CN103781769A - Ester compound and use thereof - Google Patents
Ester compound and use thereof Download PDFInfo
- Publication number
- CN103781769A CN103781769A CN201280041133.2A CN201280041133A CN103781769A CN 103781769 A CN103781769 A CN 103781769A CN 201280041133 A CN201280041133 A CN 201280041133A CN 103781769 A CN103781769 A CN 103781769A
- Authority
- CN
- China
- Prior art keywords
- configuration
- compound
- formula
- cyclopropane ring
- represented
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 CC(C)(C1*)C1C(OCN1C2OC2*1)=O Chemical compound CC(C)(C1*)C1C(OCN1C2OC2*1)=O 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings 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
- C07D233/72—Two oxygen atoms, e.g. hydantoin
- C07D233/76—Two oxygen atoms, e.g. hydantoin with substituted hydrocarbon radicals attached to the third ring carbon atom
- C07D233/78—Radicals substituted by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings 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
- C07D233/72—Two oxygen atoms, e.g. hydantoin
-
- 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
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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
- C07D249/12—Oxygen or sulfur atoms
Abstract
An ester compound represented by formula (1): wherein Q represents N(CH2C(triplebond)CH)-CH2-C*(=O) or N(CH2C(triplebond)CH)-C(CH3)=N* (where, * represents a binding position with N atom being adjacent to a carbonyl group); R3 represents a C1-C4 alkyl group; and a relative configuration between the substituent at the 1-position of the cyclopropane ring and the substituent at the 3-position of the cyclopropane ring is a trans configuration, has an excellent pest control effect.
Description
Technical field
The present invention relates to ester cpds and application thereof.
Background technology
Up to now, synthesized multiple compounds with pest control (referring to " pharmacy research and development second series (The Second series of pharmaceutical research and development) ", the 18th volume, " agrochemicals development III (Development of agrochemicals III) ", the 493rd page, Hirokawa Shoten, 1993).
For example, certain esters compound has been described in JP-A-60-16962.
Summary of the invention
(inventing problem to be solved)
The object of this invention is to provide a kind of new compound with outstanding pest controling effect.
(means of dealing with problems)
The present inventor has carried out in depth research and has found that the ester cpds being represented by formula as follows (1) has outstanding pest controling effect, and obtains the present invention.
In other words, the present invention relates to following invention:
[1] a kind of ester cpds being represented by formula (1):
Wherein
Q represents N (CH
2c ≡ CH)-CH
2-C
*(=O) or N (CH
2c ≡ CH)-C (CH
3)=N
*(herein, * represents and the binding site of the N atom in abutting connection with carbonyl);
R
3represent C1-C4 alkyl; And
Relative configuration between substituting group on substituting group on the 1-position of cyclopropane ring and the 3-position of cyclopropane ring is transconfiguration,
(hereinafter, being called compound of the present invention);
The ester cpds that [1-2] basis [1] is described, wherein, R
3represent C1-C3 alkyl;
[2] according to the ester cpds [1] or [1-2] described, wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*(=O);
[3] according to the ester cpds [1] or [1-2] described, wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*;
[4] according to any one in [1]-[3] or [1-2] described ester cpds, wherein, in formula (1), the absolute configuration on the 1-position of described cyclopropane ring is R configuration;
[5] according to any one in [1]-[4] or [1-2] described ester cpds, wherein in formula (1), the two keys that exist on substituting group on the 3-position of cyclopropane ring are in E configuration or the mix-configuration in E configuration and Z configuration, and the ratio of described E configuration is more than 50%;
[6] according to any one in [1]-[5] or [1-2] described ester cpds, wherein, in formula (1), the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration;
[7] according to the ester cpds described in any one in [1]-[6], wherein in formula (1), R
3represent methyl;
[8] according to the ester cpds described in any one in [1]-[6], wherein in formula (1), R
3represent ethyl;
[9] according to the ester cpds described in any one in [1]-[6], wherein in formula (1), R
3represent sec.-propyl;
[10] according to the ester cpds described in any one in [1]-[6], wherein in formula (1), R
3represent the tertiary butyl;
[11] pest control agent, described pest control agent comprises according to any one in [1] to [10] or [1-2] described ester cpds and inert support;
[12] method for pest control, described method comprises: the step that ester cpds according to described in any one in [1] to [10] or [1-2] of significant quantity is applied to insect or insect habitat;
[13] method for pest control, described method comprises: the step that ester cpds according to described in any one in [1] to [10] or [1-2] of significant quantity is applied to cockroach or cockroach habitat;
[14] according to the method [13] described, wherein, described cockroach is periplaneta americana (Periplaneta americana);
[15] according to the method [13] described, wherein, described cockroach is Groton bug (Blattella germanica);
[16] method for pest control, described method comprises: by spraying to the step of cockroach or cockroach habitat according to any one in [1] to [10] or [1-2] described ester cpds of significant quantity;
[17] according to the method [16] described, wherein, described cockroach is periplaneta americana (Periplaneta americana); With
[18] according to the method [16] described, wherein, described cockroach is Groton bug (Blattella germanica).
(invention effect)
Compound of the present invention has outstanding pest controling effect, therefore can be used as the activeconstituents for pest control agent.
Invention embodiment
Hereinafter, specific explanations the present invention.
The substituting group example using is in the present invention as follows:
Use in this article the example of C1-C4 alkyl group to comprise methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-and the tertiary butyl.
In compound of the present invention, there is the isomers that is derived from two unsymmetrical carbons on 1-position and the 3-position of cyclopropane ring, and be derived from the isomers of the two keys that exist on the substituting group on the 3-position of cyclopropane ring.The present invention comprises that each has the mixture of the isomers of pest control activity or the arbitrary proportion of these isomerss.
The example of compound of the present invention comprises following compound.
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*(=O), i.e. a kind of compound being represented by formula (a):
Wherein, R
3represent identical meanings as defined above, and relative configuration between substituting group on the 3-position of substituting group on the 1-position of cyclopropane ring and cyclopropane ring is transconfiguration;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*, i.e. a kind of compound being represented by formula (b):
Wherein, R
3represent identical meanings as defined above, and relative configuration between substituting group on the 3-position of substituting group on the 1-position of cyclopropane ring and cyclopropane ring is transconfiguration;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration;
The compound being represented by formula (1), wherein, the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration or the mix-configuration in E configuration and Z configuration, and the ratio of E configuration is more than 50%;
The compound being represented by formula (1), wherein, the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration;
The compound being represented by formula (1), wherein, the absolute configuration of the 1-position of cyclopropane ring be two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring in E configuration or the mix-configuration in E configuration and Z configuration, and the ratio of E configuration is more than 50%;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is that two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring are in E configuration;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*(=O);
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*absolute configuration on the 1-position of (=O) and cyclopropane ring is R configuration;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*(=O), and the two keys that exist on substituting group on the 3-position of cyclopropane ring are in E configuration or the mix-configuration in E configuration and Z configuration, and the ratio of E configuration is more than 50%;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*the two keys that exist on substituting group on the 3-position of (=O) and cyclopropane ring are in E configuration;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*(=O), and absolute configuration on the 1-position of cyclopropane ring be substituent pair of key on the 3-position of R configuration and cyclopropane ring in E configuration or the mix-configuration in E configuration and Z configuration, and the ratio of E configuration is more than 50%;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*absolute configuration on the 1-position of (=O) and cyclopropane ring is R configuration, and the two keys that exist on substituting group on the 3-position of cyclopropane ring are in E configuration;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*and the absolute configuration on the 1-position of cyclopropane ring is R configuration;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*and the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration or the mix-configuration in E configuration and Z configuration, and the ratio of E configuration is more than 50%;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*and the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*and the absolute configuration on the 1-position of cyclopropane ring be two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring in E configuration or the mix-configuration in E configuration and Z configuration, and the ratio of E configuration is more than 50%;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*and the absolute configuration on the 1-position of cyclopropane ring is R configuration, and the two keys that exist on substituting group on the 3-position of cyclopropane ring are in E configuration;
The compound being represented by formula (1), wherein, R
3represent C1-C3 alkyl;
The compound being represented by formula (1), wherein, R
3represent methyl;
The compound being represented by formula (1), wherein, R
3represent ethyl;
The compound being represented by formula (1), wherein, R
3represent sec.-propyl;
The compound being represented by formula (1), wherein, R
3represent the tertiary butyl;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration and R
3represent methyl;
The compound being represented by formula (1), wherein, the two keys that exist on the substituting group on the 3-position of cyclopropane ring are more than 50% in the ratio of E configuration or the mix-configuration in E configuration and Z configuration and E configuration, and R
3represent methyl;
The compound being represented by formula (1), wherein, the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration and R
3represent methyl;
The compound being represented by formula (1), wherein, absolute configuration on the 1-position of cyclopropane ring is that the two keys that exist on the substituting group on the 3-position of R configuration and cyclopropane ring are more than 50% in the ratio of E configuration or the mix-configuration in E configuration and Z configuration and E configuration, and R
3represent methyl;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring be two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring in E configuration, and R
3represent methyl;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration and R
3represent ethyl;
The compound being represented by formula (1), wherein, the two keys that exist on the substituting group on the 3-position of cyclopropane ring are more than 50% in the ratio of E configuration or the mix-configuration in E configuration and Z configuration and E configuration, and R
3represent ethyl;
The compound being represented by formula (1), wherein, the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration and R
3represent ethyl;
The compound being represented by formula (1), wherein, absolute configuration on the 1-position of cyclopropane ring is that the two keys that exist on the substituting group on the 3-position of R configuration and cyclopropane ring are more than 50% in the ratio of E configuration or the mix-configuration in E configuration and Z configuration and E configuration, and R
3represent ethyl;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring be two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring in E configuration, and R
3represent ethyl;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration and R
3represent sec.-propyl;
The compound being represented by formula (1), wherein, the two keys that exist on the substituting group on the 3-position of cyclopropane ring are more than 50% in the ratio of E configuration or the mix-configuration in E configuration and Z configuration and E configuration, and R
3represent sec.-propyl;
The compound being represented by formula (1), wherein, the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration, and R
3represent sec.-propyl;
The compound being represented by formula (1), wherein, absolute configuration on the 1-position of cyclopropane ring is that the two keys that exist on the substituting group on the 3-position of R configuration and cyclopropane ring are more than 50% in the ratio of E configuration or the mix-configuration in E configuration and Z configuration and E configuration, and R
3represent sec.-propyl;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring be two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring in E configuration, and R
3represent sec.-propyl;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration and R
3represent the tertiary butyl;
The compound being represented by formula (1), wherein, the two keys that exist on the substituting group on the 3-position of cyclopropane ring are more than 50% in the ratio of E configuration or the mix-configuration in E configuration and Z configuration and E configuration, and R
3represent the tertiary butyl;
The compound being represented by formula (1), wherein, the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration, and R
3represent the tertiary butyl;
The compound being represented by formula (1), wherein, absolute configuration on the 1-position of cyclopropane ring is that the two keys that exist on the substituting group on the 3-position of R configuration and cyclopropane ring are more than 50% in the ratio of E configuration or the mix-configuration in E configuration and Z configuration and E configuration, and R
3represent the tertiary butyl;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring be two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring in E configuration, and R
3represent the tertiary butyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*(=O) and R
3represent methyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*absolute configuration on the 1-position of (=O) and cyclopropane ring is R configuration, and R
3represent methyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*the two keys that exist on substituting group on the 3-position of (=O) and cyclopropane ring are more than 50% in the ratio of E configuration or the mix-configuration in E configuration and Z configuration and E configuration, and R
3represent methyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*the two keys that exist on substituting group on the 3-position of (=O) and cyclopropane ring are in E configuration, and R
3represent methyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*(=O), and absolute configuration on the 1-position of cyclopropane ring is R configuration, and the two keys that exist on substituting group on the 3-position of cyclopropane ring are in E configuration or the mix-configuration in E configuration and Z configuration, and the ratio of E configuration is more than 50%, and R
3represent methyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*absolute configuration on the 1-position of (=O) and cyclopropane ring be two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring in E configuration, and R
3represent methyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*(=O) and R
3represent ethyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*absolute configuration on the 1-position of (=O) and cyclopropane ring is R configuration, and R
3represent ethyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*the two keys that exist on substituting group on the 3-position of (=O) and cyclopropane ring are more than 50% in the ratio of E configuration or the mix-configuration in E configuration and Z configuration and E configuration, and R
3represent ethyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*the two keys that exist on substituting group on the 3-position of (=O) and cyclopropane ring are in E configuration and R
3represent ethyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*absolute configuration on the 1-position of (=O) and cyclopropane ring is that the two keys that exist on the substituting group on the 3-position of R configuration and cyclopropane ring are more than 50% in the ratio of E configuration or the mix-configuration in E configuration and Z configuration and E configuration, and R
3represent ethyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*absolute configuration on the 1-position of (=O) and cyclopropane ring be two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring in E configuration, and R
3represent ethyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*(=O) and R
3represent sec.-propyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*absolute configuration on the 1-position of (=O) and cyclopropane ring is R configuration, and R
3represent sec.-propyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*the two keys that exist on substituting group on the 3-position of (=O) and cyclopropane ring are more than 50% in the ratio of E configuration or the mix-configuration in E configuration and Z configuration and E configuration, and R
3represent sec.-propyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*the two keys that exist on substituting group on the 3-position of (=O) and cyclopropane ring are in E configuration, and R
3represent sec.-propyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*absolute configuration on the 1-position of (=O) and cyclopropane ring is that the two keys that exist on the substituting group on the 3-position of R configuration and cyclopropane ring are more than 50% in the ratio of E configuration or the mix-configuration in E configuration and Z configuration and E configuration, and R
3represent sec.-propyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*absolute configuration on the 1-position of (=O) and cyclopropane ring be two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring in E configuration, and R
3represent sec.-propyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*(=O) and R
3represent the tertiary butyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*absolute configuration on the 1-position of (=O) and cyclopropane ring is R configuration, and R
3represent the tertiary butyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*the two keys that exist on substituting group on the 3-position of (=O) and cyclopropane ring are more than 50% in the ratio of E configuration or the mix-configuration in E configuration and Z configuration and E configuration, and R
3represent the tertiary butyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*the two keys that exist on substituting group on the 3-position of (=O) and cyclopropane ring are in E configuration, and R
3represent the tertiary butyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*absolute configuration on the 1-position of (=O) and cyclopropane ring is that the two keys that exist on the substituting group on the 3-position of R configuration and cyclopropane ring are more than 50% in the ratio of E configuration or the mix-configuration in E configuration and Z configuration and E configuration, and R
3represent the tertiary butyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*absolute configuration on the 1-position of (=O) and cyclopropane ring be two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring in E configuration, and R
3represent the tertiary butyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*and R
3represent methyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*and the absolute configuration on the 1-position of cyclopropane ring is R configuration, and R
3represent methyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*and the two keys that exist on the substituting group on the 3-position of cyclopropane ring are more than 50% in the ratio of E configuration or the mix-configuration in E configuration and Z configuration and E configuration, and R
3represent methyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*and the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration, and R
3represent methyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*and the absolute configuration on the 1-position of cyclopropane ring is that the two keys that exist on the substituting group on the 3-position of R configuration and cyclopropane ring are more than 50% in the ratio of E configuration or the mix-configuration in E configuration and Z configuration and E configuration, and R
3represent methyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*and the absolute configuration on the 1-position of cyclopropane ring be two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring in E configuration, and R
3represent methyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*and R
3represent ethyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*and the absolute configuration on the 1-position of cyclopropane ring is R configuration, and R
3represent ethyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*and the two keys that exist on the substituting group on the 3-position of cyclopropane ring are more than 50% in the ratio of E configuration or the mix-configuration in E configuration and Z configuration and E configuration, and R
3represent ethyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*and the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration, and R
3represent ethyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*and the absolute configuration on the 1-position of cyclopropane ring is that the two keys that exist on the substituting group on the 3-position of R configuration and cyclopropane ring are more than 50% in the ratio of E configuration or the mix-configuration in E configuration and Z configuration and E configuration, and R
3represent ethyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*and the absolute configuration on the 1-position of cyclopropane ring be two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring in E configuration, and R
3represent ethyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*and R
3represent sec.-propyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*and the absolute configuration on the 1-position of cyclopropane ring is R configuration, and R
3represent sec.-propyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*and the two keys that exist on the substituting group on the 3-position of cyclopropane ring are more than 50% in the ratio of E configuration or the mix-configuration in E configuration and Z configuration and E configuration, and R
3represent sec.-propyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*and the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration, and R
3represent sec.-propyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*and the absolute configuration on the 1-position of cyclopropane ring is R configuration, and the two keys that exist on substituting group on the 3-position of cyclopropane ring are in E configuration or the mix-configuration in E configuration and Z configuration, and the ratio of E configuration is more than 50%, and R
3represent sec.-propyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*and the absolute configuration on the 1-position of cyclopropane ring is R configuration, and the two keys that exist on substituting group on the 3-position of cyclopropane ring are in E configuration, and R
3represent sec.-propyl.
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*and R
3represent the tertiary butyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*and the absolute configuration on the 1-position of cyclopropane ring is R configuration, and R
3represent the tertiary butyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*and the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration or the mix-configuration in E configuration and Z configuration, and the ratio of E configuration is more than 50%, and R
3represent the tertiary butyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*and the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration, and R
3represent the tertiary butyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*and the absolute configuration on the 1-position of cyclopropane ring is R configuration, and the two keys that exist on substituting group on the 3-position of cyclopropane ring are in E configuration or the mix-configuration in E configuration and Z configuration, and the ratio of E configuration is more than 50%, and R
3represent the tertiary butyl;
The compound being represented by formula (1), wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*and the absolute configuration on the 1-position of cyclopropane ring be two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring in E configuration, and R
3represent the tertiary butyl.
Method for the preparation of compound of the present invention is below described.
Compound of the present invention can for example be prepared by the following method.
(preparation method 1)
A kind of alkylol cpd that formula (3) is represented:
Wherein Q represents identical meanings as above,
Carboxylic acid cpd with formula (4) expression:
Wherein R
3represent identical meanings as above, and substituting group on the 1-position of cyclopropane ring with
Relative configuration between substituting group on the 3-position of cyclopropane ring is transconfiguration, or the method for its reactive derivatives reaction.
The ester etc. of the acid anhydrides of the carboxylic acid that the example of reactive derivatives comprises the carboxylic acid halides of the carboxylic acid cpd being represented by formula (4), represented by formula (4), the carboxylic acid being represented by formula (4).The example of carboxylic acid halides comprises chloride compounds and acylbromide compound, and the example of ester comprises methyl esters, ethyl ester etc.
This reaction is carried out conventionally under the existence of condensing agent or alkali in solvent.
The example of the condensing agent using in this reaction comprises dicyclohexylcarbodiimide and 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride.
The example of the alkali using in this reaction comprises organic bases, as triethylamine, pyridine, N, and N-diethyl-aniline, 4-dimethylaminopyridine and diisopropylethylamine.
The example of the solvent using in this reaction comprises hydrocarbon, as benzene, toluene and hexane; Ether, as Anaesthetie Ether and tetrahydrofuran (THF); Halohydrocarbon, as chloroform, methylene dichloride, 1,2-ethylene dichloride and chlorobenzene; And the mixture of these solvents; Etc..
The reaction times of this reaction is conventionally in the scope of 5 minutes to 72 hours.
The temperature of reaction of this reaction conventionally in the scope of-20 ℃ to 100 ℃ (boiling point of solvent using lower than 100 ℃,-20 ℃ of boiling points to solvent), and preferably-5 ℃ to 100 ℃ (at the boiling point of the solvent that uses lower than 100 ℃ ,-5 ℃ of boiling points to solvent).
In this reaction, the alkylol cpd being represented by formula (3) using can at random be set with the carboxylic acid cpd being represented by formula (4) or the mol ratio of its reactive derivatives, and is preferably equimolar ratio or the ratio approaching with equimolar ratio.
Based on the alkylol cpd being represented by formula (3) of 1mol, condensing agent or alkali conventionally can be to use to the arbitrary proportion in excessive scope at 0.25mol, and preferred 0.5mol to 2mol.These condensing agents or alkali depend on by the carboxylic acid cpd of formula (4) expression or the kind of its reactive derivatives suitably to be selected.
After reaction completes, conventionally reaction mixture is carried out to postprocessing working procedures, for example, reaction mixture is filtered and subsequently filtrate concentrated, or reaction mixture is poured into water and is used the solution of organic solvent extraction gained subsequently that organic layer is concentrated, can obtain thus compound of the present invention.Can be by the compound of the present invention of gained being purified as the operation such as chromatography and distillation.
The alkylol cpd being represented by formula (3) is commercially available product, or the mixture of explaining in JP-A-05-255271, JP-A-57-158765, and can therefore buy as commercially available product, or can be according to the method preparation of describing in these are open.
Intermediate of the present invention can be for example by method preparation as follows.
(with reference to preparation method 1)
The carboxylic acid cpd being represented by formula (4) can be for example by method preparation as follows.
, make carane aldehydo-ester (caronaldehyde ester) derivative by formula (5) expression:
Wherein R represents C1-C5 alkyl, and relative configuration between substituting group on the 3-position of substituting group on the 1-position of cyclopropane ring and cyclopropane ring is transconfiguration,
With by formula (6) represent phosphate compound:
Wherein R
3represent identical meanings as above,
The compound of reaction to obtain being represented by formula (7) under the existence of alkali:
Wherein R and R
3represent respectively identical meanings as above, and relative configuration between substituting group on the 3-position of substituting group on the 1-position of cyclopropane ring and cyclopropane ring is transconfiguration,
The reaction that is further hydrolyzed under the existence of alkali, to prepare the carboxylic acid cpd being represented by formula (4):
Wherein R
3represent identical meanings as above, and relative configuration between substituting group on the 3-position of substituting group on the 1-position of cyclopropane ring and cyclopropane ring is transconfiguration.
Conventionally, the carane aldehydo-ester derivative being represented by formula (5) based on 1mol, use the alkali of the phosphate compound being represented by formula (6) of the ratio in 1.0 to 1.5mol proportional ranges and the ratio within the scope of 1 to 10mol, and make they 0 ℃ to 80 ℃ and preferably the scope of 0 ℃ to 30 ℃ in polar solvent or non-polar solvent, react, and can obtain thus by formula (7) represent compound.The example of the alkali using in reaction comprises: alkali metal compound is as sodium methoxide and tert.-butoxy potassium, metal hydride compound is as sodium hydride and potassium hydride KH, and basic metal aminocompound is as two (TMS) sodium amide, two (TMS) Lithamide and lithium diisopropylamine.
The example of the polar solvent using in reaction comprises: ether is as diethyl ether and tetrahydrofuran (THF), and acid amides is as N, N-dimethylformaldehyde, and sulfoxide is as methyl-sulphoxide.The example of the non-polar solvent using in reaction comprises: hydrocarbon is as benzene, toluene and hexane.
After reaction completes, reaction mixture is carried out to postprocessing working procedures, for example, reaction mixture is added to the water and is used the solution of organic solvent extraction gained, and subsequently organic layer is dried and is concentrated, and can obtain thus the compound being represented by formula (7).
In addition, in the step of reaction that the compound being represented by formula (7) is hydrolyzed, conventionally, the compound being represented by formula (7) based on 1mol, use the alkali of the ratio within the scope of 1 to 10mol, and make subsequently they 0 ℃ to 80 ℃ and preferably the scope of 0 ℃ to 30 ℃ in solvent, react, and can obtain thus by formula (4) represent carboxylic acid cpd.The example of the alkali using in reaction comprises that alkali metal compound is as potassium hydroxide and sodium hydroxide.The embodiment of the solvent using in reaction comprises: ether is as Isosorbide-5-Nitrae-bis-
alkane, tetrahydrofuran (THF), ethylene glycol dimethyl ether, alcohol is as methyl alcohol, ethanol, propyl alcohol, and the mixture of water and these solvents.
After reaction completes, reaction mixture is carried out to postprocessing working procedures, for example, reaction soln acidifying is also used to organic solvent extraction subsequently, and subsequently organic layer is dried and is concentrated, and can obtain subsequently the carboxylic acid cpd being represented by formula (4).
The carane aldehydo-ester derivative being represented by formula (5) can be according to Tetrahedron45, described method preparation in 3039-3052 (1989).
The example that compound of the present invention has the insect of prevention effect to it comprises harmful arthropod, as harmful insect and harmful acarid, and following insect more specifically.
Hemiptera (Hemiptera): Delphacidae (Planthoppers) is (as small brown rice planthopper (Laodelphax striatellus), brown paddy plant hopper (Nilaparvata lugens) and white back of the body planthopper (Sogatella furcifera)), angle top Cicadidae (Leafhoppers) (as rice green leafhopper (Nephotettix cincticeps) and nephotettix bipunctatus (Nephotettix virescens)), Aphidiadae (Aphids) (as cotten aphid (Aphis gossypii) and black peach aphid (Myzus persicae)), Miridae (Plant bugs) (the green stinkbug Nezara of Ru Huajiao antennata), beans honeybee coried (Riptortus clavetus), Japan two star stinkbugs (Eysarcoris lewisi), wedge angle two star stinkbugs (Eysarcoris parvus), Si Shi amber stinkbug (Plautia stali) and mixed tea wing stinkbug (Halyomorpha mista)), Aleyrodidae (White flies) is (as greenhouse whitefly (Trialeurodes vaporariorum), sweet potato whitefly (Bemisia tabaci) and Bemisia argentifolii (Bemisia argentifolii)), a red-spotted lizard section (Scales) is (as red kidney Aspidiotus (Aonidiella aurantii), Sheng Qiongsikang armored scale (Comstockaspis perniciosa), oranges and tangerines point armored scales (Unaspis citri), red ceroplastes floridensis (Ceroplastes rubens) and Australia icerya purchasi (Icerya purchasi)), Tingidae (Lace bugs), Cimicidae (Bed bugs) (as bed bug (Cimex lectularius)), Psyllidae (Jumping plantlice) etc.,
Lepidopteran (Lepidoptera): Pyralidae (Pyralidae) is (as striped rice borer (Chilo suppressalis), cnaphalocrocis medinalls guenee (Cnaphalocrosis medinalis), lap leaf wild snout moth's larva (Notarcha derogata) and India paddy phycitid (Plodia interpunctella)), Spodoptera litura (Spodoptera litura), mythimna separata (Pseudaletia separata), Noctuidae (Noctuidae) is (as powder Noctua (Trichoplusia spp.), Heliothis (Heliothis spp.) and Earias (Earias spp.)), Sulfur butterfly (Pieridae) (as small white (Pieris rapae)), Tortricidae (Tortricidae) is (as Adoxophyes spp belongs to (Adoxopheys spp.), oriental fruit months (Grapholita molesta), adoxophyes moth (Adoxophyes orana fasciata) and Pericarpium Mali pumilae steinernema (Cydia pomonella)), Carposinidae (Carposinidae) (such as peach post fruit moth (Carposina niponensis)), lyonetid section (Lyonetiidae) (such as lyonetid belongs to (Lyonetia spp.)), Lymantriidae (Lymantriidae) (as Euproctis (Lymantria spp.)), Lymantriidae (Lymantriidae) (such as Euproctis (Euproctis spp.)), Yponomeutidae (Yponameutidae) (such as small cabbage moth (Plutella Xylostella)), Gelechidae (Gelechiidae) (as Pectinophora gossypiella (Pectinophora gossypiella)), Arctiidae (Arctiidae) (moth as white in America (Hyphantria cunea)), rain moth section (Tineidae) (as casemaking clothes moth (Tinea translucens) and curtain rain moth (Tineola bisselliella)) etc.,
Diptera (Diptera): Culex (Culex spp.) is (such as culex pipiens pollens (Culex pipiens pallens), Culex tritaeniorhynchus (Culex trttaeniorhynchus) and Culex quinquefasciatus (Culex quinquefasciatus)), Aedes (Aedes spp.) (such as Aedes aegypti (Aedes aegypti) and Aedes albopictus (Aedes alboptctus)), Anopheles (Anopheles spp.) (such as Anopheles sinensis (Anopheles sinensis) with just than sub-anopheles (Anopheles gambiae)), Chironomidae (Chironomidae), Nuscidae (Muscidae) (as housefly (Musca domestica) and false stable fly (Muscina stabulans)), Calliphoridae (Calliphoridae), Flesh flies (Sarcophagidae), Fannia canicularis (little housefly), Anthomyiidae (Anthomyiidae) (such as delia platura (Delia platura) and green onion ground kind fly (Delia antiqua)), Tephritidae (Tephritidae), Drosophilidae (Drosophilidae), Phoridae (Phoridae) (such as the different eye fly in East Asia (Megaselia spiracularis)), Phlebotominae (phlebotominae) (such as moth fly (Clogmia albipunctata)), Moth files (Psychodidae), Simulidae (Simuliidae), Tabanidae (Tabanidae), sting Nuscidae (Stomoxyidae), Agromyzidae (Agromyzidae) etc.,
Coleoptera (Coleoptera): root Galeruca (Diabrotica spp.) (as chrysomelid in Zea mays root firefly (Diabrotica virgifera virgifera) and cucumber 11 asterophyllite first food root subspecies (Diabrotica undecimpunctaca howardi)), Scarabaeidae (Scarabaeidae) (as bronze different beetle (Anomala cuprea) and polychrome different beetle (Anomala rufocuprea)), Curculionidae (Curculionidae) is (such as sitophilus zea-mais (Sitophilus zeamais), rice water resembles (Lissorhoptrus oryzophilus) and Callosobruchus chinensis (Callosobruchuys chienensis)), TRenebrionidae (Tenebrionidae) (such as bloom first (Tenebrio molitor) and red flour beetle (Tribolium castaneum)), Chrysomelidae (Chrysomelidae) is (such as Oulema oryzae (Oulema oryzae), aulacophora femoralis (Aulacophora femoralis), Phyllotreta striolata (Phyllotreta striolata) and colorado potato beetles (Leptinotarsa decemlineata)), Dermestidae (Dermestidae) (such as dermestes maculatus (Dermestes maculates)), Anobiidae (Anobiidae), epilachna genus (Epilachna spp.) (as ladybug of eggplant 28 stars (Epilachna vigintioctopunctata)), Lyctidae (Lyctidae), Bostrichidae (Bostrychidae), Ptinidae (Ptinidae), Cerambycidae (Cerambycidae), Paederus fuscipes Curtis (Paederus fuscipes) etc.,
Blattodea (Blattodea): Groton bug (Blattella germamca), Peroplaneta fluligginosa (Periplaneta fuliginosa), periplaneta americana (Periplaneta americana), the large Lian of foxiness (Periplaneta brunnea), oriental cockroach (Blatta orientalis) etc.;
Thysanoptera (Thysanoptera): southern golden thistle horse (Thrips palmi), onion thrips (Thrips tabaci), Frankliniella occidentalis (Frankliniella occidentalis), beautiful flower thrips (Frankliniella intonsa) etc.;
Hymenoptera (Hymenoptera): Formicidae (Formicidae) is (such as MonomoriumMayr (Monomorium pharaosis), black ant (Formica fusca japonica), without the recessed smelly ant of hair (Qchetellus glaber), crosspointer ant (Pristomyrmex pungens), wide knot major part ant (Pheidole noda) and Argentine ant (Linepithema humile)), Ma Fengke (Long-legged wasps) is (such as the long pin hornet of China (Polistes chinensis antennalis), family hornet (Polistes jadwigae) and land hornet (Polistes rothneyi)), Vespidae (Vespidae) is (such as Japanese hornet (Vespa mandariniajaponica), Vespa simillima Smith (Vespa simillima), vespala (Vespa analis insularis), yellow limit wasp (Vespa crabro flavofasciata) and black tail wasp (Vespa ducalis)), Bethylidae (Bethylidae), Xylocopa (Xylocopa), Pompilidae (Pompilidae), Sphecoidea (Sphecoidae), Guo win section (mason wasp) etc.,
Orthoptera (Orthoptera): Gryllotalpidae (Mole crickets), locust Superfamily (Grasshoppers) etc.;
Siphonaptera (Shiphonaptera): ctenocephalides felis (Ctenocephalides felis), ctenocephalides canis (Ctenocephalides canis), Pulex irritans (Pulex irritants), Xanthopsyllacheopis (Xenopsylla cheopis) etc.;
Anoplura (Anoplura): body louse (Pediculus humanus corporis), hair lice (Phthirus pubis), haematopinus eurysternus (Haematopinus eurysternus), sheep lice (Dalmalinia ovis) etc.;
Isoptera (Isoptera): Reticulitermes (Reticulitermes spp.) is (such as eastern subterranean termite (Reticulitermes speratus), Workers of Coptotermes formosanus Shiraki (Coptotermes formosanus), American-European reticulitermes flavipe (Reticulitermes flavipes), America reticulitermes flavipe (Reticulitermes hesperus), Reticulitermes virginicus (Reticulitermes virginicus), instep reticulitermes flavipe (Reticulitermes tibialis) and the different termite in South America (Heterotermes aureus)), principal columns of a hall Cryptotermes (Incisitermes spp.) (such as little principal columns of a hall termite (Incisitermes minor)), and moving Cryptotermes (Zootermopsis spp.) (such as the ancient termite in Nevada (Zootermopsis nevadensis)) etc.,
Acarina (Acarina): Tetranychidae (Tetranychidae) is (as Tetranychus urticae (Tetranychus urticae), god Ze Shi tetranychid (Tetranychus kanzawai), panonychus citri (Panonychus citri), panonychus ulmi (Panonychus ulmi) and Oligonychus (Oligonychus spp.)), Eriophyidae (Eriophyidae) (as tangerine peronium goitre mite (Aculops pelekassi) and steinman pin thorn goitre mite (Aculus schlechtendali)), Tarsonemidae (Tarsonemidae) (as Polyphagotarsonemus latus Banks (Polyphagotarsonemus latus)), Tenuipalpidae (Tenuipalpidae), Tuckerellidae (Tuckerellidae), Ying Pi section (Ixodxdae) is (such as haemaphysalis longicornis (Haemaphysalis longicornis), haemaphysalis flava (Haemaphysalis flava), Dermacentor variabilis (Dermacentor variabilis), ixodes ovatus (Ixodes ovatus), ixodes persulcatus (Ixodes persulcatus), the hard tick of black leg (Ixodes scapularis), boophilus microplus (Boophilus microplus), lone star tick (Amblyomma americanum) and brown dog tick (Rhipicephalus sanguineus)), Tyroglyphidae (Acaridae) (such as tyrophagus putrescentiae (Tyrophagus putrescentiae)), Dermanyssidae (Dermanyssidae) (such as dust mite (Dermatophagoides farinae) and dermatophagoides pteronyssinus (Dermatophagoides ptrenyssnus)), cheyletidae (Cheyletidae) is (as Cheyletus eruditus (Cheyletus eruditus), Malacca cheyletid mite (Cheyletus malaccensis) and unauspicious cheyletid mite (Cheyletus moorei)), Dermanyssus gallinae (chicken mite) is (as ornithonyssus bacoti (Ornithonyssus bacoti), northern fowl mite (Ornithonyssus sylvairum) and Dermanyssus gallinae (Dermanyssusgallinae)), Trombidiidae (Trombiculidae) (as leptotrombidium akamushi (Leptotrombidium akamushi)) etc.,
Araneida (Araneae): Japanese red is bitten spider (Chiracanthium japonicum), redback spider (Latrodectus hasseltii), Tetragnathidae section (Tetragnathidae), eight knurl Chinese mugwort spiders (Cyclosa octotuberculata), Argiope amoena (Argiope amoena), golden spider (Argiope bruennichii), large abdomen circle spider (Araneus yentricosus), forest Atrax robustus (Agelena silvatica), black panther spider (Pardosa astrigera), yellowish-brown crafty spider (Dolomedes sulfurous), black panther spider (Pardosa astrigera), yellowish-brown crafty spider (Dolomedes sulfureus), black cat jumps spider (Carrhotus xanthogramma), spider (Achaearanea tepidariorum) is wished in greenhouse, stable gap spider (Coelotes insidiosus), Salticadae (Salticidae), hunting kingcrab spider (Heteropoda venatoria) etc.,
Chilopoda (Chilopoda): centipede (Centipedes) (as scutigera cleopatra (Thereuonema hilgendorfi), Vietnam giant centipede (Scolopendra subspinipes), Japanese sour jujube centipede (Scolopendra subspinipes japonica), the blind centipede of red sour jujube (Scolopocryptops rubiginosus) of becoming rusty, rough back of the body stone centipede (Bothropolys asperatus)) etc.;
Diplopoda (Diplopoda): julid (Millipedes) is (as greenhouse julid (Oxidus gracilis), red julid (Nedyopus tambanus), train julid (Parafontaria laminata laminata), train julid (Parafontaria laminata armigera), pointed tooth julid (Parafontaria acutidens), east band julid (Epanerchodus orientalis) etc.;
Isopoda (Isopoda): pillworm (Sow bugs) (as how white wax pillworm (Porcellionides pruinosus (Brandt)) and smooth pillworm (Porcellio scaberLatreille)), ball pillworm (Pill bugs) (as common volume beetle (Armadillidium vulgare)), extra large lice (Sea louses) (as extra large cockroach (Ligia exotica))) etc.;
Gastropoda (Gastropoda): tree slug (Limax marginatus) and yellow slug (Linax flavus) etc.
Pest control agent of the present invention comprises compound of the present invention and inert support.Conventionally pest control agent of the present invention is mixed with to preparation described below.The example of preparation comprises oily solution, emulsifiable concentrates, wettable powder, can flow preparation (for example, waterborne suspension, or water-based emulsion), microcapsule, powder agent, granula, aerosol, carbonic acid gas preparation, hot flashing preparation (for example, insecticidal incense coil, electricity pesticide tablet or imbibition core pattern hot flashing sterilant), piezoelectricity pesticide preparation, hot smoking agent (for example, self-ignition type fumigant, chemical reaction type fumigant or porous ceramic plate fumigant), that does not heat (for example evapotranspires preparation, the resin preparation that evapotranspires, the paper preparation that evapotranspires, the nonwoven fabric preparation that evapotranspires, knit goods evapotranspire preparation or distillation tablet), aerosol formulation (for example, atomization preparation), directly contact preparation (for example, sheet shape contact preparation, band shape contact preparation or net form contact preparation), ULV preparation and poison bait.
The example of the method for preparation comprises following methods.
(1) comprise compound of the present invention is mixed with solid carrier, liquid vehicle, gaseous carrier, poison bait etc., if need to add afterwards tensio-active agent and other auxiliary agents for preparation, and the method being further processed.
(2) comprise and will not contain the method for compound dipping of the present invention for the base material of activeconstituents.
(3) comprise compound of the present invention is mixed with base material, afterwards mixture is carried out the method for mold treatment.
Depend on dosage form, these preparations contain the compound of the present invention of 0.001 to 98 % by weight conventionally.
The example of the inert support using in preparation comprises inert solid carrier, inertia liquid carrier and inertia gaseous carrier.
The example of the solid carrier using in preparation comprises: clay (for example, kaolinton, diatomite, wilkinite, Fubasami clay or acid kaolin), synthetic oxidizing aqueous silicon, talcum, pottery, other inorganic minerals are (for example, sericite, quartz, sulphur, activated carbon, calcium carbonate or aqueous silicon dioxide) or fine powder or the particle of chemical fertilizer (for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ammonium chloride or urea) etc.; Material (for example, 2,4,6-triisopropyl-1,3,5-tri-in room temperature in solid form
alkane, naphthalene, santochlor, camphor or diamantane); And the felt, fiber, fabric, cloth, thin slice, paper, line, foam, porous material and the multifilament that comprise one or more materials in the group of selecting free the following composition: (for example, polyvinyl resin is as Low Density Polyethylene, straight-chain low density polyethylene and high density polyethylene(HDPE) for wool, silk, cotton, fiber crops, paper pulp, synthetic resins; Ethylene-vinyl ester copolymer is as vinyl-vinyl acetate copolymer; Ethylene-methyl acrylate multipolymer is as ethylene-methyl methacrylate methyl terpolymer and ethylene-methyl methacrylate ethyl ester multipolymer; Ethylene-acrylate copolymer is as ethylene-methyl acrylate copolymer and ethylene-ethyl acrylate copolymer; Vinyl-vinyl polymers of carboxylic acid is as ethylene-acrylic acid copolymer; Ethene-tetracyclododecane multipolymer; Acrylic resin is as alfon and propylene-ethylene copolymers; Poly--4-methylpentene-1, polybutene-1, polyhutadiene, polystyrene; Acrylonitrile styrene resin (AS); Acrylonitrile-butadiene-styrene resin; Styrenic elastomer is as styrene-conjugated diene segmented copolymer and hydrogenated styrene-conjugated diene block copolymer; Fluoro-resin; Acrylic resin is as polymethylmethacrylate; Polyamide resin is as nylon 6 and nylon 66; Vibrin is as polyethylene terephthalate, PEN, polybutylene terephthalate and poly-tetrahydrobenzene-terephthalic acid two methylene esters (polycyclohexylene dimethylene terephthalate); Or porous resin is as polycarbonate, polyacetal, polypropylene acyl group sulfone, polyarylate, hydroxy-benzoic acid polyester, polyimide, polyestercarbonate, polyhenylene ether resin, polyvinyl chloride, polyvinylidene dichloride, urethane, foamed polyurethane, foam polypropylene and foam ethene), glass, metal and pottery.
The example of liquid vehicle (for example comprises aromatic series or aliphatic hydrocrbon, dimethylbenzene, toluene, alkylnaphthalene, phenyl xylyl ethane, kerosene, light oil, hexane or hexanaphthene), halohydrocarbon (for example, chlorobenzene, methylene dichloride, ethylene dichloride or trichloroethane), alcohol (for example, methyl alcohol, ethanol, Virahol, butanols, hexanol, benzylalcohol or ethylene glycol), ether (for example, diethyl ether, glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, tetrahydrofuran (THF) or two
alkane), ester (for example, ethyl acetate or butylacetate), ketone (for example, acetone, methyl ethyl ketone, mibk or pimelinketone), nitrile (for example, acetonitrile or isopropyl cyanide), sulfoxide (for example, methyl-sulphoxide), acid amides (for example, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE or N-methyl-pyrrolidone), alkylene carbonates (for example, propylene carbonate), vegetables oil (for example, soybean oil or Oleum Gossypii semen), plants essential oil (for example, orange oil, Hyssop oil or lemon oil) and water.
The example of gaseous carrier comprises butane gas, Chlorofluorocarbons (CFCs), liquefied petroleum gas (LPG) (LPG), dme and carbonic acid gas.
The example of tensio-active agent comprises alkyl aryl ether, polyglycol ether, polyol ester and the sugar alcohol derivant of alkyl-sulphate, alkylsulfonate, alkylaryl sulphonate, alkyl aryl ether, polyoxyethylene.
The example of other auxiliary agents that preparation is used comprises tackiness agent, dispersion agent and stablizer.Specific examples comprises: casein, gelatin, polysaccharide are (for example, starch, Sudan Gum-arabic, derivatived cellulose or Lalgine), lignin derivative, wilkinite, carbohydrate, synthetic polymer (for example, polyvinyl alcohol or Polyvinylpyrolidone (PVP)), polyacrylic acid, BHT (2,6-, bis--tertiary butyl-4-cresols) and BHA (mixture of the 2-tertiary butyl-4-methoxyphenol and the 3-tertiary butyl-4-methoxyphenol).
Example for the base material of insecticidal incense coil comprises: plant powder is if wood powder and vinasse powder and tackiness agent are as the mixture of stacte material powder, starch and glutelin.
Example for the base material of electric pesticide tablet comprises: the sheet that the fibril of the sheet obtaining by sclerosis velveteen and the mixture by sclerosis velveteen and paper pulp obtains.
The example that is used for the base material of self-ignition type fumigant comprises that flammable heat release reagent is as nitrate, nitrite, guanidinesalt, Potcrate, Nitrocellulose, ethyl cellulose and wood powder; Thermolysis stimulant is as an alkali metal salt, alkaline earth salt, dichromate and chromic salt; Oxygen carrier is as saltpetre; Burning supporting agent is as trimeric cyanamide and flour starch; Extender is as diatomite, and tackiness agent is as synthetical glue.
The example that is used for the base material of chemical reaction type fumigant comprises that heat release reagent is as alkali metalsulphide, polysulfide, sulfhydrate and calcium oxide; Catalytic reagent is as carbonaceous material, iron carbide and alukalin; Organic foam agent is as Cellmic C 121, benzol sulfohydrazide, dinitropentamethylenetetramine, polystyrene and urethane; And filler is as natural fiber bar and synthetic fibre strip.
Comprise that as the resin example of resin that the base material of agent uses that evapotranspires polyvinyl resin is as Low Density Polyethylene, straight-chain low density polyethylene and high density polyethylene(HDPE); Ethylene-vinyl ester copolymer is as vinyl-vinyl acetate copolymer; Ethylene-methyl acrylate multipolymer is as ethylene-methyl methacrylate methyl terpolymer and ethylene-methyl methacrylate ethyl ester multipolymer; Ethylene-acrylate copolymer is as ethylene-methyl acrylate copolymer and ethylene-ethyl acrylate copolymer; Vinyl-vinyl polymers of carboxylic acid is as ethylene-acrylic acid copolymer; Ethene-tetracyclododecane multipolymer; Acrylic resin is as propylene copolymer and propylene-ethylene copolymers; Poly--4-methylpentene-1, polybutene-1, polyhutadiene, polystyrene, acrylonitrile styrene resin (AS); Acrylonitrile-butadiene-styrene resin; Styrenic elastomer is as the styrene-conjugated diene segmented copolymer of vinylbenzene-conjugated diene block copolymer and hydrogenation; Fluoro-resin; Acrylic resin is as polymethylmethacrylate; Polyamide resin is as nylon 6 and nylon 66; Vibrin is as polyethylene terephthalate, PEN, poly butylene succinate (polybutylene butalate) and poly-tetrahydrobenzene-terephthalic acid two methylene esters; Polycarbonate, polyacetal, polypropylene acyl group sulfone, polyarylate, hydroxy-benzoic acid polyester, polyetherimide, polyestercarbonate, polyhenylene ether resin, polyvinyl chloride, polyvinylidene dichloride and urethane.These base materials can use separately or being used in combination with two or more types.If needed, softening agent for example, can be added in these base materials as phthalic ester (, dimethyl phthalate, dioctyl phthalate (DOP) etc.), adipic acid ester and stearic acid.The resin agent of evapotranspiring can be prepared in the following manner: compound of the present invention is mixed with above-mentioned base material, mixture is mediated, afterwards it undertaken molded by injection moulding, extrusion molding or compression moulding.If needed, can carry out further molded or cutting step to obtained resin formulation, to be processed as sheet shape, film shape, with shape, net form or linear and so on shape.These resin formulation can be processed as to Animal neck ring, animal ear tag, sheet product, trap strips, gardening support and other products.
The example that is used for the base material of poison bait comprises that bait composition is as flour, vegetables oil, sugar and crystalline cellulose, antioxidant is as butylated hydroxytoluene and nordihydroguaiaretic acid, sanitas is as dehydroacetic acid (DHA), for the unexpected food rcstriction agent of children and pet as red chilly powder; Attract insects spices is as cheese spices, onion spice and peanut oil.
Insect pest control method of the present invention is conventionally for example, by being applied to insect or its habitat (plant materials by the compound of the present invention of significant quantity with the form of pest control agent of the present invention, soil, indoor, animal body, Che Nei or outdoor open space) carry out.
Comprise following methods for the method that applies pest control agent of the present invention, and depend on pest control agent of the present invention form, apply area etc. and suitably select.
(1) comprise the method that pest control agent former state of the present invention is applied to the habitat of insect or insect.
(2) comprise pest control agent of the present invention solvent as water dilutes, afterwards dilution is sprayed to the method for the habitat of insect or insect.
In this case, conventionally pest control agent of the present invention is configured to emulsifiable concentrates, wettable powder, preparation, microcapsule etc. can flow.Conventionally said preparation is diluted to make the concentration of compound of the present invention can be in 0.1 to 10,000ppm scope.
(3) comprise pest control agent of the present invention is heated in the habitat of insect, thus the method that makes activeconstituents volatilize and spread from pest control agent.
In this case, the applied amount of compound of the present invention and any of concentration can depend on pest control agent of the present invention formulation, apply the cycle, apply area or applying method, or the kind of insect, the destruction of causing etc. and suitably determine.
When pest control agent of the present invention is during for the prevention of epidemic disease, be in application to the amount that applies in the situation in space conventionally 0.0001 to 1,000mg/m
3the scope of compound of the present invention in, and be in application in the situation of plane 0.0001 to 1 000mg/m
2the scope of compound of the present invention in.The form that depends on preparation, insecticidal incense coil or electric pesticide tablet etc. volatilizees activeconstituents and is spread by heating, to reach application.Resin agent, paper agent, nonwoven fabric agent, the knit goods former state in the space that will apply such as agent or distillation tablet of evapotranspiring of evapotranspiring of evapotranspiring of evapotranspiring is left standstill, and place under air blows.
In the time pest control agent of the present invention being applied to space for preventing the object of epidemic disease, the example in space comprises closet, Japanese cupboard, Japanese cabinet, cupboard, lavatory, bathroom, goods shed, freight depot, living room, dining room, garage, automotive interior etc.Also pest control agent can be applied to outdoor open space.
When pest control agent of the present invention during as the epizoon of dog, cat, rat and mouse, can be applied to these animals by the currently known methods in veterinary applications as ox, horse, pig, sheep, goat and chicken and animalcule by pest control agent of the present invention for preventing and treating domestic animal.Particularly, in the time that needs system is prevented and treated, using pest control agent of the present invention as tablet, with mixture or the suppository of feed, or (comprise muscle, subcutaneous, vein and peritonaeum injection) by injecting and be administered to animal.On the other hand, in the time that needs nonsystematic is prevented and treated, pest control agent of the present invention is applied to animal in the following manner: the spraying of oil solution or the aqueous solution, topple over or smear processing, or with hair washing preparation washing animal, or necklace or ear tag that the agent of being evapotranspired by resin is made are placed to animal.In the situation that being administered to animal body, the dosage of compound of the present invention is conventionally in the weight of animals of every 1kg is 0.01 to 1,000mg scope.
In the time that pest control agent of the present invention is used for preventing and treating the insect in farmland, the example of applying method comprises spraying processing, soil treatment, seed treatment and immersion treatment.
When pest control agent of the present invention is when preventing and treating the insect in farmland, consumption can depend on the cycle of applying, applies area, applying method and other factors and vary widely, and with every 10,000m
2compound meter of the present invention is conventionally in 1 to 10,000g scope.In the time that pest control agent of the present invention is configured to emulsifiable concentrates, wettable powder, the preparation that can flow etc.; conventionally by pest control agent at dilute with water to make the concentration of activeconstituents become 0.01 to 10; after the scope of 000ppm, apply, and conventionally particle or pulvis are in statu quo applied.
Can by the water dilution Direct spraying of these preparations or preparation insect maybe to protect its be not subject to plant that insect affects as crop plants on, or it can be used in soil treatment with control and perch the insect on the soil of ploughing.
Apply also and can carry out by the following method: directly the resin formulation that is configured as sheet or wire or rope form preparation is twisted in around plant, preparation is placed near plant, or preparation is dispersed on the soil surface at root place.
Can be by compound of the present invention as ploughing as farm, rice field, lawn or orchard, or pest control agent in untilled ground.Compound of the present invention can be below plantation be prevented and treated the insect perching in arable land in the arable land etc. of " plant crop ".
Farm crop: corn, rice, wheat, barley, rye, oat, Chinese sorghum, cotton, soybean, peanut, buckwheat, sugar beet, Semen Brassicae campestris, Sunflower Receptacle, sugar are used sugarcane, tobacco etc.;
Vegetables: Solanaceae (Solanaceae) plant (eggplant, tomato, green pepper, capsicum, potato etc.), Curcurbitaceae (Cucurbitaceae) plant (cucumber, pumpkin, summer squash, watermelon, muskmelon etc.), Cruciferae (Cruciferae) plant (white turnip (Japanese radish), turnip, horseradish, thumb dish, Chinese cabbage, wild cabbage, leaf mustard, Caulis et Folium Brassicae capitatae, Cauliflower etc.), composite family (Compositae) plant (burdock, crowndaisy chrysanthemum, arithoke, lettuce etc.), Liliaceae (Liliaceae) plant (shallot, onion, garlic, asparagus etc.), umbelliferae (Umbelliferae) plant (Radix Dauci Sativae, parsley, celery, Selinum pastinaca etc.), Chenopodiaceae (Chenopodiaceae) plant (spinach, chard etc.), Labiatae (Labiatae) plant (Japanese purple perilla, peppermint, sweet basil etc.), strawberry, sweet potato, Chinese yam, aroid etc.,
Fruit tree: pomaceous fruits (apple, European pear, sand pear, pawpaw, Quinces Quince etc.), drupe class (peach, plum, peach are refuted Lee, Japanese plum, cherry, apricot, Lee etc.), hesperidium aurantium class (satsuma orange, tangerine, lemon, come lemon, natsudaidai etc.); Nuts (chestnut, English walnut, hazel, almond, Pistacia vera, cashew nut, Queensland nut etc.), berry fruit (cowberry, cranderry, blackberry, blueberry, Rubus idaeus etc.), grape, persimmon, olive, loquat, banana, coffee, nipa palm, coconut, oil palm etc.;
Other trees except fruit tree: tea, mulberry, xylophyta (rhododendron, camellia, silk ball, tea plum, star anise (Illicium religiosum), cherry tree, Liriodendron, crape myrtle, sweet-scented osmanthus etc.), shade tree (Ash, birch, Lai wood, eucalyptus, ginkgo, cloves, maple, oak, poplar, cercis, sweetgum, plane tree, beech tree, Japanese arbor-vitae, fir, Tsuga sieboldii, Chinese juniper, pine, dragon spruce, Ramulus et folium taxi cuspidatae, elm, horse-chestnut etc.), Jia Opulus, Podocarpus macrophyllus (Podocarpus macrophyllus), Japanese cypress, Japanese cypress, crotons, winged euonymus, hawthorn (Chinease howthorn) etc.,
Lawn: jielu grass (Japanese lawn grass, manilagrass etc.), Bermuda grass (honeysuckle Bermuda grass (Cynodon dactylon) etc.), bent grass (common bent grass, the bent grass (Agrostis stolonifera) of crawling, thin and delicate bent grass (Agrostis tenuis) etc.), annual bluegrass (English grass, rough stalked blue grass etc.), fescue grass (huge fescue grass, red fescue, red fescue etc. crawls), rye grass (lolium temulentum, rye grass etc.), orchardgrass, thimothy grass etc.,
Other: flower (rose, carnation, chrysanthemum, Lisianthus (purple Lisianthus), silk China pink, African daisy, mary bush, Salvia japonica Thunb., green winter eggplant, vervain, turmeric, aster, rough gentian, lily, wild pansy, Cyclamen persicum, Herba Orchidis Latifoliae, the lily of the valley, lavandula angustifolia, violet (stock), rape, Flower of Beltleaf Primrose, poinsettia gladiolus, Bowring cattleya, daisy, vervain, blue, Flower of Evans Begonia etc.), biofuel plant (manioca, red blue flower, flax shepherd's purse, switchgrass, awns (Miscanthus), Phalaris grass, giantreed, hibiscus cannabinus, cassava, willow etc.), ornamental foliage plant, Deng.
" plant crop " comprises transgenic plant crop above.
Compound of the present invention can mix or be used in combination with other insecticides, miticide, nematocides, soil pests control agent, mycocide, weedicide, plant-growth regulator, repellent, synergistic agent, fertilizer or soil modifier.
The example of this insecticide and acaricidal activeconstituents comprises:
(1) synthetic pyrethroid compound:
Acrinathrin (acrinathrin), allethrin (allethrin), betacyfluthrin (beta-cyfluthrin), bifenthrin (bifenthrin), cycloprothrin (cycloprothrin), cyfloxylate (cyfluthrin), cyhalothrin (cyhalothrin), Cypermethrin (cypermethrin), empenthrin (empenthrin), Deltamethrin (deltamethrin), S-fenvalerate (esfenvalerate), ether chrysanthemum ester (ethofenprox), Fenvalerate (fenpropathrin), fenvalerate (fenvalerate), flucythrinate (flucythrinate), trifluoro chrysanthemum ester (flufenoprox), flumethrin (flumethrin), taufluvalinate (fluvalinate), halfenprox (halfenprox), Imiprothrin (imiprothrin), permethrin (permethrin), prallethrin (prallethrin), pyrethrin (pyrethrins), resmethrin (resmethrin), effective cypermethrin (sigma-cypermethrin), salifluofen (silafluofen), tefluthrin (tefluthrin), tralomethrin (tralomethrin), transfluthrin (transfluthrin), Tetramethrin (tetramethrin), phenothrin (phenothrin), cyphenothrin (cyphenothrin), alphacypermethrin (alpha-cypermethrin), zeta-Cypermethrin (zeta-cypermethrin), lambda-cyhalothrin (lambda-cyhalothrin), essence lambda-cyhalothrin (gamma-cyhalothrin), PH (furamethrin), taufluvalinate (tau-fluvalinate), methoxy benzyl Flumethrin (metofluthrin), 2,2-dimethyl-3-(1-propenyl) cyclopropane-carboxylic acid [2,3,5,6-tetrafluoro-4-methyl-benzyl] ester, 2,2-dimethyl-3-(2-methyl-1-propylene base) cyclopropane-carboxylic acid [2,3,5,6-tetrafluoro-4-(methoxymethyl) benzyl] ester, 2,2,3,3-tetramethyl-cyclopropane-carboxylic acid [2,3,5,6-tetrafluoro-4-(methoxymethyl) benzyl] ester etc.,
(2) organo phosphorous compounds:
Acephate (acephate), aluminium phosphide (Aluminium phosphide), demethylation fourth Pyrimithate (butathiofos), cadusafos (cadusafos), chlorethoxyfos (chlorethoxyfos), Zaprawa enolofos (chlorfenvinphos), Chlorpyrifos 94 (chlorpyrifos), chlorpyrifos_methyl (chlorpyrifos-methyl), cynock (cyanophos (abbreviation CYAP)), diazinon (diazinon), DCIP (dichlorodiisopropyl ether), dichlofenthion (dichlofenthion (abbreviation ECP)), SD-1750 (dichlorvos (abbreviation DDVP)), Rogor (dimethoate), dimethylvinphos (dimethylvinphos), thiodemeton (disulfoton), EPN (EPN), Nialate (ethion), ethoprophos (ethoprophos), etrimfos (etrimfos), Tiguvon (fenthion (abbreviation MPP)), fenitrothion 95 (fenitrothion (abbreviation MEP)), lythidathion (fosthiazate), formothion (formothion), phosphuret-(t)ed hydrogen (hydrogen phosphide), isofenphos (isofenphos),
azoles phosphorus (isoxathion), Malathion (malathion), Tiguvon sulfoxide (mesulfenfos), methidathion (methidathion (abbreviation DMTP)), monocrotophos (monocrotophos), naled (naled (abbreviation BRP)), Thiometan (oxydeprofos (abbreviation ESP)), thiophos (parathion), Phosalone (phosalone), R-1504 (phosmet (abbreviation PMP)), pririmiphos_methyl (pirimiphos-methyl), pyridaphenthione (pyridafenthion), Resitox (quinalphos), Tsidial (phenthoate (abbreviation PAP)), Profenofos (profenofos), Kayaphos (propaphos), Toyodan (prothiofos), pyraclofos (pyraclorfos), dioxabenzofos (salithion), sulprofos (sulprofos), butyl pyrimidine phosphorus (tebupirimfos), temephos (temephos), tetrachlorvinphos (tetrachlorvinphos), terbufos (terbufos), thiometon (thiometon), Trichlorphon (trichlorphon (abbreviation DEP)), vamidothion (vamidothion), phorate (phorate), cadusafos (cadusafos) etc.,
(3) carbamate compounds:
Alanycarb (alanycarb),
worm prestige (bendiocarb), benfuracarb (benfuracarb), fenobucarb (BPMC), carbaryl (carbaryl), carbofuran (carbofuran), carbosulfan (carbosulfan), cloethocarb (cloethocarb), ethiofencarb (ethiofencarb), fenobucarb (fenobucarb), fenothiocarb (fenothiocarb), fenoxycarb (fenoxycarb), furathiocarb (furathiocarb), isoprocarb (isoprocarb (abbreviation MIPC)), meta-tolyl-N-methylcarbamate (MTMC) (metolcarb), methomyl (methomyl), methiocarb (methiocarb), carbaryl (NAC), oxamyl (oxamyl), Aphox (pirimicarb), Propoxur (propoxur (abbreviation PHC)), XMC (xMC), thiodicarb (thiodicarb), xylylcarb (xylylcarb), aldicarb (aldicarb) etc.,
(4) nereistoxin (Nereistoxin) compound:
Cartap (cartap), bensultap (bensultap), thiocyclam (thiocyclam), desinsection list (monosultap), disosultap (bisultap) etc.;
(5) anabasine compound:
Provado (imidacloprid), Ti304 (nitenpyram), acetamiprid (acetamiprid), Diacloden (thiamethoxam), thiacloprid (thiacloprid), MTI-446 (dinotefuran), clothianidin (clothianidin) etc.;
(6) benzoyl carbamide compound:
Fluorine pyridine urea (chlorfluazuron), two two flufenoxuron (bistrifluron), diafenthiuron (diafenthiuron), diflubenzuron (diflubenzuron), fluazuron (fluazuron), flucycloxuron (flucycloxuron), flufenoxuron (flufenoxuron), HEXAFLUMURON (hexaflumuron), lufenuron (lufenuron), fluorine uride (novaluron), noviflumuron (noviflumuron), fluorobenzene urea (teflubenzuron), triflumuron (triflumuron), triaxamate (triazuron) etc.,
(7) phenyl pyrazole compounds:
Acetyl worm nitrile (acetoprole), second worm nitrile (ethiprole), ethiprole (fipronil), methylene ethiprole (vaniliprole), pyridine ethiprole (pyriprole), pyrazine ethiprole (pyrafluprole) etc.;
(8) Bt toxin insecticide:
Derive from the spore alive of Bacillus thuringiensis (Bacillus thuringiesis) and the crystal toxin of being prepared by Bacillus thuringiensis, and their mixture;
(9) hydrazine compound:
Ring worm hydrazides (chromafenozide), chlorine worm hydrazides (halofenozide), methoxyfenozide (methoxyfenozide), worm hydrazides (tebufenozide) etc.;
(10) organochlorine compound:
Aldrin (aldrin), Dieldrin-attapulgite mixture (dieldrin), gram (dienochlor), 5a,6,9,9a-hexahydro-6,9-methano-2,4 (endosulfan), methoxychlor (methoxychlor) etc. everywhere;
(11) natural insecticide:
Machine oil, nicotine sulfate (nicotine-sulfate);
(12) other insecticides:
Avrmectin (avermectin-B), bromopropylate (bromopropylate), Buprofezin (buprofezin), Chlorfenapyr (chlorphenapyr), cyromazine (cyromazine), D-D (1,3-dichloropropylene), emamectin-benzoate (emamectin-benzoate), fenazaquin (fenazaquin), pyrrole fluorine sulphur phosphorus (flupyrazofos), hydroprene (hydroprene), methoprene (methoprene), indoxacarb (indoxacarb),
worm ketone (metoxadiazone), milbemectin (milbemycin-A), pymetrozine (pymetrozine), pyridine worm ether (pyridalyl), Nylar (pyriproxyfen), polyoxin (spinosad), sulfluramid (sulfluramid), Tolfenpyrad (tolfenpyrad), triaxamate (triazamate), Flubendiamide (flubendiamide), woods skin does not have fourth (lepimectin), arsenic acid, different thiophene worm azoles (benclothiaz), calcium cyanamide, calcium polysulfide, Niran (chlordane), dichlorodiphenyl trichloroethane (DDT), DSP, phonetic worm amine (flufenerim), flonicamid (flonicamid), phonetic worm amine (flurimfen), formetanate (formetanate), metaammonium (metam-ammonium), metamsodium (metam-sodium), monobromethane (methyl bromide), potassium oleate, propyl benzene hydrocarbon chrysanthemum ester (protrifenbute), Spiromesifen (spiromesifen), sulphur, metaflumizone (metaflumizone), spiral shell worm ethyl ester (spirotetramat), fluorine worm pyrrole quinoline (pyrifluquinazone), ethyl pleocidin (spinetoram), Rynaxypyr (chlorantraniliprole), bromine spiral shell nitrile (tralopyril) etc.
The example of the activeconstituents of repellent comprises N, N-diethyl-m-toluamide, limonene, linalool, geranial, menthol, piperitone, hinokitiol (hinokitiol), geraniol, eucalyptol, indoxacarb (indoxacarb), carane-3,4-glycol, MGK-R-326, MGK-R-874 and BAY-KBR-3023.
The example of the activeconstituents of synergistic agent comprises 5-[2-(2-butoxy oxyethyl group) ethoxyl methyl]-6-propyl group-1,3-benzo dioxole (benzodioxol), N-(2-ethylhexyl) dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboximide, eight chlorine dipropyl ethers, sulfo-cyanoacetic acid isobornyl and N-(2-ethylhexyl)-1-isopropyl-4-methyl dicyclo [2.2.2] be pungent-5-alkene-2, and 3-dicarboximide.
Embodiment
Below by preparation example, describe in more detail the present invention with reference to preparation example, formulation example and test case, but the invention is not restricted to these embodiment.
First, the preparation example of compound of the present invention is as follows.?
1in H-NMR, for example, the description list of " 1.17+1.18 (s+s, 3H) " is shown in 1.17ppm and 1.18ppm and exists the peak of substance, and the integrated value at these two peaks add up to 3H.
Preparation example 1
To 3-methylol-1-(2-propynyl) imidazolidine-2,4-diketone (252mg, 1.50mmol) with (1R)-trans-3-[(1E)-2-cyano group-2-methoxy-ethylene base]-2,2-dinethyl cyclopropane carboxylic acid (293mg, in chloroformic solution (5mL) 1.50mmol), add 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (302mg, 1.58mmol) and 4-dimethylaminopyridine (30mg).By reaction mixture after stirring at room temperature 12 hours, water is poured in reaction mixture, and is extracted with ethyl acetate the solution of gained.By organic layer process dried over mgso, and under reduced pressure concentrated subsequently, and resistates is carried out to silica gel column chromatography, obtain 2 of 210mg, 5-dioxy-3-(2-propynyl) imidazolidyl methyl 1-(1R)-trans-3-[(1E)-2-cyano group-2-methoxy-ethylene base)-2,2-dinethyl cyclopropane carboxylic acid ester (hereinafter, being called compound of the present invention (1)), it is expressed from the next:
Weak yellow liquid:
1h-NMR (CDCl
3, TMS) and δ (ppm): 1.17 (s, 3H), 1.32 (s, 3H), 1.58 (d, 1H), 2.27 (dd, 1H), 2.36 (d, 1H), 3.62 (s, 3H), 4.05 (s, 2H), 4.27 (d, 2H), 5.25 (d, 1H), 5.49-5.62 (dd, 2H)
Preparation example 2
3-methylol-1-(2-propynyl) imidazolidine-2,4-dione (193mg, 1.15mmol) is dissolved in tetrahydrofuran (THF) (3mL), and adds wherein the pyridine of 0.15mL.Under ice-cooled, in this solution, add (1R)-trans-3-[(1EZ)-2-cyano group-2-vinyl ethyl ether base]-2,2-dimethylcyclopropane formyl chloride (250mg, 1.10mmol, E: Z=2: tetrahydrofuran solution (1mL) 1).By reaction mixture after stirring at room temperature 12 hours, water is poured in reaction soln, and is extracted with ethyl acetate solution.Wash organic layer with 5% hydrochloric acid, saturated sodium bicarbonate aqueous solution and saturated brine successively, pass through subsequently dried over mgso.After under reduced pressure organic layer being concentrated, resistates is carried out to silicagel column column chromatography, obtain (1R)-trans-3-[(1EZ of 261mg)-2-cyano group-2-vinyl ethyl ether base]-2,2-dinethyl cyclopropane carboxylic acid 2,5-dioxy-3-(2-propynyl) imidazolidyl methyl esters (E: Z=2: 1) (hereinafter, be called compound of the present invention (2)), it is expressed from the next:
Weak yellow liquid:
1h-NMR (CDCl
3, TMS) and δ (ppm): 1.17+1.18 (s+s, 3H), 1.26-1.31 (m, 3H), 1.32+1.33 (s+s, 3H), 1.58 (d, 0.67H), 1.63 (d, 0.33H), 2.27 (m, 0.67H), 2.37 (m, 1H), 2.43-2.47 (m, 0.33H), 3.84 (q, 1.34H), 4.04 (q, 0.66H), 4.06 (m, 2H), 4.27 (m, 2H), 5.18 (d, 0.33H), 5.29 (d, 0.67H), 5.47-5.62 (m, 2H)
Preparation example 3
To (1R)-trans-3-[(1EZ obtaining in preparation example 2)-2-cyano group-2-(oxyethyl group) vinyl]-2, 2-dinethyl cyclopropane carboxylic acid 2, 5-dioxy-3-(2-propynyl) imidazolidyl methyl esters (E: Z=2: 1) carry out silica gel column chromatography (elutriant: hexane/ethyl acetate=2: 1), obtain (1R)-trans-3-[(1E that conduct has the cut of high polarity)-2-cyano group-2-vinyl ethyl ether base]-2, 2-dinethyl cyclopropane carboxylic acid 2.5-dioxy-3-(2-propynyl) imidazolidyl methyl esters (hereinafter, be called compound of the present invention (3)), it is expressed from the next:
Weak yellow liquid:
1h-NMR (CDCl
3, TMS) and δ (ppm): 1.17 (s, 3H), 1.24-1.31 (m, 3H), 1.33 (s, 3H), 1.58 (d, 1H), 2.27 (m, 1H), 2.37 (m, 1H), 3.84 (q, 2H), 4.05 (s, 2H), 4.27 (d, 2H), 5.29 (d, 1H), 5.49-5.62 (dd, 2H)
Preparation example 4
Except using 2-methylol-5-methyl-4-(2-propynyl)-2,4-dihydro-[1,2,4]-triazole-3-ketone replaces 3-methylol-1-(2-propynyl) imidazolidine-2, outside 4-diketone, operate in the mode identical with preparation example 1, obtain (1R)-trans-3-[(1E)-2-cyano group-2-vinyl ethyl ether base]-2,2-dinethyl cyclopropane carboxylic acid 3-methyl-5-oxo-4-(2-propynyl)-4,5-dihydro-[1,2,4]-triazolyl methyl esters (hereinafter, be called compound of the present invention (4)), it is expressed from the next:
Weak yellow liquid:
1h-NMR (CDCl
3, TMS) and δ (ppm): 1.17 (s, 3H), 1.24-1.31 (m, 3H), 1.32 (s, 3H), 1.61 (d, 1H), 2.29 (m, 1H), 2.34 (m, 1H), 2.35 (s, 3H), 3.84 (q, 2H), 4.43 (d, 2H), 5.23 (d, 1H), 5.68-5.81 (dd, 2H)
Preparation example 5
Except using (1R)-trans-3-[(1EZ)-2-cyano group-2-(isopropoxy) vinyl]-2, 2-dinethyl cyclopropane carboxylic acid (E: Z=4: 1) replace (1R)-trans-3-[(1E)-2-cyano group-2-methoxy-ethylene base]-2, outside 2-dinethyl cyclopropane carboxylic acid, operate in the mode identical with preparation example 1, obtain (1R)-trans-3-[(1EZ)-2-cyano group-2-(isopropoxy) vinyl]-2, 2-dinethyl cyclopropane carboxylic acid 2, 5-dioxy-3-(2-propynyl) imidazolidyl methyl esters (E: Z=78: 22) (hereinafter, be called compound of the present invention (5)), it is expressed from the next:
Colourless liquid:
1h-NMR (CDCl
3, TMS) and δ (ppm): 1.16-1.32 (m, 12H), 1.59-1.64 (m, 1H), 2.28 (m, 0.78H), 2.36 (m, 1H), 2.43-2.46 (m, 0.22H), 4.06 (s, 2H), 4.28 (d, 2H), 4.27-4.36 (m, 1H), 5.24 (d, 0.22H), 5.42 (d, 0.78H), 5.49-5.62 (m, 2H)
Preparation example 6
To (1R)-trans-3-[(1EZ obtaining in preparation example 5)-2-cyano group-2-(isopropoxy) vinyl]-2, 2-dinethyl cyclopropane carboxylic acid 2, 5-dioxy-3-(2-propynyl) imidazolidyl methyl esters (E: Z=78: 22) carry out silica gel column chromatography (elutriant: hexane/ethyl acetate=2: 1), obtain (1R)-trans-3-[(1E that conduct has the cut of high polarity)-2-cyano group-(isopropoxy) vinyl]-2, 2-dinethyl cyclopropane carboxylic acid 2, 5-dioxy-3-(2-propynyl) imidazolidyl methyl esters (hereinafter, be called compound of the present invention (6)), it is expressed from the next:
Colourless liquid:
1h-NMR (CDCl
3, TMS) and δ (ppm): 1.16 (s, 3H), 1.24-1.28 (m, 6H), 1.32 (s, 3H), 1.59 (d, 1H), 2.28 (m, 1H), 2.36 (m, 1H), 4.06 (s, 2H), 4.27-4.31 (m, 3H), 5.42 (d, 1H), 5.49-5.62 (m, 2H)
Preparation example 7
Except using 2-methylol-5-methyl-4-(2-propynyl)-2,4-dihydro-[1,2,4]-triazole-3-ketone replaces 3-methylol-1-(2-propynyl) imidazolidine-2, outside 4-diketone, operate in the mode identical with preparation example 1, obtain (1R)-trans-3-[(1E)-2-cyano group-2-methoxy-ethylene base]-2,2-dinethyl cyclopropane carboxylic acid 3-methyl-5-oxo-4-(2-propynyl)-4,5-dihydro-[1,2,4]-triazolyl methyl esters (hereinafter, be called compound of the present invention (7)), it is expressed from the next:
Weak yellow liquid:
1h-NMR (CDCl
3, TMS) and δ (ppm): 1.17 (s, 3H), 1.32 (s, 3H), 1.60 (d, 1H), 2.29 (m, 1H), 2.34 (m, 1H), 2.36 (s, 3H), 3.62 (s, 3H), 4.43 (d, 2H), 5.23 (d, 1H), 5.68-5.81 (dd, 2H)
Preparation example 8
Except using (1R)-trans-3-[(1EZ)-2-cyano group-2-(tert.-butoxy) vinyl]-2, 2-dinethyl cyclopropane carboxylic acid (E: Z=4: 1) replace (1R)-trans-3-[(1E)-2-cyano group-2-methoxy-ethylene base]-2, outside 2-dinethyl cyclopropane carboxylic acid, operate in the mode identical with preparation example 1, obtain (1R)-trans-3-[(1EZ)-2-cyano group-2-(tert.-butoxy) vinyl]-2, 2-dinethyl cyclopropane carboxylic acid 2, 5-dioxy-3-(2-propynyl) imidazolidyl methyl esters (E: Z=78: 22).
To (1R)-trans-3-[(1EZ)-2-cyano group-2-(tert.-butoxy) vinyl]-2, 2-dinethyl cyclopropane carboxylic acid 2, 5-dioxy-3-(2-propynyl) imidazolidyl methyl esters (E: Z=78: 22) carry out silica gel column chromatography (elutriant: hexane/ethyl acetate=2: 1), acquisition has cut (1R)-trans-3-[(1E of high polarity)-2-cyano group-(tert.-butoxy) vinyl]-2, 2-dinethyl cyclopropane carboxylic acid 2, 5-dioxy-3-(2-propynyl) imidazolidyl methyl esters (hereinafter, be called compound of the present invention (8)), it is expressed from the next:
Colourless liquid:
1h-NMR (CDCl
3, TMS) and δ (ppm): 1.16 (s, 3H), 1.28 (s, 9H), 1.32 (s, 3H), 1.59 (d, 1H), 2.28 (m, 1H), 2.36 (m, 1H), 4.06 (s, 2H), 4.27-4.31 (m, 2H), 5.42 (d, 1H), 5.49-5.62 (m, 2H)
Show the particular compound different from above-claimed cpd below.
(example compound 1)
(1R)-trans-3-[(1E)-2-cyano group-2-(propoxy-) vinyl]-2,2-dinethyl cyclopropane carboxylic acid 2,5-dioxy-3-(2-propynyl) imidazolidyl methyl esters, it is expressed from the next:
(example compound 2)
(1R)-trans-3-[(1EZ)-2-cyano group-2-methoxy-ethylene base]-2,2-dinethyl cyclopropane carboxylic acid 2,5-dioxy-3-(2-propynyl) imidazolidyl methyl esters (E: Z=1: 1), it is expressed from the next:
(example compound 3)
(1R)-trans-3-[(1EZ)-2-cyano group-2-vinyl ethyl ether base]-2,2-dinethyl cyclopropane carboxylic acid 2,5-dioxy-3-(2-propynyl) imidazolidyl methyl esters (E: Z=1: 1), it is expressed from the next:
(example compound 4)
(1R)-trans-3-[(1EZ)-2-cyano group-2-methoxy-ethylene base]-2,2-dinethyl cyclopropane carboxylic acid 2,5-dioxy-3-(2-propynyl) imidazolidyl methyl esters (E: Z=2: 1), it is expressed from the next:
Then, show the reference preparation example about the preparation of intermediate (it is for the preparation of the compound of the invention described above) below.
With reference to preparation example 1
Sodium hydride (55.2%, oil dispersion) (0.42g, 9.7mmol) is added in round-bottomed flask, and add wherein the anhydrous tetrahydro furan of 15mL.Under ice-cooled, under nitrogen atmosphere, drip wherein the solution that is dissolved in methoxyl group (cyano group) the methyl acid phosphate diethyl ester (2.0g, 9.7mmol) in anhydrous tetrahydro furan (5mL).Under ice-cooled, stirred reaction mixture 30 minutes, and stir again 1 hour at 25 ℃.Drip wherein (1R)-trans-3-formyl radical-2 that are dissolved in anhydrous tetrahydro furan (5mL), the solution of 2-dinethyl cyclopropane carboxylic acid methyl esters (1.40g, 9.0mmol).After mixture being stirred to 2 hours at 25 ℃, reaction soln is joined in the mixing solutions being made up of 5% hydrochloric acid of 10mL and the frozen water of 30mL, and use the ethyl acetate of 50mL by reaction mixture extracting twice at every turn.The ethyl acetate layer of gained is merged, and wash with the saturated brine of saturated sodium bicarbonate aqueous solution and 30mL successively, and through dried over mgso.The solution of gained is under reduced pressure concentrated, and resistates is carried out to silica gel column chromatography, obtain 480mg as (1R)-trans-3-[(1E of cut with high polarity)-2-cyano group-2-methoxy-ethylene base]-2,2-dinethyl cyclopropane carboxylic acid methyl esters, it is expressed from the next:
Colourless liquid:
1h-NMR (CDCl
3, TMS) and δ (ppm): 1.19 (s, 3H), 1.31 (s, 3H), 1.61 (m, 1H), 2.27 (m, 1H), 3.63 (s, 3H), 3.70 (s, 3H), 5.29 (d, 1H)
Also obtain 591mg as (1R)-trans-3-[(1Z of cut with lower polarity)-2-cyano group-2-methoxy-ethylene base]-2,2-dinethyl cyclopropane carboxylic acid methyl esters, it is expressed from the next:
Colourless liquid:
1h-NMR (CDCl
3, TMS) and δ (ppm): 1.31 (s, 3H), 1.35 (s, 3H), 1.66 (m, 1H), 2.46 (m, 1H), 3.69 (s, 3H), 3.77 (s, 3H), 5.21 (d, 1H)
(with reference to preparation example 2)
By (1R)-trans-3-[(1E)-2-cyano group-2-methoxy-ethylene base]-2,2-dinethyl cyclopropane carboxylic acid methyl esters (463mg, 2.2mmol) be dissolved in the mixture solution being formed by the methyl alcohol of 1.5mL and the water of 0.5mL, and add wherein subsequently potassium hydroxide (200mg, 3.6mmol), and by reaction mixture stirring at room temperature 12 hours.Reaction soln is added in the frozen water of 20mL, and with the ethyl acetate extractive reaction mixture of 20mL.In the water layer of gained, adding hydrochloric acid, is pH2 until make water layer, and subsequently with twice, the mixture of 20mL ethyl acetate extraction gained.The ethyl acetate layer of gained is merged, and by the saturated brine washed twice of 20mL, and pass through subsequently dried over mgso.Solution is under reduced pressure concentrated, obtain 336mg (1R)-trans-3-[(1E)-2-cyano group-2-methoxy-ethylene base]-2,2-dinethyl cyclopropane carboxylic acid, it is expressed from the next:
Light yellow crystal:
1h-NMR (CDCl
3, TMS) and δ (ppm): 1.22 (s, 3H), 1.36 (s, 3H), 1.62 (d, 1H), 2.32 (m, 1H), 3.64 (s, 3H), 5.29 (d, 1H)
(with reference to preparation example 3)
Sodium hydride (50.0%, oil dispersion) (1.56g, 32.5mmol) is added in 200mL round-bottomed flask, and add wherein the anhydrous tetrahydro furan of 43mL.Under ice-cooled, under nitrogen atmosphere, drip wherein the solution that is dissolved in oxyethyl group (cyano group) the methyl acid phosphate diethyl ester in anhydrous tetrahydro furan (11mL).Ice-cooled lower to reaction mixture stirring 40 minutes, and stir again one hour at 25 ℃.Drip wherein (1R)-trans-3-formyl radical-2 that are dissolved in anhydrous tetrahydro furan (11mL), the solution of 2-dinethyl cyclopropane carboxylic acid methyl esters (3.17g, 20.3mmol).At 25 ℃, reaction mixture was stirred after 12 hours, reaction soln is joined in mixing solutions be made up of 5% hydrochloric acid of 10mL and the frozen water of 100mL, and extract twice, the mixture of gained at every turn by the ethyl acetate of 100mL.The ethyl acetate layer of gained is merged, and wash with the saturated brine of saturated sodium bicarbonate aqueous solution and 50mL successively, and pass through subsequently dried over mgso.The mixture of gained is under reduced pressure concentrated, and resistates is carried out to silica gel column chromatography, obtain 6.00g (1R)-trans-3-[(1EZ)-2-cyano group-2-vinyl ethyl ether base]-2,2-dinethyl cyclopropane carboxylic acid methyl esters (E: Z=2: 1), it is expressed from the next:
Colourless liquid:
1h-NMR (CDCl
3, TMS) and δ (ppm); 1.18+1.19 (s+s, 3H), 1.29+1.31 (s+s, 3H), 1.29-1.34 (m, 3H), 1.61 (d, 0.67H), 1.65 (d, 0.33H), 2.25-2.29 (m, 0.67H), 2.42-2.46 (m, 0.33H), 3.69+3.70 (s+s, 3H), 3.83 (q, 1.34H), 4.03 (q, 0.66H), 5.24 (d, 0.33H), 5.34 (d, 0.67H)
(with reference to preparation example 4)
To 4.0g at (1R) that obtain with reference to preparation example 3-trans-3-[(1EZ)-2-cyano group-2-vinyl ethyl ether base]-2,2-dinethyl cyclopropane carboxylic acid methyl esters (E: Z=2: 1) carry out silica gel column chromatography (elutriant: hexane/ethyl acetate=10: 1), obtain 2.91g as (1R)-trans-3-[(1E of cut with high polarity)-2-cyano group-2-vinyl ethyl ether base]-2,2-dinethyl cyclopropane carboxylic acid methyl esters, it is expressed from the next:
Colourless liquid:
1h-NMR (CDCl
3, TMS) and δ (ppm): 1.18 (s, 3H), 1.31 (s, 3H), 1.29-1.33 (m, 3H), 1.61 (d, 1H), 2.25-2.29 (m, 1H), 3.70 (s, 3H), 3.83 (q, 2H), 5.34 (d, 1H)
(with reference to preparation example 5)
By (1R)-trans-3-[(1E)-2-cyano group-2-vinyl ethyl ether base]-2,2-dinethyl cyclopropane carboxylic acid methyl esters (2.91g, 13.0mmol) be dissolved in the mixing solutions being formed by the methyl alcohol of 17mL and the water of 6mL, and add wherein subsequently potassium hydroxide (1.56g, 27.9mmol), and by reaction mixture stirring at room temperature 12 hours.The reaction soln of gained is joined in the frozen water of 45mL, and extract the mixture of gained by the ethyl acetate of 45mL.In the water layer of gained, adding hydrochloric acid, is pH2 until make water layer, and subsequently with twice, the mixture of the ethyl acetate extraction gained of 45mL.The ethyl acetate layer of gained is merged, and by the saturated brine washed twice of 50mL, and pass through subsequently dried over mgso.The solution of gained is under reduced pressure concentrated, (1R)-trans-3-[(1E of acquisition 2.64g)-2-cyano group-2-vinyl ethyl ether base]-2,2-dinethyl cyclopropane carboxylic acid, it is expressed from the next:
White crystal:
1h-NMR (CDCl
3, TMS) and δ (ppm): 1.21 (s, 3H), 1.33 (s, 3H), 1.31-1.35 (t, 3H), 1.66 (d, 1H), 2.46 (m, 1H), 4.05 (q, 2H), 5.24 (d, 1H)
With reference to preparation example 6
To (1R)-trans-3-[(1EZ)-2-cyano group-2-vinyl ethyl ether base]-2,2-dinethyl cyclopropane carboxylic acid (E: Z=2: 1) (500mg, 2.39mmol) in, add the toluene of 3mL, add subsequently thionyl chloride (370mg, 3.11mmol), and further add the N of 10mg, dinethylformamide, and at the internal temperature of 60 to 70 ℃, reaction mixture is stirred 4 hours.Reaction soln is left standstill and is cooled to room temperature, and under reduced pressure concentrated, obtain (1R)-trans-3-[(1EZ of 550mg)-2-cyano group-2-vinyl ethyl ether base]-2,2-dimethylcyclopropane formyl chloride (E: Z=2: 1), it is expressed from the next:
With reference to preparation example 7
Except using isopropoxy (cyano group) methyl acid phosphate diethyl ester to replace oxyethyl group (cyano group) methyl acid phosphate diethyl ester, with with react with reference to the identical mode of preparation example 3, obtain (1R)-trans-3-[(1EZ)-2-cyano group-2-(isopropoxy) vinyl]-2,2-dinethyl cyclopropane carboxylic acid methyl esters (E: Z=4: 1), it is expressed from the next:
Colourless liquid:
1h-NMR (CDCl
3, TMS) and δ (ppm): 1.19-1.31 (m, 12H), 1.62 (d, 0.8H), 1.65 (d, 0.2H), 2.28 (m, 0.8H), 2.43 (m, 0.2H), 3.69+3.70 (s+s, 3H), 4.29 (q, 0.8H), 4.37 (q, 0.2H), 5.29 (d, 0.2H), 5.46 (d, 0.8H)
With reference to preparation example 8
Except using (1R)-trans-3-[(1EZ)-2-cyano group-2-isopropoxy vinyl]-2,2-dinethyl cyclopropane carboxylic acid methyl esters replaces (1R)-trans-3-[(1E)-2-cyano group-2-vinyl ethyl ether base]-2, outside 2-dinethyl cyclopropane carboxylic acid methyl esters, with with react with reference to the identical mode of preparation example 5, obtain (1R)-trans-3-[(1EZ)-2-cyano group-2-isopropoxy vinyl]-2,2-dinethyl cyclopropane carboxylic acid (E: Z=4: 1), it is expressed from the next:
Faint yellow solid:
1h-NMR (CDCl
3, TMS) and δ (ppm): 1.20-1.36 (m, 12H), 1.62 (d, 0.8H), 1.66 (d, 0.2H), 2.31 (m, 0.8H), 2.48 (m, 0.2H), 4.30 (q, 0.8H), 4.39 (q, 0.2H), 5.29 (d, 0.2H), 5.46 (d, 0.8H)
Then, the method for the preparation of the phosphate compound being represented by formula (6) is below described:
Wherein R
3represent identical meanings as above.
According in J.Org.Chem. (1976), 41 volumes, the method described in 2846-2849 page, synthetic by R wherein
3represent the compound of formula (6) expression of methyl, that is, and methoxyl group (cyano group) methyl acid phosphate diethyl ester.Also according at J.Org.Chem. (1976) 41 volumes, the method described in 2846-2849 page, except using oxyethyl group acetonitrile, propoxy-acetonitrile or isopropoxy acetonitrile to replace methoxyacetonitrile, synthetic by R wherein similarly
3represent the phosphate compound of formula (6) expression of ethyl, propyl group or sec.-propyl,, oxyethyl group (cyano group) methyl acid phosphate diethyl ester, propoxy-(cyano group) methyl acid phosphate diethyl ester or isopropoxy (cyano group) methyl acid phosphate diethyl ester.
Show formulation example below.Umber in mass.
Formulation example 1
The compound of the present invention (1) of 20 (20) parts is dissolved in separately to (8) in the dimethylbenzene of 65 parts, and by the SOLPOL3005X of 15 parts (TOHO Chemical Industry Co., Ltd. registered trademark) add wherein, and thoroughly mix to obtain emulsifiable concentrates by stirring.
Formulation example 2
The SORPOL3005X of five (5) parts is added in each of compound of the present invention (1) to (8) of 40 parts, and mixture is thoroughly mixed, and by the CARPLEX#80 of 32 parts (synthetic oxidizing aqueous silicon, SHIONOGI & CO., LTD. registered trademark) and the 300 order diatomite of 23 parts add wherein, by being uniformly mixed of mixing tank, obtain wettable powder afterwards.
Formulation example 3
By the compound of the present invention (1) to (8) of 1.5 parts separately with TOKUSIL GUN (the synthetic oxidizing aqueous silicon of 1 part, produced by Tokuyama Corporation), the REAX85A (sodium lignosulfonate of 2 parts, produced by West Vaco Chemicals), the BENTONITE FUJI (wilkinite of 30 parts, produced by Houjin) and 65.5 parts of SHOUKOUZAN A clay (kaolinton, produced by Shoukouzan Kougyousho) mixture thoroughly clay into power and mix, and water is added wherein.Mixture is thoroughly mediated, by extruding granulator granulation, dry afterwards, obtain 1.5% granule.
Formulation example 4
To the compounds of the present invention (1) to (8) of 10 parts separately with the phenyl xylyl ethane of 10 parts and the SUMIDUR L-75 (tolylene diisocyanate of 0.5 part, by Sumitomo Bayer Urethane Co., Ltd. produce) mixture in, add 10% Arabic gum aqueous solution of 20 parts, and mixture is stirred with homogenizer, obtain the emulsion of the median size with 20 μ m.Add 2 parts of ethylene glycol and mixture is further stirred in the temperature of 60 ℃ of temperature is bathed to 24 hours to obtain microcapsule slurry to emulsion.On the other hand, the VEEGUM R of the xanthan gum of 0.2 part and 1.0 parts (neusilin, by Sanyo Chemical Industries, Ltd. produces) is dispersed in the ion exchanged water of 56.3 parts to obtain thickening fluid.Afterwards, the above-mentioned thickening fluid of the above-mentioned microcapsule slurry of 42.5 parts and 57.5 parts mixed and obtain microcapsule.
Formulation example 5
The compound of the present invention (1) to (8) of 10 parts is added in 10% Aqueous Solutions of Polyethylene Glycol of 20 parts with the mixture of the phenyl xylyl ethane of 10 parts separately, and mixture is stirred by mixing tank, obtain the emulsion of the median size with 3 μ m.On the other hand, the VEEGUM R of the xanthan gum of 0.2 part and 1.0 parts (magnesium aluminum silicate, by Sanyo Chemical Industries, Ltd. produces) is dispersed in the ion exchanged water of 58.8 parts to obtain thickening fluid.Afterwards, the above-mentioned thickening fluid of the above-mentioned emulsion solution of 40 parts and 60 parts mixed and obtain the preparation that can flow.
Formulation example 6
In each of the compounds of the present invention (1) to (8) of 5 parts, add CARPLEX#80 (the synthetic oxidizing aqueous silicon of 3 parts, SHIONOGI & CO., LTD. registered trademark), the PAP (mixture of mono phosphoric acid ester isopropyl ester and diisopropyl phosphate) of 0.3 part and the talcum (300 order) of 91.7 parts, mixture is stirred and is obtained pulvis by mixing tank.
Formulation example 7
The compound of the present invention (1) of 0. 1 (0.1) parts is dissolved in separately to (8) in the methylene dichloride of 10 parts, and solution is mixed with the deodorized kerosine of 89.9 parts and obtain oily solution.
Formulation example 8
The compound of the present invention (1) to (8) of 0. 1 (0.1) parts is mixed and dissolved with the deodorized kerosine of 39.9 parts separately, and solution is filled in aerosol container, and mounted valve part.Afterwards, the energy propelling agent (liquefied petroleum gas (LPG)) of 60 parts is filled in wherein by valve part under pressure, to obtain oil base aerosol formulation.
Formulation example 9
By the compound of the present invention (1) to (8) of 0. 6 (0.6) parts separately with the dimethylbenzene of 5 parts, the deodorized kerosine of 3.4 parts and the Reodol MO-60 (emulsifying agent of 1 part, the registered trademark of Kao Corporation) elder brother merges dissolving, and the water of the solution of gained and 50 parts is filled in aerosol container, afterwards the energy propelling agent (liquefied petroleum gas (LPG)) of 40 parts is inserted wherein by valve part under pressure, obtained waterborne aerosol agent formulation.
Formulation example 10
The compound of the present invention (1) of 0. 3 (0.3) g is dissolved in the acetone of 20mL separately to (8), and the solution of gained is under agitation evenly mixed with the base material for incense coil (by Tabu powder, pyrethrum slag (mark) and wood powder are mixed to acquisition with the ratio of 4: 3: 3) of 99.7g.Afterwards, the water of 100mL is added wherein, and by mixture thoroughly mediate, dry and molded, obtain insecticidal incense coil.
Formulation example 11
The compound of the present invention (1) to (8) of 0.8g is dissolved in acetone with the mixture of the piperonyl butoxide of 0.4g separately, and cumulative volume is adjusted to 10ml.Afterwards, this solution of 0.5mL is flooded equably to the base material for electrically heated pesticide tablet with the size of 2.5cm × 1.5cm and the thickness of 0.3cm (sheet that the fibril sclerosis of the mixture of velveteen and paper pulp is obtained), obtain electrically heated insecticidal mat.
Formulation example 12
The compounds of this invention by by 3 parts (1) is dissolved in separately to the solution obtaining in the deodorized kerosine of 97 parts is poured in the container of being made up of vinylchlorid to (8).Its top can be inserted wherein by the wick of heater heats (with the inorganic flour of tackiness agent sclerosis sintering), obtain the parts that use for imbibition core pattern heat evaporating device.
Formulation example 13
The compounds of this invention of 100 (100) mg (1) is dissolved in the acetone of appropriate amount separately to (8), and the solution of gained is soaked into and obtains hot smoking agent to having in the size of 4.0cm × 4.0cm and the porous ceramic plate of 1.2cm thickness.
Formulation example 14
The compounds of this invention of 100 (100) μ g (1) is dissolved in separately to (8) in the acetone of appropriate amount, and the solution of gained is applied to equably and has the size of 2cm × 2cm and the filter paper of 0.3mm thickness, and dry air is to remove acetone, thereby the volatile reagent of acquisition for using in room temperature.
Formulation example 15
The compounds of this invention (1) to (8) of ten (10) parts separately with 35 parts of white carbon blacks (the Voranol EP 2001 ammonium sulfate that contains 50 parts), and the water of 55 parts mixes, levigate by wet milling process afterwards, obtain 10% mobility preparation.
Then test case, has illustrated that compound of the present invention is effective as the activeconstituents of pest control agent.
Test case 1
Each each 0.00156 part of compound of the present invention (1) to (5) is dissolved in 10 parts of Virahols, and the solution of gained is mixed with 89.998 parts of deodorized kerosines, to prepare the oily solution of 0.00156% (w/v).
By ten (10) only adult Groton bug (Blattella germanica, 5 male and 5 female) be discharged into (diameter 8.75cm in the test container that is coated with butter on its internal surface, height 7.5cm, lower surface is made up of 16 order metal wires), and container is placed on to the bottom (lower surface: 46cm × 46cm, highly: 70cm) of test cabinet.Use fog gun with 0.42kg/cm
2pressure from the each 1.5mL of the high 60cm of container end face spraying compound of the present invention (1) to (5) oily solution separately.Spraying after 30 seconds, container is pulled out from test cabinet, and cockroach is transferred in clean polyethylene cup.After specific time, number and the definite rate of knockdown (repeating twice) of the cockroach that number goes out to knock down.Calculate rate of knockdown by following formula.
Rate of knockdown (%)=(number of number/test cockroach of the cockroach of knocking down) × 100
As the contrast for comparing, to test with above identical mode, difference is to use (1R)-trans-3-(2-methyl-1-propylene base)-2,2-dinethyl cyclopropane carboxylic acid 2,5-dioxy-3-(2-propynyl) imidazolidyl methyl esters (at Pesticide Science, the compound of describing in 10,291 pages (1979), hereinafter referred to as comparative compound (1)), it is expressed from the next:
(1R)-cis-3-((Z)-2-cyano group-2-methoxy-ethylene base)-2,2-dinethyl cyclopropane carboxylic acid 2,5-dioxy-3-(2-propynyl) imidazolidyl methyl esters (compound of describing in JP-A-60-16962, hereinafter referred to as comparative compound (2)), it is expressed from the next:
With
(1R)-trans-3-(2-methyl-1-propylene base)-2,2-dinethyl cyclopropane carboxylic acid 3-methyl-5-oxo-4-(2-propynyl)-4,5-dihydro-[1,2,4]-triazolyl methyl esters (compound of describing in JP-A-57-158765, hereinafter referred to as comparative compound (3)), it is expressed from the next:
Result (spraying 0.7 minute afterwards) is shown in Table 1.
Table 1
| Test compounds | The rate of knockdown (%) of 0.7 minute after spraying |
| Compound of the present invention (1) | 95 |
| Compound of the present invention (2) | 85 |
| Compound of the present invention (3) | 90 |
| Compound of the present invention (4) | 75 |
| Compound of the present invention (5) | 80 |
| Comparative compound (1) | 50 |
| Comparative compound (2) | 45 |
| Comparative compound (3) | 10 |
Test case 2
Each each 0.00625 part of compound of the present invention (1) to (8) is dissolved in 10 parts of Virahols, and the solution of gained is mixed with 89.99375 parts of deodorized kerosines, to prepare the oily solution of 0.00625% (w/v).
By ten (10) only adult Groton bug (Blattella germanica, 5 male and 5 female) be discharged into (diameter 8.75cm in the test container that is coated with butter on its internal surface, height 7.5cm, lower surface is made up of 16 order metal wires), and container is placed on to the bottom (lower surface: 46cm × 46cm, highly: 70cm) of test cabinet.Use fog gun with 0.42kg/cm
2pressure from the each 1.5mL of the high 60cm of container end face spraying compound of the present invention (1) to (8) oily solution separately.Spraying after 30 seconds, container is pulled out in test cabinet, and cockroach is transferred in clean polyethylene cup.After specific time, number and the definite rate of knockdown (repeating twice) of the cockroach that number goes out to knock down.Calculate rate of knockdown by following formula.
Rate of knockdown (%)=(number of number/test cockroach of the cockroach of knocking down) × 100
Result (spraying 0.7 minute afterwards) is shown in Table 2.
Table 2
| Test compounds | The rate of knockdown (%) of 0.7 minute after spraying |
| Compound of the present invention (1) | 100 |
| Compound of the present invention (2) | 100 |
| Compound of the present invention (3) | 100 |
| Compound of the present invention (4) | 100 |
| Compound of the present invention (5) | 100 |
| Compound of the present invention (6) | 100 |
| Compound of the present invention (7) | 100 |
| Compound of the present invention (8) | 100 |
Test case 3
Each each 0.1 part of compound of the present invention (1) to (8) is dissolved in 10 parts of Virahols, and the solution of gained is mixed with 89.9 parts of deodorized kerosines, to prepare the oily solution of 0.1% (w/v).
By six (6) only adult periplaneta americana (Periplaneta americana, 3 male and 3 female) be discharged into test container (the diameter 12.5cm that is coated with butter on its internal surface, height 10cm, lower surface is made up of 32 order metal wires) in, and container is placed on to the bottom (lower surface: 46cm × 46cm, highly: 70cm) of test cabinet.Use fog gun with 0.42kg/cm
2pressure from the each 1.5mL of the high 60cm of container end face spraying compound of the present invention (1) to (8) oily solution separately.Spraying after 30 seconds, container is pulled out in test cabinet, and cockroach is transferred in clean polyethylene cup.After specific time, number and the definite rate of knockdown (repeating twice) of the cockroach that number goes out to knock down.Calculate rate of knockdown by following formula.
Rate of knockdown (%)=(number of number/test cockroach of the cockroach of knocking down) × 100
Result (spraying 5 minutes afterwards) is shown in Table 3.
Table 3
| Test compounds | The rate of knockdown (%) of 5 minutes after spraying |
| Compound of the present invention (1) | 100 |
| Compound of the present invention (2) | 100 |
| Compound of the present invention (3) | 100 |
| Compound of the present invention (4) | 100 |
| Compound of the present invention (5) | 100 |
| Compound of the present invention (6) | 100 |
| Compound of the present invention (7) | 92 |
| Compound of the present invention (8) | 100 |
Test case 4
Each each 0.1 part of compound of the present invention (1) to (7) is dissolved in 10 parts of Virahols, and the solution of gained is mixed with 89.9 parts of deodorized kerosines, to prepare the oily solution of 0.1% (w/v).
By ten (10) only adult housefly (Musca domestica, 5 male and 5 female) be discharged into bottom and be covered with polyethylene cup (the lower diameter 10.6cm of filter paper, upper diameter 12cm, height 7cm) in, and cover this polyethylene cup with 16 order nylon gauzes.This glass is placed on to the bottom (lower surface: 46cm × 46cm, highly: 70cm) of test cabinet.Use fog gun with 0.9kg/cm
2pressure from than the each 1.5mL of the high 30cm of the end face of cup spraying compound of the present invention (1) to (7) oily solution separately.After spraying, at once cup is pulled out from test cabinet.After specific time, number and the definite rate of knockdown (repeating twice) of the housefly that number goes out to knock down.
The results are shown in table 4.
Table 4
| Test compounds | The rate of knockdown (%) of 1 minute after spraying |
| Compound of the present invention (1) | 100 |
| Compound of the present invention (2) | 100 |
| Compound of the present invention (3) | 100 |
| Compound of the present invention (4) | 100 |
| Compound of the present invention (5) | 100 |
| Compound of the present invention (6) | 100 |
| Compound of the present invention (7) | 100 |
Test case 5
Each each 0.00625 part of compound of the present invention (1) to (7) is dissolved in 10 parts of Virahols, and the solution of gained is mixed with 89.99375 parts of deodorized kerosines, to prepare 0.00625 part of (w/v) oily solution.
Ten (10) the female common house mosquitos (Culex pipens pallens) of only growing up are discharged in polyethylene cup (lower diameter 10.6cm, upper diameter 12cm, height 7cm), and cover this cup with 16 order nylon gauzes.This glass is placed on to the bottom (lower surface: 46cm × 46cm, highly: 70cm) of test cabinet.Use fog gun with 0.4kg/cm
2pressure from than the each 1.5mL of the high 30cm of the end face of cup spraying compound of the present invention (1) to (7) oily solution separately.After spraying, at once cup is pulled out from test cabinet, and at the appointed time, number and definite rate of knockdown (repeating twice) of the common house mosquito that number goes out to knock down.
The results are shown in table 5.
Table 5
| Test compounds | The rate of knockdown (%) of 0.5 minute after spraying |
| Compound of the present invention (1) | 100 |
| Compound of the present invention (2) | 100 |
| Compound of the present invention (3) | 100 |
| Compound of the present invention (4) | 100 |
| Compound of the present invention (5) | 100 |
| Compound of the present invention (6) | 100 |
| Compound of the present invention (7) | 100 |
Industrial applicibility
Compound of the present invention has outstanding pest controling effect, therefore can be used as the activeconstituents of pest control agent.
Claims (18)
1. the ester cpds being represented by formula (1):
Wherein
Q represents N (CH
2c ≡ CH)-CH
2-C
*(=O) or N (CH
2c ≡ CH)-C (CH
3)=N
*(herein, * represents and the binding site of the N atom in abutting connection with carbonyl);
R
3represent C1-C4 alkyl; And
Relative configuration between substituting group on substituting group on the 1-position of cyclopropane ring and the 3-position of cyclopropane ring is transconfiguration.
2. ester cpds according to claim 1, wherein, Q represents N (CH
2c ≡ CH)-CH
2-C
*(=O).
3. ester cpds according to claim 1, wherein, Q represents N (CH
2c ≡ CH)-C (CH
3)=N
*.
4. according to the ester cpds described in any one in claims 1 to 3, wherein, in formula (1), the absolute configuration on the 1-position of described cyclopropane ring is R configuration.
5. according to the ester cpds described in any one in claim 1 to 4, wherein in formula (1), the two keys that exist on substituting group on the 3-position of cyclopropane ring are in E configuration or the mix-configuration in E configuration and Z configuration, and the ratio of described E configuration is more than 50%.
6. according to the ester cpds described in any one in claim 1 to 5, wherein, in formula (1), the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration.
7. according to the ester cpds described in any one in claim 1 to 6, wherein in formula (1), R
3represent methyl.
8. according to the ester cpds described in any one in claim 1 to 6, wherein in formula (1), R
3represent ethyl.
9. according to the ester cpds described in any one in claim 1 to 6, wherein in formula (1), R
3represent sec.-propyl.
10. according to the ester cpds described in any one in claim 1 to 6, wherein in formula (1), R
3represent the tertiary butyl.
11. 1 kinds of pest control agents, described pest control agent comprises according to the ester cpds described in any one in claim 1 to 10 and inert support.
The method of 12. 1 kinds of pest controls, described method comprises: the step that the ester cpds according to described in any one in claim 1 to 10 of significant quantity is applied to insect or insect habitat.
The method of 13. 1 kinds of pest controls, described method comprises: the step that the ester cpds according to described in any one in claim 1 to 10 of significant quantity is applied to cockroach or cockroach habitat.
14. methods according to claim 13, wherein, described cockroach is periplaneta americana.
15. methods according to claim 13, wherein, described cockroach is Groton bug.
The method of 16. 1 kinds of pest controls, described method comprises: the step that the ester cpds according to described in any one in claim 1 to 10 of significant quantity is sprayed to cockroach or cockroach habitat.
17. methods according to claim 16, wherein, described cockroach is periplaneta americana.
18. methods according to claim 16, wherein, described cockroach is Groton bug.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011182317 | 2011-08-24 | ||
| JP2011-182317 | 2011-08-24 | ||
| PCT/JP2012/071937 WO2013027864A1 (en) | 2011-08-24 | 2012-08-23 | Ester compound and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103781769A true CN103781769A (en) | 2014-05-07 |
| CN103781769B CN103781769B (en) | 2015-09-09 |
Family
ID=46845962
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280041133.2A Expired - Fee Related CN103781769B (en) | 2011-08-24 | 2012-08-23 | Ester cpds and application thereof |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2013060435A (en) |
| CN (1) | CN103781769B (en) |
| AR (1) | AR087650A1 (en) |
| TW (1) | TW201328601A (en) |
| WO (1) | WO2013027864A1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4176189A (en) * | 1977-06-20 | 1979-11-27 | Sumitomo Chemical Company, Limited | Insecticidal and acaricidal hydantoin N-methylol esters |
| JPS57158765A (en) * | 1981-03-24 | 1982-09-30 | Sumitomo Chem Co Ltd | Carboxylic acid ester, its preparation, and insecticide containing said ester as active component |
| US4602038A (en) * | 1983-06-14 | 1986-07-22 | Roussel Uclaf | Insecticidal cyclopropane carboxylates |
| WO2010087419A2 (en) * | 2009-01-28 | 2010-08-05 | Sumitomo Chemical Company, Limited | Ester compound and use thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3146596B2 (en) | 1992-03-10 | 2001-03-19 | 住友化学工業株式会社 | Method for producing 3-hydroxymethyl-1-propargylimidazolidine-2,4-dione |
| AR080192A1 (en) * | 2010-02-25 | 2012-03-21 | Sumitomo Chemical Co | ESTER COMPOUNDS AND ITS USE IN PEST CONTROL |
-
2012
- 2012-08-23 TW TW101130650A patent/TW201328601A/en unknown
- 2012-08-23 JP JP2012183891A patent/JP2013060435A/en active Pending
- 2012-08-23 AR ARP120103108 patent/AR087650A1/en unknown
- 2012-08-23 WO PCT/JP2012/071937 patent/WO2013027864A1/en active Application Filing
- 2012-08-23 CN CN201280041133.2A patent/CN103781769B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4176189A (en) * | 1977-06-20 | 1979-11-27 | Sumitomo Chemical Company, Limited | Insecticidal and acaricidal hydantoin N-methylol esters |
| JPS57158765A (en) * | 1981-03-24 | 1982-09-30 | Sumitomo Chem Co Ltd | Carboxylic acid ester, its preparation, and insecticide containing said ester as active component |
| US4602038A (en) * | 1983-06-14 | 1986-07-22 | Roussel Uclaf | Insecticidal cyclopropane carboxylates |
| WO2010087419A2 (en) * | 2009-01-28 | 2010-08-05 | Sumitomo Chemical Company, Limited | Ester compound and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2013060435A (en) | 2013-04-04 |
| WO2013027864A1 (en) | 2013-02-28 |
| TW201328601A (en) | 2013-07-16 |
| CN103781769B (en) | 2015-09-09 |
| AR087650A1 (en) | 2014-04-09 |
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