CN1061321A - Insecticidal and acaricidal compositions containing pyrazole oxime derivatives - Google Patents
Insecticidal and acaricidal compositions containing pyrazole oxime derivatives Download PDFInfo
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- CN1061321A CN1061321A CN 91108000 CN91108000A CN1061321A CN 1061321 A CN1061321 A CN 1061321A CN 91108000 CN91108000 CN 91108000 CN 91108000 A CN91108000 A CN 91108000A CN 1061321 A CN1061321 A CN 1061321A
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Abstract
The invention relates to insecticidal and acaricidal compositions containing pyrazole oxime derivatives of general formula , which are useful in agriculture and in the garden as effective insecticides, wherein the symbols in formula are defined in the description.
Description
The present invention relates to the pyrazoles 9 oxime derivate, its preparation method and contain the pyrazoles 9 oxime derivate and be used for the agricultural and the desinsection and the miticide composition of gardening as active ingredient, general formula (I) is represented this pyrazoles 9 oxime derivate
R wherein
1Represent C
1～
4The alkyl or phenyl of C; R
2Represent H, C
1-5Alkyl, C
1-3Fontanel substituted alkyl 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 fontanel element, cyano group, hydroxyl, C
1-5Alkoxyl or C
2-6The alkyl that alkoxy carbonyl group has replaced, C
3-8Cycloalkyl; The cycloalkyl that has been replaced by following 1 to 3 group; C
1-4Alkyl, fontanel element or cyano group; By fontanel element, hydroxyl, C
2-4Alkoxy carbonyl group or C
2-6The C that alkyl-carbonyl has replaced
2-4Alkenyl; Phenyl; Hydroxyl; C
1-6Alkoxyl; By fontanel element or C
2-6The C that alkoxy carbonyl group has replaced
2-4Alkoxyl; Phenoxy group (its can by or not by C
1-3The fontanel substituted alkyl replaces); Benzyloxy; The C that constitutes by two adjacent Xs
1-3Alkylidene dioxygen is for base; Pyridine oxo base (its not by or by fontanel element or C
1-3The fontanel substituted alkyl replaces); Formula-S(O)
PR
5Substituting group (R wherein
5Represent C
1-6Alkyl, C
1-5Fontanel substituted alkyl or phenyl, p are represented 0,1 or 2 integer); Cyano group; Formoxyl; Nitro; Formula-COOR
6Substituting group (R wherein
6Represent hydrogen; Alkali metal; C
1-10Alkyl; By fontanel element, C
1-4Alkoxyl, phenoxy group, C
2-4The C that alkoxy carbonyl group 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 alkoxy carbonyl group has replaced
2-6Alkyl-carbonyl; Benzoyl (its not by or can be by fontanel element or C
1-6Alkyl replaces); C
2-6The alkane thiocarbonyl group; C
3-7The alkoxy carbonyl group carbonyl; Formula
Substituting group (R wherein
10And R
11Can be identical or different, represent hydrogen, C
1-6Alkyl or phenyl); The piperidino 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 formoxyl, C
2-12Alkoxy carbonyl, or by fontanel element or C
1-4The C that alkoxyl has replaced
2-5Alkoxy carbonyl); Formula
Replacement (R wherein
14Represent hydrogen, C
1-4Alkyl, C
2-6Alkoxyalkyl; Formula
Substituting group (R wherein
15And R
16Can be identical also can be different, represent C
1-4Alkyl or can generate C jointly
1-4 alkylidenes, 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 1～5 integer, and when n represented 2～5 integer, X can be identical or different); Y represents hydrogen; C
1-6Alkyl, C
1-4The fontanel substituted alkyl, fontanel element, hydroxyl, C
1-4Alkoxyl, C
1-4Fontanel is for alkoxyl, C
1-3Alkylene dioxo base, phenoxy group (replace or can be replaced), the qR of formula-S(O) by trifluoromethyl
27(R wherein
27Represent C
1-3Alkyl, q are represented 0,1 or 2 integer), hydroxycarbonyl group, C
2-5Alkoxy carbonyl group or formula
Substituting group (R wherein
28And R
29Can identical or different representative hydrogen, C
1-4Alkyl or benzyl (do not replace or can be by C
2-6Alkoxy carbonyl group replaces); Z
1Represent oxygen or sulphur; Z
2Represent oxygen, sulphur or singly-bound; Q represents C
1-8Alkylidene, the C that has been replaced by fontanel element or phenyl
1-8Alkylidene, C
3-12Alkylidene, C
3-12Fontanel is for alkylidene or C
3-6Alkynyl; M represents 1～3 integer, and when m represented 2 or 3 integer, Y can be identical or different.
Used in this application noun " alkyl, alkylidene, alkenyl and alkynyl " is meant alkyl, alkylidene, alkenyl and the alkynyl of straight or branched respectively.Noun " fontanel base " refers to that fontanel is plain as fluorine, and bromine, chlorine etc., noun " fontanel substituted alkyl " refer to the alkyl that replaced by 1 or more a plurality of identical or different fontanelle atom.
The represented compound of general formula (I) with the front is the new compound of not addressing in the document.For belonging to lepidopterous insect such as diamond-back moth, tomato moth, prodenia litura, striped rice borer etc. and belonging to insect such as brown plant-hopper, black peach aphid etc. and the mite class of Semiptera, they have good insecticidal action.In addition, for the damage by disease and insect of vegetables, fruit tree, flowers and plants and ornamental plants etc. such as rice blast, powdery mildew, downy mildew, crown rust, leaf blight, shell rot, purple rust etc., they also have good bactericidal action.
In compound of the present invention, be used as insecticide 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) benzoic acid tert-pentyl ester
4-(1,3-dimethyl-5-phenoxy group pyrazoles-4-yl) methene amido oxygen methyl) benzoic acid cyclohexyl
4-((1,3-dimethyl-5-phenoxy group pyrazoles-4-yl) methene amido oxygen methyl) benzoic acid 1-methyl cyclohexane ester
4-((1,3-dimethyl-5-phenoxy group pyrazoles-4-yl) methene amido oxygen methyl) formic acid-2-chloromethyl-2-propyl ester
4-((1-methyl-5-phenoxy group-3-trifluoromethyl pyrazol-4-yl) methene amido oxygen methyl) benzoic acid tert-pentyl ester
1,3-dimethyl-5-phenoxy group pyrazolyl-4-carbonyl aldoxime neighbour-4-tert-butyl group benzyl oxide
1,3-dimethyl-5-phenoxy group pyrazolyl-4-carbonyl aldoxime neighbour-4-(1-cyano group cyclopenta) 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 benzyl ether
1,3-dimethyl-5-phenoxy group pyrazolyl-4-carbonyl aldoxime neighbour-4-(1,1,2,2-tetrafluoro ethyoxyl) benzyl ether
1,3-dimethyl-5-phenoxy group pyrazolyl-4-carbonyl aldoxime neighbour-4-tert-butoxy benzyl ether
1,3-dimethyl-5-phenoxy group pyrazolyl-4-carbonyl aldoxime neighbour-4-(seven fluoropropyl sulphur) benzyl ether
1,3-dimethyl-5-phenoxy group pyrazolyl-4-carbonyl aldoxime neighbour-4-(seven fluoropropyl sulfinyls) benzyl ether
1,3-dimethyl-5-phenoxy group pyrazolyl-4-carbonyl aldoxime neighbour-4-(1,1,2,2-tetrafluoro ethyl sulphur) benzyl ether
N, N-diisopropyl-4-((1, the methene amido oxygen methyl of 3-dimethyl-5-phenoxy group pyrazolyl-4-)) benzamide
Tert-butyl group 4-((1, the methene amido oxygen methyl of 3-dimethyl-5-phenoxy group pyrazolyl-4-)) phenyl ketone
2-isopropyl-2-(4-(1, the methene amido oxygen methyl of 3-dimethyl-5-phenoxy group pyrazolyl-4-) } phenyl)-1, the 3-dioxolanes
2-isopropyl-2-(4-(1, the methene amido oxygen methyl of 3-dimethyl-5-phenoxy group pyrazolyl-4-) } phenyl)-1, the 3-dithiolane
N-4-((1, the methene amido oxygen methyl of 3-dimethyl-5-phenoxy group pyrazolyl-4-))-phenyl-N-ethyl carbamic acid tert-butyl ester
1,3-dimethyl-5-phenoxy group pyrazolyl-4-carbonyl aldoxime neighbour-2-(4-tert-butyl group phenoxy group) ether
The compound that is used as bactericide specially also is recited in down:
4-((1,3-dimethyl-5-phenoxy group pyrazolyl-4-)-and 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-(methyl mercapto) benzyl ether
1,3-dimethyl-5-phenoxy group pyrazoles-4-base carbonyl aldoxime neighbour-4-(difluoromethyl sulfonyl) benzyl 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 compound, for example, can synthesize with following A, B, C and D method with chemical formulation with general formula (I) expression.
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 fontanelle atom, M
1Expression hydrogen atom or alkali metal atom.
By the pyrazoles 9 oxime derivate of general formula (I) expression can by the compound of the compound of general formula (II) and general formula (III) contain or alkali free atent 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 isopropyl alcohol, the tert-butyl alcohol, diethylidene glycol), ketone (as acetone, MEK, cyclohexanone), ethers (as diethyl ether, diisopropyl ether, oxolane, diox, glyme, diethylene glycol dimethyl ether), fontanel hydro carbons (as dichloroethane, chloroform, carbon tetrachloride, tetrachloroethanes), arene (as benzene, chlorobenzene, nitrobenzene, 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 inorganic base and organic base.Inorganic base comprises the carbonate of alkali for example or alkaline earth metal such as sodium carbonate, potash, calcium carbonate, sodium bicarbonate etc., the hydroxide of alkali or alkaline earth metal such as sodium hydroxide, potassium hydroxide, slaked lime etc. and alkali-metal hydride such as lithium hydride, sodium hydride etc.
Organic bases comprises for example diethylamine, triethylamine, pyridine, 4-dimethylamino naphthyridine etc.
As for the consumption of used alkali, use the equimolar consumption of representing with general formula (II) of compound just enough, but, can use excessive consumption.
For example, can by the following stated method produce general 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 that is general formula (II) can be reacted in appropriate solvent by the compound of general formula (IV) and the compound of general formula (V), the compound of resulting general formula (VI) and hydroxylamine is reacted make.
In all represented compounds of general formula (III), particularly working as Q is methylene, Z
2Be singly-bound and R
4When being the phenyl of a replacement, they also are some new compounds, 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.
Can in atent solvent, react by the compound of the compound of general formula (VI) and general formula (VII) with the pyrazoles 9 oxime derivate of general formula (I) expression and to prepare.
The solvent that can be used for this reaction except that the ketone that is used for method A, the solvent of addressing previously in addition.
Compound with 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 nitrogenous compound first 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 general formula (I) can by with the compound of the compound of general formula (VIII) and general formula (IX) in atent solvent or alkali 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 alkali-metal substituting group; C
1To C
10Alkyl; By fontanel element, C
1To C
4Alkyl oxy, 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; Can yes or no 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 the atent solvent that contains or do not contain dehydrating agent by the compound of the compound of general formula (X) and general formula (XI) and prepare by general formula.After being translated into acid chloride, 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, oxolane, diox, diethylene glycol (DEG)), fontanel hydro carbons (as carrene, chloroform, carbon tetrachloride), 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 reaction temperature at method A in room temperature.Reaction time is depended on the reaction temperature and the extent of reaction, but can suitably select in 1 minute to 48 hours scope.
Because this reaction is a reaction with same mole, so in carrying out course of reaction 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 separating method etc. are purified.
Pyrazoles 9 oxime derivate with general formula (I) expression 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.
Representative instance with the pyrazoles oxime of general formula (I) expression is listed in table 1, but this derivative is not limited in these examples.
Annotate 1: the No. 180 compound
1The HNMR 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
1The HNMR 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-carbonyl aldoxime.1.98 the potash of the 4-bromomethyl-benzoic acid methyl ester of gram (0.00865 mole) and 1.19 grams (0.009 mole) adds in 50 milliliters of acetone, and under refluxad heats resulting mixture about 8 hours.After reacting completely, remove acetone, in residue, add entry then and extract with ethyl acetate with the method for reduction vaporization.Wash the ethyl acetate extraction thing with water and make its drying, remove ethyl acetate with the method for evaporation again, obtain the oily product thus.With silica gel column chromatography purification oily product, obtain 2.0 gram required 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)s, 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 reaction is finished, add entry, extract with ethyl acetate then to reaction solution.Wash the ethyl acetate extraction thing with water and carry out drying, with method of evaporating ethyl acetate is removed then, obtain coarse crystallization thus.This crystal through crystallization again, 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 solution, add entry, with ethyl acetate this solution is extracted then, wash the ethyl acetate extraction thing with water and carry out drying, remove ethyl acetate 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 MEK that the sodium carbonate 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 MEK, and in residue, add entry, extract with ethyl acetate with method of evaporating.Wash the ethyl acetate extraction thing with water and carry out drying, remove ethyl acetate 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 potash 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 residue, add entry then and extract, wash the ethyl acetate extraction thing with water and carry out drying, remove ethyl acetate, obtain the coarse crystallization body thus with method of evaporating with ethyl acetate with method of evaporating.This crystalline solid obtains 2.8 gram required compounds thus through methyl alcohol crystallization again.
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) benzoic 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)s, 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 solution, add entry, then with this solution of ethyl acetate extraction.Wash the ethyl acetate extraction thing with water and carry out drying, remove ethyl acetate 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-base carbonyl the aldehyde of 1.0 grams (0.0049 mole) and the tert-butyl group 4-amino oxygen methyl benzoic acid 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 residue, add entry then and extract with ethyl acetate with method of evaporating.Wash this ethyl acetate extraction thing with water and carry out drying, remove ethyl acetate 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.
Productive rate 80% product form: pulpous state.
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
2-phenoxy group ethyl 4-(the 5-(4-fluorinated phenoxy) and-1,3-dimethyl pyrazole-4-yl } methene amido oxygen methyl) benzoic ether (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 dimethyl sulfoxide (DMSO)s, the powdered potassium hydroxide that adds 0.65 gram (0.0116 mole) then stirred this gained mixture 30 minutes down at 30 ℃.The 2-phenoxy group ethyl-4-chloromethyl benzoic acid 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 solution, add entry, then with this reaction solution of ethyl acetate extraction.Wash this ethyl acetate extraction thing with water and carry out drying, remove ethyl acetate, 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) benzoic 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) the triphenyl phosphatization thing of the phenol of benzoic 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) benzoic acid (No. 14 compound)
4-((1,3-dimethyl-5-phenoxy group pyrazoles-4-yl) methene amido oxygen the methyl)-methyl benzoates 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 hydrochloric acid, produce the crystal of precipitation.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) benzoic 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 neighbour-benzyl ether (No. 181 compound)
With 1 of 2.0 grams (0.00866 mole), the potash of the benzyl bromide a-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 ethyl acetate with method of evaporating.Wash the ethyl acetate extraction thing with water and carry out drying, remove ethyl acetate 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-base-carbonyl aldoxime neighbour-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 oxolanes, at room temperature adds the sodium hydride of 0.19 gram (0.0079 mole) then, stirs this gained solution.The 4-trifluoromethylbenzene methyl bromide that adds 1.7 grams (0.0071 mole) then then under refluxad makes its heating 3 hours.After reacting completely, in reaction solution, add 100 ml waters, extract with ethyl acetate then.Wash the ethyl acetate extraction thing with water and carry out drying, remove ethyl acetate, obtain the oily product thus with vaporization method.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 neighbour-4-(1-cyano group cyclopropyl) benzyl 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 continuous 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 solution, add 100 ml waters, extract with ethyl acetate then.Wash the ethyl acetate extraction thing with water and carry out drying, remove ethyl acetate 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-butyl benzene 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)s, after the potassium hydroxide that adds 1.0 grams (0.0178 mole), at room temperature stirs this gained solution 30 minutes.4-tert-butyl benzene 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 solution extract with ethyl acetate then.Wash this ethyl acetate extraction thing with water and carry out drying, remove ethyl acetate 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 neighbour-benzyl ether (No. 279 compound)
5-(4-chlorophenoxy with 2.0 grams (0.0092 mole))-1-methylpyrazole-4-carbonyl aldoxime, 1.5 the potash of the benzyl bromide a-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 solution, extract with ethyl acetate then.Wash this ethyl acetate extraction thing with water and carry out drying, remove ethyl acetate, 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 neighbour-4-cyclohexyl benzene 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 dioxanes, 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 solution, under refluxad added 5 hours.After reacting completely, in reaction solution, add 100 ml waters and extract with ethyl acetate.Wash this ethyl acetate extraction thing with water and carry out drying, remove ethyl acetate, 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-chlorphenyl sulphur)-1,3-dimethyl pyrazole-4-carbonyl aldoxime neighbour-benzyl ether (No. 290 compound)
With the 5-(4-chlorphenyl sulphur-1 of 2.0 grams (0.0071 mole), 3-dimethyl pyrazole-4-carbonyl aldoxime is dissolved in 20 milliliters of dimethyl sulfoxide (DMSO)s, 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 solution, add 100 ml waters and extract with ethyl acetate.Wash the ethyl acetate extraction thing with water and carry out drying, remove ethyl acetate, 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 neighbour-4-(1-cyano group cyclopenta)-benzyl 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 cyclopenta) the benzyl 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 ethyl acetate with method of evaporating.Wash the ethyl acetate extraction thing with water and carry out drying, remove ethyl acetate, 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 neighbour-4-(2,2-dibromo vinyl) benzyl 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, neighbour-the 4-(2 that in this solution, adds 2.8 grams (0.0091 mole), the 2-dibromo vinyl) the benzyl azanol, and under refluxad heated 3 hours.After reacting completely, under reduced pressure, remove methyl alcohol, add entry then and extract with ethyl acetate with method of evaporating.Wash this ethyl acetate extraction thing with water and carry out drying, remove ethyl acetate, 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 neighbour-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)s, and after adding the powdered potassium hydroxide of 0.3 gram (0.0053 mole), stirs this gained solution.4-fluoro benzyl bromide a-bromotoluene to this reaction solution adding 0.81 gram (0.0043 mole) at room temperature reacted 3 hours.After reacting completely, in this reaction solution, add 200 ml waters, and extract with ethyl acetate.Wash this ethyl acetate extraction thing with water and carry out drying, remove ethyl acetate, obtain the oily product thus with method of evaporating.Separate with silica gel column chromatography
This oily product obtains 1.3 gram required products thus.
Productive rate 89% n
20 D1.5681
Embodiment 22
The 5-(4-chlorophenoxy)-1,3-dimethyl pyrazole-4-carbonyl aldoxime neighbour-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 potash of the 2-chlorine benzyl bromide a-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 ethyl acetate with method of evaporating.Wash this ethyl acetate extraction thing with water and carry out drying, remove ethyl acetate, 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, benzyl ether (No. 322 compound) 3-dimethyl pyrazole-4-carbonyl aldoxime neighbour-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)) sodium carbonate 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 ethyl acetate with method of evaporating.Wash this ethyl acetate extraction thing with water and carry out drying, remove ethyl acetate, 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 neighbour-4-trimethyl silyl benzyl 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)s, 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 silyloxy benzyl bromide a-bromotoluene of 1.0 grams (0.0041 mole), at room temperature reacted 4 hours.After reacting completely, in this reaction solution, add 200 ml waters and extract with ethyl acetate.Wash this ethyl acetate extraction thing with water and carry out drying, remove ethyl acetate, 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 neighbour-4-(1,1,2,2-tetrafluoro ethyoxyl) benzyl 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 ethyoxyl) benzyl bromide a-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 ethyl acetate with method of evaporating.Wash this ethyl acetate extraction thing with water and carry out drying, remove ethyl acetate, 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 neighbour-4-tert-butoxy benzyl 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 oxolanes, and adds 0.092 gram sodium hydride so that carry out the synthetic reaction of the sodium salt of above-mentioned oxime.The 4-tert-butoxy benzyl bromide a-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 solution, add 200 ml waters, extract with ethyl acetate then.Wash this ethyl acetate extraction thing with water and carry out drying, remove ethyl acetate, obtain the oily product thus with method of evaporating.Separate this oily product with silica gel column chromatography, obtain 1.3 gram required products thus
Productive rate 80% n
20 D1.5653
Embodiment 27
The 5-(4-fluorophenoxy)-1,3-dimethyl pyrazole-4-carbonyl aldoxime neighbour-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 solution, add 0.86 gram (0.004 mole)
3,4-Methylenedioxybenzyl bromine, and under 40 ℃ to 50 ℃ conditions, reacting 3 hours.After reacting completely, in reaction solution, add 200 ml waters, extract with ethyl acetate then.Wash the ethyl acetate extraction thing with water and carry out drying, remove ethyl acetate, 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 neighbour-4-methyl sulphonyl benzyl 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 oxolanes.In this solution, add 1 of 0.6 gram (0.0039 mole), the two heterocycles (5.4.0) of 8-phenodiazine-7-endecatylene, and under 40 ℃ to 50 ℃ conditions, reacted 5 hours.After reacting completely, in this reaction solution, add 200 ml waters and extract with ethyl acetate.Wash this ethyl acetate extraction thing with water and carry out drying, remove ethyl acetate, obtain the oily product thus with method of evaporating.Separate this oily product with silica gel column chromatography, obtain 1.2 gram required products thus.
Productive rate 74% n
20 D1.5866
Embodiment 29
1,3-dimethyl-5-phenoxy group pyrazoles-4-base phenyl ketoxime neighbour-4-difluoromethyl sulphur benzyl 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 potash of the 4-difluoromethyl sulphur benzyl bromide a-bromotoluene of gram (0.0033 mole) and 1.0 grams (0.0072 mole) adds in 50 milliliters of acetone, and this gained mixture heating was reacted in 6 hours.After reacting completely, under reduced pressure, remove acetone, add entry then and extract with ethyl acetate with method of evaporating.Wash this ethyl acetate extraction thing with water and carry out drying, remove ethyl acetate, obtain containing oil product thus with method of evaporating.In silica gel, separate this with the column chromatography separating method and contain oil product, 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 neighbour-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) neighbour-(4-(1,1,2,2-tetrafluoro ethylmercapto group) benzyls) hydroxylamine.Be reflected at 50～60 ℃ and carried out 2 hours, after reaction was finished, decompression steamed ethanol, adds entry then, uses 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 neighbour-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 adjacent (the 4-seven fluorine rosickyite base benzyls) hydroxylamine of 1.4 grams (0.0043 mole) are added in 30 ml methanol, and the mixture that obtains added thermal response 5 hours.After reacting completely, methyl alcohol is steamed in decompression, 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
S-ethyl 4-((1,3)-dimethyl-5-phenoxy group pyrazoles-4-yl) methylene ammonia oxygen methyl) benzoic acid thioesters
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)s, adds 0.3 gram (0.0053 mole) potassium hydroxide powder then, mixes solution.Add 0.92 gram (0.0043 mole) S-ethyl 4-chloromethyl benzoic acid thioesters in this solution, being reflected at room temperature carried out 3 hours, after reacting completely, add 200 ml waters to using in the reactant liquor of 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-tert-butyl group 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-tert-butyl group-4-chloromethylbenzene formamide and 1.0 gram (0.0072 mole) potash are added in 20 milliliters of acetonitriles, the mixture that obtains refluxes and heated 6 hours.After reacting completely, remove acetonitrile under reduced pressure.Add water then in residue, 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 neighbour-4-pivaloyl 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) sodium carbonate are added in 40 milliliters of acetone, the mixture heating is reacted.After reacting completely, remove acetone under reduced pressure.After residue adds entry, use ethyl acetate extraction, acetic acid ethyl acetate extract washes with water, and dry then, steaming removes ethyl acetate and obtains oily product.This grease 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-dioxolanes (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-dioxolanes, heating 3 hours then refluxes.After reacting completely, reactant liquor 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-dioxolanes (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-dioxolanes is added in 20 milliliters of ethanol.The mixture that obtains added thermal response 3 hours, after reacting completely, removed ethanol under reduced pressure, added water behind residue, used 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 neighbour-4-(1-ethoxy) benzylic ether (compound 584)
1.0 gram (0.0028 mole) 1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime-neighbour-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 added hot reflux 3 hours then.After reacting completely, remove methyl alcohol under reduced pressure, after residue 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 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)s, 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) formamide in reactant liquor, be reflected at room temperature and carried out 3 hours.After reacting completely, reactant liquor 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 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) potash are added in 20 milliliters of acetonitriles, the mixture that obtains added hot reflux 6 hours.After reacting completely, remove acetonitrile under reduced pressure, after residue 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) sodium carbonate are added in 40 milliliters of acetone, the mixture heating that obtains is reacted.After reacting completely, remove acetone under reduced pressure, after the residue 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-isopropyl formamide (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-bromoethyl phenyl-N-isopropyl formamides in this reactant liquor, be reflected at 40 ° to 50 ℃ reactions 3 hours.After reacting completely, reactant liquor 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 acetamide (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-bromoethyl phenyl-N-ethyl-trimethyl acetamide and 0.2 gram (0.005 mole) potassium hydroxide are dissolved in 30 milliliters of dimethyl sulfoxide (DMSO)s, are reflected at 40 °～50 ℃ and carry out 6 hours.After reacting completely, reactant liquor is poured in 200 ml waters, uses ethyl acetate extraction then, and acetic acid ethyl acetate extract washes with water dry then, steams 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 shape: starchiness
Embodiment 43
5-ethyl-3-(N-4 (the 5-(4-fluorophenoxy) and-1,3-dimethyl pyrazole-4-yl } methylene 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)s, adds 0.3 gram (0.0053 mole) potassium hydroxide powder.Being reflected at 40 °～50 ℃ carried out 5 hours.After reacting completely, reactant liquor 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 neighbour-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)s, 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 reactant liquor, 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 neighbour-2-(4-tert-butyl group 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 gram (0.0034 mole) is right-(2-bromine oxethyl)-tert-butyl benzene and 1.38 gram potash are added in 50 milliliters of acetonitriles, the heating 8 hours that refluxes of the mixture that obtains.After reacting completely, add water in reactant liquor, 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 } ethyoxyl) 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 reactant liquor, 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 neighbour-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-dichloro-benzenes and 0.58 gram (0.0038 mole) 1.8-phenodiazine, two heterocycles (5,4,0)-and the 7-endecatylene 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 reactant liquor, 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-lutidines-4-carbonyl aldoxime neighbour-2-phenoxy propyl ether (compound number 741)
1.0 gram (0.0037 mole) 5-(4-chlorophenoxy)-1,3-lutidines-4-carbonyl aldoxime sodium and 0.63 gram (0.037 mole) 2-chloro-1-methyl ethoxy benzene are added in 50 milliliters of oxolanes, reactant mixture is followed stirring and refluxing heating 5 hours.After reacting completely, add water in reactant liquor, 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 neighbour-2-(4-tert-butyl benzene sulfenyl)
1.0 gram (0.0030 mole) 1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime neighbour-2-bromoethyl ether, 0.5 gram (0.0030 mole) is right-and tert-butyl benzene sulphur and 1.0 gram (0.0072 mole) potash are added in 60 milliliters of acetonitriles, and heating 5 hours then refluxes.After reacting completely, add water in reactant liquor, 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 neighbour-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)s.Add 1.07 the gram (0.0043 mole) right-chloro-3-bromine propoxyl group benzene, be reflected at 40 °～50 ℃ and carried out 4 hours.After reacting completely, add water in reactant liquor, 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 neighbour-4-(4-chlorophenoxy)-2-cyclobutenyl ether (compound number 776)
1.0 gram (0.0031 mole) 1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime neighbour-4-chloro-2-cyclobutenyl ether and 0.6 restrains (0.0036 mole), and right-chlorophenol sylvite is added in 40 milliliters of oxolanes, follows stirring and refluxing heating 3 hours then.After reacting completely, add water in reactant liquor, 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 neighbour-6-phenoxy group hexyl ether (chemical combination
Thing numbers 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)s, adds sodium hydride 0.11 gram (0.0045 mole) in room temperature then.Reactant liquor stirred 30 minutes.Add the own oxygen base of 1.1 gram (0.0043 mole) 6-bromines benzene in this solution, be reflected at 50 °～60 ℃ and carried out 3 hours.After reacting completely, add water in reactant liquor, 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)s, and mixture stirred 30 minutes.Add 0.8 gram (0.0043 mole) benzoic acid 2-chloroethene ester, be reflected at 40 °～50 ℃ and carried out 3 hours.After reacting completely, add water in reactant liquor, 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 neighbour-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) neighbour-(2-ethoxyethyl group) azanol.Being reflected at room temperature carried out 3 hours.After reacting completely, add water in reactant liquor, 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 neighbour-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)s, adds 0.3 gram (0.0053 mole) potassium hydroxide powder then, stirs this mixture.Add 1.0 gram (0.0063 mole) iodomethane to this reactant liquor, be reflected at room temperature and carried out 3 hours.After reacting completely, reactant liquor 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 neighbour-2-propine ether (compound number 795)
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) potash are added in 50 milliliters of acetone, and the mixture that obtains refluxes and heats.After reacting completely, reactant liquor is poured in 200 ml waters, 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 neighbour-2-(4-fluorophenyl)-ethyl ether (compound number 815)
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) bromic ether in reactant liquor, be reflected at 40 °～50 ℃ and carried out 3 hours.After reacting completely, reactant liquor 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 neighbour-3-(4-chlorphenyl)-propyl ether (compound number 824)
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) neighbour-(3-(4-chlorphenyl) propyl group) hydroxylamine.Being reflected at 40 °～50 ℃ then carried out 2 hours.Remove methyl alcohol under reduced pressure, add water then in residue, 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 neighbour-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)s.After reacting completely, reactant liquor is poured in 200 ml waters, uses ethyl acetate extraction then.Acetic acid ethyl acetate extract washes with water 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 aldoxime neighbour-allyl ether (compound number
857）
1.0 gram (0.0033 mole) 1,3-dimethyl-5-phenoxy group pyrazoles-4-base phenyl aldoxime, 0.5 gram (0.0041 mole) allyl bromide, bromoallylene and 1.0 gram potash are added in 50 milliliters of acetone, and the mixture heating was reacted in 6 hours.After reacting completely, reactant liquor is poured in 200 ml waters, uses ethyl acetate extraction.Acetic acid ethyl acetate extract washes with water 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-methyl benzoic acid tert-butyl ester, 0.3 gram (0.0012 mole) benzoyl peroxide and 6g(0.006 mole) sodium carbonate is suspended in 100 milliliters of carbon tetrachloride, 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 reactant liquor then, filter and remove the material that is insoluble to carbon tetrachloride.Remove carbon tetrachloride then under reduced pressure and get 16.2 gram 4-bromo methyl acid tert-butyl esters of crystallization.
53.4 ℃ of productive rate 90% fusing points
Synthetic embodiment 2
15.0 gram (0.0049 mole) 4-bromo ethyl phenenyl t-butyl formate, 8.2 gram (0.05 mole) N-hydroxyl-phthalimide 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.Reactant liquor cools off with frozen water, filters then and obtains crystallization.Crystallization is dissolved in 50 milliliters of carrene, slowly drips 3 milliliters of isopropyl alcohols that contain 0.5 gram (0.05 mole) hydrazine hydrate in room temperature in solution then.After dropwising, reactant liquor refluxes and heated 2 hours.Reactant liquor 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 carbon tetrachloride, drips 3.2 gram bromines under refluxing in time-consuming more than 30 minutes.After dropwising, reaction is proceeded 30 minutes.Reactant liquor cooling back is steamed except that carbon tetrachloride 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)s, follow ice-cooled adding 14.4 gram (0.219 mole) 85% potassium hydroxide powders after, reactant liquor stirred 30 minutes.After reacting completely, reactant liquor is poured in 300 ml waters, divides then three times, uses 80 milliliters of extracted by ether at every turn, washs with 300 ml waters then.The ether extracted liquid anhydrous sodium sulfate drying steams and removes ether.Residue obtains 5.2 grams 1,3-dimethyl-5-phenoxy group pyrazoles-4-carbonyl aldoxime neighbour-2-bromoethyl ether by the dried chromatographic column of silica gel.
Productive rate 71.2% n
23.8 D1.5721
The invention provides with physiologically active compound of the present invention and kill and control harmful insect and mite.One of imbody of the present invention is: compound directly is used as protection purpose 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 particles 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 harmful 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 carrier, if necessary, can mix with adjuvant, 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 carrier and the adjuvant (if necessary) of suitable proportion, disperses, and suspends, blending, perfusion absorbs or adhesion, thereby form suitable preparation and resemble solution, suspending agent, concentration emulsifier, the oil spray agent, wet-milling, granula, tablet, pill, ointment, aerosol or the like.
The form that inert carrier adopts i.e. also liquid of solid.The solid carrier example has plant dust figure soybean meal, flour, wood powder, bark powder, sawdust, ground offal, walnut parting, the extraction residue of wheat bran, fiber powder and plant; Fibrous substance resembles paper, corrugated plating and useless cloth; The synthetic polymer class resembles powdery synthetic resin: 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, contain silica sand, mica and " white carbon " (synthetic silica of high dispersive, think segregative hydration silicon and hydrated SiO 2, contain the commercial product of calcium silicates as main component)) activated carbon, sulphur powder, float stone, ripe diatomite, cob brick, lime-ash, slag, calcium 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-carrier is from those solubilized active components and can not dissolve them but can disperse to select their material with adjuvant.For example, following material can use or mix use separately: water, alcohols (example: methyl alcohol, ethanol, isopropyl alcohol, butanols, the ethene glycol), ketone (example: acetone, MEK, methyl iso-butyl ketone (MIBK), diisobutyl ketone and cyclohexanone), ethers (example, ether ， diox, methylcellulose, dipropyl ether and oxolane, aliphatic carbon hydride (routine gasoline and mineral oil), aromatic carbon hydride (example, benzene, toluene, dimethylbenzene, naphthalene, Fluhyzon), fontanel is for hydrocarbons (example, dichloroethane, chlorobenzene, chloroform, carbon tetrachloride), ester class (example, ethyl acetate, the dibutyl phthalate ester, diisopropyl phthalate ester and dioctyl phthalate (dop)), acid acylamide (example, dimethyl formamide, diethylformamide and dimethylacetylamide), nitrile (example, acetonitrile), and dimethyl sulfoxide (DMSO).
Gaseous carrier comprises it being freon and other aerosol propellants of gas under normal operation.
Adjuvant cited below uses according to various objectives.Under certain conditions, they are used in combination with other material.Under other conditions, then without adjuvant.
Resemble polyoxyethylene alkyl aryl ether, polyoxyethylene alkyl ether, polyoxyethylene high fatty acid ester, polyoxyethylene resinate with surfactant, polyoxyethylenesorbitan monolaurate, polyoxyethylene sorbitan monoleate, alkyl aryl sulfonate, the dignified thing of naphthalane sulfonic acid, lignosulfonates and high alcohol sulfate are in order to make the emulsification of active component energy, dispersion, dissolving and/or moistening.
In order to make the dispersion of active component, gluing, agglomerating stable, use usually: casein, gelatin, starch, alginic acid, methylcellulose, carboxymethyl cellulose, gum Arabic, polyvinyl alcohol, turpentine oil, rice bran oil, bentonite and lignosulfonates.
In order to improve the solid composite flowability, suggestion wax, stearate and alkyl phosphate.
But the peptizing agent of naphthalane sulfonic acid cooling thing and polyphosphate conduct dispersive composition is used in suggestion.
Adding defoamer resembles silicone oil and is fine.
The content of active component is adjusted according to actual needs.For powder or shot-like particle, content accounts for weight 0.5～20% usually.For emulsification concentrate, suspending concentrate or 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 applied on agricultural and the gardening with effective insecticidal, the amount of killing mite or sterilization.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 active component consumption relies on various factors, example, application aims, the vegetative period in crops, weather, environmental condition, composition forms, application mode, institute's agrotype to be processed or the like.
When using bactericidal composition separately, active ingredient agent; Amount 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 auximone and uses in addition, even these reagent can combine with The compounds of this invention and use.
The pesticide example that can mix with insecticide of the present invention is face as follows:
Neighbour-(4-nitro-3-aminomethyl phenyl)-D2EHDTPA neighbour, neighbour-dimethyl ester (phenittrothion)
Neighbour-(3-methyl-4-methyl mercapto phenyl)-D2EHDTPA neighbour, adjacent dimethyl ester (fenthion)
S-(ethoxycarbonyl phenyl methyl)-and the neighbour, neighbour-dimethyl-phosphorodithioate (phenthoate dimephenthoate cidial)
Adjacent-(2-isopropyl-4-methylpyrimidine base-6-)-neighbour, neighbour-systox (basudin)
2,2,2-three chloro-1-ethoxy-neighbours, neighbour-dimethyl phosphate (Diptox)
Neighbour-ethyl, neighbour-right-nitrobenzophenone, phenyl thiophosphate (EPN)
Neighbour-ethyl, neighbour-right-cyano-phenyl, phenyl phosphinylidyne thioesters (Surecide)
The neighbour, neighbour-dimethyl, S-phthalimidomethyl phosphorodithioate (Kayaphos)
The neighbour, neighbour-dimethyl, the adjacent stupid diformazan imide diethyldithioposphoric acid ester (phosmet) of S-
The neighbour, neighbour-dimethyl, neighbour-dichloroethylene phosphate (dichlorvos)
The neighbour, neighbour-dimethyl, S-(N-methylamino formoxyl methyl)-phosphorodithioate (Rogor)
The neighbour, neighbour-dimethyl, S-(1,2-diethyl-ester group ethyl)-phosphorodithioate (marathon)
1-naphthyl N-methyl carbamate (sevin)
Between the N-methyl carbamic acid-toluene ester (meta-tolyl-N-methylcarbamate (MTMC))
The different third oxygen phenyl ester (unden) of N-methyl carbamic acid 2-
N-(diethyl-two thiophosphoryl base acetyl group)-N-methyl carbamic acid ethyl ester (Afos)
3,4-xylyl N-methyl carbamate (Meobal)
2-S-butyl phenyl N-methyl carbamate (Osbac)
2-cumenyl N-methyl carbamate (Mobucin)
N-methyl carbamic acid 2-chlorobenzene ester (Hopside)
3,5-xylyl N-methyl carbamate (Cosban)
2-(1, the phenyl N-methyl carbamate (Elacron) of 3-dioxolanes-2-)
3-2-methyl-2-phenylpropane base N-methyl carbamate (terbam)
4-2 allylamine-3,5-3,5-dimethylphenyl N-methyl carbamate (allyxycarb)
S-methyl-N(methylamino formoxyl oxygen base) thioacetyl amidine ester (Metbomil)
N-(2-methyl-4-chlorphenyl)-and N, N-diformazan ethyl-formyl amidine pyridine hydrochloric acid (pyridine of Chlorophenamidine chlorobenzene miaow)
1, two (carbamyl the sulfenyl)-2-(N of 3-, N-dimethylamino)-propane hydrochloride (Padan)
Diisopropyl-1,3-dithiolane-2-pitches malonate (Fujione)
N-((4-chlorphenyl) amino) carbonyl)-2,6-difluorobenzamide (Diflubenzuron)
The neighbour, the different rosickyite base of neighbour-dimethyl-S-2-() diethyldithioposphoric acid ester (Hosdon)
The neighbour, neighbour-diethyl-S-2-(ethylmercapto group)-diethyldithioposphoric acid ester (disulfoton)
Neighbour-(2,3-dihydro-2,2-dimethyl-7-benzofuranyl)-N-methyl carbamate (furadan)
Neighbour-ethyl S, S-diphenyl phosphorodithioate (Edibenfos)
The N-(trichloro-methylthio) cyclohexene-4-1,2-dicarboximide (captan)
2,4,5,6-daconil M (tpn)
N-(1,1,2,2-tetrachloro ethylmercapto group) hexamethylene-4-alkene-1,2-dicarboximide (difoltan)
4, two (the 3-ghiourea group formic acid) dimethyl esters (thiophanate methyl) of 4-neighbour-phenylene
3-(butyl carbamoyl)-3H-benzimidazolyl-2 radicals-Ji Methyl anthranilate (benomyl)
Ethylene-1,2-bisdithiocarbamic zinc (zineb)
Ethylene-1, two (aminodithioformic 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 experiment embodiments.
Experiment embodiment 1
Bactericidal activity (Erysiphe graminisfsp.bordei) for the barley meal mildew
Barley seedlings sprayed one day with experimental compound (200ppm) with the conidium inoculation back of Erysiphe graminisfsp.bordei at two leaf stage.Seedling preserves a week under 25 ℃ of constant temperature, detects the percentage that every leaf is attacked area then.Bactericidal 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
Table 2(is continuous)
Table 2(is continuous)
Table 2(is continuous)
Table2（Cont′d）
Table2（Cont′d）
Table2（Cont′d）
Experimental example 2
Bactericidal activity (Puccinia Cororata f.S Pavenae) for oat rhizome rust
Oat seedlings was sprayed one day with experimental compound (200ppm) with the uredospore inoculation back of Puccinia coronata f.S P.avenae in 8 leaf phases.Seedling preserved ten days at 25 ℃ of constant temperature.Detect every leaf and attacked the percentage of area.Bactericidal activity is pressed the same standard of experimental example 1 and is judged.
The results are shown in Table 3.
Table 3
Table3（Cont′d）
Table3（Cont′d）
Table3（Cont′d）
Table3（Cont′d）
Table3（Cont′d）
Table3（Cont′d）
Experimental example 3
For the cucumber rotten bactericidal activity (Pseudoperonosporq cubensis) that becomes mildewed
The cucumber of 2 leaf phases is at inoculation Pserdopernospora cubersi) 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, bactericidal activity is pressed the same standard of experimental example 1 and is judged.
The results are shown in Table 4.
Table 4
4（Cont′d）
4（Cont′d）
4（Cont′d）
4（Cont′d）
4（Cont′d）
4（Cont′d）
4（Cont′d）
Experimental example 4
Insecticidal activity (Nilaparvata lugens) for the brown lantern fly
After the rice seedling being immersed the emulsion 30 seconds, air drying of compound (200ppm), the seedling kind is in teat glass, then with on nymph inoculation in the 3rd length of time plant.After inoculation the 8th day, the calculation correction lethality 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
5（Cont′d）
5（Cont′d）
5（Cont′d）
5（Cont′d）
5（Cont′d）
Table5（Cont′d）
Experimental example 5
Insecticidal activity (Plutella xylostella) for the pickles pretty young woman
(pupa of the insect on the 6cm * 5cm) is immersed in the emulsion 30 seconds of The compounds of this invention will to be arranged in a slice China cabbage leaves.After the air drying, insect and plant are placed in the culture dish together, went into behind the culture dish the 6th day, the lethality of calculation correction is also judged according to the same standard of experimental example 4.
The results are shown in Table 6.
Table 6
6（Cont′d）
6（Cont′d）
6（Cont′d）
6（Cont′d）
6（Cont′d）
6（Cont′d）
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
7（Cont′d）
7（Cont′d）
7（Cont′d）
7（Cont′d）
7（Cont′d）
7（Cont′d）
Experimental example 7
Acaricidal activity (Panonychus citri) for the red mite of both citrus
Female insect is inoculated on Zhu's mountains in a range leaf, uses The compounds of this invention (200ppm) emulsion 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
8（Cont′d）
8（Cont′d）
8（Cont′d）
8（Cont′d）
8（Cont′d）
8（Cont′d）
Experimental example 8
Acaricidal activity for 2 two spotted spider mite.(Tetrarychusurticae) become 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
9（Cont′d）
9（Cont′d）
9（Cont′d）
9（Cont′d）
9（Cont′d）
9（Cont′d）
9（Cont′d）
Be formulation examples below, in these examples, umber is meant shared weight.
〈 ﹠﹠〉formulation examples 1 wet-milling
60 50 parts of compound numbers
45 parts of diatomite and clay mixtures
5 parts of polyoxyethylene nonyl ethers
Above-mentioned substance evenly mixes and thereby grinding obtains wet-milling.
〈 ﹠﹠〉formulation examples 2 emulsion
154 20 parts of compound numbers
20 parts of oxolanes
45 parts of dimethylbenzene
15 parts of ether and alkylbenzenesulfonates
Above-mentioned substance evenly mix, dissolve emulsion.
〈 ﹠﹠〉formulation examples 3 powder
503 4 parts of compound numbers
95 parts in the mixture of diatomite, clay and talcum
1 part of calcium stearate
Above-mentioned substance evenly mix, grind powder.
〈 ﹠﹠〉formulation examples 4 granulas
237 3 parts of compound numbers
92 parts in the mixture of bentonite and clay
5 parts in lignin calcium sulphate
Above-mentioned substance evenly mixes also and grinds, the mixture of grinding and an amount of water integrate fully granulate then granula.
Claims (4)
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP295759/85 | 1985-12-27 | ||
| JP295760/85 | 1985-12-27 | ||
| JP29575985 | 1985-12-27 | ||
| JP26582/86 | 1986-02-08 | ||
| JP151187/86 | 1986-06-27 | ||
| JP177447/86 | 1986-07-28 | ||
| JP206442/86 | 1986-09-02 | ||
| JP20699386 | 1986-09-03 | ||
| JP206993/86 | 1986-09-03 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 86108691 Division CN1022919C (en) | 1985-12-27 | 1986-12-26 | Method for preparing pyrazole oxime derivatives |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1061321A true CN1061321A (en) | 1992-05-27 |
| CN1023287C CN1023287C (en) | 1993-12-29 |
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 | Method for preparing pyrazole oxime derivatives |
| CN 91108000 Expired - Lifetime CN1023287C (en) | 1985-12-27 | 1991-12-17 | Pesticide and miticide composition continaing pyridine oxime derivatives |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 86108691 Expired - Lifetime CN1022919C (en) | 1985-12-27 | 1986-12-26 | Method for preparing pyrazole oxime derivatives |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN1022919C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104193727A (en) * | 2014-08-04 | 2014-12-10 | 南通大学 | Preparation and application of pyrazole oxime ether compound containing trifluoro methyl pyridine |
| CN105340896A (en) * | 2015-11-06 | 2016-02-24 | 曹龙巧 | Sanitizer for reproductive medicine inspection room |
| CN106946782A (en) * | 2017-02-08 | 2017-07-14 | 南通大学 | Pyrazole Oxime Esters of the biphenyl structures containing pyrazoles and its production and use |
| CN106946856A (en) * | 2017-02-08 | 2017-07-14 | 南通大学 | Pyrazoles 9 oxime derivate of the biphenyl structures containing tetrazole and its production and use |
| CN107428694A (en) * | 2015-03-19 | 2017-12-01 | 杜邦公司 | Antifungal pyrazoles |
| CN110092776A (en) * | 2019-04-30 | 2019-08-06 | 南通大学 | The pyrazoles oxime ester compound and its preparation method and application of the connection polyfluoro pyrrazole structure containing pyridine |
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| 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 |
| 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 |
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| 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 |
| CN118440050B (en) * | 2024-05-23 | 2025-02-11 | 南通大学 | Preparation and use of pyrazole derivatives containing p-fluorophenylthiobipyridine structure |
| CN118440051B (en) * | 2024-05-23 | 2025-04-01 | 南通大学 | Preparation and application of pyridine compounds containing 1,3-dimethyl-5-aryloxypyrazole-4-carbaldehyde oxime units |
| CN118440049A (en) * | 2024-05-23 | 2024-08-06 | 南通大学 | Pyrazoloxime compound containing pyridine aryl mercapto structural 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
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104193727A (en) * | 2014-08-04 | 2014-12-10 | 南通大学 | Preparation and application of pyrazole oxime ether compound containing trifluoro methyl pyridine |
| CN104193727B (en) * | 2014-08-04 | 2018-12-04 | 南通大学 | The preparation and application of Pyrazole Oxime Esters containing trifluoromethyl pyridine |
| CN107428694A (en) * | 2015-03-19 | 2017-12-01 | 杜邦公司 | Antifungal pyrazoles |
| CN105340896A (en) * | 2015-11-06 | 2016-02-24 | 曹龙巧 | Sanitizer for reproductive medicine inspection room |
| CN106946782A (en) * | 2017-02-08 | 2017-07-14 | 南通大学 | Pyrazole Oxime Esters of the biphenyl structures containing pyrazoles and its production and use |
| CN106946856A (en) * | 2017-02-08 | 2017-07-14 | 南通大学 | Pyrazoles 9 oxime derivate of the biphenyl structures containing tetrazole and its production and use |
| 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 |
| 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 |
| CN110092776A (en) * | 2019-04-30 | 2019-08-06 | 南通大学 | The pyrazoles oxime ester compound and its preparation method and application of the connection polyfluoro pyrrazole structure containing pyridine |
| CN110092776B (en) * | 2019-04-30 | 2021-09-07 | 南通大学 | Pyrazole oxime ester compound containing pyridine bipolyfluoropyrazole structure and preparation method and use thereof |
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| CN111635399B (en) * | 2020-07-01 | 2022-05-03 | 南通大学 | Pyrazole derivative containing thiadiazole heterocyclic unit and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1022919C (en) | 1993-12-01 |
| CN1023287C (en) | 1993-12-29 |
| CN86108691A (en) | 1988-01-20 |
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