CN1410418A - Derivative containing alkyl sulfanyl hydrazone having insecticidal, antibacterial and herbicidal activity and its preparation method - Google Patents

Derivative containing alkyl sulfanyl hydrazone having insecticidal, antibacterial and herbicidal activity and its preparation method Download PDF

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CN1410418A
CN1410418A CN 02139612 CN02139612A CN1410418A CN 1410418 A CN1410418 A CN 1410418A CN 02139612 CN02139612 CN 02139612 CN 02139612 A CN02139612 A CN 02139612A CN 1410418 A CN1410418 A CN 1410418A
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alkyl
hydrazone
ethyl ketone
group
methylthio group
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CN1199939C (en
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黄明智
王晓光
黄路
陈灿
柳爱平
欧晓明
王永江
张承来
毛春晖
侯仲轲
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Hunan Research Institute of Chemical Industry
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Priority to PCT/CN2003/000503 priority patent/WO2004024680A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/48—Two nitrogen atoms
    • 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
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen
    • A01N35/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen containing a carbon-to-nitrogen double bond
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/46—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms
    • C07C323/48—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms to nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/52—Two oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/56—One oxygen atom and one sulfur atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles 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 in position 2
    • C07D277/82—Nitrogen atoms

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Alkyl hydrazone derivatives containing alkyl sulfur and with insecticiding, bactericiding and herbiciding activities and its preparing process are disclosed. Its bactericiding activity is more than 95%. Its herbiciding effect is class A. Its insecticiding effect is more than 90%.

Description

What have desinsection, sterilization, weeding activity contains alkyl sulfanyl hydrazone derivative and preparation method thereof
One, technical field: the present invention relates to have desinsection, sterilization, weeding activity contain alkyl sulfanyl hydrazone derivative and preparation method thereof.
Two, technical background: Chinese patent CN1099747A discloses the benzyl hydrazone compounds of being represented by following general formula that contains methoxy acrylate or acid amides, and has described their application as sterilant on the agricultural or on the gardening.
Figure A0213961200061
T.Hirase (JP09,143,143/1997,6,3, CA127:95101) reported the sterilant that following formula is represented, be used to prevent and treat pyricularia oryzae.
The sterilant ferimzone (TF-164, trade(brand)name Blasin) of Japan's military field drug company exploitation has tall and erect the effect to rice blast, and is also effective to banded sclerotial blight.
Three, summary of the invention: the purpose of this invention is to provide by following general formula (I) expression have desinsection, sterilization, a weeding activity contain the alkyl sulfanyl hydrazone derivative: X in the general formula (I), they can be identical or inequality, is hydrogen atom, halogen atom, cyano group, nitro, C1-6 alkyl, halo C1-6 alkyl, C1-6 alkoxyl group, cyano group C1-6 alkyl, C3-6 cycloalkyl, C2-6 alkenyl, C2-6 alkynyl group; M is the integer between zero or the 1-5; R 1Be hydrogen atom, C1-6 alkyl, halo C1-6 alkyl, C1-6 alkoxyl group, C1-6 alkylthio; R 2Be hydrogen atom, C1-6 alkyl, halo C1-6 alkyl; R 3Be hydrogen atom, C1-6 alkyl-carbonyl, C1-6 alkoxy carbonyl, halo C1-6 alkyl-carbonyl, C1-6 alkyl sulfide acyl group, C1-6 alkoxyl group sulfonyl, halo C1-6 alkyl sulfide acyl group; Q is following group: Y, they can be identical or inequality, is hydrogen atom, cyano group, nitro, halogen atom, C1-6 alkyl, halo C1-6 alkyl, C1-6 alkoxyl group, cyano group C1-6 alkyl, C3-6 cycloalkyl, C2-6 alkenyl, C2-6 alkynyl group; S is the integer between zero or the 1-5; T is the integer between zero or the 1-4; R 4And R 5, can be identical or different, be hydrogen atom, halogen atom, C1-6 alkyl, halo C1-6 alkyl, C1-6 alkoxyl group, halo C1-6 alkoxyl group, C1-6 alkylthio, C1-6 alkylamino radical, the C3-6 cycloalkyl, C2-6 alkenyl, C2-6 alkynyl group, C3-6 alkenyloxy, C3-6 chain oxy-acetylene; Z is nitrogen-atoms or CH.
Halogen atom comprises chlorine atom, bromine atoms, fluorine atom, iodine atom in above-mentioned; In substituting group, " C1-6 alkyl " refers to have the alkyl of 1-6 carbon atom, such as methyl, and ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl or similar group; " C1-6 alkoxyl group " refers to have the alkoxyl group of 1-6 carbon atom, such as methoxyl group, and oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert.-butoxy, n-pentyloxy, positive hexyloxy or similar group; " C1-6 alkylthio " refers to have the alkylthio of 1-6 carbon atom, such as methylthio group, and ethylmercapto group, positive rosickyite base, iprotiazem base, positive butylthio, isobutyl sulfenyl, secondary butylthio, uncle's butylthio, positive penta sulfenyl, just own sulfenyl or similar group; " C1-6 alkylamino radical " refers to have the alkylamino radical of 1-6 carbon atom, such as methylamino, and ethylamino-, Tri N-Propyl Amine base, isopropylamine base, n-butylamine-based, isobutyl amine, sec-butylamine base, TERTIARY BUTYL AMINE base, n-amylamine base, normal hexyl Amine base or similar group; Prefix " halo " is used for representing to have one or more groups as substituent halogen atom, and this halogen atom can be identical or different; " halo C1-6 alkyl " refers to have the substituted alkyl of one or more halogen atoms as a substituent 1-6 carbon atom, and each halogen atom can be identical or different.
Another object of the present invention provides the preparation method who contains the alkyl sulfanyl hydrazone derivative of general formula (I) expression, and reaction formula is as follows:
Figure A0213961200081
R wherein 1, R 2, R 3, Q, m as above defines.
In single or mixed solvent, under the normal pressure, suitable temperature, adopt the compound of general formula (II) and general formula (III) compound stoichiometric number hour and the compound of general formula (I).
As the solvent that is used for this reaction, can use any solvent, as long as its not obvious inhibited reaction process.The solvent that can select for use has methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, C1-6 alkyl alcohols such as Pentyl alcohol, 1,4-dioxane, tetrahydrofuran (THF), acetone, dimethyl sulfoxide (DMSO), N, dinethylformamide, acetate, water.These solvents can use separately or use as mixture.The mixture of preferred dehydrated alcohol and acetate when using as mixed solvent, the mixture of anhydrous methanol and acetate, the ratio of mixed solvent can be any ratio, acetate and methyl alcohol or alcoholic acid volume ratio are preferably 0.5-5: 100.
Temperature of reaction is-20～180 ℃, and preferred temperature is the reflux temperature of room temperature to selected solvent.
Reaction times is chosen in 0.1～10 hour usually, preferred 1-6 hour.
After reaction is finished, from reaction mixture, isolate needed compound, can pass through purifications such as column chromatography, recrystallization method or distillation method if desired, thereby make the alkyl sulfanyl hydrazone compound of general formula (I) by common method.
The compound of general formula (II) can be by the method preparation of narration in the European patent EP 1125931.
The preparation method of the compound of general formula (III):
When Q is benzoyl, benzothiazole-2 base of phenyl, benzoyl, the replacement of phenyl, replacement, benzothiazole-2 base of replacement etc., can purchases and obtain.When Q is pyrimidine-2-base, triazine-2-base etc., the method preparation of describing with reference to Journal ChemistrySociety 1952:4691.
The present invention represents the compound shown in the synthetic part general formula (I) with table 1, but does not limit the scope of the invention.
Table 1 general formula (I) expression contain alkyl sulfanyl hydrazone derivative and fusing point thereof
Figure A0213961200101
????25 ????4-CH 3 ??H ??CH 3 ??H ????3-Cl，4-ClPh ????106.4-107.8
????26 ????2-CH 3 ??H ??CH 3 ??H ????4-NO 2Ph ????142.0
????27 ????2-Cl，4-Cl ??H ??CH 3 ??H ????2-NO 2，4-NO 2Ph ????114.3-114.8
????28 ????2-Cl，4-Cl ??H ??CH 3 ??H ????2-Cl，4-ClPh ????60.8-61.3
????29 ????2-Cl，4-Cl ??H ??CH 3 ??H ????4-NO 2Ph ????117.3-117.8
????30 ????2-Cl，4-Cl ??H ??CH 3 ??H ????2-Cl，4-Cl，5-ClPh ????138.6-139.2
????31 ????2-Cl，4-Cl ??H ??CH 3 ??H ????3-Cl，4-ClPh ????109.4-110.6
????32 ????2-Cl，4-Cl ??H ??CH 3 ??H ????3-ClPh ????88.7-89.5
????33 ????2-Cl ??H ??CH 3 ??H ????2-NO 2，4-NO 2Ph ????149.4-149.6
????34 ????3-Br，4-F ??CH 3 ??CH 3 ??H ????4-NO 2Ph ????177.8-178.6
????35 ????4-F ??H ??CH 3 ??H ????2-NO 2，4-NO 2Ph ????159.0-160.8
????36 ????4-F ??H ??CH 3 ??H ????4-NO 2Ph ????186.3-186.5
????37 ????4-F ??H ??CH 3 ??H ????2-Cl，4-ClPh ????98.4-101.9
????38 ????4-F ??H ??CH 3 ??H ????3-Cl，5-ClPh ????105.9-106.3
????39 ????4-Cl ??H ??CH 3 ??H ????4-CH 3O，6-CH 3OPy ????124.0-124.7
????40 ????4-CH 3 ??H ??CH 3 ??H ????4-CH 3O，6-CH 3OPy ????110.8-111.0
????41 ????4-Br ??H ??CH 3 ??H ????4-CH 3O，6-CH 3OPy ????118.0-119.0
????42 ????4-CH 3 ??H ??CH 3 ??H ????4-CH 3S，6-CH 3SPy ????133.0-134.0
????43 ????4-CH 3 ??H ??CH 3 ??H ????4-CH 3O，6-CH 3SPy 94 (decomposition)
????44 ????4-Cl ??H ??CH 3 ??H ????4-CH 3O，6-CH 3SPy 114 (decomposition)
????45 ????2-Cl，4-Cl ??H ??CH 3 ??H ????4-CH 3O，6-CH 3OPy ????148.9-150.4
????46 ????4-Cl ??H ??CH 3 ??H ????4-CH 3O，6-C 2H 5SPy ????79.6-81.7
????47 ????4-Cl ??H ??CH 3 ??H ????4-C 2H 5O，6-C 2H 5OPy ????122.3-123.0
????48 ????4-CH 3 ??H ??CH 3 ??H ????4-C 2H 5O，6-C 2H 5OPy ????101.0-101.5
????49 ????2-Cl，4-Cl ??H ??CH 3 ??H ????4-C 2H 5O，6-C 2H 5OPy ????/
????50 ????4-F ??H ??CH 3 ??H ????4-CH 3O，6-CH 3OPy ????112.5-113.1
????51 ????4-F ??H ??CH 3 ??H ????4-CH 3，6-CH 3Py ????/
????52 ????4-F ??H ??CH 3 ??H ????4-C 2H 5O，6-C 2H 5OPy ????93.0-95.5
????53 ????4-CH 3 ??H ??CH 3 ??H ????4-CH 3，6-CH 3Py ????97.9-99.0
????54 ????4-Cl ??H ??CH 3 ??H ????4-CH 3，6-CH 3Py ????/
????55 ????4-F ??H ??CH 3 ??H ????PhCO ????128.9-129.9
????56 ????4-Cl ??H ??CH 3 ??H ????PhCO ????135.1-136.0
????57 ????4-CH 3 ??H ??CH 3 ??H ????PhCO ????138.7-139.5
????58 ????2-Cl，4-Cl ??H ??CH 3 ??H ????PhCO ????152.9-153.4
????59 ????4-Cl ??H ??CH 3 ??H ????4-BrPhCO ????168.7-170.5
????60 ????4-Cl ??H ??CH 3 ??H ????3-ClPhCO ????127.9-128.7
????61 ????4-Cl ??H ??CH 3 ??H ????4-ClPhCO ????164.4-166.0
????62 ????4-F ??H ??CH 3 ??H ????4-BrPhCO ????151.0-151.4
????63 ????4-CH 3 ??H ??CH 3 ??H ????4-CH 3PhCO ????/
????64 ????4-CH 3 ??H ??CH 3 ??H ????2-Cl，4-ClPhCO ????141.6-144.3
????65 ????4-CH 3 ??H ??CH 3 ??H ????4-ClPhCO ????146.0-149.8
????66 ????4-CH 3 ??H ??CH 3 ??H ????2-ClPhCO ????136.2-136.4
????67 ????4-CH 3 ??H ??CH 3 ??H ????3-NO 2PhCO ????/
????68 ????4-F ??H ??CH 3 ??H ????Q 4 ????118.7-122.4
????69 ????4-CH 3 ??H ??CH 3 ??H ????Q 4 ????103.5-106.7
????70 ????4-Cl ??H ??CH 3 ??H ????Q 4 (114.6 decomposition)
Annotate: Ph is a phenyl; Py is a pyrimidine-2-base; Q 4Be benzothiazole-2 base; / expression is test not.
The present invention represents synthetic part general formula (I) compound is carried out with table 2 1H NMR determination data, but do not limit the present invention.
Table 2 general formula (I) expression contain the alkyl sulfanyl hydrazone derivative 1H NMR data
Sequence number ???????????? 1H?NMR(ppm)
????1 ?2.29(s，3H，SCH 3)，3.87(s，2H，CH 2)，7.42-9.17(m，7H，ph-H)，11.80(s，1H，NH)
????2 ?2.18(s，3H，SCH 3)，3.86(s，2H，CH 2)，7.23-8.25(m，8H，ph-H)，9.08(s，1H，NH)
????3 ?2.12(s，3H，SCH 3)，3.80(s，2H，CH 2)，6.90-7.74(m，9H，ph-H)
????4 ?2.14(s，3H，SCH 3)，3.81(s，2H，CH 2)，7.23-7.73(m，7H，ph-H)，8.92(s，1H，NH)
????7 2.12(s，3H，SCH 3)，2.27(s，3H，ph-CH 3)，3.79(s，2H，CH 2)，7.10-7.93(m，8H，ph-H)
????8 ?2.16(s，3H，SCH 3)，3.83(s，2H，CH 2SCH 3)，7.37-7.75(m，6H，ph-H)，8.93(s，1H，NH)
????9 ?2.13(s，3H，SCH 3)，3.79(s，2H，CH 2SCH 3)，7.26-7.72(m，7H，ph-H)，8.54(s，1H，NH)
????10 ?2.29(s，3H，SCH 3)，3.88(s，2H，CH 2)，7.56-9.16(m，7H，ph-H)，11.80(s，1H，NH)
????11 ?2.16(s，3H，SCH 3)，3.83(s，2H，CH 2)，7.21-8.22(m，8H，ph-H)，9.04(s，1H，NH)
????12 ?2.11(s，3H，SCH 3)，2.28(s，6H，ph-CH 3)，3.84(s，2H，CH 2)，6.94-7.68(m，7H，ph-H)
????14 ?2.15(s，3H，SCH 3)，3.82(s，2H，CH 2SCH 3)，7.26-7.68(m，6H，ph-H)，8.94(s，1H，NH)
????15 ?2.12(s，3H，SCH 3)，3.78(s，2H，CH 2SCH 3)，6.95-7.63(m，7H，ph-H)，8.58(s，1H，NH)
????16 ?2.16(s，3H，SCH 3)，3.83(s，2H，CH 2SCH 3)，6.93-7.69(m，8H，ph-H)，8.60(s，1H，NH)
????17 ?2.27(s，3H，SCH 3)，2.41(s，3H，CH 3)，3.89(s，2H，CH 2)，7.28-9.18(m，7H，ph-H)，11.80(s，1H，NH)
????18 ?2.14(s，3H，SCH 3)，2.39(s，3H，ph-CH 3)，3.84(s，2H，CH 2)，7.21-8.21(m，8H，ph-H)，9.06(s，1H，NH)
????19 ?2.30(s，3H，SCH 3)，2.51(s，3H，ph-CH 3)，3.83(s，2H，CH 2)，7.29-9.18(m，7H，ph-H)，11.84(s，1H，NH)
????20 ?2.11(s，3H，SCH 3)，2.29(s，6H，ph-CH 3)，2.37(s，3H，ph-CH 3)，3.87(s，2H，CH 2)， 6.93-7.71(m，7H，ph-H)
????21 ?2.11(s，3H，SCH 3)，2.37(s，3H，ph-CH 3)，3.83(s，2H，CH 2)，6.90-7.71(m，9H，ph-H)
????23 ?2.15(s，3H，SCH 3)，2.39(s，3H，phCH 3)，3.84(s，2H，CH 2SCH 3)，7.21-7.71(m，6H，ph-H)， 8.94(s，1H，NH)
????24 ?2.11(s，3H，SCH 3)，2.38(s，3H，phCH 3)，3.82(s，2H，CH 2SCH 3)，7.19-7.70(m，8H，ph-H)
????25 ?2.11(s，3H，SCH 3)，2.38(s，3H，phCH 3)，3.81(s，2H，CH 2SCH 3)，6.96-7.66(m，7H，ph-H)，
????26 ?2.17(s，3H，SCH 3)，2.39(s，3H，ph-CH 3)，3.85(s，2H，CH 2)，7.20-7.72(m，8H，ph-H)，8.89(s，1H，NH)
????27 ?2.24(s，3H，SCH 3)，3.88(s，2H，CH 2)，7.26-9.18(m，6H，ph-H)，11.92(s，1H，NH)
????28 ?2.17(s，3H，SCH 3)，3.83(s，2H，CH 2)，7.26-7.45(m，6H，ph-H)，9.20(s，1H，NH)
????29 ?2.17(s，3H，SCH 3)，3.83(s，2H，CH 2)，7.25-8.19(m，7H，ph-H)，9.36(s，1H，NH)
????30 ?2.14(s，3H，SCH 3)，3.82(s，2H，CH 2SCH 3)，7.25-7.756(m，5H，ph-H)，9.22(s，1H，NH)
????31 ?2.13(s，3H，SCH 3)，3.80(s，2H，CH 2SCH 3)，6.95-7.44(m，6H，ph-H)，8.90(s，1H，NH)
????32 ?2.12(s，3H，SCH 3)，3.81(s，2H，CH 2SCH 3)，6.86-7.44(m，7H，ph-H)，
????33 ?2.25(s，3H，SCH 3)，3.92(s，2H，CH 2SCH 3)，7.26-8.03(m，7H，ph-H)，11.91(s，1H，NH)
????34 ?1.42-1.44(d，3H，CH 3)，2.12(s，3H，SCH 3)，3.72-3.74[q，1H，(CH 3)CHSCH 3]，6.98-8.15(m，7H，ph-H)
????35 ?2.30(s，3H，SCH 3)，3.89(s，2H，CH 2SCH 3)，7.12-9.18(m，7H，ph-H)，11.80(s，1H，NH)
????36 ?2.17(s，3H，SCH 3)，3.84(s，2H，CH 2SCH 3)，7.20-8.22(m，8H，ph-H)，9.00(s，1H，NH)
????37 ?2.18(s，3H，SCH 3)，3.84(s，2H，CH 2SCH 3)，7.09-7.56(m，7H，ph-H)，8.86(s，1H，NH)
????38 ?2.14(s，3H，SCH 3)，3.79(s，2H，CH 2SCH 3)，6.88-7.78(m，7H，ph-H)，8.60(s，1H，NH)
????39 ?2.24(s，3H，SCH 3)，3.90(s，2H，CH 2)，4.04(s，6H，2*OCH 3)，5.65(s，1H，CH)，7.26-7.82(m，4H，ph-H)， ?10.38(s，1H，NH)
????40 ?2.08(s，3H，SCH 3)，2.25(s，3H，ph-CH 3)，3.99(s，2H，CH 2)，4.06(s，6H，2*OCH 3)，5.60(s，1H，＝CH)， ?7.23-7.78(m，4H，ph-H)
????41 ?2.20(s，3H，SCH 3)，3.83(s，2H，CH 2)，4.00(s，6H，2*OCH 3)，5.65(s，1H，＝CH)， ?7.51-7.76(m，4H，ph-H)，9.48(s，1H，NH)
????42 ?2.27(s，3H，SCH 3)，2.42(s，3H，phCH 3)，3.97(s，2H，CH 2SCH 3)，6.59(s，1H，＝CH)，6.96- ?7.66(m，7H，ph-H)，
????43 ?2.26(s，3H，CH 2SCH 3)，2.40(s，3H，phCH 3)，2.67(s，3H，SCH 3)3.95(s，2H，CH 2SCH 3)， ?4.09(s，3H，OCH 3)，6.13(s，1H?，＝CH)，7.22-7.82(m，4H，ph-H)
????44 ?2.17(s，3H，CH 2SCH 3)，2.55(s，3H，SCH 3)，3.80(s，2H，CH 2SCH 3)，3.99(s，3H，OCH 3)， ?6.14(s，1H，＝CH)，7.26-7.82(m，4H，ph-H)，9.06(s，1H，NH)
????45 ?2.16(s，3H，SCH 3)，3.87(s，2H，CH 2SCH 3)，3.96(s，6H，2×OCH 3)，5.64(s，1H，＝CH)， ?7.28-7.48(m，3H，ph-H)
????46 ?1.40-1.44(t，3H，CH 3)，2.19(s，3H，SCH 3)，3.17-3.19(q，2H，SCH 2CH 3)，3.84(s，2H，CH 2SCH 3)，4.01(s，3 ?H，OCH 3)，6.14(s，1H，CH)，7.35-7.83(m，4H，ph-H)，9.52(s，1H，NH)
????47 ?1.40-1.44(t，6H，2×OCH 2CH 3)，2.19(s，3H，SCH 3)，3.83(s，2H，CH 2SCH 3)，4.38-4.40 ?(q，4H，2×OCH 2CH 3)，5.60(s，1H，＝CH)，7.35-7.82(m，4H，ph-H)，9.58(s，1H，NH)
????48 ?1.39-1.44(t，6H，2×OCH 2CH 3)，2.19(s，3H，SCH 3)，2.37(s，3H，phCH 3)，3.86(s，2H，CH 2SCH 3)， ?4.38-4.41(q，4H，2×OCH 2CH 3)，5.58(s，1H，＝CH)，7.21-7.77(m，4H，ph-H)，9.60(s，1H，NH)
????49 ?1.38-1.43(t，6H，2×OCH 2CH 3)，2.17(s，3H，SCH 3)，3.93(s，2H，CH 2SCH 3)，4.36-4.38 ?(q，4H，2×OCH 2CH 3)，5.59(s，1H，＝CH)，7.27-7.45(m，3H，ph-H)
????50 ?2.19(s，3H，SCH 3)，3.83(s，2H，CH 2SCH 3)，3.98(s，6H，2×OCH 3)，5.65(s，1H，＝CH)， ?7.08-7.88(m，4H，ph-H)，9.15(s，1H，NH)
????51 ?2.17(s，3H，SCH 3)，2.44(s，6H，2×CH 3)，3.83(s，2H，CH 2SCH 3)，6.59(s，1H，＝CH)，7.08 ?-7.86(m，4H，ph-H)，9.16(s，1H，NH)
????52 ?1.39-1.43(t，6H，2×OCH 2CH 3)，2.17(s，3H，SCH 3)，3.81(s，2H，CH 2SCH 3)，4.35-4.38 ?(q，4H，2×OCH 2CH 3)，5.60(s，1H，＝CH)，7.08-7.26(m，4H，ph-H)，9.10(s，1H，NH)
????53 ?2.15(s，3H，SCH 3)，2.37(s，3H，phCH 3)，2.44(s，6H，2×CH 3)，3.86(s，2H，CH 2SCH 3)，6.58(s，1H， ?＝CH)，7.27-7.78(m，4H，ph-H)，9.40(s，1H，NH)
????54 ?2.15(s，3H，SCH 3)，2.43(s，6H，2×CH 3)，3.83(s，2H，CH 2SCH 3)，6.59(s，1H，＝CH)，7.34 ?-7.83(m，4H，ph-H)，9.36(s，1H，NH)
????55 ?2.20(s，3H，SCH 3)，3.86(s，2H，CH 2SCH 3)，7.08-8.03(m，9H，ph-H)
????56 ?2.18(s，3H，SCH 3)，3.85(s，2H，CH 2SCH 3)，7.37-7.95(m，9H，ph-H)，10.55(s，1H，NH)
????57 ?2.17(s，3H，CH 2SCH 3)，2.44(s，3H，phCH 3)，3.86(s，2H，CH 2SCH 3)，7.23-7.97(m，9H，ph-H)， ?10.58(s，1H，NH)
????58 ?2.19(s，3H?，SCH 3)，3.86(s，2H，CH 2SCH 3)，7.27-7.62(m，8H，ph-H)，8.65(s，1H，NH)
????59 ?2.17(s，3H，SCH 3)，3.84(s，2H，CH 2SCH 3)，7.36-7.81(m，8H，ph-H)，10.55(s，1H，NH)
????60 ?2.19(s，3H，SCH 3)，3.84(s，2H，CH 2SCH 3)，7.35-7.85(m，8H，ph-H)
????61 ?2.18(s，3H，SCH 3)，3.84(s，2H，CH 2SCH 3)，7.37-7.90(m，8H，ph-H)
????62 ?2.18(s，3H，SCH 3)，3.84(s，2H，CH 2SCH 3)，7.18-7.82(m，8H，ph-H)
????63 ?2.08(s，3H，SCH 3)，2.39(s，3H，phCH 3)，3.70(s，2H，CH 2SCH 3)，4.13(s，2H，COCH 2)， ?7.21-7.69(m，9H，ph-H)，9.44(s，1H，NH)
????64 ?2.15(s，3H，SCH 3)，2.38(s，3H，phCH 3)，3.80(s，2H，CH 2SCH 3)，7.14-7.76(m，7H，ph-H)， ?10.22(s，1H，NH)
????65 ?2.16(s，3H，SCH 3)，2.44(s，3H，phCH 3)，3.84(s，2H，CH 2SCH 3)，7.20-7.90(m，8H，ph-H)， ?9.04(s，1H，NH)
????66 ?2.16(s，3H，SCH 3)，2.44(s，3H，phCH 3)，3.84(s，2H，CH 2SCH 3)，7.06-7.95(m，8H，ph-H)， ?10.60(s，1H，NH)
????67 ?2.12(s，3H，SCH 3)，2.26(s，3H，phCH 3)，3.98(s，2H，CH 2SCH 3)，7.08-8.20(m，7H，ph-H)
????68 ?2.18(s，3H，SCH 3)，3.86(s，2H，CH 2SCH 3)，7.12-7.86(m，8H，ph-H)
????69 ?2.17(s，3H，SCH 3)，2.40(s，3H，phCH 3)，3.87(s，2H，CH 2SCH 3)，7.15-7.76(m，9H，ph-H)
????70 ?2.15(s，3H，SCH 3)，3.85(s，2H，CH 2SCH 3)，7.16-7.80(m，9H，ph-H)
The present invention also provides the biological activity that contains the alkyl sulfanyl hydrazone derivative of general formula (I) expression, and not only part has fungicidal activity, and part also has weeding activity and insecticidal activity.For example compound 53,54 grades are to paddy rice rice blast, compound 2,51,53,54,61,64,65 grades are to the rape sclerotium, compound 54,61,65 grades are to botrytis cinerea pers, and compound 65 grades are to fusarium graminearum, compound 12,13,40 grades have good fungicidal activity to wheat powdery mildew, and its inhibiting rate reaches more than 95%.When using dosage was 1500 g a.i/ha, soil treatment was the A level to the preventive effect of piemarker, lamb's-quarters before compound 36 seedlings such as grade.During 500ppm, compound 13,27,29,56,57,58 compounds such as grade to the preventive effect of aphid more than 90%.
Four, embodiment: the invention will be further described to enumerate following examples, but do not limit scope of the present invention.
The preparation of embodiment 1:1-(4-fluorophenyl)-2-methylthio group ethyl ketone-4-nitro phenylhydrazone (compound 36 in the table 1)
In the 50ml three-necked bottle, add dehydrated alcohol (20ml), paranitrophenylhydrazine (0.77g) and a small amount of Glacial acetic acid, stir half an hour under the room temperature, slowly drip 1-(4-fluorophenyl)-2-methylthio group ethyl ketone (1.00g) then, be warming up to backflow, and kept back flow reaction 2 hours.The yellow velvet-like solids of separating out is filtered in cooling, dries to such an extent that title compound 1.21 restrains yield 71%.Fusing point 186.3-186.5 ℃. 1H?NMR(CDCl 3，ppm)：2.17(s，3H，SCH 3)，3.84(s，2H，CH 2SCH 3)，7.20-8.22(m，8H，ph-H)，9.00(s，1H，NH)。
The preparation of embodiment 2:1-(4-aminomethyl phenyl)-2-methylthio group ethyl ketone-benzoyl hydrazone (compound 57 in the table 1)
In the 25ml round-bottomed flask, under room temperature, add dehydrated alcohol (10ml), benzoyl calf (1.5g), 1-(4-aminomethyl phenyl)-2-methylthio group ethyl ketone (2.00g) and a small amount of Glacial acetic acid, stir and slowly be warming up to backflow down, and kept back flow reaction 7 hours.The yellow solid of separating out is filtered in cooling, uses absolute ethanol washing, gets white title compound 1.43 grams, yield 43%.Fusing point 138.7-139.5 ℃. 1H?NMR(CDCl 3，ppm)：2.17(s，3H，CH 2SCH 3)，2.44(s，3H，phCH 3)，3.86(s，2H，CH 2SCH 3)，7.23-7.97(m，9H，ph-H)，10.58(s，1H，NH)。
Embodiment 3:1-(4-aminomethyl phenyl)-2-methylthio group ethyl ketone 4, the preparation of 6-dimethyl-2-pyrimidine hydrazone (compound 53 in the table 1)
In the 25ml round-bottomed flask, under room temperature, add dehydrated alcohol (5ml), 4,6-dimethyl-2-pyrimidine hydrazine (0.60g), 1-(4-aminomethyl phenyl)-2-methylthio group ethyl ketone (0.78g) and a small amount of Glacial acetic acid, stir, slowly be warming up to backflow then, and kept back flow reaction 6 hours.Get brown liquid behind the precipitation, add a small amount of ether, freezing, separate out yellow solid, filter, dry to such an extent that title compound 0.67 restrains yield 51%.Fusing point 97.9-99.0 ℃. 1H?NMR(CDCl 3，ppm)：2.15(s，3H，SCH 3)，2.37(s，3H，phCH 3)，2.44(s，6H，2×CH 3)，3.86(s，2H，CH 2SCH 3)，6.58(s，1H，＝CH)，7.27-7.78(m，4H，ph-H)，9.40(s，1H，NH)。
The preparation of embodiment 4:1-(4-aminomethyl phenyl)-2-methylthio group ethyl ketone-benzothiazole hydrazone (compound 69 in the table 1)
In the 25ml round-bottomed flask, under room temperature, add dehydrated alcohol (2ml), benzothiazole hydrazine (0.50g), 1-(4-aminomethyl phenyl)-2-methylthio group ethyl ketone (0.54g) and a small amount of Glacial acetic acid, stir and slowly be warming up to backflow down, and kept back flow reaction 6 hours.The yellow solid of separating out is filtered in cooling, uses absolute ethanol washing, gets canescence title compound 0.93 gram, yield 94%.Fusing point 114.6 (decomposition). 1H?NMR(CDCl 3，ppm)：2.15(s，3H，SCH 3)，3.85(s，2H，CH 2SCH 3)，7.16-7.80(m，9H，ph-H)。
Embodiment 5: the fungicidal activity shaker test
Select Pyricularia oryzae (Pyricularia oryzae), Rhizoctonia solani Kuhn (Rhizoctonia solani), botrytis cinerea pers (Botrytis cinerea), Sclerotinia sclerotiorum (Sclerotonia sclerotiorum), fusarium graminearum (Gibberellazeae), wheat powdery mildew etc. are the test target.Above bacterial classification all is kept in the refrigerator (4-8 ℃), is inoculated in the culture dish from the test tube slant in 2-3 days before the test, cultivates to be for experiment under optimal temperature.Experiment is potato agar substratum (PDA) with substratum.Accurately take by weighing an amount of new compound to be measured before the experiment, with suitable solvent dissolving and adding small amounts of emulsifiers, be diluted to finite concentration earlier with clear water.Adopt the activity of excised leaf culture method and pot-culture method test new compound to Rhizoctonia solani Kuhn, botrytis cinerea pers, Sclerotinia sclerotiorum and fusarium graminearum, concentration is 500ppm.Adopt the activity of pot-culture method and toxic medium therapy test new compound to Pyricularia oryzae, concentration is respectively 500ppm and 25ppm.Handle incidence and the mycelial growth situation of back routine observation record blade, plant,, calculate preventive effect and inhibiting rate according to disease index and hyphal diameter.The fungicidal activity grade standard is divided: A level-preventive effect (inhibiting rate) 〉=95%, B level-70%≤preventive effect (inhibiting rate)＜95%, C level-50%≤preventive effect (inhibiting rate)＜70%, D level-preventive effect (inhibiting rate)＜50%.
Test finds that compound 53,54 grades are to paddy rice rice blast, compound 2,51,53,54,61,64,65 grades are to the rape sclerotium, compound 54,61,65 grades are to botrytis cinerea pers, and compound 65 grades are to fusarium graminearum, compound 12, to having good fungicidal activity, its inhibiting rate reaches more than 95% 13,40 grades to wheat powdery mildew; Compound 51,64 grades are to the paddy rice rice blast, compound 3,27,30,44 grades are to the rape sclerotium, compound 5,6,7,21 grades are to botrytis cinerea pers, compound 27,61 grades are to fusarium graminearum, compound 5,7,17,20,21, to having good fungicidal activity, its inhibiting rate reaches 70%95% to 41,44 grades to wheat powdery mildew.
Embodiment 6: the weeding activity shaker test
Select monocotyledon weed lady's-grass Digitaria sanguinalis (H.B.K) Henrard for use, barnyard grass grass Echinochloacrus-galli L., Herba Setariae Viridis Setaria viridis (L.) Beauv. and broadleaf weed piemarker Abutilon theophrasti Medic, lamb's-quarters Chenopodium album L., Amaranthus retroflexus Amaranthus retroflexus L., Tender Catchweed Bedstraw Herb Galium aparine L., purslane Portulaca oleracea L., volume stem knotweed Chenopodium convulvolus L., 3 kinds among the pale persicaria Polygonumlapothifolium L. are the screening target.Quantitatively the dress soil pressure is flat in the plastic tub alms bowl of sectional area 64cm2, place Stainless steel basin, choose full seed, seed of the same size, divide single, double cotyledon plant to divide the alms bowl sowing, respectively account for 1/3 of alms bowl area, cover the thick fine earth of 1cm, add water to upper layer of soil from plastic tub alms bowl bottom and soak into, place hot-house culture, material to be tried grows to required leaf age to be handled; Soil treatment before examination material sowing the carrying out next day seedling, unifacial leaf examination material grow to 1 heart stage of 1 leaf, dicotyledonous examination material grow to 2 leaf periods and carry out seedling after cauline leaf handle; Accurately take by weighing sample, add a little emulsifying agent, add the distilled water of 50mL low-grade fever again with suitable solvent dissolving back; Pipetting quantitatively by dosage is set that soup carries out cauline leaf spraying and the soil spraying is handled, is contrast with spray solvent and clear water respectively; Handle the examination material and place hot-house culture; Handle 15 back range estimation overground part growing states, calculate growth inhibition ratio.According to investigation result, calculate the preventive effect of each compound as follows to weeds:
Preventive effect (%)=100* (contrast plant height-processing plant height)/contrast plant height
Carry out the weeding activity classification according to preventive effect: the A level: preventive effect＞90%; B level: preventive effect 75～90%; C level: preventive effect 50～75%; D level: preventive effect 25～50%; E level: preventive effect＜25%.
Test-results shows that the compound of general formula (I) expression has good result to broadleaf weed, when being 2250g a.i./ha as using dosage, and soil treatment before compound 55,68 seedlings such as grade, compound 37,54,60, the cauline leaf processing is the A level to the preventive effect of piemarker behind 62,63,65 seedlings such as grade; Soil treatment before the compound 34,36,55,68 seedlings such as grade, compound 37,62, the cauline leaf processing is the A level to the preventive effect of lamb's-quarters behind 63 seedlings such as grade, the cauline leaf processing is the B level to the preventive effect of lamb's-quarters behind compound 65 seedlings such as grade; Soil treatment before the compound 34,36,55,68 seedlings such as grade, the cauline leaf processing is the A level to the preventive effect of purslane behind compound 62,63 seedlings such as grade.When using dosage was 1500g a.i./ha, soil treatment was the A level to the preventive effect of piemarker, lamb's-quarters before compound 36 seedlings such as grade.When using dosage was 750g a.i./ha, soil treatment was the A level to the preventive effect of piemarker before compound 36 seedlings such as grade.
Embodiment 7: to the control test of aphid
Accurately take by weighing an amount of new compound to be measured, with suitable solvent dissolving and adding small amounts of emulsifiers, be diluted to 500ppm with clear water more earlier.Adopt pickling process that the standard aphid (Aphisfabae) of indoor feeding is handled, handle the survival condition of back routine observation and record examination worm, calculate mortality ratio.The insecticidal activity grade standard: mortality ratio is the A level more than or equal to 90%; Mortality ratio is the B level between 70～90%; Mortality ratio is the C level between 50～70%; Mortality ratio is the D level less than 50%.
Test-results shows that the compound of general formula (I) expression has good preventive effect to aphid, and as compound 13,27,29,56,57,58 compounds such as grade have A level activity.Concrete test-results sees the following form:
Compound number Aphid
Mortality ratio (%) The virulence rank
????13 ????100 ????A
????27 ????100 ????A
????29 ????100 ????A
????56 ????90.48 ????A
????57 ????97.30 ????A
????58 ????92.86 ????A

Claims (6)

  1. What 1, have desinsection, sterilization, a weeding activity contains the alkyl sulfanyl hydrazone derivative, it is characterized in that the having general formula structure of (I),
    Figure A0213961200021
    X in the general formula (I), they can be identical or inequality, is hydrogen atom, halogen atom, cyano group, nitro, C1-6 alkyl, halo C1-6 alkyl, C1-6 alkoxyl group, cyano group C1-6 alkyl, C3-6 cycloalkyl, C2-6 alkenyl, C2-6 alkynyl group; M is the integer between zero or the 1-5; R1 is a hydrogen atom, C1-6 alkyl, halo C1-6 alkyl, C1-6 alkoxyl group, C1-6 alkylthio; R2 is a hydrogen atom, C1-6 alkyl, halo C1-6 alkyl; R3 is a hydrogen atom, C1-6 alkyl-carbonyl, C1-6 alkoxy carbonyl, halo C1-6 alkyl-carbonyl, C1-6 alkyl sulfide acyl group, C1-6 alkoxyl group sulfonyl, halo C1-6 alkyl sulfide acyl group; Q is following group: Y, they can be identical or inequality, is hydrogen atom, cyano group, nitro, halogen atom, C1-6 alkyl, halo C1-6 alkyl, C1-6 alkoxyl group, cyano group C1-6 alkyl, C3-6 cycloalkyl, C2-6 alkenyl, C2-6 alkynyl group; S is the integer between zero or the 1-5; T is the integer between zero or the 1-4; R 4And R 5, can be identical or different, be hydrogen atom, halogen atom, C1-6 alkyl, halo C1-6 alkyl, C1-6 alkoxyl group, halo C1-6 alkoxyl group, C1-6 alkylthio, C1-6 alkylamino radical, the C3-6 cycloalkyl, C2-6 alkenyl, C2-6 alkynyl group, C3-6 alkenyloxy, C3-6 chain oxy-acetylene; Z is nitrogen-atoms or CH.
  2. 2, according to claim 1 have desinsection, sterilization, a weeding activity contain the alkyl sulfanyl hydrazone derivative, it is characterized in that: the definition of Q is the same; X, they can be identical or inequality, is hydrogen atom, halogen atom, cyano group, nitro, C1-6 alkyl, halo C1-6 alkyl, C1-6 alkoxyl group; Y, they can be identical or inequality, is hydrogen atom, cyano group, nitro, halogen atom, C1-6 alkyl, halo C1-6 alkyl, C1-6 alkoxyl group; M is the integer between zero or the 1-5; S is the integer between zero or the 1-5; T is the integer between zero or the 1-4; R 1Be hydrogen atom, methyl, ethyl, n-propyl, sec.-propyl, methylthio group; R 2Be hydrogen atom, methyl, ethyl, n-propyl, sec.-propyl; R 3Be hydrogen atom, C1-6 alkyl-carbonyl, C1-6 alkoxy carbonyl; R 4And R 5, can be identical or different, be hydrogen atom, halogen atom, methyl, difluoromethyl, trifluoromethyl, methoxyl group, oxyethyl group, trifluoromethoxy, difluoro-methoxy, methylthio group, ethylmercapto group, methylamino, cyclopropane base, propenyloxy group, third alkynyloxy group; Z is nitrogen-atoms or CH.
  3. 3, according to claim 1 and 2 have desinsection, sterilization, a weeding activity contain the alkyl sulfanyl hydrazone derivative, it is characterized in that preferred compound is:
    1-(4-chloro-phenyl-)-2-methylthio group ethyl ketone-4-nitro phenylhydrazone
    1-(4-bromophenyl)-2-methylthio group ethyl ketone-2,4-dimethyl phenylhydrazone
    1-(4-bromophenyl)-2-methylthio group ethyl ketone-2,4 dichloro benzene hydrazone
    1-(2,4 dichloro benzene base)-2-methylthio group ethyl ketone-2, the 4-dinitrophenylhydrazone
    1-(2,4 dichloro benzene base)-2-methylthio group ethyl ketone-4-nitro phenylhydrazone
    1-(3-bromo-4-fluorophenyl)-2-methylthio group ethyl ketone-4-nitro phenylhydrazone
    1-(4-fluorophenyl)-2-methylthio group ethyl ketone-4-nitro phenylhydrazone
    1-(4-fluorophenyl)-2-methylthio group ethyl ketone-2,4 dichloro benzene hydrazone
    1-(4-aminomethyl phenyl)-2-methylthio group ethyl ketone-4,6-dimethoxy-2-pyrimidine hydrazone
    1-(4-fluorophenyl)-2-methylthio group ethyl ketone-4,6-dimethyl-2-pyrimidine hydrazone
    1-(4-aminomethyl phenyl)-2-methylthio group ethyl ketone-4,6-dimethyl-2-pyrimidine hydrazone
    1-(4-chloro-phenyl-)-2-methylthio group ethyl ketone-4,6-dimethyl-2-pyrimidine hydrazone
    1-(4-fluorophenyl)-2-methylthio group ethyl ketone-benzoyl hydrazone
    1-(4-chloro-phenyl-)-2-methylthio group ethyl ketone-benzoyl hydrazone
    1-(4-aminomethyl phenyl)-2-methylthio group ethyl ketone-benzoyl hydrazone
    1-(2,4 dichloro benzene base)-2-methylthio group ethyl ketone-benzoyl hydrazone
    1-(4-chloro-phenyl-)-2-methylthio group ethyl ketone-3-chlorobenzoyl hydrazone
    1-(4-chloro-phenyl-)-2-methylthio group ethyl ketone-4-chlorobenzoyl hydrazone
    1-(4-fluorophenyl)-2-methylthio group ethyl ketone-4-bromobenzene formyl hydrazone
    1-(4-aminomethyl phenyl)-2-methylthio group ethyl ketone-4-toluyl hydrazone
    1-(4-aminomethyl phenyl)-2-methylthio group ethyl ketone-2,4 dichloro benzene formyl hydrazone
    1-(4-aminomethyl phenyl)-2-methylthio group ethyl ketone-4-chlorobenzoyl hydrazone
    1-(4-fluorophenyl)-2-methylthio group ethyl ketone-benzothiazole hydrazone
  4. 4, according to claim 1 or the 2 or 3 described preparation methods that contain the alkyl sulfanyl hydrazone derivative with desinsection, sterilization, weeding activity, it is characterized in that reaction pressure is a normal pressure, temperature of reaction is-20 ℃～180 ℃, preferred temperature is the reflux temperature of room temperature to selected solvent, and in solvent, adopt the compound reaction 0.1～10 hour of the compound of general formula (II) and general formula (III) and get, the preferred reaction time is 1～6 hour, and reaction equation is as follows: R wherein 1, R 2, R 3, Q, R 4, R 5, X, Y, m, s, t as above defines.
  5. 5, the preparation method who contains the alkyl sulfanyl hydrazone derivative with desinsection, sterilization, weeding activity according to claim 4, it is characterized in that the solvent that reacts selected is the C1-6 alkyl alcohol, 1,4-dioxane, tetrahydrofuran (THF), acetone, dimethyl sulfoxide (DMSO), N, dinethylformamide, acetate, water; The C1-6 alkyl alcohol is preferably methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, sec-butyl alcohol, the trimethyl carbinol, Pentyl alcohol; These solvents can use or mix use separately, the mixture of mixture, anhydrous methanol and the acetate of preferred dehydrated alcohol and acetate when mixing use, and the ratio of mixed solvent can be any ratio, acetate and methyl alcohol or the preferred 0.5-5 of alcoholic acid volume ratio: 100.
  6. 6, according to claim 1 or the 2 or 3 described alkyl sulfanyl hydrazone derivatives that contain, it is characterized in that having desinsection, sterilization, weeding biological activity, can use as effective constituent separately, also can mix as sterilant, weedicide or sterilant and on agricultural or gardening, use with other agricultural chemicals.
CN 02139612 2002-09-13 2002-09-13 Derivative containing alkyl sulfanyl hydrazone having insecticidal, antibacterial and herbicidal activity and its preparation method Expired - Fee Related CN1199939C (en)

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AU2003297071A AU2003297071A1 (en) 2002-09-13 2003-06-27 Alkyl-s-alkyl hydrazone compounds with insecticide, fungicide, herbicide activities and their preparation
PCT/CN2003/000503 WO2004024680A1 (en) 2002-09-13 2003-06-27 Alkyl-s-alkyl hydrazone compounds with insecticide, fungicide, herbicide activities and their preparation

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100400505C (en) * 2006-05-26 2008-07-09 上海大学 5,5,5, trifluoro methyl-4-(2-phenylhydrazone) menthyl valerate, and its synthesizing method
CN111848441A (en) * 2020-07-28 2020-10-30 朱翠萍 N-substituted benzoyl hydrazone compound and preparation method and application thereof
CN114195707A (en) * 2021-12-17 2022-03-18 西北农林科技大学 High-efficiency broad-spectrum plant antibacterial agent BZ

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PT2595965T (en) 2010-07-20 2016-08-22 Vestaron Corp Insecticidal triazines and pyrimidines

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3859441A (en) * 1970-11-27 1975-01-07 Upjohn Co Anti-arthropodal cyclic dithioketals of glyoxyloyl halide 1-phenylhydrazones
AU660874B2 (en) * 1993-04-30 1995-07-06 Nihon Nohyaku Co., Ltd. Benzylhydrazone derivatives, a process for production thereof, and agricultural and horticultural fungicides
US5556885A (en) * 1994-10-27 1996-09-17 American Cyanamid Company N-aryl- and N-heteroarylhydrazones of substituted thioacids and the s-oxides thereof as insecticidal and acaricidal agents

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100400505C (en) * 2006-05-26 2008-07-09 上海大学 5,5,5, trifluoro methyl-4-(2-phenylhydrazone) menthyl valerate, and its synthesizing method
CN111848441A (en) * 2020-07-28 2020-10-30 朱翠萍 N-substituted benzoyl hydrazone compound and preparation method and application thereof
CN111848441B (en) * 2020-07-28 2023-02-17 山东中新科农生物科技有限公司 N-substituted benzoyl hydrazone compound and preparation method and application thereof
CN114195707A (en) * 2021-12-17 2022-03-18 西北农林科技大学 High-efficiency broad-spectrum plant antibacterial agent BZ

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