CN1072211C - Pyrazole compounds used as agricultrial germicide and insecticide and acaricide and its preparation - Google Patents

Pyrazole compounds used as agricultrial germicide and insecticide and acaricide and its preparation Download PDF

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CN1072211C
CN1072211C CN 97105050 CN97105050A CN1072211C CN 1072211 C CN1072211 C CN 1072211C CN 97105050 CN97105050 CN 97105050 CN 97105050 A CN97105050 A CN 97105050A CN 1072211 C CN1072211 C CN 1072211C
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CN1188764A (en
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刘长令
刘晓楠
张弘
雷新
刘武成
张立新
李斌
满瀛
胡性之
李宗成
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Shenyang Research Institute of Chemical Industry Co Ltd
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Abstract

The present invention relates to pyrazole compounds used as agricultural germicide, insecticide and acaricide and a preparation thereof. The general formula is disclosed in the specification. The compound (I) has sterilization activity, disinsection activity and acaricidal activity, and can be used for preventing and curing the harmful diseases, insects and mites.

Description

Pyrazole compound and preparation thereof as disinfectant use in agriculture and insecticidal/acaricidal agent
The present invention relates to new pyrazole compound, their preparation method and they are as the application of agricultural chemicals.
As everyone knows, many compounds that contain pyrazoles have good pesticide and miticide actility.As the compound of the following general formula of CN86-108691A report, in this general formula, R 3Be H, C 1～C 4Alkyl or phenyl.This compounds is not perfect in every way, still need develop new better compound.
Figure C9710505000031
The new pyrazole compound that the present invention relates to following general formula is as disinfectant use in agriculture and insecticidal/acaricidal agent
Figure C9710505000032
In the logical formula I:
R 1, R 2Be H, halogen, C 1～C 6Alkyl, C 2～C 16Thiazolinyl, alkynyl, C 3～C 6Cycloalkyl, C 1～C 6Haloalkyl (C 2～C 6Thiazolinyl, C 2～C 6Alkynyl, C 3～C 6Cycloalkyl), R 1, R 2Can be identical or different.
R 3Be hydrogen, halogen, (halo) C 1～C 6Alkyl, (halo) C 2～C 6Thiazolinyl, (halo) C 2～C 6Alkynyl, (halo) C 3～C 6Cycloalkyl, (halo) C 3～C 6Cycloalkenyl group, NR 5R 6[R 5Be H, halo) C 1～C 6Alkyl, (halo) C 2～C 6Thiazolinyl, (halo) C 2～C 6Alkynyl, (halo) C 3～C 6Cycloalkyl, (halo) C 3～C 6Cycloalkenyl group, R 6Be R 5, (replacement) aryl, (replacement) heteroaryl], (replacement) aryl, (replacement) heteroaryl,
R 4Be H, C 1～C 6Alkyl, halogen, NR 5R 7[R 7Be R 5, (replacement) aryl, (replacement) heteroaryl], CN, (replacement) benzyl, (replacement) aryl, (replacement) heteroaryl, CO-Z 1-R 8(Z 1Be key, O, S, NR 5R 7R 8Be H, (halo) C 1～C 6Alkyl, (halo) C 2～C 6Thiazolinyl, (halo) C 2～C 6Alkynyl, (halo) C 3～C 6Cycloalkyl, (halo) C 3～C 6Cycloalkenyl group, (replacement) aryl, CH 2CO-Z 1-R 7, CH 2CN), PX 1(X 2R 9) X 3R 10(X 1Be O, S; X 2, X 3Be O, S, NH; X 1, X 2, X 3Can be identical or different; R 9, R 10Be R 8, can be identical or different.
X is a key, O, S, NR 11(R 11Be H, R 8).
Y is a key, O, NR 11, CH 2
Z is a key, H, CO, S (O) n, CHR 12[R 12Be H, (halo) C 1～C 6Alkyl].
R 4But with Z also makeup ring [saturated or unsaturated any replacement five the circle or six annulus: imidazoles, glyoxalidine, triazole, evil (two) azoles, oxazoline (ketone), thiophene (two) azoles, thiazoline (ketone), pyrimidine, two (four) hydrogen pyrimidines (quinoline ketone), (three hydrogen) oxazines].
Q is H, R 3, CH 2R 3, OR 3, CO-Z 1-R 8, OR 7, S (O) nR 8, CN, PX1 (X2R9) X3R10.
When Q is (replacement) aryl, can be (replacement) phenyl, substituting group can be H, C 1～C 6Alkyl, C 2～C 6Thiazolinyl, C 2～C 6Alkynyl, C 3～C 6Cycloalkyl, C 3～C 6Cycloalkenyl group, C 1～C 6Haloalkyl (C 2～C 6Thiazolinyl, C 2～C 6Alkynyl, C 3～C 6Cycloalkyl, C 3～C 6Cycloalkenyl group), OR 8, CO-Z 1-R 8, CH 2CO-Z 1-R 8, CH 2CN, NR 5R 8, S (O) nR 8, SiR 12R 13R 14[R 12～R 14Be (halo) C 1～C 6Alkyl can be identical or different], COSiR 12R 13R 14, OSiR 12R 13R 14, CR 12R 13CN, CR 12R 13CC L3, SF 5,
m=0～1； n=0～2。
Used in this application noun " alkyl, thiazolinyl, alkynyl " is meant the alkyl of side chain or straight chain, thiazolinyl, alkynyl respectively." halogen " refers to fluorine, chlorine, bromine, iodine." haloalkyl (thiazolinyl, alkynyl, cycloalkyl, cycloalkenyl group) " refers to the alkyl (thiazolinyl, alkynyl, cycloalkyl, cycloalkenyl group) that replaced by 1 or more a plurality of identical or different halogen atom.(replacement) aryl, (replacement) heteroaryl, substituting group can be H, C 1～C 6Alkyl, thiazolinyl, alkynyl, cycloalkyl, cycloalkenyl group, C 1～C 6Halo (alkyl, thiazolinyl, alkynyl, cycloalkyl) cycloalkenyl group, OR 7, CO-Z 1-R 7, NR 5R 6, S (O) nR 7, SiR 12R 13R 14, COSiR 12R 13R 14, OSiR 12R 13R 14, CR 15R 16CN, CR 15R 16CC L3, SF 5, substituting group can be in the optional position of aryl and heteroaryl; Aryl, heteroaryl refers to phenyl, naphthyl, furyl, thienyl, pyridyl, pyrazolyl, imidazolyl, imidazopyridine, triazolyl, triazolo pyrimidine, thiophene (two) azoles base is disliked (two) azoles base, pyrimidyl.
In logical formula I, R 1Usually 1 of pyrazoles, other groups can be respectively in 3,4,5 optional positions of pyrazoles.
Work as R 4During=OH, logical formula I can be its tautomer:
Figure C9710505000041
The represented compound of logical formula I has special efficacy for the insect that belongs to Homoptera such as plant hopper, aleyrodid, leafhopper and aphid etc. and mite class.In addition, for disease such as the oidium of vegetables, fruit tree and ornamental plant etc., Powdery Mildew, rust etc. have good germicidal action.
The synthetic method of the compound shown in the logical formula I is as follows.
Method A (when Y=O):
R wherein 1, R 2, R 3, R 4, Z is identical with the front definition with Qm.Hal represents halogen atom such as Cl or Br.
Used solvent can be any solvent that does not hinder this reaction in above-mentioned reaction, they comprise that halogenated hydrocarbon is (as methylene dichloride, ethylene dichloride, chloroform, tetracol phenixin, tetrachloroethane), alcohols is (as butanols, Virahol, ethanol, ethylene glycol), ethers is (as tetrahydrofuran (THF), dioxane, ethylene glycol bis (first) ether, ether, isopropyl ether), ketone is (as acetone, butanone, pimelinketone), arene is (as benzene, toluene, chlorobenzene, oil of mirbane), the ester class is (as ethyl acetate, methyl acetate), nitrile (as acetonitrile), methyl-sulphoxide, dimethyl formamide and water.These solvents can use separately also can mix use.When mixing these solvent amount of carrying out phase reactions of use, can use phase-transfer catalyst, for example Tetrabutyl amonium bromide, chlorination triethylbenzene ammonium methyl etc.
Used alkali is mineral alkali or organic bases in above-mentioned reaction.Mineral alkali comprises as the carbonate of alkali or alkaline-earth metal such as yellow soda ash, salt of wormwood, lime carbonate, sodium bicarbonate etc., the oxyhydroxide of alkali or alkaline-earth metal such as sodium hydroxide, potassium hydroxide, calcium hydroxide and alkali-metal hydride such as lithium hydride, sodium hydride etc.
Organic bases comprises triethylamine, pyridine, 4-Dimethylamino pyridine etc.The consumption of alkali uses mole or the excess such as compound represented with logical formula II.
In reaction, as using solid caustic soda, solid-liquid two phase times appear, for example can use poly(oxyethylene glycol) 400,600, phase-transfer catalysts such as 900.
The available following method of compound (II) makes:
Figure C9710505000051
In above-mentioned reaction, used solvent is alcohols (as methyl alcohol, ethanol, Virahol etc.) and water normally, and normally room temperature is to refluxing for temperature, and the time is 30 minutes to 6 hours.
Compound (IV) can be synthetic by currently known methods.
The also available following method of compound (II) makes:
In above-mentioned reaction, (V) and chlorizating agent such as chlorine, chlorination sulfone, NCS equal inert solvent such as ethyl acetate, react in methylene dichloride, ethylene dichloride, the dioxane to obtain (VI) in 30 minutes to 6 hours under-15～70 ℃; (VI) and HR4 (comprise the carbonate of alkali or alkaline-earth metal such as yellow soda ash, salt of wormwood, lime carbonate, sodium bicarbonate etc., the oxyhydroxide of alkali or alkaline-earth metal such as sodium hydroxide, potassium hydroxide, calcium hydroxide and alkali-metal hydride such as lithium hydride, sodium hydride etc. as mineral alkali at alkali; Organic bases comprises triethylamine, pyridine, 4-Dimethylamino pyridine etc.) and inert solvent exists down, and reaction makes (II).
Method B (Y=NR 11, Z=CR 12The time):
Figure C9710505000053
In above-mentioned reaction, used solvent is alcohols (as methyl alcohol, ethanol, Virahol etc.) and water normally, and normally room temperature is to refluxing for temperature, and the time is 30 minutes to 10 hours.
Method C (works as R 4=NR 5R 7The time):
Figure C9710505000061
In above-mentioned reaction, (I A) same alkylating reagent, acylating reagent etc. (comprise the carbonate of alkali or alkaline-earth metal such as yellow soda ash, salt of wormwood, lime carbonate, sodium bicarbonate etc., the oxyhydroxide of alkali or alkaline-earth metal such as sodium hydroxide, potassium hydroxide, calcium hydroxide and alkali-metal hydride such as lithium hydride, sodium hydride etc. as mineral alkali at alkali; Organic bases comprises triethylamine, pyridine, 4-Dimethylamino pyridine etc.) and the inert solvent existence is down, makes (I B) in 30 minutes to 24 hours in-15 ℃～150 ℃ reactions.
Method D (works as R 4=NR 5R 7The time):
Intermediate (VIII) and NR 5R 6(comprise the carbonate of alkali or alkaline-earth metal such as yellow soda ash, salt of wormwood, lime carbonate, sodium bicarbonate etc., the oxyhydroxide of alkali or alkaline-earth metal such as sodium hydroxide, potassium hydroxide, calcium hydroxide and alkali-metal hydride such as lithium hydride, sodium hydride etc. at alkali as mineral alkali; Organic bases comprises triethylamine, pyridine, 4-Dimethylamino pyridine etc.) and inert solvent have down that reaction makes (II), temperature is-20～150 ℃, the time is 30 minutes to 24 hours.
Method E is (as Y=O or NR 10, R 4=NH, Z=CO, R 4During with the Z makeup ring):
Figure C9710505000063
In above-mentioned reaction, solvent is generally toluene, benzene, dioxane, and temperature of reaction is a room temperature to refluxing, and the reaction times is generally 30 minutes to 48 hours, have or alkali-free in the presence of carry out.
Method F (works as Y=NH, R 4=NH 2, Z=CO, R 4During with the Z makeup ring):
Figure C9710505000064
In above-mentioned reaction, intermediate (XI) and (XII) are in the presence of solvent such as benzene class, alcohols (methyl alcohol, ethanol, Virahol) or its corresponding sodium alkoxide, and reaction made (I) in 30 minutes～24 hours in room temperature to reflux temperature.
Method G
Figure C9710505000071
Method H
Figure C9710505000072
The operation of method G and H is with method E.
Method I
Figure C9710505000073
Used solvent can be any solvent that does not hinder this reaction in above-mentioned reaction, they comprise that halogenated hydrocarbon is (as methylene dichloride, ethylene dichloride, chloroform, tetracol phenixin, tetrachloroethane), alcohols (as butanols, Virahol, ethanol, ethylene glycol), ethers is (as tetrahydrofuran (THF), dioxane, ethylene glycol bis (first) ether, ether, isopropyl ether), arene is (as benzene, toluene, chlorobenzene, oil of mirbane), ester class (as ethyl acetate, methyl acetate), nitrile (as acetonitrile), methyl-sulphoxide, dimethyl formamide and water.These solvents can use separately also can mix use.When mixing these solvent amount of carrying out phase reactions of use, can use phase-transfer catalyst, for example Tetrabutyl amonium bromide, chlorination triethylbenzene ammonium methyl etc.
Used alkali is mineral alkali or organic bases in above-mentioned reaction.Mineral alkali comprises as the carbonate of alkali or alkaline-earth metal such as yellow soda ash, salt of wormwood, lime carbonate, sodium bicarbonate etc., the oxyhydroxide of alkali or alkaline-earth metal such as sodium hydroxide, potassium hydroxide, calcium hydroxide and alkali-metal hydride such as lithium hydride, sodium hydride etc.
Organic bases comprises triethylamine, pyridine, 4-Dimethylamino pyridine etc.
Compound shown in the logical formula I can be made as solution, emulsion, wettable powder, suspension agent, pulvis, paste, soluble powder, granule, flood the natural materials of active compound and wrapped into micro-fine capsule in the polymer materials.
These prescriptions are produced with currently known methods, for example are that liquid solvent and/or solid carrier mix with active compound and weighting agent, and optional use tensio-active agent is emulsifying agent and/or dispersion agent.
Under the situation that makes water as weighting agent, organic solvent etc. also can be used as solubility promoter.As liquid solvent, what be suitable for mainly contains: aromatic hydrocarbons such as dimethylbenzene, toluene or alkylnaphthalene, chlorinated aromatic hydrocarbons or chlorinated aliphatic hydrocarbon such as chlorobenzene, vinylchlorid or methylene dichloride, aliphatic hydrocarbon such as hexanaphthene or paraffinic hydrocarbons such as petroleum fractions, mineral oil and vegetables oil, alcohols such as butanols or glycol, and ethers and ester class, ketone such as acetone, butanone, methyl iso-butyl ketone (MIBK) or pimelinketone, intensive polar solvent such as dimethyl formamide and dimethyl sulfoxide (DMSO), and water etc.
As solid carrier, suitable has: the natural inorganic thing of ammonium salt and grinding such as kaolin, clay, talcum, chalk, quartz, U.S.'s atlapulgite, polynite, and the synthesizing inorganic thing that grinds such as silicon-dioxide, aluminum oxide and the silicate of high dispersive; Solid carrier as granule, what be suitable for has: the natural rock of pulverizing such as calcite, marble, float stone, sepiolite and rhombspar, and the synthetic particle of inorganic and organic dust and the particle of organic materials such as sawdust, Exocarpium cocois (Cocos nucifera L), corn cob and tobacco rods.
As emulsifying agent, suitable has: non-ionic type and anionic emulsifier such as polyoxyethylene fatty acid ester, polyoxyethylene aliphatic alcohol ether, alkaryl polyglycol ether, alkylsulfonate, alkyl-sulphate, arylsulphonate and albumin hydrolysate; As dispersion agent, suitable has: xylogen sulphite and methylcellulose gum.
Natural and synthetic polymer such as Sudan Gum-arabic, polyvinyl alcohol and the polyvinyl acetate that in these prescriptions, can use tackiness agent such as carboxymethyl cellulose and powder, particle or latex etc. to form, and natural phospholipid such as kephalin, Yelkin TTS and synthetic phospholipid.Further possible additive is mineral oil and vegetables oil.
These prescriptions generally contain the compound shown in the promptly logical formula I of 0.1%～95% (weight) active compound, are 0.5%～95% preferably.
Active compound of the present invention can be made into preparation separately and use, and also can mix use with known sterilant and insecticidal/acaricidal agent.
Can be as follows with the sterilant that compound of the present invention is used with:
Karbam Black; thiram; ziram; maneb; zineb; zinc manganese ethylenebisdithiocarbamate; derosal; F-1991; RP-26019; triazolone; cyproconazole (cyproconazole); own azoles alcohol (hexaconazole); alkene azoles alcohol (diniconazole); flutriafol (flutriafol); diclobutrazol (diclobutrazol); Bitertanol (bitertanol); tebuconazole (tebuconazole); fluorine bacterium azoles (triflumizole); furconazole (furconazole); nitrile bacterium azoles (myclobutanil); azoles bacterium nitrile (propanenitrile); bromuconazole (bromuconazole); Wocosin 50TK (propiconazole); furconazole_cis (furconazole-cis); fluzilazol (flusilazolle); acid amides azoles (imibenconazole) Difenoconazole (difenconazole); fluorine ether azoles (tetraconazole); nuarimol (nuarimol); dimethomorph (dimethomorph); metaxanin; furalaxyl; M 9834 Evil acid amides (oxadixyl); prochloraz (prochloraz); frost urea cyanogen (DPX-3217); Propamocarb (propamocarb); phosethyl Al; the mould prestige of second (diethofencarb); azoles fenpiclonil (fenpiclonil); seed dressing strong (CGA173506); fenpropimorph (fenpropimorph); fenpropidin (fenpropidin); pyrifenox (pyrifenox); pencycuron (pencycuron); ferimzone (ferimzone); azoles bacterium piperazine (triazoxide); thicyofen (thicyofen); fluazinam (fluazinam); mepanipyrim; pyrimethanil; cyprodinil; fluquinconazole; BAS480F; BAS490F; CGA245704; CGA 329531; DE-795; DPX-JE874; ICIA0858; ICIA0054; KNF-S474; KTU 3616; KWG4168; LY214352; Mon 24000, XRD563; SSF126; SSF129 (compound of above test code number can be found from Britain's plant protection proceeding etc.).
Can be as follows with the insecticidal/acaricidal agent that compound of the present invention is used with:
Pyrethroid coumpound: as fluorine ester chrysanthemum ester (aerinathrin), Fenvalerate (fenpropathrin), alphacypermethrin (alphamethrin), bifenthrin (bifenthrin), cycloprothrin (cycloprothrin), cyfloxylate (beta-cyfluthrin), cyhalothrin (cyhalothrin, PP563), Cypermethrin (cypermethrin), nail body Cypermethrin (alpha-cypermethrin), second body Cypermethrin (beta-cypermethrin), esfenvalerate (esfenvalerate), ether chrysanthemum ester (etofenprox), fenpirithrin (fenpirithrin), flucythrinate (flucythrinate), taufluvalinate (fluvalinate), cyhalothrin (lambda-cyhalothrin, PP 321), tefluthrin (tefluthrin), tralomethrin (tralomethrin), brofluthrinate, brofenprox, Cis-resmethrin, clocythrindeltamethrin, ICIA5682, MTI-732, pyresmethrin, Silafluofen, silafluofen (Hoe498), SSI-126, zetamethrin.
Amino formate compounds: as carbofuran, carbosulfan, benfuracarb, methomyl, the two methomyls of alkali, alanycarb, fenothiocarb.
Organophosphorus compound: as Kayaphos, Toyodan, first Toyodan, Profenofos, isazofos, Terbufos, azamethiphos, butylbenzene alkali phosphorus, thiazole alkali phosphorus, pyrazoles alkali phosphorus, Chlorpyrifos 94, chlorpyrifos_methyl, hot alkali phosphorus, diazinon, Dowco429, MAT-7484.
Benzoyl urea compound: as fluorine bell urea, Teflubenzuron, UC 62644, flufenoxuron, PH-7023, GR-572, CGA157419, CGA184699.
Pyridyl-methanamine compounds: as Provado, NI-25, TLA-304.
Pyrazole compound: as NN1850, MK-239, Fipronil.
Pyridazinone compound: as NC-129, NC-170, NC-184, NC-194, NC-196.
Natural product: as abamectin, amitrazin, avermectin, azadirachtin.
Other heterogeneous ring compounds: as methamidophos, fenazaquin, four mite piperazines, AC303630, SU8801, YI-5301, SZI121, CGA 59205, D2341, DPX-MP062, MP-599, PFR-97, RH-5992, RH-2485, RH-0345 (compound of above test code number can be found from Britain's plant protection proceeding etc.).
Example 1: wettable powder
50 parts of The compounds of this invention, respectively with 3 parts of calcium lignin sulphonates, 2 parts of sodium lauryl sulphate and 45 parts of synthetic hydrated silicon oxides mix.Mixture grinds equably and mixes, and obtains 50% wettable powder.
Example 2: suspension agent
25 parts of compounds mix with 3 parts of polyoxyethylene polyoxyethylene-sorbitan mono-oleates and 72 parts of water respectively.Mixture by wet-milling to 25% the suspension agent that needs.
Example 3: pulvis
2 parts of The compounds of this invention mix with 88 parts of kaolin and 10 parts of talcums respectively.Mixture is ground fully, obtains 2% pulvis.
Example 4: missible oil
20 parts of The compounds of this invention, respectively with 14 parts of polyoxyethylene styryl phenyl ethers, 6 parts of calcium dodecylbenzene sulphonates and 60 parts of dimethylbenzene mix.Mixture is mixed fully, obtains 20% missible oil.
Example 5: granule
2 parts of The compounds of this invention, respectively with 1 part of synthetic hydrated silicon oxide, 2 parts of calcium lignosulfonates, 30 parts of wilkinites and 65 parts of kaolin mix.After mixture fully grinds and mixes, add water, evenly kneading, granulating, drying obtain 2% granule.
Example 6: water base suspension
20 parts of The compounds of this invention with 1.5 parts of sorbitan trioleate and 28.5 parts of aqueous solution that contain 2 parts of polyvinyl alcohol, are worn into particle diameter with sand mill with mixture and are not more than 3 fine powder respectively.Every kind of mixture again with 40 parts of aqueous solution that contain 0.05 part of xanthan gum and 0.1 part of magnesium aluminum silicate, then, with 10 parts of mixed with propylene glycol, obtain 20% water base suspension again.
Example 7: oil solution
0.1 part of The compounds of this invention is dissolved in respectively in 5 parts of dimethylbenzene and the 5 parts of trichloroethane, and gained solution mixes with 89.9 parts of deodorized kerosines, obtains 0.1% oil solution.
Example 8 (compound 79) reaction formula:
Figure C9710505000101
Synthesizing of (1) 1,3-dimethyl-5-benzene chloro-4-pyrazoles formonitrile HCN
1,3-dimethyl-5-benzene chloro-4-pyrazolyl aldoxime 21.3 grams and 100 ml acetic anhydride back flow reaction 2 hours behind recovery part diacetyl oxide and the acetate, are cooled off and are added 100 milliliters of stirrings of water, promptly get solid, and filtration, washing, dry 20.5 restrain the colourless crystallization bodies.73～75 ℃ of fusing points.
(2) 1.3-dimethyl-5-phenoxy group-4-pyrazole amide oxime is synthetic
1,3-dimethyl-5-phenoxy group-4-pyrazoles formonitrile HCN (8.5 gram), salt of wormwood (8.0 gram), oxammonium hydrochloride (4.0 gram) in 50 ml methanol, spend the night by backflow, reclaim most of methyl alcohol after, add water and stir, filter, be drying to obtain required thing 9.8 grams.Fusing point: 157～160 ℃.
(3) object is synthetic
Last step intermediate (1.5 gram), to the bromo methyl acid tert-butyl ester (1.8 gram), hydrochlorinate sodium (0.3 gram) in 30 milliliters of butanone, reacted 8 hours by back flow reaction, and the precipitation postcooling adds water, ethyl acetate extraction, drying, precipitation.Column chromatography gets object 2.0 grams.Fusing point: 84～86 ℃.
HNMR(CDCl 3,TMS)ppm:7.84～7.98(d,2H),7.11～7.49(m,5H),6.82～7.00(d,2H),5.06(s,2H),4.77(bs,2H),3.58(s,3H),2.37(s,3H),1.62(s,9H).
Example 9 (compound 306) reaction formula:
Figure C9710505000102
With 1,3-dimethyl-5-phenoxy group-4-pyrazolyl aldoxime 2.3 grams, chloromethyl triazolium salt hydrochlorate (1.5 gram), the mixed solution heating reflux reaction of salt of wormwood (3.0 gram) in 30 milliliters of acetone 8 hours, after reclaiming most of solvent, add 20 milliliters in water, it is object that ethyl acetate extraction, dry, precipitation get oily matter (2.8 gram).
Example 10 (compound 309) reaction formula:
Figure C9710505000111
With 1,3-dimethyl-5-phenoxy group-4-pyrazolyl aldoxime (1.0 gram) is dissolved in 10 milliliters of tetrahydrofuran (THF)s, adds p-trifluoromethyl phenyl isocyanic ester (1.0 gram) and 1 triethylamine, and stirring reaction is after 2 hours, filter and promptly get object (1.8 gram), 110～112 ℃ of fusing points.
HNMR(DMCO,TMS)ppm:8.71(bs,1H),8.09(s,1H),7.64(s.4H),7.45(m,2H),7.27(m,1H),3.64(s,3H),2.41(s,3H).
Example 11 (compound 231) reaction formula:
Figure C9710505000112
With 1,3-dimethyl-5-phenoxy group-4-pyrazoles formaldehyde (0.5 gram) is with 2, and 6-dichlor-4-trifluoromethyl phenylhydrazine (0.53 gram) and 1 Glacial acetic acid are dissolved in 20 ml methanol, heating reflux reaction 5 hours, and cooling, ethyl acetate extraction, washing, precipitation gets oily matter.Place solid (0.95 gram).Fusing point: 70～74 ℃.
HNMR(CDCl 3,TMS)ppm:6.84～7.67(7H),3.62(s,3H),2.49(s,3H).
Example 12 (compound 145) reaction formula:
Figure C9710505000113
With 1,3-dimethyl-5-chloro-4-pyrazol formyl chloride (3.0 gram) is dissolved in 20 milliliters of ether, drips 4-trifluoromethyl benzylamine (2.8 gram), and stirring at room 1 hour is filtered and washed with ether and promptly get object 4.8 and restrain.Fusing point: 201～203 ℃.
HNMR(CDCl 3,TMS)PPM:7.87(bs,1H),7.42～7.55(d,2H),6.84～7.06(d,2H),6.49(bs,1H),3.86(s,3H),2.46(s,3H).
Example 13 (compound 315) reaction formula:
Figure C9710505000114
With 1,3-dimethyl-5-phenoxy group-4-pyrazoles formaldehyde 4.0 grams react in 10 ml methanol with hydrazine hydrate (10 milliliters) and spend the night, and add 50 milliliters in water, stir and promptly separate out solid hydrazone 3.0 grams.Get this hydrazone 0.5 gram be dissolved in 10 milliliters of ether with 0.45 gram to trifluoro j p-methoxy-phenyl isocyanate reaction, separate out precipitation immediately, filter, ether wash product 0.85 gram.Fusing point: 119～120 ℃.
HNMR(DMSO,TMS)ppm:10.51(s,1H),8.11(1H),7.72(1H),6.94～7.60(m,9H),3.57(s,3H),2.39(s,3H).
Example 14 (compound 389) reaction formula:
With 0.8 gram 1.3-dimethyl-5-phenoxy group 4-pyrazole amide oxime and 0.7 gram 2, the 6-difluoro benzoyl chloride is dissolved in 20 milliliters the toluene, back flow reaction 8 hours, precipitation.Column chromatography is purified to such an extent that product 0.9 restrains.Fusing point: 106～108 ℃.
HNMR(CDCl 3, TMS)ppm:6.82～7.45(m,8H),3.68(s,3H),2.58(s,3H).
Example 15 (compound 87) reaction formula:
The preparation of (1) 1,3-dimethyl-5-phenoxy group-4-α-chlorine pyrazolyl aldoxime
With 15 grams 1,3-dimethyl-5-phenoxy group-4-pyrazolyl aldoxime is dissolved in 100 milliliters of chloroforms, feeds excessive slightly chlorine below 10 ℃, filters, and chloroform is washed, and gets product 8.8g.Fusing point: 138～152 ℃.
HNMR(DMCO,TMS)ppm:6.82～7.14(m,5H),3.58(s,3H),2.27(s,3H).
The preparation of (2) 1,3-dimethyl-5-phenoxy group-4-α-(1,2, the 4-triazole) pyrazolyl aldoxime
1,3-dimethyl-5-phenoxy group-4-α-chlorine pyrazolyl aldoxime (6 gram), 1,2,4-triazole (3.2 gram), salt of wormwood (4.7 gram) is mixed and heated to backflow with 60 milliliters of DMF, reacts 8 hours.Cooling, ethyl acetate extraction, the organic layer pickling, washing, the saturated common salt washing, anhydrous magnesium sulfate drying, precipitation promptly gets product 3 grams, fusing point: 150～153 ℃.
HNMR(DMSO,TMS)ppm:8.64(s,1H),8.00(s,1H),7.00～7.40(m,3H),6.67～6.89(m,2H),3.53(s,3H),1.96(s,3H).
(3) preparation of object
1,3-dimethyl-5-phenoxy group-4-α-1,2,4-triazole pyrazolyl aldoxime 1 gram, sodium hydride 1 gram mixes with 20 milliliters of butanone, and stirring at room added para Toluic Acid's tertiary butyl ester benzyl bromine 1 gram after 0.5 hour, refluxed 4 hours.Add water, ethyl acetate extraction, the organic layer pickling, washing, anhydrous magnesium sulfate drying, precipitation, column chromatography purify product, be oily matter 1.2 grams.
HNMR(CDCl 3,TMS)ppm:8.42(s,1H),7.99(s,1H),7.84～7.99(m,2H),7.00～7.38(m,3H),6.67～6.84(m,2H),5.11(s,2H),3.67(s,3H),2.09(s,3H),1.65(s,9H).
Can prepare other compound shown in table 1～7 with similar method:
Table 1
Figure C9710505000131
Compound number X R 3R 4R
1 O C 6H 5 Cl C 4H 9t
2 O C 6H 5 NH 2 C 4H 9t
3 O C 6H 5 NHCH 3 C 4H 9t
4 O C 6H 5 NHCO 2CH 3 C 4H 9t
5 O C 6H 5 NHCOCH 3 C 4H 9t
6 O C 6H 5 N(Me) 2 C 4H 9t
7 O C 6H 5 NHSO 2CH 3 C 4H 9t
8 O C 6H 6 OCH 3 C 4H 9t
9 O C 6H 5 SCH 3 C 4H 9t
10 O C 6H 51,2,4-triazol-1-yl C 4H 9t
11 O C 6H 5Imidazoles-1-base C 4H 9t
12 S C 6H 5 Cl C 4H 9t
13 S C 6H 5 NH 2 C 4H 9t
14 S C 6H 5 NHCH 3 C 4H 9t
15 S C 6H 5 NHCO 2CH 3 C 4H 9t
16 S C 6H 6 NHCOCH 3 C 4H 9t
17 S C 6H 5 N(Me) 2 C 4H 9t
18 S C 6H 5 NHSO 2CH 3 C 4H 9t
19 S C 6H 5 OCH 3 C 4H 9t
20 S C 6H 5 SCH 3 C 4H 9t
21 S C 6H 51,2,4-triazol-1-yl C 4H 9t
22 S C 6H 5Imidazoles-1-base C 4H 9t
23 S C 10H 7 Cl C 4H 9t
24 S C 10H 7 NH 2 C 4H 9t
25 S C 10H 7 NHCH 3 C 4H 9t
26 S C 10H 7 NHCO 2CH 3 C 4H 9t
27 S C 10H 7 NHCOCH 3 C 4H 9t
28 S C 10H 7 N(Me) 2 C 4H 9t
29 S C 10H 7 NHSO 2CH 3 C 4H 9t
30 S C 10H 7 OCH 3 C 4H 9t
31 S C 10H 7 SCH 3 C 4H 9t
32 S C 10H 71,2,4-triazol-1-yl C 4H 9t
33 S C 10H 7Imidazoles-1-base C 4H 9t
34 O C 10H 7 Cl C 4H 9t
35 O C 10H 7 NH 2 C 4H 9t
36 O C 10H 7 NHCH 3 C 4H 9t
37 O C 10H 7 NHCO 2CH 3 C 4H 9t
38 O C 10H 7 NHCOCH 3 C 4H 9t
39 O C 10H 7 N(Me) 2 C 4H 9t
40 O C 10H 7 NHSO 2CH 3 C 4H 9t
41 O C 10H 7 OCH 3 C 4H 9t
42 O C 10H 7 SCH 3 C 4H 9t
43 O C 10H 71,2,4-triazol-1-yl C 4H 9t
44 O C 10H 7Imidazoles-1-base C 4H 9t
45 O C 10H 7 Cl CO 2C 4H 9t
46 O C 10H 7 NH 2 CO 2C 4H 9t
47 O C 10H 7 NHCH 3 CO 2C 4H 9t
48 O C 10H 7 NHCO 2CH 3 CO 2C 4H 9t
49 O C 10H 7 NHCOCH 3 CO 2C 4H 9t
50 O C 10H 7 N(Me) 2 CO 2C 4H 9t
51 O C 10H 7 NHSO 2CH 3 CO 2C 4H 9t
52 O C 10H 7 OCH 3 CO 2C 4H 9t
53 O C 10H 7 SCH 3 CO 2C 4H 9t
54 O C 10H 71,2,4-triazol-1-yl CO 2C 4H 9t
55 O C 10H 7Imidazoles-1-base CO 2C 4H 9t
56 S C 10H 7 Cl CO 2C 4H 9t
57 S C 10H 7 NH 2 CO 2C 4H 9t
58 S C 10H 7 NHCH 3 CO 2C 4H 9t
59 S C 10H 7 NHCO 2CH 3 CO 2C 4H 9t
60 S C 10H 7 NHCOCH 3 CO 2C 4H 9t
61 S C 10H 7 N(Me) 2 CO 2C 4H 9t
62 S C 10H 7 NHSO 2CH 3 CO 2C 4H 9t
63 S C 10H 7 OCH 3 CO 2C 4H 9t
64 S C 10H 7 SCH 3 CO 2C 4H 9t
65 S C 10H 71,2,4-triazol-1-yl CO 2C 4H 9t
66 S C 10H 7Imidazoles-1-base CO 2C 4H 9t
67 S C 6H 5 Cl CO 2C 4H 9t
68 S C 6H 5 NH 2 CO 2C 4H 9t
69 S C 6H 5 NHCH 3 CO 2C 4H 9t
70 S C 6H 5 NHCO 2CH 3 CO 2C 4H 9t
71 S C 6H 5 NHCOCH 3 CO 2C 4H 9t
72 S C 6H 5 N(Me) 2 CO 2C 4H 9t
73 S C 6H 5 NHSO 2CH 3 CO 2C 4H 9t
74 S C 6H 6 OCH 3 CO 2C 4H 9t
75 S C 6H 5 SCH 3 CO 2C 4H 9t
76 S C 6H 51,2,4-triazol-1-yl CO 2C 4H 9t
77 S C 6H 5Imidazoles-1-base CO 2C 4H 9t
78 O C 6H 5 Cl CO 2C 4H 9t
79 O C 6H 5 NH 2 CO 2C 4H 9t
80 O C 6H 5 NHCH 3 CO 2C 4H 9t
81 O C 6H 5 NHCO 2CH 3 CO 2C 4H 9t
82 O C 6H 6 NHCOCH 3 CO 2C 4H 9t
83 O C 6H 5 N(Me) 2 CO 2C 4H 9t
84 O C 6H 5 NHSO 2CH 3 CO 2C 4H 9t
85 O C 6H 5 OCH 3 CO 2C 4H 9t
86 O C 6H 5 SCH 3 CO 2C 4H 9t
87 O C 6H 51,2,4-triazol-1-yl CO 2C 4H 9t
88 O C 6H 5Imidazoles-1-base CO 2C 4H 9t
89 O C 6H 6 CN CO 2C 4H 9t
90 O C 6H 6 CN C 4H 9t
91 O C 6H 6 NHCH 2CO 2CH 3 C 4H 9t
92 O C 6H 6 NHCH 2CO 2CH 3 CO 2C 4H 9t
93 O C 6H 5 H CO 2C(Me) 2CN
94 O C 6H 5 H CO 2C(Me) 2CCl 3
95 O C 6H 5 Cl CO 2C(Me) 2CN
96 O C 6H 5 Cl CO 2C(Me) 2CCl 3
Table 2
Figure C9710505000161
Compound number X R 3R 4R
97 O C 6H 5 Cl C 4H 9t
98 O C 6H 5 NH 2 C 4H 9t
99 O C 6H 5 NHCH 3 C 4H 9t
100 O C 6H 5 NHCO 2CH 3 C 4H 9t
101 O C 6H 5 NHCOCH 3 C 4H 9t
102 O C 6H 5 N(Me) 2 C 4H 9t
103 O C 6H 5 NHSO 2CH 3 C 4H 9t
104 O C 6H 6 OCH 3 C 4H 9t
105 O C 6H 5 SCH 3 C 4H 9t
106 O C 6H 51,2,4-triazol-1-yl C 4H 9t
107 O C 6H 5Imidazoles-1-base C 4H 9t
108 S C 6H 5 Cl C 4H 9t
109 S C 6H 5 NH 2 C 4H 9t
110 S C 6H 5 NHCH 3 C 4H 9t
111 S C 6H 5 NHCO 2CH 3 C 4H 9t
112 S C 6H 6 NHCOCH 3 C 4H 9t
113 S C 6H 5 N(Me) 2 C 4H 9t
114 S C 6H 5 NHSO 2CH 3 C 4H 9t
115 S C 6H 5 OCH 3 C 4H 9t
116 S C 6H 5 SCH 3 C 4H 9t
117 S C 6H 51,2,4-triazol-1-yl C 4H 9t
118 S C 6H 5Imidazoles-1-base C 4H 9t
119 S C 6H 5 Cl CO 2C 4H 9t
120 S C 6H 5 NH 2 CO 2C 4H 9t
121 S C 6H 5 NHCH 3 CO 2C 4H 9t
122 S C 6H 5 NHCO 2CH 3 CO 2C 4H 9t
123 S C 6H 5 NHCOCH 3 CO 2C 4H 9t
124 S C 6H 5 N(Me) 2 CO 2C 4H 9t
125 S C 6H 5 NHSO 2CH 3 CO 2C 4H 9t
126 S C 6H 6 OCH 3 CO 2C 4H 9t
127 S C 6H 5 SCH 3 CO 2C 4H 9t
128 S C 6H 51,2,4-triazol-1-yl CO 2C 4H 9t
129 S C 6H 5Imidazoles-1-base CO 2C 4H 9t
130 O C 6H 5 Cl CO 2C 4H 9t
131 O C 6H 5 NH 2 CO 2C 4H 9t
132 O C 6H 5 NHCH 3 CO 2C 4H 9t
133 O C 6H 5 NHCO 2CH 3 CO 2C 4H 9t
134 O C 6H 6 NHCOCH 3 CO 2C 4H 9t
135 O C 6H 5 N(Me) 2 CO 2C 4H 9t
136 O C 6H 5 NHSO 2CH 3 CO 2C 4H 9t
137 O C 6H 5 OCH 3 CO 2C 4H 9t
138 O C 6H 5 SCH 3 CO 2C 4H 9t
139 O C 6H 51,2,4-triazol-1-yl CO 2C 4H 9t
140 O C 6H 5Imidazoles-1-base CO 2C 4H 9t
141 O C 6H 5 H CO 2C(Me) 2CN
142 O C 6H 5 H CO 2C(Me) 2CCl 3
143 O C 6H 5 Cl CO 2C(Me) 2CN
144 O C 6H 5 Cl CO 2C(Me) 2CCl 3
Table 3
Figure C9710505000181
Compound number XR 3R 1Z Q
145 Cl CH 3 - CH 2C 6H 4-4-CF 3
146 Cl CH 3 - CH 2C 6H 4-4-C 4H 9t
147 Cl CH 3 - CH 2C 6H 4-4-Cl
148 Cl CH 3 - CH 2C 6H 4-4-OCF 3
149 OPh CH 3 - CH 2C 6H 4-4-OCF 3
150 Cl CH 3 - NHC 6H 4-4-CF 3
151 Cl CH 3 - NHC 6H 4-4-C 4H 9t
152 Cl CH 3 - NHC 6H 4-4-Cl
153 Cl CH 3 - NHC 6H 4-4-OCF 3
154 Cl CH 3 - NHC 6H 4-4-OC 2HF 4
155 Cl CH 3 - C 6H 4-3-OCH(CH 3) 2
156 Cl CH 3 O CH 2C 6H 4-4-But
157 OPh CH 3 O CH 2C 6H 4-4-CO 2But
158 Cl CH 3 - NH 2C 6H 3-2,6-(Me) 2
159 Cl CH 3 - NHC 6H 4-4-NO 2
160 Cl CH 3 - NHC 6H 5
161 Cl CH 3 O CH 2C 6H 4-4-OCF 3
162 Cl CH 3O CH 2-1-(1,2, the 4-triazole)
163 Cl CH 3 - C 6H 4-4-F
164 Cl Cl - C 6H 4-4-CF 3
165 Cl Cl - C 6H 4-4-C 4H 9t
166 Cl Cl - C 6H 4-4-Cl
167 Cl Cl - C 6H 4-4-OCF 3
168 Cl Cl - C 6H 4-3-OCH(CH 3) 2
169 Cl Cl - C 6H 4-4-F
170 Cl Cl - CH 2C 6H 4-4-CF 3
171 Cl Cl - CH 2C 6H 4-4-C 4H 9t
172 Cl Cl - CH 2C 6H 4-4-Cl
173 Cl Cl - CH 2C 6H 4-4-OCF 3
174 Cl Cl - CH 2C 6H 4-4-OC 2HF 4
175 Cl Cl - NHC 6H 4-4-CF 3
176 Cl Cl - NHC 6H 4-4-C 4H 9t
177 Cl Cl - NHC 6H 4-4-Cl
178 Cl Cl - NHC 6H 4-4-OCF 3
179 Cl Cl - NHC 6H 4-4-OC 2HF 4
180 OPh CH 3 - C 6H 4-3-OCH(CH 3) 2
181 Cl Cl - NHC 6H 2-2,6-Cl 2-4-CF 3
182 Cl CH 3 - NHC 6H 2-2,6-Cl 2-4-CF 3
183 Cl Cl - CH 2C 6H 2-2,6-Cl 2-4-CF 3
184 Cl CH 3 - CH 2C 6H 2-2Cl 2-4-CF 3
185 Cl CF 3-CH 2-2-thiophene phenol-4-CO 2CH 3
186 Cl CF 3 - CH 2-3-C 5H 3N-6-Cl
187 Cl CF 3-3-C 5H 3N-6-Cl (pyridine)
188 Cl CF 3-CH 2-2-C 4H 3O (furans
189 Cl CF 3 - NHC 6H 4-4-CF 3
190 CF 3Cl-CH 2-2-thiophene phenol-4-CO 2CH 3
191 CF 3 Cl - CH 2-3-C 5H 3N-6-Cl
192 CF 3 Cl - 3-C 5H 3N-6Cl
193 CF 3 Cl - CH 2C 6H 4-4-CF 3
194 CF 3 Cl - NHC 6H 4-4-CF 3
195 Cl CH 3 -
196 Cl CF 3 - C 6H 2-2,6-(Br) 2-4-OCF 3
197 OPh CF 3 - NHC 6H 4-4-CF 3
198 OPh CF 3 - NHC 6H 4-4-NO 2
199 Cl CF 3 - NHC 6H 4-4-CN
200 Cl CF 3 - C 6H 2-2,6-(Br) 2-4-OCF 3
Table 4 Compound number XR 3R 4YR
201 Cl NH 2 CH 2C 6H 4-4-CF 3
202 Cl NH 2 CH 2C 6H 4-4-C 4H 9t
203 Cl NH 2 CH 2C 6H 4-4-Cl
204 Cl NH 2 CH 2C 6H 4-4-OCF 3
205 Cl NH 2 CH 2C 6H 4-4-OC 2HF 4
206 Cl NH 2 NHC 6H 4-4-CF 3
207 Cl NH 2 NHC 6H 4-4-C 4H 9t
208 Cl NH 2 NHC 6H 4-4-Cl
209 Cl NH 2 NHC 6H 4-4-OCF 3
210 Cl NH 2 NHC 6H 4-4-OC 2HF 4
211 Cl NH 2 C 6H 4-3-OCH(CH 3) 2
212 Cl NH 2 NHC 6H 2-2,6-Cl 2-4-CF 3
213 Cl NH 2 CH 2C 6H 2-2,6-Cl 2-4-CF 3
214 Cl NH 2 C 6H 4-4-CF 3
215 Cl NH 2 C 6H 4-4-C 4H 9t
216 Cl NH 2 C 6H 4-4-Cl
217 Cl NH 2 C 6H 4-4-OCF 3
218 Cl NH 2 C 6H 4-4-OC 2HF 4
219 Cl NH 2 C 6H 4-4-F
220 OPh H CH 2C 6H 4-4-CF 3
221 OPh H CH 2C 6H 4-4-C 4H 9t
222 OPh H CH 2C 6H 4-4-Cl
223 OPh H CH 2C 6H 4-4-OCF 3
224 OPh H CH 2C 6H 4-4-OC 2HF 4
225 OPh H NHC 6H 4-4-CF 3
226 OPh H NHC 6H 4-4-C 4H 9t
227 OPh H NHC 6H 4-4-Cl
228 OPh H NHC 6H 4-4-OCF 3
229 OPh H NHC 6H 4-4-OC 2HF 4
230 OPh H C 6H 4-3-OCH(CH 3) 2
231 OPh H NHC 6H 2-2,6-Cl 2-4-CF 3
232 OPh H CH 2C 6H 2-2,6-Cl 2-4-CF 3
233 OPh H C 6H 4-4-CF 3
234 OPh H C 6H 4-4-C 4H 9t
235 OPh H C 6H 4-4-Cl
236 OPh H C 6H 4-4-OCF 3
237 OPh H C 6H 4-4-OC 2HF 4
238 OPh H C 6H 4-4-F
239 OPh Cl CH 2C 6H 4-4-CF 3
240 OPh Cl CH 2C 6H 4-4-C 4H 9t
241 OPh Cl CH 2C 6H 4-4-Cl
242 OPh Cl CH 2C 6H 4-4-OCF 3
243 OPh Cl CH 2C 6H 4-4-OC 2HF 4
244 OPh Cl NHC 6H 4-4-CF 3
245 OPh Cl NHC 6H 4-4-C 4H 9t
246 OPh Cl NHC 6H 4-4-Cl
247 OPh Cl NHC 6H 4-4-OCF 3
248 OPh Cl NHC 6H 4-4-OC 2HF 4
249 OPh Cl C 6H 4-3-OCH(CH 3) 2
250 OPh Cl NHC 6H 2-2,6-Cl 2-4-CF 3
251 OPh Cl CH 2C 6H 2-2,6Cl 2-4-CF 3
252 OPh Cl C 6H 4-4CF 3
253 OPh Cl C 6H 4-4-C 4H 9t
254 OPh Cl C 6H 4-4-Cl
255 OPh Cl C 6H 4-4-OCF 3
256 OPh Cl C 6H 4-4-OC 2HF 4
257 OPh Cl C 6H 4-4-F
258 Cl Cl CH 2C 6H 4-4-CF 3
259 Cl Cl CH 2C 6H 4-4-C 4H 9t
260 Cl Cl CH 2C 6H 4-4-Cl
261 Cl Cl CH 2C 6H 4-4-OCF 3
262 Cl Cl CH 2C 6H 4-4-OC 2HF 4
263 Cl Cl NHC 6H 4-4-CF 3
264 Cl Cl NHC 6H 4-4-C 4H 9t
265 Cl Cl NHC 6H 4-4-Cl
266 Cl Cl NHC 6H 4-4-OCF 3
267 Cl Cl NHC 6H 4-4-OC 2HF 4
268 Cl Cl C 6H 4-3-OCH(CH 3) 2
269 Cl Cl NHC 6H 2-2,6-Cl 2-4-CF 3
270 Cl Cl CH 2C 6H 2-2,6-Cl 2-4CF 3
271 Cl Cl C 6H 4-4-CF 3
272 Cl Cl C 6H 4-4-C 4H 9t
273 Cl Cl C 6H 4-4-Cl
274 Cl Cl C 6H 4-4-OCF 3
275 Cl Cl C 6H 4-4-OC 2HF 4
276 Cl Cl C 6H 4-4-F
277 Cl H OCH 2CO 2C 2H 5
278 Cl H OCH(Me)CO 2C 2H 5
279 Cl H OCH 2-1-(1,2, the 4-triazole)
280 Cl H OCONHCH 3
281 Cl H OCONHC 6H 4-4-Cl
282 Cl H OCONHC 6H 4-4CF 3
283 Cl H OCONHC 6H 4-4-OCF 3
284 Cl H OCONHC 6H 3-3,4-Cl 2
285 Cl H NHCONHC 6H 4-4-Cl
286 Cl H N(CH 3)CONHC 6H 4-4-Cl
287 Cl H NHCONHC 6H 4-4-CF 3
288 Cl H NHCONHC 6H 4-4-OCF 3
289 Cl H NHCONHC 6H 3-3,4-Cl 2
290 Cl H OCOC 6H 4-4-F
291 Cl H OCOC 6H 4-4-Cl
292 Cl H OCOC 6H 3-2,6-F 2
293 Cl H NHCOC 6H 4-4-F
294 Cl H NHCOC 6H 4-4-Cl
295 Cl H NHCOC 6H 3-2,6-F 2
296 Cl H OCONHCOC 6H 3-2,6-F 2
297 Cl H OCONHCOC 6H 4-2-F
298 Cl H OCONHCOC 6H 3-2,6-Cl 2
299 Cl H OCONHCOC 6H 4-2-Cl
300 Cl H NHCONHCOC 6H 3-2,6-F2
301 Cl H NHCONHCOC 6H 4-2-F
302 Cl H NHCONHCOC 6H 3-2,6-Cl 2
303 Cl H NHCONHCOC 6H 4-2-Cl
304 OPh H OCH 2CO 2C 2H 5
305 OPh H OCH(Me)CO 2C 2H 5
306 OPh H OCH 2-1-(1,2, the 4-triazole)
307 OPh H OCONHCH 3
308 OPh H OCONHC 6H 4-4-Cl
309 OPh H OCONHC 6H 4-4-CF 3
310 OPh H OCONC 6H 4-4-OCF 3
311 OPh H OCONHC 6H 3-3,4-Cl 2
312 OPh H NHCONHC 6H 4-4Cl
313 OPh H N(CH 3)CONHC 6H 4-4Cl
314 OPh H NHCONHC 6H 4-4-CF 3
315 OPh H NHCONHC 6H 4-4-OCF 3
316 OPh H NHCONHC 6H 3-3,4-Cl 2
317 OPh H OCOC 6H 4-4-F
318 OPh H OCOC 6H 4-4-Cl
319 OPh H OCOC 6H 3-2,6-F 2
320 OPh H NHCOC 6H 4-4-F
321 OPh H NHCOC 6H 4-4-Cl
322 OPh H NHCOC 6H 3-2,6-F 2
323 OPh H OCONHCOC 6H 3-2,6-F 2
324 OPh H OCONHCOC 6H 4-2-F
325 OPh H OCONHCOC 6H 3-2,6-Cl 2
326 OPh H OCONHCOC 6H 4-2-Cl
327 OPh H NHCONHCOC 6H 3-2,6-F 2
328 OPh H NHCONHCOC 6H 4-2-F
329 OPh H NHCONHCOC 6H 3-2,6-Cl 2
330 OPh H NHCONHCOC 6H 4-2-Cl
33l Cl H OCH 2C 6H 4-4-C 4H 9t
332 Cl H OCH 2C 6H 4-4-CO 2C 4H 9t
333 Cl H NHCH 2C 6H 4-4-C 4H 9t
334 Cl H NHCH 2C 6H 4-4-CO 2C 4H 9t
335 OPh H OCH 2C 6H 4-4-C 4H 9t
336 OPh H OCH 2C 6H 4-4-CO 2C 4H 9t
337 OPh H NHCH 2C 6H 4-4-C 4H 9t
338 OPh H NHCH 2C 6H 4-4-CO 2C 4H 9t
339 OPh H OCH 2P(S)(OC 2H 5) 2
340 OPh H OCH 2P(O)OC 2H 5(SC 3H 7)
34l OPh H P(S)(OC 2H 5) 2
342 OPh H P(O)OC 2H 5(SC 3H 7)
343 OPh H OCH 2-3-C 6H 3N-6-Cl
344 OPh NH 2 OCH 2-3-C 6H 3N-6-Cl
345 OPh CN OCONHCH 3
346 OPh CO 2CH 3 OCH 3
347 OPh H OCOCH 2CH 2CO 2H
348 OPh H OCOCH=CHCO 2CH 3
349 OPh
Table 5 Compound number R 1XR 3Y R
350 CH 3 Cl O CH 2C 6H 4-4-Cl
351 CH 3 Cl O CH 2C 6H 4-4-F
352 CH 3 Cl O CH 2C 6H 4-4-C 4H 9t
353 CH 3 Cl O CH 2C 6H 4-4-CO 2CH 3
354 CH 3 Cl O CH 2C 6H 4-4-CO 2C 4H 9t
355 CH 3 Cl O CH 2-5-C 5H 3N-2-Cl
356 CH 3 Cl O CH 2-3-C 5H 3N-2-Cl
357 CH 3 Cl O C 6H 3-2,6-F 2
358 CH 3 Cl O C 6H 4-3-Cl
359 CH 3 Cl O C 6H 4-4-Cl
360 CH 3 Cl O C 6H 4-4-F
361 CH 3 Cl O C 6H 4-4-C 4H 9t
362 CH 3 Cl O C 6H 4-4-CO 2CH 3
363 CH 3 Cl O C 6H 4-4-CO 2C 4H 9t
364 CH 3 Cl O 5-C 5H 3N-2-Cl
365 CH 3 Cl O 3-C 5H 3N-2-Cl
366 CH 3 Cl NCH 3 CH 2C 6H 4-4-Cl
367 CH 3 Cl NCH 3 CH 2C 6H 4-4-F
368 CH 3 Cl NCH 3 CH 2C 6H 4-4-C 4H 9t
369 CH 3 Cl NCH 3 CH 2C 6H 4-4-CO 2CH 3
370 CH 3 Cl NCH 3 CH 2C 6H 4-4-CO 2C 4H 9t
371 CH 3 Cl NCH 3 CH 2-5-C 5H 3N-2-Cl
372 CH 3 Cl NCH 3 CH 2-3-C 5H 3N-2-Cl
373 CH 3 Cl NCH 3 C 6H 4-4-Cl
374 CH 3 Cl NCH 3 C 6H 4-4-F
375 CH 3 Cl NCH 3 C 6H 4-4-C 4H 9t
376 CH 3 Cl NCH 3 C 6H 4-4-CO 2CH 3
377 CH 3 Cl NCH 3 C 6H 4-4-CO 2C 4H 9t
378 CH 3 Cl NCH 3 5-C 5H 3N-2-Cl
379 CH 3 Cl NCH 3 3-C 5H 3N-2-Cl
380 CH 3 Cl NCH 3 C 6H 3-2,6-F 2
381 CH 3 Cl NCH 3 C 6H 4-3-Cl
382 CH 3 OPh O CH 2C 6H 4-4-Cl
383 CH 3 OPh O CH 2C 6H 4-4-F
384 CH 3 OPh O CH 2C 6H 4-4-C 4H 9t
385 CH 3 OPh O CH 2C 6H 4-4-CO 2CH 3
386 CH 3 OPh O CH 2C 6H 4-4-CO 2C 4H 9t
387 CH 3 OPh O CH 2-5-C 5H 3N-2-Cl
388 CH 3 OPh O CH 2-3-C 5H 3N-2-Cl
389 CH 3 OPh O C 6H 3-2,6-F 2
390 CH 3 OPh O C 6H 4-3-Cl
391 CH 3 OPh O C 6H 4-4-Cl
392 CH 3 OPh O C 6H 4-4-F
393 CH 3 OPh O C 6H 4-4-C 4H 9t
394 CH 3 OPh O C 6H 4-4-CO 2CH 3
395 CH 3 OPh O C 6H 4-4-CO 2C 4H 9t
396 CH 3 OPh O 5-C 5H 3N-2-Cl
397 CH 3 OPh O 3-C 5H 3N-2-Cl
398 CH 3 OPh NCH 3 CH 2C 6H 4-4-Cl
399 CH 3 OPh NCH 3 CH 2C 6H 4-4-F
400 CH 3 OPh NCH 3 CH 2C 6H 4-4-C 4H 9t
401 CH 3 OPh NCH 3 CH 2C 6H 4-4-CO 2CH 3
402 CH 3 OPh NCH 3 CH 2C 6H 4-4-CO 2C 4H 9t
403 CH 3 OPh NCH 3 CH 2-5-C 5H 3N-2-Cl
404 CH 3 OPh NCH 3 CH 2-3-C 5H 3N-2-Cl
405 CH 3 OPh NCH 3 C 6H 4-4-Cl
406 CH 3 OPh NCH 3 C 6H 4-4-F
407 CH 3 OPh NCH 3 C 6H 4-4-C 4H 9t
408 CH 3 OPh NCH 3 C 6H 4-4-CO 2CH 3
409 CH 3 OPh NCH 3 C 6H 4-4-CO 2C 4H 9t
410 CH 3 OPh NCH 3 5-C 5H 3N-2-Cl
411 CH 3 OPh NCH 3 3-C 5H 3N-2-Cl
412 CH 3 OPh NCH 3 C 6H 3-2,6-F 2
413 CH 3 OPh NCH 3 C 6H 4-3-Cl
414 Cl OPh NCH 3 C 6H 4-4-Cl
415 Cl OPh NCH 3 C 6H 4-4-F
416 Cl OPh NCH 3 C 6H 4-4-C 4H 9t
417 Cl OPh NCH 3 C 6H 4-4-CO 2CH 3
418 Cl Cl O C 6H 4-4-Cl
419 Cl Cl O C 6H 4-4-F
420 Cl Cl O C 6H 4-4-C 4H 9t
421 Cl Cl O C 6H 4-4-CO 2CH 3
Table 6
Figure C9710505000261
R 1And XR 3The position can be 3,4 or 5 of pyrazoles.
R 1 XR 3 R 2 Q
CH 3 Cl CH 3 CH 2C 6H 4-4-Cl
CH 3 Cl CH 3 CH 2C 6H 4-4-F
CH 3 Cl CH 3 CH 2C 6H 4-4-C 4H 9t
CH 3 Cl CH 3 CH 2C 6H 4-4-CO 2CH 3
CH 3 Cl CH 3 CH 2C 6H 4-4-CO 2C 4H 9t
CH 3 OPh CH 3 CH 2-3-C 5H 3N-6-Cl
CH 3 Cl CH 3 CH 2-3-C 5H 3N-2-Cl
CH 3 Cl CH 3 C 6H 3-2,6-F 2
CH 3 Cl CH 3 C 6H 4-3-Cl
CH 3 Cl CH 3 C 6H 4-4-Cl
CH 3 Cl CH 3 C 6H 4-4-F
CH 3 Cl CH 3 C 6H 4-4-C 4H 9t
CH 3 Cl CH 3 C 6H 4-4CO 2CH 3
CH 3 Cl CH 3 C 6H 4-4-CO 2C 4H 9t
CH 3 Cl CH 3 5-C 5H 3N-2-Cl
CH 3 OPh CH 3 3-C 5H 3N-2-Cl
CH 3 Cl CH 3 NHC 6H 5
CH 3 Cl CH 3 NH-3-C 5H 3N-6-Cl
CH 3 F CH 3 CH 2C 6H 4-4-Cl
CH 3 F CH 3 CH 2C 6H 4-4-F
CH 3 F CH 3 CH 2C 6H 4-4-C 4H 9t
CH 3 F CH 3 CH 2C 6H 4-4-CO 2CH 3
CH 3 F CH 3 CH 2C 6H 4-4-CO 2C 4H 9t
CH 3 F CH 3 CH 2-3-C 5H 3N-6-Cl
CH 3 F CH 3 CH 2-3-C 5H 3N-2-Cl
H H Ph C 6H 3-2,6-F 2
CH 3 F CH 3 C 6H 4-3-Cl
CH 3 F CH 3 C 6H 4-4-Cl
CH 3 F CH 3 C 6H 4-4-F
CH 3 F CH 3 C 6H 4-4-C 4H 9t
CH 3 F CH 3 C 6H 4-4-CO 2CH 3
CH 3 F CH 3 C 6H 4-4-CO 2C 4H 9t
CH 3 F CH 3 5-C 5H 3N-2-Cl
CH 3 F CH 3 3-C 5H 3N-2-Cl
CH 3 F CH 3 NHC 6H 5
CH 3 F CH 3 NH-5-C 5H 3N-2Cl
F F CH 3 CH 2C 6H 4-4-Cl
F F CH 3 CH 2C 6H 4-4-F
F F CH 3 CH 2C 6H 4-4-C 4H 9t
F F CH 3 CH 2C 6H 4-4-CO 2CH 3
F F CH 3 CH 2C 6H 4-4-CO 2C 4H 9t
F F CH 3 CH 2-3-C 5H 3N-6-Cl
F F CH 3 CH 2-3-C 5H 3N-2-Cl
F F CH 3 C 6H 3-2,6F 2
F F CH 3 C 6H 4-3-Cl
F F CH 3 C 6H 4-4-Cl
F F CH 3 C 6H 4-4-F
F F CH 3 C 6H 4-4-C 4H 9t
F F CH 3 C 6H 4-4-CO 2CH 3
F F CH 3 C 6H 4-4-CO 2C 4H 9t
F F CH 3 5-C 5H 3N-2-Cl
F F CH 3 3-C 5H 3N-2Cl
F F CH 3 NHC 6H 5
CF 3 H CH 3 C 6H 4-3-CF 3
CF 3 H C 2H 5 C 6H 4-4-C 4H 9t
F CH 3 F C 6H 3-2-OC 2H 5-4-C 4H 9t
F F CH 3 NH-5-C 5H 3N-2-Cl
Table 7
Figure C9710505000281
R 1 R 2 R 3 ZQ
CH 3 CH 3 H OCH 2C 6H 4-4-C 4H 9t
CH 3 CH 3 H OCH 2C 6H 4-4-CO 2C 4H 9t
CH 3 CH 3 H OCH 2C 6H 4-4-CO 2CH 3
CH 3 CH 3 H OCH 2C 6H 4-4-Cl
CH 3 C 2H 5 H OCH 2C 6H 4-4-CN
CH 3 CH 3 H OCH 2C 6H 4-4-CF 3
CH 3 CH 3 H OCH 2C 6H 4-4-OCF 3
CH 3 CH 3 H OCH 2C 6H 4-4-NO 2
CH 3CH 3H OCH 2-3-pyridine-6-Cl
CH 3CH 3H OCH 2-2-furans
CH 3CH 3H OCH 2-2-thiophene phenol
CH 3CH 3H OCH 2-1-1,2, the 4-triazole
CH 3CH 3H OCH 2-1-pyrazoles
CH 3CH 3H OCH 2-2-pyrimidine
CH 3 CH 3 H C 6H 4-3-OCH(CH 3)
CH 3 CH 3 Cl OCH 2C 6H 4-4-C 4H 9t
CH 3 CH 3 Cl OCH 2C 6H 4-4-CO 2C 4H 9t
CH 3 CH 3 Cl OCH 2C 6H 4-4-CO 2CH 3
CH 3 CH 3 Cl OCH 2C 6H 4-4-Cl
CH 3 C 2H 5 Cl OCH 2C 6H 4-4-CN
CH 3 CH 3 Cl OCH 2C 6H 4-4-CF 3
CH 3 CH 3 Cl OCH 2C 6H 4-4-OCF 3
CH 3 CH 3 Cl OCH 2C 6H 4-4-NO 2
CH 3CH 3Cl OCH 2-3-pyridine-6-Cl
CH 3CH 3Cl OCH 2-2-furans
CH 3CH 3Cl OCH 2-2-thiophene phenol
CH 3CH 3Cl OCH 2-1-1,2, the 4-triazole
CH 3CH 3Cl OCH 2-1-pyrazoles
CH 3CH 3Cl OCH 2-2-pyrimidine
CH 3 CH 3 Cl C 6H 4-3-OCH(CH 3) 2
C 4H 9t CH 3 H OCH 2C 6H 4-4-C 4H 9t
C 4H 9t CH 3 H OCH 2C 6H 4-4-CO 2C 4H 9t
C 4H 9t CH 3 H OCH 2C 6H 4-4-CO 2CH 3
C 4H 9t CH 3 H OCH 2C 6H 4-4-Cl
C 4H 9t CH 3 H OCH 2C 6H 4-4-CN
C 4H 9t CH 3 H OCH 2C 6H 4-4-CF 3
C 4H 9t CH 3 H OCH 2C 6H 4-4-OCF 3
C 4H 9t CH 3 H OCH 2C 6H 4-4-NO 2
C 4H 9T CH 3H OCH 2-3-pyridine-6-Cl
C 4H 9T CH 3H OCH 2-2-furans
C 4H 9T CH 3H OCH 2-2-thiophene phenol
C 4H 9T CH 3H OCH 2-1-1,2, the 4-triazole
C 4H 9T CH 3H OCH 2-1-pyrazoles
C 4H 9T CH 3H OCH 2-2-pyrimidine
C 4H 9t CH 3 H C 6H 4-3-OCH(CH 3)
C 4H 9t CH 3 Cl OCH 2C 6H 4-4-C 4H 9t
C 4H 9t CH 3 Cl OCH 2C 6H 4-4-CO 2C 4H 9t
C 4H 9t CH 3 Cl OCH 2C 6H 4-4-CO 2CH 3
C 4H 9t CH 3 Cl OCH 2C 6H 4-4-Cl
C 4H 9t CH 3 Cl OCH 2C 6H 4-4-CN
C 4H 9t CH 3 Cl OCH 2C 6H 4-4-CF 3
C 4H 9t CH 3 Cl OCH 2C 6H 4-4-OCF 3
C 4H 9t CH 3 Cl OCH 2C 6H 4-4-NO 2
C 4H 9T CH 3Cl OCH 2-3-pyridine-6-Cl
C 4H 9T CH 3Cl OCH 2-2-furans
C 4H 9T CH 3Cl OCH 2-2-thiophene phenol
C 4H 9T CH 3Cl OCH 2-1-1,2, the 4-triazole
C 4H 9T CH 3Cl OCH 2-1-pyrazoles
C 4H 9T CH 3Cl OCH 2-2-pyrimidine
C 4H 9t CH 3 Cl C 6H 4-3-OCH(CH 3) 2
C 2H 5 CH 3 H OCH 2C 6H 4-4-C 4H 9t
C 2H 5 CH 3 H OCH 2C 6H 4-4-CO 2C 4H 9t
C 2H 5 CH 3 H OCH 2C 6H 4-4-CO 2CH 3
C 2H 5 CH 3 H OCH 2C 6H 4-4-Cl
C 2H 5 CH 3 H OCH 2C 6H 4-4-CN
C 2H 5 CH 3 H OCH 2C 6H 4-4-CF 3
C 2H 5 CH 3 H OCH 2C 6H 4-4-OCF 3
C 2H 5 CH 3 H OCH 2C 6H 4-4-NO 2
C 2H 5CH 3H OCH 2-3-pyridine-6-Cl
C 2H 5CH 3H OCH 2-2-furans
C 2H 5CH 3H OCH 2-2-thiophene phenol
C 2H 5CH 3H OCH 2-1-1,2, the 4-triazole
C 2H 5CH 3H OCH 2-1-pyrazoles
C 2H 5CH 3H OCH 2-2-pyrimidine
C 2H 5 CH 3 H C 6H 4-3-OCH(CH 3)
C 2H 5 CH 3 Cl OCH 2C 6H 4-4-C 4H 9t
C 2H 5 CH 3 Cl OCH 2C 6H 4-4-CO 2C 4H 9t
C 2H 5 CH 3 Cl OCH 2C 6H 4-4-CO 2CH 3
C 2H 5 CH 3 Cl OCH 2C 6H 4-4-Cl
C 2H 5 CH 3 Cl OCH 2C 6H 4-4-CN
C 2H 5 CH 3 Cl OCH 2C 6H 4-4-CF 3
C 2H 5 CH 3 Cl OCH 2C 6H 4-4-OCF 3
C 2H 5 CH 3 Cl OCH 2C 6H 4-4-NO 2
C 2H 5CH 3Cl OCH 2-3-pyridine-6-Cl
C 2H 5CH 3Cl OCH 2-2-furans
C 2H 5CH 3Cl OCH 2-2-thiophene phenol
C 2H 5CH 3Cl OCH 2-1-1,2, the 4-triazole
C 2H 5CH 3Cl OCH 2-1-pyrazoles
C 2H 5CH 3Cl OCH 2-2-pyrimidine
C 2H 5 CH 3 Cl C 6H 4-3OCH(CH 3) 2
CH 3 CH 3 Cl NHC 6H 4-4-C 4H 9t
CH 3 CH 3 Cl NHC 6H 4-4-CO 2C 4H 9t
CH 3 CH 3 Cl NHC 6H 4-4-CO 2CH 3
CH 3 CH 3 Cl NHC 6H 4-4-Cl
CH 3 CH 3 Cl NHC 6H 4-4-CN
CH 3 CH 3 Cl NHC 6H 4-4-CF 3
CH 3 CH 3 Cl NHC 6H 4-4-OCF 3
CH 3 CH 3 Cl NHC 6H 4-4-NO 2
CH 3CH 3Cl NHCH 2-3-pyridine-6-Cl
CH 3CH 3Cl NHCH 2-2-furans
CH 3CH 3Cl NHCH 2-2-thiophene phenol
CH 3CH 3Cl NHCH 2-1-1,2, the 4-triazole
CH 3CH 3Cl NHCH 2-1-pyrazoles
CH 3CH 3Cl NHCH 2-2-pyrimidine
CH 3 CH 3 Cl NHCH 2C 6H 4-4-OCH(CH 3)
CH 3 CH 3 Cl NHCH 2C 6H 4-4-C 4H 9t
CH 3 CH 3 Cl NHCH 2C 6H 4-4-CO 2C 4H 9t
CH 3 CH 3 Cl NHCH 2C 6H 4-4-CO 2CH 3
CH 3 CH 3 Cl NHCH 2C 6H 4-4-Cl
CH 3 CH 3 Cl NHCH 2C 6H 4-4-CN
CH 3 CH 3 Cl NHCH 2C 6H 4-4-CF 3
CH 3 CH 3 Cl NHCH 2C 6H 2-2,6-Cl 2-4-OCF 3
CH 3 CH 3 Cl NHCH 2C 6H 4-4-NO 2
CH 3CH 3Cl NH-3-pyridine-6-Cl
CH 3CH 3Cl NH-2-furans
CH 3CH 3Cl NH-2-thiophene phenol
CH 3CH 3Cl NH-1-1,2, the 4-triazole
CH 3CH 3Cl NH-2-pyrimidine
CH 3CH 3Cl NH-2-pyrimidine-4,6-(OMe) 2
CH 3CH 3Cl NH-2-pyrimidine-4,6-(Me) 2
CH 3 CH 3 H NHC 6H 4-4-C 4H 9t
CH 3 CH 3 H NHC 6H 4-4-CO 2C 4H 9t
CH 3 CH 3 H NHC 6H 4-4-CO 2CH 3
CH 3 CH 3 H NHC 6H 4-4-Cl
CH 3 CH 3 H NHC 6H 4-4-CN
CH 3 CH 3 H NHC 6H 4-4-CF 3
CH 3 CH 3 H NHC 6H 4-4-OCF 3
CH 3 CH 3 H NHC 6H 4-4-NO 2
CH 3CH 3H NHCH 2-3-pyridine-6-Cl
CH 3CH 3H NHCH 2-2-furans
CH 3CH 3H NHCH 2-2-thiophene phenol
CH 3CH 3H NHCH 2-1-1,2, the 4-triazole
CH 3CH 3H NHCH 2-1-pyrazoles
CH 3CH 3H NHCH 2-2-pyrimidine
CH 3 CH 3 H NHCH 2C 6H 4-4-OCH(CH 3)
CH 3 CH 3 H NHCH 2C 6H 4-4-C 4H 9t
CH 3 CH 3 H NHCH 2C 6H 4-4-CO 2C 4H 9t
CH 3 CH 3 H NHCH 2C 6H 4-4-CO 2CH 3
CH 3 CH 3 H NHCH 2C 6H 4-4-Cl
CH 3 CH 3 H NHCH 2C 6H 4-4-CN
CH 3 CH 3 H NHCH 2C 6H 4-4-CF 3
CH 3 CH 3 H NHCH 2C 6H 2-2,6-Cl 2-4-OCF 3
CH 3 CH 3 H NHCH 2C 6H 4-4-NO 2
CH 3CH 3H NH-3-pyridine-6-Cl
CH 3CH 3H NH-2-furans
CH 3CH 3H NH-2-thiophene phenol
CH 3CH 3H NH-1-1,2, the 4-triazole
CH 3CH 3H NH-2-pyrimidine
CH 3CH 3H NH-2-pyrimidine-46-(Me) 2
CF 3 CH 3 H OCH 2C 6H 4-4-C 4H 9t
CF 3 CH 3 H OCH 2C 6H 4-4-CO 2C 4H 9t
CF 3 CH 3 H OCH 2C 6H 4-4-CO 2CH 3
CF 3 CH 3 H OCH 2C 6H 4-4-Cl
CF 3 CH 3 H OCH 2C 6H 4-4-CN
CF 3 CH 3 H OCH 2C 6H 4-4-CF 3
CF 3 CH 3 H OCH 2C 6H 4-4-OCF 3
CF 3 CH 3 H OCH 2C 6H 4-4-NO 2
CF 3CH 3H OCH 2-3-pyridine-6-Cl
CF 3CH 3H OCH 2-2-furans
CF 3CH 3H OCH 2-2-thiophene phenol
CF 3CH 3H OCH 2-1-1,2, the 4-triazole
CF 3CH 3H OCH 2-1-pyrazoles
CF 3CH 3H OCH 2-2-pyrimidine
CF 3 CH 3 H C 6H 4-3-OCH(CH 3) 2
CF 3 CH 3 H NHC 6H 4-4-C 4H 9t
CF 3 CH 3 H NHC 6H 4-4-CO 2C 4H 9t
CF 3 CH 3 H NHC 6H 4-4-CO 2CH 3
CF 3 CH 3 H NHC 6H 4-4-Cl
CF 3 CH 3 H NHC 6H 4-4-CN
CF 3 CH 3 H NHC 6H 4-4-CF 3
CF 3 CH 3 H NHC 6H 4-4-OCF 3
CF 3 CH 3 H NHC 6H 4-4-NO 2
CF 3CH 3H NHCH 2-3-pyridine-6-Cl
CF 3CH 3H NHCH 2-2-furans
CF 3CH 3H NHCH 2-2-thiophene phenol
CF 3CH 3H NHCH 2-1-1,2, the 4-triazole
CF 3CH 3H NHCH 2-1-pyrazoles
CF 3CH 3H NHCH 2-2-pyrimidine
CF 3 CH 3 H NHCH 2C 6H 4-4-OCH(CH 3)
CF 3 CH 3 H NHCH 2C 6H 4-4-C 4H 9t
CF 3 CH 3 H NHCH 2C 6H 4-4-CO 2C 4H 9t
CF 3 CH 3 H NHCH 2C 6H 4-4-CO 2CH 3
CF 3 CH 3 H NHCH 2C 6H 4-4-Cl
CF 3 CH 3 H NHCH 2C 6H 4-4-CN
CF 3 CH 3 H NHCH 2C 6H 4-4-CF 3
CF 3 CH 3 H NHCH 2C 6H 2-2,6-Cl 2-4-OCF 3
CF 3 CH 3 H NHCH 2C 6H 4-4-NO 2
CF 3CH 3H NH-3-pyridine-6-Cl
CF 3CH 3H NH-2-furans
CF 3CH 3H NH-2-thiophene phenol
CF 3CH 3H NH-1-1,2, the 4-triazole
CF 3CH 3H NH-2-pyrimidine
CF 3CH 3H NH-2-pyrimidine-4,6-(Me) 2
CF 3 CH 3 Cl NHC 6H 4-4-C 4H 9t
CF 3 CH 3 Cl NHC 6H 4-4-CO 2C 4H 9t
CF 3 CH 3 Cl NHC 6H 4-4-CO 2CH 3
CF 3 CH 3 Cl NHC 6H 4-4-Cl
CF 3 CH 3 Cl NHC 6H 4-4-CN
CF 3 CH 3 Cl NHC 6H 4-4-CF 3
CF 3 CH 3 Cl NHC 6H 4-4-OCF 3
CF 3 CH 3 Cl NHC 6H 4-4-NO 2
CF 3CH 3Cl NHCH 2-3-pyridine-6-Cl
CF 3CH 3Cl NHCH 2-2-furans
CF 3CH 3Cl NHCH 2-2-thiophene phenol
CF 3CH 3Cl NHCH 2-1-1,2, the 4-triazole
CF 3CH 3Cl NHCH 2-1-pyrazoles
CF 3CH 3Cl NHCH 2-2-pyrimidine
CF 3 CH 3 Cl NHCH 2C 6H 4-4-OCH(CH 3)
CF 3 CH 3 Cl NHCH 2C 6H 4-4-C 4H 9t
CF 3 CH 3 Cl NHCH 2C 6H 4-4-CO 2C 4H 9t
CF 3 CH 3 Cl NHCH 2C 6H 4-4-CO 2CH 3
CF 3 CH 3 Cl NHCH 2C 6H 4-4-Cl
CF 3 CH 3 Cl NHCH 2C 6H 4-4-CN
CF 3 CH 3 Cl NHCH 2C 6H 4-4-CF 3
CF 3 CH 3 Cl NHCH 2C 6H 2-2,6-Cl 2-4-OCF 3
CF 3 CH 3 Cl NHCH 2C 6H 4-4-NO 2
CF 3CH 3Cl NH-3-pyridine-6-Cl
CF 3CH 3Cl NH-2-furans
CF 3CH 3Cl NH-2-thiophene phenol
CF 3CH 3Cl NH-1-1,2, the 4-triazole
CF 3CH 3Cl NH-2-pyrimidine
CF 3CH 3Cl NH-2-pyrimidine-4,6-(OMe) 2
CF 3CH 3Cl NH-2-pyrimidine-4,6-(Me) 2
The rerum natura of part of compounds and nuclear-magnetism (90MHz) data:
2 fusing points: 98-100 ℃.
10 oily matter, HNMR (CDCl 3, TMS) ppm:8.42 (s, 1H), 7.90 (s, 1H), 6.44～7.44 (m, 9H), 5.02 (s, 2H), 3.65 (s, 3H), 2.01 (s, 3H), 1.31 (s, 9H)
146 fusing points: 91～93 ℃ of .HNMR (CDCl 3, TMS) ppm:7.71 (q, 4H), 6.40 (bs, 1H), 4.57 (d, 2H), 3.78 (s, 3H), 2.48 (s, 3H), 1.31 (d, 6H)
150 fusing points: 190～192 ℃. 152 fusing points: 210～212 ℃.
155v fusing point: 90～92 ℃ of .HNMR (CDCl 3, TMS) ppm:7.78 (bs, 1H), 6.91～7.40 (m, 3H), 6.57～6.75 (d, 2H), 4.58 (m, 1H), 3.83 (s, 3H), 2.52 (s, 3H), 1.31 (d, 6H)
159 fusing points: 200 ℃ (decomposition). 160 fusing points: 74～76 ℃.
169 fusing points: 173～175 ℃ of .HNMR (CDCl 3, TMS) ppm:8.08 (bs, 1H), 7.45～7.69 (m, 2H), 6.88～7.15 (m, 2H), 3.88 (s, 3H)
170 fusing points: 135～136 ℃ of .HNMR (CDCl 3, TMS) ppm:7.53 (q, 4H), 6.84 (bs, 1H), 4.69 (d, 2H), 3.87 (s, 3H)
182 fusing points: 170～172 ℃.
277 fusing points: 75～78 ℃ of .HNMR (CDCl 3, TMS) ppm:7.98 (s, 1H), 4.58 (s, 2H), 4.15 (q, 2H), 3.75 (s, 3H), 2.24 (s, 3H), 1.22 (t, 3H)
285 fusing points: 227～230 ℃ of (d) .HNMR (DMSO, TMS) ppm:10.73 (bs, 1H), 8.53 (bs, 1H), 7.87 (s, 1H), 7.64 (d, 2H), 7.33 (d, 2H), 3.76 (s, 3H), 2.41 (s, 3H)
286 fusing points: 175～177 ℃ of .HNMR (DMSO, TMS) ppm:8.96 (s, 1H), 8.84 (s, 1H), 7.56 (s, 1H), 7.42 (d, 2H), 7.31 (d, 2H), 3.78 (s, 3H), 3,67 (s, 3H), 2.41 (s, 3H)
287 fusing points: 231～233 ℃. 288 fusing points: 222～224 ℃.
289 fusing points: 176～178 ℃. 295 fusing points: 196～199 ℃.
304 oily matter, HNMR (DMCO, TMS) ppm:7.69 (s, 1H), 6.89 (m, 2H), 7.47 (m, 2H), 7.19 (m, 1H), 4.42 (s, 2H), 4.15 (q, 2H), 3.57 (s, 3H), 2.26 (s, 3H), 1.20 (t, 3H)
308 fusing points: 115～118 ℃ of .HNMR (CDCl 3+ DMSO, TMS) ppm:8.32 (bs, 1H), 8.08 (s, 1H), 7.36 (m, 2H), 7.28 (m, 4H), 7.16 (m, 1H), 7.07 (m, 2H), 3.65 (s, 3H), 2.24 (s, 3H)
312 fusing points: 200～203 ℃ of .HNMR (DMSO, TMS) ppm:10.48 (bs, 1H), 8.89 (bs, 1H), 7.61 (s, 1H), 7.18～7.55 (m, 7H), 7.00 (d, 2H), 3.58 (s, 3H), 2.39 (s, 3H)
318 fusing points: 113～115 ℃ of .HNMR (CDCl 3+ DMSO, TMS) ppm:8.19 (s, 1H), 7.97 (d, 2H), 7.52 (d, 2H), 6.95～7.50 (m, 5H), 3.62 (s, 3H), 2.39 (s, 3H)
324 fusing points: 135～137 ℃ of .HNMR (CDCl 3, TMS) ppm:9.91 (bs, 1H), 8.13 (m, 1H), 8.06 (s, 1H), 7.61 (m, 1H), 6.89 (m, 2H), 7.00～7.55 (m, 5H), 3.65 (s, 3H), 2.47 (s, 3H)
344 fusing points: 112～114 ℃ of .HNMR (CDCl 3, TMS) ppm:8.40 (s, 1H), 7.56～7.78 (m, 1H), 7.04～7.56 (m, 5H), 6.77～7.04 (d, 2H), 5.00 (s, 2H), 4.80 (bs, 1H), 3.58 (s, 3H), 2.37 (s, 3H)
349 oily matter, 385 fusing points: 180～182 ℃.
Compound of the present invention has good sterilization, desinsection and acaricidal activity.Be used to prevent and treat multiple cause of disease microbial disease as oidium, gray mold, Powdery Mildew, banded sclerotial blight, rice blast, rust etc.; Also can be used for preventing and treating lepidopterous insects such as mythimna separata, small cabbage moth, Homoptera insect such as plant hopper, aphid etc., dipteral insect such as mosquito, fly etc. and mite class such as two-spotted spider mite, carmine spider mite etc. comprise particularly ovum of nymph, adult, promptly ovum are had excellent activity.
1, to the test of black bean aphid
Using compound of the present invention, is 500ppm with concentration, is 3 day age for the examination aphid, and each the processing tried 50～100 of worms, and with the clear water contrast, triplicate is handled the back and placed in 20～23 ℃ of observation ward, 24 hours " Invest, Then Investigate " mortality ratio, and partial results is as follows:
Compound number Mortality ratio (%)
2 79 100 100
2, to the test of carmine spider mite
Adopt immersion method, compound concentration of the present invention is 500ppm.With moving 2 Kidney bean seedling true leaves that are connected into 50～70 of mites, put into and take out after the soup that has prepared soaked for 5 seconds, place in 20～25 ℃ of observation ward, with the clear water contrast, triplicate, 24 hours " Invest, Then Investigate " mortality ratio, partial results is seen as follows:
Compound number Mortality ratio (%)
2 79 146 100 100 100
3, ovicidal activity test-pot-culture method
Become 5 of mites to be connected on the potted plant Kidney bean seedling of two true leaves healthy and strong carmine spider mite, remove into mite after 2 days, investigation mite ovum radix, in the good soup of dilution, flooded for 5 seconds, place then in the room temperature and cultivate, handle treated in back 6 days blank all hatching finish the hatching of investigation ovum and hatch the survival condition of young mite.Partial results is as follows:
Compound number Concentration (ppm) Ovum radix (grain) Mite number alive Net effect (%)
2 79 10 10 102 255 0 0 100 100
Methamidophos 10 230 109 46.4
4, ovicidal activity test-Ye dish method
Becoming 5 of mites to be connected to diameter healthy and strong carmine spider mite is on 1 centimetre the Kidney bean seedling leaf dish, in observation ward preserve moisture cultivation, remove into mite after 24 hours, investigation mite ovum radix, in the good soup of dilution, flooded for 5 seconds, treated in 7th blank all hatching finish the hatching of investigation ovum and hatch the survival condition of young mite.Partial results is as follows:
Compound number Concentration (ppm) Ovum radix (grain) Do not hatch and count (grain) Inhibiting rate (%)
79 12.5 63 62 98.4
5, gray mold test
Compound concentration of the present invention is 1000ppm.Spray method is handled cucumber seedling, utilizes ash arrhizus bacteria to carry out artificial inoculation after 24 hours, with the clear water contrast, and triplicate, the 5 days " Invest, Then Investigate " incidences of preserving moisture, partial results is as follows:
Compound number Preventive effect (%)
288 100
6, Powdery Mildew test
Compound concentration of the present invention is 1000ppm.Potted plant wheat grows to two leaf stage, and artificial inoculation Powdery Mildew oidium after 24 hours is handled in spraying, with the clear water contrast, and triplicate, the 7 days " Invest, Then Investigate " incidences of preserving moisture, partial results is seen as follows:
Compound number Preventive effect (%) Compound number Preventive effect (%)
277 278 304 95 95 100 305 331 343 100 100 90
7, oidium test
Compound concentration of the present invention is 1000ppm.Spray method is handled cucumber seedling, utilizes sporangia suspension to carry out artificial inoculation after 24 hours, with the clear water contrast, and triplicate, the 7 days " Invest, Then Investigate " incidences of preserving moisture, partial results is seen as follows:
Compound number Preventive effect (%)
2 306 385 95 95 75
8, banded sclerotial blight test
Compound concentration of the present invention is 1000ppm.Spray method treating water rice seedling utilizes sheath blight fungus to carry out artificial inoculation after 24 hours, with the clear water contrast, and triplicate, the 3 days " Invest, Then Investigate " incidences of preserving moisture, partial results is as follows:
Compound number Preventive effect (%) Compound number Preventive effect (%)
145 150 100 100 155 159 100 100

Claims (5)

1, as the pyrazole compound of disinfectant use in agriculture and insecticidal/acaricidal agent, its general formula is: In the formula: R 1, R 2Be methyl, be positioned at 1 and 3 of pyrazoles ring;
X is key or O;
R 3Be chlorine or phenyl;
R 4Be OH, NH 2Or triazolyl;
Y is key, O or NH;
Z is key, methylene radical, CO and and R 4The carbon atom that reaches Y, N and link to each other with N is together formed undersaturated five-ring;
Q is a substituted-phenyl, and its substituting group is selected from-C 4H 9(t) ,-CO 2C 4H 9(t) ,-CF 3,-OCH (CH 3) 2,-NO 2
m=1。
2, according to the described compound of claim 1, it is characterized in that: Z and R 4The carbon atom one that reaches Y, N and link to each other with N becomes the oxadiazole ring on the same group.
3, contain the mixed preparation of logical formula I compound, it is characterized in that: the logical weight percentage of formula I compound in preparation is 0.5-95%.
4, according to the described preparation of claim 3, it is characterized in that: said preparation can be for solution, emulsion, wettable powder, suspension agent, pulvis, paste, soluble powder, granule, flooded the natural materials of active compound and wrapped into micro-fine capsule in the polymer materials.
5, the logical application of formula I compound aspect sterilization and Insecticiding-miticiding, described compound is used to prevent and treat oidium, gray mold, Powdery Mildew, banded sclerotial blight, rice blast, rust; Perhaps also be used to prevent and treat mythimna separata, small cabbage moth, plant hopper, aphid, two-spotted spider mite and carmine spider mite and ovum.
CN 97105050 1997-01-23 1997-01-23 Pyrazole compounds used as agricultrial germicide and insecticide and acaricide and its preparation Expired - Fee Related CN1072211C (en)

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