CN1022919C - Method for preparing pyrazole oxime derivatives - Google Patents

Abstract

The invention relates to compounds of general formula , to a method for the production thereof and to the use thereof as pesticides,

Description

The present invention relates to a method for preparing pyrazole oxime derivatives, wherein the pyrazole oxime derivatives are represented by the general formula (I).

（Ⅰ）

(I)

Wherein R ¹ represents C _1-4 alkyl or phenyl; R ² represents H, C _1-5 alkyl, C _1-3 haloalkyl or phenyl; R ³ represents hydrogen, C _1-4 alkyl or Phenyl; R ⁴ represents hydrogen, C _2-4 alkylcarbonyl, benzoyl, naphthyl or formula

The substituent represented [wherein, X represents hydrogen; halogen; C _1-12 alkyl; C _1-6 is substituted by halogen, cyano, hydroxyl, C _1-5 alkoxy or C _2-6 alkoxycarbonyl Alkyl; C _3-8 cycloalkyl; cycloalkyl substituted by the following 1 to 3 groups; C _1-4 alkyl, halogen or cyano; halogen, hydroxyl, C _2-4 C _2-4 alkenyl substituted by alkoxycarbonyl or C _2-6 alkylcarbonyl; phenyl; hydroxyl; C _1-6 alkoxy; C ₂ substituted by halogen or C _2-6 alkoxycarbonyl _-4 alkoxy; phenoxy (which may or may not be substituted by C _1-3 haloalkyl); benzyloxy; C _1-3 alkylenedioxo consisting of two adjacent Xs; Pyridyloxy (which is unsubstituted or substituted by halogen or C _1-3 haloalkyl); substituents of formula -S(O)pR ⁵ (wherein R ⁵ represents C _1-6 alkyl, C _1-5 haloalkyl or phenyl, p represents an integer of 0, 1 or 2); cyano; formyl; nitro; formula -COOR ⁶ substituent [wherein R ⁶ represents hydrogen; alkali metal; C _1-10 alkyl; by halogen, C _1-4 alkoxy, phenoxy, C _2-4 alkoxycarbonyl or phenoxyphenyl substituted C _1-5 alkyl; C _2-7 alkenyl; C _3-7 alkynyl; C _3-8 cycloalkyl; C _3-8 cycloalkyl substituted by C _1-3 alkyl; phenyl; or formula

Substituents (where R ⁷ , R ⁸ and R ⁹ can be the same or different, representing C _1-4 alkyl or C _3-8 cycloalkyl)]; C _2-6 alkylcarbonyl; by cyano or C C _2-6 alkylcarbonyl substituted by _1-6 alkoxycarbonyl; benzoyl (which is not or may be substituted by halogen or C _1-6 alkyl); C _2-6 alkylthiocarbonyl; C _3-7 Alkoxycarbonylcarbonyl; formula

Substituents (where R ¹⁰ and R ¹¹ can be the same or different, represent hydrogen, C _1-6 alkyl or phenyl); piperidinocarbonyl; morpholinocarbonyl (which is not or can be replaced by one or two C _1-4 alkyl substituted); formula

Substituents (where R ¹² represents hydrogen or C _1-5 alkyl, R ¹³ represents formyl, C _2-12 alkoxycarbonyl, or C _2-5 substituted by halogen or C _1-4 alkoxy alkoxycarbonyl); formula

Substituents (where R ¹⁴ represents hydrogen, C _1-4 , C _2-6 alkoxyalkyl); formula

(where R ¹⁵ and R ¹⁶ can be the same or different, represent C _1-4 alkyl or can jointly form C _1-4 alkylene, R ¹⁷ represents C _1-5 alkyl, cyano or C _{2 -6} alkoxycarbonyl, B represents oxygen or sulfur); formula

(where R ¹⁸ represents hydrogen or C _2-4 alkylcarbonyl, R ¹⁹ and R ²⁰ can be the same or different, representing hydrogen or C _1-6 alkyl); formula

(where R ²¹ , R ²² and R ²³ can be the same or different, and represent C _1-4 alkyl); or the formula

(where R ²⁴ , R ²⁵ and R ²⁶ can be the same or different, representing C _1-4 alkyl); n represents an integer of 1-5, when n represents an integer of 2-5, X can be the same or Can be different]; Y represents hydrogen, C _1-6 alkyl, C _1-4 haloalkyl, halogen, hydroxyl, C _1-4 alkoxy, C _1-4 haloalkoxy, C _1-3 alkylene dioxy Substituent, phenoxy (unsubstituted or may be substituted by trifluoromethyl), substituent of formula -S(O)qR ²⁷ (wherein R ²⁷ represents C _1-3 alkyl, q represents 0, 1 or 2 Integer), hydroxycarbonyl, C _2-5 alkoxycarbonyl or formula

Substituents (where R ²⁸ and R ²⁹ can be the same or different, represent hydrogen, C _1-4 alkyl or benzyl (unsubstituted or can be substituted by C _2-6 alkoxycarbonyl); Z ¹ represents oxygen or sulfur ; Z ² represents oxygen, sulfur or a single bond; Q represents C _1-8 alkylene, C _1-8 alkylene substituted by halogen or phenyl, C _3-12 alkenylene, C _3-12 halogen Alkenylene or C _3-6 alkynylene; when m represents an integer of 2 or 3, Y may be the same or different.

The terms "alkyl, alkylene, alkenylene and alkynylene" as used in this application refer to straight or branched chain alkyl, alkylene, alkenylene and alkynylene, respectively. The term "halo" refers to halogen such as fluorine, bromine, chlorine, etc., and the term "haloalkyl" refers to an alkyl group substituted by one or more same or different halogen atoms.

The compounds represented by the foregoing general formula (I) are novel compounds not described in literature. They have excellent insecticidal effects on insects belonging to the order Lepidoptera such as diamondback moth, cabbage armyworm, Spodoptera litura, Chilo borer, etc., and insects belonging to the order Hemiptera such as brown planthopper, green peach aphid, etc. In addition, they also have excellent fungicidal effects on diseases and insect pests of vegetables, fruit trees, flowers and ornamental plants, such as rice blast, powdery mildew, downy mildew, crown rust, leaf blight, shell blight, purple rust, etc.

Among the compounds of the present invention, the compounds which are especially useful as insecticides and acaricides are listed below:

4-[(1,3-Dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]benzoic acid tert-butyl ester

tert-butyl 4-[{5-(4-fluorophenoxy)-1,3-dimethyl-pyrazol-4-yl}methyleneaminooxymethyl]benzoate

tert-Amyl 4-[(1,3-Dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]benzoate

4-[1,3-Dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]cyclohexyl benzoate

1-methylcyclohexyl 4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]benzoate

4-[(1,3-Dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]benzoic acid-2-chloromethyl-2-propyl ester

tert-Amyl 4-[(1-methyl-5-phenoxy-3-trifluoromethylpyrazol-4-yl)methyleneaminooxymethyl]benzoate

1,3-Dimethyl-5-phenoxypyrazolyl-4-carbonylaldoxime o-4-tert-butylbenzyl ether

1,3-Dimethyl-5-phenoxypyrazolyl-4-carbonylaldoxime o-4-(1-cyanocyclopentyl)benzyl ether

1,3-Dimethyl-5-phenoxypyrazolyl-4-carbonylaldoxime o-4-(2,2-dichloro-1-methylcyclopropyl)benzyl ether

1,3-Dimethyl-5-phenoxypyrazolyl-4-carbonylaldoxime o-4-trimethylsilylbenzyl ether

1,3-Dimethyl-5-phenoxypyrazolyl-4-carbonylaldoxime o-4-(1,1,2,2-tetrafluoroethoxy)benzyl ether

1,3-Dimethyl-5-phenoxypyrazolyl-4-carbonylaldoxime o-4-tert-butoxybenzyl ether

1,3-Dimethyl-5-phenoxypyrazolyl-4-carbonylaldoxime o-4-(heptafluoropropylthio)benzyl ether

1,3-Dimethyl-5-phenoxypyrazolyl-4-carbonylaldoxime o-4-(heptafluoropropylsulfinyl)benzyl ether

1,3-Dimethyl-5-phenoxypyrazolyl-4-carbonylaldoxime o-4-(1,1,2,2-tetrafluoroethylthio)benzyl ether

N,N-Diisopropyl 4-[(1,3-Dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]benzamide

tert-Butyl 4-[(1,3-Dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]phenyl ketone

2-isopropyl-2-[4-{(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl}phenyl]-1,3-di Oxolane

2-isopropyl-2-[4-{(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl}phenyl]-1,3-di Thiolane

N-4-[(1,3-Dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]-phenyl-N-ethylcarbamate tert-butyl ester

1,3-Dimethyl-5-phenoxypyrazolyl-4-carbonylaldoxime o-2-(4-tert-butylphenoxy)ether

Compounds specifically used as fungicides are also listed below:

4-[(1,3-Dimethyl-5-phenoxypyrazol-4-yl)-methyleneaminooxymethyl]benzoic acid isopropyl ester

Isopropyl 4-[{5-(4-fluorophenoxy)-1,3-dimethylpyrazol-4-yl}-methyleneaminooxymethyl]benzoate

1,3-Dimethyl-5-phenoxypyrazol-4-ylcarbonylaldoxime o-4-(methylthio)benzyl ether

1,3-Dimethyl-5-phenoxypyrazol-4-ylcarbonylaldoxime o-4-(difluoromethylsulfinyl)benzyl ether

4-[(1,3-Dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]benzoyl N,N-dimethylbenzylamine

Methyl N-4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]phenyl-N-ethylcarbamate

5-Ethyl-3-[N'-4-{(1,3-Dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl}phenyl]-2-oxa oxazolidinone

The compounds represented by the general formula (I) can be synthesized, for example, by methods A, B, C and D represented by the following chemical formulas.

Method A:

Wherein R ¹ , R ² , R ³ , R ⁴ , Q, Y, Z ¹ , Z ² , m and n are the same as defined above, Hal represents a halogen atom, and M ¹ represents a hydrogen atom or an alkali metal atom.

The pyrazole oxime derivative represented by the general formula (I) can be obtained by reacting a compound of the general formula (II) with a compound of the general formula (III) in an inert solvent with or without a base.

Solvents that can be used in the present invention can be any solvents that do not interfere with the reaction, and they include alcohols (such as isopropanol, tert-butanol, diethylene glycol), ketones (such as acetone, methyl ethyl ketone, cyclohexane Ketones), ethers (such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, glyme, diglyme), halogenated hydrocarbons (such as dichloroethane, chloroform, tetrahydrofuran, carbon chloride, tetrachloroethane), aromatic hydrocarbons (such as benzene, chlorobenzene, nitrobenzene, toluene), nitriles (such as acetonitrile), dimethylsulfoxide, dimethylformamide and water. These solvents may be used alone or in combination. When these solvents are used in combination to perform a two-phase reaction, a phase transfer catalyst such as triethylbenzylammonium chloride, trioctylmethylammonium chloride, or the like can be used.

As the base, inorganic bases and organic bases can be used. Inorganic bases include, for example, carbonates of alkali or alkaline earth metals such as sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate, etc., hydroxides of alkali or alkaline earth metals such as sodium hydroxide, potassium hydroxide, calcium hydroxide, etc. and Alkali metal hydrides such as lithium hydride, sodium hydride, etc.

Organic bases include, for example, diethylamine, triethylamine, pyridine, 4-dimethylaminopyridine, and the like.

As for the amount of the base to be used, it is sufficient to use an amount equimolar to that of the compound represented by the general formula (II), however, an excessive amount may be used.

For example, the compound used in the present invention represented by the general formula (II) can be produced by the method described below:

wherein R ¹ , R ² , R ³ , Y, Z ¹ , m, Hal and M ¹ are the same as defined above.

That is, the compound of general formula (II) can be prepared by reacting the compound of general formula (IV) with the compound of general formula (V) in a suitable solvent, and then reacting the obtained compound of general formula (VI) with hydroxylamine become.

Among all the compounds represented by the general formula (III), especially when Q is methylene, ^Z2 is a single bond and ^R4 is a substituted phenyl group, they are also some novel compounds, which can be used with known Compounds were prepared in the same manner.

Method B:

wherein R ¹ , R ² , R ³ , R ⁴ , Q, Y, Z ¹ , Z ² , m and n are as defined above.

The pyrazole oxime derivative represented by the general formula (I) can be prepared by reacting a compound of the general formula (VI) with a compound of the general formula (VII) in an inert solvent.

Solvents that can be used in this reaction are solvents other than ketones used in method A.

The compound represented by the general formula (VII) can be obtained according to a known method, for example, described in Hougen Weyl "Methods of Organic Chemistry" (Methoden der Organishen Chemie), Volume X/I Nitrogen Compounds Part I, page 1192 method to prepare.

Method C:

wherein R ¹ , R ² , R ³ , R ⁴ , Q, Y, Z ¹ , Z ² , m and n are as defined above, and M ² represents a hydrogen atom or an alkali metal atom.

The pyrazole oxime derivatives of the general formula (I) can be prepared by reacting the compound of the general formula (VIII) with the compound of the general formula (IX) in an inert solvent with or without the presence of a base.

The solvents and bases used in this reaction were as described in Method A.

Method D:

的取代基（其中R⁷、R⁸、R⁹代表C₁至C₄烷基或C₃至C₈环烷基，三者可以相同，也可不同）｝，式 的取代基（其中R¹⁰和R¹¹代表氢、C₁至C₆烷基或苯基，二者可以相同，也可不同）;哌啶子基;可以被或不被一或二个C₁至C₄的烷基取代的吗啉基;或C₂至C₆的烷基硫。Wherein R ¹ , R ² , R ³ , Q, Y, Z ¹ , Z ² and m are the same as defined above; X ¹ represents hydrogen or C ₁ to C ₄ alkyl; R represents the formula -OW{Wherein W represents a base Metal; C ₁ to C ₁₀ alkyl; C ₁ to C ₄ alkoxy, phenoxy, C ₂ to C ₄ alkoxycarbonyl or phenyl substituted alkyl; C ₂ to C ₇ Alkenyl; C ₃ to C ₈ cycloalkyl; C ₁ -C ₃ alkyl substituted C ₃ to C ₈ cycloalkyl; phenyl or formula

(where R ⁷ , R ⁸ , R ⁹ represent C ₁ to C ₄ alkyl or C ₃ to C ₈ cycloalkyl, the three may be the same or different)}, the formula (where R ¹⁰ and R ¹¹ represent hydrogen, C ₁ to C ₆ alkyl or phenyl, both of which may be the same or different); piperidino; may or may not be replaced by one or two C ₁ to _C4 alkyl substituted morpholinyl; or _C2 to _C6 alkylthio.

That is, the pyrazole oxime derivative represented by the general formula (Ia) can be prepared by reacting a compound of the general formula (X) with a compound of the general formula (XI) in an inert solvent containing a dehydrating agent. Compound (X) can be reacted with compound (XI) after converting it into an acid chloride.

The solvent that can be used for this reaction can be any solvent that does not hinder this reaction, for example includes ethers (such as diethyl ether, tetrahydrofuran, dioxane, diethylene glycol), halogenated hydrocarbons (such as dichloromethane, chloroform , carbon tetrachloride), dimethyl sulfoxide, dimethylformamide, etc. These solvents may be used alone or in combination.

In method A to method D, the reaction temperature thereof can be appropriately selected within the temperature range of room temperature to the boiling point of the solvent. The reaction time depends on the reaction temperature and the degree of reaction, but can be appropriately selected within the range of 1 minute to 48 hours.

Because the reaction is an equimolar reaction, the molar ratios of the reagents are used in equimolar amounts during the reaction of the present invention, but one of them can also be used in excess than the other.

After completion of the reaction, the desired compound can be isolated by a conventional method and, if necessary, purified by recrystallization, column chromatography and the like.

The pyrazole oxime derivatives represented by the general formula (I) have two isomers, E-isomer and Z-isomer. Both these isomers and mixtures thereof are included within the scope of the present invention.

Typical examples of pyrazole oximes represented by the general formula (I) are listed in Table 1, but the derivatives are not limited to these examples.

Note 1: ¹ H NMR value of compound No. 180 (CDCl, TMS):

1.62 (6H, s), 2.33 (3H, s), 3.53 (3H, s),

4.83 (2H, d, J = 48Hz), 4.95 (2H, s),

6.7-7.9 (9H, m), 7.75 (1H, s)

Note 2: ¹ H NMR value of compound No. 299 (CDCl, TMS):

1.37 (6H, s), 2.34 (3H, s), 3.55 (3H, s),

4.53 (2H, d, J = 47.5Hz), 4.95 (2H, s),

6.7-7.4 (9H, m), 7.76 (1H, s)

The preparation of the compounds of the present invention can refer to the following examples, but these examples do not limit the present invention.

Example 1

4-[(1,3-Dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]benzyl Acid methyl ester (compound No. 16)

Mix 2.0 g (0.00865 mol) of 1,3-dimethyl-5-phenoxypyrazole-4-carbonyl aldoxime with 1.98 g (0.00865 mol) of methyl 4-bromomethylbenzoate and 1.19 g (0.009 mol) of potassium carbonate was added to 50 ml of acetone, and the resulting mixture was heated under reflux for about 8 hours. After the reaction was complete, the acetone was removed by evaporation under reduced pressure, and then water was added to the residue and extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and the ethyl acetate was removed by evaporation to give an oily product. The oily product was purified by silica gel column chromatography, whereby 2.0 g of the desired product were obtained.

Yield 61%, n ²⁰ _D 1.5612

Example 2

tert-Butyl 4-[(1,3-Dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]benzoate (Compound No. 60)

Dissolve 2.0 g (0.00855 mol) of 1,3-dimethyl-5-phenoxypyrazole-4-carbonylaldoxime in 20 ml of DMSO, then add 0.65 g (0.0116 mol) of the powder potassium hydroxide, and the resulting mixture was stirred at 30°C for about 30 minutes. To this solution was added 2.32 g (0.00855 mol) of tert-butyl 4-bromomethylbenzoate, and reacted at 50°C to 60°C for 1 hour. After the reaction was complete, water was added to the reaction solution, followed by extraction with ethyl acetate. The ethyl acetate extract was washed with water and dried, and then the ethyl acetate was removed by evaporation, whereby crude crystals were obtained. The crystals were recrystallized from methanol to obtain 2.4 g of the desired compound.

Yield 67.0% Melting point 101.7°C

Example 3

Methyl 2-[{5-(4-chlorophenoxy)-1,3-dimethyl-pyrazol-4-yl}methyleneaminooxymethyl]benzoate (Compound No. 3)

2.0 g (0.00755 moles) of 5-(4-chlorophenoxy)-1,3-dimethyl-pyrazole-4- The carbonyl aldoxime was dissolved in 20 ml of dimethylformamide, then 0.5 g (0.0125 mol) of powdered sodium hydroxide was added, and the resulting mixture was stirred well. To this solution was added 1.73 g (0.00755 mol) of methyl 2-bromomethylbenzoate, and the reaction was carried out at 70°C to 80°C for 5 hours. After the reaction is complete, water is added to the reaction solution, and then the solution is extracted with ethyl acetate, the ethyl acetate extract is washed with water and dried, and then the ethyl acetate is removed by evaporation to obtain an oily product. The oily product was separated by silica gel column chromatography, whereby 2.0 g of the desired compound were obtained.

Yield 64.0% n ²⁰ _D 1.5788

Example 4

Isopropyl 4-[(1,3-Dimethyl-5-phenylthiopyrazol-4-yl)methyleneaminooxymethyl]benzoate (Compound No. 174)

3.0 grams (0.0121 moles) of 1,3-dimethyl-5-phenylthiopyrazole-4-carbonylaldoxime, 2.57 grams (0.0121 moles) of isopropyl 4-chloromethylbenzoate and 2.8 G (0.026 mol) of sodium carbonate was added to 50 ml of methyl ethyl ketone, and the resulting mixture was heated under reflux for 5 hours. After the reaction was complete, methyl ethyl ketone was removed by evaporation under reduced pressure, water was added to the residue, and ethyl acetate was used for extraction. The ethyl acetate extract was washed with water and dried, then the ethyl acetate was removed by evaporation to give an oily product. The oily product was separated by silica gel column chromatography, whereby 3.0 g of the desired compound were obtained.

Yield 59.0% n ²⁰ _D 1.5821

Example 5

tert-Butyl 4-[1-(1,3-dimethyl-5-phenoxypyrazol-4-yl)ethylideneaminooxymethyl]benzoate (Compound No. 166).

2.0 g (0.00816 mol) of methyl 1,3-dimethyl-5-phenoxy-pyrazol-4-ylketoxime, 2.2 g (0.00816 mol) of tert-butyl 4-bromomethylbenzoate and 4.0 g (0.028 mol) of potassium carbonate were added to 50 ml of acetonitrile, and the resulting mixture was heated under reflux for 5 hours. After the reaction is complete, acetonitrile is removed by evaporation under reduced pressure, then water is added to the residue and extracted with ethyl acetate, the ethyl acetate extract is washed with water and dried, and ethyl acetate is removed by evaporation, thus Crude crystals were obtained. The crystals were recrystallized from methanol, whereby 2.8 g of the desired compound were obtained.

Yield 79.0% Melting point 94.4°C

Example 6

Cyclohexyl 4-[{5-(4-fluorophenoxy)-1,3-dimethylpyrazol-4-yl}methyleneaminooxymethyl]benzoate (Compound No. 119)

Add 2.0 g (0.008 mol) of 5-(4-fluorophenoxy)-1,3-dimethylpyrazole-4-carbonylaldoxime and 0.5 g (0.0125 mol) of powdered sodium hydroxide in 50 mL of dimethyl sulfoxide, and the resulting mixture was stirred for 30 minutes. To this solution was added 2.38 g (0.008 mol) of cyclohexyl 4-bromomethylbenzoate, and the reaction was carried out at 70°C to 80°C for 6 hours. After the reaction was complete, water was added to the reaction solution, and the solution was extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and the ethyl acetate was removed by evaporation to give an oily product. The oily product was separated by silica gel column chromatography, whereby 3.0 g of the desired compound were obtained.

Yield 80.0% n ²⁰ _D 1.5863

Example 7

tert-butyl 4-[(1-methyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl)]benzoate (Compound No. 174)

Add 1.0 g (0.0049 mol) of 1-methyl-5-phenoxypyrazole-4-carbonylaldehyde and 1.1 g (0.0049 mol) of tert-butyl 4-aminooxymethylbenzoate to 20 mL of ethanol , and the resulting mixture was heated under reflux to react. After the reaction was complete, ethanol was removed by evaporation, and then water was added to the residue and extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and the ethyl acetate was removed by evaporation to obtain an oily product. The oily product was separated by silica gel column chromatography, whereby 1.6 g of the desired compound were obtained.

NMR ( _CDCl3 , TMS):

δ (ppm) 1.56 (s, 9H), 3.60 (s, 3H),

4.96 (s, 2H), 6.60-7.40 (m, 7H),

7.63(s, 1H), 7.66(s, 1H),

7.75-8.00 (m, 2H).

Example 8

2-phenoxyethyl 4-[{5-(4-fluorophenoxy)-1,3-dimethylpyrazol-4-yl}methyleneaminooxymethyl]benzoate (No. Compound No. 142)

Dissolve 2.0 g (0.008 mol) of 5-(4-fluorophenoxy)-1,3-dimethylpyrazole-4-carbonyl aldoxime in 20 ml of dimethyl sulfoxide, then add 0.65 g ( 0.0116 mol) of powdered potassium hydroxide, and the resulting mixture was stirred at 30°C for 30 minutes. 2.5 g (0.00865 mol) of 2-phenoxyethyl 4-chloromethylbenzoate was added to the solution, and the reaction was carried out at 50°C to 60°C for 1 hour. After the reaction was completed, water was added to the reaction solution, and then the reaction solution was extracted with ethyl alkyd. The ethyl acetate extract was washed with water and dried, and the ethyl acetate was removed by evaporation to obtain an oily product. The oily product was separated by silica gel column chromatography, whereby 3.0 g of the desired compound were obtained.

Yield 75.0% n ²⁰ _D 1.5655

Example 9

4-[(1,3-Dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxy]phenylbenzoate (Compound No. 161)

1.0 grams (0.0027 moles) of 4-[(1,3-dimethyl-5-phenoxypyrazol-4-ylmethyleneaminooxymethyl] benzoic acid, 0.25 grams (0.0027 moles) of phenol and 0.7 gram (0.0027 mole) of triphenylphosphine were added in 50 milliliters of ether, and the resulting mixture was stirred. 0.47 gram (0.0027 mole) of diethyl azodicarboxylate was added to the solution, and the resulting mixture was heated under reflux solution for 3 hours. After the reaction was complete, the ether layer was filtered off, and the ether was removed by evaporation to obtain an oily product. The oily product was separated by silica gel column chromatography to obtain 0.9 g of the desired compound.

Yield 76.0% n ²⁰ _D 1.5656

Example 10

4-[(1,3-Dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]benzoic acid (Compound No. 14)

Dissolve 3 g (0.0079 mol) of 4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]-benzoic acid methyl ester in 20 ml methanol and 0.24 g of lithium hydroxide was added to the solution along with 5 ml of water. Then react at room temperature for 2 hours. After the reaction was complete, methanol was removed by evaporation, and after adding water, the solution was acidified with hydrochloric acid to produce precipitated crystals. The crystals were collected by filtration, whereby 2 g of the desired compound were obtained.

Yield 70% Melting point 183.3°C

Example 11

Sodium 4-[(1,3-Dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]benzoate (Compound No. 15)

1.0 grams (0.0027 moles) of 4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl) methyleneaminooxymethyl] benzoic acid and 0.7 grams (0.0028 moles) of Sodium hydroxide was added to 10 ml of water, and the resulting mixture was stirred for 2 hours. After completion of the reaction, water was removed by evaporation under reduced pressure, thereby obtaining the desired compound in quantitative yield.

Melting point>300℃

Example 12

1,3-Dimethyl-5-phenoxypyrazole-4-carbonylaldoxime O-benzyl ether (Compound No. 181)

2.0 g (0.00866 mol) of 1,3-dimethyl-5-phenoxypyrazole-4-carbonylaldoxime, 1.5 g (0.0087 mol) of benzyl bromide and 2.0 g (0.0145 mol) of potassium carbonate Dissolve in 50 ml of acetone and heat the resulting solution under reflux for 7 hours. After the reaction was complete, the acetone was removed by evaporation under reduced pressure, then water was added and extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, then the ethyl acetate was removed by evaporation to give an oily product. The oily product was separated by silica gel column chromatography, whereby 2.6 g of the desired compound were obtained.

Yield 93.0% n ²⁰ _D 1.5517

Example 13

5-(4-Chlorophenoxy)-1,3-dimethylpyrazole-4-carbonylaldoxime O-4-trifluoromethylbenzyl ether (Compound No. 195)

Dissolve 2.0 g (0.0075 mol) of 5-(chlorophenoxy)-1,3-dimethylpyrazole-4-carbonyl aldoxime in 40 ml THF, then add 0.19 g (0.0079 mol) at room temperature of sodium hydride, and the resulting solution was stirred. Then 1.7 g (0.0071 mol) of 4-trifluoromethylbenzyl bromide was added, followed by heating under reflux for 3 hours. After the reaction was complete, 100 ml of water was added to the reaction solution, followed by extraction with ethyl acetate. The ethyl acetate extract was washed with water and dried, and the ethyl acetate was removed by evaporation to give an oily product. The oily product was separated by silica gel column chromatography, whereby 2.7 g of the desired compound were obtained.

Yield 85.0% n ²⁰ _D 1.5539

Example 14

1,3-Dimethyl-5-phenoxypyrazole-4-carbonylaldoxime O-4-(1-cyanocyclopropyl)benzyl ether (Compound No. 199)

Dissolve 2.0 g (0.0086 mol) of 1,3-dimethyl-5-phenoxypyrazole-4-carbonylaldoxime in 30 ml of dimethylformamide, and 0.5 g (0.0125 mol) of Sodium hydroxide (dissolved in 5 ml of water) was added thereto. After continuous stirring for 30 minutes, 2.0 g (0.0086 mol) of 1-(4-bromomethylphenyl)cyclopropane-1-carbonitrile was added to the solution and reacted at 60°C to 70°C for 3 hours. After the reaction was complete, 100 ml of water was added to the reaction solution, followed by extraction with ethyl acetate. The ethyl acetate extract was washed with water and dried, and the ethyl acetate was removed by evaporation to give an oily product. The oily product was separated by silica gel column chromatography, whereby 2.8 g of the desired compound were obtained.

Yield 84.0% Melting point 109.1℃

Example 15

1,3-Dimethyl-5-phenoxypyrazole-4-carbonylaldoxime 4-tert-butylbenzyl ether (Compound No. 205)

Dissolve 2.0 g (0.0086 mol) of 1,3-dimethyl-5-phenoxypyrazole-4-carbonyl aldoxime in 20 ml of dimethyl sulfoxide, add 1.0 g (0.0178 mol) of After potassium addition, the resulting solution was stirred at room temperature for 30 minutes. 1.5 g (0.0086 mol) of 4-tert-butylbenzyl chloride was added to the solution and reacted at 50°C to 60°C for 3 hours. After the reaction was complete, 100 ml of water was added to the reaction solution followed by extraction with ethyl acetate. The ethyl acetate extract was washed with water and dried, then the ethyl acetate was removed by evaporation to give an oily product. The oily product was separated by silica gel column chromatography, whereby 2.4 g of the desired compound were obtained.

Yield 74.0% n ²⁰ _D 1.5402

Example 16

5-(4-Chlorophenoxy)-1-methylpyrazole-4-carbonylaldoxime O-benzyl ether (Compound No. 279)

2.0 g (0.0092 mol) of 5-(4-chlorophenoxy)-1-methylpyrazole-4-carbonylaldoxime, 1.5 g (0.0092 mol) of benzyl bromide and 2.0 g (0.0145 mol) of Potassium carbonate was dissolved in 50 ml of acetonitrile, and the resulting solution was heated under reflux for 9 hours. After the reaction was complete, 100 ml of water was added to the reaction solution, followed by extraction with ethyl acetate. wash it with water The ethyl acetate extract was dried and the ethyl acetate was removed by evaporation to give an oily product. The oily product was separated by silica gel column chromatography, whereby 2.2 g of the desired compound were obtained.

Yield 78.0% n ²⁰ _D 1.5933

Example 17

1,3-Dimethyl-5-phenoxypyrazol-4-ylmethylketoxime O-4-cyclohexylbenzyl ether (Compound No. 283)

2.0 g (0.0040 mol) of 1,3-dimethyl-5-phenoxypyrazol-4-yl-methylketoxime was dissolved in 30 ml of dioxane, and 0.1 g (0.0042 mol) of sodium borohydride and stirred thoroughly. After 30 minutes, 1.6 g (0.0038 mol) of 4-cyclohexylbenzyl bromide was added to the reaction solution, which was heated under reflux for 5 hours. After the reaction was complete, 100 ml of water was added to the reaction solution and extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and the ethyl acetate was removed by evaporation to give an oily product. The oily product was separated by silica gel column chromatography, whereby 1.2 g of the desired compound were obtained.

Yield 72.0% n ²⁰ _D 1.5775

Example 18

5-(4-Chlorophenylthio)-1,3-dimethylpyrazole-4-carbonylaldoxime O-benzyl ether (Compound No. 290)

Dissolve 2.0 g (0.0071 mol) of 5-(4-chlorophenylthio-1,3-dimethylpyrazole-4-carbonyl aldoxime in 20 ml of dimethyl sulfoxide, and add 0.5 grams (0.009 moles) of potassium hydroxide in 5 milliliters of aqueous solution. After stirring well, add 0.9 grams (0.0071 moles) of benzyl chloride, and react at 60°C to 70°C for 2 hours. After the reaction is complete, add to the reaction solution 100 milliliters of water were added and extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and the ethyl acetate was removed by evaporation to obtain an oily product. The oily product was separated by silica gel column chromatography to obtain 2.3 grams of the desired compound.

Yield 87.0% n ²⁰ _D 1.5562

Example 19

5-(4-Methoxyphenoxy)-1,3-dimethylpyrazole-4-carbonylaldoxime O-4-(1-cyanocyclopentyl)-benzyl ether (No. 238 compound)

Dissolve 2.0 g (0.0081 mol) of 1,3-dimethyl-5-(4-methoxyphenoxy)pyrazole-4-carbonylaldehyde in 50 ml of ethanol and add 1.7 g (0.0081 mol) o-4(1-cyanocyclopentyl)benzyl hydroxylamine, and then reacted at 50°C to 60°C for 3 hours. After the reaction was complete, the ethanol was removed by evaporation under reduced pressure, then water was added and extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and the ethyl acetate was removed by evaporation to give an oily product. The oily product was separated by silica gel column chromatography, whereby 3.0 g of the desired compound were obtained.

Yield 83.0% n ²⁰ _D 1.5632

Example 20

1,3-Dimethyl-5-phenoxypyrazole-4-carbonylaldoxime O-4-(2,2-dibromovinyl)benzyl ether (Compound No. 262)

Dissolve 2.0 g (0.0093 mol) of 1,3-dimethyl-5-phenoxypyrazole-4-carbonylaldehyde in 50 ml of methanol, and add 2.8 g (0.0091 mol) of O-4 to the solution -(2,2-Dibromovinyl)benzylhydroxylamine and heated at reflux for 3 hours. After the reaction was complete, methanol was removed by evaporation under reduced pressure, then water was added and extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and the ethyl acetate was removed by evaporation to give an oily product. The oily product was separated by silica gel column chromatography, whereby 3.5 g of the desired compound were obtained.

Yield 76.0% Melting point 109.3°C

Example 21

1,3-Dimethyl-5-phenoxypyrazole-4-carbonylaldoxime O-4-fluorobenzyl ether (Compound No. 305)

Dissolve 1.0 g (0.0043 mol) of 1,3-dimethyl-5-phenoxypyrazole-4-carbonylaldoxime in 20 ml of DMSO and add 0.3 g (0.0053 mol) of the powder After adding potassium hydroxide, the resulting solution was stirred. To the reaction solution was added 0.81 g (0.0043 mol) of 4-fluorobenzyl bromide, and the reaction was carried out at room temperature for 3 hours. After the reaction was complete, 200 ml of water was added to the reaction solution, and extraction was performed with ethyl acetate. The ethyl acetate extract was washed with water and dried, and the ethyl acetate was removed by evaporation to give an oily product. Separation by silica gel column chromatography As an oily product, 1.3 g of the desired product are thus obtained.

Yield 89% n ²⁰ _D 1.5681

Example 22

5-(4-Chlorophenoxy)-1,3-dimethylpyrazole-4-carbonylaldoxime O-2-chlorobenzyl ether (Compound No. 309)

1.0 grams (0.0038 moles) of 5-(4-chlorophenoxy)-1,3-dimethylpyrazole-4-carbonylaldoxime, 0.78 grams (0.0038 moles) of 2-chlorobenzyl bromide and 1.0 G (0.0072 mol) of potassium carbonate was added to 20 ml of acetonitrile, and the resulting mixture was heated at reflux for 6 hours. After the reaction was complete, acetonitrile was removed by evaporation under reduced pressure, then water was added and extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and the ethyl acetate was removed by evaporation to give an oily product. The oily product was separated by silica gel column chromatography, whereby 1.2 g of the desired compound were obtained.

Yield 81% n ²⁰ _D 1.5760

Example 23

5-(4-Chlorophenoxy)-1,3-dimethylpyrazole-4-carbonylaldoxime O-4-(4-trifluoromethyl-phenoxy)benzyl ether (No. 322 compound)

1.0 grams (0.0038 moles) of 5-(4-chlorophenoxy)-1,3-dimethylpyrazole-4-carbonyl aldoxime, 1.1 grams (0.0038 moles) of 4-(4-trifluoroform phenoxy)benzyl chloride and 0.8 g (0.076 mol) of sodium carbonate were added to 40 ml of acetone, and the resulting mixture was heated under reflux for 8 hours. After the reaction was complete, the acetone was removed by evaporation under reduced pressure, then water was added and extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and the ethyl acetate was removed by evaporation to give an oily product. The oily product was separated by silica gel column chromatography, whereby 1.4 g of the desired compound were obtained.

Yield 72% Melting point 97.8°C

Example 24

1,3-Dimethyl-5-phenoxypyrazol-4-ylmethylketoxime O-4-trimethylsilylbenzyl ether (Compound No. 334)

Dissolve 1.0 g (0.0041 mol) of 1,3-dimethyl-5-phenoxypyrazol-4-yl-methylketoxime in 20 ml of DMSO, and add 0.3 g (0.0053 mol) of potassium hydroxide, the resulting solution was stirred. To the resulting solution was added 1.0 g (0.0041 mol) of 4-trimethylsilylbenzyl bromide and reacted at room temperature for 4 hours. After the reaction was complete, 200 ml of water was added to the reaction solution and extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and the ethyl acetate was removed by evaporation to give an oily product. The oily product was separated by silica gel column chromatography, whereby 1.5 g of the desired compound were obtained.

Yield 92% Melting point 61.2°C

Example 25

1,3-Dimethyl-5-phenoxypyrazol-4-ylethylketoxime O-4-(1,1,2,2-tetrafluoroethoxy)benzyl ether (No. 354 compound)

1.0 g (0.0035 moles) of 1,3-dimethyl-5-phenoxypyrazol-4-yl-ethylketoxime sodium salt and 1.0 g (0.0035 moles) of 4-(1,1, 2,2-Tetrafluoroethoxy)benzyl bromide was added to 50 ml of acetone, and the resulting mixture was heated for 5 hours to effect a reaction. After the reaction was complete, the acetone was removed by evaporation under reduced pressure, then water was added and extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and the ethyl acetate was removed by evaporation to give an oily product. The oily product was separated by silica gel column chromatography, whereby 1.3 g of the desired compound were obtained.

Yield 76% n ²⁰ _D 1.5252

Example 26

5-(4-Methoxyphenoxy)-1,3-dimethylpyrazole-4-carbonylaldoxime O-4-tert-butoxybenzyl ether (Compound No. 366)

Dissolve 1.0 g (0.0038 mol) of 5-(4-methoxyphenoxy)-1,3-dimethyl-pyrazole-4-carbonyl aldoxime in 30 ml THF and add 0.092 g sodium hydride In order to carry out the synthesis reaction of the sodium salt of the above-mentioned oxime. To this solution was added 0.92 g (0.0038 mol) of 4-tert-butoxybenzyl bromide and reacted at 50°C to 60°C for 5 hours. After the reaction was complete, 200 ml of water was added to the reaction solution, followed by extraction with ethyl acetate. The ethyl acetate extract was washed with water and dried, and the ethyl acetate was removed by evaporation to give an oily product. The oily product was separated by silica gel column chromatography, whereby 1.3 g of the desired product were obtained

Yield 80% n ²⁰ _D 1.5653

Example 27

5-(4-Fluorophenoxy)-1,3-dimethylpyrazole-4-carbonylaldoxime O-3,4-methylenedioxybenzyl ether (Compound No. 374)

Dissolve 1.0 g (0.0040 mol) of 5-(4-fluorophenoxy)-1,3-dimethylpyrazole-4-carbonylaldoxime in 20 ml of dimethylformamide, and add 0.2 g (0.005 mol) of sodium hydroxide, the resulting solution was stirred for 30 minutes. To the reaction solution was added 0.86 g (0.005 mol) 3,4-methylenedioxybenzyl bromide, and the reaction was carried out at 40°C to 50°C for 3 hours. After the reaction was complete, 200 ml of water was added to the reaction solution, followed by extraction with ethyl acetate. The ethyl acetate extract was washed with water and dried, and the ethyl acetate was removed by evaporation to give an oily product. The oily product was separated by silica gel column chromatography, whereby 1.1 g of the desired compound was obtained.

Yield 72% n ²⁰ _D 1.5750

Example 28

5-(4-Methoxyphenoxy)-1,3-dimethylpyrazole-4-carbonylaldoxime O-4-methylsulfonylbenzyl ether (Compound No. 401)

1.0 g (0.0038 mol) of 5-(4-methoxyphenoxy)-1,3-dimethylpyrazole-4-carbonyl aldoxime and 0.79 g (0.0038 mol) of 4-methylsulfonyl Benzyl chloride was dissolved in 30 ml THF. To this solution was added 0.6 g (0.0039 mol) of 1,8-diazabicyclo[5.4.0]-7-undecene, and the reaction was carried out at 40°C to 50°C for 5 hours. After the reaction was complete, 200 ml of water was added to the reaction solution and extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and the ethyl acetate was removed by evaporation to give an oily product. The oily product was separated by silica gel column chromatography, whereby 1.2 g of the desired product were obtained.

Yield 74% n ²⁰ _D 1.5866

Example 29

1,3-Dimethyl-5-phenoxypyrazol-4-ylphenylketoxime O-4-difluoromethylthiobenzyl ether (Compound No. 426)

1.0 g (0.0033 mol) of 1,3-dimethyl-5-phenoxypyrazol-4-yl-phenylketoxime, 0.82 g (0.0033 mol) of 4-difluoromethylthiobenzyl bromide and 1.0 g (0.0072 mol) of potassium carbonate were added to 50 ml of acetone, and the resulting mixture The mixture was heated for 6 hours to react. After the reaction was complete, the acetone was removed by evaporation under reduced pressure, then water was added and extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and the ethyl acetate was removed by evaporation to give an oily product. The oily product was separated by silica gel column chromatography, whereby 1.4 g of the desired compound were obtained.

Yield 86% n ²⁰ _D 1.5917

Example 30

5-(2-fluorophenoxy)-1,3-dimethylpyrazole-4-carbonylaldoxime O-4-(1,1,2,2-tetrafluoroethylthio)benzyl ether (compound No. 467)

1.1 g (0.0043 moles) of 5-(2-fluorophenoxy)-1,3-dimethylpyrazole-4-carbonylaldehyde was dissolved in 30 ml of ethanol, and 1.1 g (0.0043 moles) of O-[4- (1,1,2,2-Tetrafluoroethylthio)benzyl]hydroxylamine. The reaction was carried out at 50-60° C. for 2 hours. After the reaction was completed, the ethanol was evaporated under reduced pressure, then water was added, and extracted with chloroform. The chloroform extract was dried, and the chloroform was distilled off under reduced pressure to obtain an oily product. The oily product was subjected to silica gel column chromatography to obtain 1.3 g of the desired compound.

Yield 64% n ²⁰ _D 1.5462

Example 31

1,3-Dimethyl-5-phenoxypyrazol-4-ylmethylketoxime O-4-heptafluoropropylthiobenzyl ether (Compound No. 494)

To 30 mL of methanol, and the resulting mixture was heated for 5 hours. After the reaction was complete, the methanol was distilled off under reduced pressure, and water was added, followed by extraction with chloroform. The chloroform extract was dried, and then the chloroform was distilled off under reduced pressure to obtain an oily product. The oily product was subjected to silica gel column chromatography to obtain 1.4 g of the desired compound.

Yield 60% n ²⁰ _D 1.5217

Example 32

S-ethyl 4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]thiobenzoate

1.0 g (0.0043 mol) of 1,3-dimethyl-5-phenoxypyrazole-4-carbonyl aldoxime was dissolved in 20 ml of DMSO, then 0.3 g (0.0053 mol) of potassium hydroxide powder was added , and stir the mixed solution. Add 0.92 grams (0.0043 moles) of 4-chloromethylthiobenzoic acid S-ethyl ester to this solution, and react at room temperature for 3 hours. After the reaction is complete, add 200 milliliters of water to the reaction and extract with ethyl acetate. The ethyl acetate extract was washed with water, then dried, and the ethyl acetate was distilled off to obtain an oily product. The oily product was purified by silica gel column chromatography to obtain 1.4 g of the desired product.

Yield 80% n ²⁰ _D 1.5889

Example 33

N-tert-butyl 4-[{5-(4-methoxyphenoxy)-1,3-dimethylpyrazol-4-yl}methyleneaminooxymethyl]-benzamide (compound No. 525)

1.0 g (0.0038 mol) 5-(4-methoxyphenoxy)-1,3-dimethylpyrazole-4-carbonyl aldoxime, 0.86 g (0.0038 mol) N-tert-butyl-4-chloro Toluamide and 1.0 g (0.0072 mol) of potassium carbonate were added to 20 ml of acetonitrile, and the resulting mixture was heated at reflux for 6 hours. After the reaction was complete, acetonitrile was distilled off under reduced pressure. Water was then added to the residue, followed by extraction with ethyl acetate. The ethyl acetate extract was washed with water, then dried, and the ethyl acetate was distilled off to obtain an oily product. The oily product was subjected to silica gel column chromatography to obtain 1.4 g of the desired compound.

Yield 82% n ²⁰ _D 1.5662

Example 34

5-(4-fluorophenoxy)-1,3-dimethylpyrazole-4-carbonylaldoxime O-4-trimethylacetylbenzyl ether (Compound No. 548)

1.0 g (0.0040 mole) 5-(4-fluorophenoxy)-1,3-dimethylpyrazole-4-carbonyl aldoxime, 1.0 g (0.0039 mole) tert-butyl 4-bromomethylphenyl The ketone and 1.0 g (0.0094 mol) of sodium carbonate were added to 40 ml of acetone, and the mixture was heated for reaction. After the reaction was complete, the acetone was distilled off under reduced pressure. After adding water, the residue was extracted with ethyl acetate, and the ethyl acetate extract was washed with water, then dried, and the ethyl acetate was distilled off to obtain an oily substance. The oil was subjected to silica gel column chromatography to obtain 1.5 g of the desired compound.

Yield 89% n ²⁰ _D 1.5567

Example 35

2-Methyl-2-[4-{1,3-dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl}phenyl]-1,3-dioxolane Ring (Compound No. 562)

1.0 g (0.0043 mole) of 1,3-dimethyl-5-phenoxypyrazole-4-carbonylaldoxime was dissolved in 20 ml of dioxane, and 0.14 g (0.0058 mole) of sodium hydride was added. Next, 1.1 g (0.0043 mol) of 2-(4-bromomethylphenyl)-2-methyl-1,3-dioxolane was added to the solution, followed by heating under reflux for 3 hours. After the reaction was complete, the reaction solution was poured into 200 ml of cold water and then extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and the ethyl acetate was distilled off to obtain an oily product. The oily product was subjected to silica gel column chromatography to obtain 1.3 g of the desired product.

Yield 74% n ²⁰ _D 1.5698

Example 36

2-[4-[{5-(4-fluorophenoxy)-1,3-dimethylpyrazol-4-yl}methyleneaminooxymethyl]phenyl]-2-methyl-1 , 3-dioxolane (Compound No. 563)

1.1 g (0.0043 mole) 5-(4-fluorophenoxy)-1,3-dimethylpyrazole-4-carbonylaldehyde and 0.9 g (0.0043 mole) 2-[4-aminooxymethyl)phenyl ]-2-Methyl-1,3-dioxolane was added to 20 ml of ethanol. The obtained mixture was heated and reacted for 3 hours. After the reaction was complete, the ethanol was distilled off under reduced pressure. After adding water to the residue, it was extracted with ethyl acetate. The ethyl acetate extract was washed with water, then dried, and the ethyl acetate was distilled off to obtain an oily product. The oily product was subjected to silica gel column chromatography to obtain 1.3 g of the desired compound.

Yield 72% n ²⁰ _D 1.5555

Example 37

1,3-Dimethyl-5-phenoxypyrazole-4-carbonylaldoxime O-4-(1-hydroxyethyl)benzyl ether (Compound No. 584)

1.0 g (0.0028 mol) 1,3-dimethyl-5-phenoxypyrazole-4-carbonylaldoxime-O-4-acetylbenzyl ether, 1.0 g (0.0026 mol) sodium borohydride and 1 g ( 0.025 mol) of sodium hydroxide was added to 100 ml of methanol, and the mixture was heated under reflux for 3 hours. After the reaction was complete, the methanol was distilled off under reduced pressure. After adding water, the residue was extracted with ethyl acetate. The ethyl acetate extract was washed with water and then dried, and the ethyl acetate was distilled off to obtain an oily product. The oily product was subjected to silica gel column chromatography to obtain 0.8 g of the desired compound.

Yield 78% n ²⁰ _D 1.5748

Example 38

N-4[(1,3-Dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxymethyl]benzamide (Compound No. 589)

1.0 g (0.0043 mol) of 1,3-dimethyl-5-phenoxypyrazole-4-carbonyl aldoxime was dissolved in 20 ml of dimethyl sulfoxide, after adding 0.3 g (0.0053 mol) of potassium hydroxide powder , stir the solution. 0.92 g (0.0043 mol) of N-(4-bromomethylphenyl)formamide was added to the reaction solution, and the reaction was carried out at room temperature for 3 hours. After the reaction was complete, the reaction solution was poured into 200 ml of water, extracted with ethyl acetate, the ethyl acetate extract was washed with water and dried, and the ethyl acetate was distilled off to obtain an oily product. The oily product was subjected to silica gel column chromatography to obtain 1.2 g of the desired compound.

Yield 76% Melting point 105.3°C

Example 39

Isopropyl N-4-[{5-(4-fluorophenoxy)-1,3-dimethylpyrazol-4-yl}methyleneaminooxymethyl]-phenylcarbamate (Compound No. 595)

1.0 g (0.0040 mol) 5-(4-fluorophenoxy)-1,3-dimethylpyrazole-4-carbonylaldoxime, 1.1 g (0.0040 mol) N-4-bromomethylphenylcarbamate Isopropyl ester and 1.0 g (0.0072 mol) of potassium carbonate were added to 20 ml of acetonitrile, and the resulting mixture was heated at reflux for 6 hours. After the reaction was complete, acetonitrile was distilled off under reduced pressure, the residue was added to water, and extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and the ethyl acetate was distilled off to obtain an oily product. The oily product was subjected to silica gel column chromatography to obtain 1.5 g of the desired compound.

Yield 85% n ²⁰ _D 1.5645

Example 40

Isobutyl N-4-[{5-(4-methoxyphenoxy)-1,3-dimethylpyrazol-4-yl}methyleneaminooxymethyl]phenylcarbamate (compound 617)

1.0 g (0.0038 mol) 5-(4-methoxyphenoxy)-1,3-dimethylpyrazole-4-carbonyl aldoxime, 1.1 g (0.0038 mol) N-4-bromomethylphenyl - Isobutyl N-methylcarbamate and 1.0 g (0.0094 mol) of sodium carbonate were added to 40 ml of acetone, and the resulting mixture was heated to effect a reaction. After the reaction is complete, distill off the acetone under reduced pressure, add water to the residue after distilling off the acetone, extract with ethyl acetate, wash the ethyl acetate extract with water and dry, distill off the ethyl acetate to obtain an oily product. The oily product was subjected to silica gel column chromatography to obtain 1.5 g of the desired compound.

Yield 83% n ²⁰ _D 1.5538

Example 41

N-4-[(1,3-Dimethyl-5-phenoxy-pyrazol-4-yl)methyleneaminooxymethyl]phenyl-N-isopropylformamide (Compound No. 636)

1.0 g (0.0043 mol) of 1,3-dimethyl-5-phenoxypyrazole-4-carbonylaldoxime was dissolved in 20 ml of dioxane, and then 0.1 g (0.0043 mol) of sodium hydride was added to synthesize the above Sodium salt of oxime. 1.1 g (0.0043 mol) of N-4-bromomethylphenyl-N-isopropylformamide was added to the reaction solution, and the reaction was carried out at 40° to 50°C for 3 hours. After the reaction was complete, the reaction solution was poured into 200 ml of water and extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, then the ethyl acetate was distilled off to obtain an oily product. The oily product was subjected to silica gel column chromatography to obtain 1.3 g of the desired product.

Yield 75% Melting point 73.3°C

Example 42

N-4-[(1,3-Dimethyl-5-phenoxypyrazol-4-yl)-methyleneaminooxymethyl]phenyl-N-ethyltrimethylacetamide (Compound No. 647)

1.0 g (0.0043 mol) 1,3-dimethyl-5-phenoxypyrazole-4-carbonylaldoxime, 1.3 g (0.0043 mol) N-4-bromomethylphenyl-N-ethyltrimethyl Acetamide and 0.2 g (0.005 moles) of potassium hydroxide were dissolved in 30 ml of dimethyl sulfoxide, and the reaction was carried out at 40° to 50°C. 6 hours. After the reaction was complete, the reaction solution was poured into 200 ml of water, then extracted with ethyl acetate, the ethyl acetate extract was washed with water, then dried, and the ethyl acetate was distilled off to obtain an oily product. The oily product was subjected to silica gel column chromatography to obtain 1.5 g of the desired product.

Yield 78% Product form: paste

Example 43

5-Ethyl-3-[N-4[[5-(4-fluorophenoxy)-1,3-dimethylpyrazol-4-yl}methyleneaminooxymethyl]-phenyl] -2-Oxazolidinone (Compound No. 657)

1.0 g (0.0040 mol) 5-(4-fluorophenoxy)-1,3-dimethylpyrazole-4-carbonylaldoxime and 1.1 g (0.0040 mol) 3-(4-bromomethylphenyl) -5-Ethyl-2-oxazolidinone was dissolved in 20 ml of dimethylsulfoxide, and 0.3 g (0.0053 mol) of potassium hydroxide powder was added. The reaction was carried out at 40°-50°C for 5 hours. After the reaction was complete, the reaction solution was poured into 200 ml of water, and then extracted with ethyl acetate. The ethyl acetate extract was washed with water, then dried, and the ethyl acetate was distilled off to obtain an oily product, which was subjected to silica gel column chromatography to obtain 1.3 g of the desired compound.

Yield 72% n ²⁰ _D 1.5601

Example 44

1,3-Dimethyl-5-phenoxypyrazole-4-carbonylaldoxime O-2-phenoxyethyl ether (Compound No. 658)

1.0 g (0.0043 mol) of 1,3-dimethyl-5-phenoxypyrazole-4-carbonyl aldoxime was dissolved in 20 ml of DMSO, then 0.3 g (0.0053 mol) of potassium hydroxide powder was added , stirring the reaction solution. Then 0.86 g (0.0043 mole) of 2-bromoethoxybenzene was added and the reaction was carried out at room temperature for 3 hours. After the reaction was complete, water was added to the reaction solution, followed by extraction with ethyl acetate. The ethyl acetate extract was washed with water and dried, and the ethyl acetate was evaporated to obtain an oily product. This oily product was subjected to silica gel column chromatography to obtain 1.3 g of the desired compound.

Yield 86% n ²⁰ _D 1.5657

Example 45

1,3-Dimethyl-5-(3-trifluoromethylphenoxy)-pyrazole-4-carbonylaldoxime O-2-(4-tert-butylphenoxy)ethyl ether (Compound No. 671)

1.0 g (0.0030 mol) 1,3-dimethyl-5-(3-trifluoromethylphenoxy)pyrazole-4-carbonylaldoxime, 0.86 g (0.0034 mol) p-(2-bromoethoxy Base)-tert-butylbenzene and 1.38 g of potassium carbonate were added to 50 ml of acetonitrile, and the resulting mixture was heated at reflux for 8 hours. After the reaction is complete, add water to the reaction liquid, then extract with ethyl acetate, wash the ethyl acetate extract with water and dry, evaporate the ethyl acetate to obtain an oily product. The oily product was subjected to silica gel column chromatography to obtain 1.4 g of the desired compound.

Yield 89% n ²⁰ _D 1.5287

Example 46

4-[2-{(1,3-Dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxy}ethoxy]ethyl benzoate (Compound No. 706)

1.0 g (0.0043 moles) of 1,3-dimethyl-5-phenoxypyrazole-4-carbonyl aldoxime and 0.3 g (0.0075 moles) of sodium hydroxide powder were added to 30 ml of dimethylformamide, stirred to get the mixture. To this solution was added 0.99 g (0.0043 mole) of ethyl p-(2-chloroethoxy)benzoate, and the reaction was carried out at 30°-40°C for 3 hours. After the reaction was complete, water was added to the reaction solution, followed by extraction with ethyl acetate. The ethyl acetate extract was washed with water and dried. Ethyl acetate was distilled off to give the product as an oil. The oily product was subjected to silica gel column chromatography to obtain 1.3 g of the desired compound.

Yield 72% n ²⁰ _D 1.5577

Example 47

5-(4-Chlorophenoxy)-1,3-dimethylpyrazole-4-carbonylaldoxime O-2-(3,4-dichlorophenoxy)-ethyl ether (Compound No. 723)

1.0 g (0.0038 mol) 5-(4-chlorophenoxy)-1,3-dimethylpyrazole-4-carbonyl aldoxime, 1.0 g (0.0038 mol) 2-bromoethoxy-3,4- Dichlorobenzene and 0.58 grams (0.0038 moles) of 1,8-diazabicyclo[5,4,0]-7-undecene are dissolved in 50 milliliters of dioxane, and the reaction is carried out with stirring at 60-80°C 5 hours. After the reaction was complete, water was added to the reaction solution, followed by extraction with ethyl acetate. The ethyl acetate extract was washed with water and dried, and then the ethyl acetate was distilled off to obtain an oily product. The oily product was subjected to silica gel column chromatography to obtain 1.5 g of the desired compound.

Yield 87% n ²⁰ _D 1.5756

Example 48

5-(4-fluorophenoxy)-1,3-dimethylpyrazole-4-carbonylaldoxime O-2-phenoxypropyl ether (Compound No. 741)

1.0 g (0.0037 mol) 5-(4-chlorophenoxy)-1,3-dimethylpyrazole-4-carbonyl aldoxime sodium and 0.63 g (0.037 mol) 2-chloro-1-methylethoxy Benzene was added to 50 ml of tetrahydrofuran, and the reaction mixture was heated under reflux with stirring for 5 hours. After the reaction was complete, water was added to the reaction solution, followed by extraction with ethyl acetate. The ethyl acetate extract was washed with water and dried, and then the ethyl acetate was distilled off to obtain an oily product. The oily product was subjected to silica gel column chromatography to obtain 1.3 g of the desired compound.

Yield 87% n ²⁰ _D 1.5484

Example 49

1. 3-Dimethyl-5-phenoxypyrazole-4-carbonylaldoxime O-2-(4-tert-butylphenylthio)ethyl ether (Compound No. 753)

1.0 g (0.0030 mol) 1,3-dimethyl-5-phenoxypyrazole-4-carbonylaldoxime O-2-bromoethyl ether, 0.5 g (0.0030 mol) p-tert-butylbenzenethiol , 1.0 g (0.0072 mol) of potassium carbonate was added to 60 ml of acetonitrile, followed by heating at reflux for 5 hours. After the reaction was complete, water was added to the reaction solution, followed by extraction with ethyl acetate. The ethyl acetate extract was washed with water and dried, and the ethyl acetate was distilled off to obtain an oily product, which was subjected to silica gel column chromatography to obtain 1.1 g of the desired compound.

Yield 87% n ²⁰ _D 1.5775

Example 50

1,3-Dimethyl-5-phenoxypyrazole-4-carbonylaldoxime O-3-(4-chlorophenoxy)propyl ether (Compound No. 761)

1.0 g (0.0043 mole) of 1,3-dimethyl-5-phenoxypyrazole-4-carbonyl aldoxime and 0.3 g (0.0053 mole) of potassium hydroxide were added to 20 ml of dimethylsulfoxide. 1.07 g (0.0043 mole) of p-chloro-3-bromopropoxybenzene was added and the reaction was carried out at 40°-50°C for 4 hours. After the reaction was complete, water was added to the reaction solution, followed by extraction with ethyl acetate. The ethyl acetate extract was washed with water and dried, and then the ethyl acetate was distilled off to obtain an oily product. The oily product was subjected to silica gel column chromatography to obtain 1.3 g of the desired compound.

Yield 76% n ²⁰ _D 1.5746

Example 51

1,3-Dimethyl-5-phenoxypyrazole-4-carbonylaldoxime O-4-(4-chlorophenoxy)-2-butenyl ether (Compound No. 776)

1.0 g (0.0031 mol) 1,3-dimethyl-5-phenoxypyrazole-4-carbonyl aldoxime O-4-chloro-2-butenyl ether and 0.6 g (0.0036 mol) p-chlorophenol The potassium salt was added to 40 ml of tetrahydrofuran, followed by heating under reflux with stirring for 3 hours. After the reaction was complete, water was added to the reaction solution, followed by extraction with ethyl acetate. The ethyl acetate extract was washed with water and dried, and then the ethyl acetate was distilled off to obtain an oily product, which was subjected to silica gel column chromatography to obtain 1.2 g of the desired compound.

Yield 93% n ²⁰ _D 1.5712

Example 52

1.3-Dimethyl-5-phenoxypyrazole-4-carbonylaldoxime O-6-phenoxyhexyl ether (compound Item No. 780)

1.0 g (0.0043 mol) of 1,3-dimethyl-5-phenoxypyrazole-4-carbonyl aldoxime was dissolved in 10 ml of dimethyl sulfoxide, then 0.11 g (0.0045 mol) of sodium hydride was added at room temperature . The reaction was stirred for 30 minutes. 1.1 g (0.0043 mole) of 6-bromohexyloxybenzene was added to the solution, and the reaction was carried out at 50°-60°C for 3 hours. After the reaction was complete, water was added to the reaction solution, followed by extraction with ethyl acetate. The ethyl acetate extract was washed with water and dried, and the ethyl acetate was distilled off to obtain an oily product. The oily product was subjected to silica gel column chromatography to obtain 1.4 g of the desired compound.

Yield 80% n ²⁰ _D 1.5583

Example 53

2-[(1,3-Dimethyl-5-phenoxypyrazol-4-yl)methyleneaminooxy]ethylbenzoate (Compound No. 787)

1.0 g (0.0043 mol) of 1,3-dimethyl-5-phenoxypyrazole-4-carbonyl aldoxime and 0.3 g (0.0054 mol) of potassium hydroxide powder were added to 20 ml of dimethyl sulfoxide, and the mixture Stir for 30 minutes. 0.8 g (0.0043 mole) of 2-chloroethyl benzoate was added and the reaction was carried out at 40°-50°C for 3 hours. After the reaction was complete, water was added to the reaction solution, followed by extraction with ethyl acetate. The ethyl acetate extract was washed with water and dried. Ethyl acetate was distilled off to give the product as an oil. The oily product was subjected to silica gel column chromatography to obtain 1.3 g of the desired compound.

Yield 86% n ²⁰ _D 1.5632

Example 54

1,3-Dimethyl-5-phenoxypyrazole-4-carbonylaldoxime O-2-ethoxyethyl ether (Compound No. 789)

1.0 g (0.0046 mol) of 1,3-dimethyl-5-phenoxypyrazole-4-carbonylaldehyde was dissolved in 40 ml of ethanol, and 0.48 (g) (0.0046 mol) of O-(2-ethane oxyethyl) hydroxylamine. The reaction was carried out at room temperature for 3 hours. After the reaction was complete, water was added to the reaction solution, followed by extraction with ethyl acetate. The ethyl acetate extract was washed with water and dried. Ethyl acetate was distilled off to obtain an oily product. The oily product was subjected to silica gel column chromatography to obtain 1.2 g of the desired compound.

Yield 86% n ²⁰ _D 1.5407

Example 55

1,3-Dimethyl-5-phenoxypyrazole-4-carbonyl aldoxime O-methyl ether (Compound No. 790)

1.0 g (0.0043 mol) of 1,3-dimethyl-5-phenoxypyrazole-4-carbonylaldoxime was dissolved in 20 ml of dimethyl sulfoxide, then 0.3 g (0.0053 mol) of potassium hydroxide powder was added, and the mixture was stirred. 1.0 g (0.0063 mole) of methyl iodide was added to the reaction solution, and the reaction was carried out at room temperature for 3 hours. After the reaction was complete, the reaction solution was poured into 200 ml of water, and then extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried. Ethyl acetate was distilled off under reduced pressure to obtain an oily product. The oily product was subjected to silica gel column chromatography to obtain 0.3 g of the desired compound.

Yield 76% Melting point 70.2°C

Example 56

5-(4-Chlorophenoxy)-1,3-dimethylpyrazole-4-carbonylaldoxime O-2-propyne ether (Compound No. 795)

1.0 g (0.0038 mol) of 5-(4-methoxyphenoxy)-1,3-dimethylpyrazole-4-carbonylaldoxime was dissolved in 20 ml of dioxane, and 0.1 g (0.0042 mol) After sodium hydride, the mixture was stirred. 0.78 g (0.0038 mol) of 2-(4-fluorophenyl)ethyl bromide was added to the reaction liquid, and the reaction was carried out at 40°-50°C for 3 hours. After the reaction was complete, the reaction solution was poured into 200 ml of water. It was then extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried. Ethyl acetate was distilled off under reduced pressure to obtain an oily product, which was subjected to silica gel column chromatography to obtain 1.2 g of the desired compound.

Yield 82% n ²⁰ _D 1.5588

Example 58

5-(4-Chlorophenoxy)-1,3-dimethylpyrazole-4-carbonylaldoxime O-3-(4-chlorophenyl)-propyl ether (Compound No. 824)

1.0 g (0.0033 mole) 5-(4-chlorophenoxy)-1,3-dimethylpyrazole-4-carbonyl aldoxime, 0.5 g (0.0042 mole) propargyl bromide and 1.0 g (0.0072 mole) Potassium carbonate was added to 50 ml of acetone, and the resulting mixture was heated under reflux. After the reaction was complete, the reaction night was poured into 200 ml of water, and then extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried, and the ethyl acetate was distilled off under reduced pressure to obtain an oily product. The oily product was subjected to silica gel column chromatography to obtain 0.9 g of the desired compound.

Yield 87% n ²⁰ _D 1.5670

Example 57

5-(4-Methoxyphenoxy)-1,3-dimethylpyrazole-4-carbonylaldoxime O-2-(4-fluorophenyl)-ethyl ether (Compound No. 815)

1.0 g (0.004 mol) of 5-(4-chlorophenoxy)-1,3-dimethylpyrazole-4-carbonylaldehyde was dissolved in 30 ml of methanol, then 0.74 g (0.004 mol) was added with stirring at room temperature O-[3-(4-chlorophenyl)propyl]hydroxylamine. The reaction was then carried out at 40°-50°C for 2 hours. Methanol was distilled off under reduced pressure, and then water was added to the residue, which was extracted with ethyl acetate. The ethyl acetate extract was washed with water and dried. Ethyl acetate was distilled off under reduced pressure to obtain an oily product. The oily product was subjected to silica gel column chromatography to obtain 1.1 g of the desired compound.

Yield 66% n ²⁰ _D 1.5751

Example 59

5-(4-Chlorophenoxy)-1-methyl-3-phenylpyrazole-4-carbonylaldoxime O-4-chlorocinnamyl ether (Compound No. 846)

1.0 g (0.0030 mole) 5-(4-chlorophenoxy)-1-methyl-3-phenylpyrazole-4-carbonyl aldoxime with 0.7 g (0.0030 mole) p-chlorocinnamyl bromide and 0.2 g (0.005 mol) sodium hydroxide was reacted in 30 ml of dimethylsulfoxide at 30°C for 6 hours. After the reaction was complete, the reaction solution was poured into 200 ml of water, and then extracted with ethyl acetate. The ethyl acetate extract was washed with water, then dried, and the ethyl acetate was distilled off under reduced pressure to obtain an oily product. The oily product was subjected to silica gel column chromatography to obtain 1.1 g of the desired compound.

Yield 76% n ²⁰ _D 1.5980

Example 60

1,3-Dimethyl-5-phenoxypyrazol-4-ylphenylketoxime O-allyl ether (Compound No. 857)

Add 1.0 g (0.0033 mol) 1,3-dimethyl-5-phenoxypyrazol-4-ylphenylketoxime, 0.5 g (0.0041 mol) allyl bromide and 1.0 g potassium carbonate to 50 ml acetone Here, the mixture was heated for 6 hours to conduct a reaction. After the reaction was complete, the reaction solution was poured into 200 ml of water and extracted with ethyl acetate. The ethyl acetate extract was washed with water, then dried, and the ethyl acetate was distilled off under reduced pressure to obtain an oily product. The oily product was subjected to silica gel column chromatography to obtain 0.9 g of the desired compound.

Yield 79% n ²⁰ _D 1.5800

Synthesis of raw materials

Synthesis Example 1

13.2 g (0.006 mol) tert-butyl 4-methylbenzoate, 0.3 g (0.0012 mol) benzoyl peroxide and 6 g (0.006 mol) sodium carbonate were suspended in 100 ml of carbon tetrachloride, with stirring at 50 ° C 9.6 g (0.06 mol) of bromine were added dropwise over 30 minutes. After the dropwise addition, the reaction continued Go for 30 minutes. Then the reaction solution was cooled, and the carbon tetrachloride-insoluble matter was removed by filtration. Carbon tetrachloride was then distilled off under reduced pressure to obtain 16.2 g of tert-butyl 4-bromomethylbenzoate as crystals.

Yield 90% Melting point 53.4°C

Synthesis Example 2

15.0 g (0.049 mol) of tert-butyl 4-bromomethylbenzoate, 8.2 g (0.05 mol) of N-hydroxy-phthalimide and 3.0 g (0.054 mol) of potassium hydrochloride were added to 200 ml of di methylformamide, and the mixture was stirred at room temperature for 30 minutes, then at 50 °C for 30 minutes. The reaction solution was cooled with ice water, and then filtered to obtain crystals. The crystals were dissolved in 50 ml of dichloromethane, and 3 ml of isopropanol containing 0.5 g (0.05 mol) of hydrazine hydrate was slowly added dropwise to the solution at room temperature. After the dropwise addition, the reaction solution was heated under reflux for 2 hours. The reaction solution was cooled, then filtered, and the filtrate was concentrated to obtain 11.0 g of tert-butyl 4-(aminooxymethyl)benzoate.

Yield 90% n ^15.6 _D 1.5296

Synthesis Example 3

3.0 g (0.02 mol) of 1-p-tolylcyclopropane-1-carbonitrile and 0.1 g (0.0004 mol) of benzoyl peroxide were dissolved in 50 ml of carbon tetrachloride and added dropwise over 30 minutes under reflux 3.2 grams of bromine. After the dropwise addition was complete, the reaction was continued for 30 minutes. After the reaction solution was cooled, carbon tetrachloride was distilled off to obtain 4.4 g of 1-(4-bromomethylphenyl)cyclopropane-1-carbonitrile.

Yield 90% Product form: ointment

NMR:

δ (ppm) 1.15-1.40 (2H, m),

2.50-2.75 (2H, m),

4.45 (1H, s), 7.35 (4H, s)

Synthesis Example 4

5.0 g (0.00216 mol) of 1,3-dimethyl-5-phenoxypyrazole-4-carbonylaldoxime and 41.0 g (0.218 mol) of 1,2-dibromomethane were dissolved in 100 ml of DMSO After adding 14.4 g (0.219 mol) of 85% potassium hydroxide powder with ice cooling, the reaction solution was stirred for 30 minutes. After the reaction was complete, the reaction solution was poured into 300 ml of water, and then extracted three times with 80 ml of ether, and then washed with 300 ml of water. The ether extract was dried over anhydrous sodium sulfate, and the ether was distilled off. The residue was passed through silica gel column chromatography to obtain 5.2 g of 1,3-dimethyl-5-phenoxypyrazole-4-carboxime O-2-bromoethyl ether.

Yield 71.2% n ^23.8 _D 1.5721

The present invention provides the use of the physiologically active compounds of the present invention for killing and controlling harmful insects and mites. One of the embodiments of the present invention is that the compound is directly used as a protective object or pest control (spraying without dilution), for example, the composition of the present invention is sprayed by an aircraft to form extremely fine liquid particles in a liquid form with a purity of 95% or higher. clouds.

The compounds of the present invention can also be used to treat ponds and ponds where insect larvae live or to treat environmental water and irrigation water where larvae grow, changing their living environment or being harmful to the larvae.

In order to kill or control harmful insects and acarids with the physiologically active compounds of the present invention, the compounds are applied in a suitable form in most cases, for example, filled or diluted with an inert carrier, and if necessary, can be mixed with adjuvants, which are well known in the art.

Typical formulations of insecticidal compositions with the compounds of the present invention are described below.

The compounds of the present invention are mixed with suitable inert carriers and adjuvants (if necessary) in suitable proportions for dissolving, dispersing, suspending, blending, perfusing, absorbing or adhering the compounds to form suitable preparations, such as solutions, suspensions, Creams, powders, oil sprays, wettable powders, granules, tablets, pills, ointments, aerosols, etc.

The inert carrier can take either solid or liquid form. Examples of solid carriers are plant meal such as soybean meal, corn meal, wood meal, bark meal, sawdust, ground tobacco stem, walnut shell meal, bran, fiber meal and vegetable extraction residues; fibrous materials like paper , corrugated board and waste cloth; synthetic polymers such as powdered synthetic resins; inorganic or mineral products such as clays (for example, kaolin, bentonite and acid clays), talcs (e.g., talc and pyrophyllite), siliceous substances (e.g., diatomaceous earth, silica-containing sands, mica, and “white carbon” (a highly dispersed synthetic silica, also known as Finely divided hydrated silica or hydrated silicon dioxide, commercial products containing calcium silicate as a major component)], activated carbon, sulfur powder, pumice, cooked diatomaceous earth, clay bricks, ash, slag, calcium carbonate and calcium phosphate; Fertilizers like ammonium sulfate, ammonium nitrate, urea, ammonium chloride; agricultural fertilizers. These substances may be used alone or in combination. Substances which may be used as liquid carriers are selected from those which can dissolve the active ingredients and which, though not dissolving them, can disperse them with auxiliaries. For example, the following substances can be used alone or in combination: water, alcohols (e.g. methanol, ethanol, isopropanol, butanol, ethylene glycol), ketones (e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone , diisobutyl ketone and cyclohexanone), ethers (such as diethyl ether, dioxane, methylcellulose, dipropyl ether and tetrahydrofuran), aliphatic hydrocarbons (such as gasoline and mineral oil), aromatic hydrocarbons substances (eg, benzene, toluene, xylene, solvent naphtha, naphthalene, alkylnaphthalene), halogenated hydrocarbons (eg, dichloroethane, chlorobenzene, chloroform, carbon tetrachloride), esters (e.g., ethyl acetate, dibutyl phthalate, diisopropyl phthalate, and dioctyl phthalate), amides (e.g., dimethylformamide, diethylformamide, and dimethylacetamide amides), nitriles (eg, acetonitrile), and dimethylsulfoxide.

Gaseous carriers include Freon and other aerosol propellants, which are gases under normal conditions.

The adjuvants mentioned below are used according to different purposes. Under certain conditions, they are used in combination with other substances. Under other conditions, no adjuvant is used.

Use surfactants like polyoxyethylene alkaryl ether, polyoxyethylene alkyl ether, polyoxyethylene high fatty acid ester, polyoxyethylene resinate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan Polysaccharide monooleate, alkylaryl sulfonate, naphthalene sulfonate condensate, lignosulfonate and high alcohol sulfate, in order to emulsify, disperse, dissolve and/or wet the active ingredient.

In order to make the dispersion, adhesion and stability of the active ingredients, usually use: casein, gelatin, starch, alginic acid, methylcellulose, carboxymethylcellulose, gum arabic, polyvinyl alcohol, turpentine, rice bran Hide oil, bentonite and lignosulfonate.

To improve the flow of solid compositions, waxes, stearates and alkyl phosphates are suggested.

Naphthalenesulfonic acid condensates and polyphosphates are recommended as peptizers for dispersible compositions.

It is possible to add defoaming agents like silicone oil.

The content of active ingredients is adjusted according to actual needs. For powder or granules, the content is usually 0.5-20% by weight. For emulsifiable concentrates, suspension concentrates, and wettable powders, the content is preferably 0.1 to 50% by weight.

In order to control various insects, mites and fungi, inhibit their growth and prevent these insects, mites and fungi from damaging useful plants, the compositions of the present invention are to be used in agriculture and horticulture in an insecticidal, acaricidal or fungicidal effective amount superior. When applying the composition, the composition is properly diluted, suspended in water or other suitable media, and then applied to the soil or leaves of crops to prevent insects, mites and fungi from attacking.

The amount of active ingredient depends on various factors, for example, the purpose of application, the growth period of crops, climate, environmental conditions, composition form, application method, the type of farmland to be treated and so on.

When the fungicidal composition is used alone, the dosage of the active ingredient is preferably selected from the range of 0.1 gram to 500 gram per 10 mu.

In addition, the compound of the present invention can be used in admixture with other fungicides, insecticides, fertilizers and auxins, and even these agents can be used in combination with the compound of the present invention.

Examples of pesticides that can be mixed with the insecticide of the present invention are given below:

O-(4-nitro-3-methylphenyl)-phosphorothioate O,O-dimethyl ester (pheni-trothion)

O-(3-methyl-4-methylthiophenyl)-O,O-dimethyl phosphorothioate (fenthion)

S-(carboethoxyphenylmethyl)-O,O-dimethyl-phosphorodithioate (Daofengsan)

O-(2-isopropyl-4-methylpyrimidinyl-6-)-O,O-diethylphosphorothioate (diazinon)

2,2,2-Trichloro-1-hydroxyethyl-O,O-dimethyl phosphate (trichlorfon)

O-ethyl, O-p-nitrophenyl, phenylphosphonothioate (fenthion)

O-Ethyl, O-p-Cyanophenyl, Phenylphosphonothioate (Phenylphosphonium)

O, O-dipropyl, O-4-methylthiophenyl phosphate (propafenphos)

O, O-Dimethyl, S-phthalimidomethyl phosphorodithioate (imophos)

O, O-Dimethyl, O-Dichlorovinyl Phosphate (Dichlorvos)

O,O-Dimethyl, S-(N-methylcarbamoylmethyl)-dithiophosphate (Dimethoate)

O,O-Dimethyl, S-(1,2-dicarboethoxyethyl)-dithiophosphate (Marathon)

1-Naphthyl N-methylcarbamate (Carbaryl)

m-cresyl N-methylcarbamate (memocarb)

2-isopropoxyphenyl N-methylcarbamate (propoxur)

Ethyl N-(Diethyl-dithiophosphoroacetyl)-N-methylcarbamate (Aphidphos)

3,4-Xylyl N-methylcarbamate (Methiocarb)

2-S-Butylphenyl N-methylcarbamate (butadienecarbamate)

2-Cumyl N-methylcarbamate (Isoprocarb)

2-Chlorophenyl N-methylcarbamate (Nopocarb)

3,5-Xylyl N-methylcarbamate (Dimethacarb)

2-(1,3-dioxolane-2-)phenyl N-methylcarbamate (dioxan)

3-tert-butylphenyl N-methylcarbamate (tert-butylcarbamate)

4-2 Allylamino-3,5-Dimethylphenyl N-methylcarbamate (Chexacarb)

S-Methyl-N-(methylcarbamoyloxy)thioacetamidine ester (Methomil)

N-(2-methyl-4-chlorophenyl)-N,N-dimethyl-formamidinidine hydrochloride (dimeform)

1,3-Bis(carbamoylthio)-2-(N,N-dimethylamino)-propane hydrochloride (butan)

Diisopropyl-1,3-dithiolane-2-ylidene malonate (Fuji No. 1)

N-[(4-Chlorophenyl)amino]carbonyl]-2,6-difluorobenzamide (fluorourea)

O,O-Dimethyl-S-[2-(isopropylthio)ethyl]phosphorodithioate (Phiphiphos)

O, O-diethyl-S-[2-(ethylthio)-ethyl] phosphorodithioate (dithionate)

(2,3-Dihydro-2,2-Dimethyl-7-benzofuryl)-N-methylcarbamate (Centacarb)

O-ethyl S,S-diphenyl phosphorodithioate (Edibenfos)

N-(trichloromethylthio)cyclohexene-4-1,2-dicarboximide (captafol)

2,4,5,6-tetrachloroisophthalonitrile (chlorothalonil)

N-(1,1,2,2-tetrachloroethylthio)cyclohex-4-ene-1,2-dicarboximide (captafol)

4,4-o-phenylene bis(3-thiourethanoate) dimethyl ester (thiophanate-methyl)

Methyl 3-(butylcarbamoyl)-3H-benzimidazol-2-ylaminobenzoate (benomyl)

Ethylene-1,2-bis(dithiocarbamate)zinc (Zinc)

Ethylene-1,2-bis(dithiocarbamate) manganese (Maneb)

In order to demonstrate the killing effect of the compounds of the present invention, see the following experimental examples and composition examples. However, the present invention is not limited to these examples.

Experimental example 1

Fungicidal activity against mold of barley flour (Erysiphe graminis f.sp.hordei)

Barley seedlings were sprayed with the test compound (200 ppm) one day after inoculation with conidia of Erysiphe graminis f. sp. hordei at the second-leaf stage. The seedlings were stored at a constant temperature of 25°C for one week, and then the percentage of the infected area of each leaf was measured. The bactericidal activity was judged by comparison with the untreated fraction and according to the following criteria.

The results are shown in Table 2

A: Disease inhibition rate 100-95%

B: Disease inhibition rate 94～80%

C: Disease inhibition rate 79～60%

D: Disease inhibition rate 59～0%

Table 2

Compound No. Bactericidal Activity Compound No. Bactericidal Activity Compound No. Bactericidal Activity

4 B 55 A 97 C

9 C 56 A 98 A

16 B 57 C 102 A

17 A 58 C 103 C

18 B 59 A 105 A

19 A 60 A 109 A

20 B 66 A 110 B

21 A 67 A 111 A

22 A 68 A 112 A

23 A 69 A 113 A

24 A 71 B 114 A

25 A 73 A 118 B

26 A 74 A 119 C

27 A 85 A 120 B

33 A 86 A 123 A

34 A 87 A 124 B

35 A 88 A 133 A

36 A 89 A 134 B

41 A 90 A 136 A

42 A 91 A 140 B

50 A 92 A 142 C

51 A 93 B 144 C

52 B 94 A 145 A

53 A 95 B 153 A

54 A 96 C 154 A

155 A 212 A 249 C

156 A 213 A 250 A

157 A 216 A 251 B

158 A 217 B 252 A

159 A 219 C 253 A

160 A 220 A 254 A

161 B 221 A 255 A

167 A 222 C 257 B

181 C 228 B 258 B

186 B 229 A 262 B

188 A 230 A 263 A

190 C 231 A 264 A

193 A 232 A 265 A

194 A 234 A 266 A

195 A 235 A 267 A

197 A 236 C 268 A

198 A 237 A 269 B

199 A 238 C 270 B

200 A 239 A 281 B

201 A 240 A 282 C

202 A 241 A 283 A

203 A 242 A 300 C

204 B 243 A 302 B

205 A 245 A 303 B

206 C 246 B 304 B

207 C 248 A 305 B

306 A 351 A 391 A

309 B 352 B 392 A

311 C 353 A 393 A

312 B 356 A 394 A

315 A 357 A 395 A

316 A 358 A 396 A

321 A 363 A 397 A

323 A 364 A 398 A

324 C 365 A 399 A

328 B 366 A 400 A

329 A 369 A 401 A

330 A 370 A 402 A

331 A 371 C 403 A

332 A 372 A 404 A

333 A 373 C 405 A

334 A 374 A 406 A

336 B 375 A 407 A

337 B 382 A 409 A

340 A 383 A 421 A

342 A 384 A 422 A

343 A 385 A 424 A

344 A 386 A 427 A

346 A 387 A 428 A

347 A 388 C 429 A

349 B 389 A 431 A

350 A 390 A 432 B

433 A 470 B 496 A

434 A 471 A 497 A

435 B 472 A 498 A

436 A 473 A 499 A

437 A 474 A 501 A

438 A 475 B 502 A

439 A 476 A 503 A

440 A 477 A 504 A

441 A 478 B 505 A

443 A 479 A 506 A

444 A 480 A 507 A

445 A 481 A 508 A

446 A 482 A 518 C

447 A 483 A 522 B

448 A 484 A 523 B

449 A 485 A 524 B

450 A 486 A 527 A

451 A 487 A 528 A

452 A 488 B 529 B

453 A 489 B 530 B

454 A 490 B 532 A

455 A 491 C 533 A

465 A 492 B 534 C

466 A 493 A 535 B

468 A 494 A 536 A

469 A 495 A 537 B

538 A 574 B 612 A

541 A 576 A 613 A

545 A 578 B 614 A

546 A 579 B 615 A

547 A 580 B 616 A

548 A 581 C 617 A

549 B 584 B 618 A

550 C 586 C 619 A

551 B 587 B 620 A

552 C 589 A 621 A

553 A 591 B 622 A

554 C 592 A 623 A

555 C 593 B 624 A

556 B 594 B 625 A

557 A 595 C 626 A

562 A 596 C 627 B

563 A 597 C 628 B

565 A 598 C 629 A

566 A 601 C 630 A

567 A 602 A 631 A

568 A 603 A 636 A

569 B 604 A 637 A

570 A 608 A 638 A

571 A 609 A 639 A

572 B 610 A 640 A

573 B 611 A 641 B

642 C 677 A 727 A

643 A 678 A 729 A

644 B 680 A 730 B

645 A 682 A 731 B

646 A 683 A 732 A

648 A 684 A 733 A

649 A 691 B 737 A

650 B 692 B 739 C

652 C 693 A 740 A

653 B 694 A 741 A

654 B 695 A 746 B

655 A 696 B 751 B

656 B 697 B 753 B

657 B 700 C 754 A

658 A 701 A 755 A

659 B 702 B 757 A

660 A 707 B 758 A

661 B 708 A 759 A

662 B 713 A 763 B

663 A 715 A 766 A

667 C 716 B 767 A

668 A 718 C 768 A

670 A 719 A 769 A

672 B 720 B 772 B

675 B 724 A 773 A

676 B 726 B 775 B

783 B 823 A 841 B

784 B 824 A 842 A

795 A 825 A 843 A

796 B 827 B 844 A

803 A 828 C 848 A

804 C 829 A 849 A

805 C 831 C 850 A

816 A 833 B 851 A

817 A 834 A 852 B

818 A 835 B 853 A

819 A 836 A 854 C

821 B 839 A 855 A

822 B 840 B

Experimental example 2

Fungicidal activity against oat root rust (Puccinia Coroata f.sp.avenae)

Oat seedlings were sprayed with the experimental compound (200 ppm) one day after inoculation with uredospores of Puccinia coronata f.SP. avenae at the 8-leaf stage. Seedlings were stored at a constant temperature of 25°C for ten days. The percentage of infected area per leaf was measured. The bactericidal activity was judged by the same standard as in Experimental Example 1.

The results are shown in Table 3.

table 3

Compound No. Bactericidal Activity Compound No. Bactericidal Activity Compound No. Bactericidal Activity

14 B 60 A 111 A

18 C 66 A 112 A

19 C 67 A 113 A

21 C 68 A 114 A

22 B 69 A 133 A

23 B 71 A 134 A

24 B 73 A 135 B

25 B 74 A 136 A

27 A 85 A 138 A

33 A 86 A 139 A

34 A 87 A 140 A

35 A 88 B 142 A

36 A 89 A 143 A

41 A 90 A 144 A

42 A 91 A 145 A

50 A 92 C 153 A

51 A 93 B 154 A

52 A 94 B 155 A

53 A 95 A 156 A

54 A 96 A 157 A

55 A 97 C 158 A

56 A 98 A 159 B

57 A 105 A 160 B

58 A 109 A 161 A

59 A 110 A 186 A

188 A 241 A 328 A

193 A 242 B 329 A

194 A 243 A 330 A

195 A 245 A 331 A

198 A 246 A 332 A

199 A 248 C 333 A

200 A 250 A 337 A

201 B 251 A 340 B

202 C 254 B 342 A

203 A 257 A 343 A

204 B 258 A 344 A

205 B 263 A 345 B

212 A 264 A 346 A

213 C 265 A 347 A

217 C 266 B 349 A

220 B 267 B 350 A

221 A 268 B 351 B

228 B 283 B 353 A

229 A 303 C 355 B

230 A 305 B 356 A

231 A 306 A 357 A

234 A 309 C 358 A

237 A 312 A 363 A

238 B 315 A 364 A

239 A 316 A 366 A

240 A 323 B 369 A

370 A 402 A 446 C

371 A 403 A 447 A

372 A 404 A 448 A

373 A 405 A 449 A

374 A 406 A 450 A

375 A 407 A 451 A

381 C 409 A 452 A

382 A 421 A 453 A

383 A 422 A 454 A

384 A 427 C 455 A

385 A 428 A 465 A

386 A 429 A 468 A

387 B 431 A 469 A

388 C 433 A 470 A

390 A 434 A 471 A

391 A 435 B 472 A

392 A 436 A 473 A

393 A 437 A 474 A

394 A 438 C 475 A

395 A 439 A 476 B

396 A 440 A 477 A

397 A 441 A 478 A

398 A 442 A 479 A

399 A 443 B 480 A

400 A 444 A 481 C

401 A 445 B 482 A

483 A 523 A 557 A

484 A 524 A 558 C

485 A 525 A 559 C

486 A 527 C 560 B

487 A 528 A 561 A

488 A 529 A 562 B

489 A 530 A 563 A

490 A 531 A 565 A

491 A 532 A 566 A

492 A 533 A 567 A

493 A 534 A 568 A

494 A 535 A 569 A

495 A 536 A 570 A

496 A 537 A 571 A

497 A 538 A 572 A

498 A 544 B 573 C

499 A 545 A 574 B

500 C 546 A 576 A

501 A 548 A 577 A

502 A 550 C 578 A

503 A 551 A 579 A

504 A 552 C 580 A

505 A 553 B 585 C

506 A 554 A 586 A

507 A 555 A 587 A

508 A 556 A 589 A

590 A 621 A 651 B

591 A 622 A 652 A

592 A 623 A 653 B

593 A 624 A 654 A

594 A 625 A 655 A

595 A 626 A 656 A

596 B 627 A 657 A

599 B 628 A 658 A

602 A 629 A 659 B

603 A 630 A 660 A

604 A 631 A 661 A

606 C 636 A 662 A

607 A 637 A 663 A

608 A 638 A 667 C

609 A 639 A 668 A

610 A 640 A 669 B

611 A 641 A 670 B

612 A 642 A 672 B

613 A 643 A 674 B

614 A 644 A 675 A

615 A 645 A 677 A

616 A 646 A 678 A

617 A 647 A 679 B

618 A 648 A 680 A

619 A 649 A 682 A

620 A 650 A 683 A

684 A 727 A 784 B

685 A 729 A 794 C

690 C 730 A 796 A

691 C 731 A 804 A

692 A 732 A 812 B

693 A 733 A 813 A

694 A 737 B 814 B

695 A 746 B 815 B

696 A 751 B 817 C

697 A 755 A 821 A

699 A 757 B 822 C

701 A 758 A 823 A

706 B 759 A 824 A

709 A 763 A 825 A

710 A 764 B 829 A

711 A 766 A 830 C

712 A 767 A 831 A

713 B 768 A 832 C

715 B 769 A 833 A

717 C 770 B 834 A

719 A 772 A 835 A

720 C 773 A 838 A

723 B 780 B 842 A

724 A 781 C 843 A

725 A 782 A 844 A

726 A 783 B 848 A

849 B 851 A 853 A

850 A 852 B 854 A

Experimental example 3

Fungicidal activity against cucumber pseudodowny mildew (Pseudoperonospora cubensis)

Cucumbers at the 2-leaf stage were sprayed with the test compound (200 ppm) one day before inoculation with zoospores of Pseudoperonospora cubensis. Plants were kept in a humid room at 25°C for one day, and then moved to a fresh air room for six days. Detect the degree of damage to each leaf, and the bactericidal activity is judged by the same standard as in Experimental Example 1.

The results are shown in Table 4.

Table 4

Compound No. Bactericidal Activity Compound No. Bactericidal Activity Compound No. Bactericidal Activity

4 B 51 B 90 A

9 A 52 B 91 A

10 B 53 C 92 A

12 C 54 A 93 A

13 B 55 A 94 A

16 C 56 A 95 A

17 A 57 A 96 A

18 C 58 C 97 A

19 A 59 C 98 A

20 B 60 A 99 A

21 A 65 C 100 A

22 A 66 A 101 A

23 A 67 A 102 A

24 A 68 A 103 B

25 A 69 B 104 C

26 A 73 C 105 B

27 A 74 A 109 B

33 A 75 B 110 A

34 A 77 B 111 A

36 A 78 A 112 B

41 A 79 C 113 A

42 A 85 A 114 A

45 A 86 B 115 A

47 C 87 A 116 A

50 A 88 C 117 B

118 B 179 A 228 B

121 C 180 A 229 B

122 A 181 230 B

123 B 182 A 231 C

130 A 183 B 232 B

131 A 186 C 234 A

133 C 188 A 237 A

136 A 192 A 239 C

137 B 193 A 240 A

138 B 194 A 242 C

139 A 195 B 243 A

140 A 196 B 245 A

141 C 197 A 246 B

145 B 198 A 251 C

147 A 199 A 252 B

153 B 200 A 253 A

154 A 201 B 254 A

155 A 202 B 255 B

156 A 203 A 256 B

159 C 204 A 257 C

160 B 205 A 258 C

161 A 212 A 262 C

162 A 213 A 263 C

171 C 216 C 264 C

173 A 220 B 265 A

178 A 221 A 266 B

267 C 336 A 376 B

269 B 337 B 377 B

270 C 342 A 378 C

284 C 343 C 383 A

288 C 344 B 385 A

292 A 346 A 386 B

293 B 350 B 387 B

296 B 351 A 388 A

297 A 352 B 389 B

298 C 353 A 390 A

299 A 354 C 391 A

302 A 355 C 392 A

303 C 356 A 393 A

304 A 357 A 394 A

305 B 358 A 395 A

306 B 363 A 396 A

312 B 364 A 397 A

316 C 365 A 398 A

321 A 366 A 399 A

326 B 369 A 400 A

328 B 370 A 401 A

329 B 371 B 402 A

330 B 372 A 403 A

331 A 373 A 404 A

332 A 374 A 405 A

333 A 375 A 406 A

407 A 452 A 492 C

409 A 453 A 493 B

420 B 454 A 496 A

421 A 455 A 497 A

424 A 465 A 498 C

428 B 468 A 499 C

429 A 469 A 502 C

431 A 471 A 503 C

432 B 473 C 504 A

433 B 474 C 505 C

434 B 476 B 506 A

436 A 477 A 507 A

437 A 478 A 508 A

438 A 479 B 511 A

439 A 480 A 512 A

440 A 481 A 513 A

441 A 482 A 514 A

442 B 483 B 515 A

444 A 484 A 516 B

445 A 485 A 518 C

446 B 486 A 523 A

447 A 487 A 524 A

448 B 488 A 525 A

449 A 489 A 527 B

450 A 490 A 528 A

451 A 491 B 529 B

531 C 572 A 609 A

532 A 574 B 610 A

533 A 576 A 611 A

534 A 577 A 612 A

535 A 578 C 613 A

536 A 579 B 614 A

537 A 584 B 615 A

538 A 585 B 616 A

541 B 586 A 617 A

544 A 588 C 618 A

546 A 589 A 619 A

548 A 590 A 620 A

551 A 591 A 621 A

553 C 592 A 622 B

554 C 593 A 623 A

555 B 594 A 624 A

556 C 595 A 625 A

557 B 596 C 626 A

562 A 597 C 627 A

563 A 598 C 628 A

565 A 599 B 629 A

566 A 602 A 630 A

567 B 603 A 631 C

568 B 604 A 632 A

569 A 605 A 633 A

570 A 608 A 636 A

637 A 663 A 699 C

638 A 668 A 700 C

639 A 669 A 701 A

640 A 670 A 702 A

641 A 673 B 705 A

642 A 674 A 706 C

643 C 675 A 709 A

644 B 676 A 713 A

645 A 677 A 714 B

646 A 678 A 715 B

647 A 680 A 716 B

648 A 681 A 717 A

649 A 682 A 719 B

650 A 683 A 720 A

651 A 684 A 725 B

652 A 685 A 726 B

653 A 686 A 727 B

654 A 690 B 728 B

655 A 691 A 729 A

656 A 692 A 730 A

657 A 693 A 731 B

658 A 694 A 732 A

659 A 695 A 733 A

660 A 696 A 737 C

661 A 697 A 739 B

662 A 698 A 740 B

741 A 780 A 836 A

742 A 782 B 837 B

746 A 783 A 838 C

751 A 784 A 839 C

752 A 787 B 840 C

754 B 789 B 841 C

755 A 804 A 842 A

756 A 812 A 843 A

757 A 813 A 844 A

758 A 814 A 845 B

759 A 815 C 848 A

761 C 817 C 849 A

763 C 820 C 850 A

764 A 821 A 851 A

765 B 822 A 852 A

766 A 823 A 853 A

767 A 824 A 854 A

768 A 825 A 855 A

769 A 826 B

770 B 827 B

772 A 828 B

773 A 829 A

774 A 831 A

775 A 833 A

776 A 834 A

777 A 835 A

Experimental example 4

Insecticidal activity against rice brown planthopper (Nilaparvata lugens)

After soaking rice seedlings in the compound (200 ppm) emulsion for 30 seconds and air drying, the seedlings were planted in glass test tubes, and the plants were inoculated with third instar nymphs. On the eighth day after the inoculation, the corrected mortality rate was calculated and the insecticidal activity was judged according to the following criteria.

The results are shown in Table 5

A: Corrected mortality rate 100-90%

B: Corrected mortality rate 89-80%

C: Corrected mortality rate 79-50%

table 5

Compound No. Insecticidal Activity Compound No. Insecticidal Activity Compound No. Insecticidal Activity

16 A 71 A 123 A

17 A 72 B 124 A

19 A 73 A 125 A

20 A 74 A 133 A

21 A 85 A 134 A

22 A 86 A 135 A

23 A 87 A 136 A

27 A 88 A 140 A

32 A 89 A 154 A

33 A 90 A 155 A

34 A 91 A 157 A

35 A 92 A 158 A

36 A 95 A 159 A

40 C 96 C 160 A

41 A 102 A 161 A

42 A 103 A 166 A

54 A 104 A 193 A

55 A 105 A 194 A

56 B 109 A 195 A

60 A 110 A 198 A

65 C 111 A 199 B

66 A 112 A 200 A

67 A 113 A 203 A

68 A 114 A 204 A

69 A 122 A 211 C

212 A 283 A 345 A

214 B 302 A 346 C

217 C 303 B 347 A

221 A 304 C 349 A

229 A 305 C 350 A

230 A 306 A 351 A

231 A 310 A 352 A

232 A 311 A 353 A

234 A 314 C 355 A

235 B 315 A 356 A

236 A 316 A 357 A

237 A 321 A 358 A

239 A 328 A 363 A

240 A 329 A 364 A

241 A 330 A 365 A

242 A 331 A 366 A

248 A 332 A 369 A

250 A 333 A 370 A

255 A 334 A 371 A

257 A 336 A 372 A

258 A 337 A 373 A

260 C 339 C 374 A

266 A 340 A 375 A

267 A 342 A 388 A

268 C 343 A 389 A

269 C 344 A 390 A

391 A 435 B 471 A

392 A 436 A 472 A

394 A 437 A 473 A

395 A 438 A 474 A

396 A 439 A 475 A

397 A 440 A 476 A

398 A 441 B 477 A

399 A 442 A 479 A

400 B 443 A 480 A

401 A 444 B 481 A

402 A 445 C 482 A

403 A 446 B 483 A

404 A 447 A 484 A

405 A 448 A 485 A

406 A 449 A 486 A

407 A 450 A 487 A

409 A 451 A 488 A

421 A 452 A 489 A

422 A 453 A 499 A

424 A 454 A 500 B

427 A 465 A 501 A

428 A 466 A 502 A

429 A 467 A 503 A

431 A 468 A 504 A

433 A 469 A 505 A

434 A 470 A 506 A

507 A 551 A 581 A

508 A 552 A 584 B

516 C 553 A 585 A

517 A 554 A 586 A

518 A 555 A 587 A

523 A 556 A 588 B

524 A 557 A 589 B

525 A 562 A 594 B

527 A 563 A 595 A

528 A 564 A 602 A

529 A 565 A 603 A

531 A 566 A 604 A

532 A 567 A 608 A

533 A 568 A 609 A

534 A 569 A 610 A

535 A 570 A 611 A

536 A 571 A 612 A

537 A 572 A 613 A

538 A 573 A 614 A

541 A 574 A 615 A

544 A 575 A 616 A

545 A 576 A 617 A

546 A 577 B 618 A

547 A 578 B 619 A

548 A 579 A 620 A

549 A 580 B 621 A

623 A 655 A 692 A

624 A 656 B 693 A

625 A 657 A 694 B

626 A 658 A 695 B

627 A 659 C 696 A

628 A 660 A 697 A

629 A 661 A 698 A

630 A 662 A 699 A

631 A 663 A 701 A

636 A 668 A 702 A

637 A 669 A 703 C

638 A 670 A 710 C

639 A 671 A 713 A

640 A 672 C 715 A

641 C 673 C 716 A

642 A 674 B 717 A

643 A 675 A 719 A

644 A 677 A 720 C

645 A 679 A 723 B

646 A 680 A 724 A

647 A 682 A 725 A

648 A 683 A 726 A

649 B 684 A 727 A

652 B 685 A 728 A

653 A 686 C 729 A

654 A 691 A 730 C

731 A 769 A 824 A

732 A 770 A 825 A

733 A 772 A 826 A

734 A 774 A 827 A

735 A 775 A 828 A

739 B 776 A 829 A

740 A 790 A 830 A

741 A 791 A 831 A

742 A 792 C 832 A

744 A 793 A 833 A

745 A 794 A 834 A

746 A 795 A 835 A

751 A 799 A 836 A

752 C 801 C 837 C

753 A 812 C 838 A

756 A 813 A 839 A

757 A 814 C 840 A

758 A 815 C 841 A

759 A 816 A 842 A

761 A 817 A 843 A

762 A 818 C 844 A

763 A 819 C 845 A

764 A 820 A 847 B

766 A 821 A 848 A

767 A 822 A 849 A

768 A 823 A 850 A

851 A 853 A 855 A

852 A 854 A

Experimental example 5

Insecticidal activity against diamondback moth (Plutella xylostella)

A pupae of an insect on a Chinese cabbage leaf (6cm x 5cm) was immersed in the emulsion of the compound of the invention for 30 seconds. After air drying, the insects and plants were placed together in a petri dish, and on the sixth day after entering the petri dish, the corrected mortality was calculated and judged according to the same standard as in Experimental Example 4.

The results are shown in Table 6.

Table 6

Compound No. Insecticidal Activity Compound No. Insecticidal Activity Compound No. Insecticidal Activity

8 A 74 A 133 A

18 C 85 A 136 B

26 A 86 C 142 C

27 C 87 A 154 A

33 A 88 B 155 A

34 A 89 A 156 A

35 A 90 A 157 B

36 B 91 A 158 A

41 A 92 A 159 B

42 A 94 A 160 A

51 C 95 A 169 C

52 A 97 C 192 A

53 B 98 A 193 A

54 B 102 A 195 A

55 B 103 A 196 A

56 A 104 A 197 B

57 C 105 C 198 A

59 A 109 A 199 A

60 A 110 B 200 A

66 A 111 B 201 A

67 A 112 A 202 A

68 A 113 A 203 A

69 A 122 A 204 A

72 A 123 A 205 B

73 A 126 C 206 B

207 A 251 C 328 A

212 A 252 C 329 A

213 A 253 A 330 A

215 A 254 A 331 B

216 A 255 B 333 A

217 A 256 A 337 A

220 B 257 A 340 A

221 C 262 A 342 A

228 A 263 A 343 A

229 A 264 A 344 A

230 A 265 C 345 B

231 A 266 A 346 A

232 B 267 A 347 A

234 B 268 A 349 A

235 A 269 C 350 A

237 C 280 B 351 A

239 B 281 A 352 A

240 A 283 A 353 A

241 A 284 A 355 A

242 A 300 A 356 A

243 A 302 C 357 A

244 A 303 A 358 A

245 A 312 A 365 A

246 A 316 A 366 A

248 B 321 A 369 A

250 B 324 A 370 B

371 B 407 A 449 A

372 A 409 A 450 A

373 A 420 A 451 A

374 A 421 A 452 A

375 A 424 B 453 A

383 C 425 A 454 A

384 B 427 A 455 A

386 C 428 A 465 A

388 A 429 A 466 A

390 A 431 A 467 A

391 A 432 B 468 A

392 A 433 A 469 A

393 A 434 A 470 A

394 A 435 A 471 A

395 A 436 A 472 A

396 A 437 A 473 A

397 A 438 A 474 A

398 A 439 A 475 A

399 A 440 A 476 A

400 A 441 A 477 A

401 A 442 A 478 A

402 A 444 A 479 A

403 A 445 A 480 A

404 A 446 A 481 A

405 A 447 A 482 A

406 A 448 A 483 A

484 A 524 B 564 A

485 A 525 B 567 A

486 A 527 A 568 A

487 A 531 A 569 A

489 A 532 A 570 A

490 A 533 A 571 A

491 A 534 A 572 A

492 A 535 C 573 A

493 A 536 A 576 A

494 A 537 A 577 A

495 A 538 C 578 A

496 A 544 C 579 A

497 A 545 A 580 B

498 A 546 A 581 A

499 A 547 A 585 C

500 C 548 A 586 B

501 A 549 A 587 C

502 A 551 A 588 C

503 A 552 C 589 B

504 A 553 B 590 C

505 A 554 B 592 B

506 A 555 C 593 C

507 A 556 C 599 C

508 A 557 C 602 A

517 C 562 A 603 A

518 C 563 A 604 A

606 C 636 A 676 A

607 C 638 A 677 A

608 A 639 C 678 A

609 A 640 A 679 A

610 A 641 A 680 A

611 B 642 A 682 A

612 A 643 A 683 A

613 B 648 B 684 A

614 B 649 A 685 A

615 B 650 A 686 B

616 A 651 C 687 C

617 B 653 B 688 C

618 A 657 A 691 C

619 A 658 A 692 B

620 A 659 B 693 A

621 A 660 A 694 A

622 A 661 A 695 A

623 A 662 A 696 B

624 A 663 A 698 C

625 B 667 C 699 C

626 A 668 A 701 A

627 A 670 A 702 A

628 A 671 C 703 C

629 A 673 A 710 C

630 A 674 A 713 A

631 A 675 B 714 A

715 A 760 B 818 A

716 A 761 B 819 A

717 A 762 A 821 A

719 A 763 C 822 A

720 A 764 A 823 A

721 A 766 A 824 A

723 A 767 A 825 A

724 A 768 A 826 A

725 A 769 A 827 A

726 A 770 A 828 A

727 A 772 A 829 A

728 A 773 A 830 A

729 A 774 A 831 A

731 A 775 A 832 B

732 A 776 C 833 A

733 A 777 A 834 A

734 A 780 C 835 A

735 A 784 C 836 A

737 B 786 C 837 A

740 A 795 A 838 A

741 A 799 C 839 A

742 A 802 A 840 B

746 A 805 C 841 A

756 A 812 C 842 A

757 A 815 C 843 A

759 B 817 A 844 A

845 A 850 A 853 A

847 A 851 A 854 A

848 B 852 A 855 A

849 A

Experimental example 6

Insecticidal activity against green peach aphid (Myzus percicae)

Adult aphids were inoculated onto Chinese cabbage. Insects and plants were then sprayed with an emulsion of the compound of the invention (200 ppm). On the third day after the application, the insecticidal activity was judged according to the same method as in Experimental Example 4.

The results are shown in Table 7

Table 7

Compound No. Insecticidal Activity Compound No. Insecticidal Activity Compound No. Insecticidal Activity

9 B 54 A 99 A

10 B 55 A 100 B

12 C 56 A 101 A

14 C 57 A 102 B

16 C 58 A 103 A

18 A 59 A 104 A

19 A 60 A 105 C

20 A 66 A 106 A

21 A 67 A 107 C

22 A 68 A 108 C

23 A 69 A 109 A

24 B 71 A 110 A

26 A 72 B 111 A

27 A 73 A 112 A

33 A 74 A 113 A

34 A 77 A 114 C

35 B 85 A 115 A

36 A 86 B 116 A

41 C 87 A 117 A

42 A 88 A 122 B

45 A 89 A 123 C

50 A 90 A 124 C

51 A 91 A 130 A

52 A 92 A 131 A

53 A 95 A 132 A

133 A 197 A 237 A

134 A 198 A 238 B

135 C 199 A 239 A

136 A 200 A 240 A

138 C 201 A 241 C

139 B 202 A 243 A

140 A 203 A 245 B

141 A 204 A 246 A

143 A 205 A 248 B

145 A 207 C 249 B

153 A 211 A 250 C

154 B 212 A 251 A

155 B 213 A 253 C

156 B 215 A 254 A

157 A 216 B 255 A

158 B 217 C 257 C

159 C 220 A 258 A

160 A 221 A 262 C

161 C 228 C 263 B

163 A 229 A 264 A

173 A 230 A 265 A

180 A 231 A 266 B

193 A 232 A 267 A

194 A 234 A 268 A

195 A 235 A 282 C

196 A 236 A 296 A

299 A 355 A 401 B

302 B 356 A 402 B

306 A 357 A 403 A

311 C 358 A 404 A

315 A 364 B 405 A

316 B 365 A 406 C

321 A 366 A 407 B

328 A 370 B 409 A

329 A 371 B 421 A

330 A 372 C 422 A

331 A 373 B 424 B

332 B 374 B 427 A

333 A 375 A 428 A

334 B 388 B 429 A

337 A 389 A 431 A

340 A 390 A 432 A

342 A 391 A 433 A

343 A 392 A 434 A

344 A 393 B 435 A

345 A 394 A 436 A

346 A 395 A 437 A

347 A 396 A 438 A

349 A 397 A 439 B

350 A 398 B 440 A

352 A 399 B 441 A

353 A 400 A 442 A

443 A 479 A 507 A

444 A 480 A 508 A

445 A 481 A 511 A

446 A 482 A 512 A

447 B 483 A 513 A

448 A 484 A 514 A

449 A 485 A 515 A

450 A 486 A 517 C

451 A 487 A 518 C

452 A 488 A 527 A

453 A 489 A 532 A

454 A 490 A 533 A

455 B 491 A 534 A

465 B 492 A 537 A

466 A 493 A 538 A

467 A 495 A 541 B

468 A 496 B 544 C

469 B 497 A 545 A

470 A 498 A 546 A

471 B 499 A 547 A

472 B 501 A 548 A

473 A 502 A 549 A

474 A 503 A 550 C

476 A 504 A 551 C

477 A 505 A 552 C

478 B 506 A 553 A

554 A 595 A 630 A

555 B 602 A 631 A

556 B 603 A 633 A

557 C 604 B 634 B

561 A 608 A 636 A

562 A 609 A 637 A

563 B 610 A 638 B

564 A 611 C 639 C

565 C 612 A 640 A

566 A 613 A 642 B

567 A 614 B 643 B

568 A 615 B 644 C

569 A 616 C 645 A

570 A 617 A 646 A

571 A 618 B 652 A

572 B 619 A 654 B

573 C 620 A 656 A

574 A 621 B 657 A

576 B 622 B 658 A

577 A 623 C 660 A

578 C 624 A 661 A

580 C 625 A 662 B

584 C 626 A 663 A

585 A 627 A 664 C

586 C 628 A 665 C

588 C 629 A 667 B

668 A 697 A 737 A

669 A 698 C 741 C

670 A 699 A 742 C

671 A 701 A 743 C

673 B 702 A 746 C

674 A 703 C 751 C

675 B 710 C 752 C

676 B 713 A 757 B

677 A 715 A 758 A

678 A 716 A 759 A

679 A 717 C 762 A

680 A 719 A 763 C

681 C 720 C 764 C

682 A 723 B 766 A

683 A 724 A 767 A

684 B 725 A 768 A

685 C 726 A 769 A

686 A 727 A 770 A

687 B 728 A 772 A

689 B 729 A 774 A

691 B 730 A 775 B

692 A 731 A 776 B

693 A 732 A 777 B

694 A 733 A 779 A

695 A 734 A 798 A

696 A 735 A 799 A

801 C 824 B 840 C

804 C 825 B 841 A

805 C 826 B 842 A

812 A 827 A 843 A

813 B 828 A 844 A

814 B 829 A 848 C

815 B 831 A 849 A

816 C 832 A 850 B

817 C 833 A 851 A

818 C 834 A 852 A

819 C 835 A 853 A

821 A 836 A 854 A

822 A 837 A 855 B

823 A 839 A

Experimental example 7

Acaricidal activity against citrus spider mites (Pannychus citri)

Adult females were inoculated on the leaves of Zhuluan, which were then sprayed with an emulsion of the compound of the present invention (200 ppm). On the 10th day after the administration, the number of surviving insects was counted, and then the acaricidal activity was judged according to the same standard as in Experimental Example 4.

The results are shown in Table 8.

Table 8

Compound No. Acaricidal Activity Compound No. Acaricidal Activity Compound No. Acaricidal Activity

8 A 71 A 122 A

9 A 74 A 124 A

10 A 86 A 125 A

11 A 87 A 126 A

12 A 88 A 133 A

13 B 89 A 134 A

24 A 90 A 135 A

25 B 91 A 136 A

27 A 92 A 140 B

32 A 94 B 147 B

33 A 95 A 150 C

34 96A 152A

35 A 97 A 153 A

41 A 98 A 154 A

42 A 102 A 155 A

50 A 103 A 156 A

51 A 105 A 157 A

53 C 109 A 158 A

54 A 112 A 159 A

55 A 113 A 160 A

56 A 114 A 161 C

57 A 118 A 164 A

65 A 119 B 166 A

68 A 120 B 167 B

69 A 121 A 169 A

170 A 235 A 269 A

171 A 237 A 282 A

193 A 238 A 283 A

194 A 239 A 284 C

195 B 240 A 300 C

196 C 241 A 329 B

197 A 242 A 330 B

198 A 243 A 333 A

199 A 245 A 334 A

200 A 246 A 335 A

201 A 248 A 337 A

202 A 251 B 342 A

206 A 252 A 343 A

207 C 253 A 344 A

211 A 254 A 347 A

212 A 255 B 349 A

214 A 256 A 350 A

217 A 257 A 351 A

218 A 258 A 353 A

219 A 262 A 354 A

220 A 263 A 355 A

221 C 264 A 356 A

227 A 265 A 357 A

230 A 266 A 358 A

232 A 267 A 363 A

233 B 268 A 364 A

365 A 403 A 465 A

366 A 404 A 466 A

367 A 406 B 467 C

369 A 407 C 468 A

370 A 408 C 469 A

371 A 409 A 470 A

373 A 410 C 471 A

374 A 421 A 472 A

375 B 422 A 473 A

376 B 431 A 476 A

377 B 432 A 477 A

381 A 433 A 478 C

385 A 434 B 479 A

387 A 437 A 480 A

388 A 439 C 481 A

389 A 442 A 482 A

390 A 443 A 483 A

391 A 444 A 484 A

392 A 447 A 485 A

393 A 448 A 486 A

394 A 449 A 487 A

397 C 450 A 488 A

399 A 451 A 489 A

400 B 452 A 516 A

401 A 453 A 517 A

402 A 455 A 518 A

523 A 563 A 595 A

524 A 564 A 596 B

525 A 565 A 597 A

527 A 566 A 598 B

529 A 567 A 599 B

532 A 568 A 602 B

533 A 569 A 603 C

534 A 570 A 604 A

535 B 571 A 605 B

537 A 572 A 606 A

538 A 573 B 607 A

541 B 574 A 608 A

543 C 575 A 609 A

544 A 576 A 610 A

545 A 577 A 611 A

546 A 578 A 612 A

547 B 579 B 613 A

548 A 580 A 614 A

549 A 584 A 615 A

552 A 585 A 616 A

553 A 586 A 617 A

554 A 587 A 618 A

555 A 588 A 619 B

556 A 589 C 620 A

557 A 592 C 621 A

562 A 594 A 623 A

624 A 654 B 682 A

625 A 655 B 683 A

626 A 656 B 684 A

627 A 657 C 685 B

628 A 658 A 686 B

629 A 659 A 688 C

630 A 660 A 690 A

631 A 661 A 691 A

636 A 662 A 692 A

637 A 663 A 693 A

638 A 664 A 694 A

639 A 665 A 695 A

640 A 666 A 696 A

641 A 667 A 697 A

642 A 668 A 698 A

643 A 669 A 699 A

644 B 670 A 700 A

645 A 671 A 701 A

646 A 672 A 702 C

647 A 673 A 703 A

648 A 674 A 705 A

649 A 675 A 710 A

650 B 677 A 711 C

651 A 678 A 712 A

652 A 680 A 713 A

653 A 681 A 714 A

715 A 750 C 812 A

716 A 751 A 813 A

717 A 754 A 815 A

719 A 755 A 816 A

720 A 756 A 817 A

725 A 757 A 818 A

726 A 758 B 819 A

727 C 759 A 821 A

728 A 760 A 822 A

729 A 761 A 823 A

730 A 763 B 824 B

731 A 764 C 825 A

732 A 766 A 826 A

733 A 767 A 827 A

734 A 768 A 828 A

735 A 769 A 829 A

737 A 772 B 830 A

739 A 773 C 831 B

740 A 774 A 832 B

741 A 775 A 834 C

742 A 777 A 835 A

743 A 778 B 836 A

744 A 795 A 839 B

745 A 800 A 840 C

746 A 801 B 842 A

749 A 802 A 843 B

845 A 851 A 854 B

848 A 852 A 856 B

850 A 853 A 857 B

Experimental example 8

Acaricidal activity against two-spot spider mite. (Tetranychus urticae) adult mites were inoculated on soybean. Mites and plants were sprayed with an emulsion of the compound of the invention (200 ppm). On the eighth day after the administration, the acaricidal activity was judged according to the same standard as in Experimental Example 4.

The results are shown in Table 9.

Table 9

Compound No. Acaricidal Activity Compound No. Acaricidal Activity Compound No. Acaricidal Activity

8 A 52 A 92 A

9 A 53 A 93 A

10 A 54 A 94 A

11 A 55 A 95 A

12 A 56 A 96 A

13 A 57 A 97 A

17 C 58 A 98 A

19 A 59 A 102 A

20 A 60 A 103 A

21 A 65 B 104 A

22 A 66 A 105 A

23 A 67 A 109 A

24 A 68 A 110 A

25 A 69 A 111 A

27 A 71 A 112 A

32 B 72 A 113 A

33 A 73 A 114 A

34 A 74 A 118 A

35 A 85 A 119 A

36 A 86 A 120 A

40 A 87 A 121 A

41 B 88 A 122 A

42 A 89 A 123 A

50 A 90 A 124 A

51 B 91 A 125 A

126 A 159 A 214 A

127 A 160 A 215 A

133 A 161 C 217 A

134 A 164 A 219 A

135 A 166 A 220 A

136 A 167 A 221 A

138 A 169 A 228 A

139 A 170 A 229 A

140 A 171 A 230 A

141 A 193 A 231 A

142 C 194 A 232 B

143 A 195 A 233 A

144 C 197 B 234 A

145 A 198 A 235 A

146 A 199 A 236 A

147 A 200 A 237 A

149 C 201 A 238 A

150 C 202 A 239 A

151 C 203 A 240 A

152 B 204 A 241 A

153 A 205 A 242 A

154 A 206 A 243 A

155 A 207 A 244 A

156 A 211 A 245 A

157 A 212 A 246 A

158 A 213 B 248 A

249 A 334 A 377 C

250 A 335 B 378 C

251 A 337 C 379 C

253 A 342 B 382 A

254 A 343 C 383 A

255 A 344 B 384 A

256 A 350 C 385 B

257 A 353 A 386 A

258 A 354 A 387 A

262 A 355 A 388 A

263 A 356 A 389 A

264 A 357 A 390 A

265 A 358 B 391 A

266 A 363 A 392 A

267 A 364 A 393 A

268 A 365 A 394 A

269 A 366 A 395 A

281 B 367 B 396 B

282 A 369 A 397 B

283 A 370 B 399 A

302 B 371 A 400 A

304 C 372 A 401 A

328 C 373 A 402 A

331 C 374 A 403 A

332 C 375 A 404 A

333 A 376 B 405 A

406 A 451 A 487 A

407 A 452 A 488 A

409 A 453 A 489 A

421 A 454 A 490 A

422 A 455 A 491 A

424 B 465 A 492 A

427 B 466 A 493 A

428 B 467 A 494 A

431 B 468 A 495 A

432 B 469 A 496 A

433 C 470 A 497 A

434 C 471 A 498 A

436 A 472 A 499 A

437 C 473 A 500 A

438 A 474 A 501 A

439 A 476 A 502 A

440 B 477 A 503 A

441 A 478 C 504 A

443 A 479 A 505 A

444 A 480 A 506 A

445 A 481 A 507 A

446 A 482 A 508 C

447 C 483 A 516 C

448 A 484 A 517 A

449 A 485 A 518 A

450 A 486 A 523 A

524 A 558 A 594 A

525 A 559 B 595 A

527 A 561 A 596 C

531 A 562 A 597 B

532 A 563 A 599 B

533 A 564 A 600 B

534 A 565 B 602 A

535 A 566 B 603 A

536 A 567 A 604 A

537 A 568 A 605 A

538 A 569 A 606 A

541 A 570 A 607 B

544 A 571 A 608 A

545 A 572 A 609 A

546 A 573 A 610 A

547 A 574 A 611 A

548 A 575 B 612 A

549 A 576 A 613 A

550 B 577 A 614 A

551 A 578 A 615 A

552 A 579 A 616 A

553 A 580 A 617 A

554 A 584 A 618 A

555 A 585 A 619 A

556 A 587 A 620 A

557 A 588 A 621 A

623 A 656 A 684 A

624 A 657 A 691 A

625 A 658 A 692 A

626 A 659 A 694 A

627 A 660 A 695 C

628 A 661 A 696 A

629 A 662 A 697 A

630 A 663 A 699 A

631 A 664 A 701 A

636 A 665 A 702 A

637 A 666 A 703 A

638 A 667 A 704 B

639 A 668 A 705 A

640 A 669 A 706 A

642 A 670 A 709 A

643 A 671 A 710 A

644 C 672 A 712 A

645 A 673 A 713 A

646 A 674 A 714 B

647 A 675 A 715 A

648 A 677 A 716 A

650 C 678 A 717 A

652 A 680 A 718 C

653 B 681 A 719 A

654 A 682 A 720 A

655 A 683 A 721 A

723 A 756 B 785 B

724 A 757 A 789 C

725 A 758 A 791 C

726 A 759 A 792 B

727 A 760 A 799 B

728 A 761 A 800 B

729 A 762 B 801 B

730 A 763 A 804 A

731 A 764 B 811 C

732 A 765 C 816 A

733 A 766 A 817 A

734 A 767 A 818 A

735 B 768 A 819 A

736 C 769 A 821 A

737 A 770 A 822 A

739 A 771 A 823 A

740 A 772 A 824 A

741 A 773 A 825 B

742 A 774 A 826 A

743 A 775 A 827 A

745 B 776 A 828 A

746 A 777 A 829 A

751 A 778 A 830 A

752 A 779 A 831 A

753 A 780 A 832 A

754 B 782 A 833 A

834 A 840 A 850 A

835 A 842 A 851 A

836 A 843 A 852 A

837 A 844 A 853 A

838 B 845 C 854 A

839 A 848 A 855 A

The following are formulation examples. In these examples, parts are by weight.

Formulation example 1 wettable powder

Compound No. 60 50 parts

Diatomaceous earth and clay mixture 45 parts

Polyoxyethylene nonyl ether 5 parts

The above substances are uniformly mixed and ground to obtain a wettable powder.

Formulation Example 2 Emulsion

Compound No. 154 20 parts

Tetrahydrofuran 20 parts

Xylene 45 parts

Ether and alkylbenzene sulfonate 15 parts

The above substances are uniformly mixed and dissolved to obtain an emulsion.

Formulation example 3 powder

Compound No. 503 4 parts

Mixture of diatomaceous earth, clay and talc 95 parts

Calcium stearate 1 part

The above substances are uniformly mixed and ground to obtain powder.

Formulation Example 4 Granules

Compound No. 237 3 parts

Mixture of bentonite and clay 92 parts

Lignocalcium sulfate 5 parts

The above-mentioned substances are uniformly mixed and ground, and the ground mixture is completely kneaded with an appropriate amount of water and then granulated to obtain granules.

Claims (1)

1, the method for preparing the pyrazole oxime derivative of general formula (I),

(Ⅰ) Wherein R ¹ represents C _1-4 alkyl or phenyl; R ² represents hydrogen, C _1-5 alkyl, C _1-3 haloalkyl or phenyl; R ³ represents hydrogen, C _1-4 alkyl or Phenyl; R ⁴ represents hydrogen, C _2-4 alkylcarbonyl, benzoyl, naphthyl or formula Substituent represented by [wherein X represents hydrogen; halogen; C _1-12 alkyl; C _1-6 alkyl substituted by halogen or hydroxyl; C _3-8 cycloalkyl; Substituted cycloalkyl: C _1-4 alkyl or cyano; C _2-4 haloalkenyl; C _1-6 alkoxy; C _1-4 haloalkoxy; A C _1-3 alkylene dioxo group composed of two adjacent Xs; a substituent of the formula -S(O) _P R ⁵ (wherein R ⁵ represents C _1-10 alkyl, C _1-5 haloalkyl or Phenyl, p represents an integer of 0, 1 or 2); the substituent of formula -COOR ⁶ {wherein R ⁶ represents hydrogen; alkali metal; C _1-10 alkyl; C _1-5 alkane substituted by phenoxy Base; Phenyl}; C _2-6 Alkylcarbonyl; C _2-6 Alkylthiocarbonyl; Formula

Substituents (where R ¹⁰ and R ¹¹ can be the same or different, representing hydrogen or C _1-6 alkyl); formula

Substituents (where R ¹² represents hydrogen or C _1-5 alkyl, R ¹³ represents formyl or C _2-12 alkoxycarbonyl); formula

The substituent (wherein R ¹⁴ represents hydrogen or C _1-4 alkyl; formula

(where R ¹⁵ and R ¹⁶ together form a C _1-4 alkylene group (unsubstituted or may be substituted by a C _1-4 alkyl group), R ¹⁷ represents a C _1-5 alkyl group, and B represents oxygen); Mode

(where R ²¹ , R ²² and R ²³ can be the same or different, and represent C _1-4 alkyl); n represents an integer of 1-5, and when n represents an integer of 2-5, X can be the same or Can be different]; Y represents hydrogen, C _1-6 alkyl, C ₁ -C ₄ haloalkyl, halogen, hydroxyl, C _1-4 alkoxy, C _1-4 haloalkoxy, C _1-3 alkylene di Oxo group, a phenoxy group substituted by trifluoromethyl, a substituent of the formula -S(O) _q R ²⁷ (wherein R ²⁷ represents a C _1-3 alkyl group, and q represents an integer of 0, 1 or 2), C _2-5 alkoxycarbonyl or formula

Substituents (wherein R ²⁸ and R ²⁹ can be the same or different, representing hydrogen or C _1-4 alkyl); Z ¹ represents oxygen or sulfur; Z ² represents oxygen, sulfur or a single bond; Q represents C _1-6 Alkylene, C _1-8 alkylene substituted by halogen or phenyl, C _3-12 alkenylene, C _3-12 haloalkenylene or C _3-6 alkynylene; m represents 1- An integer of 3, when m represents an integer of 2 or 3, Y can be the same or different, and the method is characterized in that A) the compound of general formula (II)

(Ⅱ) Wherein (R ¹ , R ² , R ³ , Y, Z ¹ and m are as defined above, M ¹ represents hydrogen or alkali metal) reacts with the compound of general formula (Ⅲ) Hal-QZ ² -R ⁴ (Ⅲ) (wherein R ⁴ , Q and Z ² are as defined above, and Hal represents halogen); B) the compound of general formula (Ⅵ) (Ⅵ) (wherein R ¹ , R ² , R ³ , Y, Z ¹ and m are as defined above) reacted with a compound of general formula (VII), H ₂ NO-QZ ² -R ⁴ (VII) (wherein R ⁴ , Q and Z ² are as defined above); C) the compound of general formula (Ⅷ)

(Ⅷ) (wherein R ¹ , R ² , R ³ , Y, Q, Z ¹ and m are as defined above, and Hal represents a halogen) reacts with a compound of general formula (IX), M ² -Z ² -R ⁴ (Ⅸ) (where R ⁴ and Z ² are as defined above, M ² represents hydrogen or alkali metal); or D) the compound of general formula (X)

(X) (wherein R ¹ , R ² , R ³ , Y, Z ¹ , Z ² , Q and m are as defined above; X ¹ represents hydrogen or C _1-4 alkyl) reacts with a compound of general formula (Ⅺ) RH (Ⅺ) (Wherein R represents the substituent of formula-OW {wherein W represents alkali metal; C _1-10 alkyl; phenoxy substituted alkyl; phenyl}; formula

Substituents (where R ¹⁰ and R ¹¹ can be the same or different, representing hydrogen or C _1-6 alkyl).