.7-3.3 (2H, m), 4.8
(1H, t), 7.17 (1H, t), 7.65 (1
H, dd), 7.95 (1H, dd)

(2) 4.20 g of 4-hydroxythiochroman-8-carboxylic acid (IX) obtained in (1) above (20.
0 mmol) to 50 ml of methanol and 3.0 ml of concentrated sulfuric acid
Was added and the mixture was heated under reflux for 2 hours. After allowing to cool, the mixture was poured into ice water, extracted with ethyl acetate, washed with saturated aqueous sodium carbonate solution and brine, dried over anhydrous sodium sulfate, and subjected to column chromatography to give 4-methoxythiochroman-8-carboxylic acid methyl ester (X). 4.77 g (yield ~ 100
%)was gotten. ¹ HNMR (CDCl ₃ , ppm): δ 1.8-3.3
(3H, m), 3.41 (3H, s), 3.90 (3
H, s), 3.9-4.2 (1H, m), 4.33 (1
H, t), 7.0-7.5 (2H, m), 7.8-8.
0 (1H, m)

(3) 4-Methoxythiochroman-8-carboxylic acid methyl ester (X) 4.7 obtained in the above (2).
Sodium hydroxide 1.67 in 7 g (20.0 mmol)
g (29.8 mmol) and 25 ml of ethanol were added,
The mixture was reacted under heating under reflux for 1 hour. After the reaction, ethanol was distilled off, water and 5% hydrochloric acid were added, the mixture was extracted with ethyl acetate, washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated to give 4-methoxythiochroman-8-carboxylic acid (IVc1 )
4.14 g (92% yield) was obtained. ¹ HNMR (CDCl ₃ , ppm): δ 1.9-3.3
(4H, m), 3.48 (3H, s), 4.35 (1
H, t), 7.12 (1H, t), 7.45 (1H, d
d) 8.09 (1H, dd)

(4) Target compound was obtained by the same oxidation procedure as in Reference Example 2 (2) except that 4-methoxythiochroman-8-carboxylic acid (IVc1) obtained in (3) above was used. Four
-Methoxythiochroman-8-carboxylic acid 1,1-dioxide (IVc2) was obtained with a yield of 59%. ¹ HNMR (acetone-d ₆ , ppm): δ2.6-
4.1 (4H, m), 3.5 (3H, s), 4.5 (1
H, t), 7.3-8.2 (3H, m)

Reference Example 4 [Production Example of Starting Material (IVc1)] 4-propargyloxythiochroman-8-carboxylic acid (IVc1 R ⁴ = propargyl group) was produced by the following formula.

[Chemical formula 26]

4-hydroxythiochroman-8-carboxylic acid (IX) obtained in Reference Example 3 (1) 1.00 g (4.76)
mmol) and propargyl alcohol 2.67 g (4
To a mixed solution of ethylene chloride (7.6 mmol), a few drops of concentrated sulfuric acid were added and reacted at 60 ° C. After the reaction, this was poured into ice water, and methylene chloride and saturated aqueous sodium hydrogen carbonate solution were added. 5% Hydrochloric acid was added to the aqueous layer, and the precipitated crystals were separated by filtration and dried under reduced pressure. 0.65 g (yield 55%) of 4-propargyloxythiochroman-8-carboxylic acid (IVc1)
was gotten. ¹ HNMR (CDCl ₃ , ppm): δ 1.9-2.2
(1H, m), 2.3-3.5 (3H, m), 2.51
(1H, t), 4.20 (2H, t), 4.7-4.8.
(1H, m), 7.13 (1H, t), 7.51 (1
H, dd), 8.10 (1H, dd)

Production Example 1 [Production Example of Compound No. 1 of the Present Invention] 4-methoxyimino-8- (1-
Ethyl-5-hydroxypyrazol-4-yl) carbonylthiochroman-1,1-dioxide (Compound No.
1) was produced by the following reaction.

[Chemical 27]

4-methoxyiminothiochroman-8-carboxylic acid obtained in Reference Example 2 (2) as a starting material
1,1-dioxide (IVb2) 1.00 g (3.71 mm)
ol), 0.46 g (4.07 mmol) of this and 1-ethyl-5-hydroxypyrazole (V) were dissolved in 10 ml of t-amyl alcohol to give 0.84 g of DCC.
(4.09 mmol) was added at room temperature. After stirring at room temperature for 2 hours, 0.38 g (2.78 mmol) of potassium carbonate was added and reacted at 90 ° C. for 8 hours. After the reaction, the solvent was distilled off, ethyl acetate was added, the mixture was extracted with a 3% aqueous sodium carbonate solution, and the insoluble portion was filtered off. The aqueous layer was neutralized with concentrated hydrochloric acid and extracted with ethyl acetate. The extract was washed with distilled water and saturated brine, dried over sodium sulfate, and concentrated to give 4-methoxyimino-8- (1-ethyl-5-hydroxypyrazol-4-yl) carbonylthiochroman-1,1-dioxide ( 1.17 g (yield 87%) of compound No. 1) was obtained. The results of IR and NMR analysis of compound No. 1 are shown in Table 4.
Shown in.

Production Example 2 [Production Example of Compound No. 2 of the Present Invention] Synthesis of 4-methoxyimino-8- (1-ethyl-5-hydroxypyrazol-4-yl) carbonylthiochroman (Compound No. 2) As a starting material in Production Example 1
4-methoxyiminothiochroman-8-carboxylic acid-1,1-dioxide (IV
The same procedure as in Production Example 1 was repeated except that the corresponding sulfide compound, that is, 4-methoxyiminothiochroman-8-carboxylic acid (VIb1) obtained in Reference Example 2 (1), was used instead of b2). . As a result, 4-methoxyimino-8- (1-ethyl-5-hydroxypyrazole-4-
Yield) carbonylthiochroman (Compound No. 2) was obtained with a yield of 18%. The IR and NMR analysis results of the compound No. 2 are shown in Table 4.

Production Example 3 [Production Example of the compound No. 3 of the present invention] 8- (1-ethyl-hydroxypyrazol-4-yl)
Carbonylthiochroman-4-one (Compound No. 3) was prepared by the following reaction.

[Chemical 28]

Thiochroman-4-one-as a starting material
8-carboxylic acid (IVa1) 1.00 g (4.81 mmo)
1) and 1-ethyl-5-hydroxypyrazole (V)
0.46 g (4.09 mmol) was dissolved in 10 ml of t-amyl alcohol, and DCC (N, N'-dicyclohexylcarbodiimide) 1.09 g (5.29 mmo).
l) was added at room temperature. After stirring at room temperature for 2 hours, 0.50 g (3.61 mmol) of potassium carbonate was added and the mixture was stirred at 90 ° C. for 1 hour.
The reaction was carried out for 6 hours. After the reaction, the solvent was distilled off, ethyl acetate was added, the mixture was extracted with a 3% aqueous sodium carbonate solution, and the insoluble portion was filtered off. The aqueous layer was neutralized with concentrated hydrochloric acid and extracted with ethyl acetate. After washing with distilled water and a saturated saline solution, it was dried over sodium sulfate and concentrated to give 8- (1-ethyl-5-hydroxypyrazol-4-yl) carbonylthiochroman-.
0.10 g (yield 7%) of 4-one (Compound No. 3) was obtained. The results of IR and NMR analyzes of compound No. 3 are shown in Table 4.

Production Example 4 [Production Example of the compound No. 4 of the present invention] 4-methoxyimino-8- (1,3-dimethyl-5-p
-Toluenesulfonyloxypyrazol-4-yl) carbonylthiochroman (Compound No. 4) was prepared by the following reaction.

[Chemical 29]

(1) As a starting material, 2.00 g of 4-methoxyiminothiochroman-8-carboxylic acid (IVb1)
(8.43 mmol) and 1,3-dimethyl-5-hydroxypyrazole (V) 0.99 g (8.85 mmol)
Was dissolved in 20 ml of t-amyl alcohol, and 1.83 g (8.85 mmol) of DCC was added at room temperature. After applying ultrasonic waves at room temperature for 2 hours, the insoluble portion was filtered off. The organic layer was concentrated and subjected to flash column chromatography (Wakogel C-300, hexane / ethyl acetate = 1: 1), which was an intermediate 4-methoxyimino-8- (1,3-
Dimethylpyrazol-5-yl) oxycarbonylthiochroman (Compound No. 4a) was obtained.

(2) 4-of the intermediate obtained in (1) above
Methoxyimino-8- (1,3-dimethylpyrazole-
5-yl) oxycarbonylthiochroman (Compound No.
0.60 g (1.81 mmol) of 4a) was charged into a reactor, 6 ml of acetonitrile was added, 0.37 g (3.62 mmol) of triethylamine and a few drops of acetone cyanohydrin were added, and the reaction was carried out for 7 hours. After distilling off acetonitrile, 6 ml of methylene chloride, 4 ml of distilled water and 0.50 g (3.62 mmol) of potassium carbonate were added, and 0.03 g of benzyltriethylammonium chloride as a catalyst was further added. 0.41 g (2.17 mmol) of p-toluenesulfonyl chloride was added to this, and 2
After stirring for an hour, the mixture was reacted under heating under reflux for 2 hours. After the reaction, the mixture was allowed to cool and water and chloroform were added. The organic layer was washed with distilled water, a saturated aqueous solution of sodium hydrogencarbonate and brine in that order, dried over anhydrous sodium sulfate, concentrated, and then recrystallized from ethanol and water to give the desired 4-methoxyimino-8- (1, 0.66 g (yield 75%) of 3-dimethyl-5-p-toluenesulfonyloxypyrazol-4-yl) carbonylthiochroman (Compound No. 4) was obtained. The results of IR and NMR analysis of the obtained compound No. 4 are shown in Table 5.

Production Example 5 [Production Example of the compound No. 5 of the present invention] 4-methoxy-8- (1-ethyl-5-hydroxypyrazol-4-yl) carbonylthiochroman-1,1-
The synthesis of the dioxide (Compound No. 5) was carried out using the 4-methoxythiochroman-obtained in Reference Example 3 (4) as a starting material.
Other than using 8-carboxylic acid-1,1-dioxide,
The same operation as in Production Example 1 was performed. As a result, the target compound No. 5 was obtained in a yield of 41%. Table 5 shows IR and NMR analysis results of the obtained compound No. 5.

Production Example 6 [Production Example of compound No. 6 of the present invention] 4-propargyloxyl-8- (1-ethyl-5-hydroxypyrazol-4-yl) carbonylthiochroman (Compound No. 6) The starting material was used in the synthesis of Reference Example 4
The same operation as in Production Example 1 was carried out except that 4-propargyloxylthiochroman-8-carboxylic acid obtained in 1. was used. As a result, the target compound No. 6 was obtained in a yield of 23.
Obtained in%. Table 5 shows IR and NMR analysis results of the obtained compound No. 6.

Production Example 7 [Production Example of Compound No. 7 of the Present Invention] 4-hydroxy-8- (1-ethyl-5-hydroxypyrazol-4-yl) carbonylthiochroman (Compound No. 7) was synthesized. , As follows.

(1) As starting material, 4-hydroxythiochroman-8-carboxylic acid obtained in Reference Example 3 (1) 1.
00 g (4.76 mmol) and 1-ethyl-5-hydroxypyrazole 0.48 g (4.29 mmol) were dissolved in 10 ml of methylene chloride to give 0.89 g of DCC.
(4.29 mmol) was added at room temperature. After applying ultrasonic waves at room temperature for 2 hours, the insoluble portion was filtered off. The organic layer was concentrated, and 4-hydroxy-8- (1-ethylpyrazol-5-yl) oxycarbonyl represented by the following structure was obtained by flash column chromatography (Wakogel C-300, hexane / ethyl acetate = 1: 1). 1.10 g (yield 85%) of thiochroman (Compound No. 7a) was obtained.

[Chemical 30]

(2) 0.40 g of 4-hydroxy-8- (1-ethylpyrazol-5-yl) oxycarbonylthiochroman (compound No. 7a) obtained in the above (1)
(1.32 mmol) was charged and acetonitrile 4 ml
Was added, followed by 0.27 g of triethylamine (2.64).
mmol) and a few drops of acetone cyanohydrin,
The reaction was carried out for 17 hours. After distilling off acetonitrile, ethyl acetate and water were added. The aqueous layer was neutralized with concentrated hydrochloric acid and extracted with ethyl acetate. After washing with distilled water and saturated saline, 4-hydroxy-8 was obtained by drying over sodium sulfate and concentrating.
0.28 g (yield 70%) of-(1-ethylpyrazol-5-yl) carbonylthiochroman (Compound No. 7) was obtained. Table 6 shows the IR and NMR analysis results of the obtained compound No. 7.

Production Example 8 [Production Example of compound No. 8 of the present invention] 4-methoxyimino-8- (1,3-dimethyl-5-p
-Toluenesulfonyloxypyrazol-4-yl) carbonylthiochroman-1,1-dioxide (Compound N
o.8) was synthesized in the same manner as in Production Example 4 except that 4-methoxyiminothiochroman-8-carboxylic acid-1,1-dioxide was used as a starting material. As a result, the target compound No. 8 was obtained in a yield of 26.2%. Table 6 shows IR and NMR analysis results of the obtained compound No. 8.

Production Example 9 [Production Example of Compound No. 9 of the Present Invention] 4-methoxyimino-8- (1,3-dimethyl-5-hydroxypyrazol-4-yl) carbonylthiochroman (Compound No. 9) 4-methoxyimino-8- obtained in Production Example 4 (1) was used as a starting material.
The same operation as in Production Example 7 (2) was performed except that (1,3-dimethylpyrazol-5-yl) oxycarbonylthiochroman (Compound No. 4a) was used. As a result, the target compound No. 9 was obtained with a yield of 58%. Table 6 shows IR and NMR analysis results of the obtained compound No. 9.

Production Example 10 [Production Example of compound No. 10 of the present invention] 4-methoxyimino-8- (1,3-dimethyl-5-hydroxypyrazol-4-yl) carbonylthiochroman triethylamine salt (Compound No. 10) The synthesis of 10) was performed as follows.

As a starting material, 0.60 g of 4-methoxyimino-8- (1,3-dimethylpyrazol-5-yl) oxycarbonylthiochroman (Compound No. 4a) obtained in Production Example 4 (1) was used. (1.81 mmol) was charged, 5 ml of acetonitrile was added, 0.37 g (3.62 mmol) of triethylamine and a few drops of acetone cyanohydrin were added, and the mixture was reacted for 6.5 hours.
The precipitated white solid was collected by filtration and washed with acetonitrile to obtain the target compound No. 10 in a yield of 49%. Table 7 shows the IR and NMR analysis results of the obtained compound No. 10.

[0100]

[Table 4]

[0101]

[Table 5]

[0102]

[Table 6]

[0103]

[Table 7]

[Examples of Herbicides] (1) Preparation of Herbicides 97 parts by weight of talc (trade name: Zyklite, manufactured by Zyklite Industry Co., Ltd.), alkylaryl sulfonic acid as a surfactant (trade name: Neoperex) 1.5 parts by weight of Kao Atlas Co., Ltd. and 1.5 parts by weight of nonionic and anionic surfactants (trade name: Solpol 800A, Toho Chemical Industry Co., Ltd.) are uniformly pulverized and mixed. A carrier for wettable powder was obtained.

90 parts by weight of this carrier for wettable powder and 10 parts by weight of each of the compounds (1) to (4) of the present invention obtained in the above Production Examples (for Comparative Examples, the following compound (A) 10) was used.
(Parts by weight) were uniformly pulverized and mixed to obtain a herbicide.

The following compound (A) used as a comparative example is
It is the compound No. 78 described in International Publication WO93 / 18031 and has the following structure.

[Chemical 31]

(2) Flooded soil treatment test: Paddy soil was packed in a magnetic pot of 1/15500 are,
On the surface layer, Cyperus japonicus and broad-leaved weeds (Cyperus, Azena)
The seeds of No. 1 were evenly sown and transplanted with paddy rice at the 2.5 leaf stage.

After that, at the time of germination of the weeds, a predetermined amount of the diluted solution of the herbicide obtained in the above (1) was uniformly dropped on the surface of the water for treatment, and then the pot was left in a greenhouse and sprinkled appropriately.

Table 6 shows the results of investigation of herbicidal effect and damage to rice crops 20 days after the treatment with the chemical solution. The dose is shown as the amount of active ingredient per 10 ares. Moreover, the damage to paddy rice and the herbicidal effect were measured by measuring the air-dried weight and displayed as follows.

Herbicidal effect Residual grass weight untreated ratio (%) 0 81-100 1 61-80 80 41-60 3 21-40 41 -20 5 0 Rice damage caused by residual grass weight untreated ratio (%) 0 100 1 95-99 2 90-94 3 80-89 4 70-795 50-69

Here, the residual grass weight / non-treatment ratio = (remaining grass weight of treated area / remaining grass weight of untreated area) × 100.

From Table 6, the compounds (1) to (4) of the present invention.
Is excellent in the herbicidal effect on the corn snail and broad-leaved weeds, and it is clear that the phytotoxicity of paddy rice is significantly reduced as compared with the comparative compound (A).

[0113]

[Table 8]

[0114]

INDUSTRIAL APPLICABILITY As described above, according to the present invention, it is possible to control a wide range of paddy field weeds, in particular, annual cyperaceae weeds such as tabular clawed weeds, and annual broad-leaved weeds such as Cyperaceae, which are highly selective for paddy rice. A pyrazole derivative and a herbicide using the same were provided.

[Brief description of drawings]

FIG. 1 is a process drawing of a compound of the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mitsuru Shibata 1280 Kamizumi, Sodegaura-shi, Chiba Idemitsu Kosan Co., Ltd.

Claims (7)

[Claims] 1. A general formula: [Wherein R ¹ is a C ₁ -C ₄ alkyl group, R ² is hydrogen or a C ₁ -C ₄ alkyl group, Q is hydrogen or an arylsulfonyl group, and R ³ is of the general formula: (Wherein R ⁴ is hydrogen, a C ₁ -C ₄ alkyl group or an alkynylalkyl group, and n is an integer of 0 to 2)]. A pyrazole derivative or a salt thereof. 2. C _{1 to} C as R ¹ in general formula (I)
_4. The pyrazole derivative or salt thereof according to claim 1, wherein the alkyl group is a methyl group or an ethyl group. 3. C _{1 to} C as R ² in the general formula (I)
_4. The pyrazole derivative or salt thereof according to claim 1, wherein the alkyl group is a methyl group. 4. The arylsulfonyl group as Q in the general formula (I) has the general formula: (Wherein X is hydrogen, a halogen atom or a C _{1 to} C ₄ alkyl group, and m is an integer of 0 to 2),
The pyrazole derivative according to claim 1 or a salt thereof. 5. R ⁴ in the general formula (IIIb) or (IIIc)
The pyrazole derivative or a salt thereof according to claim 1, wherein the C ₁ -C ₄ alkyl group as is a methyl group. 6. R ⁴ in the general formula (IIIb) or (IIIc)
The pyrazole derivative or a salt thereof according to claim 1, wherein the alkynylalkyl group as is a propargyl group. 7. A herbicide containing the pyrazole derivative represented by the general formula (I) according to any one of claims 1 to 6 and / or a salt thereof as an essential component.