CN105175335A - 3-(3,3-dichloroallyloxy)-1-methylpyrazole-5-formamide derivatives and preparation method thereof - Google Patents
3-(3,3-dichloroallyloxy)-1-methylpyrazole-5-formamide derivatives and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/18—One oxygen or sulfur atom
- C07D231/20—One oxygen atom attached in position 3 or 5
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
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- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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Abstract
The invention belongs to the pesticide technical field, and particularly relates to 3-(3,3-dichloroallyloxy)-1-methylpyrazole-5-formamide derivatives and a preparation method thereof, and a pesticide composition containing the derivatives. The 3-(3,3-dichloroallyloxy)-1-methylpyrazole-5-formamide derivatives have high bacteriostatic activity, are suitable for prevention and control of plant diseases and virus diseases in the agriculture field, the forestry field and the gardening field, and effectively prevent and control crop diseases and pests.
Description
Technical field
The invention belongs to technical field of pesticide, be specifically related to a kind of 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-carboxamides derivatives and preparation method thereof and the pesticide composition comprising said derivative.
Background technology
Nitrogen heterocyclic ring compounds has higher physiology and pharmacologically active, in the exploitation of agricultural chemicals, have important value, and wherein pyrazoles is 1, the 2-ribavirin five-membered ring containing two nitrogen-atoms.Compound containing pyrazole ring has higher biological activity, reporting 2-pyrazoles-5-ketone from nineteen forty-six Thmaposon first time can suppress after biological growth and Rubber company of the U.S. in 1949 synthesized the foliage spray sterilant of pyrazoles, pyrazole compound achieves develop rapidly at pesticide field, such as Geigy.s.A. company in nineteen fifty-two pyrazole ring is introduced carbamate, the agricultural insecticide such as Pyrolan prepared by organophosphorus, isolan, pyraclofos, pyrazoles oxygen phosphorus and dimetilan.
And in recent years, commercialization or more numerous by the commercial pesticide species containing pyrazole heterocycle, the particularly pyrazole amide series bactericidal agent that gets up of fast development in recent years, the pyrazole amide sterilant Bixafen of Bayer department exploitation, first just reaching and finding and the Isopyrazam developed, the compound fluxapyroxad that BASF AG announces just is reaching with first the sterilant Sedaxane (Zhang Yibin being in the research and development later stage, world pesticide, 2014, 4 (36): 31-33.), the common feature of these pesticide species is the amidess containing pyrazole heterocycle, there is higher fungicidal activity, but due to long-time use, plant creates higher resistance gradually.
Summary of the invention
An object of the present invention is to provide a kind of 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-carboxamides derivatives, and biological activity is high.
Two of object of the present invention is to provide the preparation method of above-mentioned 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-carboxamides derivatives.
Three of object of the present invention is also to provide a kind of pesticide composition, comprises above-mentioned 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-carboxamides derivatives.
For achieving the above object, the present invention adopts following technical scheme:
A kind of 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-carboxamides derivatives, chemical structure of general formula is as follows:
Wherein, R is methyl, sec.-propyl, cyclopropyl, cyclopentyl, cyclohexyl, morpholine, phenyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, 2-p-methoxy-phenyl, 3-p-methoxy-phenyl, 4-p-methoxy-phenyl, 4-Trifluoromethoxyphen-l, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-chloro-phenyl-, 3-chloro-phenyl-, 4-chloro-phenyl-, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-trifluoromethyl, 3-trifluoromethyl, 4-trifluoromethyl, 2-cyano-phenyl, 3-cyano-phenyl, 4-cyano-phenyl, 2-N, N-dimethylaminophenyl, 3-N, N-dimethylaminophenyl, 4-N, N-dimethylaminophenyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, pyridine-2-base, pyridin-3-yl, pyridin-4-yl, 3-picoline-2-base, 4-picoline-2-base, 5-picoline-2-base, 2-phenyl, 2-is to fluorophenyl phenyl, 2-rubigan phenyl or 5-methylthiazol-2-base.
A kind of preparation method of 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-carboxamides derivatives, comprises the following steps:
(1) preparation of intermediate 3-hydroxyl-1-methylpyrazole-5-methyl-formiate:
A. 90 ~ 110mmol methylhydrazinium sulphate is joined in three mouthfuls of round-bottomed flasks, with 180 ~ 220mL dissolve with methanol, more then add 180 ~ 220mmol triethylamine dissociate, finally add 90 ~ 110mmol butynoic acid dimethyl ester, be heated to 40 ~ 60 DEG C, magnetic agitation, backflow 10 ~ 15h;
B. after having reacted, stop heating, be cooled to 5 ~ 10 DEG C, leave standstill, until white crystal is separated out, filtration, washing, drying, namely obtain 3-hydroxyl-1-methylpyrazole-5-methyl-formiate;
(2) preparation of 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-methyl-formiate:
Acetone 15 ~ 25mL, 3-hydroxyl-1-methylpyrazole-5-methyl-formiate 4.8 ~ 5.2mmol, 1 is added successively in three mouthfuls of round-bottomed flasks, 1,3-tri chloropropene 5 ~ 6mmol, room temperature condensation reaction 8 ~ 15h under alkaline condition, filter, washing, concentrated, obtain 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-methyl-formiate;
(3) preparation of 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-formic acid:
C. by 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-methyl-formiate 1.8 ~ 2.2mmol, methyl alcohol 15 ~ 20mL, distilled water 3 ~ 5mL, lithium hydroxide 3.5 ~ 4.5mmol mixes, stirring at room temperature 8 ~ 15h;
D. after reaction terminates, concentrated, add distilled water, filter, hydrochloric acid adjusts pH to be 2.8 ~ 3.2, separates out white precipitate, filters, dry, obtains 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-formic acid;
(4) preparation of 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-formyl chloride:
By 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-formic acid 0.8 ~ 1.2mmol joins in reaction flask, add 4 ~ 6mL trichloromethane, 0.18 ~ 0.22mL sulfur oxychloride successively, 45 ~ 55 DEG C of stirring reaction 1.5 ~ 2.5h, concentrating under reduced pressure obtains 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-formyl chloride;
(5) preparation of 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-carboxamides derivatives:
E. by 3-(3,3-dichloropropylene oxygen base)-1-methyl pyrazole-5-formyl chloride 0.8 ~ 1.2mmol is dissolved in 1.5 ~ 2.5mL tetrahydrofuran solution, the organic amine of 1.0 ~ 1.5mmol, 4 ~ 6mL methylene dichloride, 1 ~ 2mmol triethylamine is added in reaction flask, be cooled to-2 ~ 0 DEG C, above-mentioned tetrahydrofuran solution is dripped under protection of inert gas, dropwise and rise to room temperature gradually, stir 1 ~ 1.5h;
F. after reaction terminates, add methylene dichloride 10 ~ 12mL, dilute above-mentioned reaction soln, washing, dry, concentrated, gained resistates column chromatography purification, obtains product.
According to the preparation method of above-mentioned 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-carboxamides derivatives, the alkaline condition described in step (2) is: salt of wormwood 6 ~ 8mmol, potassiumiodide 0.05 ~ 0.25mmol.
According to above-mentioned 3-(3,3-bis-chloroallyloxyamino) preparation method of-1-methylpyrazole-5-carboxamides derivatives, column chromatography condition described in step (5) is: 200 ~ 300 order silicagel columns, wash-out eluent is sherwood oil and ethyl acetate, and both volume ratios are 3:1 ~ 10:1.
According to the preparation method of above-mentioned 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-carboxamides derivatives, described sherwood oil boiling point is 60 ~ 90 DEG C.
According to the preparation method of above-mentioned 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-carboxamides derivatives, the washing methods described in step (5) is that dilute hydrochloric acid, saturated sodium bicarbonate solution and saturated aqueous common salt wash successively.
The reaction expression of above-mentioned preparation method is expressed as follows:
A kind of pesticide composition, comprises above-mentioned 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-carboxamides derivatives.
According to above-mentioned pesticide composition, also comprise agricultural chemical insecticide, described agricultural chemical insecticide is Chlorpyrifos 94, the sub-Nong in ground, acetamiprid, Affirm (Merck Co.), milbemectin, Avrmectin, pleocidin, fenvalerate, esfenvalerate, Cypermethrin, effective cypermethrin, lambda-cyhalothrin, Deltamethrin, Fenvalerate, Beta-cyfloxylate, cyfloxylate, Lambda-lambda-cyhalothrin, Permanone, permethrin, esbiothrin, cyhalothrin, bifenthrin, permethrin, ether chrysanthemum ester, flumethrin, fluvalinate, Provado, acetamiprid, Ti304, imidaclothiz, thiacloprid, Diacloden, clothianidin, MTI-446, clothianadin, Da Tenan, diflubenzuron, d ichlorbenzuron, Teflubenzuron, deinsectization is grand, HEXAFLUMURON, flufenoxuron, pyridine worm is grand, lufenuron, poisonous insect urea, penfluron, Noviflumuron and noviflumuron, flucycloxuron, Novaluron and Rimon, chlorfluazuron, Baysir6874 i.e. { 1-[(3.5-bis-chloro-4) 4-nitrophenoxy phenyl 3-3-(2-chlorobenzene)-urea }, BaySIR-8514 i.e. [1-(4-Trifluoromethoxyphen-l)-3-(2-chlorobenzene)-urea], piperazine worm urea, Bistrifluron and bistrifluron, furan tebufenozide, worm hydrazides, chlorine worm hydrazides, methoxyfenozide, ring worm hydrazides, Rogor, omethoate, SD-1750, acephate, triazophos, Resitox, pyridaphenthione, isazofos, Ro 7-5050, SevinCarbaryl, Aphox, meta-tolyl-N-methylcarbamate (MTMC), isoprocarb, cartap, fenobucarb, leaf disperses, carbaryl, benfuracarb, carbosulfan, cartap, bromopropylate, hexythiazox, fenpyroximate, pyridaben, clofentezine, propargite, diafenthiuron, benfuracarb, pymetrozine, spiral shell mite ester, spiral shell worm ester, spiral shell worm ethyl ester, butene-fipronil, azocyclotin, Buprofezin, ethoprophos, ethiprole, Cupric sulfate, disosultap, chlorantraniliprole, Flubendiamide, fluorine cyanogen insect amide, cyanogen insect amide, Tolfenpyrad, tebufenpyrad, bromothalonil, pyrazinones, second mite azoles, tebufenpyrad, to rattle away young ketone, Nylar, any one or a few combination in emaricin.
According to above-mentioned pesticide composition, also comprise agricultural bactericide, described agricultural bactericide is diazosulfide, tiadinil, tisocromide, first thiophene lures amine, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-formic acid, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-sodium formiate, 4-methyl isophthalic acid, 2,3-thiadiazoles-5-ethyl formate, DL-beta-aminobutyric acid, isotianil, virazole, antofine, Ningnanmycin or Whitfield's ointment, frost urea cyanogen, thiram, ziram, zinc manganese ethylenebisdithiocarbamate, phosethyl Al, thiophanate_methyl, m-tetrachlorophthalodinitrile, enemy can be loose, procymidone, fenpropidin, thiophanate methyl, thiophanate, Metalaxyl-M, Whitfield's ointment, flumorph, dimethomorph, mefenoxam, benalaxyl-M, two chlorine zarilamid, flusulfamide, first flusulfamide, thiophene fluorine bacterium amine, fultolanil, tecloftalam, ring propionyl bacterium amine, cyflufenamid, fenhexamid, zarilamid, Silthiopham, furametpyr, pyrrole metsulfovax, mandipropamid, zoxamide, fenfuram, carboxin, chlozolinate, RP-26019, Azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, SSF 126, orysastrobin, ZEN 90160, Strobilurin, oxime bacterium ester, enostroburin, alkene oxime amine, oxygen ring azoles, bromuconazole, SN-108266, difenoconazole, olefin conversion, efficient olefin conversion, epoxiconazole, RH-7592, fluquinconazole, fluzilazol, flutriafol, own azoles alcohol, imibenconazole, plant bacterium azoles, metconazole, nitrile bacterium azoles, Topaze, Wocosin 50TK, prothioconazoles, simeconazoles, tebuconazole, tertraconazole, triadimenol, triticonazole, bitertanol, thiabendazole, fuberidazole, imazalil, efficient imazalil, prochloraz, fluorine bacterium azoles, cyazofamid, fenamidone, Evil imidazoles, pefurazoate, famoxadone, SYP-Z048, hymexazo, the spirit of Evil frost, Guardian, etridiazole, octhilinone, benthiozole, dodemorph, fenpropimorph, tridemorph, fenpiclonil, fludioxonil, fluazinam, pyrifenox, ring pyridine bacterium amine, boscalid amine, fluopicolide, pyridine bacterium amine, cyprodinil, fluorine mepanipyrim, ferimzone, mepanipyrim, phonetic mould amine, fenarimol, nuarimol, chinomethionate, dithianon, ethoxyquin, hydroxyquinoline, third oxygen quinoline, benzene oxygen quinoline, the mould prestige of second, iprovalicarb, benzene metsulfovax, Propamocarb, methasulfocarb, edifenphos, iprobenfos, pyrazophos, tolclofosmethyl, miewensu, kasugamycin, polyoxin, Polyoxin, validamycin, jingganmycin, Streptomycin sulphate, metaxanin, furalaxyl, M 9834, ofurace, mebenil, derosal, F-1991, thiophanate_methyl, triazolone, bupirimate, dimethirimol, the phonetic phenol of second, Difolatan, Vancide 89, Phaltan, Vinclozoline, fluoromide, dimetachlone, m-tetrachlorophthalodinitrile, isoprothiolane, Kitazine, bismerthiazol, quintozene, zinc manganese ethylenebisdithiocarbamate, zinc 1,2-propylene bisdithiocarbamate, fosetylaluminium, sulphur, Bordeaux mixture, copper sulfate, copper oxychloride, Red copper oxide, copper hydroxide, metrafenone, pencycuron, diclomezin, phthalide, pyroquilon, volution bacterium amine, tricyclazole, triforine, the pyridine of many fruits, the pungent salt of biguanides, iminoctadine, dicloran, benzene flusulfamide, toluene flusulfamide, K-281, fenaminosulf, oxolinic acide, probenazole, bronopol, methyl iodide, metamsodium, enemy's line ester, dazomet, dichloroisopropyl ether, lythidathion, cadusafos, fensulfothion, thionazin, fenamiphos, ethoprophos, dichlofenthion, isazofos, fosthietan, oxamyl, aldicarb, carbofuran, sulfuryl fluoride, dichloropropylene, dichloro-isonicotinic acid, any one or a few combination in allyl isothiazole.
Positive beneficial effect of the present invention:
3-of the present invention (3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-carboxamides derivatives bacteriostatic activity is high, is applicable to the Plant diseases of agriculture field, field of forestry and horticultural field and the control of virus disease, effectively preventing diseases and pests of agronomic crop.
3-of the present invention (3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-carboxamides derivatives chemical yield is high, and purity is high, and preparation method is simple, and production cost is low, easy handling.
Embodiment
Below in conjunction with some specific embodiments, the present invention is further described.
Embodiment 1
A kind of 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-carboxamides derivatives, chemical structure of general formula is as follows:
Wherein, R is methyl.
The preparation method of above-mentioned 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-carboxamides derivatives comprises the following steps:
(1) preparation of intermediate 3-hydroxyl-1-methylpyrazole-5-methyl-formiate:
A. 100mmol methylhydrazinium sulphate is joined in three mouthfuls of round-bottomed flasks, uses 200mL dissolve with methanol, more then add 200mmol triethylamine dissociate, finally add 100mmol butynoic acid dimethyl ester, be heated to 60 DEG C, magnetic agitation, backflow 15h;
B. after having reacted, stop heating, be cooled to 5 DEG C, leave standstill 2 days, until white crystal is separated out, filtration, washing with alcohol, drying, namely obtain 3-hydroxyl-1-methylpyrazole-5-methyl-formiate, yield is 60%, purity>=95%,
1hNMR (400MHz, DMSO-d6): δ=3.79 (s, 3H), 3.88 (s, 3H), 6.01 (s, 1H), 10.05 (s, 1H);
(2) preparation of 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-methyl-formiate:
Acetone 20mL, 3-hydroxyl-1-methylpyrazole-5-methyl-formiate 5mmol, 1 is added successively in three mouthfuls of round-bottomed flasks, 1, room temperature condensation reaction 12h under 3-tri chloropropene 5.5mmol alkaline condition, filters, washing with acetone, concentrated, obtain white solid 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-methyl-formiate, yield 95%, purity>=95%
1hNMR (400MHz, CDCl
3) δ 6.39 (s, 1H), 6.22 (t, J=6.2Hz, 1H), 4.71 (d, J=6.1Hz, 2H), 4.01 (s, 3H), 3.82 (s, 3H);
(3) preparation of 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-formic acid:
C. by 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-methyl-formiate 2mmol, methyl alcohol 16mL, distilled water 4mL, lithium hydroxide 4mmol mixes, stirring at room temperature 12h;
D. after reaction terminates, the most of solvent of concentrated removing, adds distilled water, filters a small amount of not tolerant, aqueous phase hydrochloric acid adjusts pH to be 3, separates out white precipitate, filters, dry, obtain 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-formic acid, yield 96%, purity >=95%;
(4) preparation of 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-formyl chloride:
By 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-formic acid 1.0mmol joins in reaction flask, add 5mL trichloromethane, 0.2mL sulfur oxychloride successively, 50 DEG C of stirring reaction 2h, concentrating under reduced pressure obtains but yellow solid 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-formyl chloride;
(5) preparation of 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-carboxamides derivatives:
E. by 3-(3,3-dichloropropylene oxygen base)-1-methyl pyrazole-5-formyl chloride 1.0mmol is dissolved in 2mL tetrahydrofuran solution, the methylamine of 1.2mmol, 5mL methylene dichloride, 1.5mmol triethylamine is added in reaction flask, be cooled to 0 DEG C, oxide gas protection is lower drips above-mentioned tetrahydrofuran solution, dropwise and rise to room temperature gradually, stir 1h;
F. after reaction terminates, add methylene dichloride 10mL, dilute above-mentioned reaction soln, washing, dry, concentrated, gained resistates column chromatography purification, wash-out, obtains product, product purity >=97%.
Alkaline condition described in step (2) is: salt of wormwood 7.5mmol, potassiumiodide 0.1mmol.
Column chromatography condition described in step (5) is: 200 ~ 300 order silicagel columns, and eluent is sherwood oil and ethyl acetate, and both volume ratios are 5:1.
Described sherwood oil boiling point is 60 ~ 90 DEG C.
Washing methods described in step (5) is that dilute hydrochloric acid, saturated sodium bicarbonate solution and saturated aqueous common salt wash successively.
Embodiment 2 ~ 45 is similar with above-described embodiment ultimate principle, and do not repeat, difference is: R is respectively sec.-propyl, cyclopropyl, cyclopentyl, cyclohexyl, morpholine, phenyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, 2-p-methoxy-phenyl, 3-p-methoxy-phenyl, 4-p-methoxy-phenyl, 4-Trifluoromethoxyphen-l, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-chloro-phenyl-, 3-chloro-phenyl-, 4-chloro-phenyl-, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-trifluoromethyl, 3-trifluoromethyl, 4-trifluoromethyl, 2-cyano-phenyl, 3-cyano-phenyl, 4-cyano-phenyl, 2-N, N-dimethylaminophenyl, 3-N, N-dimethylaminophenyl, 4-N, N-dimethylaminophenyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, pyridine-2-base, pyridin-3-yl, pyridin-4-yl, 3-picoline-2-base, 4-picoline-2-base, 5-picoline-2-base, 2-phenyl, 2-is to fluorophenyl phenyl, 2-rubigan phenyl, 5-methylthiazol-2-base.。
The preparation method of 3-(3,3-bis-the chloroallyloxyamino)-1-methylpyrazole-5-carboxamides derivatives of embodiment 2 ~ 45 is similar to embodiment 1, and something in common does not repeat, and difference is: the organic amine R-NH described in step (5)
2r group respectively with described is corresponding.
The physical and chemical parameter of 3-(3,3-bis-the chloroallyloxyamino)-1-methylpyrazole-5-carboxamides derivatives prepared by above-described embodiment 1 ~ 45 is in table 1.
3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-carboxamides derivatives physical and chemical parameter prepared by table 1 embodiment of the present invention 1 ~ 45
3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-carboxamides derivatives described in embodiments of the invention 1 ~ 45 suppresses the determination experiment of pathogenic fungi growth activity:
Testing method: thalli growth rate assay method.
Detailed process is: (1) gets 5mg embodiment 1 ~ 45 3-(3 described arbitrarily, 3-bis-chloroallyloxyamino)-1-methylpyrazole-5-carboxamides derivatives is dissolved in appropriate dimethyl formamide, then with the medicament being diluted to 500 μ g/mL containing a certain amount of polysorbas20 emulsifier aqueous solution, reagent agent aseptically respectively being drawn 1mL injects in culture dish, add 9 milliliters of substratum more respectively, make 50 μ g/mL pastilles after shaking up dull and stereotyped, do blank with the flat board adding 1mL aqua sterilisa.
(2) bacterium dish is cut with the punch tool of diameter 4mm along mycelia outer rim, move on pastille flat board, put in equilateral triangle, often process repetition 3 times, culture dish is placed in 24 ± 1 DEG C of constant incubators and cultivates, after contrast colony diameter expands to 2 ~ 3cm, investigate each process bacterium dish expansion diameter, average, compare with blank and calculate relative bacteriostasis rate.
For examination bacterial classification: be the kind of the majority of plant pathogenic bacteria of the actual generation in multiple representative field in China's agriculture production, AS: tomato early blight bacterium (Alternariasolani); BC: botrytis cinerea pers (Botrytiscinerea); CA: peanut Cercospora bacteria (Cercosporaarachidicola); GZ: fusarium graminearum (Gibberellazeae); PI: phytophthora infestans (Phytophthorainfestans (Mont.) deBary); PP: Botryosphaeria berengeriana f. sp (Physalosporapiricola); PS: Rhizoctonia solani Kuhn (Pelliculariasasakii); RC: Rhizoctonia cerealis (Rhizoctoniacerealis); SS: Sclerotinia sclerotiorum (Sclerotiniasclerotiorum).
Experimental result is in table 2.
Bacteriostasis rate detected result/the % of table 23-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-carboxamides derivatives
| Compound | PI | CA | AS | GZ | PP | BC | SS | RC | PS |
| Mg-M-01 | 41.4 | 45.8 | 14.2 | 40.8 | 56.6 | 79.2 | 47.9 | 74.9 | 20.6 |
| Mg-M-02 | 36.8 | 40.1 | 16.6 | 60.0 | 71.2 | 40.7 | 46.1 | 71.2 | 24.7 |
| Mg-M-03 | 36.8 | 40.1 | 10.6 | 45.9 | 43.8 | 45.0 | 49.7 | 82.1 | 12.3 |
| Mg-M-04 | 32.2 | 28.6 | 7.1 | 47.2 | 80.3 | 62.1 | 51.4 | 71.2 | 24.7 |
| Mg-M-05 | 32.2 | 45.8 | 10.6 | 56.1 | 62.1 | 30.0 | 46.1 | 78.5 | 28.8 |
| Mg-M-06 | 36.8 | 22.9 | 17.7 | 39.5 | 65.7 | 47.1 | 55.0 | 93.5 | 24.7 |
| Mg-M-07 | 23.0 | 22.9 | 9.0 | 37.0 | 82.2 | 49.3 | 37.2 | 82.0 | 16.4 |
| Mg-M-08 | 22.0 | 50 | 33.3 | 65.4 | 61.8 | 36.9 | 60 | 90.9 | 43.7 |
| Mg-M-09 | 7.3 | 42.9 | 22.2 | 50 | 47.1 | 39.1 | 55 | 36.4 | 12.5 |
| Mg-M-10 | 65.8 | 42.9 | 22.2 | 38.5 | 50.0 | 39.1 | 50.0 | 59.1 | 12.5 |
| Mg-M-11 | 36.6 | 57.1 | 55.6 | 73.1 | 47.1 | 43.5 | 30 | 72.7 | 37.5 |
| Mg-M-12 | 41.5 | 64.3 | 50 | 65.4 | 32.4 | 36.9 | 30 | 36.4 | 18.8 |
| Mg-M-13 | 17.1 | 50 | 33.3 | 42.3 | 55.9 | 39.1 | 55 | 86.4 | 25.0 |
| Mg-M-14 | 23.0 | 17.2 | 0.0 | 38.3 | 62.1 | 45.0 | 37.2 | 30.2 | 12.3 |
| Mg-M-15 | 65.9 | 64.3 | 50 | 61.5 | 67.6 | 43.5 | 35 | 95.5 | 31.3 |
| Mg-M-16 | 56.1 | 64.3 | 50 | 65.4 | 58.8 | 52.2 | 70 | 100 | 43.8 |
| Mg-M-17 | 2.4 | 21.4 | 27.8 | 38.5 | 23.5 | 39.1 | 30 | 31.8 | 12.5 |
| Mg-M-18 | 27.6 | 11.4 | 13.1 | 28.1 | 69.4 | 47.1 | 33.7 | 82.2 | 20.6 |
| Mg-M-19 | 27.6 | 28.6 | 3.5 | 30.6 | 43.8 | 0.0 | 28.4 | 65.2 | 16.4 |
| Mg-M-20 | 32.2 | 34.3 | 7.8 | 38.3 | 63.9 | 30.0 | 39.0 | 70.9 | 12.3 |
| Mg-M-21 | 46.0 | 62.9 | 45.7 | 85.5 | 47.5 | 92.1 | 69.2 | 70.9 | 82.2 |
| Mg-M-22 | 21.2 | 19.1 | 38.8 | 56.1 | 60.8 | 48.6 | 53.2 | 66.2 | 29.9 |
| Mg-M-23 | 27.2 | 22.9 | 23.9 | 32.9 | 80.5 | 29.4 | 49.4 | 71.9 | 12.8 |
| Mg-M-24 | 12.1 | 11.4 | 12.0 | 34.2 | 78.7 | 33.3 | 41.8 | 64.7 | 17.1 |
| Mg-M-25 | 27.2 | 7.6 | 47.8 | 41.1 | 48.3 | 14.1 | 38.0 | 96.4 | 8.5 |
| Mg-M-26 | 65.9 | 64.3 | 44.4 | 69.2 | 55.8 | 47.8 | 65 | 90.9 | 50.0 |
| Mg-M-27 | 24.2 | 22.9 | 6.0 | 39.7 | 73.3 | 44.8 | 38.0 | 79.1 | 21.3 |
| Mg-M-28 | 27.2 | 15.3 | 26.9 | 49.3 | 60.8 | 32.0 | 39.9 | 94.9 | 17.1 |
| Mg-M-29 | 24.2 | 26.7 | 3.0 | 43.8 | 76.9 | 42.2 | 39.9 | 97.8 | 25.6 |
| Mg-M-30 | 30.2 | 19.1 | 0.0 | 37.0 | 71.6 | 34.5 | 43.7 | 97.8 | 21.3 |
| Mg-M-31 | 60.4 | 22.9 | 3.0 | 47.9 | 80.5 | 29.4 | 45.6 | 78.0 | 34.2 |
| Mg-M-32 | 15.1 | 64.9 | 56.8 | 84.9 | 84.1 | 90.8 | 49.4 | 92.1 | 47.0 |
| Mg-M-33 | 45.3 | 15.3 | 38.8 | 32.9 | 64.4 | 19.2 | 41.8 | 68.0 | 17.1 |
| Mg-M-34 | 60.8 | 57.2 | 71.7 | 84.9 | 62.6 | 92.1 | 70.3 | 82.2 | 89.7 |
| Mg-M-35 | 47.0 | 73.6 | 47.4 | 86.4 | 83.1 | 13.2 | 61.7 | 96.4 | 67.6 |
| Mg-M-36 | 26.8 | 12.9 | 19.3 | 47.2 | 9.7 | 29.0 | 35.4 | 84.7 | 82.6 |
| Mg-M-37 | 15.0 | 27.9 | 0.0 | 38.6 | 18.2 | 44.0 | 63.3 | 82.2 | 46.1 |
| Mg-M-38 | 16.1 | 34.3 | 6.4 | 44.0 | 3.2 | 42.9 | 70.8 | 73.7 | 38.6 |
| Mg-M-39 | 37.6 | 27.9 | 0.0 | 36.5 | 7.5 | 42.9 | 67.6 | 96.9 | 59.0 |
| Mg-M-40 | 20.4 | 44.0 | 6.4 | 46.1 | 7.5 | 32.2 | 71.9 | 90.4 | 68.7 |
| Mg-M-41 | 15.0 | 33.3 | 35.4 | 32.2 | 16.1 | 22.5 | 23.6 | 82.5 | 95.5 |
| Mg-M-42 | 15.0 | 29.0 | 46.1 | 38.6 | 26.8 | 11.8 | 0.0 | 94.0 | 30.0 |
| Mg-M-43 | 15.0 | 33.3 | 30.0 | 37.6 | 20.4 | 25.8 | 36.5 | 80.0 | 89.1 |
| Mg-M-44 | 24.7 | 37.6 | 18.2 | 33.3 | 18.2 | 40.8 | 47.2 | 75.5 | 37.6 |
| Mg-M-45 | 7.5 | 41.8 | 40.8 | 31.1 | 9.7 | 8.6 | 66.5 | 89.4 | 62.2 |
Interpretation of result: as can be seen from Table 2,3-(3,3-bis-the chloroallyloxyamino)-1-methylpyrazole-5-carboxamides derivatives good antimicrobial effect of the embodiment of the present invention 1 ~ 45.
Claims (7)
1. 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-carboxamides derivatives, chemical structure of general formula is as follows:
R is methyl, sec.-propyl, cyclopropyl, cyclopentyl, cyclohexyl, morpholine, phenyl, 2-aminomethyl phenyl, 3-aminomethyl phenyl, 4-aminomethyl phenyl, 2-p-methoxy-phenyl, 3-p-methoxy-phenyl, 4-p-methoxy-phenyl, 4-Trifluoromethoxyphen-l, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-chloro-phenyl-, 3-chloro-phenyl-, 4-chloro-phenyl-, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-trifluoromethyl, 3-trifluoromethyl, 4-trifluoromethyl, 2-cyano-phenyl, 3-cyano-phenyl, 4-cyano-phenyl, 2-N, N-dimethylaminophenyl, 3-N, N-dimethylaminophenyl, 4-N, N-dimethylaminophenyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, pyridine-2-base, pyridin-3-yl, pyridin-4-yl, 3-picoline-2-base, 4-picoline-2-base, 5-picoline-2-base, 2-phenyl, 2-is to fluorophenyl phenyl, 2-rubigan phenyl or 5-methylthiazol-2-base.
2. the preparation method of 3-according to claim 1 (3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-carboxamides derivatives, comprises the following steps:
(1) preparation of intermediate 3-hydroxyl-1-methylpyrazole-5-methyl-formiate:
A. 90 ~ 110mmol methylhydrazinium sulphate is joined in three mouthfuls of round-bottomed flasks, with 180 ~ 220mL dissolve with methanol, more then add 180 ~ 220mmol triethylamine dissociate, finally add 90 ~ 110mmol butynoic acid dimethyl ester, be heated to 40 ~ 60 DEG C, magnetic agitation, backflow 10 ~ 15h;
B. after having reacted, stop heating, be cooled to 5 ~ 10 DEG C, leave standstill, until white crystal is separated out, filtration, washing, drying, namely obtain 3-hydroxyl-1-methylpyrazole-5-methyl-formiate;
(2) preparation of 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-methyl-formiate:
Acetone 15 ~ 25mL, 3-hydroxyl-1-methylpyrazole-5-methyl-formiate 4.8 ~ 5.2mmol, 1 is added successively in three mouthfuls of round-bottomed flasks, 1,3-tri chloropropene 5 ~ 6mmol, room temperature condensation reaction 8 ~ 15h under alkaline condition, filter, washing, concentrated, obtain 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-methyl-formiate;
(3) preparation of 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-formic acid:
C. by 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-methyl-formiate 1.8 ~ 2.2mmol, methyl alcohol 15 ~ 20mL, distilled water 3 ~ 5mL, lithium hydroxide 3.5 ~ 4.5mmol mixes, stirring at room temperature 8 ~ 15h;
D. after reaction terminates, concentrated, add distilled water, filter, hydrochloric acid adjusts pH to be 2.8 ~ 3.2, separates out white precipitate, filters, dry, obtains 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-formic acid;
(4) preparation of 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-formyl chloride:
By 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-formic acid 0.8 ~ 1.2mmol joins in reaction flask, add 4 ~ 6mL trichloromethane, 0.18 ~ 0.22mL sulfur oxychloride successively, 45 ~ 55 DEG C of stirring reaction 1.5 ~ 2.5h, concentrating under reduced pressure obtains 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-formyl chloride;
(5) preparation of 3-(3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-carboxamides derivatives I:
E. by 3-(3,3-dichloropropylene oxygen base)-1-methyl pyrazole-5-formyl chloride 0.8 ~ 1.2mmol is dissolved in 1.5 ~ 2.5mL tetrahydrofuran solution, the organic amine of 1.0 ~ 1.5mmol, 4 ~ 6mL methylene dichloride, 1 ~ 2mmol triethylamine is added in reaction flask, be cooled to-2 ~ 0 DEG C, above-mentioned tetrahydrofuran solution is dripped under protection of inert gas, dropwise and rise to room temperature gradually, stir 1 ~ 1.5h;
F. after reaction terminates, add methylene dichloride 10 ~ 12mL, dilute above-mentioned reaction soln, washing, dry, concentrated, gained resistates column chromatography purification, wash-out, obtains product.
3. 3-(3 according to claim 2,3-bis-chloroallyloxyamino) preparation method of-1-methylpyrazole-5-carboxamides derivatives, it is characterized in that, the alkaline condition described in step (2) is: salt of wormwood 6 ~ 8mmol, potassiumiodide 0.05 ~ 0.25mmol.
4. 3-(3 according to claim 2,3-bis-chloroallyloxyamino) preparation method of-1-methylpyrazole-5-carboxamides derivatives, it is characterized in that, column chromatography condition described in step (5) is: 200 ~ 300 order silicagel columns, wash-out eluent is sherwood oil and ethyl acetate, and both volume ratios are 3:1 ~ 10:1.
5. the preparation method of 3-according to claim 4 (3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-carboxamides derivatives, it is characterized in that, described sherwood oil boiling point is 60 ~ 90 DEG C.
6. 3-(3 according to claim 2,3-bis-chloroallyloxyamino) preparation method of-1-methylpyrazole-5-carboxamides derivatives, it is characterized in that, the washing methods described in step (5) is that dilute hydrochloric acid, saturated sodium bicarbonate solution and saturated aqueous common salt wash successively.
7. a pesticide composition, is characterized in that, comprises 3-according to claim 1 (3,3-bis-chloroallyloxyamino)-1-methylpyrazole-5-carboxamides derivatives.
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