CN1022919C - Process for preparing pyrazoloxime derivatives - Google Patents
Process for preparing pyrazoloxime derivatives Download PDFInfo
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- CN1022919C CN1022919C CN 86108691 CN86108691A CN1022919C CN 1022919 C CN1022919 C CN 1022919C CN 86108691 CN86108691 CN 86108691 CN 86108691 A CN86108691 A CN 86108691A CN 1022919 C CN1022919 C CN 1022919C
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Abstract
A pyrazole oxime derivative represented by the general formula (I) which is useful as an insecticide and fungicide, and each defination is disclosed in the specification.
Description
The present invention relates to pyrazoles 9 oxime derivate preparation method, wherein this pyrazoles 9 oxime derivate is shown in logical formula I.
R wherein
1Represent C
1-4Alkyl or phenyl; R
2Represent H, C
1-5Alkyl, C
1-3Haloalkyl or phenyl; R
3Represent hydrogen, C
1-4Alkyl or phenyl; R
4Represent hydrogen, C
2-4Alkyl-carbonyl, benzoyl, naphthyl or formula
(wherein, X represents hydrogen to the substituting group of representative; Halogen; C
1-12Alkyl; C
1-6By halogen, cyano group, hydroxyl, C
1-5Alkoxyl group or C
2-6The alkyl that carbalkoxy has replaced; C
3-8Cycloalkyl; The cycloalkyl that has been replaced by following 1 to 3 group; C
1-4Alkyl, halogen or cyano group; By halogen, hydroxyl, C
2-4Carbalkoxy or C
2-6The C that alkyl-carbonyl has replaced
2-4Alkenyl; Phenyl; Hydroxyl; C
1-6Alkoxyl group; By halogen or C
2-6The C that carbalkoxy has replaced
2-4Alkoxyl group; Phenoxy group (its can by or not by C
1-3Haloalkyl replaces); Benzyloxy; The C that constitutes by two adjacent Xs
1-3Alkylidene dioxygen is for base; Pyridine oxo base (its not by or by halogen or C
1-3Haloalkyl replaces); The pR of formula-S(O)
5Substituting group (R wherein
5Represent C
1-6Alkyl, C
1-5Haloalkyl or phenyl, p are represented 0,1 or 2 integer); Cyano group; Formyl radical; Nitro; Formula-COOR
6Substituting group (R wherein
6Represent hydrogen; Basic metal; C
1-10Alkyl; By halogen, C
1-4Alkoxyl group, phenoxy group, C
2-4The C that carbalkoxy or Phenoxyphenyl have replaced
1-5Alkyl; C
2-7Alkenyl; C
3-7Alkynyl; C
3-8Cycloalkyl; By C
1-3Alkyl substituted C
3-8Cycloalkyl; Phenyl; Or formula
Substituting group (R wherein
7, R
8And R
9Can be identical also can be different, represent C
1-4Alkyl or C
3-8Cycloalkyl)); C
2-6Alkyl-carbonyl; By cyano group or C
1-6The C that carbalkoxy has replaced
2-6Alkyl-carbonyl; Benzoyl (its not by or can be by halogen or C
1-6Alkyl replaces); C
2-6The alkane thiocarbonyl group; C
3-7The carbalkoxy carbonyl; Formula
Substituting group (R wherein
10And R
11Can be identical or different, represent hydrogen, C
1-6Alkyl or phenyl); The piperidino-(1-position only) carbonyl; Morpholino carbonyl (its not by or can be by one or two C
1-4Alkyl replaces); Formula
Substituting group (R wherein
12Represent hydrogen or C
1-5Alkyl, R
13Represent formyl radical, C
2-12Alkoxy carbonyl, or by halogen or C
1-4The C that alkoxyl group has replaced
2-5Alkoxy carbonyl); Formula
Substituting group (R wherein
14Represent hydrogen, C
1-4, C
2-6Alkoxyalkyl); Formula
Substituting group (R wherein
15And R
16Can be identical also can be different, represent C
1-4Alkyl or can form C jointly
1-4Alkylidene group, R
17Represent C
1-5Alkyl, cyano group or C
2-6Alkoxy carbonyl, B are represented oxygen or sulphur); Formula
Substituting group (R wherein
18Represent hydrogen or C
2-4Alkyl-carbonyl, R
19And R
20Can be identical also can be different, represent hydrogen or C
1-6Alkyl); Formula
Substituting group (R wherein
21, R
22And R
23Can be identical also can be different, represent C
1-4Alkyl); Or formula
Substituting group (R wherein
24, R
25And R
26Can be identical also can be different, represent C
1-4Alkyl); N represents the integer of 1-5, when n represents the integer of 2-5, X can be identical also can be different); Y represents hydrogen, C
1-6Alkyl, C
1-4Haloalkyl, halogen, hydroxyl, C
1-4Alkoxyl group, C
1-4Halogenated alkoxy, C
1-3Alkylene dioxo base, phenoxy group (be not substituted or can be replaced), the qR of formula-S(O) by trifluoromethyl
27Substituting group (R wherein
27Represent C
1-3Alkyl, q are represented 0,1 or 2 integer), hydroxycarbonyl group, C
2-5Carbalkoxy or formula
Substituting group (R wherein
28And R
29Can be identical or different, represent hydrogen, C
1-4Alkyl or benzyl (are not substituted or can be by C
2-6Carbalkoxy replaces); Z
1Represent oxygen or sulphur; Z
2Represent oxygen, sulphur or singly-bound; Q represents C
1-8Alkylidene group, the C that has been replaced by halogen or phenyl
1-8Alkylidene group, C
3-12Alkenylene, C
3-12Halo alkenylene or C
3-6Alkynylene; When m represents 2 or 3 integer, Y can be identical also can be different.
Used in this application noun " alkyl, alkylidene group, alkenylene and alkynylene " is meant alkyl, alkylidene group, alkenylene and the alkynylene of straight or branched respectively.Noun " halogen " refers to halogen such as fluorine, and bromine, chlorine etc., noun " haloalkyl " refer to the alkyl that replaced by 1 or more a plurality of identical or different halogen atom.
With the represented compound of the logical formula I of front is the novel cpd of not addressing in the document.For belonging to lepidopterous insect such as small cabbage moth, lopper worm, prodenia litura, striped rice borer etc. and belonging to insect such as Nilaparvata lugen (brown planthopper), black peach aphid etc. and the mite class of Hemiptera, they have good insecticidal action.In addition, for the disease and pests of vegetables, fruit tree, flowers and plants and ornamental plant etc. such as rice blast, Powdery Mildew, oidium, crown rust, leaf blight, shell rot, purple rust etc., they also have good germicidal action.
In compound of the present invention, be used as sterilant specially and acaricidal compound is recited in down:
4-((1,3-dimethyl-5-phenoxy group pyrazoles-4-yl) methene amido oxygen methyl) t-butyl perbenzoate
4-(the 5-(4-fluorophenoxy) and-1,3-dimethyl-pyrazoles-4-yl } methene amido oxygen methyl) t-butyl perbenzoate
4-((1,3-dimethyl-5-phenoxy group pyrazoles-4-yl) methene amido oxygen methyl) phenylformic acid tert-pentyl ester
4-(1,3-dimethyl-5-phenoxy group pyrazoles-4-yl) methene amido oxygen methyl) phenylformic acid cyclohexyl
4-((1,3-dimethyl-5-phenoxy group pyrazoles-4-yl) methene amido oxygen methyl) phenylformic acid 1-methyl cyclohexane ester
4-((1,3-dimethyl-5-phenoxy group pyrazoles-4-yl) methene amido oxygen methyl) phenylformic acid-2-chloromethyl-2-propyl ester
4-((1-methyl-5-phenoxy group-3-trifluoromethyl pyrazol-4-yl) methene amido oxygen methyl) phenylformic acid tert-pentyl ester
1,3-dimethyl-5-phenoxy group pyrazolyl-4-carbonyl aldoxime neighbour-4-tertiary butyl benzyl oxide
1,3-dimethyl-5-phenoxy group pyrazolyl-4-carbonyl aldoxime neighbour-4-(1-cyano group cyclopentyl) benzyl oxide
1,3-dimethyl-5-phenoxy group pyrazolyl-4-carbonyl aldoxime neighbour-4-(2,2-two chloro-1-methyl cyclopropyl) benzyl oxide
1,3-dimethyl-5-phenoxy group pyrazolyl-4-carbonyl aldoxime neighbour-4-trimethyl silyl phenmethyl ether
1,3-dimethyl-5-phenoxy group pyrazolyl-4-carbonyl aldoxime neighbour-4-(1,1,2,2-tetrafluoro oxyethyl group) phenmethyl ether
1,3-dimethyl-5-phenoxy group pyrazolyl-4-carbonyl aldoxime neighbour-4-tert.-butoxy phenmethyl ether
1,3-dimethyl-5-phenoxy group pyrazolyl-4-carbonyl aldoxime neighbour-4-(seven fluoropropyl sulphur) phenmethyl ether
1,3-dimethyl-5-phenoxy group pyrazolyl-4-carbonyl aldoxime neighbour-4-(seven fluoropropyl sulfinyls) phenmethyl ether
1,3-dimethyl-5-phenoxy group pyrazolyl-4-carbonyl aldoxime neighbour-4-(1,1,2,2-tetrafluoro ethyl sulphur) phenmethyl ether
N, N-di-isopropyl 4-((1,3-dimethyl-5-phenoxy group pyrazoles-4-yl) methene amido oxygen methyl) benzamide
Tertiary butyl 4-((1,3-dimethyl-5-phenoxy group pyrazoles-4-yl) methene amido oxygen methyl) phenyl ketone
2-sec.-propyl-2-(4-{ (1,3-dimethyl-5-phenoxy group pyrazoles-4-yl) methene amido oxygen methyl } phenyl)-1, the 3-dioxolane
2-sec.-propyl-2-(4-{ (1,3-dimethyl-5-phenoxy group pyrazoles-4-yl) methene amido oxygen methyl } phenyl)-1, the 3-dithiolane
N-4-((1,3-dimethyl-5-phenoxy group pyrazoles-4-yl) methene amido oxygen methyl)-phenyl-N-ethyl carbamic acid tert-butyl ester
1,3-dimethyl-5-phenoxy group pyrazolyl-4-carbonyl aldoxime neighbour-2-(4-tertiary butyl phenoxy group) ether
The compound that is used as sterilant specially also is recited in down:
4-((1,3-dimethyl-5-phenoxy group pyrazoles-4-yl)-methene amido oxygen methyl) isopropyl benzoate
4-(the 5-(4-fluorophenoxy) and-1,3-dimethyl pyrazole-4-yl }-methene amido oxygen methyl) isopropyl benzoate
1,3-dimethyl-5-phenoxy group pyrazoles-4-base carbonyl aldoxime neighbour-4-(methylthio group) phenmethyl ether
1,3-dimethyl-5-phenoxy group pyrazoles-4-base carbonyl aldoxime neighbour-4-(difluoromethyl sulfinyl) phenmethyl ether
4-((1,3-dimethyl-5-phenoxy group pyrazoles-4-yl) methene amido oxygen methyl) benzoyl N, the N-dimethyl benzylamine
N-4-((1,3-dimethyl-5-phenoxy group pyrazoles-4-yl) methene amido oxygen methyl) phenyl-N-ethylidene dicarbamate
5-ethyl-3-(N '-4-{ (1,3-dimethyl-5-phenoxy group pyrazoles-4-yl) methene amido oxygen methyl } phenyl)-the 2-oxazolidone
Can synthesize the compound of representing with logical formula I, for example, can synthesize with following A, B, C and D method with chemical formulation.
Method A:
R wherein
1, R
2, R
3, R
4, Q, Y, Z
1, Z
2, m is identical with the front definition with n, and Hal represents halogen atom, M
1Expression hydrogen atom or alkali metal atom.
The pyrazoles 9 oxime derivate of representing by logical formula I can by the compound of the compound of logical formula II and logical formula III contain or alkali free inert solvent in react and obtain.
Can be used for solvent of the present invention can be any solvent that can not hinder this reaction, and they comprise and resemble alcohols (as Virahol, the trimethyl carbinol, diethylidene glycol), ketone (as acetone, methylethylketone, pimelinketone), ethers (as diethyl ether, diisopropyl ether, tetrahydrofuran (THF), diox, glyme, diglyme), halogenated hydrocarbons (as ethylene dichloride, trichloromethane, tetracol phenixin, tetrachloroethane), arene (as benzene, chlorobenzene, oil of mirbane, toluene), nitrile (as acetonitrile), dimethyl sulfoxide (DMSO), dimethyl formamide and water.These solvents can use or mix use separately.When mixing uses these solvents to carry out two phase reaction, can use phase-transfer catalyst, for example chlorination triethylbenzene ammonium methyl, tricaprylylmethylammchloride chloride etc.
For alkali, can use mineral alkali and organic bases.Inorganic base comprises the carbonate of alkali for example or alkaline-earth metal such as yellow soda ash, salt of wormwood, lime carbonate, sodium bicarbonate etc., the oxyhydroxide of alkali or alkaline-earth metal such as sodium hydroxide, potassium hydroxide, calcium hydroxide etc. and alkali-metal hydride such as lithium hydride, sodium hydride etc.
Organic bases comprises for example diethylamine, triethylamine, pyridine, 4-Dimethylamino pyridine etc.
As for the consumption of used alkali, use the equimolar consumption of representing with logical formula II of compound just enough, but, can use excessive consumption.
For example, can by the following stated method produce logical formula II represented be used for compound of the present invention:
R wherein
1, R
2, R
3, Y, Z
1, m, Hal and M
1Identical with the front definition.
The compound of promptly logical formula II can be reacted in appropriate solvent by the compound of logical formula IV and the compound of general formula (V), the compound of resulting logical formula VI and oxyamine is reacted make.
In all represented compounds of logical formula III, particularly working as Q is methylene radical, Z
2Be singly-bound and R
4When being the phenyl of a replacement, they also are some novel cpds, and these compounds can prepare with the method identical with known compound.
Method B:
R wherein
1, R
2, R
3, R
4, Q, Y, Z
1, Z
2, m is identical with the definition of front with n.
The pyrazoles 9 oxime derivate of representing with logical formula I can be reacted in inert solvent by the compound of the compound of logical formula VI and general formula (VII) and prepare.
The solvent that can be used for this reaction is the ketone solvent in addition that is used for method A.
The compound of general formula (VII) expression can be by known method, for example, prepare in the Hougen Weyl method described in the 1192nd page of " organic chemistry method " (Methoden der Organishen Chemie) the book X/I volume nitrogen compound first part of showing.
Method C:
R wherein
1, R
2, R
3, R
4, Q, Y, Z
1, Z
2, m and n as defined above, M
2Represent hydrogen atom or alkali metal atom.
The pyrazoles 9 oxime derivate of logical formula I can in inert solvent, have by compound the compound of general formula (VIII) and general formula (IX) or alkali-free in the presence of react and make.
Be used in this reaction in solvent and alkali with described in the method A.
Method D:
R wherein
1, R
2, R
3, Q, Y, Z
1, Z
2Identical with m with the definition of front; X
1Represent hydrogen or C
1To C
4Alkyl; R represents Shi-OW, and { wherein W represents basic metal; C
1To C
10Alkyl; By halogen, C
1To C
4Alkoxyl group, phenoxy group, C
2To C
4Alkoxy carbonyl or the alkyl that replaces of phenyl; C
2To C
7Alkenyl; C
3To C
8Cycloalkyl; C
1-C
3The C that replaces of alkyl
3To C
8Cycloalkyl; Phenyl or formula
Substituting group (R wherein
7, R
8, R
9Represent C
1To C
4Alkyl or C
3To C
8Cycloalkyl, the three can be identical, also can be different), formula
Substituting group (R wherein
10And R
11Represent hydrogen, C
1To C
6Alkyl or phenyl, the two can be identical, also can be different); Piperidino-(1-position only); Can by or not by one or two C
1To C
4The morpholinyl that replaces of alkyl; Or C
2To C
6Alkyl sulfide.
Promptly (the pyrazoles 9 oxime derivate a) represented of I can be reacted in containing the inert solvent of dewatering agent by the compound of the compound of general formula (X) and general formula (XI) and prepare by general formula.After being translated into chloride of acid, compound (X) can react with compound (XI).
The solvent that can be used for this reaction can be any solvent that does not hinder this reaction, for example comprises ethers (as Anaesthetie Ether, tetrahydrofuran (THF), diox, glycol ether), halogenated hydrocarbons (as methylene dichloride, trichloromethane, tetracol phenixin), dimethyl sulfoxide (DMSO), dimethyl formamide etc.These solvents can use separately, also can mix use.
To method D, can to the solvent boiling point temperature range, suitably select its temperature of reaction at method A in room temperature.Reaction times is depended on temperature of reaction and level of response, but can suitably select in 1 minute to 48 hours scope.
Because this reaction is a reaction with same mole, so in carrying out reaction process of the present invention, the mol ratio of reagent mole dosage such as is pressed and is used, but the excessive use of wherein a kind of also comparable other kinds.
After reacting completely, required compound can separate with the method for routine, and if necessary, also available recrystallization method, column chromatography separation method etc. are purified.
The pyrazoles 9 oxime derivate of representing with logical formula I has two kinds of isomer, E-isomer and Z-isomer.Promptly comprise this two kinds of isomer within the scope of the present invention, also comprise its mixture.
The representative instance of the pyrazoles oxime of representing with logical formula I is listed in table 1, but this derivative is not limited in these examples.
Annotate 1: the No. 180 compound
1H NMR value (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）
Annotate 2: the No. 299 compounds
1H NMR value (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 compound of the present invention can be with reference to following embodiment, but these embodiment do not limit the present invention.
Embodiment 1
4-((1,3-dimethyl-5-phenoxy group pyrazoles-4-yl) methene amido oxygen methyl) methyl benzoate (No. 16 compound)
With 1 of 2.0 grams (0.00865 mole), 3-dimethyl-5-phenoxy group pyrazoles-4-the bromomethyl-benzoic acid methyl ester of 4-carbonyl aldoxime 1.98 grams (0.00865 mole) and the salt of wormwood of 1.19 grams (0.009 mole) add in 50 milliliters of acetone, and under refluxad heat resulting mixture about 8 hours.After reacting completely, remove acetone, in residuum, add entry then and extract with vinyl acetic monomer with the method for reduction vaporization.Wash the ethyl acetate extraction thing with water and make its drying, remove vinyl acetic monomer with the method for evaporation again, obtain the oily product thus.With silica gel column chromatography purification oily product, obtain 2.0 gram desired products thus.
Productive rate 61%, n
20 D1.5612
Embodiment 2
4-((1,3-dimethyl-5-phenoxy group pyrazoles-4-yl) methene amido oxygen methyl) t-butyl perbenzoate (No. 60 compound)
With 1 of 2.0 grams (0.00855 mole), 3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime is dissolved in 20 milliliters of dimethyl sulfoxide (DMSO), adds the powder potassium hydroxide of 0.65 gram (0.0116 mole) then, stirs the gained mixture about 30 minutes down at 30 ℃.The 4-bromo methyl acid tert-butyl ester that in this solution, adds 2.32 grams (0.00855 mole), and under 50 ℃ to 60 ℃, reacted 1 hour.After reacting completely, add entry, extract with vinyl acetic monomer then to reaction soln.Wash the ethyl acetate extraction thing with water and carry out drying, with method of evaporating vinyl acetic monomer is removed then, obtain coarse crystallization thus.This crystal through recrystallize, can obtain the required compound of 2.4 grams in methyl alcohol.
101.7 ℃ of productive rate 67.0% fusing points
Embodiment 3
2-(the 5-(4-chlorophenoxy) and-1,3-dimethyl-pyrazoles-4-yl } methene amido oxygen methyl) methyl benzoate (No. 3 compound)
5-(4-chlorophenoxy with 2.0 grams (0.00755 mole))-1,3-dimethyl-pyrazoles-4-carbonyl aldoxime is dissolved in 20 milliliters the dimethyl formamide, add the powdered sodium hydroxide of 0.5 gram (0.0125 mole) then, fully stir resulting mixture.In this solution, add the 2-bromomethyl-benzoic acid methyl ester of 1.73 grams (0.00755 mole), and under 70 ℃ to 80 ℃, reacted 5 hours.After reacting completely, in reaction soln, add entry, with vinyl acetic monomer this solution is extracted then, wash the ethyl acetate extraction thing with water and carry out drying, remove vinyl acetic monomer with method of evaporating then, obtain the oily product thus.Separate this oily product with silica gel column chromatography, obtain the required compound of 2.0 grams thus.
Productive rate 64.0% n
20 D1.5788
Embodiment 4
4-((1,3-dimethyl-5-phenyl sulfo-pyrazoles-4-yl) methene amido oxygen methyl) isopropyl benzoate (No. 174 compound)
With 1 of 3.0 grams (0.0121 mole), 3-dimethyl-5-phenyl sulfo-pyrazoles-4-carbonyl aldoxime, 2.57 in the methylethylketone that the yellow soda ash adding of the 4-chloromethyl benzoic acid isopropyl ester of gram (0.0121 mole) and 2.8 grams (0.026 mole) is 50 milliliters, under refluxad heated resulting mixture 5 hours.After reacting completely, under reduced pressure, remove methylethylketone, and in residuum, add entry, extract with vinyl acetic monomer with method of evaporating.Wash the ethyl acetate extraction thing with water and carry out drying, remove vinyl acetic monomer with method of evaporating then, obtain the oily product thus.Separate this oily product with silica gel column chromatography, obtain 3.0 gram required compounds thus.
Productive rate 59.0% n
20 D1.5821
Embodiment 5
4-(1-(1,3-dimethyl-5-phenoxy group pyrazoles-4-yl) ethyleneimino oxygen methyl) t-butyl perbenzoate (No. 166 compound).
Methyl 1 with 2.0 grams (0.00816 mole), 3-dimethyl-5-phenoxy group-pyrazoles-4-base ketoxime, 2.2 the salt of wormwood of the 4-bromo methyl acid tert-butyl ester of gram (0.00816 mole) and 4.0 grams (0.028 mole) adds in 50 milliliters of acetonitriles, under refluxad heats resulting mixture 5 hours.After reacting completely, under reduced pressure, remove acetonitrile, in residuum, add entry then and extract, wash the ethyl acetate extraction thing with water and carry out drying, remove vinyl acetic monomer, obtain the coarse crystallization body thus with method of evaporating with vinyl acetic monomer with method of evaporating.This xln obtains 2.8 gram required compounds thus through the methyl alcohol recrystallize.
94.4 ℃ of productive rate 79.0% fusing points
Embodiment 6
4-(the 5-(4-fluorinated phenoxy) and-1,3-dimethyl pyrazole-4-yl } methene amido oxygen methyl) phenylformic acid cyclohexyl (No. 119 compound)
5-(4-fluorinated phenoxy with 2.0 grams (0.008 mole))-1, the powdered sodium hydroxide of 3-dimethyl pyrazole-4-carbonyl aldoxime and 0.5 gram (0.0125 mole) adds in 50 milliliters of dimethyl sulfoxide (DMSO), stirs this gained mixture 30 minutes.In this solution, add the 4-bromo methyl acid cyclohexyl of 2.38 grams (0.008 mole), and under 70 ℃ to 80 ℃, reacted 6 hours.After reacting completely, in reaction soln, add entry, then with this solution of ethyl acetate extraction.Wash the ethyl acetate extraction thing with water and carry out drying, remove vinyl acetic monomer with method of evaporating again, obtain the oily product thus.Separate this oily product with silica gel column chromatography, obtain 3.0 gram required compounds thus.
Productive rate 80.0% n
20 D1.5863
Embodiment 7
4-((1-methyl-5-phenoxy group pyrazoles-4-yl) methene amido oxygen methyl)) t-butyl perbenzoate (No. 174 compound)
1-methyl-5-phenoxy group pyrazoles-4-carbonyl the aldehyde of 1.0 grams (0.0049 mole) and the 4-amino oxygen tolyl acid tertiary butyl ester of 1.1 grams (0.0049 mole) are added in 20 milliliters of ethanol, under refluxad heat this gained mixture and react.After reacting completely, remove ethanol, in residuum, add entry then and extract with vinyl acetic monomer with method of evaporating.Wash this ethyl acetate extraction thing with water and carry out drying, remove vinyl acetic monomer with method of evaporating again, obtain the oily product thus.Separate this oily product with silica gel column chromatography, obtain 1.6 gram required compounds thus.
NMR（CDCl
3，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）。
Embodiment 8
4-(the 5-(4-fluorinated phenoxy) and-1,3-dimethyl pyrazole-4-yl } methene amido oxygen methyl) phenylformic acid 2-phenoxy group ethyl ester (No. 142 compound)
5-(4-fluorinated phenoxy with 2.0 grams (0.008 mole))-1,3-dimethyl pyrazole-4-carbonyl aldoxime is dissolved in 20 milliliters of methyl-sulphoxides, the powdered potassium hydroxide that adds 0.65 gram (0.0116 mole) then stirred this gained mixture 30 minutes down at 30 ℃.The 4-chloromethyl benzoic acid 2-phenoxy group ethyl ester of 2.5 grams (0.00865 mole) is added in the solution, under 50 ℃ to 60 ℃, reacted 1 hour.After reacting completely, in reaction soln, add entry, extract this reaction soln with the aldehydic acid ethyl ester then.Wash this ethyl acetate extraction thing with water and carry out drying, remove vinyl acetic monomer, obtain the oily product thus with method of evaporating.Separate this oily product with silica gel column chromatography, obtain 3.0 gram required compounds thus.
Productive rate 75.0% n
20 D1.5655
Embodiment 9
4-((1,3-dimethyl-5-phenoxy group pyrazoles-4-yl) methene amido oxygen) phenylformic acid phenyl ester (No. 161 compound)
4-((1 with 1.0 grams (0.0027 mole), 3-dimethyl-5-phenoxy group pyrazol-4-ylmethylene amino oxygen methyl) triphenylphosphine of the phenol of phenylformic acid, 0.25 gram (0.0027 mole) and 0.7 gram (0.0027 mole) adds in 50 milliliters of ether, stirs this gained mixture.The diethyl azodiformate of 0.47 gram (0.0027 mole) is added this solution, and under refluxad heated resulting solution 3 hours.After reacting completely, leach ether layer, and remove ether, obtain the oily product thus with method of evaporating.Separate this oily product with silica gel column chromatography and obtain 0.9 gram required compound thus.
Productive rate 76.0% n
20 D1.5656
Embodiment 10
4-((1,3-dimethyl-5-phenoxy group pyrazoles-4-yl) methene amido oxygen methyl) phenylformic acid (No. 14 compound)
4-((1,3-dimethyl-5-phenoxy group pyrazoles-4-yl) methene amido oxygen the methyl)-methyl benzoate of 3 grams (0.0079 mole) are dissolved in 20 ml methanol and 0.24 gram lithium hydroxide is added in the solution with 5 ml waters.At room temperature reacted then 2 hours.After reacting completely, remove methyl alcohol with method of evaporating, add entry after, make the solution acidifying with spirit of salt, produce sedimentary crystal.Filter and collect this crystal, obtain 2 gram required compounds thus.
183.3 ℃ of productive rate 70% fusing points
Embodiment 11
4-((1,3-dimethyl-5-phenoxy group pyrazoles-4-yl) methene amido oxygen methyl) Sodium Benzoate (No. 15 compound)
4-((1,3-dimethyl-5-phenoxy group pyrazoles-4-yl) the methene amido oxygen methyl) phenylformic acid of 1.0 grams (0.0027 mole) and the sodium hydroxide of 0.7 gram (0.0028 mole) are added in 10 ml waters, stirred this gained mixture 2 hours.After reacting completely, under reduced pressure, remove and anhydrate, obtain the required compound of quantitative yield thus with method of evaporating.
Fusing point＞300 ℃
Embodiment 12
1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime O-phenmethyl ether (No. 181 compound)
With 1 of 2.0 grams (0.00866 mole), the salt of wormwood of the bromotoluene of 3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime, 1.5 grams (0.0087 mole) and 2.0 grams (0.0145 mole) is dissolved in 50 milliliters of acetone, and under refluxad heats this gained solution 7 hours.After reacting completely, under reduced pressure, remove acetone, add entry then, and extract with vinyl acetic monomer with method of evaporating.Wash the ethyl acetate extraction thing with water and carry out drying, remove vinyl acetic monomer with method of evaporating then, obtain the oily product thus.Separate this oily product with silica gel column chromatography, obtain 2.6 gram required compounds thus.
Productive rate 93.0% n
20 D1.5517
Embodiment 13
The 5-(4-chlorophenoxy)-1,3-dimethyl pyrazole-4-carbonyl aldoxime O-4-three fluoro methylbenzene methyl ethers (No. 195 compound)
5-(chlorophenoxy with 2.0 grams (0.0075 mole))-1,3-dimethyl pyrazole-4-carbonyl aldoxime is dissolved in 40 milliliters of tetrahydrofuran (THF)s, at room temperature adds the sodium hydride of 0.19 gram (0.0079 mole) then, stirs this gained solution.The 4-trifluoromethylbenzene monobromomethane that adds 1.7 grams (0.0071 mole) then then under refluxad makes its heating 3 hours.After reacting completely, in reaction soln, add 100 ml waters, extract with vinyl acetic monomer then.Wash the ethyl acetate extraction thing with water and carry out drying, remove vinyl acetic monomer, obtain the oily product thus with method of evaporating.Separate this oily product with silica gel column chromatography, obtain 2.7 gram required compounds thus.
Productive rate 85.0% n
20 D1.5539
Embodiment 14
1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime O-4-(1-cyano group cyclopropyl) phenmethyl ether (No. 199 compound)
With 1 of 2.0 grams (0.0086 mole), 3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime is dissolved in 30 milliliters the dimethyl formamide, and the sodium hydroxide (being dissolved in 5 ml waters) of 0.5 gram (0.0125 mole) is added wherein.After the continuously stirring 30 minutes, with the 1-(4-2-bromomethylphenyl of 2.0 grams (0.0086 mole)) cyclopropane-1-nitrile adds this solution, and reaction 3 hours under 60 ℃ to 70 ℃ conditions.After reacting completely, in reaction soln, add 100 ml waters, extract with vinyl acetic monomer then.Wash the ethyl acetate extraction thing with water and carry out drying, remove vinyl acetic monomer with method of evaporating again, obtain the oily product thus.Separate this oily product with silica gel column chromatography, obtain 2.8 gram required compounds thus.
109.1 ℃ of productive rate 84.0% fusing points
Embodiment 15
1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime 4-tert.-butylbenzene methyl ether (No. 205 compound)
With 1 of 2.0 grams (0.0086 mole), 3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime is dissolved in 20 milliliters of dimethyl sulfoxide (DMSO), after the potassium hydroxide that adds 1.0 grams (0.0178 mole), at room temperature stirs this gained solution 30 minutes.4-tert.-butylbenzene methyl chloride with 1.5 grams (0.0086 mole) adds this solution again, and reacts 3 hours under 50 ℃ to 60 ℃ conditions.After reacting completely, 100 ml waters are added reaction soln extract with vinyl acetic monomer then.Wash this ethyl acetate extraction thing with water and carry out drying, remove vinyl acetic monomer with method of evaporating then, obtain the oily product thus.Separate this oily product with silica gel column chromatography, obtain 2.4 gram required compounds thus.
Productive rate 74.0% n
20 D1.5402
Embodiment 16
The 5-(4-chlorophenoxy)-1-methylpyrazole-4-carbonyl aldoxime O-phenmethyl ether (No. 279 compound)
5-(4-chlorophenoxy with 2.0 grams (0.0092 mole))-1-methylpyrazole-4-carbonyl aldoxime, 1.5 the salt of wormwood of the bromotoluene of gram (0.0092 mole) and 2.0 grams (0.0145 mole) are dissolved in 50 milliliters the acetonitrile, under refluxad heat this gained solution 9 hours.After reacting completely, 100 ml waters are added in this reaction soln, extract with vinyl acetic monomer then.Wash this ethyl acetate extraction thing with water and carry out drying, remove vinyl acetic monomer, obtain the oily product thus with method of evaporating.Separate this oily product with silica gel column chromatography, obtain 2.2 gram required compounds thus.
Productive rate 78.0% n
20 D1.5933
Embodiment 17
1,3-dimethyl-5-phenoxy group pyrazoles-4-ylmethyl ketoxime O-4-phenylcyclohexane methyl ether (No. 283 compound)
With 1 of 2.0 grams (0.0040 mole), 3-dimethyl-5-phenoxy group pyrazoles-4-base-methyl ketoxime is dissolved in 30 milliliters of dioxs, and adding 0.1 restrains the sodium borohydride of (0.0042 mole) and fully stirs in this solution.After 30 minutes, the 1.6 4-cyclohexyl benzyl bromines that restrain (0.0038 mole) are added this reaction soln, under refluxad heated 5 hours.After reacting completely, in reaction soln, add 100 ml waters and extract with vinyl acetic monomer.Wash this ethyl acetate extraction thing with water and carry out drying, remove vinyl acetic monomer, obtain the oily product thus with method of evaporating.Separate this oily product with silica gel column chromatography, obtain 1.2 gram required compounds thus.
Productive rate 72.0% n
20 D1.5775
Embodiment 18
5-(4-chloro-phenyl-sulphur)-1,3-dimethyl pyrazole-4-carbonyl aldoxime O-phenmethyl ether (No. 290 compound)
With the 5-(4-chloro-phenyl-sulphur-1 of 2.0 grams (0.0071 mole), 3-dimethyl pyrazole-4-carbonyl aldoxime is dissolved in 20 milliliters of dimethyl sulfoxide (DMSO), and adds the 5 ml water solution that contain 0.5 gram (0.009 mole) potassium hydroxide in this solution.After fully stirring, add the benzyl chloride of 0.9 gram (0.0071 mole), and under 60 ℃ to 70 ℃ conditions, reacted 2 hours.After reacting completely, in reaction soln, add 100 ml waters and extract with vinyl acetic monomer.Wash the ethyl acetate extraction thing with water and carry out drying, remove vinyl acetic monomer, obtain the oily product thus with method of evaporating.Separate this oily product with silica gel column chromatography, obtain 2.3 gram required compounds thus.
Productive rate 87.0% n
20 D1.5562
Embodiment 19
5-(4-methoxyl group phenoxy group)-1,3-dimethyl pyrazole-4-carbonyl aldoxime O-4-(1-cyano group cyclopentyl)-phenmethyl ether (No. 238 compound)
With 1 of 2.0 grams (0.0081 mole), 3-dimethyl-5-(4-methoxyl group phenoxy group) pyrazoles-4-carbonyl aldehyde is dissolved in 50 milliliters of ethanol, and add 1.7 the gram (0.0081 mole) neighbour-4(1-cyano group cyclopentyl) the phenmethyl azanol, then under 50 ℃ to 60 ℃ condition the reaction 3 hours.After reacting completely, under reduced pressure, remove ethanol, add entry then and extract with vinyl acetic monomer with method of evaporating.Wash the ethyl acetate extraction thing with water and carry out drying, remove vinyl acetic monomer, obtain the oily product thus with method of evaporating.Separate this oily product with silica gel column chromatography, obtain 3.0 gram required compounds thus.
Productive rate 83.0% n
20 D1.5632
Embodiment 20
1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime O-4-(2,2-dibromo vinyl) phenmethyl ether (No. 262 compound)
With 1 of 2.0 grams (0.0093 mole), 3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldehyde is dissolved in 50 ml methanol, the O-4-(2 that in this solution, adds 2.8 grams (0.0091 mole), the 2-dibromo vinyl) the phenmethyl azanol, and under refluxad heated 3 hours.After reacting completely, under reduced pressure, remove methyl alcohol, add entry then and extract with vinyl acetic monomer with method of evaporating.Wash this ethyl acetate extraction thing with water and carry out drying, remove vinyl acetic monomer, obtain the oily product thus with method of evaporating.Separate this oily product with silica gel column chromatography, obtain 3.5 gram required compounds thus.
109.3 ℃ of productive rate 76.0% fusing points
Embodiment 21
1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime O-4-fluorobenzene methyl ether (No. 305 compound)
With 1 of 1.0 grams (0.0043 mole), 3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime is dissolved in 20 milliliters of dimethyl sulfoxide (DMSO), and after adding the powdered potassium hydroxide of 0.3 gram (0.0053 mole), stirs this gained solution.4-fluoro bromotoluene to this reaction soln adding 0.81 gram (0.0043 mole) at room temperature reacted 3 hours.After reacting completely, in this reaction soln, add 200 ml waters, and extract with vinyl acetic monomer.Wash this ethyl acetate extraction thing with water and carry out drying, remove vinyl acetic monomer, obtain the oily product thus with method of evaporating.Separate this oily product with silica gel column chromatography, obtain 1.3 gram desired products thus.
Productive rate 89% n
20 D1.5681
Embodiment 22
The 5-(4-chlorophenoxy)-1,3-dimethyl pyrazole-4-carbonyl aldoxime O-2-chlorophenylmethyl ether (No. 309 compound)
5-(4-chlorophenoxy with 1.0 grams (0.0038 mole))-1,3-dimethyl pyrazole-4-carbonyl aldoxime, 0.78 the salt of wormwood of the 2-chlorine bromotoluene of gram (0.0038 mole) and 1.0 grams (0.0072 mole) adds in 20 milliliters of acetonitriles, under refluxad heats this gained mixture 6 hours.After reacting completely, under reduced pressure, remove acetonitrile, add entry then and extract with vinyl acetic monomer with method of evaporating.Wash this ethyl acetate extraction thing with water and carry out drying, remove vinyl acetic monomer, obtain the oily product thus with method of evaporating.Separate this oily product with silica gel column chromatography, obtain 1.2 gram required compounds thus.
Productive rate 81% n
20 D1.5760
Embodiment 23
The 5-(4-chlorophenoxy)-1, phenmethyl ether (No. 322 compound) 3-dimethyl pyrazole-4-carbonyl aldoxime O-4-(4-trifluoromethyl-phenoxy group)
5-(4-chlorophenoxy with 1.0 grams (0.0038 mole))-1,3-dimethyl pyrazole-4-carbonyl aldoxime, 1.1 the 4-(4-4-trifluoromethylphenopendant of gram (0.0038 mole)) yellow soda ash of benzyl chloride and 0.8 gram (0.076 mole) adds in 40 milliliters of acetone, under refluxad heats this gained mixture 8 hours.After reacting completely, under reduced pressure, remove acetone, add entry then and extract with vinyl acetic monomer with method of evaporating.Wash this ethyl acetate extraction thing with water and carry out drying, remove vinyl acetic monomer, obtain the oily product thus with method of evaporating.Separate this oily product with silica gel column chromatography, obtain 1.4 gram required compounds thus.
97.8 ℃ of productive rate 72% fusing points
Embodiment 24
1,3-dimethyl-5-phenoxy group pyrazoles-4-ylmethyl ketoxime O-4-trimethyl silyl phenmethyl ether (No. 334 compound)
With 1 of 1.0 grams (0.0041 mole), 3-dimethyl-5-phenoxy group pyrazoles-4-base-methyl ketoxime is dissolved in 20 milliliters of dimethyl sulfoxide (DMSO), and after the potassium hydroxide that adds 0.3 gram (0.0053 mole), stirs this gained solution.In this gained solution, add the 4-trimethyl silyl bromotoluene of 1.0 grams (0.0041 mole), at room temperature reacted 4 hours.After reacting completely, in this reaction soln, add 200 ml waters and extract with vinyl acetic monomer.Wash this ethyl acetate extraction thing with water and carry out drying, remove vinyl acetic monomer, obtain the oily product thus with method of evaporating.Separate this oily product with silica gel column chromatography, obtain 1.5 gram required compounds thus.
61.2 ℃ of productive rate 92% fusing points
Embodiment 25
1,3-dimethyl-5-phenoxy group pyrazoles-4-base ethyl ketoxime O-4-(1,1,2,2-tetrafluoro oxyethyl group) phenmethyl ether (No. 354 compound)
With 1 of 1.0 grams (0.0035 mole), the 4-(1 of the sodium salt of 3-dimethyl-5-phenoxy group pyrazoles-4-base-ethyl ketoxime and 1.0 grams (0.0035 mole), 1,2,2-tetrafluoro oxyethyl group) bromotoluene adds in 50 milliliters of acetone, heats this gained mixture and it is reacted in 5 hours.After reacting completely, under reduced pressure, remove acetone, add entry then and extract with vinyl acetic monomer with method of evaporating.Wash this ethyl acetate extraction thing with water and carry out drying, remove vinyl acetic monomer, obtain the oily product thus with method of evaporating.Separate this oily product with silica gel column chromatography, obtain 1.3 gram required compounds thus.
Productive rate 76% n
20 D1.5252
Embodiment 26
5-(4-methoxyl group phenoxy group)-1,3-dimethyl pyrazole-4-carbonyl aldoxime O-4-tert.-butoxy phenmethyl ether (No. 366 compound)
5-(4-methoxyl group phenoxy group with 1.0 grams (0.0038 mole))-1,3-dimethyl-pyrazoles-4-carbonyl aldoxime is dissolved in 30 milliliters of tetrahydrofuran (THF)s, and adds 0.092 gram sodium hydride so that carry out the building-up reactions of the sodium salt of above-mentioned oxime.The 4-tert.-butoxy bromotoluene that adds 0.92 gram (0.0038 mole) in this solution, reaction is 5 hours under 50 ℃ to 60 ℃ conditions.After reacting completely, in reaction soln, add 200 ml waters, extract with vinyl acetic monomer then.Wash this ethyl acetate extraction thing with water and carry out drying, remove vinyl acetic monomer, obtain the oily product thus with method of evaporating.Separate this oily product with silica gel column chromatography, obtain 1.3 gram desired products thus
Productive rate 80% n
20 D1.5653
Embodiment 27
The 5-(4-fluorophenoxy)-1,3-dimethyl pyrazole-4-carbonyl aldoxime O-3,4-methylenedioxy benzene methyl ether (No. 374 compound)
5-(4-fluorophenoxy with 1.0 grams (0.0040 mole))-1,3-dimethyl pyrazole-4-carbonyl aldoxime is dissolved in 20 milliliters of dimethyl formamides, and behind the sodium hydroxide that adds 0.2 gram (0.005 mole), stirs this gained solution 30 minutes.In this reaction soln, add 3 of 0.86 gram (0.005 mole), 4-Methylenedioxybenzyl bromine, and under 40 ℃ to 50 ℃ conditions, reacted 3 hours.After reacting completely, in reaction soln, add 200 ml waters, extract with vinyl acetic monomer then.Wash the ethyl acetate extraction thing with water and carry out drying, remove vinyl acetic monomer, obtain the oily product thus with method of evaporating.Separate this oily product with silica gel column chromatography, obtain 1.1 gram required compounds thus.
Productive rate 72% n
20 D1.5750
Embodiment 28
5-(4-methoxyl group phenoxy group)-1,3-dimethyl pyrazole-4-carbonyl aldoxime O-4-methyl sulphonyl phenmethyl ether (No. 401 compound)
5-(4-methoxyl group phenoxy group with 1.0 grams (0.0038 mole))-1, the 4-methyl sulphonyl benzyl chloride of 3-dimethyl pyrazole-4-carbonyl aldoxime and 0.79 gram (0.0038 mole) is dissolved in 30 milliliters of tetrahydrofuran (THF)s.In this solution, add 1 of 0.6 gram (0.0039 mole), the two heterocycles (5.4.0) of 8-phenodiazine-7-undecylene, and under 40 ℃ to 50 ℃ conditions, reacted 5 hours.After reacting completely, in this reaction soln, add 200 ml waters and extract with vinyl acetic monomer.Wash this ethyl acetate extraction thing with water and carry out drying, remove vinyl acetic monomer, obtain the oily product thus with method of evaporating.Separate this oily product with silica gel column chromatography, obtain 1.2 gram desired products thus.
Productive rate 74% n
20 D1.5866
Embodiment 29
1,3-dimethyl-5-phenoxy group pyrazoles-4-base phenyl ketoxime O-4-difluoromethyl sulphur phenmethyl ether (No. 426 compound)
With 1 of 1.0 grams (0.0033 mole), 3-dimethyl-5-phenoxy group pyrazoles-4-base-phenyl ketoxime, 0.82 the salt of wormwood of the 4-difluoromethyl sulphur bromotoluene of gram (0.0033 mole) and 1.0 grams (0.0072 mole) adds in 50 milliliters of acetone, and this gained mixture heating up was reacted in 6 hours.After reacting completely, under reduced pressure, remove acetone, add entry then and extract with vinyl acetic monomer with method of evaporating.Wash this ethyl acetate extraction thing with water and carry out drying, remove vinyl acetic monomer, obtain the oily product thus with method of evaporating.Separate this oily product with the silica gel column chromatography separation method, obtain 1.4 gram required compounds thus.
Productive rate 86% n
20 D1.5917
Embodiment 30
The 5-(2-fluorophenoxy)-1,3-dimethyl pyrazole-4-carbonyl aldoxime O-4-(1,1,2,2-tetrafluoro ethylmercapto group) benzylic ether (compound number 467)
1.1 gram (0.0043 mole) 5-(2-fluorophenoxy)-1,3-dimethyl pyrazole-4-carbonyl aldehyde is dissolved in 30 milliliters of ethanol, adds 1.1 gram (0.0043 mole) O-(4-(1,1,2,2-tetrafluoro ethylmercapto group) benzyls) oxyamine.Be reflected at 50～60 ℃ and carried out 2 hours, after reaction is finished, remove ethanol under reduced pressure, add entry then, use chloroform extraction again.Dry chloroform extracted solution removes chloroform under reduced pressure and obtains an oily product.This oily product obtains the desired compound of 1.3 grams by silica gel column chromatography.
Productive rate 64% n
20 D1.5462
Embodiment 31
1,3-dimethyl-5-phenoxy group pyrazoles-4-ylmethyl ketoxime O-4-seven fluorine rosickyite base benzylic ethers (compound number 494)
1.0 gram (0.0043 mole) 4-acetyl-1,3-dimethyl-5-phenoxy group pyrazoles and 1.4 gram (0.0043 mole) O-(4-seven fluorine rosickyite base benzyls) oxyamine is added in 30 ml methanol mixture heating up reaction that obtains 5 hours.After reacting completely, remove methyl alcohol under reduced pressure, add entry after, use chloroform extraction.Dry chloroform extracted solution removes chloroform then under reduced pressure and obtains the oily product.The oily product obtains the 1.4 gram compounds of wanting by silica gel column chromatography.
Productive rate 60% n
20 D1.5217
Embodiment 32
4-((1,3-dimethyl-5-phenoxy group pyrazoles-4-yl) methylene radical ammonia oxygen methyl) thiobenzoic acid S-ethyl ester
1.0 gram (0.0043 mole) 1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime is dissolved in 20 milliliters of dimethyl sulfoxide (DMSO), adds 0.3 gram (0.0053 mole) potassium hydroxide powder then, mixes solution.Add 0.92 gram (0.0043 mole) 4-chloromethyl thiobenzoic acid S-ethyl ester in this solution, being reflected at room temperature carried out 3 hours, after reacting completely, 200 ml waters are added reaction back ethyl acetate extraction, acetic acid ethyl acetate extract washes with water, dry then, steaming removes ethyl acetate and obtains the oily product.This oily product by silica gel column chromatography purify 1.4 the gram products of wanting.
Productive rate 80% n
20 D1.5889
Embodiment 33
N-tertiary butyl 4-(5-(4-methoxyl group phenoxy group) and-1,3-dimethyl pyrazole-4-yl } benzylidene amino oxygen methyl)-benzamide (compound number 525)
1.0 gram (0.0038 mole) 5-(4-methoxyl group phenoxy group)-1,3-dimethyl pyrazole-4-carbonyl aldoxime, 0.86 gram (0.0038 mole) N-tertiary butyl-4-chloromethylbenzene methane amide and 1.0 gram (0.0072 mole) salt of wormwood are added in 20 milliliters of acetonitriles the mixture reflux that obtains 6 hours.After reacting completely, remove acetonitrile under reduced pressure.Add water then in residuum, use ethyl acetate extraction again.Acetic acid ethyl acetate extract washes with water, and dry then, steaming removes ethyl acetate and gets the oily product.This oily product gets the 1.4 gram compounds of wanting by silica gel column chromatography.
Productive rate 82% n
20 D1.5662
Embodiment 34
The 5-(4-fluorophenoxy)-1,3-dimethyl pyrazole-4-carbonyl aldoxime O-4-pivalyl benzylic ether (compound number 548)
1.0 gram (0.0040 mole) 5-(4-fluorophenoxy)-1,3-dimethyl pyrazole-4-carbonyl aldoxime, 1.0 gram (0.0039 mole) tert-butyl 4-2-bromomethylphenyl ketone and 1.0 gram (0.0094 mole) yellow soda ash are added in 40 milliliters of acetone, mixture heating up is reacted.After reacting completely, remove acetone under reduced pressure.After residuum adds entry, use ethyl acetate extraction, acetic acid ethyl acetate extract washes with water, and dry then, steaming removes ethyl acetate and obtains oily matter.This oily matter gets the 1.5 gram compounds of wanting by silica gel column chromatography.
Productive rate 89% n
20 D1.5567
Embodiment 35
2-methyl-2-(4-1,3-dimethyl-5-phenoxy group pyrazoles-4-yl) and methene amido oxygen methyl } phenyl)-1,3-dioxolane (compound number 562)
1.0 gram (0.0043 mole) 1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime is dissolved in 20 milliliters of dioxs, adds 0.14 gram (0.0058 mole) sodium hydride.Then in this solution, add 1.1 gram (0.0043 mole) 2-(4-2-bromomethylphenyls)-the 2-methyl isophthalic acid, the 3-dioxolane, reflux is 3 hours then.After reacting completely, reaction solution is poured in 200 milliliters of cold water and is used ethyl acetate extraction then.Acetic acid ethyl acetate extract washes with water and is dry, steams and removes ethyl acetate acquisition oily product.This oily product obtains the 1.3 gram products of wanting by silica gel column chromatography.
Productive rate 74% n
20 D1.5698
Embodiment 36
2-(4-(the 5-(4-fluorophenoxy) and-1,3-dimethyl pyrazole-4-yl } methene amido oxygen methyl) phenyl)-the 2-methyl isophthalic acid, 3-dioxolane (compound number 563)
1.1 gram (0.0043 mole) 5-(4-fluorophenoxy)-1,3-dimethyl pyrazole-4-carbonyl aldehyde and 0.9 gram (0.0043 mole) 2-(4-ammonia oxygen methyl) phenyl)-the 2-methyl isophthalic acid, the 3-dioxolane is added in 20 milliliters of ethanol.The mixture heating up reaction that obtains 3 hours after reacting completely, removes ethanol under reduced pressure, adds water behind residue, uses ethyl acetate extraction, and acetic acid ethyl acetate extract washes with water, and dry then, steaming removes ethyl acetate and gets the oily product.This oily product gets the 1.3 gram compounds of wanting by silica gel column chromatography.
Productive rate 72% n
20 D1.5555
Embodiment 37
1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime O-4-(1-hydroxyethyl) benzylic ether (compound number 584)
1.0 gram (0.0028 mole) 1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime-O-4-acetyl benzylic ether, 1.0 gram (0.0026 mole) sodium borohydride and 1 gram (0.025 mole) sodium hydroxide are added in 100 ml methanol, this mixture heating up refluxed 3 hours then.After reacting completely, remove methyl alcohol under reduced pressure, after residuum adds water, use ethyl acetate extraction, acetic acid ethyl acetate extract washes with water dry then, and steaming removes ethyl acetate and gets the oily product.This oily product gets the 0.8 gram compound of wanting by silica gel column chromatography.
Productive rate 78% n
20 D1.5748
Embodiment 38
N-4 ((1,3-dimethyl-5-phenoxy group pyrazoles-4-yl) methylene radical ammonia oxygen methyl) benzamide (compound number 589)
1.0 gram (0.0043 mole) 1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime is dissolved in 20 milliliters of dimethyl sulfoxide (DMSO), and adding 0.3 gram (0.0053 mole) potassium hydroxide powder is last, stirs this solution.Add 0.92 the gram (0.0043 mole) N-(4-2-bromomethylphenyl) methane amide in reaction solution, be reflected at room temperature and carried out 3 hours.After reacting completely, reaction solution is poured in 200 ml waters, uses ethyl acetate extraction, and acetic acid ethyl acetate extract washes with water and be dry, and steaming removes ethyl acetate and gets the oily product.This oily product gets the 1.2 gram compounds of wanting by silica gel column chromatography.
105.3 ℃ of productive rate 76% fusing points
Embodiment 39
N-4-(the 5-(4-fluorophenoxy) and-1,3-dimethyl pyrazole-4-yl } methylene radical ammonia oxygen methyl)-phenylcarbamic acid isopropyl ester (compound number 595)
1.0 gram (0.0040 mole) 5-(4-fluorophenoxy)-1,3-dimethyl pyrazole-4-carbonyl aldoxime, 1.1 gram (0.0040 mole) N-4-2-bromomethylphenyl carbamic acid isopropyl ester and 1.0 gram (0.0072 mole) salt of wormwood are added in 20 milliliters of acetonitriles, the mixture heating up that obtains refluxed 6 hours.After reacting completely, remove acetonitrile under reduced pressure, after residuum adds entry, use ethyl acetate extraction, acetic acid ethyl acetate extract washes with water and is dry, and steaming removes ethyl acetate and gets the oily product.This oily product gets the 1.5 gram compounds of wanting by silica gel column chromatography.
Productive rate 85% n
20 D1.5645
Embodiment 40
N-4-(5-(4-methoxyl group phenoxy group) and-1,3-dimethyl pyrazole-4-yl } methene amido oxygen methyl) phenylcarbamic acid isobutyl ester (compound 617)
1.0 gram (0.0038 mole) 5-(4-methoxyl group phenoxy group)-1,3-dimethyl pyrazole-4-carbonyl aldoxime, 1.1 gram (0.0038 mole) N-4-2-bromomethylphenyl-N-methyl carbamic acid isobutyl ester and 1.0 gram (0.0094 mole) yellow soda ash are added in 40 milliliters of acetone, the mixture heating up that obtains is reacted.After reacting completely, remove acetone under reduced pressure, after the residuum that steam to remove acetone adds entry, use ethyl acetate extraction, acetic acid ethyl acetate extract washes with water and is dry, steams except that ethyl acetate to get the oily product.This oily product obtains the 1.5 gram compounds of wanting by silica gel column chromatography.
Productive rate 83% n
20 D1.5538
Embodiment 41
N-4-((1,3-dimethyl-5-phenoxy group-pyrazoles-4-yl) methene amido oxygen methyl) phenyl-N-sec.-propyl methane amide (compound number 636)
1.0 gram (0.0043 mole) 1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime is dissolved in 20 milliliters of dioxs, adds the sodium salt that 0.1 gram (0.0043 mole) sodium hydride synthesizes top oxime then.Add 1.1 gram (0.0043 mole) N-4-2-bromomethylphenyl-N-sec.-propyl methane amides in this reaction solution, be reflected at 40 ° to 50 ℃ reactions 3 hours.After reacting completely, reaction solution is poured in 200 ml waters, used ethyl acetate extraction.Acetic acid ethyl acetate extract washes with water and is dry, and steaming removes ethyl acetate and obtains the oily product then.This oily product gets the 1.3 gram products of wanting by silica gel column chromatography.
73.3 ℃ of productive rate 75% fusing points
Embodiment 42
N-4-((1,3-dimethyl-5-phenoxy group pyrazoles-4-yl)-methene amido oxygen methyl) phenyl-N-ethyl-trimethyl ethanamide (compound number 647)
1.0 gram (0.0043 mole) 1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime, 1.3 gram (0.0043 mole) N-4-2-bromomethylphenyl-N-ethyl-trimethyl ethanamide and 0.2 gram (0.005 mole) potassium hydroxide are dissolved in 30 milliliters of dimethyl sulfoxide (DMSO), are reflected at 40 °～50 ℃ and carry out 6 hours.After reacting completely, reaction solution is poured in 200 ml waters, uses ethyl acetate extraction then, and acetic acid ethyl acetate extract washes with water, and dry then, steaming removes ethyl acetate and obtains the oily product.This oily product obtains the 1.5 gram products of wanting by silica gel column chromatography.
Productive rate 78% product form: starchiness
Embodiment 43
5-ethyl-3-(N-4 ([the 5-(4-fluorophenoxy)-1,3-dimethyl pyrazole-4-yl } methylene radical ammonia oxygen methyl)-phenyl)-2-oxazolidone (compound number 657)
1.0 gram (0.0040 mole) 5-(4-fluorophenoxy)-1,3-dimethyl pyrazole-4-carbonyl aldoxime and 1.1 gram (0.0040 mole) 3-(4-2-bromomethylphenyls)-5-ethyl-2-oxazolidone is dissolved in 20 milliliters of dimethyl sulfoxide (DMSO), adds 0.3 gram (0.0053 mole) potassium hydroxide powder.Being reflected at 40 °～50 ℃ carried out 5 hours.After reacting completely, reaction solution is poured in 200 ml waters, uses ethyl acetate extraction then.Acetic acid ethyl acetate extract washes with water, and dry then, steaming removes ethyl acetate and gets the oily product, and this oily product gets the 1.3 gram compounds of wanting by silica gel column chromatography.
Productive rate 72% n
20 D1.5601
Embodiment 44
1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime O-2-phenoxy group ethyl ether (compound number 658)
1.0 gram (0.0043 mole) 1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime is dissolved in 20 milliliters of dimethyl sulfoxide (DMSO), adds 0.3 gram (0.0053 mole) potassium hydroxide powder then, stirring reaction liquid.Add 0.86 gram (0.0043 mole) 2-bromine oxethyl benzene then, reaction was at room temperature carried out 3 hours.After reacting completely, add water in reaction solution, use ethyl acetate extraction, acetic acid ethyl acetate extract to wash with water then and drying, steaming removes ethyl acetate and gets the oily product, and this oily product gets the 1.3 gram compounds of wanting by silica gel column chromatography.
Productive rate 86% n
20 D1.5657
Embodiment 45
1,3-dimethyl-5-(3-4-trifluoromethylphenopendant)-pyrazoles-4-carbonyl aldoxime O-2-(4-tertiary butyl phenoxy group) ethyl ether (compound number 671)
1.0 gram (0.0030 mole) 1,3-dimethyl-5-(3-4-trifluoromethylphenopendant) pyrazoles-4-carbonyl aldoxime, 0.86 the gram (0.0034 mole) right-(2-bromine oxethyl)-tert.-butylbenzene and 1.38 the gram salt of wormwood be added in 50 milliliters of acetonitriles the mixture reflux that obtains 8 hours.After reacting completely, add water in reaction solution, use ethyl acetate extraction, acetic acid ethyl acetate extract to wash with water then and drying, steaming removes ethyl acetate and gets the oily product.This oily product gets the 1.4 gram compounds of wanting by silica gel column chromatography.
Productive rate 89% n
20 D1.5287
Embodiment 46
4-(2-{ (1,3-dimethyl-5-phenoxy group pyrazoles-4-yl) methene amido oxygen } oxyethyl group) ethyl benzoate (compound number 706)
1.0 gram (0.0043 mole) 1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime and 0.3 gram (0.0075 mole) sodium hydroxide powder are added in 30 milliliters of dimethyl formamides, stir and obtain mixture.Add 0.99 the gram (0.0043 mole) to (2-chloroethoxy) ethyl benzoate in this solution, be reflected at 30 °～40 ℃ and carried out 3 hours.After reacting completely, add water in reaction solution, use ethyl acetate extraction then.Acetic acid ethyl acetate extract washes with water and is dry.Steaming removes ethyl acetate and obtains the oily product.This oily product gets the 1.3 gram compounds of wanting by silica gel column chromatography.
Productive rate 72% n
20 D1.5577
Embodiment 47
The 5-(4-chlorophenoxy)-1,3-dimethyl pyrazole-4-carbonyl aldoxime O-2-(3,4-dichlorophenoxy)-ethyl ether (compound number 723)
1.0 gram (0.0038 mole) 5-(4-chlorophenoxy)-1,3-dimethyl pyrazole-4-carbonyl aldoxime, 1.0 gram (0.0038 mole) 2-bromine oxethyl-3,4-dichlorobenzene and 0.58 gram (0.0038 mole) 1,8-diazabicyclo (5,4,0)-and the 7-undecylene is dissolved in 50 milliliters of dioxs, and be reflected at 60～80 ℃ and follow to stir and carried out 5 hours.After reacting completely, add water in reaction solution, use ethyl acetate extraction then.Acetic acid ethyl acetate extract washes with water and is dry, and steaming removes ethyl acetate and gets the oily product then.This oily product gets the 1.5 gram compounds of wanting by silica gel column chromatography.
Productive rate 87% n
20 D1.5756
Embodiment 48
The 5-(4-fluorophenoxy)-1,3-dimethyl pyrazole-4-carbonyl aldoxime O-2-phenoxy propyl ether (compound number 741)
1.0 gram (0.0037 mole) 5-(4-chlorophenoxy)-1,3-dimethyl pyrazole-4-carbonyl aldoxime sodium and 0.63 gram (0.037 mole) 2-chloro-1-methyl ethoxy benzene are added in 50 milliliters of tetrahydrofuran (THF)s, reaction mixture is followed stirring and refluxing heating 5 hours.After reacting completely, add water in reaction solution, use ethyl acetate extraction then.Acetic acid ethyl acetate extract washes with water and is dry, and steaming removes ethyl acetate and gets the oily product then.This oily product gets the 1.3 gram compounds of wanting by silica gel column chromatography.
Productive rate 87% n
20 D1.5484
Embodiment 49
1.3-ethyl ether (compound number 753) dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime O-2-(4-tert.-butylbenzene sulfenyl)
1.0 gram (0.0030 mole) 1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime O-2-bromotrifluoromethane ether, 0.5 the gram (0.0030 mole) right-tert.-butylbenzene mercaptan, 1.0 the gram (0.0072 mole) salt of wormwood is added in 60 milliliters of acetonitriles, reflux is 5 hours then.After reacting completely, add water in reaction solution, use ethyl acetate extraction then.Acetic acid ethyl acetate extract washes with water and is dry, and steaming removes ethyl acetate and gets the oily product, and this oily product gets the 1.1 gram compounds of wanting by silica gel column chromatography.
Productive rate 87% n
20 D1.5775
Embodiment 50
1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime O-3-(4-chlorophenoxy) propyl ether (compound number 761)
1.0 gram (0.0043 mole) 1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime and 0.3 gram (0.0053 mole) potassium hydroxide are added in 20 milliliters of dimethyl sulfoxide (DMSO).Add 1.07 the gram (0.0043 mole) right-chloro-3-bromine propoxy-benzene, be reflected at 40 °～50 ℃ and carried out 4 hours.After reacting completely, add water in reaction solution, use ethyl acetate extraction then.Acetic acid ethyl acetate extract washes with water and is dry, and steaming removes ethyl acetate and gets the oily product then.This oily product gets the 1.3 gram compounds of wanting by silica gel column chromatography.
Productive rate 76% n
20 D1.5746
Embodiment 51
1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime O-4-(4-chlorophenoxy)-crotyl ether (compound number 776)
1.0 gram (0.0031 mole) 1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime O-4-chloro-crotyl ether and 0.6 restrains (0.0036 mole), and right-chlorophenol sylvite is added in 40 milliliters of tetrahydrofuran (THF)s, follows stirring and refluxing heating 3 hours then.After reacting completely, add water in reaction solution, use ethyl acetate extraction then.Acetic acid ethyl acetate extract washes with water and is dry, and steaming removes ethyl acetate and gets the oily product then, and this oily product gets the 1.2 gram compounds of wanting by silica gel column chromatography.
Productive rate 93% n
20 D1.5712
Embodiment 52
1.3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime O-6-phenoxy group hexyl ether (compound number 780)
1.0 gram (0.0043 mole) 1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime is dissolved in 10 milliliters of dimethyl sulfoxide (DMSO), adds sodium hydride 0.11 gram (0.0045 mole) in room temperature then.Reaction solution stirred 30 minutes.Add 1.1 gram (0.0043 mole) 6-bromine hexyloxy benzene in this solution, be reflected at 50 °～60 ℃ and carried out 3 hours.After reacting completely, add water in reaction solution, use ethyl acetate extraction then.Acetic acid ethyl acetate extract washes with water and is dry, and steaming removes ethyl acetate and gets the oily product.This oily product gets the 1.4 gram compounds of wanting by silica gel column chromatography.
Productive rate 80% n
20 D1.5583
Embodiment 53
2-((1,3-dimethyl-5-phenoxy group pyrazoles-4-yl) methene amido oxygen) ethylamino benzonitrile acid esters (compound number 787)
1.0 gram (0.0043 mole) 1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime and 0.3 gram (0.0054 mole) potassium hydroxide powder are added in 20 milliliters of dimethyl sulfoxide (DMSO), and mixture stirred 30 minutes.Add 0.8 gram (0.0043 mole) phenylformic acid 2-chloroethene ester, be reflected at 40 °～50 ℃ and carried out 3 hours.After reacting completely, add water in reaction solution, use ethyl acetate extraction then.Acetic acid ethyl acetate extract washes with water and is dry.Steaming removes ethyl acetate and obtains the oily product.This oily product gets the 1.3 gram compounds of wanting by silica gel column chromatography.
Productive rate 86% n
20 D1.5632
Embodiment 54
1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime O-2-ethoxyethyl group ether (compound number 789)
1.0 gram (0.0046 mole) 1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldehyde is dissolved in 40 milliliters of ethanol, follows to stir to add the 0.48(gram) (0.0046 mole) O-(2-ethoxyethyl group) azanol.Being reflected at room temperature carried out 3 hours.After reacting completely, add water in reaction solution, use ethyl acetate extraction then.Acetic acid ethyl acetate extract washes with water and is dry.Steaming removes ethyl acetate and gets the oily product.This oily product gets the 1.2 gram compounds of wanting by silica gel column chromatography.
Productive rate 86% n
20 D1.5407
Embodiment 55
1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime O-methyl ether (compound number 790)
1.0 gram (0.0043 mole) 1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime is dissolved in 20 milliliters of dimethyl sulfoxide (DMSO), adds 0.3 gram (0.0053 mole) potassium hydroxide powder then, stirs this mixture.Add 1.0 gram (0.0063 mole) methyl iodide to this reaction solution, be reflected at room temperature and carried out 3 hours.After reacting completely, reaction solution is poured in 200 ml waters, used ethyl acetate extraction then.Acetic acid ethyl acetate extract washes with water, and is dry then.Remove ethyl acetate under reduced pressure and get the oily product.This oily product gets the 0.3 gram compound of wanting by silica gel column chromatography.
70.2 ℃ of productive rate 76% fusing points
Embodiment 56
The 5-(4-chlorophenoxy)-1,3-dimethyl pyrazole-4-carbonyl aldoxime O-2-propine ether (compound number 795)
1.0 gram (0.0038 mole) 5-(4-methoxyl group phenoxy group)-1,3-dimethyl pyrazole-4-carbonyl aldoxime is dissolved in 20 milliliters of dioxs, add 0.1 gram (0.0042 mole) sodium hydride after, stir and obtain mixture.Add 0.78 the gram (0.0038 mole) 2-(4-fluorophenyl) monobromoethane in reaction solution, be reflected at 40 °～50 ℃ and carried out 3 hours.After reacting completely, reaction solution is poured in 200 ml waters.Use ethyl acetate extraction then.Acetic acid ethyl acetate extract washes with water and is dry.Remove ethyl acetate under reduced pressure and get the oily product, this oily product gets the 1.2 gram compounds of wanting by silica gel column chromatography.
Productive rate 82% n
20 D1.5588
Embodiment 58
The 5-(4-chlorophenoxy)-1,3-dimethyl pyrazole-4-carbonyl aldoxime O-3-(4-chloro-phenyl-)-propyl ether (compound number 824)
1.0 gram (0.0033 mole) 5-(4-chlorophenoxy)-1,3-dimethyl pyrazole-4-carbonyl aldoxime, 0.5 gram (0.0042 mole) propargyl bromide and 1.0 gram (0.0072 mole) salt of wormwood are added in 50 milliliters of acetone the mixture reflux that obtains.After reacting completely, reaction is poured in 200 ml waters night, uses ethyl acetate extraction then.Acetic acid ethyl acetate extract washes with water and is dry, removes ethyl acetate under reduced pressure and gets the oily product.This oily product gets the 0.9 gram compound of wanting by silica gel column chromatography.
Productive rate 87% n
20 D1.5670
Embodiment 57
5-(4-methoxyl group phenoxy group)-1,3-dimethyl pyrazole-4-carbonyl aldoxime O-2-(4-fluorophenyl)-ethyl ether (compound number 815)
1.0 gram (0.004 mole) 5-(4-chlorophenoxy)-1,3-dimethyl pyrazole-4-carbonyl aldehyde is dissolved in 30 ml methanol, follows to stir in room temperature then to add 0.74 gram (0.004 mole) O-(3-(4-chloro-phenyl-) propyl group) oxyamine.Being reflected at 40 °～50 ℃ then carried out 2 hours.Remove methyl alcohol under reduced pressure, add water then in residuum, use ethyl acetate extraction.Acetic acid ethyl acetate extract washes with water dry then.Remove ethyl acetate under reduced pressure and get the oily product.The oily product gets the 1.1 gram compounds of wanting by silica gel column chromatography.
Productive rate 66% n
20 D1.5751
Embodiment 59
The 5-(4-chlorophenoxy)-1-methyl-3-phenylpyrazole-4-carbonyl aldoxime O-4-chlorine cinnamyl ether (compound number 846)
1.0 gram (0.0030 mole) 5-(4-chlorophenoxy)-1-methyl-3-phenylpyrazole-4-carbonyl aldoxime and 0.7 gram (0.0030 mole) be right-chlorine cinnamyl bromine and 0.2 restrains (0.005 mole) sodium hydroxide and reacted 6 hours in 30 ℃ of 30 milliliters of dimethyl sulfoxide (DMSO).After reacting completely, reaction solution is poured in 200 ml waters, uses ethyl acetate extraction then.Acetic acid ethyl acetate extract washes with water, and is dry then, removes ethyl acetate under reduced pressure and gets the oily product.This oily product gets the 1.1 gram compounds of wanting by silica gel column chromatography.
Productive rate 76% n
20 D1.5980
Embodiment 60
1,3-dimethyl-5-phenoxy group pyrazoles-4-base phenyl ketoxime O-allyl ethers (compound number 857)
1.0 gram (0.0033 mole) 1,3-dimethyl-5-phenoxy group pyrazoles-4-base phenyl ketoxime, 0.5 gram (0.0041 mole) allyl bromide 98 and 1.0 gram salt of wormwood are added in 50 milliliters of acetone, and mixture heating up was reacted in 6 hours.After reacting completely, reaction solution is poured in 200 ml waters, uses ethyl acetate extraction.Acetic acid ethyl acetate extract washes with water, and is dry then, removes ethyl acetate under reduced pressure and gets the oily product.This oily product gets the 0.9 gram compound of wanting by silica gel column chromatography.
Productive rate 79% n
20 D1.5800
Synthesizing of raw material
Synthetic embodiment 1
13.2 gram (0.006 mole) 4-tolyl acid tert-butyl ester, 0.3 gram (0.0012 mole) benzoyl peroxide and 6g(0.006 mole) yellow soda ash is suspended in 100 milliliters of tetracol phenixin, follows to be stirred in 50 ℃ and to spend 30 minutes and drip 9.6 gram (0.06 mole) bromines.After dropwising, reaction is proceeded 30 minutes.Cool off reaction solution then, filter and remove the material that is insoluble to tetracol phenixin.Remove tetracol phenixin then under reduced pressure and get crystalline 16.2 gram 4-bromo methyl acid tert-butyl esters.
53.4 ℃ of productive rate 90% fusing points
Synthetic embodiment 2
15.0 gram (0.049 mole) 4-bromo methyl acid tert-butyl ester, 8.2 gram (0.05 mole) N-hydroxyl-phthalic imidine and 3.0 gram (0.054 mole) hydrochlorinate potassium are added to 200 milliliters of dimethyl formamides, mixture carried out 30 minutes at 50 ℃ then stirring at room 30 minutes.Reaction solution cools off with frozen water, filters then and obtains crystallization.Crystallization is dissolved in 50 milliliters of methylene dichloride, slowly drips 3 milliliters of Virahols that contain 0.5 gram (0.05 mole) hydrazine hydrate in room temperature in solution then.After dropwising, reaction solution reflux 2 hours.Reaction solution cooling is filtered then, filtrate concentrate 11.0 gram 4-(ammonia oxygen methyl) t-butyl perbenzoate.
Productive rate 90% n
15.6 D1.5296
Synthetic embodiment 3
3.0 gram (0.02 mole) 1-is right-tolyl cyclopropane-1-carbon nitrile and 0.1 gram (0.0004 mole) benzoyl peroxide be dissolved in 50 milliliters of tetracol phenixin, drips 3.2 gram bromines under refluxing in time-consuming more than 30 minutes.After dropwising, reaction is proceeded 30 minutes.Reaction solution cooling back is steamed except that tetracol phenixin gets 4.4 and is restrained the 1-(4-2-bromomethylphenyls) cyclopropane-1-carbon nitrile.
Productive rate 90% product form: ointment shape
NMR：
δ（ppm）1.15-1.40（2H，m），
2.50-2.75（2H，m），
4.45（1H，s），7.35（4H，s）
Synthetic embodiment 4
5.0 gram (0.00216 mole) 1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime and 41.0 gram (0.218 moles) 1, the 2-methylene bromide is dissolved in 100 milliliters of dimethyl sulfoxide (DMSO), follow ice-cooled adding 14.4 gram (0.219 mole) 85% potassium hydroxide powders after, reaction solution stirred 30 minutes.After reacting completely, reaction solution is poured in 300 ml waters, divides then three times, uses 80 milliliters of ether extraction at every turn, washs with 300 ml waters then.The ether extracted liquid anhydrous sodium sulfate drying steams and removes ether.Residuum obtains 5.2 grams 1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonylic acid oxime O-2-bromotrifluoromethane ether by the silica gel column chromatography post.
Productive rate 71.2% n
23.8 D1.5721
The invention provides with physiologically active compound of the present invention and kill and control deleterious insect and mite.One of particular embodiment of the present invention is: compound directly is used as protection object or Pest Control (not diluting sprinkling), composition for example of the present invention with 95% or more the high purity liquid form form the cloud and mist that superfine liquid particle constitutes by airplane spray.
Compound of the present invention also can be used to handle the pond and the pond of insect larvae existence or handles ambient water and the irrigation water that growth has larva, its living environment is changed or harmful to larva.
In order to kill or control deleterious insect and mite with physiologically active compound of the present invention, compound is in most of the cases used with suitable form, for example, fill or dilution with inert support, if necessary, can mix with auxiliary, this is known in the present technique field.
The ordinary representation form that has the insecticides of The compounds of this invention is described in down.
Compound of the present invention mixes so that make compound dissolution with the suitable inert support and the auxiliary (if necessary) of suitable proportion, disperses, and suspends, blending, perfusion absorbs or adhesion, thereby form suitable preparation, resemble solution, suspension agent, missible oil, pulvis, oily spray agent, but wet-milling, granula, tablet, pill, ointment, smoke substance or the like.
The form that inert support adopts i.e. also liquid of solid.The solid carrier example has plant dust figure soyflour, flour, wood powder, tree bark powder, sawdust, ground offal, walnut parting, the extraction residue of wheat bran, fiber powder and plant; Fibrous substance resembles paper, waved plate and useless cloth; The synthetic polymer class resembles powdery synthetic resins; Mineral products or mineral products thing, (for example resemble the clay class, kaolin, bentonite and acid clay), talcs (example, talcum and pyrophyllite), silicon-containing material (example, diatomite, (synthetic silica of high dispersing is also referred to as finely divided hydration silica or hydrated SiO 2 to contain silica sand, mica and " hard charcoal ", the commerical prod that contains Calucium Silicate powder as main component)), gac, sulphur powder, float stone, ripe diatomite, cob brick, lime-ash, slag, lime carbonate and calcium phosphate; Chemical fertilizer resembles sulfuric acid amine, ammonium nitrate, urea, ammonium chloride; Farming is fertile.These materials can use or mix use separately.Though the material that can be used as liquid vehicle is from those solubilized activeconstituentss and can not dissolve them but can disperse to select their material with auxiliary.For example, following material can use or mix use separately: water, alcohols (example: methyl alcohol, ethanol, Virahol, butanols, ethylene glycol), ketone (example: acetone, methylethylketone, methyl iso-butyl ketone (MIBK), diisobutyl ketone and pimelinketone), ethers (example, ether ， diox, methylcellulose gum, dipropyl ether and tetrahydrofuran (THF)), aliphatic carbon hydride (routine gasoline and mineral oil), aromatic carbon hydride (example, benzene, toluene, dimethylbenzene, solvent naphtha, naphthalene, alkylnaphthalene), halo hydrocarbons (example, ethylene dichloride, chlorinated benzene, chloroform, tetracol phenixin), ester class (example, ethyl acetate, the dibutyl phthalate, di-isopropyl phthalate and dioctyl phthalate (dop)), acid amides (example, dimethyl formamide, diethylformamide and N,N-DIMETHYLACETAMIDE), nitrile (example, and dimethyl sulfoxide (DMSO) acetonitrile).
Gaseous carrier comprises it being freonll-11 and other aerosol propellants of gas under normal operation.
Auxiliary cited below uses according to various objectives.Under certain conditions, they are used in combination with other material.Under other conditions, then without auxiliary.
Resemble polyoxyethylene alkyl aryl ether, Voranol EP 2001, polyoxyethylene high fatty acid ester, polyoxyethylene resinate with tensio-active agent, polyoxyethylenesorbitan monolaurate, polyoxyethylene sorbitanic monoleate, alkyl aryl sulfonate, naphthalene sulfonic acid condensate, sulfonated lignin and high pure sulfuric ester are in order to make the emulsification of activeconstituents energy, dispersion, dissolving and/or moistening.
For the dispersion that makes activeconstituents, gluing, agglomerating stablizing, usually use: casein, gelatinum, starch, alginic acid, methylcellulose gum, carboxymethyl cellulose, Sudan Gum-arabic, polyvinyl alcohol, turps, rice bran oil, bentonite and sulfonated lignin.
In order to improve solids composition flowability, suggestion wax, stearate and alkyl phosphate.
But the peptizing agent of naphthalene sulfonic acid condensate and poly phosphate conduct dispersive composition is used in suggestion.
Adding defoaming agents resembles silicone oil and is fine.
The content of activeconstituents is adjusted according to actual needs.For powder or saccharoid, content accounts for weight 0.5～20% usually.But for missible oil, suspending concentrate wet-milling, content is preferably 0.1～50% of weight.
In order to control various insects, mite and fungi, suppress their growth and prevent these insects, mite and plant that the fungi infringement is useful, composition of the present invention will be with effective insecticidal, kill mite or germ-resistant amount is applied on agricultural and the gardening.When using this composition, suitably be suspended in the water after the dilution composition or be applied to again in other appropriate medium on the leaf in soil or crops to prevent insect, the invasion and attack of mite and fungi.
The activeconstituents consumption relies on various factors, example, application aims, the vegetative period in crops, climate, envrionment conditions, composition forms, application mode, institute's agrotype to be processed or the like.
When using fungicidal composition separately, activeconstituents dosage is preferably selected from per 10 mu of 0.1 gram to the scope of 500 grams.
The compounds of this invention can mix with other sterilization, desinsection, chemical fertilizer and plant hormone and uses in addition, even these reagent can combine with The compounds of this invention and use.
Can with sterilant blended examples of pesticides of the present invention face as follows:
O-(4-nitro-3-aminomethyl phenyl)-and thiophosphoric acid O, O-dimethyl ester (pheni-trothion)
O-(3-methyl-4-methylthio group phenyl)-and thiophosphoric acid O, O-dimethyl ester (Tiguvon)
S-(ethoxycarbonyl phenyl methyl)-and O, O-dimethyl-phosphorodithioate (Tsidial)
O-(2-sec.-propyl-4-methylpyrimidine base-6-)-O, O-systox (diazinon)
2,2,2-three chloro-1-hydroxyethyl-O, O-dimethyl phosphoric acid ester (Trichlorphon)
O-ethyl, O-be right-nitrophenyl, and phenylphosphonothioic acid ester (EPN)
O-ethyl, O-be right-cyano-phenyl, phenyl phosphonic thioesters (S-4087)
O, O-dipropyl, O-4-methyl thio-phenyl phosphoric acid ester (Kayaphos)
O, O-dimethyl, S-phthalimidomethyl phosphorodithioate (R-1504)
O, O-dimethyl, O-dichloroethylene phosphoric acid ester (SD-1750)
O, O-dimethyl, S-(N-methylamino formyl radical methyl)-phosphorodithioate (Rogor)
O, O-dimethyl, S-(1,2-diethyl-ester group ethyl)-phosphorodithioate (Phosphothion)
1-naphthyl N-methyl carbamate (SevinCarbaryl)
Between the N-methyl carbamic acid-toluene ester (meta-tolyl-N-methylcarbamate (MTMC))
The different third oxygen phenyl ester (Propoxur) of N-methyl carbamic acid 2-
N-(diethyl-dithio phosphoryl ethanoyl)-N-methyl carbamic acid ethyl ester (mecarbam)
3,4-xylyl N-methyl carbamate (xylylcarb)
2-S-butyl phenyl N-methyl carbamate (Osbac)
2-cumyl N-methyl carbamate (isoprocarb)
N-methyl carbamic acid 2-chlorobenzene ester (Hopcide)
3,5-xylyl N-methyl carbamate (Cosban)
2-(1, the phenyl N-methyl carbamate (dioxacarb) of 3-dioxolane-2-)
3-trimethylphenylmethane base N-methyl carbamate (terbam)
4-2 allylamine-3,5-3,5-dimethylphenyl N-methyl carbamate (allyxycarb)
S-methyl-N-(methylamino formyl radical oxygen base) thioacetyl amidine ester (Methomil)
N-(2-methyl-4-chloro-phenyl-)-and N, N-dimethyl-formyl amidine thiamine hydrochloride (chlordimeform)
1, two (carbamyl the sulfenyl)-2-(N of 3-, N-dimethylamino)-propane hydrochloride salt (Padan)
Di-isopropyl-1,3-dithiolane-2-pitches malonic ester (Fujione)
N-((4-chloro-phenyl-) amino) carbonyl)-2,6-difluorobenzamide (TH-6040)
O, O-dimethyl-S-(2-(iprotiazem base) ethyl) phosphorodithioate (Hosdon)
O, O-diethyl-S-(2-(ethylmercapto group)-ethyl) phosphorodithioate (thiodemeton)
(2,3-dihydro-2,2-dimethyl-7-benzofuryl)-N-methyl carbamate (carbofuran)
O-ethyl S, S-phenylbenzene phosphorodithioate (Edibenfos)
The N-(trichloro-methylthio) tetrahydrobenzene-4-1,2-dicarboximide (Difolatan)
2,4,5,6-daconil M (m-tetrachlorophthalodinitrile)
N-(1,1,2,2-tetrachloro ethylmercapto group) hexamethylene-4-alkene-1,2-dicarboximide (Difolatan)
4, two (the 3-thioureido formic acid) dimethyl esters (thiophanate methyl) of 4-neighbour-phenylene
3-(butyl formamyl)-3H-benzimidazolyl-2 radicals-Ji Methyl anthranilate (F-1991)
Ethylene-1, two (dithiocarbamic acid) zinc (zineb) of 2-
Ethylene-1, two (dithiocarbamic acid) manganese (maneb) of 2-
In order to show the killing effect of The compounds of this invention, the experiment embodiment of face and form example as follows.But the present invention is not limited in these examples.
Experiment embodiment 1
Fungicidal activity (Erysiphe graminis f.sp.hordei) for the barley meal mildew
Barley seedlings sprayed one day with experimental compound (200ppm) with the conidium inoculation back of Erysiphe graminis f.sp.hordei at two leaf stage.Seedling preserves a week under 25 ℃ of constant temperature, detects the percentage ratio that every leaf is attacked area then.Fungicidal activity is by relatively and according to following standard judging with unprocessed portion.
The results are shown in Table 2
A: disease inhibiting rate 100～95%
B: disease inhibiting rate 94～80%
C: disease inhibiting rate 79～60%
D: disease inhibiting rate 59～0%
Table 2
Compound number Fungicidal active compound Fungicidal active compound fungicidal 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 (Puccinia Coroata f.sp.avenae) for oat rhizome rust
Oat seedlings was sprayed one day with experimental compound (200ppm) with the uredospore inoculation back of Puccinia coronata f.SP.avenae in 8 leaf phases.Seedling preserved ten days at 25 ℃ of constant temperature.Detect every leaf and attacked the percentage ratio of area.Fungicidal activity is pressed the same standard of experimental example 1 and is judged.
The results are shown in Table 3.
Table 3
Compound number Fungicidal active compound Fungicidal active compound fungicidal 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 (Pseudoperonospora cubensis) for the false oidium of cucumber
The cucumber of 2 leaf phases is at inoculation Pseudoperonospora cubensis) sprinkling experimental compound (200ppm) a day before the zoospore.Plant moves on to then in the maintenance fresh air room and preserved six days after preserving one day in 25 ℃ of moist rooms.Detect every leaf and be subjected to the infringement degree, fungicidal activity is pressed the same standard of experimental example 1 and is judged.
The results are shown in Table 4.
Table 4
Compound number Fungicidal active compound Fungicidal active compound fungicidal 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 (Nilaparvata lugens) for Nilaparvata lugen (brown planthopper)
After the rice seedling being immersed the emulsion 30 seconds, dry air of compound (200ppm), the seedling kind is in glass test tube, then with on nymph inoculation in the 3rd length of time plant.After inoculation the 8th day, the calculation correction mortality ratio was also judged insecticidal activity according to following standard.
The results are shown in Table 5
A: corrected mortality 100～90%
B: corrected mortality 89～80%
C: corrected mortality 79～50%
Table 5
Compound number insecticidal active compound insecticidal active compound 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 (Plutella xylostella) for small cabbage moth
(pupa of the insect on the 6cm * 5cm) was immersed among the emulsion of The compounds of this invention 30 seconds will to be positioned at a slice China cabbage leaves.After the dry air, insect and plant are placed in the culture dish together, went into behind the culture dish the 6th day, the mortality ratio of calculation correction is also judged according to the same standard of experimental example 4.
The results are shown in Table 6.
Table 6
Compound number insecticidal active compound insecticidal active compound 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 (Myzus percicae) for black peach aphid
The adult of aphid is inoculated on the Chinese wild cabbage.Use The compounds of this invention (200ppm) emulsion to spray insect and plant then.After the medication the 3rd day, according to the same judgement insecticidal activity of experimental example 4.
The results are shown in Table 7
Table 7
Compound number insecticidal active compound insecticidal active compound 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 (Panonychus citri) for citrus red mite
Female insect is inoculated on Zhu's mountains in a range leaf, uses the emulsion of The compounds of this invention (200ppm) to spray then.After the medication the 10th day, calculate the insect number of surviving, judge acaricidal activity according to the same standard of experimental example 4 then.
The results are shown in Table 8.
Table 8
Compound number acaricidal activity compound number acaricidal activity compound number 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
96 A 152 A
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 for 2 red spiders.(Tetranychus urticae) becomes mite to be inoculated on the soybean.Mite and plant are sprayed with the emulsion of The compounds of this invention (200ppm).After the medication the 8th day, press the same standard of experimental example 4 and judge acaricidal activity.
The results are shown in Table 9.
Table 9
Compound number acaricidal activity compound number acaricidal activity compound number 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
Be formulation examples below, in these examples, umber is meant shared weight.
Formulation examples 1 wettable powder
60 50 parts of compound numbers
45 parts of diatomite and clay mixtures
5 parts of polyoxyethylene nonyl ethers
Thereby the above-mentioned substance uniform mixing also grinds the acquisition wettable powder.
Formulation examples 2 emulsions
154 20 parts of compound numbers
20 parts of tetrahydrofuran (THF)s
45 parts of dimethylbenzene
15 parts of ether and alkylbenzene sulfonates
The above-mentioned substance uniform mixing, dissolve emulsion.
Formulation examples 3 pulvis
503 4 parts of compound numbers
95 parts in diatomite, clay and steatitic mixture
1 part of calcium stearate
The above-mentioned substance uniform mixing, grind powder.
Formulation examples 4 granulas
237 3 parts of compound numbers
92 parts in the mixture of bentonite and clay
5 parts in xylogen calcium sulfate
The above-mentioned substance uniform mixing also grinds, the mixture of grinding and an amount of water integrate fully granulate then granula.
Claims (1)
1, the method for the pyrazoles 9 oxime derivate of the logical formula I of preparation,
R wherein
1Represent C
1-4Alkyl or phenyl; R
2Represent hydrogen, C
1-5Alkyl, C
1-3Haloalkyl or phenyl; R
3Represent hydrogen, C
1-4Alkyl or phenyl; R
4Represent hydrogen, C
2-4Alkyl-carbonyl, benzoyl, naphthyl or formula
[wherein X represents hydrogen to the substituting group of representative; Halogen; C
1-12Alkyl; The C that has been replaced by halogen or hydroxyl
1-6Alkyl; C
3-8Cycloalkyl; The cycloalkyl that has been replaced by following 1 to 3 group: C
1-4Alkyl or cyano group; C
2-4Halogenated alkenyl; C
1-6Alkoxyl group; C
1-4Halogenated alkoxy; Phenoxy group; The C that constitutes by two adjacent Xs
1-3Alkylidene dioxygen is for base; Formula-S (O)
PR
5Substituting group (R wherein
5Represent C
1-10Alkyl, C
1-5Haloalkyl or phenyl, p are represented 0,1 or 2 integer); Formula-COOR
6Substituting group { R wherein
6Represent hydrogen; Basic metal; C
1-10Alkyl; The C that has been replaced by phenoxy group
1-5Alkyl; Phenyl }; C
2-6Alkyl-carbonyl; C
2-6The alkane thiocarbonyl group; Formula
Substituting group (R wherein
10And R
11Can be identical or different, represent hydrogen or C
1-6Alkyl); Formula
Substituting group (R wherein
12Represent hydrogen or C
1-5Alkyl, R
13Represent formyl radical or C
2-12Alkoxy carbonyl); Formula
Substituting group (R wherein
14Represent hydrogen or C
1-4Alkyl; Formula
Substituting group (R wherein
15And R
16The common C that forms
1-4Alkylidene group (is not substituted or can be by C
1-4Alkyl replaces), R
17Represent C
1-5Alkyl, B represents oxygen); Formula
Substituting group (R wherein
21, R
22And R
23Can be identical also can be different, represent C
1-4Alkyl); N represents the integer of 1-5, when n represents the integer of 2-5, X can be identical also can be different]; Y represents hydrogen, C
1-6Alkyl, C
1-C
4Haloalkyl, halogen, hydroxyl, C
1-4Alkoxyl group, C
1-4Halogenated alkoxy, C
1-3Alkylene dioxo base, by the phenoxy group that trifluoromethyl replaces, formula-S (O)
qR
27Substituting group (R wherein
27Represent C
1-3Alkyl, q are represented 0,1 or 2 integer), C
2-5Carbalkoxy or formula
Substituting group (R wherein
28And R
29Can be identical also can be different, represent hydrogen or C
1-4Alkyl); Z
1Represent oxygen or sulphur; Z
2Represent oxygen, sulphur or singly-bound; Q represents C
1-6Alkylidene group, the C that has been replaced by halogen or phenyl
1-8Alkylidene group, C
3-12Alkenylene, C
3-12Halo alkenylene or C
3-6Alkynylene; M represents the integer of 1-3, and when m represented 2 or 3 integer, Y can identically also can have together, the method is characterized in that
A) will lead to the compound of formula II
(R wherein
1, R
2, R
3, Y, Z
1With m as defined above, M
1Represent hydrogen or basic metal) with the reaction of the compound of logical formula III
Hal-Q-Z
2-R
4(Ⅲ)
(R wherein
4, Q and Z
2As defined above, Hal represents halogen);
B) will lead to the compound of formula VI
(Ⅵ)
(R wherein
1, R
2, R
3, Y, Z
1With m as defined above) with the reaction of the compound of general formula (VII),
H
2NO-Q-Z
2-R
4(Ⅶ)
(R wherein
4, Q and Z
2As defined above);
C) with the compound of general formula (VIII)
(R wherein
1, R
2, R
3, Y, Q, Z
1With m as defined above, Hal represents halogen) with the reaction of the compound of general formula (IX),
M
2-Z
2-R
4(Ⅸ)
(R wherein
4And Z
2As defined above, M
2Represent hydrogen or basic metal); Or
D) with the compound of general formula (X)
(R wherein
1, R
2, R
3, Y, Z
1, Z
2, Q and m are as defined above; X
1Represent hydrogen or C
1-4Alkyl) compound with general formula (XI) reacts
RH (Ⅺ)
(wherein R represents the substituting group of Shi-OW { wherein W represents basic metal; C
1-10Alkyl; The alkyl that phenoxy group replaces; Phenyl }; Formula
Substituting group (R wherein
10And R
11Can be identical also can be different, represent hydrogen or C
1-6Alkyl).
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP295759/85 | 1985-12-27 | ||
| JP29575985 | 1985-12-27 | ||
| JP295760/85 | 1985-12-27 | ||
| JP26582/86 | 1986-02-08 | ||
| JP151187/86 | 1986-06-27 | ||
| JP177447/86 | 1986-07-28 | ||
| JP206442/86 | 1986-09-02 | ||
| JP206993/86 | 1986-09-03 | ||
| JP20699386 | 1986-09-03 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91108000 Division CN1023287C (en) | 1985-12-27 | 1991-12-17 | Pesticide and miticide composition continaing pyridine oxime derivatives |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86108691A CN86108691A (en) | 1988-01-20 |
| CN1022919C true CN1022919C (en) | 1993-12-01 |
Family
ID=26515997
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 86108691 Expired - Lifetime CN1022919C (en) | 1985-12-27 | 1986-12-26 | Process for preparing pyrazoloxime derivatives |
| CN 91108000 Expired - Lifetime CN1023287C (en) | 1985-12-27 | 1991-12-17 | Pesticide and miticide composition continaing pyridine oxime derivatives |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91108000 Expired - Lifetime CN1023287C (en) | 1985-12-27 | 1991-12-17 | Pesticide and miticide composition continaing pyridine oxime derivatives |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN1022919C (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055083C (en) * | 1995-09-08 | 2000-08-02 | 化学工业部沈阳化工研究院 | Insecticidal acaricidal pyrazoles compounds and preparation thereof |
| CN104151308B (en) * | 2014-07-03 | 2017-12-29 | 南通大学 | Preparation and application containing 1,2,3 thiadiazoles Pyrazole Oxime Esters |
| CN104193727B (en) * | 2014-08-04 | 2018-12-04 | 南通大学 | The preparation and application of Pyrazole Oxime Esters containing trifluoromethyl pyridine |
| CA2978066A1 (en) * | 2015-03-19 | 2016-09-22 | E I Du Pont De Nemours And Company | Fungicidal pyrazoles |
| CN104892591B (en) * | 2015-04-09 | 2017-09-15 | 南通大学 | The preparation method and application of the pyrazoles oxime compound of the oxadiazole heterocycle structure containing 3 aryl 1,2,4 |
| CN104961728A (en) * | 2015-05-22 | 2015-10-07 | 南通大学 | Preparation method and application of pyridinyl methoxybiphenyl structure-containing pyrazole oxime ester compound |
| CN105340896A (en) * | 2015-11-06 | 2016-02-24 | 曹龙巧 | Sanitizer for reproductive medicine inspection room |
| CN106946856B (en) * | 2017-02-08 | 2020-02-14 | 南通大学 | Pyrazole oxime derivative containing tetrazole biphenyl structure and preparation method and application thereof |
| CN106946782B (en) * | 2017-02-08 | 2019-09-24 | 南通大学 | Pyrazole Oxime Esters of the biphenyl structures containing pyrazoles and its preparation method and application |
| CN109867665B (en) * | 2017-12-02 | 2022-01-04 | 沈阳中化农药化工研发有限公司 | Substituted 1,3,4 oxadiazole compound and application thereof |
| CN110092776B (en) * | 2019-04-30 | 2021-09-07 | 南通大学 | Pyrazole oxime ester compound containing pyridine-difluoride pyrazole structure and preparation method and application thereof |
| CN111423413B (en) * | 2020-05-12 | 2022-06-03 | 南通大学 | Preparation and application of pyrazole derivative containing (3-methoxy-4-substituted pyridylmethoxy) phenyl unit |
| CN111440153B (en) * | 2020-05-21 | 2022-06-03 | 南通大学 | Preparation and application of pyrazole compound containing (3-methoxy-4-pyrimidinyloxy) phenyl unit |
| CN111518084B (en) * | 2020-05-21 | 2022-08-09 | 南通大学 | Pyrazole derivative containing pyrimidine heterocyclic unit and preparation method and application thereof |
| CN111635399B (en) * | 2020-07-01 | 2022-05-03 | 南通大学 | Pyrazole derivative containing thiadiazole heterocyclic unit and preparation method and application thereof |
-
1986
- 1986-12-26 CN CN 86108691 patent/CN1022919C/en not_active Expired - Lifetime
-
1991
- 1991-12-17 CN CN 91108000 patent/CN1023287C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1023287C (en) | 1993-12-29 |
| CN86108691A (en) | 1988-01-20 |
| CN1061321A (en) | 1992-05-27 |
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