CN1188764A - 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 PDFInfo
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Abstract
The present invention relates to a kind of pyrazoline-type compounds and their preparation, which can be used as agricultural miticide, disinfactant and insecticide as they have associated activities.
Description
The present invention relates to new pyrazole compound, they the 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.
The new pyrazole compound that the present invention relates to following general formula is as disinfectant use in agriculture and insecticidal/acaricidal agent
In the general formula I general formula (I):
R1, R2 are H, halogen, C1～C6 alkyl, C2～C16 thiazolinyl, alkynyl, C3～C6 cycloalkyl, C1～C6 haloalkyl (C2～C6 thiazolinyl, C2～C6 alkynyl, C3～C6 cycloalkyl), R1, and R2 can be identical or different.
R3 is hydrogen, halogen, (halo) C1～C6 alkyl, (halo) C2～C6 thiazolinyl, (halo) C2～C6 alkynyl, (halo) C3～C6 cycloalkyl, (halo) C3～C6 cycloalkenyl group, NR5R6[R5 is H, halo) C1～C6 alkyl, (halo) C2～C6 thiazolinyl, (halo) C2～C6 alkynyl, (halo) C3～C6 cycloalkyl, (halo) C3～C6 cycloalkenyl group, R6 are R5, (replacement) aryl, (replacement) heteroaryl], (replacement) aryl, (replacement) heteroaryl.
R4 is that H, C1～C6 alkyl, halogen, NR5R7[R7 are R5, (replacement) aryl, (replacement) heteroaryl], (Z1 is a key, O, S, NR5R7 for CN, (replacement) benzyl, (replacement) aryl, (replacement) heteroaryl, CO-Z1～R8; R8 is H, (halo) C1～C6 alkyl, (halo) C2～C6 thiazolinyl, (halo) C2～C6 alkynyl, (halo) C3～C6 cycloalkyl, (halo) C3～C6 cycloalkenyl group, (replacement) aryl, CH2CO-Z1-R7, CH2CN), (X1 is O to PX1 (X2R9) X3R10, S; X2, X3 are O, S, NH; X1, X2, X3 can be identical or different; R9, R10 are R8, can be identical or different.
X is a key, O, and S, (R11 is H to NR11, R8).
Y is a key, O, NR11, CH2.
Z is a key, H, and CO, S (O) n, CHR12[R12 is H, (halo) C1～C6 alkyl].
But R4 and Z be makeup ring [five circle or six annulus of saturated or unsaturated any replacement: imidazoles, glyoxalidine, triazole, evil (two) azoles, oxazoline (ketone), thiophene (two) azoles, thiazoline (ketone), pyrimidine, two (four) hydrogen pyrimidines (quinoline ketone), (three hydrogen) oxazines] also.
Q is H, R3, CH2R3, OR3, CO-Z1-R8, OR7, S (O) nR8, CN, PX1 (X2R9) X3R10.
When Q is (replacement) aryl, can be (replacement) phenyl, substituting group can be H, C1～C6 alkyl, C2～C6 thiazolinyl, C2～C6 alkynyl, C3～C6 cycloalkyl, C3～C6 cycloalkenyl group, C1～C6 haloalkyl (C2～C6 thiazolinyl, C2～C6 alkynyl, C3～C6 cycloalkyl, C3～C6 cycloalkenyl group), OR8, CO-Z1-R8, CH2CO-Z1-R8, CH2CN, NR5R8, S (O) nR8, SiR12R13R14[R12～R14 are (halo) C1～C6 alkyl, can be identical or different], COSiR12R13R14, OSiR12R13R14, CR12R13CN, CR12R13CC13, SF5
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 that replaced by 1 or more a plurality of identical or different halogen atom, alkynyl, cycloalkyl, cycloalkenyl group), (replacement) aryl, (replacement) heteroaryl, substituting group can be H, C1～C6 alkyl, thiazolinyl, alkynyl, cycloalkyl, cycloalkenyl group, C1～C6 halo (alkyl, thiazolinyl, alkynyl, cycloalkyl) cycloalkenyl group, OR7, CO-Z1-R7, NR5R6, S (O) nR7, SiR12R13R14, COSiR12R13R14, OSiR12R13R14, CR15R16CN, CR15R16CC13, SF5, 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 general formula (I), R1 is usually 1 of pyrazoles, and other groups can be respectively in 3,4,5 optional positions of pyrazoles,
When R4=OH, general formula (I) can be its tautomer:
The represented compound of general 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 general formula (I) is as follows.
Method A (when Y=O):
R1 wherein, R2, R3, R4, 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 acetate ethanol, 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 excess such as compound with general formula (II) expression.
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:
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) with chlorizating agent such as chlorine, chlorination sulfone, NCS equal inert solvent such as ethyl acetate, and methylene dichloride, ethylene dichloride obtained (VI) in 30 minutes to 6 hours-15～70 ℃ of following reactions in the dioxane; (VI) (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. with HR4 at alkali as mineral alkali; Organic bases comprises triethylamine, pyridine, 4-Dimethylamino pyridine etc.) and inert solvent exists down, and reaction makes (II).
Method B (Y=NR11 is during Z=CR12)
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 (when R4=NR5R7):
In above-mentioned reaction, (IA) 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 as mineral alkali at alkali.Potassium hydroxide, calcium hydroxide and alkali-metal hydride such as lithium hydride, sodium hydride etc.; Organic bases comprises triethylamine, pyridine, 4-Dimethylamino pyridine etc.) and the inert solvent existence is down, makes (IB) in 30 minutes to 24 hours in-15 ℃～150 ℃ reactions.
Method D (when R4=NR5R7):
Intermediate (VIII) and NR5R6 (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 have down that reaction makes (II), temperature is-20～150 ℃, the time is 30 minutes to 24 hours.
Method E (as Y=O or NR10, R4=NH, Z=CO is when R4 and Z makeup ring):
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 (work as Y=NH, R4=NH2, Z=CO is when R4 and Z makeup ring)
In above-mentioned reaction, intermediate (XI) and (XII) in the presence of solvent such as benzene class, alcohols (methyl alcohol, ethanol, Virahol) or its corresponding sodium alkoxide, reaction made (I) in 30 minutes～24 hours in room temperature to reflux temperature,
Method G
Method H
The operation of method G and H is with method E.Method I
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 general 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 with currently known methods production, for example be that liquid solvent and/or solid carrier mix with active compound and weighting agent, 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.
It is the compound shown in the general formula (I) that these prescriptions generally contain 0.1%～95% (weight) active compound, is 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 (bexaconazole); alkene azoles alcohol (diniconazole); flutriafol (tlutriafol); 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 (acrinathrin), Fenvalerate (fenpropathrin), alphacypermethrin (alphamethrin), bifenthrin (bifenthrin), cycloprothrin (cycloprothrin), cyfloxylate (beta-cyfluthrin), cyhalothrin (cyhalothrin, PP563), Cypermethrin (cypermcthrin), 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, PP321), tefluthrin (tefluthrin), tralomethrin (tralomethrin), brofluthrinate, brofenprox, Cis-resmethrin, clocythrin, deltamethrin, ICIA5682, MTI-732, pyresmethrin, Silafluofen, silafluofen (Hoe498), SSI-126, zetamethrin.
Amino formate compounds: as carbofuran, carbosulfan, interior Carbosulfan, methomyl, UC-51762, alanycarb, fenothiocarb.
Organophosphorus compound: as Kayaphos, Toyodan, first Toyodan, interior bromine phosphorus, isazofos, Terbufos, azamethiphos, fosmethilan, colophonate, pyraclofos, Chlorpyrifos 94, chlorpyrifos_methyl, Volaton, 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, TIA-304.
Pyrazole compound: as NNI850, 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 are respectively with 1 part of synthetic hydrated silicon oxide.2 parts of calcium lignosulfonates mix on 30 parts of wilkinites and 65 parts of high mountain ranges.After mixture fully grinds and mixes.Add water, even kneading, granulating, drying obtains 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:
Synthesizing of (1) 1,3-dimethyl-5-phenoxy group-4-pyrazoles formonitrile HCN
1,3-dimethyl-5-phenoxy group-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), sodium hydroxide (0.3 gram) in 30 milliliters of butanone, reacted 8 hours by back flow reaction, precipitation postcooling, Jia Shui, ethyl acetate extraction, drying, precipitation, column chromatography get 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:
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:
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:
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:
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(CDC
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:
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：6.82～714(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, reacted cooling, ethyl acetate extraction 8 hours, the organic layer pickling, washing, 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 is after 0.5 hour, add para Toluic Acid's tertiary butyl ester benzyl bromine 1 gram, refluxed 4 hours, add water, ethyl acetate extraction, 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
compound number X R3 R4 R 1 O C6H5 CI C4H9t 2 O C6H5 NH2 C4H9t 3 O C6H5 NHCH3 C4H9t 4 O C6H5 NHCO2CH3 C4H9t 5 O C6H5 NHCOCH3 C4H9t 6 O C6H5 N (Me) 2 C4H9t 7 O C6H5 NHSO2CH3 C4H9t 8 O C6H6 OCH3 C4H9t 9 O C6H5 SCH3 C4H9t 10 O C6H5 1,2,4-triazol-1-yl C4H9t 11 O C6H5 imidazoles-1-base C4H9t 12 S C6H5 CI C4H9t 13 S C6H5 NH2 C4H9t 14 S C6H5 NHCH3 C4H9t 15 S C6H5 NHCO2CH3 C4H9t 16 S C6H6 NHCOCH3 C4H9t 17 S C6H5 N (Me) 2 C4H9t 18 S C6H5 NHSO2CH3 C4H9t 19 S C6H5 OCH3 C4H9t 20 S C6H5 SCH3 C4H9t 21 S C6H5 1,2,4-triazol-1-yl C4H9t 22 S C6H5 imidazoles-1-base C4H9t 23 S C10H7 CI C4H9t 24 S C10H7 NH2 C4H9t 25 S C10H7 NHCH3 C4H9t 26 S C10H7 NHCO2CH3 C4H9t 27 S C10H7 NHCOCH3 C4H9t 28 S C10H7 N (Me) 2 C4H9t 29 S C10H7 NHSO2CH3 C4H9t 30 S C10H7 OCH3 C4H9t 31 S C10H7 SCH3 C4H9t 32 S C10H7 1,2,4-triazol-1-yl C4H9t 33 S C10H7 imidazoles-1-base C4H9t 34 O C10H7 CI C4H9t 35 O C10H7 NH2 C4H9t 36 O C10H7 NHCH3 C4H9t 37 O C10H7 NHCO2CH3 C4H9t 38 O C10H7 NHCOCH3 C4H9t 39 O C10H7 N (Me) 2 C4H9t 40 O C10H7 NHSO2CH3 C4H9t 41 O C10H7 OCH3 C4H9t 42 O C10H7 SCH3 C4H9t 43 O C10H7 1,2,4-triazol-1-yl C4H9t 44 O C10H7 imidazoles-1-base C4H9t 45 O C10H7 CI CO2C4H9t 46 O C10H7 NH2 CO2C4H9t 47 O C10H7 NHCH3 CO2C4H9t 48 O C10H7 NHCO2CH3 CO2C4H9t 49 O C10H7 NHCOCH3 CO2C4H9t 50 O C10H7 N (Me) 2 CO2C4H9t 51 O C10H7 NHSO2CH3 CO2C4H9t 52 O C10H7 OCH3 CO2C4H9t 53 O C10H7 SCH3 CO2C4H9t 54 O C10H7 1,2,4-triazol-1-yl CO2C4H9t 55 O C10H7 imidazoles-1-base CO2C4H9t 56 S C10H7 CI CO2C4H9t 57 S C10H7 NH2 CO2C4H9t 58 S C10H7 NHCH3 CO2C4H9t 59 S C10H7 NHCO2CH3 CO2C4H9t 60 S C10H7 NHCOCH3 CO2C4H9t 61 S C10H7 N (Me) 2 CO2C4H9t 62 S C10H7 NHSO2CH3 CO2C4H9t 63 S C10H7 OCH3 CO2C4H9t 64 S C10H7 SCH3 CO2C4H9t 65 S C10H7 1,2,4-triazol-1-yl CO2C4H9t 66 S C10H7 imidazoles-1-base CO2C4H9t 67 S C6H5 CI CO2C4H9t 68 S C6H5 NH2 CO2C4H9t 69 S C6H5 NHCH3 CO2C4H9t 70 S C6H5 NHCO2CH3 CO2C4H9t 71 S C6H5 NHCOCH3 CO2C4H9t 72 S C6H5 N (Me) 2 CO2C4H9t 73 S C6H5 NHSO2CH3 CO2C4H9t 74 S C6H6 OCH3 CO2C4H9t 75 S C6H5 SCH3 CO2C4H9t 76 S C6H5 1,2,4-triazol-1-yl CO2C4H9t 77 S C6H5 imidazoles-1-base CO2C4H9t 78 O C6H5 CI CO2C4H9t 79 O C6H5 NH2 CO2C4H9t 80 O C6H5 NHCH3 CO2C4H9t 81 O C6H5 NHCO2CH3 CO2C4H9t 82 O C6H6 NHCOCH3 CO2C4H9t 83 O C6H5 N (Me) 2 CO2C4H9t 84 O C6H5 NHSO2CH3 CO2C4H9t 85 O C6H5 OCH3 CO2C4H9t 86 O C6H5 SCH3 CO2C4H9t 87 O C6H5 1,2,4-triazol-1-yl CO2C4H9t 88 O C6H5 imidazoles-1-base CO2C4H9t 89 O C6H6 CN CO2C4H9t 90 O C6H6 CN C4H9t 91 O C6H6 NHCH2CO2CH3 C4H9t 92 O C6H6 NHCH2CO2CH3 CO2C4H9t 93 O C6H5 H CO2C (Me) 2CN 94 O C6H5 H CO2C (Me) 2C,CI3 95 O C6H5 CI CO2C (Me) 2CN 96 O C6H5 CI CO2C (Me) 2CCI3
Table 2
compound number X R3 R4 R 97 O C6H5 CI C4H9t 98 O C6H5 NH2 C4H9t 99 O C6H5 NHCH3 C4H9t 100 O C6H5 NHCO2CH3 C4H9t 101 O C6H5 NHCOCH3 C4H9t 102 O C6H5 N (Me) 2 C4H9t 103 O C6H5 NHSO2CH3 C4H9t 104 O C6H6 OCH3 C4H9t 105 O C6H5 SCH3 C4H9t 106 O C6H5 1,2,4-triazol-1-yl C4H9t 107 O C6H5 imidazoles-1-base C4H9t 108 S C6H5 CI C4H9t 109 S C6H5 NH2 C4H9t 110 S C6H5 NHCH3 C4H9t 111 S C6H5 NHCO2CH3 C4H9t 112 S C6H6 NHCOCH3 C4H9t 113 S C6H5 N (Me) 2 C4H9t 114 S C6H5 NHSO2CH3 C4H9t 115 S C6H5 OCH3 C4H9t 116 S C6H5 SCH3 C4H9t 117 S C6H5 1,2,4-triazol-1-yl C4H9t 118 S C6H5 imidazoles-1-base C4H9t 119 S C6H5 CI CO2C4H9t 120 S C6H5 NH2 CO2C4H9t 121 S C6H5 NHCH3 CO2C4H9t 122 S C6H5 NHCO2CH3 CO2C4H9t 123 S C6H5 NHCOCH3 CO2C4H9t 124 S C6H5 N (Me) 2 CO2C4H9t 125 S C6H5 NHSO2CH3 CO2C4H9t 126 S C6H6 OCH3 CO2C4H9t 127 S C6H5 SCH3 CO2C4H9t 128 S C6H5 1,2,4-triazol-1-yl CO2C4H9t 129 S C6H5 imidazoles-1-base CO2C4H9t 130 O C6H5 CI CO2C4H9t 131 O C6H5 NH2 CO2C4H9t 132 O C6H5 NHCH3 CO2C4H9t 133 O C6H5 NHCO2CH3 CO2C4H9t 134 O C6H6 NHCOCH3 CO2C4H9t 135 O C6H5 N (Me) 2 CO2C4H9t 136 O C6H5 NHSO2CH3 CO2C4H9t 137 O C6H5 OCH3 CO2C4H9t 138 O C6H5 SCH3 CO2C4H9t 139 O C6H5 1,2,4-triazol-1-yl CO2C4H9t 140 O C6H5 imidazoles-1-base CO2C4H9t 141 O C6H5 H CO2C (Me) 2CN 142 O C6H5 H CO2C (Me) 2,CC3 143 O C6H5 CI CO2C (Me) 2CN 144 O C6H5 CI CO2C (Me) 2CCI3 tables 3
Direction will be connected at a distance of two-way with negative electrode plate or the unidirectional conducting of the positive electrode plate of d> = 0 respectively.The positive electrode plate of induced electromotive force power supply and induced charge generation electric organ and the length of negative electrode plate or width or thickness are than the positive electrode plate of permanent electric field and negative electrode plate is little or equate greatly or preferably. induced electric field induced charge generator of the positive electrode plate and a negative electrode plate in the longitudinal direction or the width direction of the One end or both ends, respectively, of the induced electric field and the induced electromotive force power generator of the charge generating positive electrode plate and the negative electrode plates parallel to the coincident or parallel connection or docking coincident or conduction or induction field is formed integrally induced charge generator The positive electrode plate negatively charged plate inside the plane and the induced electromotive force power and charge generating generators positive electrode plate inside the plane were negative electrode plate inside the power supply and induced charge flow is unidirectional conducting positive electrode plate close to the negative electrode plate lateral conduction Connect or made into one. Be be positioned between the permanent electric field positive electrode any solid of any solid negative electrode or the parallel metal conductor utmost point inner or inside and outside can be respectively under the induction of permanent electric field, induce induced positive and induction negative electrical charge, can be from the conical surface metallic conductor tip of positive electrode plate and negative electrode plate or the wedge metal conductor tip escape the emission induced charge and the negative electrical charge of inducting automatically present rectangle or the taper of single head single face or single head single face wedge shape or two-sided taper of single head or the two-sided wedge shape of single head with parallel with negative electrode plate or the uneven cross section of permanent electric field positive electrode plate respectively, or single head single face needle point shape or single head two-sided needle point shape or the taper of double end single face or the two-sided wedge shape of double end or the two-sided needle point shape of double end or how much conductors of the two-sided taper of double end or any geometry be to solid or a pair of not parallel or parallel metal conductor plate, a termination or the two ends of long with the positive electrode plate of induction field charge inducing the generator respectively or cross direction of one or two positive electrode plate of induced electromotive force power supply and induced charge generation electric organ and one or two negative electrode plate and negative electrode plate is long or a termination of cross direction or parallel coincidences of two ends dock to be connected and lead or make one.The taper of positive electrode plate and negative electrode plate, wedge shape, needle point shape single face angle opposite face towards or opposing towards or the center symmetry towards, or the axle center symmetry towards, the taper of positive electrode plate and negative electrode plate, wedge shape pin, pointed two-sided angle, opposite face towards or opposing towards or the axle center symmetry towards, or the center symmetry is filled dielectric or is not filled dielectric except that the passage of reserving the most advanced and sophisticated emission travel path of escaping of induced charge metallic conductor towards, two parallel-plate outsides.Two relative parallel planes of positive electrode plate and negative electrode plate are close to fully mutually that conducting is connected or at a distance of spacing d> = 0, the positive electrode plate of induced electromotive force power supply and induced charge generation electric organ and negative electrode plate respectively the length overall of the positive electrode plate with the charge inducing generator after butt joint is connected conducting or makes one with negative electrode plate, beam overall, total thickness can be respectively than permanent electric field positive electrode plate and the permanent length and width of electric field negative electrode plate and thick either large or small or equal.EEBG01-EEBG02-EEBG03-EEBG04-EEBG05-EEBG06-EEBG07-EEBG08-EEBG09-EEBG10-EEBG11-EEBG12-EEBG13 -EEBG14-EEBG15-EEBG16-EEBG17-EEBG18-EEBG19-EEBG20-HHBG01-HHBG02-HHBG03-HHBG04 permanent induction electromagnetic field change-section conductor charge automatic escape emission power generator, characteristics of principle and shape structure general technical feature at first be to use permanent electric field, the secondth, the electromagnetic field inducing of the permanent electric field of application, the 3rd is that the application permanent electro magnetic field is that the mobile device of the inner unidirectional conducting of charge inducing generator and charge inducing power supply produces the principle that electromagnetic induction is isolated positive and negative charge inducing afterwards to the metallic conductor that is arranged in the permanent electric field, the 4th be make to adopt variable-section variable dimension awl wedge shape list or double end list double inclined plane does not wait or etc. gradient metallic conductor tip be induced electromotive force power supply and induced charge generation electric organ, escape and launch charge theory in the tip of induced charge escape reflector, the 5th is to use the charging photocell or friction produces electricity battery, charging capacitor, the moving forever power supply of charging environment friendly, the charge switch power-off switch, the moving forever amplifying type charger of forming of the moving forever permanent electric field of power supply waits and guarantees moving forever continuously output induced charge of moving forever power supply and electric energy energy.The induced electromotive force ε of induced electromotive force power supply and induced charge generation electric organ
...
196 CI CF3-C6H2-2,6-(Br) 2-4-OCF3 197 OPh CF3-NHC6H4-4-CF3 198 OPh CF3-NHC6H4-4-NO2 199 CI CF3-NHC6H4-4-CN 200 CI CF3-C6H2-2,6-(Br) 2-4-OCF3 table 4
Compound number XR3 R4 YR 201 CI NH2 CH2C6H4-4-CF3 202 CI NH2 CH2C6H4-4-C4H9t 203 CI NH2 CH2C6H4-4-CI 204 CI NH2 CH2C6H4-4-OCF3 205 CI NH2 CH2C6H4-4-OC2HF4 206 CI NH2 NHC6H4-4-CF3 207 CI NH2 NHC6H4-4-C4H9t 208 CI NH2 NHC6H4-4-CI 209 CI NH2 NHC6H4-4-OCF3 210 CI NH2 NHC6H4-4-OC2HF4 211 CI NH2 C6H4-3-OCH (CH3) 2 212 CI NH2 NHC6H2-2; 6-CI2-4-CF3 213 CI NH2 CH2C6H2-2; 6-CI2-4-CF3 214 CI NH2 C6H4-4-CF3 215 CI NH2 C6H4-4-C4H9t 216 CI NH2 C6H4-4-CI 217 CI NH2 C6H4-4-OCF3 218 CI NH2 C6H4-4-OC2HF4 219 CI NH2 C6H4-4-F 220 OPh H CH2C6H4-4-CF3 221 OPh H CH2C6H4-4-C4H9t 222 OPh H CH2C6H4-4-CI 223 OPh H CH2C6H4-4-OCF3 224 OPh H CH2C6H4-4-OC2HF4 225 OPh H NHC6H4-4-CF3 226 OPh H NHC6H4-4-C4H9t 227 OPh H NHC6H4-4-CI 228 OPh H NHC6H4-4-OCF3 229 OPh H NHC6H4-4-OC2HF4 230 OPh H C6H4-3-OCH ( CH3 ) 2 231 OPh H NHC6H2-26-CI2-4-CF3 232 OPh H CH2C6H2-2； 6-CI2-4-CF3 233 OPh H C6H4-4-CF3 234 OPh H C6H4-4-C4H9t 235 OPh H C6H4-4-CI 236 OPh H C6H4-4-OCF3 237 OPh H C6H4-4-OC2HF4 238 OPh H C6H4-4-F 239 OPh CI CH2C6H4-4-CF3 240 OPh CI CH2C6H4-4-C4H9t 241 OPh CI CH2C6H4-4-CI 242 OPh CI CH2C6H4-4-OCF3 243 OPh CI CH2C6H4-4-OC2HF4 244 OPh CI NHC6H4-4-CF3 245 OPh CI NHC6H4-4-C4H9t 246 OPh CI NHC6H4-4-CI 247 OPh CI NHC6H4-4-OCF3 248 OPh CI NHC6H4-4-OC2HF4 249 OPh CI C6H4-3-OCH ( CH3 ) 2 250 OPh CI NHC6H2-2； 6-CI2-4-CF3 251 OPh CI CH2C6H2-2; 6-CI2-4-CF3 252 OPh CI C6H4-4-CF3 253 OPh CI C6H4-4-C4H9t 254 OPh CI C6H4-4-CI 255 OPh CI C6H4-4-OCF3 256 OPh CI C6H4-4-OC2HF4 257 OPh CI C6H4-4-F 258 CI CI CH2C6H4-4-CF3 259 CI CI CH2C6H4-4-C4H9t 260 CI CI CH2C6H4-4-CI 261 CI CI CH2C6H4-4-OCF3 262 CI CI CH2C6H4-4-OC2HF4 263 CI CI NHC6H4-4-CF3 264 CI CI NHC6H4-4-C4H9t 265 CI CI NHC6H4-4-CI 266 CI CI NHC6H4-4-OCF3 267 CI CI NHC6H4-4-OC2HF4 268 CI CI C6H4-3-OCH ( CH3 ) 2 269 CI CI NHC6H2-2； 6-CI2-4-CF3 270 CI CI CH2C6H2-2; 6-CI2-4-CF3 271 CI CI C6H4-4-CF3 272 CI CI C6H4-4-C4H9t 273 CI CI C6H4-4-CI 274 CI CI C6H4-4-OCF3 275 CI CI C6H4-4-OC2HF4 276 CI CI C6H4-4-F 277 CI H OCH2CO2C2H5 278 CI H OCH (Mc) CO2C2H5 279 CI H OCH2-1-(1; 2; The 4-triazole) 280 CI H OCONHCH3 281 CI H OCONHC6H4-4-CI 282 CI H OCONHC6H4-4-CF3 283 CI H OCONHC6H4-4-OCF3 284 CI H OCONHC6H3-3; 4-CI2 285 CI H NHCONHC6H4-4-CI 286 CI H N (CH3) CONHC6H4-4-CI 287 CI H NHCONHC6H4-4-CF3 288 CI H NHCONHC6H4-4-OCF3 289 CI H NHCONHC6H3-3; 4-CI2 290 CI H OCOC6H4-4-F 291 CI H OCOC6H4-4-CI 292 CI H OCOC6H3-2; 6-F2 293 CI H NHCOC6H4-4-F 294 CI H NHCOC6H4-4-CI 295 CI H NHCOC6H3-2; 6-F2 296 CI H OCONHCOC6H3-2; 6-F2 297 CI H OCONHCOC6H4-2-F 298 CI H OCONHCOC6H3-2; 6-CI2 299 CI H OCONHCOC6H4-2-CI 300 CI H NHCONHCOC6H3-2; 6-F2 301 CI H NHCONHCOC6H4-2-F 302 CI H NHCONHCOC6H3-2; 6-I2 303 CI H NHCONHCOC6H4-2-CI 304 OPh H OCH2CO2C2H5 305 OPh H OCH (Me) CO2C2H5 306 OPh H OCH2-1-(1; 2; The 4-triazole) 307 OPh H OCONHCH3 308 OPh H OCONHC6H4-4-CI 309 OPh H OCONHC6H4-4-CF3 310 OPh H OCONHC6H4-4-OCF3 311 OPh H OCONHC6H3-3; 4-CI2 312 OPh H NHCONHC6H4-4CI 313 OPh H N (CH3) CONHC6H4-4CI 314 OPh H NHCONHC6H4-4-CF3 315 OPh H NHCONHC6H4-4-OCF3 316 OPh H NHCONHC6H3-3; 4-CI2 317 OPh H OCOC6H4-4-F 318 OPh H OCOC6H4-4-CI 319 OPh H OCO6H3-2; 6-F2 320 OPh H NHCOC6H4-4-F 321 OPh H NHCOC6H4-4-CI 322 OPh H NHCOC6H3-2; 6-F2 323 OPh H OCONHCOC6H3-2; 6-F2 324 OPh H OCONHCOC6H4-2-F 325 OPh H OCONHCOC6H3-2; 6-CI2 326 OPh H OCONHCOC6H4-2-CI 327 OPh H NHCONHCOC6H3-2; 6-F2 328 OPh H NHCONHCOC6H4-2-F 329 OPh H NHCONHCOC6H3-2,6-CI2 330 OPh H NHCONHCOC6H4-2-CI 331 CI H OCH2C6H4-4-C4H9t 332 CI H OCH2C6H4-4-CO2C4H9t 333 CI H NHCH2C6H4-4-C4H9t 334 CI H NHCH2C6H4-4-CO2C4H9t 335 OPh H OCH2C6H4-4-C4H9t 336 OPh H OCH2C6H4-4-CO2C4H9t 337 OPh H NHCH2C6H4-4-C4H9t 338 OPh H NHCH2C6H4-4-CO2C4H9t 339 OPh H OCH2P ( S ) ( OC2H5 ) 2 340 OPh H OCH2P ( O ) OC2H5 ( SC3H7 ) 341 OPh H P ( S ) ( OC2H5 ) 2 342 OPh H P ( O ) OC2H5 ( SC3H7 ) 343 OPh H OCH2-3-C6H3N-6-CI 344 OPh NH2 OCH2-3-C6H3N-6-CI 345 OPh CN OCONHCH3
346 OPh CO
2CH
3 OCH
3
347 OPh H OCOCH2CH2CO2H
348 OPh H OCOCH＝CHCO2CH3
349 OPh
Table 5
Compound number R1 XR3 YR 350 CH3 CI O CH2C6H4-4-CI 351 CH3 CI O CH2C6H4-4-F 352 CH3 CI O CH2C6H4-4-C4H9t 353 CH3 CI O CH2C6H4-4-CO2CH3 354 CH3 CI O CH2C6H4-4-CO2C4H9t 355 CH3 CI O CH2-5-C5H3N-2-CI 356 CH3 CI O CH2-3-C5H3N-2-CI 357 CH3 CI O C6H3-2; 6-F2 358 CH3 CI O C6H4-3-CI 359 CH3 CI O C6H4-4-CI 360 CH3 CI O C6H4-4-F 361 CH3 CI O C6H4-4-C4H9t 362 CH3 CI O C6H4-4-CO2CH3 363 CH3 CI O C6H4-4-CO2C4H9t 364 CH3 CI O 5-C5H3N-2 -CI 365 CH3 CI O 3-C5H3N-2-CI 366 CH3 CI NCH3 CH2C6H4-4-CI 367 CH3 CI NCH3 CH2C6H4-4-F 368 CH3 CI NCH3 CH2C6H4-4-C4H9t 369 CH3 CI NCH3 CH2C6H4-4-CO2CH3 370 CH3 CI NCH3 CH2C6H4-4-CO2C4H9t 371 CH3 CI NCH3 CH2-5-C5H3N-2-CI 372 CH3 CI NCH3 CH2-3-C5H3N-2-CI 373 CH3 CI NCH3 C6H4-4-CI 374 CH3 CI NCH3 C6H4-4 -F 375 CH3 CI NCH3 C6H4-4-C4H9t 376 CH3 CI NCH3 C6H4-4-CO2CH3 377 CH3 CI NCH3 C6H4-4-CO2C4H9t 378 CH3 CI NCH3 5-C5H3N-2-CI 379 CH3 CI NCH3 3-C5H3N-2- CI 380 CH3 CI NCH3 C6H3-2; 6-F2 381 CH3 CI NCH3 C6H4-3-CI 382 CH3 OPh O CH2C6H4-4-CI 383 CH3 OPh O CH2C6H4-4-F 384 CH3 OPh O CH2C6H4-4-C4H9t 385 CH3 OPh O CH2C6H4-4-CO2CH3 386 CH3 OPh O CH2C6H4-4-CO2C4H9t 387 CH3 OPh O CH2-5-C5H3N-2-CI 388 CH3 OPh O CH2-3-C5H3N-2-CI 389 CH3 OPh O C6H3-2; 6-F2 390 CH3 OPh O C6H4-3-CI 391 CH3 OPh O C6H4-4-CI 392 CH3 OPh O C6H4-4-F 393 CH3 OPh O C6H4-4-C4H9t 394 CH3 OPh O C6H4-4-CO2CH3 395 CH3 OPh O C6H4-4-CO2C4H9t 396 CH3 OPh O 5-C5H3N-2-CI 397 CH3 OPh O 3-C5H3N-2-CI 398 CH3 OPh NCH3 CH2C6H44-CI 399 CH3 OPh NCH3 CH2C6H4-4-F 400 CH3 OPh NCH3 CH2C6H4 -4-C4H9t 401 CH3 OPh NCH3 CH2C6H4-4-CO2CH3 402 CH3 OPh NCH3 CH2C6H4-4-CO2C4H9t 403 CH3 OPh NCH3 CH2-5-C5H3N-2-CI 404 CH3 OPh NCH3 CH2-3-C5H3N-2-CI 405 CH3 OPh NCH3 C6H4-4-CI 406 CH3 OPh NCH3 C6H4-4-F 407 CH3 OPh NCH3 C6H4-4-C4H9t 408 CH3 OPh NCH3 C6H4-4-CO2CH3 409 CH3 OPh NCH3 C6H4-4-CO2C4H9t 410 CH3 OPh NCH3 5-C5H3N -2-CI 411 CH3 OPh NCH3 3-C5H3N-2-CI 412 CH3 OPh NCH3 C6H3-2 ,6-F2 413 CH3 OPh NCH3 C6H4-3-CI 414 CI OPh NCH3 C6H4-4-CI 415 CI OPh NCH3 C6H4- 4-F 416 CI OPh NCH3 C6H4-4-C4H9t 417 CI OPh NCH3 C6H4-4-CO2CH3 418 CI CI O C6H4-4-CI 419 CI CI O C6H4-4-F 420 CI CI O C6H4-4-C4H9t 421 CI CI O C6H4-4-CO2CH3 Table 6...Compound number R1 XR3 YR 350 CH3 CI O CH2C6H4-4-CI 351 CH3 CI O CH2C6H4-4-F 352 CH3 CI O CH2C6H4-4-C4H9t 353 CH3 CI O CH2C6H4-4-CO2CH3 354 CH3 CI O CH2C6H4-4-CO2C4H9t 355 CH3 CI O CH2-5-C5H3N-2-CI 356 CH3 CI O CH2-3-C5H3N-2-CI 357 CH3 CI O C6H3-2; 6-F2 358 CH3 CI O C6H4-3-CI 359 CH3 CI O C6H4-4-CI 360 CH3 CI O C6H4-4-F 361 CH3 CI O C6H4-4-C4H9t 362 CH3 CI O C6H4-4-CO2CH3 363 CH3 CI O C6H4-4-CO2C4H9t 364 CH3 CI O 5-C5H3N-2 -CI 365 CH3 CI O 3-C5H3N-2-CI 366 CH3 CI NCH3 CH2C6H4-4-CI 367 CH3 CI NCH3 CH2C6H4-4-F 368 CH3 CI NCH3 CH2C6H4-4-C4H9t 369 CH3 CI NCH3 CH2C6H4-4-CO2CH3 370 CH3 CI NCH3 CH2C6H4-4-CO2C4H9t 371 CH3 CI NCH3 CH2-5-C5H3N-2-CI 372 CH3 CI NCH3 CH2-3-C5H3N-2-CI 373 CH3 CI NCH3 C6H4-4-CI 374 CH3 CI NCH3 C6H4-4 -F 375 CH3 CI NCH3 C6H4-4-C4H9t 376 CH3 CI NCH3 C6H4-4-CO2CH3 377 CH3 CI NCH3 C6H4-4-CO2C4H9t 378 CH3 CI NCH3 5-C5H3N-2-CI 379 CH3 CI NCH3 3-C5H3N-2- CI 380 CH3 CI NCH3 C6H3-2; 6-F2 381 CH3 CI NCH3 C6H4-3-CI 382 CH3 OPh O CH2C6H4-4-CI 383 CH3 OPh O CH2C6H4-4-F 384 CH3 OPh O CH2C6H4-4-C4H9t 385 CH3 OPh O CH2C6H4-4-CO2CH3 386 CH3 OPh O CH2C6H4-4-CO2C4H9t 387 CH3 OPh O CH2-5-C5H3N-2-CI 388 CH3 OPh O CH2-3-C5H3N-2-CI 389 CH3 OPh O C6H3-2; 6-F2 390 CH3 OPh O C6H4-3-CI 391 CH3 OPh O C6H4-4-CI 392 CH3 OPh O C6H4-4-F 393 CH3 OPh O C6H4-4-C4H9t 394 CH3 OPh O C6H4-4-CO2CH3 395 CH3 OPh O C6H4-4-CO2C4H9t 396 CH3 OPh O 5-C5H3N-2-CI 397 CH3 OPh O 3-C5H3N-2-CI 398 CH3 OPh NCH3 CH2C6H44-CI 399 CH3 OPh NCH3 CH2C6H4-4-F 400 CH3 OPh NCH3 CH2C6H4 -4-C4H9t 401 CH3 OPh NCH3 CH2C6H4-4-CO2CH3 402 CH3 OPh NCH3 CH2C6H4-4-CO2C4H9t 403 CH3 OPh NCH3 CH2-5-C5H3N-2-CI 404 CH3 OPh NCH3 CH2-3-C5H3N-2-CI 405 CH3 OPh NCH3 C6H4-4-CI 406 CH3 OPh NCH3 C6H4-4-F 407 CH3 OPh NCH3 C6H4-4-C4H9t 408 CH3 OPh NCH3 C6H4-4-CO2CH3 409 CH3 OPh NCH3 C6H4-4-CO2C4H9t 410 CH3 OPh NCH3 5-C5H3N -2-CI 411 CH3 OPh NCH3 3-C5H3N-2-CI 412 CH3 OPh NCH3 C6H3-2 ,6-F2 413 CH3 OPh NCH3 C6H4-3-CI 414 CI OPh NCH3 C6H4-4-CI 415 CI OPh NCH3 C6H4- 4-F 416 CI OPh NCH3 C6H4-4-C4H9t 417 CI OPh NCH3 C6H4-4-CO2CH3 418 CI CI O C6H4-4-CI 419 CI CI O C6H4-4-F 420 CI CI O C6H4-4-C4H9t 421 CI CI O C6H4-4-CO2CH3 Table 6...R1 R2 R3 ZQ
CH3 CH3 H OCH2C6H4-4-C4H9t
CH3 CH3 H OCH2C6H4-4-CO2C4H9t
CH3 CH3 H OCH2C6H4-4-CO2CH3
CH3 CH3 H OCH2C6H4-4-CI
CH3 C2H5 H OCH2C6H4-4-CN
CH3 CH3 H OCH2C6H4-4-CF3
CH3 CH3 H OCH2C6H4-4-OCF3
CH3 CH3 H OCH2C6H4-4-NO2
CH3 CH3 H OCH2-3-pyridine-6-CI
CH3 CH3 H OCH2-2-furyl
CH3 CH3 H OCH2-2-thiophene
CH3 CH3 H OCH2-1-1, 2,4 - triazole
CH3 CH3 H OCH2-1-pyrazolyl
CH3 CH3 H OCH2-2-pyrimidinyl
CH3 CH3 H C6H4-3-OCH (CH3)
CH3 CH3 CI OCH2C6H4-4-C4H9t
CH3 CH3 CI OCH2C6H4-4-CO2C4H9t
CH3 CH3 CI OCH2C6H4-4-CO2CH3
CH3 CH3 CI OCH2C6H4-4-CI
CH3 C2H5 CI OCH2C6H4-4-CN
CH3 CH3 CI OCH2C6H4-4-CF3
CH3 CH3 CI OCH2C6H4-4-OCF3
CH3 CH3 CI OCH2C6H4-4-NO2
CH3 CH3 CI OCH2-3-pyridine-6-CI
CH3 CH3 CI OCH2-2-furyl
CH3 CH3 CI OCH2-2-thiophene
CH3 CH3 CI OCH2-1-1, 2,4 - triazole
CH3 CH3 CI OCH2-1-pyrazolyl
CH3 CH3 CI OCH2-2-pyrimidinyl
CH3 CH3 CI C6H4-3-OCH (CH3) 2
C4H9t CH3 H OCH2C6H4-4-C4H9t
C4H9t CH3 H OCH2C6H4-4-CO2C4H9t
C4H9t CH3 H OCH2C6H4-4-CO2CH3
C4H9t CH3 H OCH2C6H4-4-CI
C4H9t CH3 H OCH2C6H4-4-CN
C4H9t CH3 H OCH2C6H4-4-CF3
C4H9t CH3 H OCH2C6H4-4-OCF3
C4H9t CH3 H OCH2C6H4-4-NO2
C4H9t CH3 H OCH2-3-pyridine-6-CI
C4H9t CH3 H OCH2-2-furyl
C4H9t CH3 H OCH2-2-thiophene
C4H9t CH3 H OCH2-1-1, 2,4 - triazole
C4H9t CH3 H OCH2-1-pyrazolyl
C4H9t CH3 H OCH2-2-pyrimidinyl
C4H9t CH3 H C6H4-3-OCH (CH3)
C4H9t CH3 CI OCH2C6H4-4-C4H9t
C4H9t CH3 CI OCH2C6H4-4-CO2C4H9t
C4H9t CH3 CI OCH2C6H4-4-CO2CH3
C4H9t CH3 CI OCH2C6H4-4-CI
C4H9t CH3 CI OCH2C6H4-4-CN
C4H9t CH3 CI OCH2C6H4-4-CF3
C4H9t CH3 CI OCH2C6H4-4-OCF3
C4H9t CH3 CI OCH2C6H4-4-NO2
C4H9t CH3 CI OCH2-3-pyridine-6-CI
C4H9t CH3 CI OCH2-2-furyl
C4H9t CH3 CI OCH2-2-thiophene
C4H9t CH3 CI OCH2-1-1, 2,4 - triazole
C4H9t CH3 CI OCH2-1-pyrazolyl
C4H9t CH3 CI OCH2-2-pyrimidinyl
C4H9t CH3 CI C6H4-3-OCH (CH3) 2
C2H5 CH3 H OCH2C6H4-4-C4H9t
C2H5 CH3 H OCH2C6H4-4-CO2C4H9t
C2H5 CH3 H OCH2C6H4-4-CO2CH3
C2H5 CH3 H OCH2C6H4-4-CI
C2H5 CH3 H OCH2C6H4-4-CN
C2H5 CH3 H OCH2C6H4-4-CF3
C2H5 CH3 H OCH2C6H4-4-OCF3
C2H5 CH3 H OCH2C6H4-4-NO2
C2H5 CH3 H OCH2-3-pyridine-6-CI
C2H5 CH3 H OCH2-2-furyl
C2H5 CH3 H OCH2-2-thiophene
C2H5 CH3 H OCH2-1-1, 2,4 - triazole
C2H5 CH3 H OCH2-1-pyrazolyl
C2H5 CH3 H OCH2-2-pyrimidinyl
C2H5 CH3 H C6H4-3-OCH (CH3)
C2H5 CH3 CI OCH2C6H4-4-C4H9t
C2H5 CH3 CI OCH2C6H4-4-CO2C4H9t
C2H5 CH3 CI OCH2C6H4-4-CO2CH3
C2H5 CH3 CI OCH2C6H4-4-CI
C2H5 CH3 CI OCH2C6H4-4-CN
C2H5 CH3 CI OCH2C6H4-4-CF3
C2H5 CH3 CI OCH2C6H4-4-OCF3
C2H5 CH3 CI OCH2C6H4-4-NO2
C2H5 CH3 CI OCH2-3-pyridine-6-CI
C2H5 CH3 CI OCH2-2-furyl
C2H5 CH3 CI OCH2-2-thiophene
C2H5 CH3 CI OCH2-1-1, 2,4 - triazole
C2H5 CH3 CI OCH2-1-pyrazolyl
C2H5 CH3 CI OCH2-2-pyrimidinyl
C2H5 CH3 CI C6H4-3-OCH (CH3) 2
CH3 CH3 CI NHC6H4-4-C4H9t
CH3 CH3 CI NHC6H4-4-CO2C4H9t
CH3 CH3 CI NHC6H4-4-CO2CH3
CH3 CH3 CI NHC6H4-4-CI
CH3 CH3 CI NHC6H4-4-CN
CH3 CH3 CI NHC6H4-4-CF3
CH3 CH3 CI NHC6H4-4-OCF3
CH3 CH3 CI NHC6H4-4-NO2
CH3 CH3 CI NHCH2-3-pyridine-6-CI
CH3 CH3 CI NHCH2-2-furyl
CH3 CH3 CI NHCH2-2-thiophene
CH3 CH3 CI NHCH2-1-1, 2,4 - triazole
CH3 CH3 CI NHCH2-1-pyrazolyl
CH3 CH3 CI NHCH2-2-pyrimidinyl
CH3 CH3 CI NHCH2C6H4-4-OCH (CH3)
CH3 CH3 CI NHCH2C6H4-4-C4H9t
CH3 CH3 CI NHCH2C6H4-4-CO2C4H9t
CH3 CH3 CI NHCH2C6H4-4-CO2CH3
CH3 CH3 CI NHCH2C6H4-4-CI
CH3 CH3 CI NHCH2C6H4-4-CN
CH3 CH3 CI NHCH2C6H4-4-CF3
CH3 CH3 CI NHCH2C6H2-2 ,6-CI2-4-OCF3
CH3 CH3 CI NHCH2C6H4-4-NO2
CH3 CH3 CI NH-3-pyridine-6-CI
CH3 CH3 CI NH-2-furyl
CH3 CH3 CI NH-2-thiophene
CH3 CH3 CI NH-1-1, 2,4 - triazole
CH3 CH3 CI NH-2-pyrimidinyl
CH3 CH3 CI NH-2-pyrimidine -4,6 - (OMe) 2
CH3 CH3 CI NH-2-pyrimidine -4,6 - (Me) 2
CH3 CH3 H NHC6H4-4-C4H9t
CH3 CH3 H NHC6H4-4-CO2C4H9t
CH3 CH3 H NHC6H4-4-CO2CH3
CH3 CH3 H NHC6H4-4-CI
CH3 CH3 H NHC6H4-4-CN
CH3 CH3 H NHC6H4-4-CF3
CH3 CH3 H NHC6H4-4-OCF3
CH3 CH3 H NHC6H4-4-NO2
CH3 CH3 H NHCH2-3-pyridine-6-CI
CH3 CH3 H NHCH2-2-furyl
CH3 CH3 H NHCH2-2-thiophene
CH3 CH3 H NHCH2-1-1, 2,4 - triazole
CH3 CH3 H NHCH2-1-pyrazolyl
CH3 CH3 H NHCH2-2-pyrimidinyl
CH3 CH3 H NHCH2C6H4-4-OCH (CH3)
CH3 CH3 H NHCH2C6H4-4-C4H9t
CH3 CH3 H NHCH2C6H4-4-CO2C4H9t
CH3 CH3 H NHCH2C6H4-4-CO2CH3
CH3 CH3 H NHCH2C6H4-4-CI
CH3 CH3 H NHCH2C6H4-4-CN
CH3 CH3 H NHCH2C6H4-4-CF3
CH3 CH3 H NHCH2C6H2-2 ,6-CI2-4-OCF3
CH3 CH3 H NHCH2C6H4-4-NO2
CH3 CH3 H NH-3-pyridine-6-CI
CH3 CH3 H NH-2-furyl
CH3 CH3 H NH-2-thiophene
CH3 CH3 H NH-1-1, 2,4 - triazole
CH3 CH3 H NH-2-pyrimidinyl
CH3 CH3 H NH-2-pyrimidine -4,6 - (Me) 2
CF3 CH3 H OCH2C6H4-4-C4H9t
CF3 CH3 H OCH2C6H4-4-CO2C4H9t
CF3 CH3 H OCH2C6H4-4-CO2CH3
CF3 CH3 H OCH2C6H4-4-CI
CF3 CH3 H OCH2C6H4-4-CN
CF3 CH3 H OCH2C6H4-4-CF3
CF3 CH3 H OCH2C6H4-4-OCF3
CF3 CH3 H OCH2C6H4-4-NO2
CF3 CH3 H OCH2-3-pyridine-6-CI
CF3 CH3 H OCH2-2-furyl
CF3 CH3 H OCH2-2-thiophene
CF3 CH3 H OCH2-1-1, 2,4 - triazole
CF3 CH3 H OCH2-1-pyrazolyl
CF3 CH3 H OCH2-2-pyrimidinyl
CF3 CH3 H C6H4-3-OCH (CH3) 2
CF3 CH3 H NHC6H4-4-C4H9t
CF3 CH3 H NHC6H4-4-CO2C4H9t
CF3 CH3 H NHC6H4-4-CO2CH3
CF3 CH3 H NHC6H4-4-CI
CF3 CH3 H NHC6H4-4-CN
CF3 CH3 H NHC6H4-4-CF3
CF3 CH3 H NHC6H4-4-OCF3
CF3 CH3 H NHC6H4-4-NO2
CF3 CH3 H NHCH2-3-pyridine-6-CI
CF3 CH3 H NHCH2-2-furyl
CF3 CH3 H NHCH2-2-thiophene
CF3 CH3 H NHCH2-1-1, 2,4 - triazole
CF3 CH3 H NHCH2-1-pyrazolyl
CF3 CH3 H NHCH2-2-pyrimidinyl
CF3 CH3 H NHCH2C6H4-4-OCH (CH3)
CF3 CH3 H NHCH2C6H4-4-C4H9t
CF3 CH3 H NHCH2C6H4-4-CO2C4H9t
CF3 CH3 H NHCH2C6H4-4-CO2CH3
CF3 CH3 H NHCH2C6H4-4-CI
CF3 CH3 H NHCH2C6H4-4-CN
CF3 CH3 H NHCH2C6H4-4-CF3
CF3 CH3 H NHCH2C6H2-2 ,6-CI2-4-OCF3
CF3 CH3 H NHCH2C6H4-4-NO2
CF3 CH3 H NH-3-pyridine-6-CI
CF3 CH3 H NH-2-furyl
CF3 CH3 H NH-2-thiophene
CF3 CH3 H NH-1-1, 2,4 - triazole
CF3 CH3 H NH-2-pyrimidinyl
CF3 CH3 H NH-2-pyrimidine -4,6 - (Me) 2
CF3 CH3 CI NHC6H4-4-C4H9t
CF3 CH3 CI NHC6H4-4-CO2C4H9t
CF3 CH3 CI NHC6H4-4-CO2CH3
CF3 CH3 CI NHC6H4-4-CI
CF3 CH3 CI NHC6H4-4-CN
CF3 CH3 CI NHC6H4-4-CF3
CF3 CH3 CI NHC6H4-4-OCF3
CF3 CH3 CI NHC6H4-4-NO2
CF3 CH3 CI NHCH2-3-pyridine-6-CI
CF3 CH3 CI NHCH2-2-furyl
CF3 CH3 CI NHCH2-2-thiophene
CF3 CH3 CI NHCH2-1-1, 2,4 - triazole
CF3 CH3 CI NHCH2-1-pyrazolyl
CF3 CH3 CI NHCH2-2-pyrimidinyl
CF3 CH3 CI NHCH2C6H4-4-OCH (CH3)
CF3 CH3 CI NHCH2C6H4-4-C4H9t
CF3 CH3 CI NHCH2C6H4-4-CO2C4H9t
CF3 CH3 CI NHCH2C6H4-4-CO2CH3
CF3 CH3 CI NHCH2C6H4-4-CI
CF3 CH3 CI NHCH2C6H4-4-N
CF3 CH3 CI NHCH2C6H4-4-CF3
CF3 CH3 CI NHCH2C6H2-2 ,6-CI2-4-OCF3
CF3 CH3 CI NHCH2C6H4-4-NO2
CF3 CH3 CI NH-3-pyridine-6-CI
CF3 CH3 CI NH-2-furyl
CF3 CH3 CI NH-2-thiophene
CF3 CH3 CI NH-1-1, 2,4 - triazole
CF3 CH3 CI NH-2-pyrimidinyl
CF3 CH3 CI NH-2-pyrimidine -4,6 - (OMe) 2
CF3 CH3 CI 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 (CDCl3, 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 (CDCl3, 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 ℃.
155 fusing points: 90～92 ℃ of .HNMR (CDCl3, 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 (CDCl3, 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 (CDCl3, 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 (CDCl3, 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 ℃ (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 (CDCl3+DMSO, TMS) ppm:8.32 (bs, 1H), 8.08 (s, 1H), 7.36 (H, 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 ℃, HNMR (CDCl3+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 ℃, HNMR (CDCl3, 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 ℃, HNMR (CDCl3, 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, is 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
Use compound of the present invention, with concentration is 500ppm, for the examination aphid is 3 day age, the each processing tried 50～100 of worms, with the clear water contrast, triplicate is handled the back and is placed in 20～23 ℃ of observation ward, 24 hours " Invest, Then Investigate " mortality ratio, partial results is as follows: compound number mortality ratio (%) 2 10,079 100
2, to the test of carmine spider mite
Adopt immersion method, compound concentration of the present invention is 500ppm, 2 Kidney bean seedling true leaves that are connected into 50～70 of mites will be moved, put into and take out after the soup that has prepared soaked for 5 seconds, place in 20～25 ℃ of observation ward, with clear water contrast, triplicate, 24 hours " Invest, Then Investigate " mortality ratio, partial results is seen as follows:
Compound number mortality ratio (%)
2???????????100
79???????????100
146???????????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 flooded for 5 seconds in the good soup of dilution, place then in the room temperature and cultivate.Handle the hatching for the treatment of blank whole hatchings finishing investigation ovum in back 6 days and the survival condition that hatches young mite, partial results is as follows:
Compound number concentration (ppm) ovum radix (grain) mite alive is counted net effect (%)
2????????10????????102????????0????????100
79????????10????????255????????0????????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, go old one-tenth mite after 24 hours, investigation mite ovum radix, in the good soup of dilution, flooded for 5 seconds, treated on the 7th that the whole hatchings of blank finished, 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) is not hatched and is counted (grain) inhibiting rate (%)
79????????125???????63??????????62?????????98.4
5, gray mold test
Compound concentration of the present invention is 1000ppm, and 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, and 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??????????95???????????305?????????100
278??????????95???????????331?????????100
304??????????100??????????343?????????90
7, oidium test
Compound concentration of the present invention is 1000ppm, and 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????????????95
306???????????95
385???????????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????????100????????155????????100
150????????100????????159????????100
Claims (4)
1, as the pyrazole compound of disinfectant use in agriculture and insecticidal/acaricidal agent and the general formula of preparation compound of the present invention (I) thereof be:
In the formula:
R1, R2 are H, halogen, C1～C6 alkyl, C2～C16 thiazolinyl, alkynyl, C3～C6 cycloalkyl, C1～C6 haloalkyl (C2～C6 thiazolinyl, C2～C6 alkynyl, C3～C6 cycloalkyl), R1, and R2 can be identical or different.
R3 is hydrogen, halogen, (halo) C1～C6 alkyl, (halo) C2～C6 thiazolinyl, (halo) C2～C6 alkynyl, (halo) C3～C6 cycloalkyl, (halo) C3～C6 cycloalkenyl group, NR5R6[R5 is H, halo) C1～C6 alkyl, (halo) C2～C6 thiazolinyl, (halo) C2～C6 alkynyl, (halo) C3～C6 cycloalkyl, (halo) C3～C6 cycloalkenyl group, R6 is R5, (replacement) aryl, (replacement) heteroaryl], (replacement) aryl, (replacement) heteroaryl
R4 is that H, C1～C6 alkyl, halogen, NR5R7[R7 are R5, (replacement) aryl, (replacement) heteroaryl], CN, (replacement) benzyl, (replacement) aryl, (replacement) heteroaryl, (Z1 is a key to CO-Z1～R8, O, S, NR5R7; R8 is key, H, (halo) C1～C6 alkyl, (halo) C2～C6 thiazolinyl, (halo) C2～C6 alkynyl, (halo) C3～C6 cycloalkyl, (halo) C3～C6 cycloalkenyl group, (replacement) aryl, CH2CO-Z1-R7, CH2CN), (X1 is O to PX1 (X2R9) X3R10, S:X2, X3 is O, S, NH; X1, X2, X3 can be identical or different; R9, R10 are R8, can be identical or different.
X is a key, O, and S, (R11 is H to NR11, R8).
Y is a key, O, NR11, CH2.
Z is a key, H, and CO, S (O) n, CHR12[R12 is H, (halo) C1～C6 alkyl].
But R4 and Z be makeup ring [five circle or six annulus of saturated or unsaturated any replacement: imidazoles, glyoxalidine, triazole, evil (two) azoles, oxazoline (ketone), thiophene (two) azoles, thiazoline (ketone), pyrimidine, two (four) hydrogen pyrimidines (quinoline ketone), (three hydrogen) oxazines] also.
Q is H, R3, CH2R3, OR3, CO-Z1-R8, OR8, S (O) nR8, CN, PX1 (X2R9) X3R10,
When Q is (replacement) aryl, can be (replacement) phenyl, substituting group can be H, C1～C6 alkyl, C2～C6 thiazolinyl, C2～C6 alkynyl, C3～C6 cycloalkyl, C3～C6 cycloalkenyl group, C1～C6 haloalkyl (C2～C6 thiazolinyl, C2～C6 alkynyl, C3～C6 cycloalkyl, C3～C6 cycloalkenyl group), OR8, CO-Z1-R8, CH2CO-Z1-R8, CH2CN, NR5R8, S (O) nR8, SiR13R14R15[R13～R15 is (halo) C1～C6 alkyl, can be identical or different], COSiR13R14R15, OSiR13R14R15, CR12R13CN, CR12R13CC13, SF5
m＝0～1；??????????n＝0～2，
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 that replaced by 1 or more a plurality of identical or different halogen atom, alkynyl, cycloalkyl, cycloalkenyl group), (replacement) aryl, (replacement) heteroaryl, substituting group can be H, C1～C6 alkyl, thiazolinyl, alkynyl, cycloalkyl, cycloalkenyl group, C1～C6 halo (alkyl, thiazolinyl, alkynyl, cycloalkyl) cycloalkenyl group, OR7, CO-Z1 R8, NR5R7, S (O) nR8, SiR13R14R15, COSiR13R14R15, OSiR13R14R15, CR1 2R13CN, CR12R13CC13, SF5, 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 Ji ， Evil (two) azoles base, pyrimidyl.
2, pyrazole compound according to claim 1 (1), it is characterized in that can and known sterilant and insecticidal/acaricidal agent in any one, two or more uses with.Known biocides is as Karbam Black, thiram, ziram, maneb, zineb, zinc manganese ethylenebisdithiocarbamate, derosal, F-1991, RP-26019, triazolone, cyproconazole, own azoles alcohol, alkene azoles alcohol, flutriafol, diclobutrazol, Bitertanol, tebuconazole, fluorine bacterium azoles, furconazole, nitrile bacterium azoles, azoles bacterium nitrile, bromuconazole, Wocosin 50TK, furconazole_cis, fluzilazol, acid amides azoles Difenoconazole, fluorine ether azoles, nuarimol, dimethomorph, metaxanin, furalaxyl, M 9834, dislike acid amides, prochloraz, frost urea cyanogen, Propamocarb, phosethyl Al, the mould prestige of second, fenpiclonil, seed dressing is strong; fenpropimorph; fenpropidin; pyrifenox; pencycuron; ferimzone; azoles bacterium piperazine; thicyofen; fluazinam; mepanipyrim; pyrimethanil; cyprodinil; fluquinconazole; BAS 480F; BAS490F; CGA245704; CGA 329531; DE-795; DPX-JE874; ICIA0858; ICIA0054; KNF-S474; KTU 3616; KWG4168; LY214352; Mon 24000, XRD563; SSF126; SSF129.Known insecticidal/acaricidal agent is as fluorine ester chrysanthemum ester, Fenvalerate, alphacypermethrin, bifenthrin, cycloprothrin, cyfloxylate, cyhalothrin, Cypermethrin, the nail body Cypermethrin, second body Cypermethrin, esfenvalerate, ether chrysanthemum ester, fenpirithrin, flucythrinate, taufluvalinate, cyhalothrin, tefluthrin, tralomethrin, brofluthrinate, brofenprox, Cis-resmethrin, clocythrin, deltamethrin, ICIA5682, MTI-732, pyresmethrin, Silafluofen, silafluofen (Hoe498), SSI-126, zetamethrin; Carbofuran, carbosulfan, benfuracarb, methomyl, UC-51762, alanycarb, fenothiocarb; Kayaphos, Toyodan, first Toyodan, Profenofos, isazofos, Terbufos, azamethiphos, fosmethilan, colophonate, pyraclofos, Chlorpyrifos 94, chlorpyrifos_methyl, Volaton, diazinon, Dowco429, MAT-7484; Fluorine bell urea, Teflubenzuron, UC 62644, flufenoxuron, PH-7023, GR-572, CGA157419, CGA184699; Provado, NI-25, TIA-304; NN1850, MK-239, Fipronil:NC-129, NC-170, NC-184, NC-194, NC-196; Abamectin, amitrazin, avermectin, azadirachtin; 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.
3, mixed preparation according to claim 2, the effective content that it is characterized in that compound (1) is 0.1%～95% (weight), be 0.5%～95% preferably, preparation has solution, emulsion, wettable powder, suspension agent, pulvis, blue or green agent, soluble powder, granule, flooded the natural materials of active compound and wrap into micro-fine capsule in the polymer materials.
4, compound of the present invention (1) has good sterilization and pesticide and miticide actility.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, flies 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.
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