CN1117728A - Substituted oxazoles - Google Patents

Substituted oxazoles Download PDF

Info

Publication number
CN1117728A
CN1117728A CN 94191164 CN94191164A CN1117728A CN 1117728 A CN1117728 A CN 1117728A CN 94191164 CN94191164 CN 94191164 CN 94191164 A CN94191164 A CN 94191164A CN 1117728 A CN1117728 A CN 1117728A
Authority
CN
China
Prior art keywords
alkyl
alkoxyl group
replaces
general formula
optional
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.)
Pending
Application number
CN 94191164
Other languages
Chinese (zh)
Inventor
D·阿尔特
U·瓦晨多尔夫-纽曼
C·艾尔德伦
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.)
Bayer AG
Original Assignee
Bayer AG
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 Bayer AG filed Critical Bayer AG
Publication of CN1117728A publication Critical patent/CN1117728A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D263/32—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

The invention relates to novel substituted oxazoles of the general formula (I) in which R<1> is hydrogen, alkyl or halogen; R<2> is alkyl or halogen; Ar is a phenyl radical optionally substituted by halogen, alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy, alkinyloxy, alkoxyalkyl, alkoxyalkoxy, optionally substituted cycloalkyl, optionally substituted cycloalkyloxy, optionally substituted aryl, optionally substituted aryloxy, optionally substituted arylalkyl and/or optionally substituded arylalkyloxy; X is a group of the formula: -CH2-CH2-; -CH2-CH2-CH2-; -CH=CH-; -CH2-CH=CH-; -CH2-O-; -CH2-S-; -CH2-N(R<3>)-; -CH2-O-CH2-; -CH2-O-CH2-CH2- or -CH2-O-CO-; where R<3> is hydrogen, alkyl or alkanoyl; and n is 0 or 1. Said oxazoles may be used as pesticides.

Description

Replace De oxazole compound
The present invention relates to new replacement De oxazole compound, its multiple preparation method, and as the purposes of sterilant.
Some replacement De oxadiazole compounds, 3-(3-chloro-phenyl-)-5-(2-chloro-phenyl-)-1,2 for example, 4-oxadiazole compound have extremely mite and insecticidal activity (referring to, for example, EP 36 711) be what to disclose already.
, in the various fields of using, when particularly using to some insects and/or with low dosage, it is satisfied fully that the exposure level of these compounds of the prior art and long-lasting can not be made us.
Found the new replacement De oxazole compound of general formula (I) at this:
Figure A9419116400091
Wherein
R 1Represent hydrogen, alkyl or halogen,
R 2Represent alkyl or halogen,
Ar representative can be by the optional phenyl that replaces of following radicals: halogen, alkyl, alkenyl,
Alkynyl group, alkoxyl group, alkenyloxy, chain oxy-acetylene, alkoxyalkyl, alcoxyl
Base alkoxyl group, the optional cycloalkyl that replaces, the optional cycloalkyloxy that replaces, optional
The aryl that replaces, the optional aryloxy that replaces, the optional aralkyl that replaces and/or
The optional aralkoxy that replaces; X represents the group of following formula :-CH 2-CH 2-;-CH 2-CH 2-CH 2-;
-CH＝CH-；-CH 2-CH＝CH-；-CH 2-O-；-CH 2-S-；-CH 2-N(R 3)-；
-CH 2-O-CH 2-;-CH 2-O-CH 2-CH 2-or-CH 2-O-CO-R 3Represent hydrogen, alkyl or alkanoyl; With
N is 0 or 1.
If be fit to, according to substituent character, formula (I) compound can geometrical isomer and/or the form of mixtures formed of optically active isomer or multiple isomer exist.The present invention relates to pure isomer and also relate to isomer mixture.
And, found can obtain as follows the new replacement De oxazole compounds of general formula (I), a) prepare n wherein and be 0 general formula (I) compound:
With the benzonitrile compounds of general formula (II) and the α of general formula (III)-chloro-styrene compounds reaction,
Wherein
R 1And R 2Have above-mentioned definition,
Wherein
Ar has above-mentioned definition, in the first step, react at first with chlorine (being preferably gas), in the presence of thinner, reacting in the presence of the catalyzer and if desired if desired, and in second step, in the presence of reaction promoter, react subsequently, if desired in the presence of phase-transfer catalyst and if desired, in the presence of thinner, react with water; Or b) preparation general formula (I) compound, wherein X represents Shi-CH 2-O-;-CH 2-S-;-CH 2-N (R 3)-;-CH 2-O-CH 2-;-CH 2-O-CH 2-CH 2-or-CH 2The group of-O-CO-and n are 1, R 3Have above-mentioned definition:
The chlorine first base oxazole compounds of general formula (IV) and the alcohol derivate of logical formula V, phenol derivatives, carboxylic acid derivative, sulfonamide derivatives or thiol derivative reaction,
Wherein
R 1And R 2Have above-mentioned definition,
H-X 1-Ar (V)
Wherein
X 1Representative-O-;-S-;-N (R 3)-;-O-CH 2-;-O-CH 2-CH 2-or-O-CO-, wherein R 3Have above-mentioned definition, in the presence of reaction promoter, reacting in the presence of the thinner and if desired if desired; Or c) compound of preparation general formula (I), wherein X represents Shi-CH 2-CH 2-;-CH 2-CH 2-CH 2-;-CH=CH-or-CH 2Group and the n of-CH=CH-represent 1:
With the Lv Jia Ji oxazole compounds of general formula (IV) and the phenylacetylene compounds of general formula (VI), or with the reaction of the benzyl sulfone compound of general formula (VII),
Figure A9419116400121
Wherein
R 1And R 2Have above-mentioned definition,
H-C≡C-Ar (VI)
Wherein
Ar has above-mentioned definition,
Ar-SO 2-CH 2-Ar (VII)
Wherein
Ar has above-mentioned definition, if desired in the presence of thinner, in the presence of reaction promoter, reacting in the presence of the phase-transfer catalyst and if desired if desired, and if desired in second step subsequently, in the presence of catalyzer, if desired in the presence of thinner, replace De oxazole compounds with the general formula (I) of hydrogen hydrogenation gained, wherein X representative-CH=CH-or-CH 2-CH=CH-and n represent 1, to prepare wherein X representative-CH 2-CH 2-or-CH 2-CH 2-CH 2-and n represent the compound of 1 general formula (I).
At last, found that the new replacement De oxazole compounds of general formula (I) has good pest control, particularly prevented and treated arthropods, preferably prevented and treated the activity of mite class and insects.
This paper preferred substituents or the scope above-mentioned and general formula that this paper is following are shown in hereinafter:
In general formula, the moieties of alkyl and alkoxyl group representative preferably has 1 to 18, more preferably has 1-16 and especially preferably have the straight or branched alkyl of 1-12 carbon atom.What should address especially is to have 1 to 8 and have 1-6 especially and the alkyl of the more special 1-4 of a having carbon atom.
The example that can address is: methyl, ethyl, n-propyl and sec.-propyl, normal-butyl, sec-butyl, isobutyl-and the tertiary butyl, 1,1-dimethyl propyl, n-hexyl, 1,1,3,3-tetramethyl butyl, methoxyl group, oxyethyl group, positive propoxy and isopropoxy and n-butoxy, sec-butoxy, isobutoxy and tert.-butoxy.
The alkenyl of alkenyl and alkenyloxy partly is straight or branched and preferably have 2 to 12, more preferably has 2 to 8 and more especially preferably have the alkenyl of 3 or 4 carbon atoms, and the example that can address is allyl group and allyloxy.
The alkynyl group of alkynyl group and chain oxy-acetylene partly is straight or branched and preferably have 2 to 12, more preferably has 2 to 8 and more especially preferably have the alkynyl group of 3 or 4 carbon atoms, and the example that can address is propargyl and alkynes propoxy-.
The alkyl of alkoxyalkyl and alkoxyl group alkoxyl group or alkoxyl group part preferably has 1 to 8 under each situation, more preferably have 1 to 6 and more especially preferably have 1 to 4 carbon atom, and this alkyl and alkoxy portion can be straight or brancheds.The example that can address is methoxyl methyl, methoxyethyl, ethoxy methoxyl group and ethoxy oxyethyl group.
The cycloalkyl moiety of cycloalkyl and cycloalkyloxy preferably has 3 to 8, has 3 to 7 and have 3 to 6 carbon atoms more especially especially, and the example that can address is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentyloxy and cyclohexyloxy.
The aryl moiety of aryl and aryloxy, aralkyl and aralkoxy preferably has 6 or 10 carbon atoms, is preferably phenyl or how basic especially, and the more special phenyl that is preferably.
The moieties of aralkyl and aralkoxy be straight or branched and preferably have 1 to 8, more preferably have 1 to 6 and more especially preferably have 1 to 4 carbon atom.
The moieties of alkanoyl can be straight or branched and preferably have 2 to 7, more preferably have 2 to 5 and more especially preferably have 2 to 4 carbon atoms.
Except as otherwise noted, Hal and halogen are represented fluorine, chlorine, bromine or iodine, preferably represent fluorine, chlorine or bromine and more preferably represent fluorine or chlorine.
But Ar coverlet replacement or polysubstituted is preferably replaced to five replacements by identical or different substituting group list, more preferably single the replacement to three replacements and single the replacement or two replacement.Represent at Ar under the situation of phenyl, substituting group is preferably placed at the 4-position and/or the 2-position of phenyl ring.Preferably have at least a substituting group to be connected on the Ar.
Cycloalkyl, cycloalkyloxy, aryl, aryloxy, the cycloalkyl in aralkyl and the aralkoxy, aryl and/or moieties can connect one or more thereon, and preferred 1 to 5, more preferably 1 to 3 and preferred more especially 1 to 2 identical or different substituting group.The preferred substituted that can address is preferably to have 1 to 8, the more preferably alkyl and/or the alkoxyl group of 1 to 6 and preferred more especially 1 to 4 carbon atom, and the example that can address is methyl, ethyl, n-propyl and sec.-propyl, methoxyl group and oxyethyl group.
In general formula, R 1Preferred hydrogen, fluorine, chlorine, bromine or the C of representing 1-C 6-alkyl.
In general formula, R 2Preferred fluorine, chlorine, bromine or the C of representing 1-C 6-alkyl.
In general formula, Ar preferably represents and can be chosen wantonly the phenyl that replaces by following radicals: halogen, C 1-C 18-alkyl, C 2-C 12-alkenyl, C 2-C 12-alkynyl group, C 1-C 18-alkoxyl group, C 2-C 12-alkenyloxy, C 2-C 12-chain oxy-acetylene, C 1-C 8-alkoxy-C 1-C 8-alkyl, C 1-C 8-alkoxy-C 1-C 8-alkoxyl group, can be by C 1-C 8Alkyl and/or C 1-C 8The optional C that replaces of-alkoxyl group 3-C 8Cycloalkyl, can be by C 1-C 8-alkyl and/or C 1-C 8The optional C that replaces of alkoxyl group 3-C 8-cycloalkyloxy, can be by C 1-C 8-alkyl and/or C 1-C 8The optional C that replaces of-alkoxyl group 6-or C 10-aryl, can be by C 1-C 8-alkyl and/or C 1-C 8The optional C that replaces of-alkoxyl group 6-or C 10-aryloxy, can be by C 1-C 8-alkyl and/or C 1-C 8The optional C that replaces of-alkoxyl group 6-or C 10-aryl-C 1-C 8-alkyl and/or can be by C 1-C 8-alkyl and/or C 1-C 8The optional C that replaces of-alkoxyl group 6-or C 10-aryl-C 1-C 8Alkoxyl group;
In general formula, X preferably represents-CH 2-CH 2-, CH 2-CH 2-CH 2-,-CH=CH-,-CH 2-CH=CH-,-CH 2-O-,-CH 2-S-,-CH 2-N (R 3)-,-CH 2-O-CH 2-,-CH 2-O-CH 2-CH 2-or-CH 2-O-CO, wherein R 3Represent hydrogen, C 1-C 6-alkyl or C 2-C 7-alkanoyl.
In general formula, n preferably represents 0 or 1.
In general formula, R 1More preferably represent hydrogen, fluorine, chlorine or C 1-C 4-alkyl.
In general formula, R 2More preferably represent fluorine, chlorine or C 1-C 4-alkyl.
In general formula, Ar more preferably represents and can be chosen wantonly the phenyl that replaces by following radicals: halogen, C 1-C 16-alkyl, C 2-C 8-alkenyl, C 2-C 8Alkynyl group, C 1-C 16Alkoxyl group, C 2-C 8-alkenyloxy, C 2-C 8-chain oxy-acetylene, C 1-C 6-alkoxy-C 1-C 6-alkyl, C 1-C 6-alkoxy-C 1-C 6Alkoxyl group, can be by C 1-C 6-alkyl and/or C 1-C 6The optional C that replaces of-alkoxyl group 3-C 7Cycloalkyl, can be by C 1-C 6-alkyl and/or C 1-C 6The optional C that replaces of-alkoxyl group 3-C 7-cycloalkyloxy, can be by C 1-C 6-alkyl and/or C 1-C 6The optional C that replaces of alkoxyl group 6-or C 10-aryl, can be by C 1-C 6-alkyl and/or C 1-C 6The optional C that replaces of-alkoxyl group 6-or C 10-aryloxy, can be by C 1-C 6-alkyl and/or C 1-C 6The optional C that replaces of-alkoxyl group 6-or C 10-aryl-C 1-C 6-alkyl and/or can be by C 1-C 6-alkyl and/or C 1-C 6The optional C that replaces of-alkoxyl group 6-or C 10-aryl-C 1-C 6-alkoxyl group.
In general formula, X more preferably represents-CH 2-CH 2-,-CH 2-CH 2-CH 2-,-CH=CH-,-CH 2-CH=CH-,-CH 2-O-,-CH 2-S-,-CH 2-N (R 3)-,-CH 2-O-CH 2-,-CH 2-O-CH 2-CH 2-or-CH 2-O-CO, wherein R 3Represent hydrogen, C 1-C 4-alkyl or C 2-C 5-alkanoyl.
In general formula, n more preferably represents 0 or 1.
In general formula, R 1More particularly preferably represent hydrogen, fluorine or chlorine.
In general formula, R 2More particularly preferably represent fluorine, chlorine, methyl or ethyl.
In general formula, Ar more particularly preferably represents and can be chosen wantonly the phenyl that replaces by following radicals: fluorine, chlorine, C 1-C 12-alkyl, C 2-C 8-alkenyl, C 2-C 8Alkynyl group, C 1-C 12-alkoxyl group, C 2-C 8-alkenyloxy, C 2-C 8-chain oxy-acetylene, C 1-C 4-alkoxy-C 1-C 4Alkyl, C 1-C 4-alkoxy-C 1-C 4-alkoxyl group, can be by C 1-C 4-alkyl and/or C 1-C 4The optional C that replaces of-alkoxyl group 3-C 7-cycloalkyl, can be by C 1-C 4-alkyl and/or C 1-C 4The optional C that replaces of-alkoxyl group 3-C 7-cycloalkyloxy, can be by C 1-C 4-alkyl and/or C 1-C 4The optional phenyl that replaces of-alkoxyl group, can be by C 1-C 4-alkyl and/or C 1-C 4The optional phenoxy group that replaces of-alkoxyl group, can be by C 1-C 4-alkyl and/or C 1-C 4Optional phenyl-the C that replaces of-alkoxyl group 1-C 4-alkyl and/or can be by C 1-C 4-alkyl and/or C 1-C 4Optional phenyl-the C that replaces of-alkoxyl group 1-C 4-alkoxyl group.
In general formula, X more particularly preferably represents-CH 2-CH 2-,-CH 2-CH 2-CH 2-,-CH=CH-,-CH 2-CH=CH-,-CH 2-O-,-CH 2-S-,-CH 2-N (R 3)-,-CH 2-O-CH 2-,-CH 2-O-CH 2-CH 2-or-CH 2-O-CO, wherein R 3Represent hydrogen, C 1-C 6-alkyl or C 2-C 4-alkanoyl.
In general formula, n the most particularly preferably represents 0 or 1.
In general formula, R 1The most particularly preferably represent fluorine or chlorine.
In general formula, R 2The most particularly preferably represent fluorine or chlorine.
In general formula, Ar the most particularly preferably represents and can be chosen wantonly the phenyl that replaces by following radicals: fluorine, chlorine, C 1-C 4-alkyl, C 3-C 4-alkenyl, C 3-C 4-alkynyl group, C 3-C 4-alkoxyl group, C 3-C 4-alkenyloxy, C 3-C 4-chain oxy-acetylene, C 1-C 4-alkoxy-C 1-C 4-alkyl, C 1-C 4-alkoxy-C 1-C 4-alkoxyl group, can be by C 1-C 4-alkyl and/or C 1-C 4The optional C that replaces of-alkoxyl group 3-C 6-cycloalkyl, can be by C 1-C 4-alkyl and/or C 1-C 4The optional C that replaces of-alkoxyl group 3-C 6-cycloalkyl, can be by C 1-C 4-alkyl and/or C 1-C 4The optional phenyl that replaces of-alkoxyl group, can be by C 1-C 4-alkyl and/or C 1-C 4The optional phenoxy group that replaces of-alkoxyl group, can be by C 1-C 4-alkyl and/or C 1-C 4Optional phenyl-the C that replaces of-alkoxyl group 1-C 4-alkyl and/or can be by C 1-C 4-alkyl and/or C 1-C 4Optional phenyl-the C that replaces of-alkoxyl group 1-C 4-alkoxyl group.
In general formula, X is representative-CH the most particularly preferably 2-CH 2-,-CH 2-CH 2-CH 2-,-CH=CH-,-CH 2-CH=CH-,-CH 2-O-,-CH 2-S-,-CH 2-N (R 3)-,-CH 2-O-CH 2-,-CH 2-O-CH 2-CH 2-or-CH 2-O-CO, wherein R 3Represent hydrogen, C 1-C 4-alkyl or C 2-C 4-alkanoyl.
In general formula, n the most particularly preferably represents 1.
In general formula, R 1Represent chlorine the most especially.
In general formula, R 2Represent fluorine the most especially.
In general formula, Ar represents the most especially can be by C 1-C 8-alkyl (preferred C 1-C 6-alkyl, the more preferably tertiary butyl) the optional phenyl that replaces.
In general formula, X is representative-CH the most especially 2-CH 2-,-CH=CH-,-CH 2-O-or-CH 2-O-CO.
In general formula, n represents 1 the most especially.
In general formula, Ar represents preferred in the 2-or the 4-position of phenyl ring the most especially, more preferably the phenyl that is replaced by a substituting group on the 4-position.
On the group of expression X, the key that is shown in the left side equal key Lian Yu oxazole ring under each situation, and the key that is shown in the right side under each situation all key be connected on the benzyl ring Ar.
Total or the preferred range of having addressed of the definition of above-mentioned group or illustration is free to combination with one another, i.e. scope separately and the combination between the preferred range also is possible.The above is applicable to end product and corresponding precursor and intermediate.
According to the present invention, preferably there is the above-mentioned more preferably combination of definition in those general formulas (I) compound.
According to the present invention, there is the above-mentioned more preferably combination of definition in preferred those general formulas (I) compound.
According to the present invention, there is the combination of above-mentioned more special preferred definition in more particularly preferred those general formulas (I) compound.
According to the present invention, there is the combination of above-mentioned lay special stress on definition in ben those general formulas (I) compound.
According to the present invention, there is the combination of above-mentioned more lay special stress on definition in more ben those general formulas (I) compound.
If for example use 2-fluoro-6-benzyl chloride nitrile and 4-(tertiary butyl)-α-chloro-styrene as initiator, the reaction process of the method according to this invention variant (a) can be represented by the formula:
Figure A9419116400191
If for example use 2-(2, the 6-difluorophenyl)-4-chloromethyl-1,3-oxazole and 4-(sec.-propyl) benzylalcohol is as initiator, and the reaction process of the method according to this invention variant (b) can be represented by the formula:
Figure A9419116400201
If for example use 2-(2-fluoro-6-chloro-phenyl-)-4-chloromethyl-1,3-oxazole and 4-(tertiary butyl) phenylacetylene is as initiator, and the reaction process of the method according to this invention variant (c) can be represented by the formula:
The benzonitrile compounds that carries out the needed initiator formula of the inventive method variant (a) (II) be known maybe can by the preparation of known similarity method (referring to, for example, TetrahedronLett.28,111-114[1987]; US 4,680, and 406; Tetrahedron Lett.27,2203-2206[1986]; EP 49 186; DE 29 02 877).
The a-chloro-styrene compounds that carries out the needed initiator formula of the inventive method variant (a) (III) be known maybe can by the preparation of known similarity method (referring to, for example DE 21 04 313; PCT International Application No. WO 91/19695; Liq.Cryst.5,233-249[1989] or CA 116:163143b).
Carry out the inventive method variant (b) and (c) the Lv Jia Ji oxazole compounds of needed initiator formula (IV) be new, and be a part of the present invention.
They are by 2 of the benzonitrile compounds of general formula (II) and general formula (VIII), 3-two chloro-1-propylene reactions and preparation,
Figure A9419116400221
Wherein
R 1And R 2Have above-mentioned definition,
Figure A9419116400222
In the first step, react at first with chlorine (being preferably gas form), in the presence of thinner, reacting in the presence of the catalyzer and if desired if desired, and in second step, in the presence of reaction promoter, react subsequently, if desired in the presence of phase-transfer catalyst and if desired, in the presence of thinner, react with water.
Except using general formula (VIII) compound to replace carrying out the preparation method of general formula (IV) compound by the similar approach of general formula (I) compounds process for production thereof variant (a) general formula (III) compound.
2 of formula (VIII), 3-two chloro-1-propylene are common compound known (CA registration number 78-88-6) in the organic chemistry.
Alcohol derivate, phenol derivatives, carboxylic acid derivative, sulfonamide derivatives or thiol derivative that the initiator that carrying out the inventive method variant (b) also needs leads to formula V are common compound known in the organic chemistry.
Carrying out the needed initiator formula of the inventive method variant (c) (VI) phenylacetylene compounds is common compound known in the organic chemistry.
Carrying out the inventive method variant (c), can to select the benzyl sulfone compound of the initiator general formula (VII) that needs be compound known usually in the organic chemistry.
The thinner that carries out according to the inventive method (a) the first step can be an inert organic solvents.Comprise halogenated hydrocarbon especially, for example, chlorobenzene, dichlorobenzene, methylene dichloride or chloroform.
The thinner that is fit to that carries out according to second step of the inventive method (a) is an inert organic solvents.Particularly including aliphatic series, cyclic aliphatic or aromaticly choose halogenated hydro carbons wantonly, for example, volatile oil, benzene,toluene,xylene, chlorobenzene, dichlorobenzene, sherwood oil, hexane, hexanaphthene, methylene dichloride, chloroform, tetracol phenixin; Ethers such as ether, diisopropyl ether, diox, tetrahydrofuran (THF) or ethylene glycol dimethyl ether or ethylene glycol bisthioglycolate ethyl ether; Ketone such as acetone, butanone or methyl iso-butyl ketone (MIBK); Nitrile such as acetonitrile, propionitrile or benzonitrile; Amides such as N, dinethylformamide, N,N-dimethylacetamide, N-methyl formyl aniline, N-Methyl pyrrolidone or hexamethylphosphoramide; Ester class such as methyl acetate or ethyl acetate, sulfoxide class such as dimethyl sulfoxide (DMSO); Alcohols such as methyl alcohol, ethanol, n-propyl alcohol or Virahol, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, TC, the mixture of these solvents and water, or pure water.
If be fit to, also can in two-phase system, carry out according to second step of the inventive method (a), two-phase system for example, water/toluene or water/methylene dichloride can carry out in the presence of the phase-transfer catalyst that is fit to if be fit to.
The example of the above-mentioned catalyzer that can address is: tetrabutylammonium iodide, Tetrabutylammonium bromide, tetrabutylammonium chloride, bromination tributyl Jia Ji Phosphonium, chlorination trimethylammonium-C 13/ C 15-alkylammonium, bromination trimethylammonium-C 13/ C 15-alkylammonium, methylsulfuric acid dibenzyl-dimethyl-ammonium, chlorination dimethyl-C 12/ C 14-alkyl-hexadecyldimethyl benzyl ammonium, bromination dimethyl-C 12/ C 14-alkyl-hexadecyldimethyl benzyl ammonium, tetrabutylammonium, 3-ethyl benzyl ammonium chloride, methyl tricaprylammonium chloride, Variquat B 200,15-crown ether-5, hexaoxacyclooctadecane-6-6 or three-[2-(2-methoxy (ethoxy))-ethyl]-amine.
The catalyzer that is fit to when carrying out the first step according to the inventive method (a) is conventional Friedel-Crafts catalyst.Preferred Lewis acid such as zinc chloride (II), tin chloride (IV), iron(ic) chloride (III) or the aluminum chloride (III) that uses.
Preferably in the presence of the reaction promoter that is fit to, carry out second step of the method according to this invention (a).The reaction promoter that is fit to is the inorganic or organic bases of various routines.These alkali comprise, for example, and alkaline-earth metal or alkali-metal oxyhydroxide, carbonate or supercarbonate, for example, sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, saleratus or sodium bicarbonate, and tertiary amine such as triethylamine, tributylamine, N, accelerine or pyridine.
When the first step of carrying out according to the inventive method (a), temperature of reaction can change in quite wide scope.Usually, present method is preferably carried out under 0 ℃ to+40 ℃ temperature under-20 ℃ to+60 ℃ temperature.
When second when step of carrying out according to the inventive method (a), temperature of reaction also can change in quite wide scope.Usually, present method is preferably carried out under 40 ℃ to 100 ℃ temperature under 20 ℃ to 120 ℃ temperature.
The first step and second step according to the inventive method (a) carry out under barometric point routinely., also may under boosting, carry out present method.
In order to carry out the method according to this invention (a), formula (II) benzonitrile of every mol is used 1.0 usually to 4.0mol, preferred 1.0 to 2.0mol formula (III) α-chloro-styrene.React and processing and reaction product isolated (also comparing in this article) by currently known methods with preparation embodiment.The chlorizating agent composition that uses is preferably chlorine, and its usage quantity is at least 1mol, is preferably 1.5 to 2mol (based on formula (II) compounds).The usage quantity of water is at least 1mol, but preferably excessive (1.5 to 10mol) (based on formula (II) compound).
The suitable thinner that carries out according to the inventive method (b) is an inert organic solvents.Particularly including aliphatic series, cyclic aliphatic or aromaticly choose halogenated hydro carbons wantonly, for example, volatile oil, benzene,toluene,xylene, chlorobenzene, dichlorobenzene, sherwood oil, hexane, hexanaphthene, methylene dichloride, chloroform, tetracol phenixin; Ethers such as ether, diisopropyl ether, diox, tetrahydrofuran (THF) or ethylene glycol dimethyl ether or ethylene glycol bisthioglycolate ethyl ether; Ketone such as acetone, butanone or methyl iso-butyl ketone (MIBK); Nitrile such as acetonitrile, propionitrile or benzonitrile; Amides such as N, dinethylformamide, N,N-dimethylacetamide, N-methyl formyl aniline, N-Methyl pyrrolidone or hexamethylphosphoramide; Ester class such as methyl acetate or ethyl acetate, sulfoxide class such as dimethyl sulfoxide (DMSO).
Preferably carry out the method according to this invention (b) in the presence of the reaction promoter that is fit to, the reaction promoter that is fit to is the inorganic or organic bases of various routines.These alkali comprise, for example, and alkaline-earth metal or alkali-metal oxyhydroxide, carbonate or supercarbonate, for example, sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, Quilonum Retard, saleratus or sodium bicarbonate, and tertiary amine such as triethylamine, tributylamine, N, accelerine or pyridine.
The method according to this invention (b) is carried out under barometric point routinely., also may boost or reduced pressure under carry out present method.
When carrying out according to the inventive method (b), temperature of reaction can change in quite wide scope.Usually, present method is preferably carried out under 40 ℃ to 120 ℃ temperature under 20 ℃ to 150 ℃ temperature.
In order to carry out the method according to this invention, Lv Jia Ji oxazole to every mol formula (IV) uses 1.0 usually to 2.0mol, the alcohol derivate of preferred 1.0 to 1.5mol formula V, phenol derivatives, carboxylic acid derivative, sulfonamide derivatives or thiol derivative, if desired, use 1.0 to 2.0mol, preferred 1.0 to 1.5mol alkali reaction auxiliary agent.Use the pure composition of the formula V of its corresponding alkali metal salt form, the phenol composition, the carboxylic acid composition, amine component or mercaptan composition are superior especially.In this preferred method, can not add additional alkaline assistant.Carry out this reaction and processing and reaction product isolated by general conventional currently known methods.
The suitable thinner that carries out according to the inventive method (c) is an inert organic solvents.Particularly including aliphatic series, cyclic aliphatic or aromaticly choose halogenated hydro carbons wantonly, for example, volatile oil, benzene,toluene,xylene, chlorobenzene, dichlorobenzene, sherwood oil, hexane, hexanaphthene, methylene dichloride, chloroform, tetracol phenixin; Ethers such as ether, diisopropyl ether, diox, tetrahydrofuran (THF) or ethylene glycol dimethyl ether or ethylene glycol bisthioglycolate ethyl ether, or amides such as N, dinethylformamide, N,N-dimethylacetamide, N-methyl formyl aniline, N-Methyl pyrrolidone or hexamethylphosphoramide.
The method according to this invention (c) is preferably carried out in the presence of the reaction promoter that is fit to.The reaction promoter that is fit to is the inorganic or organic bases of various routines.They comprise, for example, and alkyl lithium compounds such as butyllithium; Alkaline-earth metal or alkali-metal hydride, oxyhydroxide, amides, alcoholate, carbonate or supercarbonate, for example, sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert.-butoxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, yellow soda ash, salt of wormwood, saleratus or volatile salt.
If desired, particularly under the situation of the sulfoxide of formula (VII) reaction, the method according to this invention (c) also can be carried out in biphasic system, and for example, water/toluene or water/methylene dichloride react in the presence of phase-transfer catalyst if desired.The example of the above-mentioned catalyzer that can address is: tetrabutylammonium iodide, Tetrabutylammonium bromide, tetrabutylammonium chloride, bromination tributyl Jia Ji Phosphonium, chlorination trimethylammonium-C 13/ C 15-alkylammonium, bromination trimethylammonium-C 13/ C 15-alkylammonium, methylsulfuric acid dibenzyl-dimethyl-ammonium, chlorination dimethyl-C 12/ C 14-alkyl-hexadecyldimethyl benzyl ammonium, bromination dimethyl-C 12/ C 14-alkyl-hexadecyldimethyl benzyl ammonium, tetrabutylammonium, 3-ethyl benzyl ammonium chloride, methyl tricaprylammonium chloride, Variquat B 200,15-crown ether-5, hexaoxacyclooctadecane-6-6 or three-[2-(2-methoxy (ethoxy))-ethyl]-amine.
When carrying out the method according to this invention (c), temperature of reaction can change in quite wide scope.Usually, present method is preferably carried out under-20 ℃ to 100 ℃ temperature under-80 ℃ to 180 ℃ temperature.
In order to carry out the method according to this invention (c), formula (IV) Lv Jia Ji oxazole to every mol uses 1.0 usually to 2.0mol, the benzyl sulphones of preferred 1.0 to 1.2mol formula (VI) phenylacetylene compound or formula (VII), and if desired, usually use 1.0 to 5.0mol, preferred 1.0 to 2.5mol alkali reaction auxiliary agent.Adopt similar currently known methods to carry out this reaction and processing and reaction product isolated.
Finishing catalytic hydrogenation according to the needed pair of key in the inventive method (c) back is similar to general ordinary method and carries out.The thinner that this purpose is fit to is the inert organic solvents of various routines.What especially preferably use is alcohols, as methyl alcohol, ethanol, n-propyl alcohol or Virahol, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether or TC.The catalyzer of hydrogenization is the catalyzer that is suitable for various conventional hydrogenizations, for example, nickel, platinum or palladium, catalyzer also can be on the solid support material that is fit to if desired, for example carbon or silicon-dioxide.Hydrogenization adopts hydrogen molecule usually, carries out in the pressure of 1 to 100 crust and 20 ℃ to 200 ℃ temperature range.Adopt similarly general conventional currently known methods to carry out this reaction and processing and reaction product isolated.
By means of ordinary method, for example by the column chromatography separation or by the end product of recrystallization purifying formula (I) and the intermediate of formula (IV).
Adopt mode conventional in the organic chemistry,, or do not having under the situation of compound crystal for example by fusing point, by proton NMR spectrum ( 1H NMR) they is identified.
The pest that this active compound is suitable for preventing and treating in the protection of agricultural, forest industry, storage article and material and health field runs into, preferred arthropods and nematode, and particularly insect and spider guiding principle animal.Preferably they are prevented and treated to the deleterious insect of plant mite class and nematode (preferred insect and mite class) as the plant protection product.They have activity to normal sensitive strain and resistant strain, and can have activity to all etap or some etap.
Above-mentioned insect comprises:
Isopoda, for example damp worm, pillworm and band pillworm (Porcellio scaber);
Diplopoda, for example, tool zebra land;
Chcilopoda, for example, ground snout moth's larva centipede (Geophilus Carpophagus) and common house centipede;
Symphyla, for example, the flower garden common house centipede;
Thysanura, for example, silverfiss;
Collembola, for example, Onychiurus arcticus (Onychiurus armatus);
Orthoptera for example, oriental cockroach, periplaneta americana, Ma Dela blattaria, Groton bug, acheta domestica, mole cricket, tropical migratory locusts, is very planted grasshopper and desert locust;
Dermaptera, for example, European earwig;
Isoptera, for example, termite;
Anoplura, for example, grape phylloxera, woolly aphid, head louse, blind lice and jaw lice;
Mallophaga, for example, poultry louse and nibble lice;
Thysanoptera, for example, greenhouse Hercinothrips spp and onion thrips;
Hemiptera, for example, brown scutteleerid, red cotton bug, beet are intended lace bug, bedbug, Rhodniusprolixus and triatoma sanguisuga;
Homoptera, for example, wild cabbage aleyrodid, whitefly in bt cotton, Trialeurodes vaporariorum Westwood, cotten aphid, brevicoryne brassicae, the latent knurl volume aphid of tea sugarcane, aphis fabae, apple aphid, apple aphid, mealy plum aphid, grain aphid, black peach aphid, hops knurl volume aphid, grain Rhopalosiphum spp, leafhopper tail, line leafhopper, rice green leafhopper, brown apricot scale, olive pearl lecanium, small brown rice planthopper, brown paddy plant hopper, California red scale, spring rattan garden armored scale, mealybug and wood louse;
Lepidopteran, for example, pink bollworm, loose looper, winter geometrid moth, thin moth, apple ermine moth, small cabbage moth, tent caterpillar, pornography and drug moth (Euproctis chrysorrhoea), Euproctis, cotton leaf miner, the tangerine leaf miner, Agrotis, cutworm belongs to, brown noctuid, earias insulana, bollworm, beet armyworm, lopper worm, small noctuid, prodenia litura, Noctua, cabbage looper, carpocapsa pononella, Pier, striped rice borer, Pyrausta nubilalis (Hubern)., Mediterranean flour moth, greater wax moth, the bag casemaking clothes moth, the etting moth, brown oecophorid, leaf roller (Cacoecia podana), the cigarette moth, choristoneura fumigerana, grape codling moth (Clysia ambiguella), long leaf roller of tea and oak are indulged leaf roller.
Coleoptera, for example, furniture death watch beetle, lesser grain borer, bean weevil (Bruchidius obtectus), bean weevil, house longhorn beetle, blue hair stern, firefly is chrysomelid, colorado potato bug, the horseradish daikon leaf beetle, the chrysomelid genus of bar, the rape flea beetle, mexican bean ladybird, Atomaria spp. saw-toothed grain beetle, Anthonomus spp belongs to, grain weevil, vine black ear beak resembles, broccoli pod weevil, alfalfa weevil, kidney spot khapra beetle, khapra beetle belongs to, attagenus piceus belongs to, Anthrenus, the black wool khapra beetle belongs to, powder is moth-eaten to be belonged to, pollen beetle, Ptinus, golden yellow ptinid, the wheat ptinid, Tribolium, the bloom first, click beetle belongs to, the acupuncture needle Eimeria, cockchafer, June cockchafer and Costelytra zealandica;
Hymenoptera, for example, pine sawfoy, sawfly, ant, kitchen ant and wasp;
Diptera, for example, yellow-fever mosquito, anopheles, culex pipiens pollens, drosophila yellow gorilla, housefly, stable fly, calliphora erythrocephala, lucilia, golden fly, cuterbrid, stomach fly, Hyppobosoa spp. sting fly, nose fly, torsalo, the gadfly, Tannia spp. march fly (bibio hortulanus), Sweden's wheat stem chloropid fly, eye fly, kmangold fly, Mediterranean fruitfly, dacus oleae and European daddy-longlegs;
Siphonaptera, for example, Xenopsyllacheopis and flea;
Arachnida, for example scorpion and black widow's ball abdomen pearl;
Acarina, for example, Acarus siro, latent beak tick, blunt beak tick genus, Dermanyssus gallinae, rabbit goitre mite, tangerine rust mite, tick genus, carrapato genus, Amblyomma, Hyalomma, hard tick genus, Psoroptes, skin Psoroptes, itch mite genus, line mite genus, Bryobia praetiosa, red spider, tetranychus telarius belong to.
Famous according to active compound of the present invention mainly due to having high desinsection and acaricidal activity.
Use their controls successful especially to the deleterious insect of plant, for example, the larva of control horseradish daikon leaf beetle (Phaedon cochleariae) or control two-spotted spider mite (Tetranychusurticae).
According to them specific physics and/or chemical property, this active compound can change into conventional preparation, as liquor, emulsion, suspension agent, pulvis, foaming agent, paste, granule, aerosol, natural and synthetic materials with the active compound dipping, micro-fine capsule in the polymkeric substance and seed coating composition, also can change into the preparation that is used for combustion equipment, as smog bucket, smoke candle, smog circle or the like, and cold mist agent of ultra-low volume and thermal fog.
These preparations are produced by currently known methods, for example, by mixed active composition and weighting agent, selectively can use tensio-active agent and prepare preparation, weighting agent is a liquid solvent, the gas that liquefies under pressure, and/or solid carrier, tensio-active agent are emulsifying agent and/or dispersion agent and/or foam agent.Under the situation of water as weighting agent, also can be with an organic solvent, for example as solubility promoter.The liquid solvent that is fit to mainly contains: arene, and as dimethylbenzene, toluene or alkylnaphthalene, chlorinated aromatic hydrocarbons class or chloro aliphatic hydrocarbon, as chlorobenzene, ethylene dichloride or methylene dichloride, aliphatic hydrocarbon is as hexanaphthene or paraffin, mineral oil fractions for example, alcohols is as butanols or ethylene glycol and their ether and ester class, ketone, as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) or pimelinketone, intensive polar solvent, as dimethyl formamide and dimethyl sulfoxide (DMSO), and water; To mean under room temperature and barometric point be the liquid of gas for the gas weighting agent of liquefaction or carrier, and aerosol propellant for example is as halogenated hydrocarbon and butane, propane, nitrogen and carbonic acid gas; The solid carrier that is fit to for example is a natural mineral soil, as kaolin, clay, talcum, chalk, quartz, attapulgite, polynite or diatomite and synthetic mineral particle, and as high dispersive silicon-dioxide, aluminum oxide and silicate; The solid carrier that is suitable as granule is: for example grind and fractionated natural rock such as calcite, marble, float stone, sepiolite and rhombspar, and synthetic inorganic particle and organic dust, and the particle of organic materials such as sawdust, nutshell, mealie core and tobacco stem; The emulsifying agent and/or the foam agent that are fit to have: for example nonionic and anionic emulsifier, and as polyoxyethylene fatty acid ester, polyoxyethylene aliphatic alcohol ether, alkyl benzyl polyglycol ether for example, alkylsulfonate, alkyl-sulphate, arylsulphonate and albumin hydrolysate; The dispersion agent that is fit to has: for example xylogen sulfite waste liquor and methylcellulose gum.
Tackiness agent such as carboxymethyl cellulose and be the natural and synthetic polymer of powder, particle or latex form, as gum arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipid, as kephalin and Yelkin TTS, and synthetic phospholipid, also can in preparation, use.Other additive can be mineral oil and vegetables oil.
Tinting material that may use such as mineral dye, ferric oxide for example, titanium oxide and Prussian orchid, and organic dye, as alizarine dyestuff, the nutrient substance of azoic dyestuff and metal phthalocyanine dyestuff and trace such as iron, manganese, boron, copper, cobalt, molybdenum and zinc salt.
In a preferred embodiment, comprise a kind of tensio-active agent at least according to sterilant of the present invention.
Usually contain 0.1 to 95% activeconstituents by weight in the preparation, preferably contain 0.5 to 90%.
Can be present in their commercial preparation and in application form according to active compound of the present invention by these formulation preparation, it and other active compound are as the mixture of sterilant, attractive substance, sterilizing agent, miticide, nematocides, mycocide, growth regulatory substance or weedicide.Sterilant for example comprises, phosphoric acid ester, amino formate, carboxylic acid esters, chlorinated hydrocarbon, phenyl ureas and by the material of microorganisms producing, or the like.
Also can be present in its commercial preparation and from the application form of these formulation preparation according to active compound of the present invention, as with the mixture of synergistic agent.Synergistic agent is to increase the active compound activity, and synergistic agent itself does not need to have active compound.
The active compound content of the application form for preparing from the commercial preparation can change in wide range.The activity compound concentration of application form is 0.0000001 to 95% active compound by weight, is preferably by weight 0.0001 to 1%.
Use this compound with the usual manner that is suitable for application form.
Following embodiment has explained according to the preparation of active compound of the present invention and application.
Preparation embodiment
Embodiment 1
Figure A9419116400321
(method b)
Will be the 4-tert.-butylbenzene sodium phenolate reflux of the 2-of the 5g in the 60ml acetonitrile (0.02mol) (2-chloro-6-fluorophenyl)-4-chlorine first base oxazole and 3.5g (0.02mol) 12 hours.After reaction is finished, under vacuum, remove and desolvate and residuum separates (eluent: hexanes/ch 10: 1) on silica gel chromatography.
Obtain buttery 4.8g (theoretical value 67%) 2-(2-chloro-6-fluorophenyl)-4-(4-tertiary butyl phenoxymethyl) oxazole.MS：m/e(rel.Int.)＝359(M +，23)，344(M +-CH 3，2)，210(100)，182(87)，
The preparation of 155 (22) initial compounds: embodiment 1A:
Figure A9419116400331
Follow stirring at room temperature to the 30.3g in 75ml toluene (0.1mol) N-(1,3-dichloropropylene-2-yl)-and be added in 17.5g (0.435mol) sodium hydroxide and 2g benzyl-dimethyl-dodecyl chlorination ammonium in the 50ml water in the 2-chloro-6-fluoro-benzyl imino-choride (E/Z mixture), subsequently mixture heating up was refluxed 5 hours.After reaction was finished, water and methylene dichloride were handled the refrigerative mixture, and isolate organic phase and use the sodium sulfate thorough drying, solvent removed in vacuo, residuum dissolves with the 250ml acetonitrile.Add the 0.4g acid chloride, and mixture heating up was refluxed 24 hours.Distilling solvent and residuum subsequently distills under high vacuum.
Obtain 2-(2-chloro-6-fluorophenyl)-4-Lv Jia Ji oxazole of 18.3g (theoretical value 75%), its boiling point is 118-120 ℃ under 0.1mbar.MS：m/e(rel.Int.)＝245(M +，52)，210(M +-Cl，100)，182(70)，155(45)，
120(34)
At 10 ℃ to 15 ℃ chlorine is passed into 17.5g (0.255mol) 2-chloro-6-fluoro-benzonitrile (relatively, for example, DE 25 47 037), 2 of 25g (0.22mol) is in the mixture of 3-dichloropropylene and 0.2g iron(ic) chloride (III).2, the 3-dichloropropylene has reacted back (gas-chromatography control), adds 2 of 25g again, and the 3-dichloropropylene also continues to feed chlorine.After reaction is finished, the straight-forward fractional distillation reaction mixture.
Obtaining N-(1,3-dichloropropylene-2-yl)-2-chloro-6-luorobenzyl imino-choride (benzimide chloride) (E/Z mixture) of 24.7g (theoretical value 7 5%), is 150 ℃ to 165 ℃ in the boiling spread of 0.1mbar.
Adopt similarity method and obtain following formula (I) compound according to general preparation introduction:
Figure A9419116400341
Figure A9419116400342
Biological Examples
Embodiment A
Tetranychid test (organophosphorus resistance)
Solvent: the dimethyl formamide of 7 weight parts
Emulsifying agent: the alkylaryl polyglycol ether of 1 weight part
In order to prepare the prepared product that is fit to of active compound, with active compound and the solvent of predetermined amount and the emulsifier mix of predetermined amount of 1 weight part, and the dilute with water enriched material is to desired concn.
Soybean plant strain dipping in the prepared product of the active compound of desired concn that will seriously be infected by the two-spotted spider mite of various etap (Tetranychus urticae).
After one period fixed time, determine to kill and wound per-cent.100% means all tetranychids is killed; 0% means and does not have tetranychid to be killed.
In this test, for example use the compound of preparation embodiment 1 and 2 with typical concn 0.01% (weight), the kill rate that shows after 7 days is 95 to 98%.
Embodiment B
The test of daikon leaf beetle larva
Solvent: the dimethyl formamide of 7 weight parts
Emulsifying agent: the alkylaryl polyglycol ether of 1 weight part
In order to prepare the prepared product that is fit to of active compound, with active compound and the solvent of predetermined amount and the emulsifier mix of predetermined amount of 1 weight part, and the dilute with water enriched material is to desired concn.
Handle cabbage leaves (Brassica oleracea) by dipping in the prepared product of the active compound of desired concn, and when blade still keeps humidity, infect with the larva of horseradish daikon leaf beetle (Phaedon cochleariae).
After one period fixed time, determine to kill and wound per-cent.100% larva that means all daikon leaf beetles is killed; 0% means and does not have daikon leaf beetle to be killed.
In this experiment, for example use the compound of preparation embodiment 1 with typical concn 0.1% (weight), the kill rate of demonstration is 100%.

Claims (11)

1. the replacement De oxazole compounds of general formula (I):
Figure A9419116400021
R wherein 1Represent hydrogen, alkyl or halogen, R 2Represent alkyl or halogen, Ar represents the phenyl that can be chosen wantonly replacement by following radicals: halogen, alkyl, alkenyl, alkynyl group, alkoxyl group, alkenyloxy, chain oxy-acetylene, alkoxyalkyl, alkoxyl group alkoxyl group, the optional cycloalkyl that replaces, the cycloalkyloxy of choosing replacement wantonly, the aryloxy of choosing the aryl that replaces, optional replacement wantonly, the aralkyl of choosing replacement wantonly and/or the optional aralkoxy that replaces; X represents the group of following formula :-CH 2-CH 2-;-CH 2-CH 2-CH 2-;-CH=CH-;-CH 2-CH=CH-;-CH 2-O-;-CH 2-S-;-CH 2-N (R 3)-;-CH 2-O-CH 2-;-CH 2-O-CH 2-CH 2-or-CH 2-O-CO; R 3Represent hydrogen, alkyl or alkanoyl; With n be 0 or 1.
2. according to the replacement De oxazole compounds of claim 1, R wherein 1Represent hydrogen, fluorine, chlorine, bromine or C 1-C 6-alkyl;
R 2Represent fluorine, chlorine, bromine or C 1-C 6-alkyl;
The Ar representative can be chosen wantonly the phenyl that replaces by following radicals: halogen, C 1-C 18-alkyl, C 2-C 12-alkenyl, C 2-C 12-alkynyl group, C 1-C 18-alkoxyl group, C 2-C 12-alkenyloxy, C 2-C 12-chain oxy-acetylene, C 1-C 8-alkoxy-C 1-C 8-alkyl, C 1-C 8-alkoxy-C 1-C 8-alkoxyl group, can be by C 1-C 8Alkyl and/or C 1-C 8The optional C that replaces of-alkoxyl group 3-C 8Cycloalkyl, can be by C 1-C 8-alkyl and/or C 1-C 8The optional C that replaces of alkoxyl group 3-C 8-cycloalkyloxy, can be by C 1-C 8-alkyl and/or C 1-C 8The optional C that replaces of-alkoxyl group 6-or C 10-aryl, can be by C 1-C 8-alkyl and/or C 1-C 8The optional C that replaces of-alkoxyl group 6-or C 10-aryloxy, can be by C 1-C 8-alkyl and/or C 1-C 8The optional C that replaces of-alkoxyl group 6-or C 10-aryl-C 1-C 8-alkyl and/or can be by C 1-C 8-alkyl and/or C 1-C 8The optional C that replaces of-alkoxyl group 6-or C 10-aryl-C 1-C 8Alkoxyl group;
X preferably represents-CH 2-CH 2-, CH 2-CH 2-CH 2-,-CH=CH-,-CH 2-CH=CH-,-CH 2-O-,-CH 2-S-,-CH 2-N (R 3)-,-CH 2-O-CH 2-,-CH 2-O-CH 2-CH 2-or-CH 2-O-CO-and, wherein
R 3Represent hydrogen, C 1-C 6-alkyl or C 2-C 7-alkanoyl; With
N represents 0 or 1.
3. according to the replacement De oxazole compounds of claim 1, wherein
R 1Represent hydrogen, fluorine, chlorine or C 1-C 4-alkyl;
R 2Represent fluorine, chlorine or C 1-C 4-alkyl;
The Ar representative can be chosen wantonly the phenyl that replaces by following radicals: halogen, C 1-C 16-alkyl, C 2-C 8-alkenyl, C 2-C 8Alkynyl group, C 1-C 16Alkoxyl group, C 2-C 8-alkenyloxy, C 2-C 8-chain oxy-acetylene, C 1-C 6-alkoxy-C 1-C 6-alkyl, C 1-C 6-alkoxy-C 1-C 6Alkoxyl group, can be by C 1-C 6-alkyl and/or C 1-C 6The optional C that replaces of-alkoxyl group 3-C 7Cycloalkyl, can be by C 1-C 6-alkyl and/or C 1-C 6The optional C that replaces of-alkoxyl group 3-C 7-cycloalkyloxy, can be by C 1-C 6-alkyl and/or C 1-C 6The optional C that replaces of alkoxyl group 6-or C 10-aryl, can be by C 1-C 6-alkyl and/or C 1-C 6The optional C that replaces of-alkoxyl group 6-or C 10-aryloxy, can be by C 1-C 6-alkyl and/or C 1-C 6The optional C that replaces of-alkoxyl group 6-or C 10-aryl-C 1-C 6-alkyl and/or can be by C 1-C 6-alkyl and/or C 1-C 6The optional C that replaces of-alkoxyl group 6-or C 10-aryl-C 1-C 6-alkoxyl group.
X representative-CH 2-CH 2-,-CH 2-CH 2-CH 2-,-CH=CH-,-CH 2-CH=CH-,-CH 2-O-,-CH 2-S-,-CH 2-N (R 3)-,-CH 2-O-CH 2-,-CH 2-O-CH 2-CH 2-or-CH 2-O-CO,
R wherein 3Represent hydrogen, C 1-C 4-alkyl or C 2-C 5-alkanoyl; With
N represents 0 or 1.
4. according to the replacement De oxazole compounds of claim 1, wherein
R 1Represent chlorine;
R 2Represent fluorine;
The Ar representative can be by C 1-C 8The phenyl that-alkyl replaces;
X represents CH 2-CH 2-,-CH=CH-,-CH 2-O-or-CH 2-O-CO and
N represents 1.
5. replace the preparation method of De oxazole compounds according to the general formula (I) of claim 1, it is characterized in that, a) prepare n wherein and be 0 general formula (I) compound:
With the benzonitrile compounds of general formula (II) and the α of general formula (III)-chloro-styrene compounds reaction,
Wherein
R 1And R 2Have above-mentioned definition,
Figure A9419116400052
Wherein
Ar has above-mentioned definition, in the first step, react at first with chlorine (being preferably gas), in the presence of thinner, reacting in the presence of the catalyzer and if desired if desired, and water reaction in the presence of reaction promoter in second step is subsequently reacted in the presence of thinner if desired in the presence of phase-transfer catalyst and if desired; Or b) preparation general formula (I) compound, wherein X represents Shi-CH 2-O-;-CH 2-S-;-CH 2-N (R 3)-;-CH 2-O-CH 2-;-CH 2-O-CH 2-CH 2-or-CH 2The group of-O-CO-and n are 1, R 3Have above-mentioned definition:
The chlorine first base oxazole compounds of general formula (IV) and the alcohol derivate of logical formula V, phenol derivatives, carboxylic acid derivative, sulfonamide derivatives or thiol derivative reaction,
Figure A9419116400061
Wherein
R 1And R 2Have above-mentioned definition,
H-X 1-Ar (V)
Wherein
X 1Representative-O-;-S-;-N (R 3)-;-O-CH 2-;-O-CH 2-CH 2-or-O-CO-, wherein R 3Have above-mentioned definition, in the presence of reaction promoter, reacting in the presence of the thinner and if desired if desired; Or c) compound of preparation general formula (I), wherein X represents Shi-CH 2-CH 2-;-CH 2-CH 2-CH 2-;-CH=CH-or-CH 2Group and the n of-CH=CH-represent 1:
With the Lv Jia Ji oxazole compounds of general formula (IV) and the phenylacetylene compounds of general formula (VI), or with the reaction of the benzyl sulfone compound of general formula (VII),
Wherein
R 1And R 2Have above-mentioned definition,
H-C≡C-Ar (VI)
Wherein
Ar has above-mentioned definition,
Ar-SO 2-CH 2-Ar (VII)
Wherein
Ar has above-mentioned definition, if desired in the presence of thinner, in the presence of reaction promoter, reacting in the presence of the phase-transfer catalyst and if desired if desired, and if desired in second step subsequently, in the presence of catalyzer, if desired in the presence of thinner, replace De oxazole compounds with the general formula (I) of hydrogen hydrogenation gained, wherein X representative-CH=CH-or-CH 2-CH=CH-and n represent 1, to prepare wherein X representative-CH 2-CH 2Or-CH 2-CH 2-CH 2-and n represent the compound of 1 general formula (I).
6. sterilant is characterized in that it contains a kind of formula according to claim 1 (I) compound at least.
7. use formula (I) compound pest control according to claim 1.
8. the method for pest control is characterized in that making formula (I) compound effects according to claim 1 in insect and/or their environment.
9. method for producing insecticide is characterized in that general formula (I) compound according to claim 1 is mixed with weighting agent and/or tensio-active agent.
10. the Lv Jia Ji oxazole compounds of general formula (IV)
Wherein
R 1Represent hydrogen, alkyl or halogen; With
R 2Represent alkyl or halogen.
11. according to the preparation method of the chlorine first base oxazole compounds of claim 10, it is characterized in that 2 of the benzonitrile compounds of general formula (II) and general formula (VIII), the reaction of 3-two chloro-1-propylene,
Figure A9419116400082
Wherein
R 1And R 2Have the definition that provides in the claim 10,
In the first step, react at first with chlorine, in the presence of thinner, reacting in the presence of the catalyzer and if desired if desired, and water reaction in the presence of reaction promoter in second step is subsequently reacted in the presence of thinner if desired in the presence of phase-transfer catalyst and if desired.
CN 94191164 1993-02-12 1994-01-31 Substituted oxazoles Pending CN1117728A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4304197.3 1993-02-12
DE19934304197 DE4304197A1 (en) 1993-02-12 1993-02-12 Substituted oxazoles

Publications (1)

Publication Number Publication Date
CN1117728A true CN1117728A (en) 1996-02-28

Family

ID=6480288

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 94191164 Pending CN1117728A (en) 1993-02-12 1994-01-31 Substituted oxazoles

Country Status (7)

Country Link
EP (1) EP0683771A1 (en)
JP (1) JPH08506330A (en)
CN (1) CN1117728A (en)
AU (1) AU5972394A (en)
BR (1) BR9405830A (en)
DE (1) DE4304197A1 (en)
WO (1) WO1994018180A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111635398A (en) * 2020-06-23 2020-09-08 南通大学 Preparation and application of pyrazole derivative containing oxazole methoxy biaryl unit

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE240728T1 (en) * 1996-10-07 2003-06-15 Lilly Co Eli NEW COMPOUNDS USEFUL AS NEUROPROTECTIVE AGENTS
US6472387B1 (en) 1996-10-07 2002-10-29 Eli Lilly And Company Methods of using compounds as neuro-protective agents
TR200100352T2 (en) 1997-10-06 2001-06-21 Eli Lilly And Company New compounds useful as neuroprotective agents

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0036711B1 (en) * 1980-03-22 1985-12-04 Fbc Limited Pesticidal heterocyclic compounds, processes for preparing them, compositions containing them, and their use
DE3819037A1 (en) * 1988-06-04 1989-12-14 Hoechst Ag 2,4-disubstituted oxazole derivatives, process for their preparation, and their use as agents for the therapy of diseases caused by rhinoviruses
US4977171A (en) * 1988-06-09 1990-12-11 Yashima Chemical Industrial Co., Ltd. Oxa- or thia-zoline derivative

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111635398A (en) * 2020-06-23 2020-09-08 南通大学 Preparation and application of pyrazole derivative containing oxazole methoxy biaryl unit
CN111635398B (en) * 2020-06-23 2022-08-05 南通大学 Preparation and application of pyrazole derivative containing oxazole methoxy biaryl unit

Also Published As

Publication number Publication date
AU5972394A (en) 1994-08-29
DE4304197A1 (en) 1994-08-18
EP0683771A1 (en) 1995-11-29
WO1994018180A1 (en) 1994-08-18
JPH08506330A (en) 1996-07-09
BR9405830A (en) 1996-01-16

Similar Documents

Publication Publication Date Title
CN1035539C (en) Hydrazine derivative and pesticidal composition comprising said derivative as an effective ingredient
CN1193983C (en) Acylacetonitriles, process for preparation thereof and miticides containing the same
CN1025501C (en) Novel silane derivs., process for prepn. thereof, the derivs.-contg. composition and uses as pecticide thereof
CN1059672C (en) 1,2,4-oxadiazole derivatives and their use as parasiticides for animals
CN1017396B (en) 1,2,3-6-tetrahydro-5-nitro-pyrimidine derivatives
CN1021011C (en) 2,2-difluocyclopropylethane derivatives processes for their preparation and their use as pesticides
CN1117071C (en) Pesticides
CN1028228C (en) 1-arylpyrazoles
CN1100768C (en) Substituted diphenyl oxazolines
CN1061774A (en) Hydrazone derivative, the preparation method of this derivative and application thereof
CN1159290C (en) Method for preparing biocide alkyl-substituted (hetero)-aryl-ketoxime-o-ether and its intermediate ketone or oxime compounds
CN1117728A (en) Substituted oxazoles
CN1113238A (en) Substituted pyrazoline derivatives
CN1071322C (en) Process for producing 5,6-dihydro-1,3-oxazines
CN1013861B (en) Vinylcyclopropanecarboxylic acid esters
CN87102802A (en) N-phenyl (sulphur) urea and functional derivatives thereof prepare their method and they are as the purposes of sterilant
CN1086513A (en) The 2-aryl-pyrrolidine that replaces
CN1057523C (en) Diphenyl oxazoline derivatives
CN1059671C (en) 3-aryl akenyl-1,2,4-oxadiazole derivatives and their use as parasiticides for animals
CN1042630C (en) Substituted AZA(Cyclo)Alkanes
CN1052008C (en) Phosphoric acid derivatives
CN86102369A (en) The preparation of difluoro cyclopropane derivative and application thereof
CN1075473A (en) Pyrethroid and method for making and purposes that 6-(trifluoromethyl) benzylalcohol deutero-is new
CN85108797A (en) A kind of preparation method of new benzoylphenylurea derivative and as the application of sterilant
CN88101407A (en) Benzadoxime derivatives

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C01 Deemed withdrawal of patent application (patent law 1993)
WD01 Invention patent application deemed withdrawn after publication