CN1131417A - Substituted 4-carbamoyl pyrrolin-2-one and dihydrofuran-2-one derivatives and their use as pesticides - Google Patents

Substituted 4-carbamoyl pyrrolin-2-one and dihydrofuran-2-one derivatives and their use as pesticides Download PDF

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CN1131417A
CN1131417A CN 94193467 CN94193467A CN1131417A CN 1131417 A CN1131417 A CN 1131417A CN 94193467 CN94193467 CN 94193467 CN 94193467 A CN94193467 A CN 94193467A CN 1131417 A CN1131417 A CN 1131417A
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R·费希尔
G·克里费尔德
K·沃特勒
C·艾德伦
J·哈韦格
A·图尔堡
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Bayer AG
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/36—Oxygen or sulfur atoms
    • C07D207/38—2-Pyrrolones
    • 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
    • A01N47/18—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, directly attached to a heterocyclic or cycloaliphatic 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
    • A01N47/20—N-Aryl derivatives thereof
    • 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
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/54—Spiro-condensed
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/60—Two oxygen atoms, e.g. succinic anhydride
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/94—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom spiro-condensed with carbocyclic rings or ring systems, e.g. griseofulvins

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  • Pest Control & Pesticides (AREA)
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  • Engineering & Computer Science (AREA)
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Abstract

The present invention relates to novel substituted 4-carbamoyl pyrrolin-2-one and dihydrofuran-2-one derivatives of formula (I) in which A, B, Z, G, X, R<1> and R<2> have the meanings given in the description, several processes for their production and their use as pesticides.

Description

4-formamyl-the pyrroline-2-one derivative that replaces and 4-formamyl-dihydrofuran-2-ketone derivatives and as the purposes of agricultural chemicals
The present invention relates to new 4-formamyl-pyrroline-2-one derivative and 4-formamyl-dihydrofuran-2-ketone derivatives, the several method of its preparation and as the purposes of agricultural chemicals (particularly as sterilant).
3-aryl-4-formamyl-pyrroline-2-one and weeding, desinsection or acaricidal action open already (for example referring to: EP-A-442077, EP-A-528156 and EP-A-529334).
, in all cases, the effect of above-claimed cpd can not be satisfactory.
The present invention relates to the 4-formamyl-pyrroline-2-one derivative and the 4-formamyl-dihydrofuran-2-ketone derivatives of the new replacement of new formula (I), Wherein: A represents hydrogen or can be chosen wantonly the alkane of replacement separately by halogen, alkoxyl group or halogenated alkoxy
Base or cycloalkyl, or the representative aryl or aralkyl that can be optionally substituted separately, B represents hydrogen or alkyl, or A and B are with adjacent C atom, the ring of the optional replacement that representative can be interrupted by heteroatoms, Z represents nitrogen or oxygen, X represent hydrogen or separately can by halogen, alkyl, alkoxyl group, alkylthio, haloalkyl,
Optional alkyl, cycloalkyl, alkoxyl group or the alkane that replaces of halogenated alkoxy or halogenated alkylthio
Sulfenyl, R 1Represent alkyl, alkenyl or acyl group, R 2Representative can be chosen wantonly alkyl, alkenyl, alkoxyalkyl or the aryl that replaces by halogen separately,
Or represent and to be chosen wantonly the cycloalkyl of being interrupted by heteroatoms, or R 1And R 2And the nitrogen-atoms that connects with its key, representative is optional that replace and can choose quilt wantonly
The ring that other heteroatoms is interrupted, G if Z represents nitrogen, then represents hydrogen or separately can be by halogen, alkoxyl group or halogenated alkoxy
Optional alkyl, alkenyl or the cycloalkyl that replaces, or representative can be optionally substituted separately
Aryl or aralkyl, or represent acyl group, or A and G and the atom that connects with its key, representative is optional that replace and can be by other heteroatoms
The ring that is interrupted.
Because have one or more chiral centre, formula (I) compound is generally where necessary can be by the mixture of common process and the isolating steric isomer of method.They both can also can use with the form of pure diastereomer or enantiomorph with the form of mixtures of its diastereomer.Simultaneously, for simplicity's sake, formula (I) compound that this paper is following means pure compound and contains the isomery of different ratios, the mixture of enantiomorphous and stereomeric compound.
The invention still further relates to and prepare wherein A, B.X, Z, G, R 1And R 2Have formula (I) the 4-formamyl pyrroline-2-one of above-mentioned definition and the method for 4-formamyl-dihydrofuran-2-ketone, It is characterized in that making wherein A, B, X, Z and G have formula (II) compound of above-mentioned definition
Figure A9419346700142
A) with the carbamyl halogen of formula (III)
Figure A9419346700143
R wherein 1And R 2Have above-mentioned definition and Hal and represent halogen, particularly chlorine or bromine
In the presence of acid binding agent, reacting in the presence of the thinner and in case of necessity in case of necessity, or b) the first step, with the chloro-formic ester of phosgene or formula (IV)
R 3-O-CO-Cl????(IV)
Wherein
R 3Representative can be chosen the alkyl that is replaced by halogen wantonly, is reacting in the presence of acid binding agent in the presence of the thinner and in case of necessity in case of necessity, makes the amine of gained compound and formula V in second step
Wherein
R 1And R 2Has above-mentioned definition
Reaction in the presence of thinner in case of necessity.
It is well-known owing to have outstanding insecticidal action that the present invention has also found new formula (I) 4-formamyl-pyrroline-2-one derivative and 4-formamyl-dihydrofuran-2-ketone derivatives.
The compounds of this invention generally is defined as follows by formula (I).A preferably represents hydrogen, or separately can be by halogen, C 1-C 4-alkoxyl group and/or C 1
-C 4-halogenated alkoxy can be chosen the C of replacement wantonly 1-C 10-alkyl or C 3-
C 10-cycloalkyl, or separately can be by halogen, CN, nitro, C 1-C 8-alkyl,
C 1-C 8-alkoxyl group, C 1-C 8-alkylthio, C 1-C 8-halo
Alkyl and/or C 1-C 8Optional phenyl, naphthyl or the phenyl that replaces of halogenated alkoxy
-C 1-C 6-alkyl.B preferably represents hydrogen or C 1-C 8-alkyl, or the C atom that preferably connects of A and B with its key represent can be by halogen, alkyl and/or alcoxyl
Base optional that replace and can choose wantonly comprise nitrogen, oxygen, sulphur or-3-of O-CO-group
To 8-unit ring.X preferably represents hydrogen, or separately can be randomly by halogen, C 1-C 6-alkyl, C 1
-C 6Alkoxyl group, C 1-C 6Alkylthio, C 1-C 6-haloalkyl and/
Or C 1-C 6The C that-halogenated alkoxy replaces 1-C 6-alkyl, C 1-
C 6-alkoxyl group, C 1-C 6-alkylthio or C 3-C 7-cycloalkyl.R 1The preferred C that represents 1-C 6-alkyl, C 3-C 6-alkenyl, or following radicals
One of: ,-SO 2-NRR ',
Figure A9419346700162
Or-SO 2-OR
Wherein
R and R ' represent independently of one another separately can be by halogen, C 1-C 6-alkyl,
C 1-C 6-alkoxyl group, C 1-C-haloalkyl and/or C 1-
C 6The optional C that replaces of-halogenated alkoxy 1-C 10-alkyl, C 3-
C 10-cycloalkyl, phenyl, phenyl-C 1-C 4-alkyl or heteroaryl,
With
R ' also can represent hydrogen, or
The N atom that R and R ' connect with its key is represented can be by C 1-C 4-alkyl is appointed
Choose generation and can choose other nitrogen-atoms of containing the most nearly two or Sauerstoffatom wantonly
5-to 7-unit ring.R 2Preferred representative can be chosen the C that is replaced by halogen wantonly separately 1-C 20-alkyl, C 3-C 20-alkenyl, C 1-C 8Alkoxy-C 1-C 8-alkyl, C 1-C 8-alkylthio-C 1-C 8-alkyl, phenyl maybe can be chosen wantonly and comprise the C that reaches two Sauerstoffatoms and/or sulphur atom most 3-C 8-cycloalkyl, or R 1And R 2Preferably representing with its key nitrogen-atoms even can be by C 1-C 4The optional replacement of-alkyl contains 3-to the 7-unit ring that reaches two Sauerstoffatoms and/or sulphur atom most with choosing wantonly.Z preferably represents nitrogen or oxygen.G if Z represents nitrogen, then preferably represents hydrogen, or separately can be by halogen, C 1-C 6-alkoxyl group and/or C 1-C 6The optional C that replaces of-halogenated alkoxy 1-C 8-alkyl, C 3-C 8-alkenyl or C 3-C 8-cycloalkyl, or separately can be by halogen, CN, nitro, C 1-C 6-alkyl, C 1-C 6-alkoxyl group, C 1-C 6-alkylthio, C 1-C-haloalkyl, C 1-C 6-halogenated alkylthio and/or C 1-C 6Optional phenyl, naphthyl or the phenyl-C that replaces of-halogenated alkoxy 1-C 4-alkyl, or following radicals it-:
Figure A9419346700171
-SO 2-R, ,-SO 2-NRR '
Figure A9419346700173
Or-SO 2-OR
Wherein
R and R ', representative separately can be by halogen, C independently of one another 1-C 6-alkyl,
C 1-C 6-alkoxyl group, C 1-C-haloalkyl and/or C 1-
C 6The optional C that replaces of-halogenated alkoxy 1-C 8-alkyl, C 3-
C 7-cycloalkyl, phenyl, phenyl-C 1-C 4-alkyl or heteroaryl,
With
R ' also can represent hydrogen, or
The N atom that R and R ' connect with its key is represented can be by C 1-C 4-alkyl is appointed
Choose generation and can choose wantonly and comprise the most nearly two other nitrogen-atoms or Sauerstoffatoms
5-to 7-unit ring, or the atom that connects with its key of A and G represent can be by halogen and/or C 1-C 4-alkyl
Optional 4-to the 8-unit ring that replaces, its can choose wantonly comprise Sauerstoffatom or sulphur atom and
It can randomly be unsaturated ring.A particularly preferably represents hydrogen or separately can be by fluorine, chlorine, bromine, C 1-C 4-alcoxyl
The optional C that replaces of base, trifluoromethoxy and/or five fluorine oxyethyl groups 1-C 8-alkyl
Or C 3-C 8-cycloalkyl, or separately can by fluorine, chlorine, bromine, CN, nitro,
C 1-C 4-alkyl, C 1-C 4-alkoxyl group, C 1-C 4-alkylthio,
C 1-C 4-haloalkyl and/or C 1-C 4-halogenated alkoxy is optional to be replaced
Phenyl, naphthyl or phenyl-C 1-C 4-alkyl.B particularly preferably represents hydrogen or C 1-C 6-alkyl, or the C atom that connects with its key of A and B particularly preferably represent can by fluorine, chlorine, bromine,
C 1-C 4-alkyl and/or C 1-C 4-alkoxyl group is optional that replace and can appoint
Choosing ground comprises 3-to the 7-unit ring of Sauerstoffatom or sulphur atom.X particularly preferably represents hydrogen, or separately can be by fluorine, chlorine, bromine, C 1-C 4-alkyl,
C 1-C 4-alkoxyl group, C 1-C 4-alkylthio, C 1-C 4-halo
Alkyl and/or C 1-C 4The optional C that replaces of-halogenated alkoxy 1-C 4-alkane
Base or C 3-C 6-cycloalkyl.R 1Particularly preferably represent C 1-C 4-alkyl, C 3-C 4-alkenyl, or Or-SO 2-R,
Wherein
The R representative separately can be by fluorine, chlorine, bromine, C 1-C 4-alkyl, C 1-C 4
-alkoxyl group, C 1-C 4-haloalkyl and/or C 1-C 4-halo
The optional C that replaces of alkoxyl group 1-C 8-alkyl, C 3-C 8-cycloalkyl,
Phenyl, benzyl, pyrryl, thienyl or pyridyl.R 2Representative particularly preferably can be chosen wantonly separately by the C of fluorine and/or chlorine replacement 1-C 14-alkyl, C 3-C 14-alkenyl, C 1-C 4-alkoxy-C 1-C 6-alkyl, C 1-C 4-alkylthio-C 1-C 6-alkyl, phenyl or can randomly comprise the C of oxygen and/or sulphur atom 3-C 7-cycloalkyl, or R 1And R 2Particularly preferably representing with its key nitrogen-atoms even can be by C 1-C 3
-alkyl can choose wantonly replace and can randomly comprise Sauerstoffatom and/or sulphur atom 3-extremely
6-unit ring.Z particularly preferably represents nitrogen or oxygen.G if Z represents nitrogen, then particularly preferably represents hydrogen, or separately can by fluorine, chlorine, bromine,
C 1-C 4-alkoxyl group and/or C 1-C 4The optional replacement of-halogenated alkoxy
C 1-C 6-alkyl, C 3-C 6-alkenyl or C 3-C 6-cycloalkyl,
Or separately can be by fluorine, chlorine, bromine, CN, nitro, C 1-C 4-alkyl, C 1-
C 4-alkoxyl group, C 1-C 4-alkylthio, C 1-C 4-haloalkyl,
C 1-C 4-halogenated alkoxy and/or C 1-C 4-halogenated alkylthio is optional to be got
The phenyl in generation, naphthyl, benzyl or phenylethyl, or represent one of following radicals: Wherein R and R ', representative separately can be by fluorine, chlorine, bromine, C independently of one another 1-C 4-
Alkyl, C 1-C 4-alkoxyl group, C 1-C 4-haloalkyl and/or
C 1-C 4The optional C that replaces of-halogenated alkoxy 1-C 8-alkyl,
C 3-C 8-cycloalkyl, phenyl, benzyl, pyrryl, thienyl or pyridine
Base, and R ' also can represent hydrogen, or the N atom that connects with its key of R and R ', representative can be by C 1-C 4-alkyl
Choose replacement wantonly and can randomly comprise other the Sauerstoffatom and/or the 5-of nitrogen-atoms
To 7-unit ring, or the atom that connects with its key of A and G represent can be by C 1-C 4The optional replacement of-alkyl
5-to 8-unit carbocyclic ring.A more particularly preferably represent hydrogen or separately can by identical or different one or more fluorine or
The methyl that chlorine replaces, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, isobutyl-,
The tertiary butyl, phenyl or benzyl.B more particularly preferably represents hydrogen, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, the second month in a season
Butyl, isobutyl-or the tertiary butyl, or A and B more particularly preferably represent one of following radicals together
-(CH 2) 4-，-(CH 2) 5-，-(CH 2) 6-，-(CH 2) 4-CH(CH 3)-，
-(CH 2) 3-CH(CH 3)-CH 2-，-(CH 2) 2-CH(CH 3)-(CH 2) 2-，
-(CH 2) 2-CH(C 2H 5)-(CH 2) 2-，-(CH 2) 2-CH(C 3H 7)-(CH 2) 2-，
-(CH 2) 2-CH(C 4H 9)-(CH 2) 2-，-CH 2O(CH 2) 2-，-CH 2S-(CH 2) 2-，
-(CH 2) 2-O-(CH 2) 2-or-(CH 2) 2-S-(CH 2) 2-, X more particularly preferably represents hydrogen or can be chosen wantonly methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, methoxyl group, oxyethyl group, cyclopropyl, cyclopentyl or the cyclohexyl that replaces by fluorine, chlorine, bromine, methyl, ethyl, propyl group, sec.-propyl, methoxyl group, oxyethyl group, trifluoromethyl and/or trifluoromethoxy separately.R 1More particularly preferably represent methylidene, ethyl, propyl group, sec.-propyl, allyl group, methylsulfonyl, ethylsulfonyl or third alkylsulfonyl.R 2Representative more particularly preferably separately can be by fluorine and/or the optional C that replaces of chlorine 1-C 10-alkyl, C 3-C 10-alkenyl, C 3-C 6-cycloalkyl, C 1-C 3-alkoxy-C 1-C 4-alkyl or phenyl, or R 1And R 2More particularly preferably represent by methyl and/or the first ring of the optional 3-to 6-that replace and that can randomly comprise Sauerstoffatom of ethyl with the nitrogen-atoms that its key connects.Z more particularly preferably represents nitrogen or oxygen.G if Z represents nitrogen, then more particularly preferably represents hydrogen, or can be chosen wantonly methyl, ethyl, propyl group, sec.-propyl, butyl, sec-butyl, isobutyl-or the tertiary butyl that replaces by fluorine and/or chlorine separately, or by fluorine, chlorine, nitro, C 1-C 4-alkyl and/or C 1-C 4The optional phenyl that replaces of-alkoxyl group, or represent group
Figure A9419346700211
Wherein
R and R ', representative separately can be by fluorine and/or the optional C that replaces of chlorine independently of one another 1
-C 6-alkyl, C 3-C 6-alkenyl, phenyl or benzyl and
R ' also can represent hydrogen, or
R and R ' represent one of following radicals together:
-(CH 2) 3-，-(CH 2) 4-，-(CH 2) 5-，-CH 2-CH(CH 3)(CH 2) 2-，
-CH 2O-(CH 2) 2-or-CH 2S-(CH 2) 2-or A and G more particularly preferably represent one of following radicals together:
-(CH 2) 3-，-(CH 2) 4-，
Figure A9419346700212
Figure A9419346700213
The total definition or the explanation of the above-mentioned group that lists, or the preferable range of definition that lists or explanation can mutually combine, and also can divide combination arbitrarily between other scope and the preferred range.It is applicable to end product and precursor and intermediate in the corresponding way.
According to the present invention, preferred general formula (I) compound is for wherein existing above-mentioned combination as preferred definition.
According to the present invention, general formula (I) compound is preferably the combination that wherein has the special preferred definition of above-mentioned conduct especially.
According to the present invention, general formula (I) compound is more special to be preferably the combination that wherein has the more particularly preferred definition of above-mentioned conduct.
Following formula (Ia) and (Ib) compound addressed respectively:
Table 1
Figure A9419346700232
Figure A9419346700241
Figure A9419346700261
Figure A9419346700271
Figure A9419346700281
Figure A9419346700291
Figure A9419346700301
Figure A9419346700321
Figure A9419346700331
Figure A9419346700341
Figure A9419346700361
Figure A9419346700371
Figure A9419346700391
Figure A9419346700421
Figure A9419346700431
Figure A9419346700441
Figure A9419346700451
Figure A9419346700461
Figure A9419346700471
Figure A9419346700491
Figure A9419346700501
Figure A9419346700521
Figure A9419346700531
Figure A9419346700551
Figure A9419346700571
Figure A9419346700581
Figure A9419346700591
Figure A9419346700601
Figure A9419346700611
Figure A9419346700621
Table 2
Figure A9419346700631
Figure A9419346700632
Figure A9419346700641
Figure A9419346700661
Figure A9419346700681
Figure A9419346700691
Figure A9419346700701
Figure A9419346700731
Figure A9419346700741
If 3-ethyl-5,5-(2, the 3-dimethyl)-pentamethylene-4-hydroxyl-pyrroline-2-one and dimethylcarbamyl chloride are as the initiator of preparation formula (I) compound, and then available following route is represented reaction process:
Figure A9419346700751
If 5,5-dimethyl-4-hydroxyl-dihydrofuran-2-ketone and morpholine urea chloride are as the initiator of preparation formula (I) compound, then available following route is represented reaction process:
Figure A9419346700752
Required formula (II) compound part as initiator is known or passes through known method preparation in the document in the methods of the invention, for example
Matsuo，Tanaka；Chem.Pharm.Bull.32，3724(1984)；Noland，Sundberg，J.Org.Chem.28，3150(1963)；S.Brandnge.J.Org.Chem.49，927(1984).
Addressed the pyrroline-2-one of formula (IIa) below respectively:
Table 3
????A ????B ????G ????X
?CH 3 ????H ????H ????H
?i-C 3H 7 ????H ????H ????H
?i-C 4H 9 ????H ????H ????H
?s-C 4H 9 ????H ????H ????H
?CH 3 ????CH 3 ????H ????H
?C 2H 5 ????CH 3 ????H ????H
?C 3H 7 ????CH 3 ????H ????H
?i-C 3H 7 ????CH 3 ????H ????H
?i-C 4H 9 ????CH 3 ????H ????H
?s-C 4H 9 ????CH 3 ????H ????H
?t-C 4H 9 ????CH 3 ????H ????H
?C 2H 5 ????C 2H 5 ????H ????H
Figure A9419346700771
????A ????B ????G ?????X
?CH 3 ????H ????H ????CH 3
?i-C 3H 7 ????H ????H ????CH 3
?i-C 4H 9 ????H ????H ????CH 3
?s-C 4H 9 ????H ????H ????CH 3
?CH 3 ????CH 3 ????H ????CH 3
?C 2H 5 ????CH 3 ????H ????CH 3
?C 3H 7 ????CH 3 ????H ????CH 3
?i-C 3H 7 ????CH 3 ????H ????CH 3
?i-C 4H 9 ????CH 3 ????H ????CH 3
?s-C 4H 9 ????CH 3 ????H ????CH 3
?t-C 4H 9 ????CH 3 ????H ????CH 3
?C 2H 5 ????C 2H 5 ????H ????CH 3
-(CH 2) 4- ????H ????CH 3
-(CH 2) 5- ????H ????CH 3
-(CH 2) 6- ????H ????CH 3
????A ????B ????G ??????X
?CH 3 ????H ????H ????i-C 3H 7
?i-C 3H 7 ????H ????H ????i-C 3H 7
?i-C 4H 9 ????H ????H ????i-C 3H 7
?s-C 4H 9 ????H ????H ????i-C 3H 7
?CH 3 ????CH 3 ????H ????i-C 3H 7
?C 2H 5 ????CH 3 ????H ????i-C 3H 7
?C 3H 7 ????CH 3 ????H ????i-C 3H 7
?i-C 3H 7 ????CH 3 ????H ????i-C 3H 7
?i-C 4H 9 ????CH 3 ????H ????i-C 3H 7
?s-C 4H 9 ????CH 3 ????H ????i-C 3H 7
?t-C 4H 9 ????CH 3 ????H ????i-C 3H 7
?C 2H 5 ????C 2H 5 ????H ????i-C 3H 7
-(CH 2) 4- ????H ????i-C 3H 7
-(CH 2) 5- ????H ????i-C 3H 7
-(CH 2) 6- ????H ????i-C 3H 7
Figure A9419346700811
????A ????B ????G ??????X
?CH 3 ????H ????H ????t-C 4H 9
?i-C 3H 7 ????H ????H ????t-C 4H 9
?i-C 4H 9 ????H ????H ????t-C 4H 9
?s-C 4H 9 ????H ????H ????t-C 4H 9
?CH 3 ????CH 3 ????H ????t-C 4H 9
?C 2H 5 ????CH 3 ????H ????t-C 4H 9
?C 3H 7 ????CH 3 ????H ????t-C 4H 9
?i-C 3H 7 ????CH 3 ????H ????t-C 4H 9
?i-C 4H 9 ????CH 3 ????H ????t-C 4H 9
?s-C 4H 9 ????CH 3 ????H ????t-C 4H 9
?t-C 4H 9 ????CH 3 ????H ????t-C 4H 9
?C 2H 5 ????C 2H 5 ????H ????t-C 4H 9
?-(CH 2) 4- ????H ????t-C 4H 9
?-(CH 2) 5- ????H ????t-C 4H 9
?-(CH 2) 6- ????H ????t-C 4H 9
Figure A9419346700831
????A ????G ????B ????X
-(CH 2) 3- ????H ????H
-(CH 2) 4- ????H ????H
-CH 2-S-CH 2- ????H ????H
-CH 2S-(CH 2) 2- ????H ????H
????H ?CH 3 ????H ????H
????H ?C 2H 5 ????H ????H
????H ?C 3H 7 ????H ????H
????H ?i-C 3H 7 ????H ????H
????H ?i-C 4H 9 ????H ????H
????H ?s-C 4H 9 ????H ????H
????H ?t-C 4H 9 ????H ????H
-(CH 2) 3- ????H ????CH 3
-(CH 2) 4- ????H ????CH 3
-CH 2-S-CH 2- ????H ????CH 3
-CH 2-S-(CH 2) 2- ????H ????CH 3
????A ??G ????B ????X
????H ?CH 3 ????H ????CH 3
????H ?C 2H 5 ????H ????CH 3
????H ?C 3H 7 ????H ????CH 3
????H ?i-C 3H 7 ????H ????CH 3
????H ?i-C 4H 9 ????H ????CH 3
????H ?s-C 4H 9 ????H ????CH 3
????H ?t-C 4H 9 ????H ????CH 3
????CH 3 ?CH 3 ????H ????CH 3
????CH 3 ?C 2H 5 ????H ????CH 3
????CH 3 ?C 3H 7 ????H ????CH 3
????CH 3 ?i-C 3H 7 ????H ????CH 3
????CH 3 ?i-C 4H 9 ????H ????CH 3
????CH 3 ?s-C 4H 9 ????H ????CH 3
????CH 3 ?t-C 4H 9 ????H ????CH 3
Addressed the dihydrofuran-2-ketone of formula (IIb) below respectively:
Table 4
??A ????B ????X
?CH 3 ????H ????H
?i-C 3H 7 ????H ????H
?i-C 4H 9 ????H ????H
?s-C 4H 9 ????H ????H
?CH 3 ????CH 3 ????H
?C 2H 5 ????CH 3 ????H
?C 3H 7 ????CH 3 ????H
?i-C 3H 7 ????CH 3 ????H
?i-C 4H 9 ????CH 3 ????H
?s-C 4H 9 ????CH 3 ????H
?t-C 4H 9 ????CH 3 ????H
?C 2H 5 ????C 2H 5 ????H
Figure A9419346700871
???A ????B ????X
?CH 3 ????H ????CH 3
?i-C 3H 7 ????H ????CH 3
?i-C 4H 9 ????H ????CH 3
?s-C 4H 9 ????H ????CH 3
?CH 3 ????CH 3 ????CH 3
?C 2H 5 ????CH 3 ????CH 3
?C 3H 7 ????CH 3 ????CH 3
?i-C 3H 7 ????CH 3 ????CH 3
?i-C 4H 9 ????CH 3 ????CH 3
?s-C 4H 9 ????CH 3 ????CH 3
?t-C 4H 9 ????CH 3 ????CH 3
?C 2H 5 ????C 2H 5 ????CH 3
-(CH 2) 4- ????CH 3
-(CH 2) 5- ????CH 3
-(CH 2) 6- ????CH 3
Figure A9419346700891
????A ????B ??????X
?CH 3 ????H ????i-C 3H 7
?i-C 3H 7 ????H ????i-C 3H 7
?i-C 4H 9 ????H ????i-C 3H 7
?s-C 4H 9 ????H ????i-C 3H 7
?CH 3 ????CH 3 ????i-C 3H 7
?C 2H 5 ????CH 3 ????i-C 3H 7
?C 3H 7 ????CH 3 ????i-C 3H 7
?i-C 3H 7 ????CH 3 ????i-C 3H 7
?i-C 4H 9 ????CH 3 ????i-C 3H 7
?s-C 4H 9 ????CH 3 ????i-C 3H 7
?t-C 4H 9 ????CH 3 ????i-C 3H 7
?C 2H 5 ????C 2H 5 ????i-C 3H 7
-(CH 2) 4- ????i-C 3H 7
-(CH 2) 5- ????i-C 3H 7
-(CH 2) 6- ????i-C 3H 7
???A ????B ??????X
?CH 3 ????H ????t-C 4H 9
?i-C 3H 7 ????H ????t-C 4H 9
?i-C 4H 9 ????H ????t-C 4H 9
?s-C 4H 9 ????H ????t-C 4H 9
?CH 3 ????CH 3 ????t-C 4H 9
?C 2H 5 ????CH 3 ????t-C 4H 9
?C 3H 7 ????CH 3 ????t-C 4H 9
?i-C 3H 7 ????CH 3 ????t-C 4H 9
?i-C 4H 9 ????CH 3 ????t-C 4H 9
?s-C 4H 9 ????CH 3 ????t-C 4H 9
?t-C 4H 9 ????CH 3 ????t-C 4H 9
?C 2H 5 ????C 2H 5 ????t-C 4H 9
-(CH 2) 4- ????t-C 4H 9
-(CH 2) 5- ????t-C 4H 9
-(CH 2) 6- ????t-C 4H 9
Figure A9419346700931
The carbamyl halogen of formula (III) is known synthesis of chemicals in the organic chemistry.
The formula of addressing respectively below (III) compound is:
Dimethylcarbamyl chloride, diethylamino formyl chloride, dipropyl urea chloride, diisopropylaminoethyl formyl chloride, dibutylamino formyl chloride, ethylmethylamino formyl chloride, diallyl urea chloride, tetramethyleneimine urea chloride, piperidines urea chloride and morpholine urea chloride.
The reaction of formula (II) compound and formula (III) carbamyl halogen can be carried out in the presence of thinner and acid binding agent.
To compound (II) and (III) the inert all kinds of SOLVENTS all can be used as thinner.The preferred thinner that uses is hydro carbons, as gasoline, benzene,toluene,xylene and tetraline, and halogenated hydrocarbon, as methylene dichloride, chloroform, tetracol phenixin, chlorobenzene and orthodichlorobenzene and ketone,, also has ethers as acetone and methyl isopropyl Ketone, as ether, tetrahydrofuran (THF) He diox, in addition also have carboxylic acid esters, as ethyl acetate, and intensive polar solvent such as dimethyl sulfoxide (DMSO) and tetramethylene sulfone.If to hydrolysis-stable, also can making to be reflected under the water existence, carboxylic acid halides carries out.
The acid acceptor of various routines all can be used as acid binding agent, the preferred above-mentioned acid binding agent that uses is tertiary amine, as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicylo undecylene (DBU), Diazabicyclononene (DBN), H ü nig alkali and N, accelerine, also have alkaline earth metal oxide in addition, as magnesium oxide and calcium oxide, and alkaline carbonate and alkaline earth metal carbonate, as yellow soda ash, salt of wormwood and lime carbonate, and alkali metal hydroxide are as sodium hydroxide and potassium hydroxide.
Temperature of reaction can change in quite wide scope.Usually, temperature of reaction between-20 ℃ to+150 ℃, preferred 0 ° to 100 ℃.
When carrying out present method, use formula (II) initial compounds of about equivalent and the carbamyl halogen of formula (III) usually.Also may use the carbamyl halogen of excessive greatly (5Mol at the most), carry out processing treatment according to conventional methods.
If 5,5-(2-methyl)-tetramethylene-tetramethyleneimine-2,4-diketone and superpalite and morpholine can represent the reaction process of the inventive method by following reaction scheme as the initial compounds of preparation formula (I) compound:
Figure A9419346700951
Aforesaid method be characterised in that formula (II) compound at first with the reaction of the chloro-formic ester of phosgene or formula (IV), be reflected at thinner in case of necessity and exist down and in the presence of acid binding agent, carry out.
The acid acceptor of various routines all can be used as acid binding agent.The preferred above-mentioned acid binding agent that uses is tertiary amine, as triethylamine, pyridine, DABCO, DBU, DBA, H ü nig alkali and N, accelerine, also has alkaline earth metal oxide in addition, as magnesium oxide and calcium oxide, and alkaline carbonate and alkaline earth metal carbonate, as yellow soda ash, salt of wormwood and lime carbonate, and alkali metal hydroxide, as sodium hydroxide and potassium hydroxide.
To compound (IV) and (V) the inert all kinds of SOLVENTS all can be used as thinner.The preferred above-mentioned solvent that uses is hydro carbons, as gasoline, benzene,toluene,xylene and tetraline, and halogenated hydrocarbon, as methylene dichloride, chloroform, tetracol phenixin, chlorobenzene and orthodichlorobenzene, and ketone, as acetone and methyl isopropyl Ketone, and ethers, as ether, tetrahydrofuran (THF) is with diox, also has carboxylic acid esters in addition, as ethyl acetate and intensive polar solvent such as dimethyl sulfoxide (DMSO) and tetramethylene sulfone.
Temperature of reaction can change in quite wide scope.Carry out if be reflected under the existence of thinner and acid binding agent, temperature of reaction is usually at-20 ℃ to+100 ℃, between preferred 0 ℃ to 50 ℃.
The inventive method is carried out under normal pressure usually.
When carrying out the inventive method, use formula (II) initial compounds of about equivalent and suitable formula (IV) chloro-formic ester usually., also can use excessive relatively (as many as 2Mol) a kind of or other kind composition.
After reaction takes place, the amine of formula V is joined in the reaction soln.Above-mentioned amidation (Umamidierung) preferably carries out under the solvent boiling point that uses under 80 to 200 ℃ temperature.
Formula of the present invention (I) compound can be used to prevent and treat pest.Pest is the unwanted animals of people, particularly damages the insect of plant or higher animal.
Active compound of the present invention is suitable for the pest that exists in agricultural, forestry, storage product and material and the health field, the control of preferred arthropods, particularly insect, and has good plant tolerance and nontoxic to warm-blooded animal.They are to normal sensitive strain and resistant strain, and all there is activity in all stages or some stages of growing.Above-mentioned harmful insect comprises: Isopoda, for example, damp worm, pillworm and band pillworm (Porcellio scaber).Diplopoda, for example, tool zebra land.Chcilopoda, for example, DIWUGONG (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, Gryllotalpa spp, tropical migratory locusts, negative locust of long volume and grasshopper.Dermaptera, for example, European earwig.Isoptera, for example, Cryptotermes.Anoplura, for example, grape phylloxera, pemphigus belongs to, head louse, Haematopinus, Linognathus.Mallophaga, for example, Trichodectes is nibbled lice and is belonged to.Thysanoptera, for example: greenhouse Hercinothrips spp and onion thrips.Hemiptera, for example: scutteleerid belongs to, red cotton bug (Dysdercus intermedius), beet is intended lace bug, bedbug, Rhodnius prolixus and Reduvius.Homoptera, for example, the wild cabbage aleyrodid, whitefly in bt cotton, Trialeurodes vaporariorum Westwood, cotten aphid, brevicoryne brassicae, the tea sugarcane conceals knurl volume aphid, aphis fabae, apple aphid, eriosoma lanigerum, mealy plum aphid, grain aphid, knurl
The volume Aphis, hops knurl volume aphid, the grain Rhopalosiphum spp, leafhopper belongs to, 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, Aleyrodes and Psylla spp.Lepidopteran, for example, red worm septempunctata, loose looper, winter geometrid moth, thin moth (Lithocolletisblancardella), apple ermine moth, small cabbage moth, admired caterpillar, pornography and drug moth, Euproctis, cotton leaf miner in yellowish-brown day, the tangerine leaf miner, Agrotis, cutworm belongs to, brown Noctua, the real moth of cotton spot, genus heliothis, beet armyworm, lopper worm, small noctuid, twill leaf moth, Noctua, cabbage looper, carpocapsa pononella, Pier, striped rice borer belongs to, Pyrausta nubilalis (Hubern)., Mediterranean flour moth, greater wax moth, bag casemaking clothes moth, etting moth, brown oecophorid, leaf roller (Cacoecia podana), 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, bean weevil (Acanthoscelidesobtectus), house longhorn beetle, blue hair stern firefly is chrysomelid, colorado potato bug, horseradish daikon leaf beetle, the chrysomelid genus of bar, rape flea beetle, Mexico's beans first, Atomaria spp., saw-toothed grain beetle, Anthonomus spp belongs to, grain weevil belongs to, and vine black ear beak resembles, banana root weevil, broccoli English weevil, alfalfa weevil, khapra beetle belongs to, and attagenus piceus belongs to, the garden khapra beetle, the black wool khapra beetle belongs to, and powder is moth-eaten to belong to pollen beetle, Ptinus, golden yellow ptinid, 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 belongs to, tenthredinidae, the field ant belongs to, kitchen ant and Vespa.Diptera, for example, Aedes, Anopheles, culex pipiens pollens belongs to, drosophila yellow gorilla, Musca, stable fly belongs to, calliphora erythrocephala, Lucilia, Carysomyia, cuterbrid belongs to, Gasterophilus, Hippoboscaspp., the chela fly belongs to, and the nose fly belongs to, Hypoderma, and the horsefly fly belongs to, Tannia spp., march fly (Bibio hortu lanus), Sweden's wheat stem chloropid fly, Aphiochaeta, kmangold fly, Mediterranean fruitfly, dacus oleae, European daddy-longlegs.Siphonaptera, for example, Xenopsyllacheopis, flea belongs to.Arachnida, for example scorpion and black widow's ball film spider.
When as sterilant, active compound of the present invention can be with its commercial available preparation with from the type of service of above-mentioned formulation preparation, as with other active compound, as sterilant, attractive substance, sterilizing agent, miticide, nematocides, mycocide, the mixture of growth regulatory substance or weedicide exists.Sterilant comprises, for example, and phosphoric acid ester especially, amino formate, carboxylic acid esters, chlorinated hydrocarbons, phenyl ureas and by material of microorganisms etc.
Can mention following compound:
Fluorine ester chrysanthemum ester, alphacypermethrin, cyfloxylate, fluoro-Cyano chrysanthemate, Brofenprox, the cis resmethrin, lambda-cyhalothrin, cycloprothrin, cyhalofop-butyl, cyhalothrin, Cypermethrin, Deltamethrin, esfenvalerate, ether chrysanthemum ester, Fenvalerate, fenvalerate, chlorine fenvalerate, taufluvalinate, go into-cyhalothrin permethrin, the anti-chrysanthemum ester that goes out, pyrethrin, Silafluofen, tralomethrin, Zetamethrin
Alanycarb ， Ben Evil prestige, benfuracarb mixes penta prestige, butanone oxygen prestige, SevinCarbaryl, Padan, ethiofencarb, Fenobucarb, ABG-6215, isoprocarb, methiocarb, methomyl, Metolcarb, careless oxime prestige, Aphox, first third prestige, Propoxur, terbam, two sulphur methomyls, enemy's gram prestige, front three prestige (Trimethacarb), Cosban, Xylylcarb
Acephate, triazotion, methyl R-1582, bromophos_ethyl, cadusafos, carbophenothion, Zaprawa enolofos, chlormephos, Chlorpyrifos 94, chlorpyrifos_methyl, cynock, demeton_S_methyl, different suction sulphur phosphorus-II, different Systox, diazinon, SD-1750, Dicliphos, chloro line phosphorus, Carbicron, Rogor, dimethylvinphos ， delnav, thiodemeton, Hinosan, Nialate, etrimfos, fenitrothion 95, Tiguvon, N-2790, peace fruit, heptan worm phosphorus, Iprobenfos, the different third triazophos ， isoxazole sulphur phosphorus, phorate, Malathion, menazon, Phosdrin, Tiguvon sulfoxide, butylene sulphur phosphorus, acephatemet, naled, omethoate, sulfone is inhaled sulphur phosphorus, Oxydeprofos, ethyl parathion, parathion-methyl, Tsidial, phorate, Phosalone, R-1504, phosphamidon, Volaton, ethyl-pyrimidine sulphur phosphorus, methylpyrimidine sulphur phosphorus, the third worm sulphur phosphorus, low toxicity sulphur phosphorus, Fac, pyraclofos, Ofunack, Resitox, salithion, Sebufos, sulfotep, the first Toyodan, tetrachlorvinphos, temephos, thiometon, piperazine line phosphorus, Trichlorphon, triazophos, the intact sulphur phosphorus that goes out
Buprofezin, UC 62644, diflubenzuron, flucycloxuron, flufenoxuron, fluorine bell urea, pyriproxyfen, Tebufenozide, Teflubenzuron, desinsection is grand,
Imidacloprid, Nitenpyram, N-[(6-chloro-3-pyridyl) methyl]-N '-cyano group-N-methyl ethanamidine (Ethanimidamide) (NI-25),
Abamectin, amitraz, avermectin, azadirachtin, bensultap, Bacillus thuringiensis, fly eradication amine, methamidophos, Emamectin, ethoprop, Fenpyrad, Fipronil, Flufenprox, Lufenuron, Halizan, Milbemectin, Pymetrozine, Tebufenpyrad, Triazuron
Aldicarb, benzene Evil prestige, benfuracarb, Ke Dancheng, carbosulfan, Chlorethoxyfos, Cloethocarb, thiodemeton, ethoprop, etrimfos, Nemacur, Fipronil, N-2790, colophonate, furathiocarb, phenyl-hexachloride, different third triazophos, isofenphos, methiocarb, monocrotophos, Nitenpyram, careless oxime prestige, phorate, Volaton, low toxicity sulphur phosphorus, pyraclofos, gram line pellet, Silafluofen, butyl pyrimidine sulphur phosphorus (Tebupirimphos), tefluthrin, special fourth phorate, two sulphur methomyls, Thiafenox
Azocyclotin, butyl pyridaben (Butylpyridaben), four mite piperazines, cyhexatin, methamidophos, Nialate, Emamectin, fenazaquin, mite is finished tin, fenothiocarb, first cyanogen chrysanthemum ether, Fenpyrad, azoles mite ester, fluazinam, Fluazuron, flucycloxuron, flufenoxuron, taufluvalinate, Fubfenprox, hexythiazox, avermectin, first thiophene sulphur phosphorus, monocrotophos, Moxidectin, naled, Phosalone, bromine third phosphorus, pyraclofos, pyridaben, Pyrimidifen, Tebufenpyrad, Bacillus thuringiensis, Triarathene and 4-bromo-2-(4-chloro-phenyl-)-1-(ethoxyl methyl)-5-(trifluoromethyl)-1H-pyrroles-3-nitrile (AC303630).
Also may with other known activity compound, mix as birds repellant, plant nutrient and soil structure conditioner.
This active compound can use by its dosage form, or uses with the administration form that further dilutes preparation from above-mentioned preparation, as now using solution, suspension, emulsion, pulvis, paste and granule.Can ordinary method use above-mentioned preparation, for example sprinkle and water, spraying, atomizing or the form of broadcasting sowing.
Both can before plant germination, also can behind plant germination, use active compound of the present invention.
Also can prior to seeding above-mentioned active compound be manured into soil.
The amount of application of active compound can be used in quite wide scope.The character of this required effect that places one's entire reliance upon.Usually the usage quantity of per hectare soil surface active compound 0.01 to 10kg, between the preferred per hectare 0.05 to 5kg.
In order to prepare agricultural chemicals, can be converted to regular dosage form according to its physics and/or chemical property active compound of the present invention separately, as solution, emulsion, suspension agent, pulvis, foaming agent, paste, granule, aerosol, the natural and synthetic with the active compound dipping is used for the polymkeric substance of seed and the microcapsule of coated composition, with combustion equipment, as fumigation tube, fumigation tank, the preparation that stifling volume etc. use together, and cold mist of ULV and hot mist preparation.
These formulations are produced in known manner, for example, active compound and weighting agent are mixed together.Weighting agent is a liquid solvent, and pressure is the gas of liquefaction down, and/or solid carrier, can randomly adopt tensio-active agent, i.e. emulsifying agent and/or dispersion agent, and/or give birth to infusion.When using water as weighting agent, for example also available organic solvent is made solubility promoter.As liquid solvent, suitable mainly contains: aromatic substance, and as dimethylbenzene, toluene or alkylnaphthalene class; Chloro aromatic substance or chloro fat hydro carbons, as the chlorobenzene class, chloro vinyl or methylene dichloride; Fat hydrocarbon is as hexanaphthene or paraffins, for example mineral oil fractions; Alcohols is as butanols or ethylene glycol and ethers and ester class; Ketone, as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) or pimelinketone; Intensive polar solvent, as dimethyl formamide and methyl-sulphoxide, and water; The gaseous state weighting agent or the carrier of liquefaction are to be the liquid of gas under normal temperature and normal atmosphere, aerosol propellant for example, and as halogenated hydrocarbon and butane, propane, nitrogen and carbonic acid gas; The solid carrier that is fit to is the natural mineral of for example pulverizing, as the synthetic mineral of kaolin, clay, talcum, chalk, quartz, attapulgite, montmorillonite or diatomite and pulverizing, and as high dispersive silicon-dioxide, aluminum oxide and silicate; The solid carrier that is suitable as granule has for example crushing and fractionated natural rock such as calcite, marble, float stone, sepiolite and rhombspar, and synthetic is inorganic and the particle of organic dust, organic particle such as sawdust, Exocarpium cocois (Cocos nucifera L), corn cob and tobacco stem; Be suitable as emulsifying agent and/or give birth to having of infusion: for example non-ionic type and anionic emulsifier, as polyoxyethylene fatty acid ester, polyoxyethylene aliphatic alcohol ether, alkylaryl polyglycol ether for example, alkylsulfonate, alkyl-sulphate, arylsulphonate and albumin hydrolysate; What be suitable as dispersion agent has: for example xylogen sulfite waste lye and methylcellulose gum.
Can use the natural and synthetic polymer of tackiness agent such as carboxymethyl cellulose and powder, particle or latex form in the preparation, as gum arabic, polyvinyl alcohol and polyvinyl acetate, and natural phospholipid class are as kephalin class and Yelkin TTS class and synthetic phospholipid class.Other additive can be mineral oil and vegetables oil.
Can adopt tinting material, as mineral dye, ferric oxide for example, titanium dioxide and Prussian blue, and organic dye, as alizarine dyestuff, azoic dyestuff and metal phthalocyanine dyestuff and micro-nutrients such as iron, manganese, boron, copper, cobalt, the salt of molybdenum and zinc.
The active compound that in preparation, contains 0.1 to 95% (weight) usually, preferred 0.1 to 95% (weight), the more preferably active compound of 0.5 to 90% (weight).
Because the warm-blooded animal kind is had hypotoxicity, described active compound is suitable for preventing and treating domestic animal and poultry is used domestic animal, and zoo animal, laboratory animal, the animal pest that runs in animal rearing of experimental animal and pet and the livestock culturing is as arthropods, preferred insect and spider shape guiding principle (Ektoparasiten), in this case, they are to the whole or independent growth period of insect, and the pest population of antagonism and common sensitivity is all effective.
The control animal pest, be intended to reduce disease and propagation thereof, it is low (for example at product meat, milk, hair, animal skin to reduce animal dead and performance thereof, the egg aspect), add this active substance and make more economical and simpler animal rearing become possibility, or become possibility in some aspects by using described active compound only to make.
Above-mentioned insect comprises: Anoplura, for example, and Haematopinus, Linognathus, blind lice belongs to, and lice belongs to, Pthirus.Mallophaga, for example, the hair bird lice belongs to, and short angle bird lice belongs to Eomenacanthus spp., Menoponidae (Menacanthus spp.), Trichodectes, beastly black lice section (Felicolaspp.), beastly Ricinidae (Damalinea spp.), Bovicola spp.; Diptera, for example, the spot uranotaenia, the horsefly fly belongs to, Musca, Hydrotaea spp., Muscina, blood beak fly belongs to, Haematobia, the chela fly belongs to, Fannia spp., Glossina, Lucilia, Calliphora, Auchmeromyia, Cordylobia, Callitroga, Carysomyia, Sarcophaga, flesh fly belongs to, Gasterophilus, Oesteromyia spp., Oedemagena spp., Hypoderma, Oestrus, Rhinoestrus, Lipoptena, Hippobosca.Siphonaptera, for example, Ct, Echidnophaga, Ceratophyllus.Metaspiracle suborder (Metastigmata), for example, Hyalomma, Rh, Boophilus, Amblyomma, Haemaphysalis, Dermacentor, tick belongs to, and latent beak tick belongs to, Ornithodoros, residual edge tick belongs to; Prothoracic spiracles suborder (Mesastigmata), for example, Dermanyssus, Ornithonyssus, Pneumonyssus.Preceding valve suborder, for example, Cheyletiella, sheep itch mite belongs to, Myobia, Demodex, Neotrombicula.Astigmata, for example, Tyroglyphus, Myocoptes spp., Psoroptes, Chorioptes, the ear Psoroptes, itch mite belongs to, Notoedres, Knemidokoptes, Necknemidocoptes spp., Lytodites spp., Laminosioptes.
Raise animal and domestic animal comprises Mammals, as ox, horse, sheep, pig, goat, camel, buffalo, donkey, Tu, Fallow deer, reinder; Produce the fur coat animal as mink, South America grain mouse and racoon, birds are as poultry, goose, turkey and duck; Fresh-water fishes and saltwater fish are as trout, carp, common eel; Reptilia and insect such as honeybee and silkworm.
Laboratory animal and experimental animal comprise: mouse, rat, cavy, yellow hamster, dog and cat.
Pet comprises: dog and cat.
Active compound can be directly or the dosage form to be fit to, through intestines, through skin, by environmental treatment or by the shaping thing that contains active compound, for example, band, plate, band, neck ring, ear tag, limb girdle, marking arrangement administration.
Active compound can be through enteral administration, and for example, per os is with the mode administration of the feed or the tap water of pulvis, suppository, tablet, capsule, paste, potus, granule, immersion liquid, Boli, pastille.Can carry out using through skin, for example, to soak, spraying, flushing, to sprinkle and water and the spot printing and the mode administration of dusting.
The prepared product that is fit to is:
Solution as the enriched material of oral liquid, dilution back oral administration, be used in the solution of skin or body cavity, sprinkles and waters preparation and glue;
The emulsion and the suspension of oral or percutaneous dosing, and semi-solid preparation;
Preparation can be prepared in ointment base or oil-in-water or water-in-oil emulsion matrix at active compound.
Solid preparation, as pulvis, pre-composition or enriched material, granule, pill, tablet, Boil or capsule, aerosol and the shaping thing that contains active compound.
The preparation of solution is by active compound being dissolved in the suitable solvent, adding other additive then, as solubilizing agent, acid, alkali, buffering salt, antioxidant or sanitas.
Can mention as solvent: solvent that can tolerate on the physiology such as water, alcohols, as ethanol, butanols, benzylalcohol or glycerine, hydro carbons, propylene glycol, polyoxyethylene glycol, N-Methyl pyrrolidone, and composition thereof.
In appropriate circumstances, also active compound can be dissolved in the vegetables oil or synthetic oil that can tolerate on the physiology that is suitable for injecting.
Can mention as solubilizing agent: promote that active compound dissolves in main solvent, or prevent its sedimentary solvent.The example is the Viscotrol C of polyvinylpyrrolidone, polyoxyethyleneization and the Isosorbide Dinitrate of polyoxyethyleneization.
Sanitas is: benzylalcohol, Trichloroisobutyl Alcohol, p-Hydroxybenzoate and propyl carbinol.
Oral solution can directly use.Enriched material is to orally use after dilution in advance becomes application concentration.
The solution that uses through skin be drop, brushing, wiping, spray cloth or be sprayed on the skin.These solutions are by method for preparing.
Adding thickening material in the preparation is preferably.Thickening material is: inorganic thickening agent, and as wilkinite, colloid silicic acid and aluminum monostearate, and organic thickening agent, as derivatived cellulose, polyvinyl alcohol and multipolymer thereof, acrylate and methacrylic ester.
Colloid can be administered to or brush in skin or introducing body cavity.The colloidal preparation is by handling with a large amount of thickening materials by the solution of above-mentioned preparation in the injection liquid, to generate the limpid ointment piece of denseness unanimity.The thickening material that uses is above-mentioned thickening material.
The spot printing preparation be with or porous is gone in the skin or the active compound point with systemic effect is coated onto or is sprayed on the skin on certain area.
The preparation of spot printing preparation be by with active compound dissolving, suspend or be emulsifiable in solvent that suitable skin can tolerate or the solvent mixture.Add other auxiliary material such as dyestuff in case of necessity, absorb promotion material, antioxidant, light stabilizer or tackiness agent.
Above-mentioned solvent is: water, alkanol, dibasic alcohol, polyoxyethylene glycol, polypropylene glycol, glycerine, aromatic alcohol, as benzylalcohol, phenylethyl alcohol or phenoxyethyl alcohol, ester class, as ethyl acetate, butylacetate or peruscabin, ethers, as aklylene glycol alkyl oxide such as dipropylene glycol monomethyl ether or Diethylene Glycol single-butyl ether, ketone, as acetone or methyl ethyl ketone, fragrance and/or fat hydrocarbon, vegetables oil or synthetic oils, DMF, N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone or 2,2-dimethyl-4-oxygen base-methylene radical-1, the 3-dioxolane.
Dyestuff be mainly used in animal can be dissolved or the various dyestuffs that suspend.
Absorb and promote that material for example is DMSO, dispersion oils such as tetradecanoic acid isopropyl esters, n-nonanoic acid dipropylene glycol ester, silicone oil, fatty acid ester, triglyceride level or Fatty Alcohol(C12-C14 and C12-C18).
Antioxidant is sulphite or metabisulphite, as inclined to one side Potassium hydrogen sulfite.Xitix, butylhydroxy toluene, butylated hydroxy anisole or tocopherol.
Light stabilizer is Novantisols  ure for example.
Tackiness agent is for for example derivatived cellulose, starch derivative, polyacrylic ester or natural polymer, as alginate or gelatin.
Emulsion can be oral, use or use as injection through skin.
Emulsion both can be that water-in-oil-type also can be an oil-in-water-type.
The preparation of emulsion both active compound can be dissolved in that hydrophobic phase also can be dissolved in aqueous favoring and by suitable emulsifying agent with the latter and other solvent mixing mutually, and also can dissolve in other auxiliary material such as dyestuff where necessary, absorb the promotion material, sanitas, antioxidant, light stabilizer or viscosity raising material.
The hydrophobic phase (oil) that can address is: paraffin oil, silicone oil, crude vegetal, as sesame oil, Prunus amygdalus oil or Viscotrol C, synthetic glycerine three esters are as octyl group/capric acid two glyceryl ester, triglyceride level and C 8-12The vegetable fatty acid of chain length or other be the mixture of the natural acid of selection specifically, also can contain the partial glyceride mixture of the saturated or unsaturated fatty acids of hydroxyl, or C 8/ C 10The direactive glyceride of lipid acid and two glyceryl ester.
The branched chain fatty acid and the C of fatty acid ester such as Stearic ethyl stearate, Di-n-butyl Adipate, lauric acid hexyl ester, n-nonanoic acid dipropylene glycol ester, medium chain 16-C 18The C of the ester of chain length saturated fatty alcohol, Isopropyl myristate, Wickenol 111, suffering/capric acid 12-C 18The saturated fatty alcohol ester of chain length, isopropyl stearate, Oleyl oleate, decyl oleate, ethyl oleate, ethyl lactate, wax fatty acid ester, dibutyl phthalate, Wickenol 116, the mixture of above-mentioned ester, or the like.
Fatty Alcohol(C12-C14 and C12-C18) is as isotrideyl alcohol, 2-Standamul G, hexadecyl Stearyl alcohol or oleyl alcohol.
Lipid acid is as oleic acid and composition thereof.
The aqueous favoring of addressing is: water, alcohols, as propylene glycol, glycerine, sorbyl alcohol and composition thereof.
The emulsifying agent of addressing is: nonionogenic tenside, for example polyoxyethylenated castor oil, polyoxyethylene polyoxyethylene-sorbitan mono-oleate, Arlacel-60, Zerol, polyoxy ethyl stearate or alkyl phenol polyethylene glycol ethers;
Amphoterics is as N-lauryl-β-imino-disodium beclomethasone or Yelkin TTS;
Anion surfactant is as sodium lauryl sulphate, fatty alcohol ether sulphate, list/dialkyl group polyglycol ether ortho-phosphoric acid ester-monoethanolamine salt;
Cats product is as cetyltrimethylammonium chloride.
Other auxiliary agent that can address is: the material that can increase emulsion viscosity and stable emulsion, as carboxymethyl cellulose, methylcellulose gum and other Mierocrystalline cellulose and starch derivative, the multipolymer of polyacrylate alginate, gelatin, gum arabic, polyvinylpyrrolidone, polyvinyl alcohol, methylvinylether and maleic anhydride, polyoxyethylene glycol, wax, colloid silicic acid or more than list the mixture of material.
Suspension can be oral or be used through skin.The preparation of suspension is by active compound being suspended in the vehicle liquid, adding other auxiliary agent such as wetting agent, dyestuff promotion absorbing material, sanitas, antioxidant or light stabilizer simultaneously in appropriate circumstances.
The vehicle liquid that can address is various homogeneous solvents and solvent mixture.
The wetting agent that can address (dispersion agent) is above-mentioned tensio-active agent.
Other auxiliary agent that can address is the above-mentioned material that provides.
Semi-solid preparation can pass through oral or percutaneous drug delivery.They are just different with above-mentioned suspension and emulsion in its high viscosity.
In order to produce solid preparation, active compound is mixed with the carrier substance that is fit to, add auxiliary agent in due course and make the shape of wanting simultaneously.
The carrier substance that can address is the solid, inert solid that can tolerate on the various physiology.Can use inorganic and organism as carrier.The example of inorganics is sodium-chlor, carbonate such as lime carbonate, supercarbonate, aluminum oxide, silicic acid, shale soil, precipitation or colloid silica or phosphoric acid salt.
Organic example is sugar, Mierocrystalline cellulose, nutrition and feed, as milk powder, beastly powder, grain and meal or starch.
Auxiliary agent is the above-mentioned sanitas that lists, antioxidant or dyestuff.
Other auxiliary agent that is fit to is lubricant and antiseize paste such as Magnesium Stearate, stearic acid, talcum, wilkinite, promotion decomposed substance such as starch or cross-linked polyvinylpyrrolidone; Tackiness agent such as starch gelatin or linear polyethylene pyrrolidone and dried tackiness agent such as Microcrystalline Cellulose.
The result the invention still further relates to as the general formula of combatting ectoparasites agent (I) compound and uses general formula (I) compound and prevent and treat verminal composition.
The concentration that ready-to-use formulation contains active compound is 10ppm-20% (weight), preferred 0.1-10% (weight).
The concentration of the active compound that contains in the preparation that needed to dilute before using is 0.5-90% (weight), preferred 5 to 50% (weight).
Usually, in order to obtain effective result, proved dosage be every day per kilogram of body weight about 1 to about 100mg active compound be superior.
Except as otherwise noted, all percent value are weight percentage.
Following preparation embodiment and following biological Examples are for the preparation and the biological activity thereof of general formula of the present invention (I) compound are described respectively.
Embodiment 1
First with 5 of 2.54g (20mmol), 5-dimethyl-tetramethyleneimine-2, the 4-diketone is poured in the 70ml anhydrous methylene chloride, and adds the 2.8ml triethylamine.At 0 °-10 ℃ morpholine urea chlorides that drip 2.34ml, and continuously stirring mixture at room temperature, detect with thin-layer chromatography simultaneously.With 0.5N NaOH flushing reaction soln twice, dry organic phase is also distilled to remove under vacuum and is desolvated.With residuum recrystallization from ethyl acetate/normal hexane.Obtain the above-claimed cpd of 1.3g (being about ≌ 27% of theoretical value).198 ℃ of fusing point m.p..
The employing similar methods prepares the compound in the table 5:
Table 5
Figure A9419346701091
Figure A9419346701092
Table 5 (continuing)
Table 5 (continuing)
Figure A9419346701111
Table 5 (continuing)
Table 5 (continuing)
Figure A9419346701131
Table 5 (continuing)
Figure A9419346701141
Table 5 (continuing)
Table 5 (continuing)
Figure A9419346701161
Table 5 (continuing)
Table 5 (continuing)
Figure A9419346701181
Table 5 (continuing)
Figure A9419346701191
Table 5 (continuing)
The preparation of initial compounds
Embodiment (II-1)
Figure A9419346701211
At room temperature, 100.6g (0.898mol) potassium tert.-butoxide is joined in the 2-isoamyl acyloxy-ethyl isobutyrate solution of the 49.5g (0.229mol) in 500mlTHF.At room temperature stir spend the night after, mixture is joined in the water of 500ml and with the whole solution of concentrated hydrochloric acid acidifying.Isolate organic phase and use ethyl acetate extraction water secondary.The organic phase MgSO that merges 4Drying is filtered and is removed and desolvate.With the residuum crystallization petroleum ether and stirring purifying for preparing in a manner described.Water flushing and dry then.
Productive rate: 21.5g; About 55% of theoretical value is light yellow crystal powder.
Fusing point: 188-189 ℃
Embodiment
Figure A9419346701212
2-isoamyl acyloxy ethyl isobutyrate
At 40 ℃, the isoveryl chloride of 30.1g (0.25mol) is added drop-wise in the 2-ethyl butyrate of hydroxyl iso of 33.0g (0.25mol).Stirring the mixture no longer produces up to gas, is heated to 100 ℃ then rapidly.Gained crude product (yellow oil) is outgased in the vacuum oil pump, and not needing further purifies reacts.Productive rate 53.3g (theoretical value 99%).
Example II-2
At 10-20 ℃, N-(2-cyclopropyl alanine the methyl esters)-drips of solution of propanedioic acid methyl esters acid amides in the 100ml anhydrous tetrahydro furan of 949 (0.386mol) is added in the 200ml anhydrous tetrahydrofuran solution of 26.2g (0.386mol) sodium ethylate.After 1 hour, under 0-10 ℃, be added in the vitriol oil of the 37.8g (0.386mol) in the 50ml anhydrous methanol, stirred the mixture 15 minutes.Suction filtration mixture and concentrated filtrate, residuum CH 2Cl 2Absorb, wash above-mentioned solution twice, use MgSO with 40ml water 4Dry and concentrated once more.Residuum is suspended in the acetonitrile of 380ml, adds 9g water.Under refluxad make the mixture boiling up to CO 2Volatilization finish.Evaporation and make the residuum recrystallization from ethyl acetate/normal hexane after, obtain 26.9g (theoretical value
Figure A9419346701222
46%) above-claimed cpd.Fusing point: 114 ℃.
Employing is similar to the method for example II-1 and II-2, the compound that lists in the preparation table 6:
Table 6
Figure A9419346701232
Table 6 (continuing)
Figure A9419346701241
Embodiment A
The experiment of daikon leaf beetle larva
Solvent: 3 weight part dimethyl formamides
Emulsifying agent: 1 weight part alkylaryl polyglycol ether
In order to produce the preparation of suitable active compound, with active compound and the solvent of set amount and the emulsifier mix of set amount of 1 weight part, the dilute with water enriched material is to desired concn.
Cabbage leaves (Brassica oleracea) dipping in the preparation of the active compound of desired concn is handled, made blade still keep moistening, infect with horseradish daikon leaf beetle larva (Phaedoncochleariae).
Behind required time, determine kill rate %.100% means all daikon leaf beetle larvas is killed entirely; 0% means the death of no ape leaf larva.
In this test, for example according to the compound of preparation embodiment 3 productions, under the illustration concentration of the active compound 0.1%, kill rate is 100% after 7 days.
Embodiment B
Threshold concentration test/root absorption effect
For trying insect: black bean aphid
Solvent: 4 weight part acetone
Emulsifying agent: 1 weight part alkylaryl polyglycol ether
In order to produce the preparation of suitable active compound, with the solvent of the active compound of 1 weight part and set amount and add the emulsifying agent of set amount, the dilute with water enriched material is to desired concn.
The preparation of active compound is mixed closely with soil.The concentration of active compound in preparation is in fact unimportant, and what need to determine only is the weight of active compound in the per unit volume soil, and (=mg/l) form provides with ppm.The soil of handling is moved in the basin, planted wild cabbage (Brassica oleracea) in the basin.With above-mentioned mode plant roots assimilating activity compound and being transported in the blade from soil.
In order to determine the root absorption effect, infect and remove blade after 7 days for trying animal with above-mentioned.After 2 days, by counting or estimate that dead borer population estimates.Infer the root absorption effect of active compound from the numerical value of mortality ratio.If whole all being killed for the examination insect is 100%.
In this test, compounds of producing according to preparation embodiment 1 and 2 for example, under the illustration concentration of the active compound of 70ppm, kill rate is 100%.
Embodiment C
The black peach aphid test
Solvent: 7 weight part dimethyl formamides
Emulsifying agent: 1 weight part alkylaryl polyglycol ether
In order to produce the preparation of suitable active compound, with active compound and the solvent of set amount and the emulsifier mix of set amount of 1 weight part, the dilute with water enriched material is to desired concn.
Cabbage leaves (Brassicaoleracea) dipping that will seriously have been infected by black peach aphid (Myzns Persicae) is handled in the prepared product of the active compound of desired concn.
Behind required time, determine kill rate %.100% means all black peach aphids is killed entirely; 0% means no aphid death.
In this test, for example according to preparation embodiment 2,4 and 5 compounds of producing, under the illustration concentration of the active compound 0.1%, the kill rate after 6 days is at least 95%.
Embodiment D
Aphid test (sorption)
Solvent: the dimethyl formamide of 7 weight parts
Emulsifying agent: the alkylaryl polyglycol ether of 1 weight part
In order to produce the preparation of suitable active compound, with active compound and the solvent of set amount and the emulsifier mix of set amount of 1 weight part, the dilute with water enriched material is to desired concn.
Water the preparation of the active compound of 20ml desired concn separately to the broad bean plant (Viciafaba) of using black bean aphid (Aphis fabae) seriously to infect, by this way, make the preparation of active compound infiltrate through soil in the mode of the seedling of not getting wet.Root assimilating activity compound also is transported on the seedling.
Behind required time, determine kill rate %.100% means all aphids is killed entirely; 0% means no aphid death.
In this test, for example according to the compound of preparation embodiment 1 production, under 0.1% active compound illustration concentration, the kill rate after 4 days is 100%.
Embodiment E
The test of lucilia (Lucilia cuprina resistent) larva
Emulsifying agent: 35 weight part glycol monomethyl methyl ethers
35 weight part Nonoxynol-9s
In order to produce the preparation of suitable active compound, the active compound of 3 weight parts is mixed with the mixture that 7 weight parts provide above, the dilute with water enriched material is to desired concn.
About 20 lucilia larvas are put into contain about 1cm 3In the test tube of horseflesh and 0.5ml active agent preparations.After 24 hours, determine the degree of killing.
In this test, for example according to the compound of embodiment 3,4 and 6 preparations, under the active compound illustration concentration of 1000ppm, kill rate is 100%.

Claims (10)

1. the 4-formamyl-pyrroline-2-one derivative of the replacement of formula (I) and 4-formamyl-dihydrofuran-2-ketone derivatives Wherein: A represents hydrogen or can be chosen wantonly the alkyl or cycloalkyl of replacement separately by halogen, alkoxyl group or halogenated alkoxy, or the representative aryl or aralkyl that can be optionally substituted separately, B represents hydrogen or alkyl, or A and B are with adjacent C atom, the ring of the optional replacement that representative can be interrupted by heteroatoms, Z represents nitrogen or oxygen, X represents hydrogen or can be chosen wantonly alkyl, cycloalkyl, alkoxyl group or the alkylthio that replaces, R by halogen, alkyl, alkoxyl group, alkylthio, haloalkyl, halogenated alkoxy or halogenated alkylthio separately 1Represent alkyl, alkenyl or acyl group, R 2Representative can be chosen wantonly alkyl, alkenyl, alkoxyalkyl or the aryl that replaces by halogen separately, or represents and can be chosen wantonly the cycloalkyl of being interrupted by heteroatoms, or R 1And R 2And the nitrogen-atoms that connects with its key, representative is optional that replace and can choose the ring that is interrupted by other heteroatoms wantonly, and G if Z represents nitrogen, then represents hydrogen or separately can be by halogen, alkoxyl group or halogenated alkoxy
Optional alkyl, alkenyl or the cycloalkyl that replaces, or representative can be optionally substituted separately
Aryl or aralkyl, or represent acyl group, or A and G and the atom that connects with its key, representative is optional that replace and can be by other heteroatoms
The ring that is interrupted.
2. according to formula (I) compound of claim 1,
Wherein A represents hydrogen, or separately can be by halogen, C 1-C 4-alkoxyl group and/or C 1-
C 4The optional C that replaces of-halogenated alkoxy 1-C 10-alkyl or C 3-C 10-
Cycloalkyl, or separately can be by halogen, CN, nitro, C 1-C 8-alkyl, C 1
-C 8-alkoxyl group, C 1-C 8X-alkylthio, C 1-C 8-haloalkyl
And/or C 1-C 8Optional phenyl, naphthyl or the phenyl that replaces of halogenated alkoxy-
C 1-C 6-alkyl, B are represented hydrogen or C 1-C 8-alkyl, or A and B represent and can be appointed by halogen, alkyl and/or alkoxyl group with the C atom that its key connects
Choose generation and can randomly comprise nitrogen, oxygen, sulphur or-3-of O-CO-group extremely
8-unit ring, X represents hydrogen, or separately can be randomly by halogen, C 1-C 6-alkyl, C 1-
C 5Alkoxyl group, C 1-C 6Alkylthio, C 1-C 6-haloalkyl and/or
C 1-C 5The C that-halogenated alkoxy replaces 1-C 6-alkyl, C 1-C 5
-alkoxyl group, C 1-C 6-alkylthio or C 3-C 7-cycloalkyl, R 1Represent C 1-C 6-alkyl, C 3-C 6One of-alkenyl, or following radicals: -SO 2-R, ,-SO 2-NRR ',
Figure A9419346700033
Or-SO 2-OR
Wherein
R and R ' represent independently of one another separately can be by halogen, C 1-C 6-alkyl,
C 1-C 6-alkoxyl group, C 1-C-haloalkyl and/or C 1-
C 5The optional C that replaces of-halogenated alkoxy 1-C 10-alkyl, C 3-
C 10-cycloalkyl, phenyl, phenyl-C 1-C 4-alkyl or heteroaryl,
With
R ' also can represent hydrogen, or
The N atom that R and R ' connect with its key is represented can be by C 1-C 4-alkyl is appointed
That chooses generation reaches two other nitrogen-atoms or Sauerstoffatom most with can randomly containing
5-to 7-unit ring, R 2Representative can be chosen the C that is replaced by halogen wantonly separately 1-C 20-alkyl, C 3-C 20-
Alkenyl, C 1-C 8Alkoxy-C 1-C 8-alkyl, C 1-C 8-
Alkylthio-C 1-C 8-alkyl, phenyl or can randomly comprise the most nearly two oxygen
The C of atom and/or sulphur atom 3-C 8-cycloalkyl, or R 1And R 2With its key connect nitrogen-atoms-playing representative can be by C 1-C 4-alkyl is optional
The 3-that replaces and can randomly contain the most nearly two Sauerstoffatoms and/or sulphur atom extremely
7-unit ring, Z represents nitrogen or oxygen, and G if Z represents nitrogen, then represents hydrogen, or separately can be by halogen, C 1-C 6-alcoxyl
Base and/or C 1-C 6The optional C that replaces of-halogenated alkoxy 1-C 8-alkyl,
C 3-C 8-alkenyl or C 3-C 8-cycloalkyl, or separately can by halogen,
CN, nitro, C 1-C 6-alkyl, C 1-C 6-alkoxyl group, C 1-
C 5-alkylthio, C 1-C-haloalkyl, C 1-C 6-halogenated alkylthio
And/or C 1-C 6Optional phenyl, naphthyl or the phenyl that replaces of-halogenated alkoxy-
C 1-C 4One of-alkyl, or following radicals:
-SO 2-R, ,-SO 2-NRR ',
Figure A9419346700053
Or-SO 2-OR
Wherein
R and R ', representative separately can be by halogen, C independently of one another 1-C 6-alkyl,
C 1-C 6-alkoxyl group, C 1-C-haloalkyl and/or C 1-
C 6The optional C that replaces of-halogenated alkoxy 1-C 8-alkyl, C 3-
C 7-cycloalkyl, phenyl, phenyl-C 1-C 4-alkyl or heteroaryl,
With
R ' also can represent hydrogen, or
The N atom that R and R ' connect with its key is represented can be by C 1-C 4-alkyl is appointed
Choose generation and can randomly comprise the most nearly two other nitrogen-atoms or Sauerstoffatoms
5-to 7-unit ring, or the atom that connects with its key of A and G represent can be by halogen and/or C 1-C 4-alkyl
Optional 4-to the 8-unit ring that replaces, it can randomly comprise Sauerstoffatom or sulphur atom,
With it can randomly be unsaturated ring.
3. according to formula (I) compound of claim 1, wherein A represents hydrogen or separately can be by fluorine, chlorine, bromine, C 1-C 4-alkoxyl group, fluoroform
The optional C that replaces of oxygen base and/or five fluorine oxyethyl groups 1-C 8-alkyl or C 3-
C 8-cycloalkyl, or separately can be by fluorine, chlorine, bromine, CN, nitro, C 1-C 4
-alkyl, C 1-C 4-alkoxyl group, C 1-C 4-alkylthio, C 1-
C 4-haloalkyl and/or C 1-C 4The optional phenyl that replaces of-halogenated alkoxy,
Naphthyl or phenyl-C 1-C 4-alkyl, B are represented hydrogen or C 1-C 6-alkyl, or the C atom that connects with its key of A and B represent can be by fluorine, chlorine, bromine, C 1-C 4-
Alkyl and/or C 1-C 4-alkoxyl group is optional that replace and can randomly to comprise oxygen former
3-to the 7-unit ring of son or sulphur atom, X represents hydrogen, or separately can be by fluorine, chlorine, bromine, C 1-C 4-alkyl, C 1-
C 4-alkoxyl group, C 1-C 4-alkylthio, C 1-C 4-haloalkyl and
/ or C 1-C 4The optional C that replaces of-halogenated alkoxy 1-C 4-alkyl or
C 3-C 6-cycloalkyl, R 1Represent C 1-C 4-alkyl or C 3-C 4-alkenyl, or
Figure A9419346700061
Or-SO 2-R,
Wherein
The R representative separately can be by fluorine, chlorine, bromine, C 1-C 4-alkyl, C 1-C 4
-alkoxyl group, C 1-C 4-haloalkyl and/or C 1-C 4-halo
The optional C that replaces of alkoxyl group 1-C 8-alkyl, C 3-C 8-cycloalkyl,
Phenyl, benzyl, pyrryl, thienyl or pyridyl, R 2Representative can be chosen wantonly separately by the C of fluorine and/or chlorine replacement 1-C 14-alkyl, C 3-C 14-alkenyl, C 1-C 4-alkoxy-C 1-C 6-alkyl, C 1-C 4-alkylthio-C 1-C 6-alkyl, phenyl or can randomly comprise the C of oxygen and/or sulphur atom 3-C 7-cycloalkyl, or R 1And R 2Representing with its key nitrogen-atoms even can be by C 1-C 3-alkyl can be chosen 3-to the 6-unit ring that replaces and can randomly comprise Sauerstoffatom and/or sulphur atom wantonly, and Z represents nitrogen or oxygen, and G if Z represents nitrogen, then represents hydrogen, or separately can be by fluorine, chlorine, bromine, C 1-C 4-alkoxyl group and/or C 1-C 4The optional C that replaces of-halogenated alkoxy 1-C 6-alkyl, C 3-C 6-alkenyl or C 3-C 6-cycloalkyl, or separately can
By fluorine, chlorine, bromine, CN, nitro, C 1-C 4-alkyl, C 1-C 4-alkane
Oxygen base, C 1-C 4-alkylthio, C 1-C 4-haloalkyl, C 1-
C 4-halogenated alkoxy and/or C 1-C 4The optional benzene that replaces of-halogenated alkylthio
Base, naphthyl, benzyl or phenylethyl, or represent one of following radicals:
Figure A9419346700071
Wherein
R and R ', representative separately can be by fluorine, chlorine, bromine, C independently of one another 1-C 4-
Alkyl, C 1-C 4-alkoxyl group, C 1-C 4-haloalkyl and/or
C 1-C 4The optional C that replaces of-halogenated alkoxy 1-C 8-alkyl,
C 3-C 8-cycloalkyl, phenyl, benzyl, pyrryl, thienyl or pyridine
Base and
R ' also can represent hydrogen, or
The N atom that R and R ' connect with its key, representative can be by C 1-C 4-alkyl
Choose replacement wantonly and can randomly comprise other the Sauerstoffatom and/or the 5-of nitrogen-atoms
To 7-unit ring, or the atom that connects with its key of A and G represent can be by C 1-C 4The optional replacement of-alkyl
5-to 8-unit saturated carbon ring.
4. according to formula (I) compound of claim 1, wherein A represent hydrogen or the methyl that can be replaced by identical or different one or more fluorine or chlorines separately,
Ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, phenyl
Or benzyl, B represents hydrogen, methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, isobutyl-
Or the tertiary butyl, or A and B represent one of following radicals together
-(CH 2) 4-，-(CH 2) 5-，-(CH 2) 6-，-(CH 2) 4-CH(CH 3)-，
-(CH 2) 3-CH(CH 3)-CH 2-，-(CH 2) 2-CH(CH 3)-(CH 2) 2-，
-(CH 2) 2-CH(C 2H 5)-(CH 2) 2-，-(CH 2) 2-CH(C 3H 7)-(CH 2) 2-，
-(CH 2) 2-CH(C 4H 9)-(CH 2) 2-，-CH 2O(CH 2) 2-，-CH 2S-(CH 2) 2-，
-(CH 2) 2-O-(CH 2) 2-or-(CH 2) 2-S-(CH 2) 2-X represent hydrogen or separately can by fluorine, chlorine, bromine, methyl, ethyl, propyl group, sec.-propyl,
The optional methyl that replaces of methoxyl group, oxyethyl group, trifluoromethyl and/or trifluoromethoxy,
Ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, methoxy
Base, oxyethyl group, cyclopropyl, cyclopentyl or cyclohexyl, R 1Represent methylidene, ethyl, propyl group, sec.-propyl, allyl group, methylsulfonyl, ethylsulfonyl
Or third alkylsulfonyl, R 2Representative separately can be by fluorine and/or the optional C that replaces of chlorine 1-C 10-alkyl, C 3-
C 10-alkenyl, C 3-C 6-cycloalkyl, C 1-C 3-alkoxyl group-
C 1-C 4-alkyl or phenyl, or R 1And R 2Represent by methyl and/or the optional replacement of ethyl with the nitrogen-atoms that its key connects
And 3-to the 6-unit ring that can randomly comprise Sauerstoffatom, Z represent nitrogen or oxygen, G if Z represent nitrogen, then represents hydrogen, or can be chosen wantonly the first of replacement separately by fluorine and/or chlorine
Base, ethyl, propyl group, sec.-propyl, butyl, sec-butyl, isobutyl-or the tertiary butyl, or
By fluorine, chlorine, nitro, C 1-C 4-alkyl and/or C 1-C 4-alkoxyl group
The optional phenyl that replaces, or group
Figure A9419346700081
Wherein
R and R ', representative separately can be by fluorine and/or the optional C that replaces of chlorine independently of one another 1
-C 6-alkyl, C 3-C 6-alkenyl, phenyl or benzyl and
R ' also can represent hydrogen, or
R and R ' represent one of following radicals together:
-(CH 2) 3-，-(CH 2) 4-，-(CH 2) 5-，
-CH 2-CH(CH 3)(CH 2) 2-，
-CH 2O-(CH 2) 2-or-CH 2S-(CH 2) 2-or A and G represent one of following radicals together :-(CH 2) 3-,-(CH 2) 4-,
Figure A9419346700091
Figure A9419346700092
Figure A9419346700093
Or
Figure A9419346700094
5. the preparation method of formula (I) 4-formamyl-pyrroline-2-one and 4-formamyl-dihydrofuran-2-ketone,
Figure A9419346700095
Wherein
A, B, X, Z, G, R 1And R 2Be the definition that provides in the claim 1, it is characterized in that making the compound of formula (II)
Figure A9419346700101
Wherein
A, B, X, Z and G are the above-mentioned definition that provides, and a) the carbamyl halogen with formula (III) reacts
Figure A9419346700102
Wherein
R 1And R 2For the definition that provides in the claim 1 and
Hal represents halogen, in the presence of thinner and in case of necessity, in the presence of acid binding agent, reacts in case of necessity, or b) the first step, with the chloro-formic ester reaction of phosgene or formula (IV)
R 3-O-CO-Cl????(IV)
Wherein
R 3Representative can be chosen the alkyl that is replaced by halogen wantonly, and in the presence of acid binding agent, reacting in the presence of the thinner and in case of necessity in case of necessity, and in second step, making the amine reaction of the compound and the formula V of gained,
Wherein
R 1And R 2Be the definition that provides in the claim 1, reaction in the presence of thinner in case of necessity.
6. agricultural chemicals is characterized in that it contains at least a formula according to claim 1 (I) compound.
7. arthropodicide is characterized in that it contains at least a formula according to claim 1 (I) compound.
8. use formula (I) compound according to claim 1 in plant protection, in the room, at health field, in the protection of storage product with on animal body, prevent and treat pest.
9. use formula (I) compound according to claim 1 in plant protection, in the room, at health field, in the protection of storage product with on animal body, prevent and treat arthropods.
10. produce the method for agricultural chemicals, it is characterized in that formula (I) compound according to claim 1 is mixed with weighting agent and/or tensio-active agent.
CN 94193467 1993-08-05 1994-07-25 Substituted 4-carbamoyl pyrrolin-2-one and dihydrofuran-2-one derivatives and their use as pesticides Pending CN1131417A (en)

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CN106008419A (en) * 2016-06-15 2016-10-12 上海丸全化学科技有限公司 Novel synthesis technology of tetronic acid
CN114127042A (en) * 2019-07-19 2022-03-01 三菱瓦斯化学株式会社 Process for producing alpha-acyloxycarboxylic acid ester

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DE19822247A1 (en) * 1998-05-18 1999-11-25 Bayer Ag New diphenylpyrrole derivatives useful for control of animal pests, e.g. in protection of plants, goods and materials and in veterinary medicine
DE19847076A1 (en) 1998-10-14 2000-04-20 Bayer Ag New 2-heteroaryl-5-phenyl-3,4-dihydro-2H-pyrrole derivatives, useful as insecticides, acaricides or nematocides, e.g. for protection of plants or wood, or as veterinary ectoparasiticides

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JPS5865272A (en) * 1981-10-14 1983-04-18 Takeda Chem Ind Ltd 4-substituted-2-pyrrolidinone compound and its preparation
DE4032090A1 (en) * 1990-02-13 1991-08-14 Bayer Ag POLYCYCLIC 3-ARYL-PYRROLIDIN-2,4-DION DERIVATIVES
DE4004496A1 (en) * 1990-02-14 1991-08-22 Bayer Ag New 3-aryl-pyrrolidine -2,4-di:one deriv(s) - useful as insecticides, acaricides and herbicides, esp. effective against tetranychus urticae
DE4121365A1 (en) * 1991-06-28 1993-01-14 Bayer Ag SUBSTITUTED 1-H-3-ARYL-PYRROLIDIN-2,4-DION DERIVATIVES

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CN103459370A (en) * 2011-01-25 2013-12-18 拜耳知识产权有限责任公司 Process for preparing 1-H-pyrrolidine-2, 4-dione derivatives
CN106905215A (en) * 2011-01-25 2017-06-30 拜耳知识产权有限责任公司 Process for preparing 1-H-pyrrolidine-2, 4-dione derivatives
CN106905215B (en) * 2011-01-25 2021-10-01 拜耳知识产权有限责任公司 Process for preparing 1-H-pyrrolidine-2, 4-dione derivatives
CN106008419A (en) * 2016-06-15 2016-10-12 上海丸全化学科技有限公司 Novel synthesis technology of tetronic acid
CN106008419B (en) * 2016-06-15 2022-02-15 上海丸全化学科技有限公司 Synthesis process of tetronic acid
CN114127042A (en) * 2019-07-19 2022-03-01 三菱瓦斯化学株式会社 Process for producing alpha-acyloxycarboxylic acid ester

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