CN1171775A - Fluorobutenyl esters - Google Patents

Fluorobutenyl esters Download PDF

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Publication number
CN1171775A
CN1171775A CN95197158A CN95197158A CN1171775A CN 1171775 A CN1171775 A CN 1171775A CN 95197158 A CN95197158 A CN 95197158A CN 95197158 A CN95197158 A CN 95197158A CN 1171775 A CN1171775 A CN 1171775A
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compound
general formula
group
alkyl
implication
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Inventor
U·克拉兹
J·哈特维格
W·安得斯彻
C·厄德林
A·特伯格
N·门克
G·耶拉曼彻利
P·G·鲁明斯基
D·P·菲尔利思
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Bayer AG
Monsanto Co
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Bayer AG
Monsanto Co
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • A01N47/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
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    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
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    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
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    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/20—N-Aryl derivatives thereof
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    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
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    • C07C271/06—Esters of carbamic acids
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    • C07C271/12—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
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    • C07C271/14—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by halogen atoms or by nitro or nitroso groups
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    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/24—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a ring other than a six-membered aromatic ring
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/26—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
    • C07C271/28—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a non-condensed six-membered aromatic ring
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    • C07C271/62—Compounds containing any of the groups, X being a hetero atom, Y being any atom, e.g. N-acylcarbamates
    • C07C271/66—Y being a hetero atom
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/50—Compounds containing any of the groups, X being a hetero atom, Y being any atom
    • C07C311/52—Y being a hetero atom
    • C07C311/53—X and Y not being nitrogen atoms, e.g. N-sulfonylcarbamic acid
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C329/00—Thiocarbonic acids; Halides, esters or anhydrides thereof
    • C07C329/02—Monothiocarbonic acids; Derivatives thereof
    • C07C329/04—Esters of monothiocarbonic acids
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    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
    • C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
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Abstract

Fluorobutenyl esters have the formula (I), in which R1 stands for hydrogen or a halogen, and R2 stands for one of the groups, in which V, Y, Z, R3 and R5 have the meanings given in the description. Also disclosed are a process and intermediate products for preparing said esters, as well as their use for controlling animal pests.

Description

Fluorobutenyl esters
The present invention relates to new Fluorobutenyl esters, relate to their preparation method, relate to and use their to control insect pest, especially control agricultural, forestry reach insect, Araneae and the nematode that health circle is run in product and thing material storage protection.
More known fluoro butene compounds have eelworm-killing activity (seeing WO88/00183).But these compound activity intensity and fungicidal spectrum are always dissatisfied fully, can not be satisfactory when especially low ratio use and lower concentration use.
The invention provides the new compound of general formula (I).
Figure A9519715800071
(I) R wherein 1Be hydrogen or halogen and R 2Be (a) or base one of (b)
Figure A9519715800072
(a) or (b) wherein Y is oxygen or sulphur, and Z is oxygen, sulphur or NR 4, R 3Be hydrogen, the random alkyl that replaces, thiazolinyl, cycloalkyl, aryl, aralkyl, carbalkoxy, aryloxy carbonyl, arylsulfonyl or heteroaryl, R 4Be hydrogen or the random alkyl that replaces, alkylthio, thiazolinyl, cycloalkyl, aryl, aralkyl or heteroaryl, R 3And R 4A nitrogen-atoms that links to each other with them forms the ring of random replacement, and this ring arbitrarily contains oxygen, sulphur or azo-cycle (this nitrogen is arbitrarily by alkyl, and aryl or aralkyl replaces), or R 2Be (c) base,
Figure A9519715800074
(c)
Wherein
V is oxygen or NR 6With
R 5And R 6Independent separately is hydrogen, has the fatty group of 1 to 12 carbon atom, aryl or heterocyclic radical, and they are replaced by 1 substituting group at least, and these substituting groups are selected from alkyl, cyano group, trimethyl silicon based, hydroxyl, alkoxyl group, halogen, nitro, amino, alkylamino, dialkyl amido, SH, alkylthio, phenyl, or by the carboxylic acid group, sulfonic group, phosphate, phosphorous acid base, ester group, the amide group of thioester substrate or the acid mentioned replaces, and this amide group optionally alkyl list replaces or two replacement, or
R 5And R 6Nitrogen-atoms of linking to each other with them forms amino acid or forms and adds an oxygen arbitrarily outward, the heterocycle of sulphur or nitrogen, and they are at least arbitrarily by alkyl, cyano group, trimethyl silicon based, hydroxyl, alkoxyl group, halogen, nitro, amino, alkylamino, dialkyl amido, SH, alkylthio, phenyl or carboxylic acid group, sulfonic group, phosphate or phosphorous acid base, or the ester group of referred carboxylic acid, thioester substrate or amide group replace, and this amide group is arbitrarily replaced or two replacement by the alkyl list, or
R 5At R 6For being OR under the situation of hydrogen 7, COR 7, NR 7R 8, SO 2R 9, or P (=O) R 10R 11In a base, wherein
R 7And R 8Independent separately is hydrogen, alkyl or aryl,
R 9Be hydrogen, alkyl, haloalkyl or aryl,
R 10And R 11Independent separately is hydrogen, alkyl, and aryl, alkoxyl group, aryloxy, alkylthio,
Arylthio, amino, alkylamino, dialkyl amido or virtue are amino,
The present invention also provides the salt of the compound of general formula (I).
The compound of general formula (I) can exist with geometrical isomer and/or optical isomer or the mixture of isomers of forming with difference.The present invention promptly relates to pure isomer and also relates to mixture of isomers.
Have carboxyl or hydroxyl general formula (I) compound can with different positively charged ion in conjunction with salify, for example with basic metal or alkaline-earth metal ions, for example with sodium ion, potassium ion, calcium ion, magnesium ion or quaternary ammonium ion, for example sec.-propyl ammonium ion or pyridinium ion salify.
Consider R 2The different modes of base obtains structure (Ia), (Ib) and (Ic):
Figure A9519715800081
(Ia) (Ib)
Figure A9519715800091
(Ic)
R wherein 1, R 3, R 5, V, Y, the implication of Z is the same,
General formula of the present invention (Ia) or compound (Ib) can make like this, work as A) the fluoro butenol of general formula (II) with
Figure A9519715800092
(II)
Wherein
R 1Implication the same, the α) compound of general formula (III) reaction
Figure A9519715800093
(III)
Y wherein, Z, and R 3Implication the same, have thinner and random alkali to exist during reaction, or β) different (sulfo-) polyisocyanate reactant of general formula (IV),
YCN-R 3 (IV)
Wherein Y and R 3Implication the same, have thinner and random catalyzer to exist during reaction, or B) the fluoro butylene mercaptan of general formula (IIa)
Figure A9519715800094
(IIa) R wherein 1Implication the same, with the reaction of the compound of general formula (IIIa),
Figure A9519715800095
(IIIa)
Wherein Y and R 3Implication the same, have thinner and random alkali to exist during reaction, or C) compound of logical formula V
Figure A9519715800101
(V)
R wherein 1The same with the implication of Y, with the compound reaction of general formula (VI),
H-Z-R 3 (VI)
Wherein Z and R 3Implication the same, have thinner and random alkali to exist during reaction, or D) compound of general formula (VII) (VII)
R wherein 1The same with the implication of Y, with the compound reaction of general formula (VIII),
H-S-R 3 (VIII)
R wherein 3Implication the same, have thinner and random alkali to exist during reaction,
The compound of general formula (Ic) can be by known compound (wherein some compound can be used as commodity bought) preparation, or from press the currently known methods compound of preparation (referring to preparing embodiment) easily,
The new compound of finding general formula (I) at last has strong biological activity, particularly is suitable for controlling animal pest, especially is controlled at agricultural, forestry, reaches insect, Araneae and the nematode that health circle is run in product and the protection of thing material.
General formula (I) provides the General Definition of compound of the present invention,
Preferred substituted or the substituting group scope listed in the general formula of mentioning in the present interpretive context.
R 1Be preferably hydrogen, fluorine or chlorine
R 2Be preferably following a kind of substituting group
Figure A9519715800103
Or
Wherein Y is oxygen or sulphur
Z is an oxygen, sulphur or NR 4
R 3Be hydrogen, or C 1-C 10Alkyl, this alkyl be arbitrarily by halogen, cyano group, and carboxyl, phenyl, it is amino that (this amino is arbitrarily by C 2-C 7Alkylidene group (C 2-C 7Alkanediyl) replace or by identical or different C 1-C 8The alkyl list replaces or two replacement), C 1-C 8Alkoxyl group, C 1-C 8(this aminocarbonyl is arbitrarily by C for alkylthio or aminocarbonyl 2-C 7-alkylidene group (C 2-C 7-alkanediyl) replace, by identical or different C 1-C 8Alkyl, C 1-C 8Haloalkyl, C 1-C 8Alkoxyl group, C 3-C 8Cycloalkyl, C 3-C 8Halogenated cycloalkyl, C 1-C 4Alkyl-C 3-C 8Cycloalkyl, or by phenyl or benzyl replacement, phenyl and benzyl all can be optionally by halogens, cyano group, nitro, C 1-C 8Alkyl, C 1-C 8Haloalkyl, C 1-C 8Alkoxyl group, C 1-C 8Halogenated alkoxy, C 1-C 8Alkylthio or C 1-C 8Halogenated alkylthio replaces), or the C for arbitrarily being replaced by halogen 3-C 8Thiazolinyl, or for arbitrarily by halogen or C 1-C 6The C that alkyl replaces 3-C 8Cycloalkyl, or be phenyl, benzyl, carbobenzoxy or phenyl sulfuryl, they are arbitrarily separately by halogen, cyano group, nitro, C 1-C 8Alkyl, C 1-C 8Haloalkyl, C 1-C 8Alkoxyl group, C 1-C 8Halogenated alkoxy, C 1-C 8Alkylthio, C 1-C 8Halogenated alkylthio, C 1-C 8Carbalkoxy or SCN replace, or are halogen or C 1-C 65 yuan or 6 yuan of heterocycles containing 1 to 3 nitrogen-atoms that alkyl arbitrarily replaces, or be halogen or C 1-C 6The C that alkoxyl group arbitrarily replaces 1-C 8Carbalkoxy.R 4Be preferably hydrogen, or arbitrarily by halogen, cyano group, it is amino that (this amino is arbitrarily by C 2-C 7Alkylidene group (C 2-C 7-alkanediyl) replace or arbitrarily by identical or different C 1-C 8The alkyl list replaces or two replacement), C 1-C 8Alkoxyl group, C 1-C 8(this aminocarbonyl is arbitrarily by C for alkylthio or aminocarbonyl 2-C 7-alkylidene group (C 2-C 7-alkanediyl) replace or by identical or different C 1-C 8Alkyl, C 1-C 8Haloalkyl, C 3-C 8Cycloalkyl, C 3-C 8Halogenated cycloalkyl, C 1-C 4Alkyl-C 3-C 8Cycloalkyl is single to be replaced or two replacement, or is replaced by phenyl or benzyl, and they are separately arbitrarily by halogen, cyano group, nitro, C 1-C 8Alkyl, C 1-C 8Haloalkyl, C 1-C 8Alkoxyl group, C 1-C 8Halogenated alkoxy, C 1-C 8Alkylthio, or C 1-C 8Halogenated alkylthio replaces), or be the C that halogen arbitrarily replaces 1-C 6Alkylthio, or be the C that halogen arbitrarily replaces 3-C 8Thiazolinyl, or be halogen or C 1-C 6The cycloalkyl that alkyl arbitrarily replaces, or be phenyl or benzyl, they are separately arbitrarily by halogen, cyano group, nitro, C 1-C 8Alkyl, C 1-C 8Haloalkyl, C 1-C 8Alkoxyl group, C 1-C 8Halogenated alkoxy, C 1-C 8Alkylthio, C 1-C 8Halogenated alkylthio, C 1-C 8Carbalkoxy or SCN replace, or are halogen or C 1-C 65 yuan or 6 yuan of heterocycles of the random replacement that contains 1 to 3 nitrogen-atoms that alkyl arbitrarily replaces, or R 3And R 4A nitrogen-atoms that links to each other with them forms 4 to 8 yuan of rings, forms arbitrarily by C 1-C 8(this nitrogen is arbitrarily by C for arbitrarily contain oxygen, sulphur or nitrogen that alkyl replaces 1-C 8Alkyl, phenyl or benzyl replace) ring.R 1Especially be preferably fluorine.R 2Especially be preferably the base of following formula
Figure A9519715800121
Wherein Y is oxygen or sulphur, and Z is an oxygen, sulphur or NR 4, R 3Be hydrogen, or arbitrarily by fluorine, chlorine, cyano group, carboxyl, phenyl, it is amino that (this amino is arbitrarily by C 2-C 6Alkylidene group (C 2-C 6-alkanediyl) replace or by identical or different C 1-C 6The alkyl list replaces or two replacement), C 1-C 6Alkoxyl group, C 1-C 6(this aminocarbonyl is arbitrarily by C for alkylthio or aminocarbonyl 2-C 6Alkylidene group (C 2-C 6-alkanediyl) replace or by identical or different C 1-C 6Alkyl, C 1-C 6Haloalkyl, C 1-C 6Alkoxyl group, C 3-C 7Cycloalkyl, C 3-C 7Halogenated cycloalkyl, C 1-C 3-alkyl-C 3-C 7Cycloalkyl is single to be replaced or two replacement, or is replaced by phenyl or benzyl, and they are separately arbitrarily by halogen, cyano group, nitro, C 1-C 6Alkyl, C 1-C 6Haloalkyl, C 1-C 6Alkoxyl group, C 1-C 6Halogenated alkoxy, C 1-C 6Alkylthio or C 1-C 6Halogenated alkylthio) C of Qu Daiing 1-C 6Alkyl, or for arbitrarily by fluorine, chlorine or C 1-C 4The C that alkyl replaces 4-C 8Cycloalkyl, or be phenyl, benzyl, carbobenzoxy or benzene sulfuryl, they are separately arbitrarily by fluorine, chlorine, cyano group, nitro, C 1-C 6Alkyl, C 1-C 6Haloalkyl, C 1-C 6Alkoxyl group, C 1-C 6Halogenated alkoxy, C 1-C 6Alkylthio, C 1-C 6Halogenated alkylthio, C 1-C 6Carbalkoxy or SCN replace, or are fluorine, chlorine or C 1-C 4The C that alkoxyl group arbitrarily replaces 1-C 6Carbalkoxy.R 4Especially be preferably hydrogen, or be C 1-C 6Alkyl, the C that fluorine or chlorine arbitrarily replaces 1-C 4Alkylthio, or C 4-C 8Cycloalkyl, or R 3And R 4A nitrogen-atoms that is connected with them forms 4 to 8 yuan of rings, forms arbitrarily by C 1-C 6Alkyl replaces arbitrarily contains oxygen, and (this nitrogen is arbitrarily by C for sulphur or nitrogen 1-C 6Alkyl, phenyl or benzyl replace) ring.R 1It very particularly preferably is fluorine.R 2It very particularly preferably is the base of following formula
Figure A9519715800131
Wherein Y is an oxygen, and Z is an oxygen, sulphur or NR 4, R 3Be hydrogen, or arbitrarily by fluorine, chlorine, cyano group, carboxyl, phenyl, it is amino that (this amino is arbitrarily by C 2-C 6Alkylidene group (C 2-C 6-alkanediyl) replace or by identical or different C 1-C 6The alkyl list replaces or two replacement), C 1-C 6Alkoxyl group, C 1-C 6(this aminocarbonyl is arbitrarily by C for alkylthio or aminocarbonyl 2-C 6Alkylidene group (C 2-C 6-alkanediyl) replace or by identical or different C 1-C 4Alkyl, C 1-C 4The alkoxyl group list replaces or two replacement, or is replaced by phenyl or benzyl, and they are separately arbitrarily by halogen, cyano group, nitro, C 1-C 6Alkyl, C 1-C 6Haloalkyl, C 1-C 6Alkoxyl group, C 1-C 6Halogenated alkoxy, C 1-C 6Alkylthio or C 1-C 6Halogenated alkylthio) C of Qu Daiing 1-C 6Alkyl, or be C 1-C 4The C that alkyl arbitrarily replaces 4-C 8Cycloalkyl, or be phenyl, benzyl, carbobenzoxy or benzene sulfuryl, they are separately arbitrarily by fluorine, chlorine, cyano group, nitro, C 1-C 4Alkyl, C 1-C 4Haloalkyl, C 1-C 4Alkoxyl group, C 1-C 4Halogenated alkoxy, C 1-C 4Alkylthio, C 1-C 4Halogenated alkylthio or C 1-C 4Carbalkoxy replaces, or is fluorine, chlorine, or C 1-C 4The C that alkoxyl group arbitrarily replaces 1-C 4Carbalkoxy.R 4Very particularly preferably be hydrogen, or be C 1-C 4Alkyl is the random C that replaces of fluorine or chlorine 1-C 3Alkylthio, or C 4-C 6Cycloalkyl, or R 3And R 4The nitrogen-atoms that links to each other with them together forms 4 to 8 yuan of rings, or forms C 1-C 4Alkyl replaces arbitrarily contains oxygen, and (this nitrogen is arbitrarily by C for sulphur or nitrogen 1-C 4Alkyl or benzyl arbitrarily replace) ring.
General or the preferred definition of above-mentioned group or description is used for end product and is used for raw material and intermediate accordingly.The definition of these groups can mutually combine as required, and that is to say may be in combination between the preferred range separately.
According to the present invention, preferably contain the general formula (Ia) and the compound (Ib) of the combination of the preferred implication of above-mentioned conduct.
According to the present invention, preferably contain above-mentioned general formula (Ia) and compound (Ib) especially as particularly preferred combination.
According to the present invention, preferably contain the general formula (Ia) and the compound (Ib) of above-mentioned conduct combination very particularly preferably very especially.
Further preferred compound group is the compound of general formula (Ic), and particularly wherein Z is that oxygen and R5 are that fatty group is preferably the particularly compound of ethyl of low alkyl group.
In the definition of the given base of context, alkyl, alkyl or alkenyl-and link to each other for example, for example alkoxyl group or alkylthio-be straight or branched in all cases as far as possible with heteroatoms.
With radicals R 5, R 6, R 7, R 8, R 9, R 10And R 11Definition in the term that uses understand as follows:
Term " halogen " means fluorine, chlorine, bromine, iodine.
Term " alkyl " is straight or branched C 1-C 7Alkyl.
Term " low alkyl group " is straight or branched C 1-C 4Alkyl.
Term " fatty group " is saturated or undersaturated, contains the straight or branched alkyl of 1 to 10 carbon atom (or as said), or contains the straight or branched thiazolinyl of 2 to 10 carbon atoms (or as said).
Term " alkoxyl group " is the low alkyl group that connects via Sauerstoffatom.
Term " alkylthio " is the low alkyl group that connects via sulphur atom.
Term " carbalkoxy " is the low-grade carboxylic acid's of carboxyl a alkyl ester.
Term " carboxylic acid group; sulfonic group; the ester of phosphate or phosphorous acid base or the acid mentioned; thioesters or acid amides " means wherein at least one carbon atom by the fatty group of carboxyl substituted, or wherein at least one hydrogen atom by sulfonic group, the fatty group that lower alkyl esters, low alkyl group thioesters or the acid amides of phosphorous acid base or phosphate and the acid mentioned (this acid amides is arbitrarily replaced by 1 or 2 low alkyl groups) replaces.
Term " amino acid " means NR 5R 6Arbitrarily replaced by the amino of natural or alpha-non-natural amino acid.
Term " aromatic base " or " aryl " mean the phenyl with image replacement recited above.
At least any ring that contains 1 non-carbon in term " heterocyclic radical " finger ring.Heteroatoms can be an oxygen, nitrogen, sulphur or other element.The heterocyclic example has thiadiazoles, pyridine, thiazole, isothiazole ， oxazole, imidazoles, pyrazoles, triazole, benzothiazole, sulfur heterocyclic ring, morpholine, piperidines, piperazine, or tetramethyleneimine, they are replaced by a substituting group at least, and these substituting groups are from cyano group, and are trimethyl silicon based, hydroxyl, alkoxyl group, halogen, nitro, amino, SH, alkylthio, carboxyl, carbalkoxy, phenyl, carboxylic acid group, sulfonic group, phosphate, phosphorous acid base, or these sour ester, monothioester or acid amides.
According to method A α of the present invention) during the compound of preparation general formula (I), if with for example 3,4,4-three fluoro-fourth-3-enol and chloro ethyl formate are made raw material, can describe reaction with following reaction scheme so:
Figure A9519715800151
According to method A β of the present invention) during the compound of preparation general formula (I), if with for example 3,4,4-three fluoro-fourth-3-enol and phenylcarbimide are made raw material, can describe reaction with following reaction scheme so:
According to method B of the present invention) during the compound of preparation general formula (I), if with for example 3,4,4-three fluoro-fourth-3-enol and chloro sulphur methyl-formiate are made raw material, can describe reaction with following reaction scheme so:
Figure A9519715800153
According to method C of the present invention) during the compound of preparation general formula (I),, can reaction be described with following reaction scheme so if be raw material with for example chloroformic acid-(3,4,4-three fluoro-fourth-3-alkene)-ester and hexahydroaniline:
According to method D of the present invention) during the compound of preparation general formula (I), if with for example chloro sulphur formic acid-(3,4,4-three fluoro-fourth-3-alkene)-ester and 2, the 6-thebaine is a raw material, can describe reaction with following reaction scheme so:
Figure A9519715800162
The method A α of the compound of all above-described preparation general formulas (I), A β, B, C and D are characterised in that under the existence that wherein is reflected at thinner and carry out.
Suitable diluents in these methods is conventional solvent.
Particularly suitable thinner is random halogenated aliphatic hydrocarbon or aromatic hydrocarbon, ether or nitrile, for example hexanaphthene, toluene, chlorobenzene, chloroform, methylene dichloride, ethylene dichloride, dioxane, tetrahydrofuran (THF), ether or acetonitrile.
The method A α of the compound of all above-described preparation general formulas (I), B, C and D are characterised in that wherein reaction is optionally carried out in the presence of alkali.
Method A α, B, alkali suitable among C and the D is conventional proton acceptor, and Shi Yi alkali is alkali metal hydroxide especially, or alkaline earth metal hydroxides, alkaline carbonate, or alkaline earth metal carbonate, or alkali metal hydrocarbonate, or alkali metal bicarbonates, or nitrogenous base.Example comprises sodium hydroxide, calcium hydroxide, salt of wormwood, sodium bicarbonate, triethylamine, dibenzylamine, Diisopropylamine, pyridine, quinoline, diazabicyclo octane (DABCO), diazabicyclo-nonene (DBN) and diazabicyclo hendecene (DBU).
The method A β of the compound of above-described preparation general formula (I) is characterised in that wherein reaction is optionally carried out in the presence of catalyzer.
Suitable catalyzer is for example diazabicyclo octane (DABCO), triethylamine or pyridine or organic tin compound, for example dibutyl tin laurate.
Above-described method A α, A β, B, C in all cases can be in relative wide range with the temperature of reaction among the D.At method A α, B, among C and the D, reaction is generally carried out between-10 ℃ and 150 ℃.Preferably between 0 ℃ and 90 ℃, carry out.In method A β, reaction is generally carried out between 0 ℃ and 120 ℃, preferably carries out between 20 ℃ and 100 ℃.
Method A α formula of (II) and (III) and method B formula of (IIa) and raw material ratio (III) be 1: 1 to 2: 1.
At method A β formula of (II) and material rate (IV) generally at 2: 1 and l: between 2; Being preferably equivalent uses.
The general formula (VII) among logical formula V in method C and raw material (VI) and the method D and the material rate of general formula (VIII) are generally respectively between 1: 1 and 10: 1.
Above-described method A α, A β, B, C and D generally under atmospheric pressure implement.Above-described method A α, A β, B when C and D aftertreatment, with reaction mixture dilute with water for example, uses organic solvent extraction, concentrates organic phase then.
The raw material of the general formula (II) that uses in method A α and A β is known, and can prepare (referring to for example WO 92/15555) by currently known methods.
The general formula (III) or the raw material (IIIa) that also use in method A α and B are known and/or can prepare by currently known methods.General formula (III) or compound (IIIa) for example can be by alcohol, the amine of mercaptan or general formula (VI) makes (referring to for example Houben-Weyl by currently known methods and phosgene or thio phosgene reaction, Methoden der Organischem Chemie, BandE4, S.407 ff., Georg Thieme Verlag Stuttgart, NeW York, 1983).
The different thiocyanide that is used as the general formula (IV) of raw material in method A β is to be used for the synthetic known compound in the organic chemistry.
Though the raw material of the logical formula V that uses in method C is a new compound, can prepare by currently known methods.For example (see above) and phosgene or thio phosgene reaction can make the compound of logical formula V to the compound of general formula (II) according to a conventional method.
The raw material of the general formula (VI) that also uses in method C generally is to be used for the synthetic known compound in the organic chemistry.
The general formula that in method D, uses (VII) though raw material be new compound, can prepare by currently known methods.For example the compound of general formula (IIa) can make the compound of general formula (VII) by method (see above) known per se and phosgene or thio phosgene reaction.
The raw material of the general formula (VIII) that also uses in method D generally is to be used for the synthetic known compound in the organic chemistry.
This class active compound is suitable for controlling pest, especially is controlled at agricultural, and forestry reaches insect, Araneae and the nematode that health circle is run in product and the preservation of thing material.No matter they are to the insect of normal sensitivity or the insect of antagonistic drug, and the growth whole process of described insect or some stage of growth are all had antagonistic activity.Insect above-mentioned comprises:
From Isopoda, for example Oniscus asellus, Armadillidium vulgare and Porcellio Scaber.
From Isopoda, Blaniulus guttulatus for example.
From Chcilopoda, for example the DIWUGONG of Carpophagus belongs to and the kind of common house centipede dragonfly section.
From comprehensive subclass, the common house centipede section of immaculata for example.
From total tail purpose, for example silverfish.
From Collembola, for example the sour jujube of spinosity jumps.
From Orthoptera, Blatta seu periplaneta for example, U.S. blattaria, leucophaea maderae, blatta germanica, tame Xi, mole cricket kind, African migratory locust, different black locust and desert locust.
From Dermaptera, European earwig for example.
From Isoptera, reticulitermes flavipe kind for example.
From Anoplura, for example body louse, blood lice kind and a hair lice kind.
From Mallophaga, for example chew lice kind and poultry lice kind.
From Thysanoptera, for example greenhouse bar hedge thrips and onion thrips.
From Hemiptera, for example flat fleahopper kind, red cotton bug intermedius, square butt stinkbug, bed bug, phodnius prolixus and dimension are hunted the stinkbug kind.
From Hemiptera, wild cabbage aleyrodid for example, cassava aleyrodid, greenhouse whitefly, cotten aphid, brevicoryne brassicae, the tea Fischer conceals knurl aphid, beans winged euonymus aphid, apple aphid, apple aphid, mealy plum aphid, grape phylloxera, goitre woolly aphid kind, grain aphid, knurl aphid kind, phorodon aphid, rhopalosiphum padi, jassids kind, bilobate blunt nose calamity leafhopper, rice green leafhopper, the hard a red-spotted lizard of water wood, black scale, small brown rice planthopper, brown paddy plant hopper, red kidney Aspidiotus, ivy Aspidiotus, mealybug kind and wood louse kind.
From lepidopterous, Pectinophora gossypiella for example, loose looper, Cheimatobia brumata, the thin moth of apple, apple ermine moth, diamond-back moth, malacosoma neustria, the pornography and drug moth, poison moth kind, cotton lyonetid, tangerine lyonetid, the cutworm kind, the cutworm kind, the noctuid kind, Egyptian golden steel bores, real noctuid kind, beet armyworm, lopper worm, pine beauty, the litura noctuid, spodoptera kind, cabbage looper, codling moth, the small white kind, dogstail snout moth's larva kind, Pyrausta nubilalis (Hubern)., Anagasta kuehniella, Galleriamellonella, curtain rain moth, bag rain moth, brownly knit moth, the yellow volume of flax moth, reticulana rolls up moth, spruce bunworm, Clysia ambiguella, the green volume of tea long paper moth and oak moth.
From Coleoptera, furniture death watch beetle for example, lesser grain borer, the awl chest bean weevil of tool quilt belongs to, acanthoscelides obtectus, the North America house longhorn beetle, the willow firefly is chrysomelid, colorado potato beetles, the horseradish ape is chrysomelid, chrysomelid kind, rape golden head flea beetle, the big Epilachna spp of Mexico, the Atomaria linearis kind, saw-toothed grain beetle, flower resembles kind, the grain weevil kind, black grape ear image, the banana collar resembles, Chinese cabbage powder tortoise resembles, and alfalfa leaf resembles, the khapra beetle kind, spot khapra beetle kind, circle khapra beetle kind, powder is moth-eaten plants, the aeneus nitidulid, ptinid kind, golden spider beetle, globose spider beetle, ostomatid kind, tenebrio molitor, Pleonomus kind, the west melolonthid in May, European chafer (Amphimallon majalis) and and the brown New Zealand rib wing melolonthid.
From hymenopteran, for example Neodiprion spp kind, sawfly kind, ant kind, little red ant and wasp kind.
From dipterous, yellow-fever mosquito kind for example, eucalyptus mosquito kind, culex kind, black-tailed fruit flies, housefly kind, latrine fly kind, reddish tone fly kind, the lucilia kind, golden fly kind, cuterbrid kind, stomach fly kind, the Hyppobosca kind, tatukira kind, botfly kind, torsalo kind, the horsefly kind, Tannia kind, black wool mosquito, auspicious bent wheat stem chloropid fly, late wheat straw kind fly, beet spring fly, Mediterranean Sea Ceratitis spp, big trypetid of olive and European daddy-longlegs.
From Siphonaptera, Xanthopsyllacheopis for example, c. leaf flea kind.
From Arachnida, for example Scorpio maurus and Latrodectus mactans.
From acarina, Acarus siro for example, sharp-edged mite kind, turicata kind, Dermanyssus gallinae, tea Fischer goitre mite, the tangerine rust mite that rues, ox tick kind, fan head tick kind, flower tick kind, glass eye tick kind, hard tick kind, the itch mite kind, overworked mite kind, Sarcoptes kind, tarsonemid mite kind, Bryobia praetiosa, golden pawl mite kind and tetranychid kind.
The phytoparasitic nematodes comprises the Pratylenchus kind, Radopholussimilis, Ditylenchus dipsaci, Tylenchulus semipenetrans, narrow body Pleonomus kind, Globodera kind, the Meloidogyne kind, Aphelenchoides kind, Longidorus kind, Xiphinema kind and Trichodorus kind.
The compound of general formula of the present invention (I) has shown outstanding insect and eelworm-killing activity extremely especially.Be used for extremely that leaf is given birth to and during the livings insect of soil, their show strong active, for example show and strong kill mustard seed pestle lavae (Phaedon cochleariae) and water chestnut is believed the Candle-sticks that carries on the back moth (Plutella maculipcunis).When being used for nematicide, they have for example strong Meloidogyne incognita activity extremely.
Compound of the present invention not only has prophylactic effect, also can be used for the leaf system root system pest-resistant evil of uniting of unifying.
The active compound of general formula of the present invention (I) also has fungicidal action further, and the effect of killing Pyricularia oryzea in the rice is for example arranged.
This class active compound can change common formulations into, for example changes solution, emulsifying agent into, wettable powder, suspension agent, pulvis, dust agent, paste, soluble powder, granule, suspension agent-emulsifying agent enriched material, with the natural goods and the synthetics of active compound dipping, and the superfine capsule of making of superpolymer.
These formulations are pressed currently known methods production, for example mix with spreading agent by active compound, promptly mix with liquid solvent and/or solid carrier, optionally use tensio-active agent, promptly use emulsifying agent and/or dispersion agent and/or foam to form agent.
When making water as spreading agent, also can be with an organic solvent as solubility promoter.As liquid solvent, suitable mainly contains: aromatic hydrocarbons, for example dimethylbenzene, toluene or alkylnaphthalene, chlorination aromatic hydrocarbon and chlorinated aliphatic hydrocarbon, for example chlorobenzene, vinylchlorid, methylene dichloride, aliphatic hydrocarbon, for example hexanaphthene or paraffinic hydrocarbons, sherwood oil cut for example, mineral oil and vegetables oil, alcohols, for example butanols or glycerine, and their ether or ester, ketone, acetone for example, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) or pimelinketone, intensive polar solvent, for example dimethyl formamide and dimethyl sulfoxide (DMSO) and water.Suitable solid carrier has: the natural material of ammonium salt and grinding for example, kaolin for example, clay, talcum, chalk, quartz, atlapulgite, polynite or diatomite, and the synthetic material that grinds, the silica gel of high dispersive for example, aluminum oxide and silicate, the suitable solid carrier of making granule has: for example pulverize with the fractionated natural rock, calcite for example, marble, float stone, sepiolite and rhombspar, and the synthetic particle of inorganic and organic powder, and the particle of organic materials, for example sawdust, cocoa shell, corn fragment and tobacco rods; Examples of suitable emulsifiers and/or foam form agent to be had: for example non-ionic type and anionic emulsifier, polyoxyethylene fatty acid ester for example, polyoxyethylene aliphatic alcohol ether, alkylaryl polyglycol ether for example, alkyl sulfonic ester, alkyl sulfuric ester, aromatic yl sulphonate and egg white hydrolysate; Suitable dispersion agent has: for example lignin sulfite waste lye and methylcellulose gum.
Tackiness agent, for example carboxymethyl cellulose and powdery, particulate state or glue lactous natural and synthetic superpolymer, for example gum arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipid, for example kephalin and Yelkin TTS, and synthetic phosphatide, can be used for prescription.It is further auxilliary that to add agent be mineral oil and vegetables oil.
Also can use tinting material, mineral dye for example, ferric oxide for example, titanium dioxide, with general Lu Shi orchid, and organic dye, for example alizarine dyestuff, azidine dye and metal phthalocyanine dyestuff and trace nutrient, for example iron, manganese, boron, copper, cobalt, the salt of metals such as molybdenum and zinc.
The active compound of the general bag of prescription (wound by weight) 0.1% to 95% preferably contains 0.5% to 90% active compound.
New active compound can exist with its commodity prescription and the form of use, can be by these formulation, as with the mixture of other active compound, for example with insecticide, attractive substance, sterilizing agent, antiseptic-germicide, miticide, nematocides, mycocide are produced the mixture of regulating material or weedicide.Insecticide comprises, phosphoric acid ester for example, carbamate, carboxylicesters, hydrochloric ether, benzene urine, and the chemical combination material by microorganisms particularly.
The example of particularly advantageous composition is as follows: mycocide:
The 2-aminobutane; 2-phenylamino-4-methyl-6-cyclopropyl-pyrimidine; 2 ', 6 '-two bromo-2-methyl-4 '-trifluoromethoxy-4 '-Trifluoromethyl-1,3-thiazole-5-carboxylic acylaniline; 2,6-two chloro-N-(4-trifluoromethyl benzyl) benzamide; (E)-2-methoxyimino-N-methyl-2-(2-phenoxy phenyl) ethanamide; The oxine sulfuric ester; (E)-and 2-{2-[6-(2-cyano-benzene oxygen)-pyrimidine-4-base oxygen] phenyl }-the 3-methoxy acrylate; (E)-methoxyimino [α-(neighbour-toluene oxygen)-O-tolyl] methyl acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole, benalaxyl, benodanil, benomyl, Niagara 9044, biphenyl, bitertanol, miewensu, bromuconazole, bupirimate, buthiobate, lime sulfur mixture, Difolatan, Vancide 89, derosal, carboxin, chinomethionate, chloroneb, trichloronitromethane, m-tetrachlorophthalodinitrile, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram, dichlorophen, diclobutrazol, diclofluanid, diclomezine, dicloran, diethofencarb, difenoconazole, Milcurb, dimethomorph, diniconazole, dinocap, pentanoic, dipyrithione, ditalimfos, the Delan, dodine, drazoxolon, Hinosan, epoxyconazole, the pyridine of second bacterium, etridiazole, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentinacetate, fentinhydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole, flusilazole, flusulphamide, flutolanil, flutriafol, Phaltan, fosetyl-aluminium, fthalide, fuberidazole, furalaxyl, furmecyclox, Guanoctine, Perchlorobenzene, hexaconazole, hymexazol, imazalil, imibenconazole, iminoctadine, iprobenfos (IBP), iprodione, Fujione, the spring thunder toxin, copper agent, for example: copper hydroxide, copper naphthenate, COPPER OXYCHLORIDE 37,5, copper sulfate, cupric oxide, oxine-copper and Bordeaux mixture.Mancopper, zinc manganese ethylenebisdithiocarbamate, maneb, mepanipyrim, mepronil, metalaxyl, metconazole, methasulphocarb, methfuroxam, Carbatene, metsulphovax, myclobutanil, good fortune magnesium nickel, nitrothal-isopropyl, muarimol, ofurace, axadixyl, oxamocarb, oxycarboxin, pefurazoate, penconazole, pencycuron, phosdiphen, phthalide, myprozine, pipron, polycarbamate, Polyoxin, thiabendazole, prochloraz, procymidone, propamocarb, propiconazole, propineb is decided the bacterium spirit, pyrifenox, pyrimethanil, pyroguilon, quintozene (PCNB), sulphur and sulphur preparation, tebuconazole, tecloftalam, tecnazene, tetraconazole, Apl-Luster, thicyofen, thiophanate methyl, thiram, tolclophosmethyl, tolylfluanid, triadimefon, triadimenol, triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole, triforine, triticonazole, Validacin (Takeda), vinclozolin, zineb, ziram, bactericide: the bromine nitre glycol that goes out, dichlorophen, nitrapyrin, Sankel, kasugamycin, octhilinone, furancarboxylic acid, terramycin, thiabendazole, Streptomycin sulphate, tecloftalam, copper sulfate and other copper agent.Insecticide/miticide/nematocides: abamectin, AC 303630, Ortho 12420, acrinathrin, alanycarb, aldicarb, alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, R-1582 A, R-1582 M, azocyclotin, bacillus thuringiesis Evil worm prestige, benfuracarb, bensultap, beta-cyfluthrin, bifenthrin, butylbenzene becomes, brofenprox, bromofos A, bufencarb, buprofezin, butocarboxim, butylpyridaben, cadusafos, SevinCarbaryl, carbofuran, carbophenothion, carbosulphan, Padan, CGA l57419, CGA 184699, chloethocarb, chlorethoxyfos, Zaprawa enolofos, chlorfluazuron, chlormephos, Chlorpyrifos 94, chlorpyrifos M, suitable-Chryson, clocythrin, clofentezine, cynock, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine, deltamethrin, one zero five nine M, one zero five nine S, methyl 1, diafenthiuron, diazinon, dichlofenthion, SD-1750, dicliphos, Carbicron, Nialate, diflubenzuron, Rogor, dimethylvinphos, dioxathion, thiodemeton, Hinosan, emamectin, esfenvalerate, ethiofencarb, Nialate, ethofenprox, ethoprophos, etrimphos, fenamiphos, fenazaquin, fenbutatinaxide, Sumithion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, Tiguvon, fenvalerate, fipronil, fluazinam, flucycloxuron, flucythrinate, flufenoxuron, flufenprox, fluvalinate, Dyfonate, the peace fruit, fosthiazate, fubfenprox, furathiocarb, phenyl-hexachloride, heptenophos, hexaflumuron, hexythiazox, imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb ， karphos, ivermectin, lambda-cyhalothrin, lufenuron, Phosphothion, mecarbam, Phosdrin, mesulphenfos, Halizan, methacrifos, acephatemet, methidathion, metmercapturon, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin, naled, NC l84, NI 25, nitenpyram, omethoate, oxamyl, oxydemeton methyl M, oxydeprofos, one six zero five A, one six zero five M, permethrin, Tsidial, phorate, zolone, R-1504, phosphamidon, phoxim, Aphox, pirimiphosmethyl M, pirimiphosmethyl A, profenofos, promecarb, Kayaphos, Propoxur, prothiofos, Fac, pymetrozin, pyrachlofos, pyridaphenthion, pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxyfen ， quinalphos, RH 5992, salithion, sebufos, silafluofen, sulphotep, sulprofos, tebufenozid, tebufenpyrad, tebupirimifos, teflubenzuron, tefluthrin, temephos, terbam, terbufos, tetrachlorvinphos, thiafenox, thiodicarb, thiofanox, thiomethon, ethyl pyrazinyl phosphorothioate, thuringiensin, tralomethrin, triarathen, triazoline, triazuron, Trichlorphon, triflumuron, trimethacarb, vamidothion, Cosban, xylylcarb, YI 5301/5302, zetamethrin
Can also with other known activity compound fusion, for example with weedicide or fertilizer and the fusion of promotes growth compound.
Active compound of the present invention can exist with their commodity prescription with the use shape from these formulation further, as with the mixture of synergist.Synergist is the compound that increases the active compound effect, and it is activated that synergist itself is provided with necessity.
Can in big limit, change from the amount of the active compound of the use form of commodity formulation.The concentration of using the active compound of form can be from 0.0000001 to 95% of the weight of active compound, preferably 0.0001 to 1% (by weight).
Compound is by being suitable for using the usual manner of form to use.
When being used for the insect of the product of health circle insect and storage extremely, active compound has outstanding residual action at timber on the clay, to having satisfactory stability with the alkali on the substrate of lime treatment.
Active compound of the present invention not only has the plant of killing, and the effect of the insect in the product of health and preservation can also be killed zooparasite (epizoon) in the animal doctor, for example hard tick, soft ticks, scab mite, sandmite, fly (sting and inhale), the tachinid larva, sends out lice, bird lice and flea at lice.These parasites comprise:
From the Anoplurida purpose, blood lice kind for example, hair mite kind, lice kind, phtirus kind, pipe lice kind;
From neck bean weevil subfamily Mallophaga and thick and Ischnocerina purpose, filoplume lice kind for example, the mallophaga kind, huge poultry louse kind, ox poultry louse kind, the Werneckiella kind, the Lepikentron kind, poultry lice kind is chewed the lice kind, cat poultry louse kind;
From dipterous and orthorrhapha suborder with orthorrhapha, yellow-fever mosquito kind for example, anopheles kind, culex kind, the buffalo gnat kind, true buffalo gnat kind, sand fly kind, Lutzomyia kind, the mosquito Superfamily, spot horsefly kind, hybomitra kind, yellow horsefly kind, Gadfly, Chrysozona, philipomyia kind, the honeybee Hippobosca, Musca, Hydrotaea, matting chela fly belongs to, east horn fly kind, and Morellia belongs to, Fannia, Glossina, Calliphora, Lucilia, Carysomyia, wohlfahrtia magnifica, Sarcophaga, Oestrus, Hypoderma, Gasterophilus, Hippobosca, Lipoptena and Melophagus.
From Siphonaptera, for example, the flea kind, Ctenocephalus, objective flea belongs to, Ceratophyllus.
From Hemiptera, for example, Cimex, Triatoma, Rhodnius and Panstrongylus kind.
From Blattodea, Blatta seu periplaneta for example, periplaneta americana, blatta germanica, brown belt Lian.
From Tyroglyphidae (Acarida) subtribe and Meta order and Mesostigmata purpose, Argas for example, Ornithodoros, the Otabius kind, hard tick belongs to Amblyomma, Boophilus, careless tick belongs to, Haemaphysalis, Hyalomma, Rh, Dermanyssus, Raillietia kind, the Pneumonyssus kind, Sternostoma kind and Vespacarus.
From Actinedida (Prostigmata) order and Acaridida (Astigmata) purpose, for example, honeybee shield mite belongs to, the Cheyletiella kind, the Ornithocheyletia kind, Myobia kind, Psorergates kind, Demodex, Trombidium, black this resembles genus, Tyroglyphus, the saprophage mite belongs to, the Caloglyphus kind, the Hypodectes kind, the Pterolichus kind, overworked mite belongs to, Psoroptes, the ear itch mite belongs to, and itch mite belongs to, Notoedres, Cnemidocoptes, Cytodites kind and Laminosioptes.
For example compare with lucilia cuprina with boophilus microplus, they show outstanding activity.
The active compound of general formula of the present invention (I) also is applicable to the arthropods of the agriculture domestic animal of control harm, for example control endangers ox, sheep, goat, horse, pig, monkey, camel, buffalo, rabbit, chicken, turkey, duck, goose, honeybee, other domestic animal, for example dog, cat, cage bird, cylinder is breeded fish and so-called laboratory animal, hamster for example, guinea pig, the arthropods of rat and mouse.By controlling these arthropodss, purpose is to reduce the mortality ratio of domestic animal and reduces workload (workload in meat, milk, fur, leather, egg, honey or the like), so that might use active compound of the present invention more economical, more simply feeding animals.
In veterinary applications, active compound of the present invention administration for oral administration in known manner is for example with tablet, capsule, beverage, liquid medicine, granule, paste, pill, food is raised agent, suppository etc. are for oral administration, by parenterai administration, for example injection (intramuscular injection, subcutaneous injection, intravenous injection, peritoneal injection or the like), drug delivery implant, intranasal administration, percutaneous dosing is for example with soaker or solution, sprays, injectant and click and enter agent, lotion, the dust agent administration, and by means of the shaping thing that contains active compound, for example by the neck ring that contains active compound, ear muff, tail note, wing band, halter, administrations such as tag device.
When giving livestock, domestic animal is during administrations such as domestic animal, the active compound of general formula (I) can be with prescription (for example powder, emulsion, the flowable materials) administration of the active compound that contains 1 to 80% amount, or directly use, or dilute by 100 to 10000 the factor, or use with the form of chemical bath.
The compound of general formula of the present invention (I) further finds to have the strong effect of killing the insect that can damage farm crop.
Following insect can be used as example and preferred example is mentioned, but without any the meaning that limits.Beetle, for example: the big ox of North America man, the Pilosis edge resembles, the furniture death watch beetle, extremely dead death watch beetle, Ptilinus pectinicornis, Dendrobium pertinex, loose death watch beetle, Priobium carpini, Lyctus brunneus Stephens, africanus powder moth, southern powder moth, bright powder moth, pubescence powder moth, Trogoxylon aequale, minthea rugicollis, material bark beetle kind, black material bark beetle kind, coffee is black long moth-eaten, and Mongolian oak is long moth-eaten, Heterobostrychusbrunneus, long moth-eaten kind, dinoderus minutus.Dermaptera, for example: big wood wasp, the big wood wasp of fir, the big wood wasp of taignus fir, the big wood wasp of augur fir.The termite subject, kalotermitid for example, flavicollis, a fiber crops heap sand termite, different termite, American-European reticulitermes flavipe, Reticulitermessantonensis, Reticulitermes lucifugus, Darwin Australia termite, nevadensis termite, Coptotermes formosanus Shtrari.Bristlefails, for example silverfish.
Industrial goods are interpreted as non-life material in this article, for example are preferably synthetic material, glue, paste, paper and cardboard, skin, wood, Wood products and coating.
The material that especially preferably prevents insect pest infestation is wood and Wood products.
Can be interpreted as construction timber for example, wooden frame with composition of the present invention or the wood and the Wood products that contain the mixture protection of this based composition; railroad tie, bridge parts, trestle; wooden wheel, axle, pallet; container, electric pole, wooden protecting jacket; timber window and timber, glued board, particle board; joiner's instrument, or be used to build house or the thin wooden very common Wood products.
Active compound can be with the form of enriched material or with common prescription, powder agent for example, and granule, solution, suspension agent, emulsifying agent, or paste uses.
The prescription of mentioning can be by the currently known methods preparation of document, for example with active compound and at least a solvent or thinner, emulsifying agent, dispersion agent, and/or tackiness agent or fixing agent, water drive is scolded agent, if appropriate with siccative and ultra-violet stabilizer, mixes with tinting material such as pigment and other auxiliary material if appropriate.
Be used to protect the insecticidal composition of timber and timber or concentrated solution to comprise active compound of the present invention, by weight, concentration is 0.0001 to 95%, is in particular 0.001 to 60%.
The consumption of composition or concentrated solution depends on the kind of the insect on the medium and the situation of insect pest takes place.The best proportion that uses can be determined according to every kind of situation of tested series.But, enough with the active compound of calculating by weight use 0.0001 to 20% of protected material in general, be preferably 0.001 to 10%.
Solvent that uses and/or thinner are the mixture of organic solvent or solvent and/or mixture and/or polar organic solvent or solvent mixture and/or water, examples of suitable emulsifiers and/or the wetting Agent for Printing Inks of oily or buttery organic solvent or low voc solvent.
The preferred organic solvent that uses is higher than 35 as evaporation number, and flash-point is higher than 30 ℃, preferably is higher than 45 ℃ oily or oil-based solvent.This class oily and the oil-based solvent that use are low as volatility, water-fast mineral oil or their aromaticity cut, or contain the solvent mixture of mineral oil, be preferably petroleum solvent, petroleum products and/or alkylbenzene.
The compound that helps using is 170 to 200 ℃ a mineral oil as boiling range, and boiling range is 170 to 220 ℃ a petroleum solvent, and boiling range is 250 to 350 ℃ a spindle oil, and boiling range is 160 to 280 ℃ petroleum products or an aromatic compound, smart terpene or the like.
Using boiling range in preferred embodiments is 180 to 210 ℃ liquid fat hydrocarbon, or boiling range is 180 to 220 ℃ aromatic hydrocarbon and high boiling mixture and/or the spindle oil and/or a chloronaphthalene of aliphatic hydrocarbon, preferably α one chloronaphthalene.
Evaporation number is higher than 35, flash-point is higher than 30 ℃, the organic oily or the oil-based solvent that are preferably the low volatility that is higher than 45 ℃ can part be replaced by the organic chemistry solvent of high or middle volatility, condition is that the evaporation number of the solvent mixture that obtains also is higher than 35, flash-point is higher than 30 ℃, preferably be higher than 45 ℃, and kill insect/fungicidal mixtures or be dissolved in this solvent mixture, maybe can be emulsifiable in this solvent mixture.
In preferred embodiments, organic chemistry solvent or solvent mixture, or the part of fatty polar organic solvent or solvent mixture is substituted.The preferred compound that uses is the fatty organic chemistry solvent of hydroxyl and/or ester and/or ether, glycol ether for example, ester or the like.
The organic chemistry tackiness agent that uses in the scope of the invention is known in synthetic resins and/or the document and energy dilute with water and/or solvable maybe can the dispersion or emulsible bonding dry oil in the organic chemistry solvent that uses, especially by following resin tackiness agent that form or that comprise following resin: acrylate resin, Vinylite, polyvinyl acetate for example, vibrin, polycondensation resin or poly-addition resin, urethane resin, the Synolac of Synolac or modification, resol, hydrocarbon resin, for example indenes/coumarone resin, silicone resin, dryness plant and/or siccative oil and/or based on the physics dry adhesive of natural and/or synthetic resins.
Synthetic resins as tackiness agent can be with emulsion, and the form of dispersion liquid or solvent is used.Pitch or pitch sample material up to 10% weight also can be used as tackiness agent.In addition, also can use tinting material, pigment, water drive is scolded agent, and smell is covered material and inhibitor or the known corrosion inhibitor of document or the like.
According to the present invention, composition or concentrated solution preferably comprise at least a as the Synolac of organic chemistry tackiness agent or the Synolac and/or the dry vegetable oil of modification.The oil-contg of the Synolac that preferably uses according to the present invention surpasses 45% by weight, is preferably 50% to 68%.
Can be fixed agent (mixture) or softening agent (mixture) of all or some tackiness agents above-mentioned replaces.The purpose of these additives is to prevent active compound volatilization and crystallization or precipitation.They preferably replace 0.01 to 30% tackiness agent (tackiness agent of use is defined as 100%).
Softening agent is from phthalate compound, for example from dibutyl phthalate, and dioctyl phthalate (DOP) or benzyl butyl phthalate, from phosphoric acid ester, tributyl phosphate for example is from adipic acid ester, hexanodioic acid two-(2-ethylhexyl) ester for example, from stearate, for example butyl stearate or amyl stearate are from oleic acid ester, butyl oleate for example, from glyceryl ether, or relative high-molecular weight glycol ether, glyceryl ester and p-toluenesulfonic esters.
The chemical fundamentals of fixing agent is the polyvinyl alkyl oxide, for example polyvinyl methyl ether, or ketone, for example benzophenone, or ethylene benzophenone.
Particularly suitable solvent or thinner or water, suitable, be water and one or more above-mentioned organic chemistry solvent or thinner, the mixture of emulsifying agent and dispersion agent.
By the operation of large-scale mill retting, vacuum operating for example, two vacuum operatings or pressurized operation can make timber reach especially effectively protection.
Suitable, the available composition can comprise other insecticide immediately, and is suitable, can contain one or more mycocide again.
The suitable extraneous component that can admix is preferably insecticide and the mycocide of mentioning in WO 94/29268.The compound of mentioning in that file is clearly with being with reference to mixing the application.
The component of admixing very particularly preferably is insecticide, for example Chlorpyrifos 94, phoxim, Silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron, and triflumuron, and mycocide, for example epoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole, cyproconazole, metconazole, imazalil, Pecudin, tolylfluanid, 3-iodo-2-propynyl butyl carbamate, N-octyl group-isothiazoline-3-ketone and 4,5-two chloro-N-octyl group isothiazoline-3-ketone.
From the following examples preparation and the application of active compound of the present invention as can be seen.
Preparation embodiment
Example I-1
CF 2＝CF-CH 2-CH 2-O-CO-OC 2H 5 (I-1)
At ice-cooled down past 6.3g (50mmol) 3,4, first Dropwise 5 .4g (50mmol) Vinyl chloroformate in the solution of 4-trifluoro fourth-3-enol and 50ml methylene dichloride, Dropwise 5 .4g (53mmol) triethylamine again.Make solution be warming up to 20 ℃, and continue to stir and spend the night.Product extracts with ethylene dichloride behind the dilute with water, the extraction liquid concentrating under reduced pressure.Residue distills under the 30mmHg column pressure, steams (3,4,4-trifluoro fourth-3-thiazolinyl) ethyl-carbonate at 80 ℃.
Output 2.9g (theoretical amount 30%).
Example I-2 (I-2)
With 3.5g (22.5mmol) isocyanic acid-2,6-difluoro phenyl ester is added to 2.8g (20mmol) 3,4, in the solution of 4-trifluoro fourth-3-enol and 20mi methylene dichloride.After 40 ℃ of stirrings were spent the night, solution with water was washed, and tells organic phase, uses anhydrous magnesium sulfate drying.Removal of solvent under reduced pressure.Residue grinds with hexanaphthene.
Output 5.4g (theoretical amount 96%).
m.p.56-60℃。Example I-3 (I-3)
10 ℃ and stir under toward 5.0g (32mmol) N, Dropwise 5 .65g (30mmol) chloroformic acid 3,4 in the solution of N-hexa-methylene hydroxyl acetamide and 3.1g (30mmol) triethylamine and 50ml methylene dichloride, 4-trifluoro fourth-3-alkene ester.Solution stirring is spent the night, and with the methylene dichloride dilution, washes with water.Tell organic phase, concentrating under reduced pressure, oily residue silica gel chromatography purifying is with chloroform/ethyl acetate (4: 1) wash-out.Obtain the carbonic ether of 4.2g (theoretical amount 45.6%) expectation, be oily matter, logp=2.47.
Obtain the compound of following general formula (I) similarly according to general preparation method: table 1
Figure A9519715800311
(I)
Figure A9519715800331
Figure A9519715800351
Figure A9519715800361
*The logarithm of the partition ratio p of logp=compound between hot alcohol and water, real by reversed-phase HPLC
Test is fixed.
Example I-38
Figure A9519715800362
Toward 10.1g (0.1mol) triethylamine, drip 3ml (0.05mmol) CS in the solution of 6.0g (0.048mol) Glycocoll hydrochloride methyl esters and 50ml tetrahydrofuran (THF) (THF) under the room temperature 2After about 25 minutes of the stirring at room, slowly add 9.45g (0.05mol) 4-bromo-1,1,2-trifluoro but-1-ene, and at room temperature continue to stir to spend the night.The pressure reducing and steaming solvent, residue dissolves in ether.Solution with water is washed 4 times, anhydrous magnesium sulfate drying, pressure reducing and steaming ether.Residue chromatogram purification (silica gel, HPLC is with 14% ethyl acetate/hexane wash-out).Get the thick product of 7.8g, wherein 4.3g is placed in the refrigerator until crystallization.Decompression is filtered fast down and is dry, obtains the above-described compound of 2.5g, is colorless solid, mp:37-39 ℃.Ultimate analysis: element calculated value measured value C 35.16 35.26H 3.69 3.70N 5.13 5.10S 23.46 23.40 example I-39
Figure A9519715800371
Add 6.24g (0.033mol) 4-bromo-1 under ice-cold in the solution of former potassium xanthate of 5g (0.03mol) and 35ml dimethyl formamide (DMF), 1.2-trifluoro but-1-ene continues under the room temperature to stir to spend the night.Mixture inclines in 300ml water and uses extracted with diethyl ether.Ether layer washes with water 4 times, anhydrous magnesium sulfate drying, concentrating under reduced pressure.Obtain the above-described compound of 5.52g, be limpid yellow liquid.Ultimate analysis: element calculated value measured value C 36.51 36.63H 3.94 3.97S 27.85 27.74
Example I-40
Figure A9519715800372
According to the method for example I-38, with the Glycocoll hydrochloride tert-butyl ester replacement glycine methyl ester of equivalent.
After the thick product aftertreatment that obtains with 20% ethyl acetate/hexane recrystallization 2 times.Obtain the above-described compound of 2.35g, be colorless solid, mp.70-72 ℃.Ultimate analysis: element calculated value measured value C 41.89 42.04H 5.11 5.05N 4.44 4.43S 20.33 20.27 example I-41 Steps A
41.43g (0.3mol) diethyl phosphite, 9g (0.3mol) Paraformaldehyde 96 and in 60 to 70 ℃ of heating of 3.04g (0.03mol) triethylamine.Thermopositive reaction takes place, and temperature rises to 120 to 125 ℃, and solution becomes is limpid.This solution was in 120 ℃ of stirrings 10 minutes, and cooling adds some methylene dichloride, and solution decompression concentrates.The residue drying under reduced pressure.Obtain 49.6g.Molecular formula is HO-CH 2-P (=O) (OC 2H 5) 2Compound be clarified liq.Step B
Ice-cooled down, the compound and the 20ml CS that obtain in 10g (0.059mol) steps A 2Solution in slowly add 3.89g (0.059mol) 85%KOH.Solution adds the 150ml ether in stirring at room 2 hours, continues to stir 2 hours again.The elimination precipitation is washed drying under reduced pressure with ether.Obtaining the 13.69g molecular formula is
Figure A9519715800382
Compound, be yellow solid.Step C
Under the room temperature,, bit by bit add the compound that obtains among 5g (0.0177mol) the step B in the solution of 2-trifluoro but-1-ene and 30mlDMF toward 4g (0.022ml) 4-bromo-1,1.The reaction mixture stirred overnight at room temperature is inclined in 300ml water and is used extracted with diethyl ether.Ether layer washes with water 4 times, and anhydrous magnesium sulfate drying concentrates.Obtain the above-described end product of 4.76g, be limpid yellow liquid.Ultimate analysis: element calculated value measured value C 34.09 34.18H 4.58 4.58S 18.20 18.14 example I-42
Ice-cooled down, the drips of solution of 10.3ml (0.078mol) bromo triethyl silicane and 10ml acetonitrile is added in the solution of the compound of 2.3g (0.0065mol) example I-41 and 15ml acetonitrile.Solution is in stirred overnight at room temperature, the pressure reducing and steaming solvent.Residue and excessive methyl alcohol stirring at room 4 hours.Pressure reducing and steaming methyl alcohol then, the product drying under reduced pressure.Obtain the above-described compound of 1.96g, be colorless solid, mp:73-75 ℃.Ultimate analysis: element calculated value measured value C 24.33 24.38H 2.72 2.70S 21.65 21.75
Example I-43
Figure A9519715800392
Use the method for example I-38, replace the Glycocoll hydrochloride methyl esters, make this compound with the equivalent hydrochloric acid sarcosine tert-butyl ester.Be colorless solid, mp:35-37 ℃.Ultimate analysis: element calculated value measured value C 43.76 43.83H 5.51 5.52N 4.25 4.23S 19.47 19.40
Example I-44
Figure A9519715800393
Example I-45
Figure A9519715800401
Example I-46
According to the method for example I-38, begin to make example I-44 from corresponding precursor, the compound of I-45 and I-46.The preparation of raw material
EXAMPLE V-1
Figure A9519715800403
(V-1)
Ice-cooled and stir down, toward 30g (0.24mol) 3,4, logical 28g (0.28mol) phosgene in 4-trifluoro fourth-3-enol, mixture are then in 20 ℃ of restir 5 hours.After removing excessive phosgene with nitrogen bubble, the distillation of buttery residue.Obtain boiling point and be the colourless muriate 21.2g (theoretical amount 46.8%) of 72-74 ℃/100mm.
Application Example
The critical concentration test of embodiment A test method: Meloidogyne incognita solvent: the acetone emulsifying agent of 4 parts of weight: the alkylaryl polyglycol ether of 1 part of weight
Be to produce the suitable goods of active compound, the active compound of 1 part of weight and the solvent of described amount add the emulsifying agent of described amount, and enriched material is diluted with water to desired concn.
The goods of active compound with closely mixed by the soil of nematode severe contamination to be measured.The concentration of the active compound in the goods does not have actual importance, the amount of the compound of per unit volume only, with ppm (=mg/l) provide, be determinative.The soil of handling is transferred in the pot and is sowed lettuce, and the greenhouse keeps 25 ℃.
The nematode (root nodule) of three weeks back inspection lettuce root parasitism, the degree of functioning of active compound is represented with percentage ratio.If prevent parasitism fully, degree of functioning is 100% so, if parasitic level with not with medicinal treatment but the plant of the equal contrast of soil pollution degree is the same, degree of functioning is 0% so.In this test, for example preparing the degree of functioning that the compound of example I-4 and I-5 shows under the illustration activity compound concentration of 20ppm is 100%.
Embodiment B
Larva test solvent: 7 parts of weight dimethyl formamide emulsifying agents: 1 part of weight alkylaryl polyglycol ether
For producing the goods of suitable active compound, the emulsifier mix of the active compound of 1 part of weight and the solvent of described amount and described amount, enriched material is diluted with water to desired concn.
Dish leaf (Brassica oleracea) injects the goods of the active compound of desired concn with injection method, and with mustard beetle larva (phaedon larva) parasitism, the dish leaf still keeps humidity.
After the special time cycle, measure destructive percentage ratio.100% refers to that all mustard beetle larvas all are killed; 0% refers to that all mustard beetle larvas have no injury.In this test, the compound that for example prepares example I-6 after 7 days produces 100% destruction to larva as illustrative active compound under 0.1% concentration.
Embodiment C plutella test solvent: 7 parts of weight dimethyl formamide emulsifying agents: 1 part of weight alkylaryl polyglycol ether
For producing the goods of suitable active compound, the emulsifier mix of the active compound of 1 part of weight and the solvent of described amount and described amount, enriched material is diluted with water to desired concn.
Dish leaf (Brassica oleracea) injects the goods of the active compound of desired concn, the Candle-sticks (plutella maculipcnnis) of thin silk fabric line back of the body moth on the parasitism when leaf is still moist with injection method.
After the specific time cycle, measure the percentage ratio that Candle-sticks damages.All Candle-sticks are killed and are decided to be 100%; None Candle-sticks is killed and is decided to be 0%.
In this test, after 7 days, for example prepare example I-2, I-4, I-5, I-6 and I-8 are as illustrative active compound, and concentration is that 0.1% o'clock kill ratio to Candle-sticks reaches 100%.Embodiment DSpodoptera test solvent: 7 parts of weight dimethyl formamide emulsifying agents: 1 part of weight alkylaryl polyglycol ether
For producing the goods of suitable active compound, the emulsifier mix of the active compound of 1 part of weight and the solvent of described amount and described amount, enriched material is diluted with water to required concentration.
Dish leaf (Brassica oleracea) injects the goods of the active compound of desired concn with injection method, when the dish leaf is still moist with the Candle-sticks parasitism of owlet moth (Spodoptera frugiperda).
After the specific time cycle, measure the percentage ratio that Candle-sticks damages.All Candle-sticks are killed and are decided to be 100%; None Candle-sticks is killed and is decided to be 0%.
In this test, after 7 days, the compound that for example prepares example I-5 and I-7 is as illustrative active compound, and concentration is that 0.1% o'clock kill ratio to Candle-sticks reaches 100%.
Embodiment E Nephotettix test solvent: 7 parts of weight dimethyl formamide emulsifying agents: 1 part of weight alkylaryl polyglycol ether
For producing the goods of suitable active compound, the emulsifier mix of the active compound of 1 part of weight and the solvent of described amount and described amount, enriched material is diluted with water to desired concn.
Paddy rice seedling (Oryzae sative) injects the active ingredient Tetramune of desired concn with injection method, when rice shoot is still moist with larva (incticeps) parasitism of clear water rice leaf springtail (Nophotettix).
After the time cycle of expectation, measure the percentage ratio that kills larva.The larva of all leaf springtails all is killed and is decided to be 100%, does not have a larva to be killed and is decided to be 0%.
In this experiment, after 6 days, for example prepare example I-2, I-4, I-5, I-6, the compound of I-7 and I-8 are as illustrative active compound, and concentration is 0.1% o'clock, and the kill ratio of springtail larva is reached 100%.
Embodiment F
Test with the drug-fast Parkhurst strain of boophilus microplus resistance/SP-.Experimental animal: the adult female tick solvent of having sucked blood: the ethylene glycol monomethyl ether emulsifying agent of 35 parts of weight: the Nonylphenyl Ether of 35 parts of weight
For producing suitable prescription, the active compound of 3 parts of weight mixes with the solvent-emulsifier mixture of 7 parts of weight pointing out above, and enriched material is diluted with water to desired concn.
10 adult Boophilus microplus res. flooded 1 minute in tested active compound.After transferring in the plastic cup and in the environmental chamber of control, preserving, record the degree that cicada is damaged.
100% is decided to be all ticks all is killed; 0% is decided to be the none tick is killed.In this test, for example prepare example I-5, the compound of I-6 and I-7 is as illustrative active compound, when concentration is 1000ppm, the kill ratio of tick reached 100%.
Embodiment G
With blow fly larva test/growth-restraining effect experimental animal: lucilia cuprina larva solvent: 25 parts of weight ethylene glycol monomethyl ether emulsifying agents: 35 parts of weight nonyl phenol polyglycol ethers
For producing suitable prescription, the active compound of 3 parts of weight mixes with the solvent-emulsifier of 7 parts of weight pointing out above, and the dense emulsion that water will obtain is diluted to desired concn.
In the test tube that about 1cm3 horseflesh and 0.5ml active ingredient Tetramune to be measured is housed, introduce about 20 larvas.After 24 hours and 48 hours, measure the activity of active ingredient Tetramune.With test tube transfer to husky shop fixtures the cup in.After 2 days, remove test tube, pupa is counted.
Judge the activity of active ingredient Tetramune with 1.5 times of fly numbers of hatching afterwards of untreated contrast development time.No fly hatches and is decided to be 100%; All flies all normally hatch and are decided to be 0%.
In this test, for example prepare example I-1, the compound of I-4 and I-8, is ruined the pupa rate and is reached 100% when concentration is 1000ppm as illustrative active compound.
Embodiment H nematicide test (potato and soybean)
United States Patent (USP) 5,389 is pressed in this test, and 680 carry out.This specification sheets clearly enrolls the application.
In this experiment (method 2), the activity that the compound of preparation example I-39 shows when every pot of 1mg concentration is 91 to 100%, and the activity that shows when every pot of 0.2mg concentration is 75 to 90%, the active less than 50% that shows when every pot of 0.04mg concentration.

Claims (11)

1. the compound of general formula (I)
Figure A9519715800021
(I) R wherein 1Be hydrogen or halogen and R 2For group (a) or (b) (a) or
Figure A9519715800023
(b) wherein Y is oxygen or sulphur, and Z is oxygen, sulphur or NR 4, R 3Be hydrogen or the random alkyl that replaces, thiazolinyl, cycloalkyl, aryl, aralkyl, carbalkoxy, aryloxy carbonyl, arylsulfonyl or heteroaryl, and R 4Be hydrogen or the random respectively aryl that replaces, alkylthio, thiazolinyl, cycloalkyl, aryl, aralkyl, heteroaryl, or R 3And R 4One of the nitrogen-atoms that links to each other with them forms the ring that arbitrarily contains oxygen, sulphur or nitrogen (this nitrogen is arbitrarily by alkyl, and aryl or aralkyl replaces) that arbitrarily replaces, or is group (C) (c) wherein V is oxygen or NR 6And R 5And R 6Independent separately is hydrogen, the fatty group of 1 to 12 carbon atom, and aromatic base or heterocyclic radical, they each all arbitrarily replaced by at least one substituting group, substituting group is from alkyl, and cyano group is trimethyl silicon based, hydroxyl, alkoxyl group, halogen, nitro, amino, alkylamino, dialkyl amido, SH, alkylthio, phenyl, or by the carboxylic acid group, sulfonic group, phosphate or phosphorous acid base or these sour esters, thioesters or acid amides replace, and this acid amides is arbitrarily replaced or two replacement by the alkyl list, or R 5And R 6One of the nitrogen-atoms that links to each other with them forms monoamino-acid or arbitrarily contains oxygen in addition, the heterocyclic radical of sulphur or nitrogen, they each all arbitrarily by alkyl, cyano group, trimethyl silicon based, hydroxyl, alkoxyl group, halogen, nitro, amino, alkylamino, dialkyl amido, SH, alkylthio, phenyl or carboxylic acid group, sulfonic group, phosphate or phosphorous acid base or these sour esters, thioesters or amide group list replace, and this amide group is arbitrarily replaced or two replacement by the alkyl list, or R 5Be OR 7, COR 7, NR 7R 8, SO 2R 9Or P (=O) R 10R 11One of base, R in all cases 6Be hydrogen, R 7And R 8Independent separately is hydrogen, alkyl or aryl, R 9Be hydrogen, alkyl, haloalkyl or aryl, and R 10And R 11Independent separately is hydrogen, alkyl, and aryl, alkoxyl group, aryloxy, alkylthio, arylthio, amino, alkylamino, dialkyl amido or virtue are amino, and their salt.
2. the compound of general formula (Ia)
Figure A9519715800031
(Ia) R wherein 1, R 3, the implication of Y and Z is with claim 1.
3. the compound of general formula (Ib)
Figure A9519715800032
(Ib) R 1, R 3With the implication of Y with claim 1.
4. the compound of general formula (Ic)
Figure A9519715800033
(Ic) R wherein 1, R 5With the implication of V with claim 1.
5. the general formula (Ia) or (Ib) method of compound of preparation claim 2 is characterized in that A) the fluorine butenol of general formula (II) (II) R wherein 1Implication with claim 1 and following compound reaction alpha) react in the presence of the alkali at thinner with being intended to the compound of general formula (III) (III) wherein Y, Z and R 3Implication with claim 1, or β) with different (sulphur) cyanate of general formula (IV) thinner and be intended to catalyzer in the presence of react,
YCN-R 3(IV) or B) the fluorine butylene mercaptan of general formula (IIa) (IIa) R wherein 1The same compound with general formula (IIIa) of implication thinner or be intended to alkali in the presence of react, (IIIa) wherein Y and R 3Implication the same, or C) compound of logical formula V
Figure A9519715800051
(V) R wherein 1The compound of and general formula (VI) the same with the implication of Y thinner or be intended to alkali in the presence of react,
H-Z-R 3(VI) wherein Z and R 3Implication the same, or D) compound of general formula (VII)
Figure A9519715800052
(VII) R wherein 1The same with the implication of Y, with the compound of general formula (VIII) at thinner or with being intended to reaction in the presence of the alkali,
H-S-R 3(VIII) R wherein 3Implication the same.
6. the compound that leads to formula V
Figure A9519715800053
(V) R wherein 1With the implication of Y with claim 1.
7. the compound of general formula (VII)
Figure A9519715800054
(VII) R wherein 1With the implication of Y with claim 1.
8. sterilant is characterized in that they comprise the compound of the general formula of at least a claim 1 (I).
9. use the compound control animal pest of the general formula (I) of claim 1.
10. the method for control animal pest, the compound that it is characterized in that general formula (I) according to claim 1 make it act on that insect goes up and/or their habitat on.
11. the method for compositions of preparation control animal pest is characterized in that the compound of the general formula (I) according to claim 1 mixes with spreading agent and/or tensio-active agent.
CN95197158A 1994-11-04 1995-11-02 Fluorobutenyl esters Pending CN1171775A (en)

Applications Claiming Priority (4)

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DEP4439335.0 1994-11-04
DE4439335A DE4439335A1 (en) 1994-11-04 1994-11-04 Carbonic acid and carbamic acid fluorobutenyl esters
US398795P 1995-10-06 1995-10-06
US08/003,987 1995-10-06

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