KR970002872B1 - Cyclhexane derivatives and its salts, and a process for the preparation thereof - Google Patents

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Description

Cyclohexane derivatives, salts thereof, and preparation methods thereof

The present invention relates to a novel cyclohexane derivative of the general formula (IA) and salts thereof and a process for preparing the same:

Wherein R ^{1 ′} is hydrogen atom, ethyl group, n-propyl group, n-butyl group, iso-butyl group or secondary-butyl group, R ² is hydrogen atom, halogen atom or C ₁ -C ₅ alkyl a group, R ^{3 'a} halogen atom, C ₁ -C ₅ alkyl group, C ₁ -C ₅ alkoxy group, C1-C ₅ alkylthio group, C ₁ -C ₅ alkylsulfinyl group, C ₁ -C ₅ alkyl sulfonic Ponyyl group or —N (R ⁷ ) R ^{8 ′} , wherein R ^{7 ′} and R ^{8 ′} may be the same or different and are each a hydrogen atom or a C ₁ -C ₃ alkyl group, and R ^{7 ′} and R ^{8 ′} are 4 to 6 methylene groups can be bonded together), R ^{4 '} is a hydrogen atom, a C ₁ -C ₅ alkyl group or a C ₂ -C ₅ alkoxycarbonyl group, R ^5' is a hydroxy group, phenyl-carbonyl-oxy group, or phenyl ring may be the same or different and is also the one to five substituents selected from the group consisting of halogen atom, C ₁ -C ₃ alkyl group and C ₁ -C ₃ alkoxy groups Phenyl-carbonyl and oxy group, R ^{6 'is} C ₁ -C ₅ alkyl group, C ₃ -C ₆ cycloalkyl group or a C ₁ -C ₃ alkyl group, a cycloalkyl group substituted by, provided that, R ^1' is When an ethyl group, R ^{2 '} is a methyl group, R ^3' is a halogen atom or a methylthio group, R ^{4 '} is a hydrogen atom, R ^5' is a hydroxy group and R ^{6 '} is an ethyl and n-propyl group. Not a group.

As a result of extensive research by the inventors seeking to develop novel pesticides, it has been found that cyclohexane derivatives of the general formula (IA) or salts thereof have significant pesticidal action as novel compounds which are not known in the literature. In this way, the present invention has been completed by the inventors.

The cyclohexane derivatives or salts thereof of the present invention represented by general formula (IA) have the following tautomers, and the tautomers are also included in the present invention.

When R ^{5 '} is a hydroxy group:

When R ^{5 '} is not a hydroxy group:

Wherein R ^{1 ′} , R ^{2 ′} , R ^{3 ′} , R ^{4 ′} and R ^{6 ′} are as defined above.

Salts of cyclohexane derivatives of formula (IA) include inorganic and organic salts. Inorganic salts include salts with inorganic acids (e.g. hydrochloric acid, sulfuric acid, nitric acid) and alkali metals (e.g. sodium, potassium), alkaline earth metals (e.g. calcium, magnesium, barium) or metals (e.g. aluminum, tin, iron, nickel And zinc). Organic salts include organic bases such as diethylamine, triethanolamine, triethylamine, dimethylaminopyridine, pyrrole, morpholine, DBU (1,8-diazabicyclo [5.4.0] -7-undecene)] Salts with and organic acids such as p-toluenesulfonic acid, trifluoroacetic acid, oxanoic acid. However, the present invention is not limited to these salts.

As a typical preparation method of the cyclohexane derivative or salt thereof of the present invention represented by general formula (IA) and the cyclohexane derivative or salt thereof of the following general formula (IB), for example, the following scheme may be mentioned.

Wherein R ¹ is a hydrogen atom, a C ₁ -C ₁₆ alkyl group, a C ₁ -C ₅ haloalkyl group, a C ₂ -C ₅ alkenyl group, a C ₂ -C alkoxyalkyl group, a phenyl group or the same or different Or a phenyl group having 1 to 5 substituents selected from a halogen atom, a C ₁ -C ₃ alkyl group and a C ₁ -C ₃ alkoxy group, a benzyl group, or the same or different and a halogen atom, C _1- A benzyl group having 1 to 5 substituents selected from a C ₃ alkyl group and a C ₁ -C ₃ alkoxy group, R ² is a hydrogen atom, a halogen atom, a C ₁ -C ₅ alkyl group, a C ₁ -C ₅ haloalkyl group Is a phenyl group or a phenyl group which may be the same or different and has 1 to 5 substituents selected from a halogen atom, a C ₁ -C ₃ alkyl group and a C ₁ -C ₃ alkoxy group, R ³ is a hydrogen atom, a halogen atom, C ₁ -C ₅ alkyl groups, C1-C5 haloalkyl groups, C ₁ -C ₅ alkoxy group, C ₁ -C ₅ haloalkenyl When group, C ₁ -C ₅ alkylthio group, C ₁ -C ₅ haloalkylthio group, C ₁ -C ₅ alkylsulfinyl group, C ₁ -C ₅ haloalkyl sulfinyl group, C ₁ -C ₅ alkyl sulfonic 1 to 5 substituents selected from the group consisting of a phenyl group, a C ₁ -C ₅ haloalkylsulfonyl group, a phenoxy group or a halogen atom, a C ₁ -C ₃ alkyl group and a C ₁ -C ₃ alkoxy group A phenoxy group having or a phenylthio group or a phenylthio group which may be the same or different and has 1 to 5 substituents selected from a halogen atom, a C ₁ -C ₃ alkyl group and a C ₁ -C ₃ alkoxy group, or N (R ⁷ ) R ⁸ , wherein R ⁷ and R ⁸ may be the same or different and each is a hydrogen atom or a C ₁ -C ₃ alkyl group and R ⁷ and R ⁸ are together through 4 to 6 methylene groups and may be), or C ₂ -C ₅ alkyl-carbonyl-oxy group that is to be bonded, R ⁴ is a hydrogen atom, C ₁ -C ₅ alkyl group or C ₂ -C ₅ Koksi carbonyl and carbonyl group, R ⁵ is from hydroxy group, a halogen atom, C ₁ -C ₅ alkylthio group, C ₁ -C ₅ alkenyl group, ^{thio, -N (R 9) R 10} ( where, R ^9, and R ¹⁰ may be the same or different and are each a hydrogen atom, a C ₁ -C ₃ alkyl group or a C ₁ -C ₃ alkenyl group), a C ₂ -C ₈ alkylcarbonyloxy group, a C ₃ -C ₆ cyclo Alkylcarbonyloxy

Group, phenylcarbonyloxy group, or phenylcarbonyloxy group which may be the same or different and has 1 to 5 substituents selected from halogen atom, C ₁ -C ₃ alkyl group and C ₁ -C ₃ alkoxy group R ⁶ is a C ₁ -C ₁₈ alkyl group, a C ₃ -C ₆ cycloalkyl group or a cycloalkyl group, which may be the same or different and has a substituent selected from a halogen atom and a C ₁ -C ₃ alkyl group, C _2- C ₁₇ alkenyl groups, C ₂ -C ₈ alkoxyalkyl groups, C ₂ -C ₈ alkylthioalkyl groups, phenoxyalkyl groups, or phenyl rings may be the same or different and are halogen atoms, C ₁ -C ₃ alkyl groups, and Phenoxyalkyl group having 1 to 5 substituents selected from C ₁ -C ₃ alkoxy groups.

In describing the preparation method, one for the cyclohexane derivatives of the general formula (IB) or salts thereof will be mentioned by way of example as they include the cyclohexane derivatives of the general formula (IA) or salts thereof.

Method (1):

Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁶ are as described above.

Cyclohexane derivatives or salts thereof represented by formula (IB) wherein R ⁵ is a hydroxy group can be produced by rearranging the compound of formula (II) in the presence of an inert solvent and a catalyst.

As the inert solvent useful for the reaction, those which do not significantly hinder the progress of the reaction can be used. For example, alcohols (e.g. methanol, ethanol, propanol, cyclohexanol), chlorinated hydrocarbons (e.g. dichloromethane, chloroform, carbon tetrachloride), aromatic sol hydrocarbons (e.g. benzene, toluene, xylene), esters (e.g. Ethyl acetate), nitrile (eg acetonitrile), cyclic ethers (eg dioxane, tetrahydrofuran) and the like.

As a catalyst which can be used for the said reaction, 4-N, N-dimethylaminopyridine, acetone cyanohydrin, potassium cyanide, sodium cyanide, etc. are mentioned, for example. The amount of catalyst used is suitably selected in the range of 0.01 to 10 mo1, preferably 0.1 to 1 mo1 based on compound 1 mo1 of formula (II).

The reaction temperature of the reaction is appropriately selected within the range of room temperature to the boiling point of the inert solvent used. Preferably, the reaction is carried out under heating. The reaction time varies depending on the amount of reactants, the reaction temperature and the like, but is selected within a range of several minutes to 48 hours. After completion of the reaction, the desired cyclohexane derivative is purified in a conventional manner, for example, by adjusting the pH with an acid, using a solvent to extract the desired product, and, if necessary, purifying the product by column chromatography, recrystallization or the like. Can be separated.

Method (2)

Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁶ are as described above.

Cyclohexane derivatives of formula (IB) or salts thereof, wherein R is a hydroxy group, are prepared by another method in which a compound of formula (III) is reacted with an acid anhydride of formula (III) in the presence of an inert solvent and a base can do.

As an inert solvent which can be used for the said reaction, there exists an inert solvent used for the method (1), for example.

In addition, the acid anhydride of formula (IV) may be used as the solvent.

As the base used in the method (2), inorganic and organic bases can be used. Inorganic bases include, for example, hydroxides, carbonates and alcoholates of alkali or alkaline earth metals such as sodium, potassium, magnesium, calcium. Organic bases include, for example, tertiary amines (eg triethylamine), pyridine, DBU (1,8-diazabicyclo [5.4.0] -7-undecene) and the like.

The reaction is carried out using equimolar amounts of compounds of formula (III) and acid anhydrides of formula (IV). However, acid anhydrides can be used in excess.

The amount of base used is appropriately selected in the range of equimolar to excessive molar amounts based on the compound of formula (III).

The reaction temperature is selected in the range of 10 ° C. to the boiling point of the inert solvent used.

The reaction time varies depending on the amount of the reactants, the reaction temperature and the like, but is appropriately selected in the range of several minutes to 48 hours.

After completion of the reaction, the desired cyclohexane derivatives can be separated from the reaction solution by conventional methods, e.g., extraction with a solvent, and, if necessary, purification of the product by column chromatography, recrystallization or the like. Can be.

Method (3):

Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁶ are as defined above and R ¹¹ is a C ₂ -C ₇ alkyl group, a C ₃ -C ₆ cycloalkyl group, a phenyl group, or the same or different And a phenyl group containing 1 to 5 substituents selected from the group consisting of a halogen atom, a C ₁ -C ₃ alkyl group and a C ₁ -C ₃ alkoxy group, Z is a halogen atom.

Cyclohexane derivatives of the general formula (IB) wherein R ⁵ is an acyloxy group include the cyclohexane derivatives of the general formula (IB-1) obtained according to the aforementioned method (1) or (2) in the presence of an inert solvent and a base. It can manufacture by reacting with the halide of general formula (V).

Since the reaction is an equimolar reaction, the halide of the general formula (V) is used in an equimolar amount with the cyclohexane derivative of the general formula (IB-1). However, halides may be used in excess.

As the inert solvent that can be used in the reaction, those which do not significantly hinder the progress of the reaction can be used. For example, chlorinated hydrocarbons (e.g. dichloromethane, chloroform, carbon tetrachloride), aromatic hydrocarbons (e.g. benzene, toluene, xylene), esters (e.g. ethyl acetate), nitrile (e.g. acetonitrile, benzonitrile), chains Ethers (eg methyl cellosolve, diethyl ether), cyclic ethers (eg dioxane, tetrahydrofuran), sulfolane, dimethyl sulfone, dimethyl sulfoxide, water and the like. These inert solvents may be used alone or in combination.

Bases that can be used in the reaction include inorganic or organic bases used in the above-mentioned method (2).

The base is used in an amount appropriately selected from the equimolar amount to the excess molar amount based on the cyclohexane derivative of general formula (IB-1).

The reaction temperature is selected in the boiling range of 0 ° C. to the inert solvent used.

The reaction time varies depending on the amount of the reactants, the reaction temperature and the like, but is appropriately selected in the range of several minutes to 48 hours.

After completion of the reaction, the cyclohexane derivative of general formula (IB-2) is separated from the desired product by conventional methods, for example by extraction with a solvent, and, if necessary, the product is purified by column chromatography, recrystallization or the like. This can be separated from the reaction solution.

Method (4):

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁶ and Z are as described above.

Cyclohexane derivatives of formula (IB-3) can be prepared by halogenating cyclohexane derivatives of formula (IB-1) with a halogenating agent in the presence or absence of an inert solvent.

As the halogenating agent used in the reaction, halogenating agents such as phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide, thionyl chloride, and oxalyl chloride may be used. The halogenating agent is used in the range of equimolar to excessive molar amounts based on the cyclohexane derivative of general formula (IB-1). Preferably, the halogenating agent is used in excess. In addition, the reaction can be carried out using an excess of halogenating agent in the absence of an inert solvent.

As the inert solvent that can be used in the reaction, those which do not significantly hinder the progress of the reaction can be used. For example, the chlorinated hydrocarbons described above (eg, dichloromethane, chloroform, carbon tetrachloride) and the like.

The reaction temperature is selected from room temperature or in the boiling point range of the inert solvent used.

The reaction time varies depending on the amount of reactants and the reaction temperature, but is appropriately selected in the range of several minutes to 48 hours.

After completion of the reaction, the cyclohexane derivatives of formula (IB-3) are separated by conventional methods, for example, by removing the solvent or extracting with solvent, and separating the desired product, if necessary by column chromatography, recrystallization or the like. It can be separated from the reaction solution by purification.

Method (5):

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁶ , R ⁹ , R ¹⁰ and Z are as described above and R ¹² is a C ₁ -C ₅ alkyl group or a C ₁ -C ₅ alkenyl group R ¹³ is a C ₁ -C ₅ alkylthio group, a C ₁ -C ₅ alkenylthio group or -N (R ⁹ ) R ¹⁰ , wherein R ⁹ and R ¹⁰ are as described above.

Cyclohexane derivatives of formula (IB-4) are prepared by reacting cyclohexane derivatives of formula (IB-3) with thiols of formula (IV) or amines of formula (IV) in the presence of an inert solvent and a base can do.

That is, the cyclohexane derivative of general formula (IB-4) can be prepared by carrying out the reaction in the same manner as in the method (3).

Method (6):

Wherein R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are as described above and R ¹⁴ is a lower acyl, lower alkoxycarbonyl, benzyl, sulfonyl, alkoxymethyl, alkenyl or trimethylsilyl group.

Cyclohexane derivatives of formula (IB-5) can be prepared by reacting cyclohexane of formula (II-1) with a deprotecting agent in the presence of an inert solvent to remove protecting group R ¹⁴ .

Deprotectants that can be used in the present invention include, for example, reducing agents (e.g. H ₂ / palladium carbon, zinc), organic and inorganic acids (e.g. acetic acid, trifluoroacetic acid, p-toluenesulfonic acid, hydrochloric acid, hydrobromide). Acids, sulfuric acids), inorganic bases (eg hydroxides or carbonates of alkali or alkaline earth metals), organic bases (eg triethylamines, DBU) and potassium fluorides, tetrabutylammonium fluorides and the like.

Inert solvents that can be used in the reaction include inert solvents, water and mixtures thereof which can be used in process (1).

The reaction temperature is selected from 0 ° C. to the boiling point of the inert solvent used.

The reaction time varies depending on the reaction temperature and the reaction scale, but is selected in the range of several minutes to 48 hours.

After completion of the reaction, the cyclohexane derivative of formula (IB-5) can be separated by the same treatment as in method (1).

Cyclohexane of the general formula (II-1) can be produced in the same manner as in the case of preparation of the cyclohexane of the general formula (II).

Method (7):

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and Z are as described above.

Cyclohexane derivatives of formula (IB) can be prepared by reacting cyclohexane derivatives of formula (IB-5) with halides of formula (VII) in the presence of an inert solvent and a base.

Cyclohexane derivatives of the general formula (IB-5) can be prepared by carrying out the reaction in the same manner as in the method (3).

Method (8):

Wherein R ¹ , R ² , R ⁴ , R ⁵ and R ⁶ are as described above, R ¹⁵ is a C ₁ -C ₅ alkyl or C ₁ -C ₅ haloalkyl group, n is an integer from 1 to 2 to be.

Cyclohexane derivatives of formula (IB-7) can be prepared by oxidizing cyclohexane derivatives of formula (IB-6) with a suitable oxidizing agent in the presence of an inert solvent.

Inert solvents that can be used in the reaction include inert solvents that can be used in the method (1).

Oxidizing agents that can be used in the reaction include, for example, nitric acid, hydrogen peroxide, perbenzoic acid, sodium m-chloroperbenzoate metaperiodate, potassium peroxymonosulfate, and the like. Since the reaction is an equimolar reaction, the oxidizing agent is used in equimolar amounts, but can also be used in excess.

The reaction temperature is selected from 0 ° C. to the boiling point of the inert solvent used. Preferably, it is selected in the range of 10 ° C to 150 ° C.

The reaction time varies depending on the reaction scale, the reaction temperature, etc., but is selected in the range of several minutes to 48 hours.

After completion of the reaction, the cyclohexane derivative of formula (IB-7) can be separated in the same manner as in method (1).

(9) salts:

Salts of the cyclohexane derivatives of the general formula (IA) and salts of the cyclohexane derivatives of the general formula (IB) may be selected from the cyclohexane derivatives prepared in the methods (1) to (8) for inorganic acids, inorganic bases, organic acids, organic bases and alkalis. It can manufacture by processing with a metal or a metal salt.

Typical examples of the cyclohexane derivative of the general formula (IA) and the cyclohexane derivative of the general formula (IB) and salts thereof are shown in Tables 1 and 2, but the present invention is not limited to these examples.

Formulas (IA) and (IB)

Table 1

Footnote: The symbol C- in Table 1 means an alicyclic compound.

In the compounds of Tables 1 and 2, NMR data of compounds whose physical properties are viscous products or vitreous products are shown in Table 3.

Table 3

The compounds of the formulas (II) and (III), which are substances for preparing the cyclohexane derivatives represented by the formulas (IA) and (IB) and salts thereof, can be prepared, for example, by the following method. :

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁶ and Z are as described above and R ¹⁶ is a lower alkyl group.

When R ⁴ is an alkyl group, the compound of formula (III) reacts pyrazole of formula (XIV) with acetate of formula (XIV) and reacts the resulting pyrazole of formula (XII) with a general formula ( It can be prepared by reacting with the ketone of X) and then ring-reacting the resulting compound.

When R ⁴ is a hydrogen atom or an alkoxycarbonyl group, the compound of formula (III-1) reacts pyrazole of general formula (XIV) with acetone, and the pyrazole of general formula (XI) produced It can be manufactured by reacting with malonate of (iii), and then ring-reacting the resulting compound.

Subsequently, the compound of the general formula (III-2) can be produced by hydrolyzing and decarboxylating the compound of the general formula (III-1).

The compound of general formula (III) can be manufactured by the method mentioned above.

The compound of formula (II) can be prepared by reacting a compound of formula (III) with an acyl halide of formula (V-1).

Examples of preparation of typical compounds of cyclohexane derivatives and their salts represented by formulas (IA) and (IB) are shown below.

(Production Example 1)

Preparation of 5- (1,3-dimethyl-lH-pyrazol-4-yl) -3-hydroxy-2-propionyl-2-cyclohexen-1-one (Compound No. 19)

1.31 g (5 mmol) of 5- (1,3-dimethyl-lH-pyrazol-4-yl) -3-oxo-1-cyclohexenyl propionate and 0.122 g (lmmol) of 4-N, N-dimethylaminopyridine ) Is dissolved in 50 ml of anhydrous tetrahydrofuran. The mixture is heated to reflux for 8 hours in nitrogen atmosphere. After the reaction is completed, the reaction solution is cooled to room temperature and the solvent is removed under reduced pressure. 50 ml of water is added to the residue, the pH is adjusted to 4 with dilute hydrochloric acid, and the product is extracted three times with 40 ml aliquots of ethyl acetate. After the extract was dried, the solvent was removed and the residue was purified by column chromatography on silica gel (ethyl acetate: n-hexane) to give 1.19 g of the desired product.

Melting Point: 90.0 ℃

Yield: 91%

(2)

Preparation of 5- (5-Chloro-1, 3-dimethyl-lH-pyrazol-4-yl) -3-hydroxy2-pyridionyl-2-cyclohexen-1-one (Compound No. 22)

1.49 g (5 mmol) of 5- (5-chloro-1, 3-dimethyl-lH-pyrazol-4-yl) -3-oxo-1-cyclohexenyl propionate and 4-N, N-dimethylaminopyridine 0.122 g (lmmol) is dissolved in 80 ml of anhydrous tetrahydrofuran. The mixture is heated to reflux for 8 hours in nitrogen atmosphere. After the reaction is completed, the reaction solution is cooled to room temperature and the solvent is removed under reduced pressure. 50 ml of water was added to the residue, and the resultant product of which the pH was adjusted to 4 with dilute hydrochloric acid was extracted three times with 40 ml aliquots of ethyl acetate. After the extract was dried, the solvent was removed and the residue was purified by column chromatography on silica gel (ethyl acetate: n-hexane) to give 1.30 g of the desired product.

nD 1.5462 (25.1 ° C)

Yield: 87%

(Production Example 3)

Preparation of 2-isobutyryl-3-hydroxy-5- (5-chloro-1, 3-dimethyl-lH-pyrazol-4-yl) -2-cyclohexen-1-one (Compound No. 25)

1.56 g (5 mmol) of 5- (5-chloro-1,3-dimethyl-lH-pyrazol-4-yl) -3-oxo-1-cyclohexenyl isobutyrate is dissolved in 15 ml of anhydrous acetonitrile and acetone 0.085 g (lmmol) of cyanohydrin and 1.0 lg (10 mmol) of triethylamine are added. The resulting mixture is heated to reflux for 1 hour. After the reaction is completed, the reaction solution is cooled to room temperature and the solvent is removed under reduced pressure. 20 ml of water is added to cinnabar, the pH is adjusted to 4 with dilute hydrochloric acid, and the desired product is extracted three times with 50 ml aliquots of diethyl ether. After the extract is dried, the solvent is removed and the residue is purified by column chromatography on silica gel (ethyl acetate: n-hexane) to give 1.13 g of the desired product.

Melting Point: 86.5 ℃

Yield: 72%

(Production Example 4)

Preparation of 2-butyryl-3-hydroxy-5- (5-methoxy-1, 3-dimethyl-lH-pyrazol-4-yl) -2-cyclohexen-1-one (Compound No. 44)

1.84 g (5 mmol) of 5- (5-methoxy-1, 3-dimethyl-lH-pyrazol-4-yl) -3-oxo-1-cyclohexenyl butyrate and 0, 4-N, N-dimethylaminopyridine 22 g (1 mmol) are dissolved in 80 mL of anhydrous tetrahydrofuran. The mixture is heated to reflux for 8 hours in nitrogen atmosphere. After the reaction is completed, the reaction solution is cooled to room temperature and the solvent is removed under reduced pressure. 50 ml of water is added to the residue, the pH is adjusted to 4 with dilute hydrochloric acid, and the product is extracted three times with 40 ml aliquots of ethyl acetate. After the extract was dried, the solvent was removed and the residue was purified by column chromatography on silica gel (ethyl acetate: n-hexane) to give 1.64 g of the desired product.

Melting Point: 73.2 ℃

Yield: 89%

(Production Example 5)

5- (1-ethyl-3-methyl-5-methylthio-1H-pyrazol-4-yl) -3-hydroxy-2-cyclopropylcarbonyl-2-cyclohexen-1-one (Compound No. 165 Manufacturing

5- (1-ethyl-3-methyl-5-methylthio-lH-pyrazol-4-yl) -3-oxo-1-cyclohexenyl cyclopropane carboxylate l2.3 g (36.8 mmol) in anhydrous acetonitrile Dissolve in 100 mL and add 0.3 g (3.7 mmol) of acetone cyanhydrin and 8.2 g (81.2 mmol) of triethylamine. The mixture is stirred for 8 h at room temperature in nitrogen atmosphere.

After the reaction is complete, the solvent is removed under reduced pressure. 100 ml of water is added to the residue, the pH is adjusted to 4 with dilute hydrochloric acid, and the desired product is extracted three times with 100 ml aliquots of ethyl acetate. After the extract is dried, the solvent is removed and the residue is purified by column chromatography on silica gel (ethyl acetate: n-hexane) to give 11.2 g of the desired product.

Melting Point: 93.1 to 93.8 ° C

Yield: 91.1%

(Production Example 6)

5- (1-ethyl-3-methyl-5-pyrrolidino-1H-pyrazol-4-yl) -3-hydroxy-2-cyclopropylcarbonyl-2-cyclohexen-1-one (compound number 202 manufacturing

2.2 g (62 mmol) of 5- (1-ethyl-3-methyl-5-pyrrolidino-H1-pyrazol-4-yl) -3-oxo-1-cyclohexenyl cyclopropane carboxylate was dissolved in anhydrous acetonitrile. Dissolve in 50 mL and add 0.1 g (1.2 mmol) of acetone cyanohydrin and 1.4 g (13.6 mmol) of triethylamine.

The mixture is stirred for 8 h at room temperature in nitrogen atmosphere. After the reaction is complete, the solvent is removed under reduced pressure. 50 ml of water is added to the residue, the pH is adjusted to 4 with dilute hydrochloric acid, and the desired product is extracted three times with 40 ml aliquots of ethyl acetate. After the extract was dried, the solvent was removed and the residue was purified by column chromatography on silica gel (ethyl acetate: n-hexane) to give 1.4 g of the desired product.

Melting Point: 65.0 ~ 67.0 ℃

Yield: 63.6%

(Production Example 7)

5- (3-Methyl-5-methylsulfinyl-1-octyl-1H-pyrazol-4-yl) -2-cyclopropylcarbonyl-3-hydroxy-2-cyclohexen-1-one (compound number 260)

20 ml of 1.7 g (3.9 mmol) of 5- (3-methyl-5-methylsulfinyl-1-octyl-H1-pyrazol-4-yl) -3-oxo-1-cyclohexenyl cyclopropanecarboxylate Is dissolved in anhydrous acetonitrile and 0.1 g (1.2 mmol) of acetone cyanohydrin and 0.9 g (8.9 mmol) triethylamine are added. The mixture is stirred for 8 h in nitrogen atmosphere at room temperature.

After completion of the reaction, the solvent was removed under reduced pressure. 150 ml of water was added to the obtained residue, the pH was adjusted to 4 with diluted hydrochloric acid, and the desired product was extracted three times with a 40 ml aliquot of ethyl acetate. After the extract is dried, the solvent is removed and the residue is purified by column chromatography on silica gel (ethyl acetate: n-hexane) to yield 1.6 g of the desired product.

nD 1.5435 (21.1 ° C)

Yield: 94.1%

(Production Example 8)

5- (3,5-dimethyl-1-n-propyl-H1-pyrazol-4-yl) -2-cyclopropylcarbonyl-3-hydroxy-2-cyclohexen-1-one (Compound No. 207) Manufacture

177 g (56 mmol) of 5- (35-dimethyl-1-n-propyl-H1-pyrazol-4-yl) -3-oxo-1-cyclohexenyl cyclopropanecarboxylate in 20 ml anhydrous acetonitrile, 0 .lg (1.1 mmol) acetone cyanhydrin and 1.24 g (12.3 mmol) triethylamine are dissolved. The mixture is stirred at room temperature under nitrogen atmosphere for 8 hours.

After completion of the reaction, the solvent was removed under reduced pressure. 50 ml of water is added to the obtained residue, the pH is adjusted to 4 with dilute hydrochloric acid and the desired product is extracted three times with 40 ml portions of ethyl acetate. After the extract is dried, the solvent is removed and purified by column chromatography on silica gel (ethyl acetate: n-hexane) to yield 1.51 g of the desired product.

nD 1.5432 (15 ° C)

Yield: 85.3%

The product obtained is further purified to yield 1.48 g of crystals.

Melting Point: 79.7 ~ 79.9 ℃

Yield: 83.6%

(Production Example 9)

Preparation of 5- (1, 3-dimethyl-H1-pyrazol-5-yl) -2-propionyl-2-cyclohexen-1-one (Compound No. 320)

In 200 mL tetrahydrofuran, 17.5 g (66.7 mmol) of 5- (l, 3-dimethyl-1H-pyrazol-5-yl) -3-oxo-1-cyclohexenyl propionate and 0.85 g ( 7.0 mmol) of a mixture of 4-N, N-dimethylaminopyridine. The mixture is heated at reflux for 2 hours.

After completion of the reaction, the reaction solution is cooled and the solvent is removed under reduced pressure. The obtained residue is purified by column chromatography on silica gel (ethyl acetate: n-hexane) to give 16.40 g of the desired product.

nD 1.5331 (12.1 ° C)

Yield: 93.7%

(Production Example 10)

Preparation of 5- (1, 3-dimethyl-5-methylsulfinyl-1H-pyrazol-4-yl) -3-oxo-2-cyclopropylcarbonyl-1-cyclo hexenylbenzoate (Compound No. 110)

0.6 g (1.8 mmol) of 5- (1,3-dimethyl-5-methylsulfinyl-1H-pyrazol-4-yl) -3-hydroxy-2-cyclopropyl in 30 ml anhydrous tetrahydrofuran 0.082 g (2.1 mmol) of carbonyl-2-cyclohexen-1-one 63% sodium hydride are added and the resulting mixture is stirred for 30 minutes. Thereafter, 0.30 g (21 mmol) of benzoyl chloride is added to the reaction solution, and the mixture is stirred overnight at room temperature. After the reaction was completed, water was added to the reaction solution, and the product was extracted with ether. The extract is washed with aqueous potassium carbonate solution, washed again with water, dried and concentrated. The obtained residue is purified by column chromatography on silica gel (ethyl acetate) to yield 0.20 g of the desired product.

Physical properties: viscosity

Yield: 25%

NMR (CDC1 ₃ / TMS, δ value, ppm) 0.77-1.36 (m, 4H), 2.30 (s, 3H), 2.96 (s, 3H), 4.03 (s, 3H), 2.00-3.95 (m, 6H) , 7.40-7 .70 (m, 3H), 7.87-8 .17 (m, 2H).

(Production Example 1l)

Preparation of 3-chloro-5- (1, 3-dimethyl-5-methylthio-1H-pyrazol-4-yl) -2-propionyl-2-cyclohexen-1-one (Compound No. 79)

10 g (32.5 mmol) 3-hydroxy-5- (1, 3-dimethyl-5-methylthio-1H-pyrazol-4-yl) -2-propionyl-2 in 29 g (230 mmol) oxalyl chloride Dissolve cyclohexen-1-one. The mixture is heated at room temperature for 1 hour. After completion of the reaction, the reaction solution was poured into 100 ml of ice water, the pH was adjusted to 7 with 1 N sodium hydroxide and the desired product was extracted three times with 100 ml aliquots of ethyl acetate. After drying the extract, the solvent is removed and the residue obtained is purified by column chromatography on silica gel (ethyl acetate: n-hexane) to yield 9.5 g of the desired product.

Melting Point: 141.2 ~ 142.3 ° C

Yield: 89.5%

(Production Example 12)

Preparation of 3-diethylamino-5- (l, 3-dimethyl-5-methylthio-1H-pyrazol-4-yl) -2-propionyl-2-cyclohexen-1-one (Compound No. 84)

0.6 g (1.8 mmol) of 3-chloro-5- (1,3-dimethyl-5-methylthio-1H-pyrazol-4-yl) -2-propionyl-2- in 30 ml anhydrous tetrahydrofuran Cyclohexen-1-one and 0.16 g (2.2 mmol) of diethylamine are dissolved and 0.22 g (22 mmol) triethylamine is added.

The mixture is stirred for 4 hours at room temperature. After the reaction is completed, the solvent is removed under reduced pressure. After 50 ml of water was added to the obtained residue, the pH was adjusted to 5 using dilute hydrochloric acid, and the product was extracted three times with a 40 ml aliquot of ethyl acetate. After the extract is dried, the solvent is removed and the residue is purified by column chromatography on silica gel (ethyl acetate: n-hexene) to yield 0.4 g of the desired product.

nD 1.5729 (20.1 ℃)

Yield: 61.2%

(13)

Preparation of 5- (3, 5-dimethyl-1H-pyrazol-4-yl) -3-hydroxy-2-cyclopropylcarbonyl-2-cyclohexen-1-one (compound number 4)

5.8 g (19.3 mmol) of 5- (3, 3-dimethyl-1-vinyl-1H-pyrazol-4-yl) -3-hydride in 50 ml of 1, 4-dioxane and 50 ml of water Dissolve oxy-2-cyclopropylcarbonyl-2-cyclohexen-1-one and add dropwise 4.0 g (41.5 mmol) of 38% hydrochloric acid. After the addition is complete, the mixture is heated under reflux for 3 hours.

After completion of the reaction, the reaction solution is cooled to room temperature and the solvent is removed under reduced pressure. 100 ml of water was added to the obtained residue, the pH was adjusted to 4 with aqueous dilute sodium hydroxide solution, and the product was extracted three times with 100 ml aliquots of ethyl acetate. The extract is dried and the solvent is removed under reduced pressure. The obtained residue is purified by column chromatography on silica gel (ethyl acetate) to give 4.5 g of the desired product.

Melting Point: 188.0 ~ 191.3 ℃

Yield: 85.1%

(Production Example l4)

5- (3,5-dimethyl-1-n-propyl-1H-pyrazol-4-yl) -2-cyclopropylcarbonyl-3-hydroxy-2-cyclohexen-1-one (Compound No. 207) Manufacture

1.0 g (3, 7 mmol) of 5- (3,5-dimethyl-1H-pyrazol-4-yl) -2-cyclopropylcarbonyl-3-hydroxy-2-cyclo in 20 ml of anhydrous dimethyl sulfoxide Hexen-1-one and 0.9 g (8 mmol) of potassium tert-butoxide are dissolved and 0.8 g (4.4 mmol) of n-propyl iodide is added dropwise. After complete addition, the mixture is stirred at room temperature for 10 hours.

After completion of the reaction, 100 ml of water of the reaction solution is added and the resulting aqueous solution is washed twice with 50 ml aliquots of ether. The aqueous layer is adjusted to pH 4 with dilute hydrochloric acid and the product is extracted three times with 100 ml aliquots of ethyl acetate. The extract is dried, the solvent is removed and the residue is purified by column chromatography on silica gel (ethyl acetate: n-hexane) to afford 1.0 g of the desired product.

Melting Point: 79.7 ~ 79.9 ℃

Yield: 85.5%

(Production Example 15)

5-(3,5-Dimethyl-1-iso-propyl-1H-pyrazol-4-yl) -2-cyclopropylcarbonyl-3-hydroxy-2-cyclohexen-1-one (Compound No. 232) Manufacture

1.0 g (3.7 mmol) of 5- (3,5-dimethyl-1H-pyrazol-4-yl) -2-cyclopropylcarbonyl-3-hydroxy-2-cyclohexene in 20 mL of anhydrous dimethyl sulfoxide Dissolve 1-one and 0.9 g (8.0 mmol) of potassium tert-butoxide, and dropwise add 0.8 g (4.4 mmol) of isopropyl iodide. After the addition is complete, the mixture is stirred at room temperature for 9 hours.

After the reaction was completed, 100 ml of water was added to the reaction solution, and the resulting aqueous solution was washed three times with an aliquot of 50 ml of ether. The aqueous layer is adjusted to pH 4 with dilute hydrochloric acid and the desired product is washed three times with 100 ml aliquots of ethyl acetate. After the extract is dried, the solvent is removed and the residue is purified by column chromatography on silica gel (ethyl acetate: n-hexane) to give 1.1 g of the desired product.

Melting Point: 97.2 ~ 99.6 ℃

Yield: 95.3%

(Example 16)

5-(3,5-Dimethyl-1-iso-butyl-1H-pyrazol-4-yl) -2-cyclopropylcarbonyl-3-hydroxy-2-cyclohexen-1-one (Compound No. 248) Manufacture

0.5 g (1.8 mmol) of 5- (3,5-dimethyl-1H-pyrazol-4-yl) -2-cyclopropylcarbonyl-3-hydroxy-2-cyclohexene in 20 ml anhydrous tetrahydrofuran Dissolve 1-one and 0.4 g (3.8 mmol) of potassium tert-butoxide and add 0.4 g (2.2 mmol) of isobutyl iodide dropwise thereto. After the addition is complete, the mixture is heated under reflux for 8 hours.

After the reaction was completed, 100 ml of water was added to the reaction solution, and the resulting aqueous solution was washed twice with an aliquot of 50 ml of ether. The pH of the aqueous layer is adjusted to 4 with dilute hydrochloric acid and the product is extracted three times with an aliquot of 100 ml of ethyl acetate. After the extract is dried, the solvent is removed and purified by column chromatography on silica gel (ethyl acetate: n-hexane) to yield 0.2 g of the desired product.

nD 1.5485 (27.0 ℃)

Yield: 33.3%

(Production Example l7)

5- (3-chloro-1-ethyl-5-methylsulfinyl-1H-pyrazol-4-yl) -2-cyclopropylcarbonyl-3-hydroxy-2-cyclohexen-1-one (compound Manufacture of number 152)

0.98 g (2.8 mmol) of 5- (3-chloro-1-ethyl-5-methylthio-1H-pyrazol-4-yl) -2-cyclopropylcarbonyl-3-hydroxy- in 10 ml ethanol 2-cyclohexen-1-one is dissolved and 1.02 g (1.7 mmol) of potassium peroxymonosulfate predissolved in 5 ml of water are added thereto. The mixture is stirred at rt for 10 h.

After completion of the reaction, the solvent was removed under reduced pressure and water was added to the residue. The desired product is extracted with methylene chloride. After drying the extract, the solvent is removed and the residue is purified by column chromatography on silica gel (methanol: ethyl acetate) to afford 0.57 g of the desired product.

Melting Point: 140-140 ℃

Yield: 56%

(Production Example 18)

5- (1-ethyl-3-methyl-5-methylsulfinyl-1H-pyrazol-4-yl) -3-hydroxy-2-cyclopropylcarbonyl-2-cyclohexen-1-one (compound number 176)

9.3 g (27.8 mmol) of 5- (1-ethyl-3-methyl-5-methylthio-1H-pyrazol-4-yl) -3-hydroxy-2-cyclopropylcarbonyl- in 300 ml ethanol 2-cyclohexen-1-one is dissolved and 9.4 g (15.3 mmol) of potassium peroxymonosulfate pre-dissolved in 300 ml of water are added thereto. The mixture is stirred at room temperature for 10 hours.

After the reaction was completed, the solvent was removed under reduced pressure, and water was added to the residue. The desired product is extracted three times in 200 ml aliquots of methylene chloride. After drying the extract, the solvent is removed and purified by column chromatography on silica gel (methanol: ethyl acetate) to afford 8.0 g of the desired product.

Melting Point: 130.1 ~ 131.1 ℃

Yield: 82.1%

(Production Example 19)

5- (1-Ethyl-3-methyl-5-methylsulfinyl-lH-pyrazol-4-yl) -3-hydroxy-2-2-cyclopropylcarbonyl-2-cyclohexen-1-one (compound Sodium salt preparation of No. 177)

Dissolve 20 mg (0.87 mmol) of sodium metal in 10 mL of absolute ethanol and 0.3 g (0.86 mmol) of 5- (1-ethyl-3-methyl-5-methylsulfinyl-1H-pyrazole- in the resulting solution. 4-yl) -3-hydroxy-2-cyclopropylcarbonyl-2-cyclohexen-1-one is added.

The mixture is stirred at rt for 1 h. After the reaction was completed, the solvent was removed and the residue was dried by heating to about 70 ° C. under reduced pressure using calcium chloride as a drying agent. This gives 0.32 g of the desired product.

Physical properties: glassy

NMR (D ₂ O / DSS, δ value, ppm): 0.90-1.00 (m, 4H), 1.35 (t, 3H), 2.44 (s, 3H), 2.25-2.49 (m, 3H), 2.65-2.85 ( m, 2H), 3.11 (s, 3H), 3.53 -3.65 (m, 1H), 4. 39 (q, 2 H).

(Production Example 20)

Preparation of 5- (3,5-dimethyl-lH-pyrazol-4-yl) -2-cyclopropylcarbonyl-3-hydroxy-2-cyclohexen-1-one hydrochloride (Compound No. 5)

0.5 g (1.8 mmol) of 5- (3,5-dimethyl-1H-pyrazol-4-yl) -2-cyclopropylcarbonyl-3-hydroxy-2-cyclohexel-1-one, and 12% 2 g (6.6 mmol) of 1,4-dioxane solution containing hydrochloric acid were added to 20 ml of 1,4-dioxane. The mixture is stirred for 10 minutes at room temperature.

After completion of the reaction, the precipitated crystals are collected by filtration, washed with ether and dried at 50 ° C. under reduced pressure to yield 0.5 g of the desired product.

Melting Point: 280.9 ~ 288.2 ℃

Yield: 89%

Insecticides containing the cyclohexane derivatives of the general formula (IA) or the cyclohexane derivatives of the general formula (IB), or salts thereof as the active ingredient exhibit particularly remarkable effects on pests belonging to Hemiptera. Among these pests, the insecticides are effective against aspirated insects which hinder their growth while parasitic on fruit trees, crops and the like.

For example, the insecticide is effective against planthoppers, which are typical pests of paddy rice, and can be used in whitefly, suckers, scale and vegetables (e.g. eggplants, tomats, cucumbers). It is effective against lace bugs that cause harm to industrial crops (e.g. cotton, mulberry, tea) and fruit trees (e.g. citrus fruits, grapes, pears, apples, Japanese persimmons). Grasshoppers among the pests include brown rice grasshoppers (Nilaparvata lugens), white grasshoppers (Sogatella furcifera), small brown grasshoppers (Laodelphax striatellus) and the like. The flours include Trialurodes vaporariorum, Dialeurodes citri, Aleurocanthus spiniferus, Aleurolobus taonabae, Sweet potato powder (Bemisia tabaci) and Strawberry powder (Trialeurodes packardi). Aspirating insects include Psylla pyrisuga, Anomoneura mori, citrus psylla, Diaphorina citri, and Psylla mari. The worms include the horned beetle beetle (Ceroplastes pseudoceriferus), the cotton citrus beetle (Pulviriana a urantii), the camphor beetle (Pseudaonidia duplex), the mountain joss (Quadraspidiotus perniciosus), and all the beetle (arrowhead scale; Unaspis yanonensis). Shield bugs include Stephanitis nashi and Rhododendron shield worms.

The insecticide of the present invention exhibits particularly insecticidal effects on grasshoppers and aspirates which are harmful to fruit trees and vegetables as well as grasshoppers that penetrate rice crops. The insecticides exhibit the ability to kill by inhibiting aspiration in rice, fruit trees, vegetables and the like, especially in the above-mentioned insect pests.

After all, the expected effect of the insecticide of the present invention is that the rice cropland water required for rice, the foliage of fruit trees and the soil required for vegetables are prepared for the season in which the occurrence is expected or when the occurrence of these insects is confirmed. It can be expected to treat rice, fruit trees, and vegetables with pesticides before harming them.

However, the present invention is not limited only to these aspects.

When the cyclohexane derivatives represented by the formula (IA) or (IB) and salts thereof are used as insecticides, they may be prepared by using them in a form suitable for use according to conventional methods for the manufacture of agricultural chemicals. Is a common technique.

That is, prior to use as a pesticide, cyclohexane derivatives of formula (IA) or (IB) and their salts are mixed with a suitable inert carrier and, if necessary, with a suitable ratio of auxiliaries and dissolved, dispersed and suspended in the resulting mixture. And various treatments such as mixing, impregnation, adsorption, fixation, etc., and may be formulated in suitable forms such as suspending agents, emulsifiable concentrates, liquid preparations, wettable powders, granules, dusts, and tablets.

As the inert carrier usable in the present invention, any solid carrier or liquid carrier may be used. Materials that can be used as solid carriers are soybean powder, grain flour, wood powder, bark powder, sawdust, tobacco stem powder, walnut shell powder, bran, cellulose powder, residues after extraction of vegetable essences, synthetic polymers (e.g. pulverized) Synthetic resins), muds (e.g. kaolin, bentonite), acid clay, talc (e.g. talc, pyrophyllite), silicas (e.g. diatomaceous earth, silica sand, mica) , White carbon (highly dispersed synthetic silica, also referred to as finely divided hydrogenated silica or hydrogenated silicic acid, some of which contain calcium silicate as a main component)], inorganic mineral powders (e.g. activated carbon, sulfur, pumice, calcining) Diatomaceous earth, brick, fly ash, sand, calcium carbonate, calcium phosphate, chemical fertilizers (eg ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride), mixed fertilizers, and the like. The materials can be used alone or in combination The.

Substances which can be used as liquid carriers are selected from the group consisting of a liquid which itself has solvent capability and a liquid which does not have solvent capability but which can disperse the active ingredient with the aid of an adjuvant. For example, the following carriers which can be used alone or in combination are typical examples: water, alcohols (e.g. methanol, ethanol, isopropanol, butanol, ethylene glycol), ketones (e.g. acetone, methyl ethyl ketone, methyl Isobutyl ketone, diisobutyl ketone, cyclohexanone), ethers (e.g. ethyl ether, dioxane, cellosolve, dipropyl ether, tetrahydrofuran), aliphatic hydrocarbons (e.g. gasoline, mineral oil), aromatic hydrocarbons (E.g. benzene, toluene, xylene, solvent naphtha, alkyl naphthalenes), halogenated hydrocarbons (e.g. dichloroethene, chloroform, carbon tetrachloride, chlorinated benzene, etc.), esters (e.g. ethyl acetate, diisopropyl phthalate, dibutyl) Phthalates, dioctyl phthalates), amides (eg dimethyl formamide, diethyl amide, dimethylacetamide), nitriles (eg acetonitrile), dimethyl sulfide Side and so on.

As another adjuvant, the following typical can be mentioned. These adjuvants are used depending on the purpose. These may be used alone or in combination, and in some cases, all of these may not be used at all.

For the emulsification, dispersion, solubilization and / or wetting of the active ingredients, for example, the following surfactants can be used: polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene higher fatty acid esters, poly Oxyethylene resinate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, alkylarylsulfonate, naphthalenesulfonic acid concentrated product, ligninsulfonate, higher alcohol sulfate esters and the like.

To stabilize and disperse the dispersion of the active ingredients, they can be imparted with adhesion and / or combined, and the following auxiliaries may be used: casein, gelatin, starch, methyl cellulose, gum arabic, polyvinyl alcohol, tufentin, bran Oil, bentonite, lignin sulfonate etc.

The following auxiliaries can be used, for example, to improve the fluidity of the solid pesticide product: waxes, stearates, alkyl phosphates and the like.

As a gelling agent for dispersible insecticide products, for example, naphthalenesulfonic acid concentrate products, polyphosphates and the like can be used as adjuvants.

Auxiliaries such as silicone oils can be used as antifoams.

The proportion of active ingredient mixed can often vary as needed. For example, dust and granules are preferred from 0.01 to 50% by weight, as are emulsifiable concentrates and wettable powders.

For the purpose of controlling pests using pesticides containing cyclohexane derivatives of the general formula (IA) or (IB) or their salts as active ingredients, the insecticide itself may be in the form of an effective insecticide or an appropriate dilute aqueous solution or suspension form. Or it is preferable to spray directly to a place where the occurrence or propagation of insects is undesirable. For example, in order to control grasshoppers, which are harmful to rice, insecticides must be sprayed on the leaves (leaf) or soil of the rice, or the water in the arable land where rice is planted.

Dosage rates of pesticides containing cyclohexane derivatives of the general formula (IA) or (IB) or salts thereof as the active ingredient may, for example, be applied to, pests to be controlled, germination / growth forms of plants, propensity to develop pests, It is determined by various factors such as climate, environmental conditions, formulation type and method of application of pesticide, location and time. However, depending on the subject, it is preferable to appropriately select a dosage within the range of 1 g to 3 kg / 10are as the active ingredient.

Insecticides containing cyclohexane derivatives of the general formula (IA) or (IB) or salts thereof as the active ingredient, in order to extend the range of pests to be controlled and the period during which the pests can be controlled or to reduce the dosage, It can be used in combination with other insecticides and fungicides.

Typical formulation and test examples of the present invention are shown below, but the present invention is not limited to these examples.

(Formulation Example 1)

Compound number 1 50 parts

Xylene 40

10 parts of a mixture of polyoxyethylene nonylphenyl ether and calcium alkylbenzenesulfonate

The components are mixed uniformly and an emulsifiable concentrate is obtained.

(Formulation Example 2)

Compound number 15 part 3

Mud Powder 82

Diatomaceous Earth Powder, Part 15

The components are mixed uniformly to obtain dust.

(Formulation Example 3)

Compound number 58 5 parts

90 parts powder mixture of bentonite and mud

Calcium Lignin Sulfonate Part 5

The ingredients are mixed uniformly, triturated with an appropriate amount of water, then granulated, dried and dried to give granules.

(4)

Compound number 72 20 parts

75 parts of a mixture of kaolin and synthetic highly dispersed silicic acid

5 parts of a mixture of polyoxyenylene nonylphenyl ether and calcium alkylbenzenesulfonate

The ingredients are mixed uniformly to obtain a wettable powder.

(1)

Insecticide Test on Brown Rice Locusts (Nilaparvata lugens)

Rice seedlings (var., Kimmaze) are soaked for 30 seconds in an insecticide solution containing 200 ppm of the compound prepared in Example as an active ingredient. After air drying, seedlings are placed in glass test tubes and inoculated with stage 3 larvae of 10 brown rice locusts. Put a cotton cap on the test tube. After 8 days of inoculation, dead or live larvae are examined and the lethality is calculated by the following formula. Pesticide activity is determined based on the following standards.

This test is carried out in a room at a constant temperature maintained at 25 ° C.

Judgment standard: fatality rate

A: 90% or more

B: 70% to less than 90%

C: 50% to less than 70%

D: less than 50%

The results are shown in Table 4.

Table 4

(Test Example 2)

Insecticide Test on Trialurodes vaporariorum

Small leaves of tomato (var., Ponteroza) are soaked for 30 seconds in an insecticide solution containing 100 ppm of the compound prepared in Example as an active ingredient. After air drying, the leaves are soaked with hygroscopic cotton moistened and placed in a glass cylinder 5 cm in diameter and 20 cm high. Ten warm powders release the adults on the leaves and cover the top opening of the cylinder with gauze. After a week of radiation, investigate dead or living adults. The mortality rate is calculated according to Test Example 1 and the same method is determined.

The test is carried out in a room at a constant temperature maintained at 25 ° C.

The results are shown in Table 5.

Table 5

Claims (3)

Cyclohexane derivatives of formula (IA) or salts thereof. (ⅠA) Wherein R ^{1 ′} is a hydrogen atom, ethyl group, n-propyl group, n-butyl group, iso-butyl group or secondary-butyl group, and R ^{2 ′} is hydrogen atom, halogen atom or C ₁ -C ₅ Alkyl group, R ^{3 ′} is a halogen atom, C ₁ -C ₅ alkyl group, C ₁ -C ₅ alkoxy group, C ₁ -C ₅ alkylthio group, C ₁ -C ₅ alkylsulfinyl group, C ₁ -C ₅ Alkylsulfonyl group or —N (R ^{7 ′} ) R ^{8 ′} wherein R ^{7 ′} and R ^{8 ′} may be the same or different and are each a hydrogen atom or a C ₁ -C ₃ alkyl group, R ^{7 ′} R ^{8 ′} may be bonded together through 4 to 6 methylene groups), R ^{4 ′} is a hydrogen atom, a C ₁ -C ₅ alkyl group or a C ₂ -C ₅ alkoxy carbonyl group, and R ^{5 '} is hydroxy group, phenyl-carbonyl, or aryloxy group, a phenyl ring may be the same or different one to five substituents selected from the group consisting of halogen atom, C ₁ -C ₃ alkyl group and C ₁ -C ₃ alkoxy groups Phenyl-carbonyl-oxy group that is oil, R ^{6 'is} C ₁ -C ₅ alkyl group, C ₃ -C ₆ cycloalkyl group or a C ₁ -C ₃ alkyl group, a cycloalkyl group substituted by, provided that, R ^1' Is an ethyl group, n-propyl group, n-butyl group, iso-butyl group or secondary-butyl group, R ^{2 '} is a hydrogen atom or a C ₁ -C ₅ alkyl group, R ^3' is a halogen atom, C ₁ -C ₅ alkyl group, C ₁ -C ₅ alkoxy group, C ₁ -C ₅ alkylthio group, C ₁ -C ₅ alkylsulfinyl group, C ₁ -C ₅ alkylsulfonyl group or -N (R ^{7 '} R ^{8 ′} , wherein R ^{7 ′} and R ^{8 ′} may be the same or different and are each a hydrogen atom or a C ₁ -C ₃ alkyl group. And R ^{4 ′} is a hydrogen atom, C ₁ -C ₃ An alkyl group or a C ₂ -C ₄ alkoxycarbonyl group, and if R ^{5 ′} is a hydroxy group, then R ^{6 ′} is not a C ₁ -C ₅ alkyl group or a C ₃ -C ₆ cycloalkyl group. The cyclohexane derivative according to claim 1, or a salt thereof, wherein R ^{2 ′} is a halogen atom and R ^{6 ′} is a cycloalkyl group substituted with a C ₁ -C ₃ alkyl group. A process for preparing a cyclohexane derivative of formula (IA ′) or a salt thereof, characterized in that the cyclohexane compound of formula (IIA) is reacted in the presence of a catalyst. Wherein R ^{1 ′} is a hydrogen atom, ethyl group, n-propyl group, n-butyl group, iso-butyl group or secondary-butyl group, and R ^{2 ′} is hydrogen atom, halogen atom or C ₁ -C ₅ An alkyl group, R ^{3 ′} is a halogen atom, a C ₁ -C ₅ alkyl group, a C ₁ -C ₅ alkoxy group, a C ₁ -C ₅ alkylthio group, a C ₁ -C ₅ alkylsulfinyl group, C ₁ -C ₅ alkylsulfonyl group or —N (R ^{7 ′} ) R ^{8 ′} wherein R ^{7 ′} and R ^{8 ′} may be the same or different and are each a hydrogen atom or a C ₁ -C ₃ alkyl group, R ^{7 ′} and R ^{8 '} may be bonded together through 4 to 6 methylene groups), R ^4' is a hydrogen atom, a C ₁ -C ₅ alkyl group or a C ₂ -C ₅ alkoxy carbonyl group, and R ^{6 '} is A C ₁ -C ₅ alkyl group, a C ₃ -C ₆ cycloalkyl group or a cycloalkyl group substituted with a C ₁ -C ₃ alkyl group, provided that R ^{1 ′} is an ethyl group, n-propyl group, n-butyl group , Iso-butyl group or secondary-butyl group And, R ^{2 'is} a _5-alkyl group, a hydrogen atom or a C ₁ -C, R ^3' is a halogen atom, C ₁ -C ₅ alkyl group, C ₁ -C ₅ alkoxy group, C ₁ -C ₅ alkylthio group, C ₁ -C ₅ alkylsulfinyl group, C ₁ -C ₅ alkylsulfonyl group or —N (R ^{7 ′} ) R ^{8 ′} wherein R ^{7 ′} and R ^{8 ′} may be the same or different and each hydrogen Is an atom or a C ₁ -C ₃ alkyl group), and R ^{4 ′} is a hydrogen atom, a C ₁ -C ₃ alkyl group or a C ₂ -C ₄ alkoxycarbonyl group, R ^{6 '} is a C ₁ -C ₅ alkyl No group or a C ₃ -C ₆ cycloalkyl group.