[go: up one dir, main page]

CN1546462A - Insecticidal antibacterial sulphur , oxygen and oxime-containing ether compounds - Google Patents

Insecticidal antibacterial sulphur , oxygen and oxime-containing ether compounds Download PDF

Info

Publication number
CN1546462A
CN1546462A CNA2003101106471A CN200310110647A CN1546462A CN 1546462 A CN1546462 A CN 1546462A CN A2003101106471 A CNA2003101106471 A CN A2003101106471A CN 200310110647 A CN200310110647 A CN 200310110647A CN 1546462 A CN1546462 A CN 1546462A
Authority
CN
China
Prior art keywords
methyl
oxime
group
formula
phenyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CNA2003101106471A
Other languages
Chinese (zh)
Other versions
CN100579956C (en
Inventor
柳爱平
王晓光
欧晓明
刘兴平
黄明智
王永江
裴晖
陈灿
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hunan Research Institute of Chemical Industry
Original Assignee
Hunan Research Institute of Chemical Industry
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hunan Research Institute of Chemical Industry filed Critical Hunan Research Institute of Chemical Industry
Priority to CN 200310110647 priority Critical patent/CN100579956C/en
Priority to PCT/CN2004/001282 priority patent/WO2005056518A1/en
Publication of CN1546462A publication Critical patent/CN1546462A/en
Application granted granted Critical
Publication of CN100579956C publication Critical patent/CN100579956C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/53—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C317/28—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to acyclic carbon atoms of the carbon skeleton
    • 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
    • C07C323/47—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 oxygen atoms

Landscapes

  • 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a series of oxime ether compounds containing sulfur and oxygen shown by general formula (I), wherein R, R1, X, n, Ar and Ft are defined in the description. The compound has very good biological activity, thus can carry out quick-speed and continuous disinsection without any harm to the crops.

Description

Desinsection, germ-resistant sulfur-bearing, oxime-containing ether compound
Technical field
The present invention relates to have desinsection, the sulfur-bearing of fungicidal activity, oxime-containing ether compound and preparation method.
Background technology
Chinese patent CN 1288002 discloses a part of biocidal sulfur-bearing, oxygen oxime ether compound and intermediate ketone oxime compounds.
Summary of the invention
In order to obtain just can control under more low dose of the active compound of various pests and pathogenic bacteria, the present invention has carried out more extensive research to sulfur-bearing, oxime-containing ether compound, has synthesized sulfur-bearing, oxime-containing ether compound with general formula (I).Find that a series of compounds have broad spectrum of activity, these compounds can be used to prevent and treat insect and pathogenic bacteria on the various crop, and the compound that has still can obtain good effect under very low dosage.
The present invention represents sulfur-bearing, oxime-containing ether compound with general formula (I):
In the general formula (I):
The I.Ar representative
(a) (C 6-C 12The heteroaryl of)-aryl or 10 carbon atoms of band as many as;
(b) as determined implication in (I.a), be selected from case of necessity following in 0 to 5 identical or different substituting group replace:
Hydrogen, halogen, alkyl, alkoxyl group, alkylthio, carbalkoxy, haloalkyl, halogenated alkoxy, halogenated alkylthio, halo alkoxy carbonyl;
II.R represents alkyl or haloalkyl;
III.R 1Represent hydrogen, halogen, alkyl or haloalkyl;
IV.F tRepresentative
(a) 0 to 5 identical or different substituting group in following: hydrogen, halogen, alkyl, alkoxyl group, haloalkyl, halogenated alkoxy, carbalkoxy, nitro, (C 6-C 12The heteroaryl of)-aryl or 10 carbon atoms of band as many as, (C 6-C 12The heteroaryl oxygen base of)-aryloxy or 10 carbon atoms of band as many as, (C 6-C 12The heteroaryl methyl of)-arylmethyl or 10 carbon atoms of band as many as, (C 6-C 12The heteroaryl amido of)-arylamine group or 10 carbon atoms of band as many as;
(b) as determined implication in (IV.a), be selected from case of necessity following in 0 to 5 identical or different substituting group replace:
Hydrogen, halogen, alkyl, alkoxyl group, haloalkyl, halogenated alkoxy, aryl, heteroaryl;
V.t represents 0 to 5 integer;
VI.X represents O, S, SO or SO 2
VII.n represents 0 or 1.
In general formula (I), work as F t=3-phenoxy group, R=methyl, R 1=hydrogen or methyl, X=S, during n=1, Ar ≠ 4-chloro-phenyl-.
In the definition of the general formula that provides above (I) compound, no matter the separately use or be used in the compound word the following substituting group of general proxy of used term:
Alkyl: refer to have the straight or branched alkyl of 1-6 carbon atom, for example methyl, ethyl, n-propyl, sec.-propyl or different butyl, amyl group, hexyl isomer.
Halogen: refer to fluorine, chlorine, bromine and iodine.
Haloalkyl: refer to have the straight or branched alkyl of 1-6 carbon atom, the hydrogen atom on these alkyl can partly or entirely be replaced by halogen atom, for example, and C 1Haloalkyl such as chloromethyl, brooethyl, methyl fluoride, dichloromethyl, two brooethyls, difluoromethyl, trichloromethyl, trisbromomethyl, trifluoromethyl, chlorine methyl fluoride, chlorine brooethyl, Halothane methyl.
Alkoxyl group: refer to have the straight or branched alkoxyl group of 1-6 carbon atom, be connected on the structure through the Sauerstoffatom key.
Alkylthio: refer to have the straight or branched alkylthio of 1-6 carbon atom, be connected on the structure through the sulphur atom key.
Halogenated alkoxy: refer to have the straight or branched alkoxyl group of 1-6 carbon atom, the hydrogen atom on these alkoxyl groups can partly or entirely be replaced by halogen atom, for example, and C 1Halogenated alkoxy such as chlorine methoxyl group, bromine methoxyl group, fluorine methoxyl group, dichloro methoxyl group, dibromo methoxyl group, difluoro-methoxy, trichlorine methoxyl group, tribromo methoxyl group, trifluoromethoxy, chlorine fluorine methoxyl group, chlorine bromine methoxyl group, chlorine fluorine bromine methoxyl group.
Aryl: the naphthyl that refers to have the phenyl of 6 carbon atoms and have 12 carbon atoms, xenyl.
Heteroaryl: refer to have one or more heteroatomic 5 yuan of rings, 6 yuan of rings, 5 yuan of rings of benzo or 6 yuan of rings of benzo.For example thienyl, benzothienyl, furyl, benzofuryl, pyrryl, indyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, oxazolyl, isoxazolyl, thiazolyl and isothiazolyl.
Group shown in Ar is preferably as follows in general formula (1):
Figure A20031011064700071
Shown in above-mentioned in the group:
R p 1Be identical or different, and represent hydrogen, halogen, alkyl, alkoxyl group, alkylthio, alkoxy carbonyl, haloalkyl, halogenated alkoxy, halogenated alkylthio, halo alkoxy carbonyl;
P is one 0 to 5 a integer;
Z is O, S or NR 2, R 2Be hydrogen, (C 1-C 4)-alkyl, (C 6-C 12)-aryl, the heteroaryl of 10 carbon atoms of band as many as.
Group shown in Ar is preferably as follows especially in general formula (I):
Shown in above-mentioned in the group:
R 1 1And R 2 1Be identical or different, and represent hydrogen, halogen, alkyl, haloalkyl, alkoxyl group, halogenated alkoxy.
Preferred compound is following general formula (I) compound, wherein:
Ar is selected from a group as follows:
R is selected from methyl, trifluoromethyl;
R 1Be selected from methyl, trifluoromethyl;
F tBe selected from hydrogen, methyl, trifluoromethyl, phenoxy group, pyridyloxy, phenyl, 4-fluorophenyl oxygen base, 4-fluoro-3-phenoxy group;
T represents the integer of 1-5;
N is selected from 0,1;
X is selected from sulphur or oxygen.
Particularly preferred compound is following general formula (I) compound, wherein:
Ar is selected from a group as follows:
R 1 1And R 2 1Be identical or different, and represent hydrogen, halogen, alkyl, haloalkyl, alkoxyl group, halogenated alkoxy;
The R represent methylidene;
R 1Represent methylidene;
F tRepresent the 3-phenoxy group, 2-methyl-3-phenyl or 3-phenoxy group-4-fluorine;
N represents 0 or 1;
X represents sulphur or oxygen.
Compound shown in the formula (I) can occur with Z formula and two kinds of geometrical isomer forms of E formula, and the Z formula is that oxime-oxygen and Ar are in the two key homonymies of C=N, and the E formula is that oxime-oxygen and Ar are in the two key heteropleurals of C=N,
Z formula E formula
In addition, the compound shown in the general formula (I), as have one or more unsymmetrical carbons, it can be a racemic modification, diastereomer or pure optical isomer;
Compound shown in the general formula (I) not only relates to pure isomer, also relates to various mixture of isomers.
Particularly preferably be following compound:
1-(3-fluoro-4-aminomethyl phenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone;
1-(3-fluoro-4-chloro-phenyl-)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone;
1-(4-trifluoromethyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone;
1-(4-fluorophenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone;
1-(4-p-methoxy-phenyl)-2-methoxyl group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone;
1-(4-fluorophenyl)-2-methylthio group-O-[(3-phenoxy phenyl) methyl] oxime-1-acetone
1-phenyl-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone;
1-(4-chloro-phenyl-)-1-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ketone;
1-(2-naphthyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone;
1-(3-bromo-4-aminomethyl phenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone;
1-(3-fluoro-4-bromophenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone;
1-(3-chloro-4-aminomethyl phenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone;
1-(3-chloro-4-fluorophenyl)-2-methylthio group-O-[(2-methyl-xenyl-3-yl) methyl] oxime-1-ethyl ketone;
1-(4-phenelyl)-2-methoxyl group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone;
1-(3, the 4-dichlorophenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone;
1-(3, the 4-3,5-dimethylphenyl)-2-methoxyl group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone;
1-(2, the 4-3,5-dimethylphenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone;
1-(3-fluoro-4-aminomethyl phenyl)-2-methylthio group-O-[(3-phenoxy phenyl) methyl] oxime-1-ethyl ketone;
1-(4-trifluoromethyl)-2-methylthio group-O-[(3-phenoxy phenyl) methyl] oxime-1-ethyl ketone;
1-(4-Trifluoromethoxyphen-l)-2-methylthio group-O-[(3-phenoxy phenyl) methyl] oxime-1-ethyl ketone;
1-(4-Trifluoromethoxyphen-l)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone;
1-(3-Trifluoromethoxyphen-l)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone;
1-(4-ethoxyl phenenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone;
1-(4-chloro-phenyl-)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone;
1-(4-bromophenyl)-2-methylthio group-O-[(3-phenoxy phenyl) methyl] oxime-1-acetone;
1-(4-phenelyl)-2-methylthio group-O-[(3-phenoxy phenyl) methyl] oxime-1-acetone;
The 1-4-phenelyl)-and 2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-acetone;
The present invention also provides the sulfur-bearing shown in the general formula (I), oxygen, oxime ether compound preparation method, substituting group wherein except that specifying all as preceding qualification.
The preparation method of formula (I) compound is:
A) compound shown in compound shown in the employing formula (II) and the formula (III)
At an appropriate base such as alkali metal hydroxide, alkaline carbonate, alkali metal alcoholates, basic metal, alkalimetal hydride, pyridine or tertiary amine exist down, adding suitable solvent, is to be selected from the following solvents one or both as suitable solvent: water, tetrahydrofuran (THF), toluene, benzene, acetonitrile, dimethyl sulfoxide (DMSO), add phase-transfer catalyst again, as tetrabutylammonium iodide, Tetrabutyl amonium bromide, tetraethylammonium bromide or hexaoxacyclooctadecane-6-6, in normal pressure, reaction is 1-10 hour and get under the 0-120 ℃ of condition, in formula (II) and the formula (III), and Ar, R, R 1, n, X and F tAs mentioned above, L represents a leavings group, as chlorine, and bromine; Or
B) with the compound shown in formula (IV) at an appropriate base such as sodium hydroxide, triethylamine or yellow soda ash exist down with the compound shown in the formula V or their reactant salt and get,
Figure A20031011064700092
In formula (IV) and the formula V, Ar, R, R 1, n, X and F tAs mentioned above; Or
C) with the compound shown in compound shown in formula (II) and the formula (VI)
In the presence of an appropriate base such as sodium hydroxide or potassium hydroxide, add suitable solvent, as water and toluene mixed solvent, in normal pressure, reaction is 3-10 hour and get under the 60-100 ℃ of condition.In formula (II) and the formula (VI), Ar, R, R 1, n, X and F tAs mentioned above, X represents a leavings group, as chlorine, and bromine.
The preparation method of formula provided by the invention (II) compound:
A) with a compound shown in the formula (IV)
Figure A20031011064700102
With hydroxylamine hydrochloride or hydroxylamine sulfate, at an appropriate base such as alkali metal hydroxide, alkaline carbonate, alkali metal hydrocarbonate, pyridine or triethylamine exist down, in a suitable solvent such as water and/or alcohol, in normal pressure, 0-100 ℃ of reaction 1-10 hour and get, the middle Ar of formula (IV) and formula (II), R, R 1, n, X are as mentioned above; Or
B) with reference to Brouwer W.G et al.Eur.Pat.Appl.EP 104940,1984.Synthesize by following formula.
The invention provides the preparation method of formula (IV) compound:
A) work as n=1, during X=S, with the compound shown in the formula (VII)
With the sodium salt of mercaptan at a suitable solvent such as a water, in the ethanol,, 40-100 ℃, reacted 1-10 hour and get Ar in formula (VII) and the formula (IV), R in normal pressure 1, n as mentioned above, L represents a leavings group, as chlorine, bromine;
B) work as n=1, during X=O, with reference to Pratt and Robinson, J.Chem.Soc., 1923,748.Synthesize by following formula.
Ar as mentioned above in the formula.
The invention provides the preparation method of formula (VII) compound,, adopt corresponding synthetic method according to the difference of Ar:
A) n=1, when Ar in the presence of catalyzer such as aluminum chloride, can with carboxylic acid halides such as chloroacetyl chloride, the 2-chlorpromazine chloride carries out Fu-Ke reaction, then utilizes Fu-described compound of Ke reaction synthesis type (VII).
B) n=1, when Ar in the presence of catalyzer such as aluminum chloride, can not carry out Fu-Ke reaction with carboxylic acid halides, then with reference to Liu Shudong, Liu Aiping, the hair light of spring etc., chemical reagent, Vol.24 No.1,2002.It is synthetic to press following formula.
General formula of the present invention (I) sulfur-bearing, oxime-containing ether compound can effectively be prevented and treated and grow or insect and the pathogenic bacteria on the harvesting crops.
Usually working concentration is general formula (I) sulfur-bearing, the oxime-containing ether compound of 100ppm to 10000ppm, it is dispersed in water or other liquid vehicle, impose in the soil of plant, crop or plant growth, can prevent effectively that crop from suffering the infringement of insect, pathogenic bacteria.
General formula of the present invention (I) sulfur-bearing, oxime-containing ether compound impose in the soil of plant, crop or plant growth to the consumption of about 4.000kg/ha when being 0.060kg/ha with the effective ingredient, effectively Pest Control.
When using general formula of the present invention (I) sulfur-bearing, oxime-containing ether compound separately, be that effectively they also can use with the other biological chemical substance to Pest Control, these biochemical substances comprise other sterilants.General formula for example of the present invention (I) sulfur-bearing, oxime-containing ether compound can be effectively with eliminate, pyrethroid, carbamate, process for preparation of benzoylurea compounds, hydrazides insecticides etc. is mixed together use.
For simplicity, above-mentioned general formula (I) sulfur-bearing, oxime-containing ether compound can be made pulvis, wettable powder; granula, granule, missible oil; suspension agent, dry suspension, soluble powder; microemulsion, emulsifiable concentrate, water-dispersible granules; sustained release dosage; tablets etc., above-mentioned all kinds all are suitable for being applied on soil, water and/or the plant, for plant provides required protection.Contain the compound of the present invention that same inert, the acceptable solid of pharmacology or liquid diluent have mixed in these preparations.
For example: wettable powder of the present invention, pulvis, can be by with general formula (I) sulfur-bearing, the oxime-containing ether compound of the about 5%-20% of weight, mill together and prepare with the solid anion surfactant of the about 5%-20% of weight.In these preparations, also used weight 60-90% inert solid diluent, as talcum, kaolin, diatomite, Wingdale, silicate, chalk etc.
The preparation method of granule is about equivalent, about usually 5-20 part, and the gypsum of general formula (I) sulfur-bearing, oxime-containing ether compound and solid surfactant and about 60-90 part grinds fiber crops mill, about 24/48 sieve mesh of mixture boil down to or bigger particle then together.
The preparation method of missible oil is with 5-20 part general formula (I) sulfur-bearing, oxime-containing ether compound, 86-73 part thinner such as dimethylbenzene and 9-7 part auxiliary agent uniform mixing that suits.
Except that above-mentioned pulvis and emulsifiable concentrate, also can use wettable powder and other liquid preparation, these liquid preparations are used with aqueous solution composition on the spot, are sprayed on the plant that needs protection.
The same body preparation of general formula (I) sulfur-bearing, oxime-containing ether compound can mix use with other sterilant, can use as multicomponent mixture, perhaps uses by turns.
Equally, when liquid general formula (I) sulfur-bearing, oxime-containing ether compound formulation and other sterilant are used in combination, can in container, mix or use successively respectively in the mode of liquid spray.
Embodiment
Embodiment 1:1-(3-fluoro-4-aminomethyl phenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] synthetic [No. 001 general formula (I) compound in the table 1] (systhesis of 1-(3-fluoro-4-methyIphenyl)-2-methylthio-O-[(2-methylbiphenyl-3-yl) methyl] oxime 1-ethanone) of oxime-1-ethyl ketone
To the reflux condensing tube (drying tube links to each other with the alkali absorption liquid) that band Calcium Chloride Powder Anhydrous drying tube is housed, thermometer, dropping funnel, add aluminum trichloride (anhydrous) 7.8 grams (0.059 mole) in the there-necked flask of stirring magneton, 20 milliliters of dithiocarbonic anhydride, o-fluorotobuene 6.0 grams (0.054 mole) slowly drip chloroacetyl chloride 6.2 grams (0.054 mole) in 10～15 ℃ from the water clock bucket.After dropwising, slowly be warming up to 40～50 ℃ of reactions to emission-free emitting, after the cooling, under the vigorous stirring, with reaction mixture slowly in 200 milliliters of frozen water of impouring, after continuing to stir half an hour, with ethyl acetate extraction 2 times.United extraction thing and with icy salt solution washing 3 times, anhydrous sodium sulfate drying, concentrating under reduced pressure gets yellow liquid 9.08 grams, with petroleum ether-ethyl acetate reduce pressure column chromatography for separation purify 96% 1-(3-fluoro-4-aminomethyl phenyl)-2-chloroethene ketone yellow liquid 7.05 grams, yield 69.3%. 1H?NMR(CDCl 3/TMS)：δ(ppm)：2.336(s，3H)；4.645(s，2H)；7.069-7.857(m，3H)。MS：M +(186)。
To reflux condensing tube is housed, thermometer adds above-mentioned product 1-(3-fluoro-4-aminomethyl phenyl)-2-chloroethene ketone 5.0 grams (96%, 0.026 mole) in the there-necked flask of stirring magneton, 25% sodium methyl mercaptide, 12.0 grams (0.043 mole).Slowly be warming up to 50～70 ℃ of reactions 2-4 hour.After the cooling, mixture is poured in the frozen water, used ethyl acetate extraction 2 times.United extraction thing and with icy salt solution washing 3 times, anhydrous sodium sulfate drying is purified with the petroleum ether-ethyl acetate column chromatography for separation that reduces pressure behind the concentrating under reduced pressure, 1-(3-fluoro-4-aminomethyl phenyl)-2-methylthio group ethyl ketone yellow liquid 4.68 grams, yield 91.9%. 1H?NMR(CDCl 3/TMS)：δ(ppm)：2.130(s，3H)；2.326(s，3H)；3.705(s，2H)；7.036-7.866(m，3H)。MS：M +(198)。
To reflux condensing tube is housed, thermometer, add above-mentioned product 1-(3-fluoro-4-aminomethyl phenyl)-2-methylthio group ethyl ketone 4.0 grams (0.020 mole) in the there-necked flask of stirring magneton, 15 milliliters of ethanol, oxammonium hydrochloride 1.78 grams (0.026 mole) stir down to sodium hydroxide solution 8.0 grams (0.06 mole) that wherein drip 30%.Slowly be warming up to 80 ℃ of reactions 3-5 hour.Slough part ethanol under the decompression.After the cooling, mixture is poured in the frozen water, used ethyl acetate extraction 2 times.United extraction thing and with icy salt solution washing 3 times, anhydrous sodium sulfate drying, concentrating under reduced pressure, get pale brown look solid 3.78 grams (10.0% (Z)+85.0% (E)), get yellow needle-like crystal 2.5 grams (10.0% (Z)+85.0% (E)) of 1-(3-fluoro-4-aminomethyl phenyl)-2-methylmercaptan ethyl ketoxime with the sherwood oil recrystallization, yield 58.1%, fusing point: 71.6～72.3 ℃. 1H?NMR(CDCl 3)：δ(ppm)：2.134(s，3H)；2.297(s，3H)；3.811(s，2H)；6.986-7.547(m，3H)。MS：M +(213)。
By method c) Synthetic 2 .5 gram (0.011 mole) above-mentioned product 1-(3-fluoro-4-aminomethyl phenyl)-2-methylmercaptan ethyl ketoxime (10% (Z)+85% (E)) is dissolved in the 15ml toluene, restrain 30% sodium hydroxide (0.021 mole) solution in 10-20 ℃ to wherein dripping 2.8, after stirring 10-15min, in batches to wherein adding 4.5 gram (0.014 mole) ([(2-methyl biphenyl-3-yl) methyl] triethyl ammonium chlorides.Slowly be warming up to 80-90 ℃ of reaction 3-4 hour.After the cooling, mixture is poured in the frozen water, used ethyl acetate extraction 2 times.United extraction thing and with icy salt solution washing 3 times, anhydrous sodium sulfate drying, concentrating under reduced pressure, thick product 4.5 grams (4.3% (Z)+90.5% (E)).Get white solid 2.45 grams (E body), fusing point: 72.7-73.0 with sherwood oil and re-crystallizing in ethyl acetate.Yield 56.2%. 1H?NMR(CDCl 3/TMS)：δ(ppm)：2.057(s，3H，SCH 3)，2.278(s，3H，CH 3)，2.302(S，3H，CH 3)，3.801(s，2H，CH 2)，5.310(s，2H，NOCH 2)6.976～7.593(m，11H，ph)。MS：M +(393)。
By a) Synthetic 2 .5 gram (0.011 mole) 1-(3-fluoro-4-aminomethyl phenyl)-2-methylmercaptan ethyl ketoxime (10% (Z)+85% (E)) of method, 15ml toluene, 2.8 restrain 30% sodium hydroxide (0.021 mole) solution, 2.62 gram (0.012 mole) 2-methyl-3-phenyl benzyl chloride, 0.20 gram Tetrabutyl amonium bromide was in 60-70 ℃ of reaction 3-8 hour.After the cooling, mixture is poured in the frozen water, used ethyl acetate extraction 2 times.United extraction thing and with icy salt solution washing 3 times, anhydrous sodium sulfate drying, concentrating under reduced pressure, thick product 4.8 grams (4.8% (Z)+78.5% (E)).Get white solid 2.02 grams (E body), fusing point: 72.7-73.0 with sherwood oil and re-crystallizing in ethyl acetate.Yield 46.3%. 1H NMR and MS are the same.
Embodiment 2:1-(4-chloro-3-fluorophenyl)-2-methylthio group-O-[(2-methyl-3-xenyl) methyl] synthetic [No. 002 general formula (I) compound in the table 1] (systhesis of 1-(4-chloro-3-fluorophenyl)-2-methylthio-O-[(2-methyl-3-biphenyl) methyl] oxime1-ethanone) of oxime 1-ethyl ketone
To the reflux condensing tube (drying tube links to each other with the alkali absorption liquid) that band Calcium Chloride Powder Anhydrous drying tube is housed, thermometer, dropping funnel, add aluminum trichloride (anhydrous) 98.6 grams (0.74 mole) in the there-necked flask of stirring magneton, 150 milliliters of dithiocarbonic anhydride, adjacent fluorochlorobenzene 89.0 grams (0.68 mole), slowly drip after chloroacetyl chloride 76.2 gram (0.672 mole) dropwises from the water clock bucket in 15～20 ℃, slowly be warming up to 40～45 ℃ of reactions to emission-free emitting, after the cooling, under the vigorous stirring, with reaction mixture slowly in 800 milliliters of frozen water of impouring, after continuing to stir half an hour, use ethyl acetate extraction 2 times.United extraction thing and with icy salt solution washing 3 times, anhydrous sodium sulfate drying, concentrating under reduced pressure, yellow liquid 115.2 grams, LC-MS:M-(Neg)=205, content 90%, yield 74.9%.
To reflux condensing tube is housed, thermometer adds above-mentioned product 1-(4-chloro-3-fluorophenyl)-2-chloroethene ketone 115.2 grams (90%, 0.50 mole) in the there-necked flask of stirring magneton, 25% sodium methyl mercaptide, 200 grams (0.71 mole).Slowly be warming up to 55～70 ℃ of reactions 2-4 hour.After the cooling, mixture is poured in the frozen water, used ethyl acetate extraction 2 times.United extraction thing and with icy salt solution washing 3 times, anhydrous sodium sulfate drying, concentrating under reduced pressure get 1-(4-chloro-3-fluorophenyl)-2-methylthio group ethyl ketone yellow liquid 110 grams, LC-MS:M -(Neg)=217, content 95.5%, yield 96.2%.
To reflux condensing tube is housed, thermometer, add above-mentioned product 1-(4-chloro-3-fluorophenyl)-2-methylthio group ethyl ketone 110 grams (95.5% in the there-necked flask of stirring magneton, 0.481 mole), 280 milliliters of ethanol, oxammonium hydrochloride 41.55 grams (0.598 mole) stir down to sodium hydroxide solution 200 grams (1.50 moles) that wherein drip 30%.Slowly be warming up to 80-85 ℃ of reaction 3-5 hour.Slough part ethanol under the decompression.After the cooling, mixture is poured in the frozen water, used ethyl acetate extraction 2 times.United extraction thing and with icy salt solution washing 3 times, anhydrous sodium sulfate drying, concentrating under reduced pressure, pale brown look solid 90 grams, LC-MS:M -(Neg)=232, content 70.5%, yield 57.0%.
60 grams (70.5%, 0.18 mole) 1-(4-chloro-3-fluorophenyl)-2-methylmercaptan ethyl ketoxime is dissolved in the 300ml toluene, restrain 30% sodium hydroxide (0.34 mole) solution in 10-20 ℃ to wherein dripping 45, after stirring 10-15min, in batches to wherein adding 66 gram (0.20 mole) ([(2-methyl biphenyl-3-yl) methyl] triethyl ammonium chlorides.Slowly be warming up to 80-90 ℃ of reaction 3-4 hour.After the cooling, mixture is poured in the frozen water, used ethyl acetate extraction 2 times.United extraction thing and with icy salt solution washing 3 times, anhydrous sodium sulfate drying, concentrating under reduced pressure, thick product 90 grams (65.8%).With petroleum ether-ethyl acetate reduce pressure column chromatography for separation purify white solid 40.5 gram, fusing point: 71.0-71.2.Yield 54.0%. 1HNMR(CDCl 3/TMS)：δ(ppm)：2.051(s，3H，SCH 3)，2.275(s，3H，CH 3)，3.778(s，2H，CH 2S)，5.317(s，2H，NOCH 2)7.114～7.847(m，11H，ph)。MS: molecular ion peak M +(413).
Embodiment 3:1-(3-chloro-4-fluorophenyl)-2-methylthio group-O-[(2-methyl-3-xenyl) methyl] synthetic [No. 003 general formula (I) compound in the table 1] (systhesis of 1-(3-chloro-4-fluorophenyl)-2-methylthio-O-[(2-methyl-3-biphenyl) methyl] oxime1-ethanone) of oxime 1-ethyl ketone
With reference to Liu Shudong, Liu Aiping, the hair light of spring etc., chemical reagent, Vol.24 No.1,2002 synthetic 3-chloro-4-fluoro acetophenones.Organic synthesis topical reference book first version Beijing of writing with reference to Fan Nengting: press of Beijing Institute of Technology, 1992.10 synthetic 1-(3-chloro-4-fluorophenyl)-2-bromine ethyl ketones.With reference to the synthetic 1-(3-chloro-4-fluorophenyl) of the method for embodiment 1-2-methylthio group ethyl ketone and 1-(3-chloro-4-fluorophenyl)-2-first sulphur ethyl ketone oxime.
1.3 gram (0.005 mole) 1-(3-chloro-4-fluorophenyl)-2-methylmercaptan ethyl ketoxime and 1.8 gram 20% sodium hydroxide (0.009 mole) solution are dissolved in the 5ml toluene, be warming up to 80-85 ℃, to ([(2-methyl biphenyl-3-yl) methyl] triethyl ammonium chloride (0.0054 mole) solution, continuation stirring 4-6 hour that wherein drip 3.4 grams 50%.After the cooling, mixture is poured in the frozen water, used ethyl acetate extraction 2 times.United extraction thing and with icy salt solution washing 3 times, anhydrous sodium sulfate drying, concentrating under reduced pressure, thick product 2.15 grams (4.5% (Z)+91.5% (E)).With petroleum ether-ethyl acetate reduce pressure column chromatography for separation purify yellow liquid 0.86 gram (E body), yield 41.6%. 1H?NMR(CDCl 3/TMS)：δ(ppm)：2.051(s，3H，SCH 3)，2.279(s，3H，CH 3)，3.782(s，2H，CH 2S)，5.318(s，2H，NOCH 2)，7.120～7.851(m，11H，ph)。MS: molecular ion peak M +(413).
Embodiment 4.1-(4-chloro-phenyl-)-1-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] synthetic [No. 099 general formula (I) compound in the table 1] (synthesis of methanone, 1-(4-chlorophenyl)-1-methylthio-O-[(2-methyl-3-biphenyl) methyl] oxime) of oxime 1-ketone
Figure A20031011064700142
15.5 gram (0.1 mole) 4-chlorobenzaldehyde oxime is dissolved in the 150ml trichloromethane, under-5-0 ℃, logical chlorine becomes transparent sky blue or liquid spectrum up to reaction solution and tracks to and react completely.The evaporated under reduced pressure solvent gets crude product 15.2 grams, and it is synthetic to be directly used in down the step.
To reflux condensing tube is housed, thermometer adds above-mentioned product 1-(4-chloro-phenyl-)-1-chloromethane ketoxime 7.6 grams (0.04 mole) in the there-necked flask of stirring magneton, 20% sodium methyl mercaptide, 17.5 grams (0.05 mole).Slowly be warming up to 50～70 ℃ of reactions 2-4 hour.After the cooling, mixture is poured in the frozen water, used ethyl acetate extraction 2 times.United extraction thing and with icy salt solution washing 3 times, anhydrous sodium sulfate drying, concentrating under reduced pressure, yellow liquid 4.68 grams, being directly used in down the step will synthesize.
Take by weighing 1-(4-chloro-phenyl-)-1-methylthio group ketoxime (E isomer, content 90%) 1.8 grams (0.008 mole), 2-methyl-3-phenyl benzyl chloride (content 90%) 2.12 grams (0.0088 mole), 0.3 gram tetrabutylammonium iodide, 8 milliliters of toluene stir down to sodium hydroxide solution 3.2 grams (0.016 mole) that wherein drip 20% in reaction flask.Slowly be warming up to 60～70 ℃ of reactions 6～8 hours.After the cooling, mixture is poured in the frozen water, used ethyl acetate extraction 2 times.United extraction thing and with icy salt solution washing 3 times, anhydrous sodium sulfate drying, concentrating under reduced pressure, thick product 2.74 grams.With petroleum ether-ethyl acetate reduce pressure column chromatography for separation purify yellow liquid 1.18 gram, yield 38.7%. 1H?NMR(CDCl 3/TMS)：δ(ppm)：2.706(s，3H，SCH 3)，2.273(s，3H，CH 3)，5.346(s，2H，NOCH 2)，7.236～7.421(m，12H，ph)。MS：M +(381)。
Embodiment 5:1-(4-p-methoxy-phenyl)-2-methoxyl group-O-[(2-methyl biphenyl-3-yl) methyl] synthetic [No. 029 general formula (I) compound in the table 1] (systhesis of 1-(4-methoxylphenyl)-2-methoxy-O-[(2-methyl-biphenyl-3-yl) methyl] oxime1-ethanone) of oxime 1-ethyl ketone
Figure A20031011064700151
Table 1In 029Number compound
To the reflux condensing tube (drying tube links to each other with the alkali absorption liquid) that band Calcium Chloride Powder Anhydrous drying tube is housed, thermometer, dropping funnel, add aluminum trichloride (anhydrous) 13.0 grams (0.010 mole) in the there-necked flask of stirring magneton, methyl-phenoxide 23.0 grams (0.220 mole), slowly drip after methoxyacetyl chloride 9.7 grams (0.090 mole) dropwise from the water clock bucket down in ice bath cooling, in 10-25 ℃ of reaction 1 hour, under the vigorous stirring, slowly in 200 milliliters of frozen water of impouring, after continuing to stir half an hour, use ethyl acetate extraction 2 times.United extraction thing and with icy salt solution washing 3 times, anhydrous sodium sulfate drying, concentrating under reduced pressure, yellow liquid 29.08 grams (wherein still methyl-phenoxide), gas spectrum content 58.8% not purifiedly directly carries out next step oximate test.
To reflux condensing tube is housed, thermometer, add above-mentioned product 1-(4-p-methoxy-phenyl)-2-methoxyl group ethyl ketone 29.08 grams (0.097 mole) in the there-necked flask of stirring magneton, 50 milliliters of ethanol, oxammonium hydrochloride 7.00 grams (0.101 mole) stir down to sodium hydroxide solution 20.0 grams (0.125 mole) that wherein drip 25%.Slowly be warming up to 70 ℃ of reactions 3-5 hour.Slough part ethanol under the decompression.After the cooling, mixture is poured in the frozen water, used ethyl acetate extraction 2 times.United extraction thing and with icy salt solution washing 3 times, anhydrous sodium sulfate drying, concentrating under reduced pressure, pale brown look liquid 24 grams, gas spectrum content 40.8% not purifiedly directly carries out next step test.
By method c) synthetic 12 gram (0.025 mole) above-mentioned product 1-(4-p-methoxy-phenyl)-2-methylmercaptan ethyl ketoximes are dissolved in the 10ml toluene, restrain 30% sodium hydroxide (0.043 mole) solution in 10-20 ℃ to Dropwise 5 .8 wherein, after stirring 10-15min, in batches to wherein adding 7.9 gram (0.025 mole) ([(2-methyl biphenyl-3-yl) methyl] triethyl ammonium chlorides.Slowly be warming up to 75-80 ℃ of reaction 3-4 hour.After the cooling, mixture is poured in the frozen water, used ethyl acetate extraction 2 times.United extraction thing and with icy salt solution washing 3 times, anhydrous sodium sulfate drying, concentrating under reduced pressure, get thick product 8.5 grams, with petroleum ether-ethyl acetate reduce pressure column chromatography for separation purify 1-(4-p-methoxy-phenyl)-2-methoxyl group-O-[(2-methyl biphenyl-3-yl of 96%) methyl] second ketoxime ether 1.06 grams (E body) and 0.87 restrain (Z body), yield 21.3%. 1H NMR (CDCl 3/ TMS): δ (ppm): (Z body) 2.20 (s, 3H), 3.33 (s, 3H), 3.78 (s, 3H), 4.31 (s, 2H), 5.26 (s, 2H), 6.88～7.74 (m, 12H).MS：M +(375)。(E body) 2.27 (s, 3H), 2.30 (s, 3H), 3.81 (s, 3H), 4.64 (s, 2H), 5.30 (s, and 2H) 6.87～7.67 (m, 12H).MS：M +(375)。
According to the method described above, synthetic all general formulas (I) compound, institute's synthetic general formula (I) compound are all through the hydrogen spectrum, and mass spectrum is or/and the ultimate analysis conclusive evidence.
N=1 in general formula (I), R=CH 3, R 1=H during the Ar=substituted-phenyl, represents general formula (I) compound with formula (Ia);
N=1 in general formula (I), R=CH 3, R 1=CH 3,, X=S during the Ar=substituted-phenyl, represents general formula (I) compound with formula (Ib);
N=0 in general formula (I), R=CH 3, during the Ar=substituted-phenyl, represent general formula (I) compound with formula (Ic);
N=1 in general formula (I), R=CH 3, R 1=H, X=S represents general formula (I) compound with formula (Id);
R=CH in general formula (I) 3, X=S during the Ar=substituted-phenyl, represents general formula (I) compound with formula (Ie);
The compound of segment bounds of the present invention (I) shows as table 1, but the compound of formula (I) is not limited only to the compound shown in the table 1.
The biological activity test of 6 pairs of mythimna separatas of embodiment (Mythimna separata)
Will be by the sulfur-bearing provided by the invention of above-mentioned Agrotechnical formulation embodiment method preparation, the missible oil or the wettable powder of oxime-containing ether compound, dilute with water is made into the pesticidal solutions of predetermined concentration, choose 10-15 three ages or three ages above mythimna separata and one cun long maize leaf of 5-8 sheet be put in the culture dish and quantitatively spray, dry the back and move into normal raising the in the observation ward, after 24 hours, the statistics death toll.Experiment repeats 3 times, results averaged.
The activity experiment of 7 pairs of bean aphids of embodiment (Aphis fabae)
Will be by the sulfur-bearing provided by the invention of above-mentioned Agrotechnical formulation embodiment method preparation, the missible oil or the wettable powder of oxime-containing ether compound, dilute with water is made into the pesticidal solutions of predetermined concentration, bean aphid is connected on the bean seedlings that just have been unearthed, and every strain connects more than 25, then bean seedlings is dipped in the soup together with the examination worm, take out after 5 seconds, unnecessary soup is removed in suction, inserts in the sponge of suction, covers with glass-tube, after 24 hours, check survival and dead borer population.Repeat results averaged 3 times.
The insecticidal test of 8 pairs of rice green leafhoppers of embodiment (Nephotetlix cincticeps)
Will be by the sulfur-bearing provided by the invention of above-mentioned Agrotechnical formulation embodiment method preparation, the missible oil or the wettable powder of oxime-containing ether compound, dilute with water is made into the pesticidal solutions of predetermined concentration, choosing two core rice seedlings immerses in the soup, take out after 5 seconds and dry, place Boiling tube, 20 rice green leafhopper nymphs in 5 age are introduced in every pipe 20 strains then, the mouth of pipe is placed under observation ward's condition with white gauze wrapping, checks survival and dead borer population after 24 hours.Experiment repeats 3 times, results averaged.
Institute's synthetic compound also has extremely significant active to other insect such as beet armyworm, cabbage looper, U.S. state tobacco budworm, black peach aphid etc.
Part synthetic general formula (I) compound the biological activity of mythimna separata, leafhopper and bean sprouts is seen Table 2.
Embodiment 9 fungicidal activity determination tests
Method A (toxic medium therapy): the mother liquor that sulfur-bearing provided by the invention, oxime-containing ether compound is made into predetermined concentration with suitable thinner (as acetone), get 1 milliliter of soup in 50 milliliters of PDA substratum that dissolve with transfer pipet, after fully shaking up, pour into respectively in 2 culture dish and repeat as 2 times, cooling back is that 4 millimeters bacterium cake places culture dish central authorities with inoculating needle picking diameter, establishes thinner simultaneously for contrasting.Put into the incubator of optimal temperature after inoculation finishes, measure the mycelial growth diameter after 72 hours, calculate mycelial growth inhibition rate.
Method B (pot-culture method): plant is tried material carry out potted plant.Sulfur-bearing provided by the invention, oxime-containing ether compound are made into the mother liquor of predetermined concentration with suitable thinner (as acetone).Spray pesticide carries out the disease inoculation after 24 hours to plant examination material.After the inoculation, plant is placed in the constant incubator, makes and infect to continue, carry out result's investigation after waiting to contrast abundant morbidity.
Active classification is as follows: A (preventive effect is 90-100%), B (preventive effect is 70-90%), C (preventive effect is 50-70%), D (preventive effect is below 50%).
Part institute's synthetic general formula (I) compound is to Pyricularia oryzae, botrytis cinerea pers, and the biological activity of Sclerotinia sclerotiorum the results are shown in Table 3.
Table 1: part general formula (I) compound
Figure A20031011064700181
Continuous table 1
No. ?L m ?X ?F 1 F 2 Fusing point (℃) 1H NMR δ (ppm) and MS (M +)
023 ?3-Br-4-CH 3 ?S ?CH3 Phenyl Oily matter 2.04(s，3H)，2.27(s，3H)，2.34(s，3H)，3.79(s，2H)，5.32 (s，2H)7.23～7.52(m，11H).M +(453).
024 ?3，5-(CF 3) 2 ?S ?CH3 Phenyl Oily matter 2.06(s，3H)，2.29(s，3H)，3.85(s，2H)，5.38(s，2H) 7.19～8.20(m，12H).M +(497).
025 ?4-Cl ?S ?CH3 Phenyl Oily matter 2.08(s，3H)，2.31(s，3H)，3.83(s，2H)，5.35(s，2H) 7.27～7.73(m，12H).M +(395).
026 ?4-CH 3 ?S ?CH3 Phenyl Oily matter 2.06(s，3H)，2.28(s，3H)，2.37(s，3H)，3.82(s，2H)，5.32 (s，2H)7.21～7.64(m，12H).M +(375).
027 ?H ?O ?CH3 Phenyl Oily matter Z body 2.28 (s, 3H), 3.35 (s, 3H), 4.33 (s, 2H), 5.26 (s, 2H) 6.99～7.44 (m, 13H) .M +(345). E body 2.28 (s, 3H), 3.31 (s, 3H), 4.66 (s, 2H), 5.33 (s, 2H) 7.24～7.79 (m, 13H) .M +(345).
028 ?4-CH 3 ?O ?CH3 Phenyl Oily matter Z body 2.19 (s, 3H), 2.36 (s, 3H), 3.34 (s, 3H), 4.31 (s, 2H), 5.28 (s, 2H) 7.17～7.59 (m, 12H) .M +(359). E body 2.30 (s, 3H), 2.38 (s, 3H), 3.33 (s, 3H), 4.68 (s, 2H) 5.35 (s, 2H) 7.18～7.67 (m, 12H) .M +(359).
029 ?4-OCH 3 ?O ?CH3 Phenyl Oily matter Z body 2.20 (s, 3H), 3.33 (s, 3H), 3.78 (s, 3H), 4.31 (s, 2H), 5.26 (s, 2H) 6.88～7.74 (m, 12H) .M +(375). E body 2.27 (s, 3H), 2.30 (s, 3H), 3.81 (s, 3H), 4.64 (s, 2H), 5.30 (s, 2H) 6.87～7.67 (m, 12H) .M +(375).
030 ?3，4-(CH 3) 2 ?O ?CH3 Phenyl Oily matter Z body 2.27 (s, 3 *3H)，3.34(s，3H)，4.31(s，2H)，5.25 (s，2H)，5.25(s，2H)，7.13～7.42(m，11H).M +(373). E body 2.27 (s, 3 *3H)，3.30(s，3H)，4.64(s，2H)，5.32 (s，2H)7.10～7.42(m，11H).M +(373).
031 ?4-Cl ?O ?CH3 Phenyl
032 ?4-CF 3 ?O ?CH3 Phenyl
033 ?4-Cl-3-F ?O ?CH3 Phenyl
034 ?4-CH 3-3-F ?O ?CH3 Phenyl
035 ?4-F ?O ?CH3 Phenyl
036 ?4-OCH 2CH 3 ?O ?CH3 Phenyl Oily matter 1.41(t，3H)，2.27(s，3H)，3.30(s，3H)，4.06(q，2H)，4.64 (s，2H)，5.31(s，2H)6.87～7.65(m，12H).M +(389).
037 ?H ?S ?H 4-bromine phenoxy group Oily matter 1.98(s，3H)，3.76(s，2H)，5.19(s，2H)，6.85～7.68 (m，13H).M +(441).
038 ?4-CH 3 ?S ?H Phenoxy group Oily matter 2.06(s，3H)，2.29(s，3H)，3.80(s，2H)，5.35(s，2H) 7.29～7.91(m，13H).M +(377).
039 ?4-OCH 3 ?S ?H Phenoxy group Oily matter 2.00(s，3H)，3.75(s，3H)，3.80(s，2H)，5.30(s，2H) 7.45～8.05(m，13H).M +(393).
040 ?4-Br ?S ?H Phenoxy group Oily matter 2.19(s，3H)，3.76(s，2H)，5.20(s，2H)，7.00～7.53 (m，13H).M +(441).
041 ?4-CH(CH 3) 2 ?S ?H Phenoxy group Oily matter 1.24(d，6H)，2.01(s，3H)，2.28(s，3H)，2.90(m，1H)，3.7 7(s，2H)，5.18(s，2H)，6.96～7.62(m，13H).M +(405)
042 ?4-CH 2CH 3 ?S ?H Phenoxy group Oily matter 1.22(t，3H)，2.01(s，3H)，2.62(q，2H)，3.78(s，2H)，5.19 (s，2H)7.03～7.62(m，13H).M +(391).
043 ?4-OCH 2CH 3 ?S ?H Phenoxy group Oily matter 1.43(d，3H)，2.05(s，3H)，3.77(s，2H)，4.03(q，2H)，5.1 9(s，2H)6.87～7.65(m，13H).M +(407).
044 ?4-F ?S ?H Phenoxy group Oily matter 2.01(s，3H)，3.76(s，2H)，5.18(s，2H)，6.98～7.69 (m，13H).M +(381).
045 ?4-F ?S ?H 4-bromine phenoxy group Oily matter 2.00(s，3H)，3.75(s，2H)，5.18(s，2H)，6.86～7.69 (m，12H).M +(459).
Continuous table 1
No. ?L m ?X ?F 1 F 2 Fusing point (℃) 1H NMR δ (ppm) and MS (M +)
046 ?4-CH 3 ?S ?H 4-bromine phenoxy group 60.4-61.1 1.98(s，3H)，2.37(s，3H)，3.76(s，2H)，5.19(s，2H) 6.87～7.58(m，12H).MS：M +(455).
047 ?4-F ?S ?H The 4-chlorophenoxy Oily matter 2.02(s，3H)，3.75(s，2H)，5.18(s，2H)， 6.92～7.73(m，12H).M +(415)
048 ?3-CF 3 ?S ?H Phenoxy group Oily matter 2.03(s，3H)，3.80(s，2H)，5.23(s，2H)， 7.00～7.99(m，13H).M +(431).
049 ?4-CF 3 ?S ?H Phenoxy group Oily matter 2.01(s，3H)，3.79(s，2H)，5.22(s，2H)，7.00～7.82 (m，13H).M +(431).
050 ?4-OCHF 2 ?S ?H Phenoxy group Oily matter 2.00(s，3H)，3.73(s，2H)，5.32(s，2H)，6.95～7.55 (m，14H).M +(429).
051 ?4-OCHF 2 ?S ?H 4-bromine phenoxy group Oily matter 2.02(s，3H)，3.76(s，2H)，5.19(s，2H)，6.90～7.68 (m，14H).M +(507).
052 ?3-NO 2 ?S ?H Phenoxy group Oily matter 2.02(s，3H)，3.81(s，2H)，5.23(s，2H)，7.00～8.59 (m，13H).M +(408).
053 ?4-OCF 3 ?S ?H Phenoxy group Oily matter 2.01(s，3H)，3.75(s，2H)，5.18(s，2H)，6.99～7.73 (m，13H).M +(447).
054 ?4-OCF 3 ?S ?H 4-bromine phenoxy group Oily matter 2.03(s，3H)，3.76(s，2H)，5.19(s，2H)，6.87～7.74 (m，13H).M +(525).
055 ?2-CH 3 ?S ?H Phenoxy group Oily matter 2.03(s，3H)，2.36(s，3H)，3.79(s，2H)，5.19(s，2H)7.16 ～7.63(m，13H)M +(377).
056 ?3，4-(CH 3) 2 ?S ?H Phenoxy group Oily matter 2.00(s，3H)，2.26(d，2 *3H)，3.76(s，2H)，5.18(s，2H) 7.00～7.34(m，12H).M +(391).
057 ?3，4-(Cl) 2 ?S ?H Phenoxy group Oily matter 2.01(s，3H)，3.74(s，2H)，5.21(s，2H)，6.92～7.84 (m，12H).M +(431).
058 ?3-Cl-4-CH 3 ?S ?H Phenoxy group Oily matter 2.00(s，3H)，2.37(s，3H)，3.73(s，2H)，5.18(s，2H) 6.99～7.34(m，12H).M +(411).
059 ?4-Br-3-F- ?S ?H Phenoxy group Oily matter 2.00(s，3H)，3.73(s，2H)，5.18(s，2H)，6.99～7.35 (m，12H).M +(459).
060 ?2，4-(CH 3) 2 ?S ?H Phenoxy group Oily matter Z body 1.99 (s, 3H), 2.15 (s, 3H), 2.33 (s, 3H), 3.38 (s, 2H), 5.04 (s, 2H) 6.95～7.44 (m, 12H) .M +(391). E body 2.01 (s, 3H), 2.26 (s, 3H), 2.30 (s, 3H), 3.66 (s, 2H), 5.15 (s, 2H) 7.00～7.33 (m, 12H) .M +(391).
061 ?2-Cl-4-CH 3 ?S ?H Phenoxy group Oily matter Z body 1.96 (s, 3H), 2.13 (s, 3H), 3.33 (s, 2H), 5.01 (s, 2H), 6.90～7.34 (m, 12H) .M +(411). E body 1.98 (s, 3H), 2.34 (s, 3H), 3.79 (s, 2H), 5.17 (s, 2H), 6.70～7.34 (m, 12H) .M +(411).
062 ?4-Cl-2-CH 3 ?S ?H Phenoxy group Oily matter 2.00(s，3H)，2.26(s，3H)，3.64(s，2H)，5.15(s，2H)， 6.99～7.33(m，12H).M +(411).
063 ?3-F-4-CH 3 ?S ?H Phenoxy group Oily matter 2.00(s，3H)，2.28(s，3H)，3.75(s，2H)，5.18(s，2H)， 6.95～7.54(m，12H).M +(395).
064 ?3-Br-4-CH 3 ?S ?H Phenoxy group Oily matter 2.00(s，3H)，2.41(s，3H)，3.74(s，2H)，5.19(s，2H)， 6.99～7.46(m，12H).M +(455).
065 ?3，5-(CF 3) 2 ?S ?H Phenoxy group Oily matter 2.01(s，3H)，3.80(s，2H)，5.24(s，2H)7.00～8.16 (m，12H).M +(499).
066 ?H ?O ?H Phenoxy group Oily matter 3.27(s，3H)，4.62(s，2H)，5.20(s，2H)，7.26～7.66 (m，14H).M +(347).
Continuous table 1
Figure A20031011064700211
Continuous table 1
Continuous table 1
Figure A20031011064700231
Continuous table 1
No. ?L m ?n ?R 1 ??F t Fusing point (℃) 1H NMR δ (ppm) and MS (M +)
119 ?4-Cl ?1 ?H ??2，3，4，5，6-F 5 ??76.1-76.6 2.03(s，3H)，3.72(s，2H)，5.29(s，2H)，7.27～7.65 (m，4H).M +(395).
120 ?4-CH 3 ?1 ?H ??2，3，4，5，6-F 5 Oily matter 2.04(s，3H)，2.38(s，3H)，3.75(s，2H)，5.29(s，2H)， 7.20～7.62(m，4H).M +(375).
121 ?4-Cl ?1 ?H ??2，5-(CH 3) 2 Oily matter 2.03(s，3H)，2.32(s，3H)，2.35(s，3H)，3.76(s，2H)， 5.21(s，2H)，7.06～7.68(m，7H).M +(333).
122 ?4-Cl ?1 ?H ??2，4-(CH 3) 2 Oily matter 2.02(s，3H)，2.32(s，3H)，2.40(s，3H)，3.75(s，2H)， 5.20(s，2H)，7.02～7.67(m，7H).M +(333).
123 ?4-Cl ?1 ?H ??2，6-(Cl) 2 ??79.9-80.5 2.04(s，3H)，3.76(s，2H)，5.52(s，2H)，7.17～7.71 (m，7H).M +(373).
124 ?4-Cl ?1 ?H ??2-Cl-6-F ??64.6-65.7 1.99(s，3H)，3.73(s，2H)，5.38(s，2H)，7.03～7.67 (m，7H).M +(357).
125 ?4-Cl ?1 ?H ??4-COOC(CH 3) 3 Oily matter 1.59(s，9H)，2.05(s，3H)，3.78(s，2H)，5.26(s，2H)， 7.26～8.00(m，8H).M +(405).
126 ?4-Cl ?1 ?H ??4-C(CH 3) 3 Oily matter 1.32(s，9H)，2.03(s，3H)，3.77(s，2H)，5.19(s，2H)， 7.20～7.61(m，8H).M +(361).
127 ?4-Cl ?1 ?H ??4-Cl Oily matter 2.00(s，3H)，3.86(s，2H)，5.18(s，2H)，7.16～7.68 (m，8H).M +(339).
128 ?4-F ?1 ?H ??2-Cl Oily matter 2.06(s，3H)，3.80(s，2H)，5.34(s，2H)，7.02～7.73 (m，8H).M +(323).
129 ?4-Cl ?1 ?CH 3 ??2，6-(Cl) 2 ??72.9-73.8 E body 1.30 (d, 3H), 2.07 (s, 3H), 4.79 (q, 1H), 5.46 (s, 2H), 7.18～7.74 (m, 7H) .M +(387).
130 ?4-Cl ?1 ?CH 3 ??2，3，4，5，6-F 5 ??82.0-82.6 E body 1.28 (d, 3H), 2.07 (s, 3H), 4.68 (q, 1H), 5.24 (s, 2H), 7.26～7.69 (m, 4H) .M +(409).
131 ?4-Cl ?1 ?CH 3 ??2，5-(CH 3) 2 Oily matter Z body 1.32 (d, 3H), 1.93 (s, 3H), 2.18 (s, 3H), 2.28 (s, 3H), 3.66 (q, 1H), 5.04 (s, 2H), 7.00～7.32 (m, 7 H) .M +(347) .E body 1.3 1 (d, 3H), 2.08 (s, 3H), 2.33 (s, 3H), 2.34 (s, 3H), 4.90 (q, 1H), 5.17 (s, 2H), 7.06～7.71 (m, 7H) .M +(347).
132 ?4-Cl ?1 ?CH 3 ??2，4-(CH 3) 2 Oily matter Z body 1.32 (d, 3H), 1.94 (s, 3H), 2.20 (s, 3H), 2.29 (s, 3H), 3.63 (q, 1H), 5.04 (s, 2H), 6.95～7.34 (m, 7 H) .M +(347) .E body 1.30 (d, 3H), 2.07 (s, 3H), 2.33 (s, 3H), 2.36 (s, 3H), 4.79 (q, 1H), 5.17 (s, 2H), 7.02～7.70 (m, 7H) .M +(347).
133 ?4-Cl ?1 ?CH 3 ??2-Cl-6-F Z body 58.9-59.5 E body 40.6-41.0 Z body 1.30 (d, 3H), 1.86 (s, 3H), 3.61 (q, 1H), 5.22 (s, 2H), 6.94～7.34 (m, 7H) .M +(371) .E body 1.26 (d, 3H), 2.06 (s, 3H), 4.78 (q, 1H), 5.34 (s, 2H), 6.94～7.72 (m, 7H) .M +(371).
134 ?4-Cl ?1 ?CH 3 ??4-COOC(CH 3) 3 E body 68.7-69.3 E body 1.33 (d, 3H), 1.60 (s, 9H), 2.10 (s, 3H), 4.78 (q, 1H), 5.22 (s, 2H), 7.30～8.00 (m, 8H) .M +(419).
135 ?4-Cl ?1 ?CH 3 ??4-C(CH 3) 3 E body 103.1-103.9 E body 1.28 (d, 3H), 1.33 (s, 9H), 2.09 (s, 3H), 4.81 (q, 1H), 5.15 (s, 2H), 7.26～7.39 (m, 8H) .M +(375).
136 ?4-CH 3 ?1 ?CH 3 ??4-C(CH 3) 3 E body 89.4-89.8 Z body oily matter E body 1.29 (d, 3H), 1.32 (s, 9H), 2.10 (s, 3H), 2.36 (s, 3H), 4.80 (q, 1H), 5.18 (s, 2H), 7.12～7.62 (m, 8H) .M +(355) .Z body 1.29 (d, 3H), 1.32 (s, 9H), 1.85 (s, 3H), 2.34 (s, 3H), 3.64 (q, 1H), 5.04 (s, 2H), 7.19～7.31 (m, 8H) .M +(355).
137 ?4-F ?1 ?CH 3 ??4-C(CH 3) 3 E body 88.5-89.1 Z body oily matter E body 1.27 (d, 3H), 1.32 (s, 9H), 2.10 (s, 3H), 4.82 (q, 1H), 5.15 (s, 2H), 7.06～7.36 (m, 8H) .M +(359). Z body 1.29 (d, 3H), 1.30 (s, 9H), 1.86 (s, 3H), 3.62 (q, 1H), 5.04 (s, 2H), 7.06～7.36 (m, 8H) .M +(359).
Continuous table 1
No. ?L m ?n ?R 1 ?F t Fusing point (℃) 1H NMR δ (ppm) and MS (M +)
138 ?4-F ?1 ?CH 3 ?2-Cl Oily matter E body 1.31 (d, 3H), 2.11 (s, 3H), 4.82 (q, 1H), 5.30 (s, 2H), 7.00-7.74 (m, 8H) .M +(337).
139 ?4-Cl ?1 ?C 2H 5 ?2-CH 3-3-phenyl Z body oily matter E body solid Z body 1.01 (t, 3H), 1.62 (m, 2H), 1.96 (s, 3H), 2.13 (s, 3H), 3.42 (t, 1H), 5.19 (s, 2H), 7.19～7.43 (m, 12H) .M +(423) .E body 0.88 (t, 3H), 1.68 (m, 2H), 2.11 (s, 3H), 2.26 (s, 3H), 3.65 (t, 1H), 5.27 (s, 2H), 7.24～7.77 (m, 12H) .M +(423).
140 ?4-Cl ?1 ?C 2H 5 The 3-phenoxy group Oily matter Z body 0.98 (t, 3H), 1.60 (m, 2H), 1.94 (s, 3H), 3.58 (t, 1H), 5.06 (s, 2H), 7.00～7.37 (m, 13H) .M +(425). E body 0.86 (t, 3H), 1.65 (m, 2H), 2.07 (s, 3H), 4.61 (t, 1H), 5.17 (s, 2H), 7.01～7.73 (m, 13H) .M +(425).
141 ?4-CH 3 ?1 ?C 2H 5 ?2-CH 3-3-phenyl Z body oily matter E body solid Z body 1.00 (t, 3H), 1.62 (m, 2H), 1.95 (s, 3H), 2.12 (s, 3H), 2.36 (s, 3H), 3.43 (t, 1H), 5.18 (s, 2H), 7.17～7.41 (m, 12H) .E body 0.91 (t, 3H), 1.72 (m, 2H), 2.1 3 (s, 3H), 2.28 (s, 3H), 2.37 (s, 3H), 4.65 (t, 1H), 5.29 (s, 2H), 7.15～7.70 (m, 12H) .M +(403).
142 ?4-CH 3 ?1 ?C 2H 5 The 3-phenoxy group Oily matter Z body 0.97 (t, 3H), 1.60 (m, 2H), 1.93 (s, 3H), 2.36 (s, 3H), 3.37 (t, 1H), 5.05 (s, 2H), 6.94～7.35 (m, 13 H) .M +(405) .E body 0.86 (t, 3H), 1.66 (m, 2H), 2.07 (s, 3H), 2.35 (s, 3H), 4.58 (t, 1H), 5.16 (s, 2H), 7.00～7.63 (m, 13H) .M +(405).
143 ?4-Cl ?1 ?CH(CH 3) 2 The 3-phenoxy group Oily matter 0.93(d，3H)，1.02(d，3H)，1.80(m，1H)，1.91(s，3H) ，3.10(d，1H)，5.04(s，2H)，6.97～7.39(m，13H).M +(439).
144 ?4-Cl ?1 ?H ?4-NO 2 78.1-78.5 2.08(s，3H)，3.80(s，2H)，5.32(s，2H)，7.26～8.25( m，8H).
Annotate: all hydrogen spectrum data δ (ppm) are with CDCl 3Make solvent, mark in TMS does.All fusing points are not calibrated.：
Table 2 part of compounds is to the biological activity (mortality ratio %) of mythimna separata (100ppm), leafhopper (100ppm) and bean sprouts (100ppm)
( *The expression compound is to the biological activity (mortality ratio %) of mythimna separata (1000ppm), leafhopper (500ppm) and bean sprouts (500ppm))
Compound Mythimna separata Leafhopper The bean sprouts
1-phenyl-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 100 100 100
1-(4-chloro-phenyl-)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 100 100 100
1-phenyl-2-methylthio group-O-[(3-(4-bromine phenoxy group) phenyl) methyl] oxime-1-ethyl ketone 90 * 100 * 65 *
1-(4-chloro-phenyl-)-2-methylthio group-O-[(2,3,4,5, the 6-pentafluorophenyl group) methyl] oxime-1-ethyl ketone 90 * 90 * 11 *
1-(4-chloro-phenyl-)-2-methylthio group-O-[(3-(4-bromine phenoxy group) phenyl) methyl] oxime-1-ethyl ketone 100 * 100 * 100 *
1-(4-chloro-phenyl-)-2-methylthio group-O-[(2, the 6-dichlorophenyl) methyl] oxime-1-ethyl ketone 30 * 0 * 30 *
1-(4-chloro-phenyl-)-2-methylthio group-O-[(2, the 5-3,5-dimethylphenyl) methyl] oxime-1-ethyl ketone 0 * 10 * 90 *
1-(4-chloro-phenyl-)-2-methylthio group-O-[(2, the 4-3,5-dimethylphenyl) methyl] oxime-1-ethyl ketone 10 * 100 * 70 *
1-(4-chloro-phenyl-)-2-methylthio group-O-[(2-chlorine 6-fluorophenyl) methyl] oxime-1-ethyl ketone 0 * 0 * 60 *
1-phenyl-2-methylthio group-O-[(4-p-methoxy-phenyl) methyl] oxime-1-ethyl ketone 0 * 60 * 10 *
1-(4-chloro-phenyl-)-2-methylthio group-O-[(4-chloro-phenyl-) methyl] oxime-1-ethyl ketone 0 * 0 * 0 *
1-(4-chloro-phenyl-)-2-methylthio group-O-[(4-tert-butyl-phenyl) methyl] oxime-1-ethyl ketone 0 * 0 * 0 *
1-(4-chloro-phenyl-)-2-methylthio group-O-[(4-tert-butoxycarbonyl phenyl) methyl] oxime-1-ethyl ketone 0 * 0 * 0 *
1-(4-aminomethyl phenyl)-2-methylthio group-O-[(3-(4-bromine phenoxy group) phenyl) methyl] oxime-1-ethyl ketone 100 * 100 * 100 *
1-(4-aminomethyl phenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl]] oxime-1-ethyl ketone 100 100 100
1-(4-aminomethyl phenyl)-2-methylthio group-O-[(3-phenoxy phenyl) methyl] oxime-1-ethyl ketone 100 100 100
1-(4-aminomethyl phenyl)-2-methylthio group-O-[(2,3,4,5, the 6-pentafluorophenyl group) methyl] oxime-1-ethyl ketone 60 * 100 * 80 *
1-(4-p-methoxy-phenyl)-2-methylthio group-O-[(3-phenoxy phenyl) methyl] oxime-1-ethyl ketone 100 * 100 * 100 *
1-(4-bromophenyl)-2-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-ethyl ketone 100 100 100
1-(4-bromophenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 100 100 100
1-(4-isopropyl phenyl)-2-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-ethyl ketone 100 * 100 20 *
1-(4-isopropyl phenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 100 * 100 100 *
1-(4-ethylphenyl)-2-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-ethyl ketone 100 100 100
1-(4-ethylphenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 100 100 100
1-(4-ethoxyl phenenyl)-2-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-ethyl ketone 100 * 100 100
1-(4-ethoxyl phenenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 100 100 100
1-(4-fluorophenyl)-2-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-ethyl ketone 100 * 100 100 *
1-(4-fluorophenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 100 100 100
1-(3-trifluoromethyl)-2-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-ethyl ketone 100 * 100 * 100 *
1-(3-trifluoromethyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 100 100 100
1-(4-trifluoromethyl)-2-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-ethyl ketone 100 100 100
1-(4-trifluoromethyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 100 100 100
1-(4-difluoro-methoxy phenyl)-2-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-ethyl ketone 100 * 100 100
1-(4-difluoro-methoxy phenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 100 * 100 100
1-(3-nitrophenyl)-2-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-ethyl ketone 90 * 80 * 70 *
1-(3-nitrophenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 95 * 100 85 *
1-(4-Trifluoromethoxyphen-l)-2-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-ethyl ketone 100 100 100
1-(4-Trifluoromethoxyphen-l)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 100 100 100
1-(4-tert-butyl-phenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 100 * 100 90 *
1-(4-pyridyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 100 * 100 * 100 *
1-(2-pyridyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 40 * 60 * 100 *
1-(2-thienyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 100 * 100 * 40 *
1-(2-furyl)-2-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-ethyl ketone 25 * 0 * 50 *
1-(2-furyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 100 * 100 * 100 *
1-(2-naphthyl)-2-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-ethyl ketone 80 * 100 * 60 *
1-(2-naphthyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 90* 90 * 100 *
Continuous table 2
Compound Mythimna separata Leafhopper The bean sprouts
1-(3, the 4-3,5-dimethylphenyl)-2-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-ethyl ketone 100 * 100 * ?100 *
1-(3, the 4-3,5-dimethylphenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 100 100 ?100
1-(3, the 4-dichlorophenyl)-2-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-ethyl ketone 100 * 100 ?100 *
1-(3, the 4-dichlorophenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 100 100 ?100
1-(3-chloro-4-aminomethyl phenyl)-2-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-ethyl ketone 100 * 100 ?100
1-(3-chloro-4-aminomethyl phenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 100 100 ?100
1-(3-fluoro-4-bromophenyl)-2-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-ethyl ketone 100 100 ?100
1-(3-fluoro-4-bromophenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 100 100 ?100
1-(2, the 4-3,5-dimethylphenyl)-2-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-ethyl ketone 100 100 ?100
1-(2, the 4-3,5-dimethylphenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 100 100 ?100
1-(2-chloro-4-aminomethyl phenyl)-2-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-ethyl ketone 100 100 ?100
1-(2-chloro-4-aminomethyl phenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 100 100 ?100
1-(2,4 dichloro benzene base)-2-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-ethyl ketone 100 * 70 * ?100 *
1-(2,4 dichloro benzene base)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 100 100 ?100
1-(3-fluoro-4-aminomethyl phenyl)-2-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-ethyl ketone 100 100 ?100
1-(3-fluoro-4-aminomethyl phenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 100 100 ?100
1-(3-bromo-4-aminomethyl phenyl)-2-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-ethyl ketone 100 100 ?100
1-(3-bromo-4-aminomethyl phenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 100 100 ?100
1-(3, the 5-bis trifluoromethyl phenyl)-2-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-ethyl ketone 0 * 0 * ?20 *
1-(3, the 5-bis trifluoromethyl phenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 60 * 100 ?20 *
1-(3-fluoro-4-chloro-phenyl-)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 100 100 ?100
1-(3-chloro-4-fluorophenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 100 100 ?100
1-(4-chloro-phenyl-)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-acetone 100 * 100 ?100 *
1-(4-aminomethyl phenyl)-2-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-acetone 100 * 100 ?95 *
1-(4-p-methoxy-phenyl)-2-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-acetone 100 * 100 ?85 *
1-(4-bromophenyl)-2-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-acetone 100 100 ?100
1-(4-ethoxyl phenenyl)-2-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-acetone 100 100 ?100
1-(4-ethoxyl phenenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-acetone 100 100 ?100
1-(3-chloro-phenyl-)-2-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-acetone 100 100 ?0 *
1-(4-fluorophenyl)-2-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-acetone 100 100 ?100
1-(4-fluorophenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-acetone 100 * 60 * ?90 *
1-(3, the 4-3,5-dimethylphenyl)-2-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-acetone 100 * 100 ?100 *
1-(3-fluoro-4-bromophenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-acetone 100 * 100 ?80 *
1-(3, the 4-dichlorophenyl)-2-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-acetone 100 * 100 ?100 *
1-(3-chloro-4-aminomethyl phenyl)-2-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-acetone 100 * 100 ?90 *
1-(3-chloro-4-aminomethyl phenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-acetone 100 * 70 * ?0 *
1-(4-chloro-phenyl-)-1-methylthio group-O-[(3-Phenoxyphenyl) methyl] oxime-1-ketone 100 * 50 * ?/
1-(4-chloro-phenyl-)-1-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ketone 100 0 * ?/
1-phenyl-2-methoxyl group-O-[(3-Phenoxyphenyl) methyl] oxime-1-ethyl ketone 50 * 10 * ?0 *
1-phenyl-2-methoxyl group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 100 100 ?100
1-(4-aminomethyl phenyl)-2-methoxyl group-O-[(3-Phenoxyphenyl) methyl] oxime-1-ethyl ketone 40 * 50 * ?85 *
1-(4-aminomethyl phenyl)-2-methoxyl group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 100 100 ?100
1-(4-ethoxyl phenenyl)-2-methoxyl group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 100 100 ?100 *
1-(4-p-methoxy-phenyl)-2-methoxyl group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 100 100 ?100
1-(3, the 4-3,5-dimethylphenyl)-2-methoxyl group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone 100 100 ?100
1-(4-chloro-phenyl-)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-butanone 90 * 70 * ?20 *
1-(4-chloro-phenyl-)-2-methylthio group-3-methyl-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-butanone 0 * 0 * ?0 *
Table 3 part of compounds fungicidal activity test result
Compound number The cucumber grey mold The rape sclerotium The rice blast pathogenic bacteria
????092 ????B ????D ????D
????111 ????D ????A ????D
????136(Z) ????D ????D ????A
????136(E) ????B ????D ????D
????144 ????A ????D ????D
Annotate: cucumber grey mold (500ppm, method B), rape sclerotium (500ppm, method B), rice blast pathogenic bacteria (25ppm, method A)

Claims (10)

1. sulfur-bearing, oxime-containing ether compound is characterized in that with general formula (I) expression:
Figure A2003101106470002C1
In the general formula (I):
The I.Ar representative
(a) (C 6-C 12The heteroaryl of)-aryl or 10 carbon atoms of band as many as;
(b) as determined implication in (I.a), be selected from case of necessity following in 0 to 5 identical or different substituting group replace: hydrogen, halogen, alkyl, alkoxyl group, alkylthio, carbalkoxy, haloalkyl, halogenated alkoxy, halogenated alkylthio, halo alkoxy carbonyl;
II.R represents alkyl or haloalkyl;
III.R 1Represent hydrogen, halogen, alkyl or haloalkyl;
IV.F tRepresentative
(a) 0 to 5 identical or different substituting group in following: hydrogen, halogen, alkyl, alkoxyl group, haloalkyl, halogenated alkoxy, carbalkoxy, nitro, (C 6-C 12The heteroaryl of)-aryl or 10 carbon atoms of band as many as, (C 6-C 12The heteroaryl oxygen base of)-aryloxy or 10 carbon atoms of band as many as, (C 6-C 12The heteroaryl methyl of)-arylmethyl or 10 carbon atoms of band as many as, (C 6-C 12The heteroaryl amido of)-arylamine group or 10 carbon atoms of band as many as;
(b) as determined implication in (IV.a), be selected from case of necessity following in 0 to 5 identical or different substituting group replace:
Hydrogen, halogen, alkyl, alkoxyl group, haloalkyl, halogenated alkoxy, aryl, heteroaryl;
V.t represents 0 to 5 integer;
VI.X represents O, S, SO or SO 2
VII.n represents 0 or 1;
Work as F t=3-phenoxy group, R=methyl, R 1=hydrogen or methyl, X=S, during n=1, Ar ≠ 4-chloro-phenyl-; Alkyl: refer to have the straight or branched alkyl of 1-6 carbon atom, for example methyl, ethyl, n-propyl, sec.-propyl or different butyl, amyl group, hexyl isomer;
Halogen: refer to fluorine, chlorine, bromine and iodine;
Haloalkyl: refer to have the straight or branched alkyl of 1-6 carbon atom, the hydrogen atom on these alkyl can partly or entirely be replaced by halogen atom, for example, and C 1Haloalkyl such as chloromethyl, brooethyl, methyl fluoride, dichloromethyl, two brooethyls, difluoromethyl, trichloromethyl, trisbromomethyl, trifluoromethyl, chlorine methyl fluoride, chlorine brooethyl, Halothane methyl;
Alkoxyl group: refer to have the straight or branched alkoxyl group of 1-6 carbon atom, be connected on the structure through the Sauerstoffatom key;
Alkylthio: refer to have the straight or branched alkylthio of 1-6 carbon atom, be connected on the structure through the sulphur atom key;
Halogenated alkoxy: refer to have the straight or branched alkoxyl group of 1-6 carbon atom, the hydrogen atom on these alkoxyl groups can partly or entirely be replaced by halogen atom, for example, and C 1Halogenated alkoxy such as chlorine methoxyl group, bromine methoxyl group, fluorine methoxyl group, dichloro methoxyl group, dibromo methoxyl group, difluoro-methoxy, trichlorine methoxyl group, tribromo methoxyl group, trifluoromethoxy, chlorine fluorine methoxyl group, chlorine bromine methoxyl group, chlorine fluorine bromine methoxyl group;
Aryl: the naphthyl that refers to have the phenyl of 6 carbon atoms and have 12 carbon atoms, xenyl;
Heteroaryl: refer to have one or more heteroatomic 5 yuan of rings, 6 yuan of rings, 5 yuan of rings of benzo or 6 yuan of rings of benzo.For example thienyl, benzothienyl, furyl, benzofuryl, pyrryl, indyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, oxazolyl, isoxazolyl, thiazolyl and isothiazolyl.
2. sulfur-bearing according to claim 1, oxime-containing ether compound is characterized in that Ar represents a group as follows in the general formula (I):
Figure A2003101106470003C1
Shown in above-mentioned in the group:
R p 1Be identical or different, and represent hydrogen, halogen, alkyl, alkoxyl group, alkylthio, alkoxy carbonyl, haloalkyl, halogenated alkoxy, halogenated alkylthio or halo alkoxy carbonyl; P is one 0 to 5 a integer; Z is O, S or NR 2, R 2Be hydrogen, (C 1-C 4)-alkyl, (C 6-C 12)-aryl, the heteroaryl of 10 carbon atoms of band as many as;
R and R 1Be identical or different, and represent methylidene or trifluoromethyl;
F tRepresent hydrogen, methyl, trifluoromethyl, phenoxy group, pyridyloxy, phenyl, 4-fluorophenyl oxygen base or 4-fluoro-3-phenoxy group;
T represents 1 to 5 integer;
N represents 0 or 1;
X represents sulphur or oxygen.
3. sulfur-bearing according to claim 1 and 2, oxime-containing ether compound is characterized in that Ar represents a group as follows in the general formula (I):
Figure A2003101106470003C2
Shown in above-mentioned in the group: R 1 1And R 2 1Be identical or different, and represent hydrogen, halogen, alkyl, haloalkyl, alkoxyl group, halogenated alkoxy, carbalkoxy;
R and R 1Be identical or different, and represent methylidene or trifluoromethyl;
F tRepresent hydrogen, methyl, trifluoromethyl, phenoxy group, pyridyloxy, phenyl, 4-fluorophenyl oxygen base or 4-fluoro-3-phenoxy group;
T represents 1 or 2;
N represents 0 or 1;
X represents sulphur or oxygen.
4. according to claim 1 or 3 described sulfur-bearings, oxime-containing ether compound, it is characterized in that Ar represents a group as follows in the general formula (I):
Shown in above-mentioned in the group: R 1 1And R 2 1Be identical or different, and represent hydrogen, halogen, alkyl, haloalkyl, alkoxyl group, halogenated alkoxy, carbalkoxy or halo alkoxy carbonyl;
R and R 1Represent methylidene;
F tRepresent the 3-phenoxy group, 2-methyl-3-phenyl or 3-phenoxy group-4-fluorine;
N represents 0 or 1;
X represents sulphur or oxygen.
5. according to claim 1 or 4 described sulfur-bearings, oxime-containing ether compound: 1-(3-fluoro-4-aminomethyl phenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone; 1-(3-fluoro-4-chloro-phenyl-)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone; 1-(4-trifluoromethyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone; 1-(4-fluorophenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone; 1-(4-p-methoxy-phenyl)-2-methoxyl group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone; 1-(4-chloro-phenyl-)-1-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ketone; 1-(3-fluoro-4-bromophenyl)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-1-ethyl ketone; 1-(4-Trifluoromethoxyphen-l)-2-methylthio group-O-[(2-methyl biphenyl-3-yl) methyl] oxime-]-ethyl ketone; 1-(4-phenelyl)-2-methylthio group-O-[(3-phenoxy phenyl) methyl] oxime-1-acetone; 1-(4-fluorophenyl)-2-methylthio group-O-[(3-phenoxy phenyl) methyl] oxime-1-acetone.
6. according to the described sulfur-bearing of claim 1-5, oxime-containing ether compound, it is characterized in that the compound shown in the general formula (I) can occur with Z formula and two kinds of geometrical isomer forms of E formula, the Z formula is that oxime-oxygen and Ar are in the two key homonymies of C=N, and the E formula is that oxime-oxygen and Ar are in the two key heteropleurals of C=N;
Figure A2003101106470004C1
Z formula E formula
Compound shown in the general formula (I), as have one or more unsymmetrical carbons, it can be a racemic modification, diastereomer or pure optical isomer;
Compound shown in the general formula (I) not only relates to pure isomer, also relates to various mixture of isomers.
7. the preparation method of sulfur-bearing according to claim 1, oxime-containing ether compound is characterized in that:
A) compound shown in compound shown in the employing formula (II) and the formula (III)
Figure A2003101106470004C2
At an appropriate base such as alkali metal hydroxide, alkaline carbonate, alkali metal alcoholates, basic metal, alkalimetal hydride, pyridine or tertiary amine exist down, in the adding following solvents one or both: water, tetrahydrofuran (THF), toluene, benzene, acetonitrile, dimethyl sulfoxide (DMSO) adds the phase-transfer catalyst tetrabutylammonium iodide, Tetrabutyl amonium bromide again, tetraethylammonium bromide, a kind of in the hexaoxacyclooctadecane-6-6, in normal pressure, reaction 1-10 hour under the 0-120 ℃ of condition and general formula (I) compound, in formula (II) and the formula (III), Ar, R, R 1, n, X and F tAs mentioned above, L represents a leavings group, as chlorine, and bromine;
B) with the compound shown in formula (IV) at an appropriate base such as sodium hydroxide, triethylamine or yellow soda ash exist down with the compound shown in the formula V or their reactant salt and general formula (I) compound, in formula (IV) and the formula V, Ar, R, R 1, n, X and F tAs mentioned above;
Figure A2003101106470004C3
C) with compound shown in the formula (II) and the compound shown in the formula (VI)
Figure A2003101106470005C1
In the presence of an appropriate base such as sodium hydroxide or potassium hydroxide, add suitable solvent, as water and toluene mixed solvent, in normal pressure, reaction is 3-10 hour and get under the 60-100 ℃ of condition; In formula (II) and the formula (VI), Ar, R, R 1, n, X and F tAs mentioned above, X represents a leavings group, as chlorine, bromine, formula (II) are with formula (IV) and hydroxylamine hydrochloride or hydroxylamine sulfate, at alkali metal hydroxide, alkaline carbonate, alkali metal hydrocarbonate, pyridine, a kind of alkali in the triethylamine exists down, adds entry, a kind of in the alcohol or two kinds, in normal pressure, 0-100 ℃ of reaction 1-10 hour and get, the middle Ar of formula (IV) and formula (II), R, R 1, n, X are as mentioned above.
8. a desinsection, Bactericide composition, it contains among the with good grounds claim 1-5 each compound and carrier thereof.
9. according to the described sulfur-bearing of claim 1-5, oxime-containing ether compound, it is characterized in that having the effect of control pest on crop and pathogenic bacteria.
10. contain at least one according among the claim 1-5 each compound and conventional additive and auxiliary material kill the purposes of harmful organism medicament on insect and pathogenic bacteria.
CN 200310110647 2003-12-12 2003-12-12 Insecticidal and bactericidal sulfur-containing and hydroxamic ether compounds Expired - Fee Related CN100579956C (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN 200310110647 CN100579956C (en) 2003-12-12 2003-12-12 Insecticidal and bactericidal sulfur-containing and hydroxamic ether compounds
PCT/CN2004/001282 WO2005056518A1 (en) 2003-12-12 2004-11-11 Sulfur- or oxygen-containing oxime ether compounds with biocidal activity

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 200310110647 CN100579956C (en) 2003-12-12 2003-12-12 Insecticidal and bactericidal sulfur-containing and hydroxamic ether compounds

Publications (2)

Publication Number Publication Date
CN1546462A true CN1546462A (en) 2004-11-17
CN100579956C CN100579956C (en) 2010-01-13

Family

ID=34335694

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 200310110647 Expired - Fee Related CN100579956C (en) 2003-12-12 2003-12-12 Insecticidal and bactericidal sulfur-containing and hydroxamic ether compounds

Country Status (2)

Country Link
CN (1) CN100579956C (en)
WO (1) WO2005056518A1 (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102030680A (en) * 2010-10-20 2011-04-27 湖北省生物农药工程研究中心 Novel oxime ether or ester derivatives with insecticidal activity, preparation method and application thereof
CN102228044A (en) * 2011-05-11 2011-11-02 青岛海利尔药业有限公司 Insecticidal composition containing sufluoxime
CN102239875A (en) * 2011-05-17 2011-11-16 海利尔药业集团股份有限公司 Insecticidal composition containing 1-(3-fluoro-4-chlorphenyl)-2-methylthioethanone-O-(2-hydroxymethyl-3-methyl)aether and partial nicotine compounds
CN102326538A (en) * 2011-10-31 2012-01-25 湖南化工研究院 Thiofluoximate capsule suspension, preparation method and application
CN102911093A (en) * 2012-10-25 2013-02-06 湖南化工研究院 Preparation method for sulfur fluorine oxime ether
CN103053558A (en) * 2013-01-16 2013-04-24 海利尔药业集团股份有限公司 Insecticide composition containing 1-(3-fluoro-4-chlorophenyl)-2-hexamethyl ethyl ketoxime-O-(2-methyl biphenyl) ether and spirotetramat
EP2649879A1 (en) 2012-04-10 2013-10-16 Basf Se Pesticidal mixtures containing fluxapyroxad
CN103734180A (en) * 2013-12-30 2014-04-23 孙蒙蒙 Bactericidal and insecticidal composite containing sulfur-fluorine oxime ether
CN103980179A (en) * 2014-05-29 2014-08-13 厦门大学 Indole-substituted oxime ether compounds as well as preparation method and application thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IL56878A (en) * 1978-03-31 1984-03-30 Rhone Poulenc Inc Ketoximinoethers and their use as insecticides
CN1099408C (en) * 1998-10-07 2003-01-22 湖南化工研究院 Biocidal oximido ether compound
CN1159290C (en) * 1999-09-10 2004-07-28 湖南化工研究院 Method for preparing biocide alkyl-substituted (hetero)-aryl-ketoxime-o-ether and its intermediate ketone or oxime compounds
CA2389805A1 (en) * 1999-11-05 2001-05-17 Hiroshi Sano Oxime o-ether compounds and fungicides for agricultural and horticultural use
EP1125931A1 (en) * 2000-02-17 2001-08-22 Hunan Research Institute of Chemical Industry Biocidal alkyl-substituted-(hetero)aryl-ketoxime-O-ethers and the production method thereof

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102030680A (en) * 2010-10-20 2011-04-27 湖北省生物农药工程研究中心 Novel oxime ether or ester derivatives with insecticidal activity, preparation method and application thereof
CN102228044A (en) * 2011-05-11 2011-11-02 青岛海利尔药业有限公司 Insecticidal composition containing sufluoxime
CN102228044B (en) * 2011-05-11 2013-04-24 海利尔药业集团股份有限公司 Insecticidal composition containing sufluoxime
CN102239875A (en) * 2011-05-17 2011-11-16 海利尔药业集团股份有限公司 Insecticidal composition containing 1-(3-fluoro-4-chlorphenyl)-2-methylthioethanone-O-(2-hydroxymethyl-3-methyl)aether and partial nicotine compounds
CN102326538A (en) * 2011-10-31 2012-01-25 湖南化工研究院 Thiofluoximate capsule suspension, preparation method and application
EP2649879A1 (en) 2012-04-10 2013-10-16 Basf Se Pesticidal mixtures containing fluxapyroxad
CN102911093A (en) * 2012-10-25 2013-02-06 湖南化工研究院 Preparation method for sulfur fluorine oxime ether
CN102911093B (en) * 2012-10-25 2014-08-13 湖南化工研究院 Preparation method for sulfur fluorine oxime ether
CN103053558A (en) * 2013-01-16 2013-04-24 海利尔药业集团股份有限公司 Insecticide composition containing 1-(3-fluoro-4-chlorophenyl)-2-hexamethyl ethyl ketoxime-O-(2-methyl biphenyl) ether and spirotetramat
CN103734180A (en) * 2013-12-30 2014-04-23 孙蒙蒙 Bactericidal and insecticidal composite containing sulfur-fluorine oxime ether
CN103734180B (en) * 2013-12-30 2015-12-30 刘一平 A kind of Fungicidal insecticidal composition containing sufluoxime
CN103980179A (en) * 2014-05-29 2014-08-13 厦门大学 Indole-substituted oxime ether compounds as well as preparation method and application thereof

Also Published As

Publication number Publication date
CN100579956C (en) 2010-01-13
WO2005056518A1 (en) 2005-06-23

Similar Documents

Publication Publication Date Title
CN1095837C (en) Pyridazinone and application as fungicide
CN1869034A (en) An arylether kind compound and its preparation and application
CN1437583A (en) Trifluoromethylpyrrole carboxamide and trifluoromethylpyrrole ethionamide as fungicides
CN87104974A (en) The preparation method of the hydrazone that replaces and be used as the purposes of sterilant
CN1353700A (en) Isothiazole carboxamides and their use as microbicides
CN1188764A (en) Pyrazole compounds used as agricultrial germicide and insecticide and acaricide and its preparation
CN1100761C (en) Benzyloxy substituted aromatics and their use as fungicides and insecticides
CN1025502C (en) Preparation method of novel silane derivatives
CN1126742C (en) fungicidal compound
CN1546462A (en) Insecticidal antibacterial sulphur , oxygen and oxime-containing ether compounds
CN1293083C (en) Siliconated phenyl amides derivatives useful as microbiocide
CN1802091A (en) Use of isoindolinone derivatives as insecticides
CN1159290C (en) Method for preparing biocide alkyl-substituted (hetero)-aryl-ketoxime-o-ether and its intermediate ketone or oxime compounds
CN1207725A (en) pesticide
CN1420875A (en) Isothiazolecarboxylic acid derivs. and their use as microbicides
CN1333761A (en) Isothiazolecarboxylic acid derivatives
CN1294574A (en) Fungicidal amides
CN1027448C (en) Preparation method of heterocyclic neofetane analogs
CN1060161C (en) N-substituted phenylcarbamic acid derivatives, process for production thereof, agricultural and horticultural fungicides, intermediates of derlvatives and process for production thereof
CN1439007A (en) 2-(3,5-disubstituted-4-pyridyl)-4(thienyl, thiazolylor arylphenyl)-1, 3-oxazoline compounds
CN1227551A (en) N-sulfonylimidazoles as fungicides
CN1264364A (en) Disease or insect pest control agent containing alkoxyimino-substituted bicyclic derivatives as active ingredient
CN1670016A (en) Arylpyrrole compounds with insecticidal, acaricidal and fungicidal biological activities and preparation method thereof
CN1852909A (en) Silicon compounds with microbicidal activity
CN1259118A (en) organic compounds

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
EE01 Entry into force of recordation of patent licensing contract

Assignee: HUNAN HAILI CHEMICAL INDUSTRY CO.,LTD.

Assignor: HUNAN Research Institute OF CHEMICAL INDUSTRY

Contract record no.: 2011430000170

Denomination of invention: Insecticidal antibacterial sulphur , oxygen and oxime-containing ether compounds

Granted publication date: 20100113

License type: Exclusive License

Open date: 20041117

Record date: 20110908

CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20100113

Termination date: 20211212