CN103781769B - Ester cpds and application thereof - Google Patents

Ester cpds and application thereof Download PDF

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Publication number
CN103781769B
CN103781769B CN201280041133.2A CN201280041133A CN103781769B CN 103781769 B CN103781769 B CN 103781769B CN 201280041133 A CN201280041133 A CN 201280041133A CN 103781769 B CN103781769 B CN 103781769B
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formula
compound
configuration
cyclopropane ring
represent
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CN103781769A (en
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松尾宪忠
上川彻
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • 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
    • 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
    • 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

The invention provides a kind of ester cpds 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 the binding site with the atom N adjoining carbonyl); R 3represent C1-C4 alkyl; And the relative configuration between substituting group on the 3-position of substituting group on the 1-position of cyclopropane ring and cyclopropane ring is transconfiguration, this ester cpds has outstanding pest controling effect.

Description

Ester cpds and application thereof
Technical field
The present invention relates to ester cpds and application thereof.
Background technology
Up to now, synthesize multiple compounds with pest control (see " pharmacy research and development second series (The Second series of pharmaceutical research and development) ", 18th volume, " agrochemicals development III (Development of agrochemicals III) ", 493rd page, Hirokawa Shoten, 1993).
Such as, certain esters compound is 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 represented by formula (1) as follows 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 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 the binding site with the atom N adjoining 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 referred to as compound of the present invention);
[1-2] ester cpds Gen Ju [1], wherein, R 3represent C1-C3 alkyl;
[2] according to [1] or the ester cpds described in [1-2], wherein, Q represents N (CH 2c ≡ CH)-CH 2-C *(=O);
[3] according to [1] or the ester cpds described in [1-2], wherein, Q represents N (CH 2c ≡ CH)-C (CH 3)=N *;
[4] ester cpds any one of [1]-[3] or described in [1-2], wherein in formula (1), the absolute configuration on the 1-position of described cyclopropane ring is R configuration;
[5] ester cpds any one of [1]-[4] or described in [1-2], wherein in formula (1), the double bond that substituting group on the 3-position of cyclopropane ring exists is in E or is in the mix-configuration of E and Z configuration, and the ratio of described E is more than 50%;
[6] ester cpds any one of [1]-[5] or described in [1-2], wherein in formula (1), the double bond that the substituting group on the 3-position of cyclopropane ring exists is in E;
[7] according to the ester cpds according to any one of [1]-[6], wherein in formula (1), R 3represent methyl;
[8] according to the ester cpds according to any one of [1]-[6], wherein in formula (1), R 3represent ethyl;
[9] according to the ester cpds according to any one of [1]-[6], wherein in formula (1), R 3represent sec.-propyl;
[10] according to the ester cpds according to any one of [1]-[6], wherein in formula (1), R 3represent the tertiary butyl;
[11] pest control agent, described pest control agent comprises according to the ester cpds any one of [1] to [10] or described in [1-2] and inert support;
[12] method for pest control, described method comprises: the step ester cpds any one of [1] to [10] or described in [1-2] of significant quantity being applied to insect or insect habitat;
[13] method for pest control, described method comprises: the step ester cpds any one of [1] to [10] or described in [1-2] of significant quantity being applied to cockroach or cockroach habitat;
[14] method Gen Ju [13], wherein, described cockroach is periplaneta americana (Periplaneta americana);
[15] method Gen Ju [13], wherein, described cockroach is Groton bug (Blattella germanica);
[16] method for pest control, described method comprises: the ester cpds any one of [1] to [10] or described in [1-2] of significant quantity is sprayed the step to cockroach or cockroach habitat;
[17] method Gen Ju [16], wherein, described cockroach is periplaneta americana (Periplaneta americana); With
[18] method Gen Ju [16], 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 used in the present invention is as follows:
The example of C1-C4 alkyl group is used to comprise methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-and the tertiary butyl in this article.
In compound of the present invention, there is the isomers of two unsymmetrical carbons be derived from the 1-position of cyclopropane ring and 3-position, and be derived from the isomers of the double bond that the substituting group on the 3-position of cyclopropane ring exists.The present invention comprises the mixture that each has the isomers of pest control active or the arbitrary proportion of these isomerss.
The example of compound of the present invention comprises following compound.
The compound represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-CH 2-C *(=O), i.e. a kind of compound represented by formula (a):
Wherein, R 3represent identical meanings as defined above, and the 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 represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-C (CH 3)=N *, i.e. a kind of compound represented by formula (b):
Wherein, R 3represent identical meanings as defined above, and the 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 represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration;
The compound represented by formula (1), wherein, the double bond that the substituting group on the 3-position of cyclopropane ring exists is in E or is in the mix-configuration of E and Z configuration, and the ratio of E is more than 50%;
The compound represented by formula (1), wherein, the double bond that the substituting group on the 3-position of cyclopropane ring exists is in E;
The compound represented by formula (1), wherein, the absolute configuration of the 1-position of cyclopropane ring is R configuration and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E or is in the mix-configuration of E and Z configuration, and the ratio of E is more than 50%;
The compound represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E;
The compound represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-CH 2-C *(=O);
The compound 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;
The compound represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-CH 2-C *(=O), and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E or is in the mix-configuration of E and Z configuration, and the ratio of E is more than 50%;
The compound represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-CH 2-C *(=O) and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E;
The compound represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-CH 2-C *(=O), and the absolute configuration on the 1-position of cyclopropane ring is R configuration and substituent double bond on the 3-position of cyclopropane ring is in E or is in the mix-configuration of E and Z configuration, and the ratio of E is more than 50%;
The compound 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 double bond that substituting group on the 3-position of cyclopropane ring exists is in E;
The compound represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-C (CH 3)=N *;
The compound 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 represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-C (CH 3)=N *and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E or is in the mix-configuration of E and Z configuration, and the ratio of E is more than 50%;
The compound represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-C (CH 3)=N *and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E;
The compound 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 double bond that substituting group on the 3-position of cyclopropane ring exists is in E or is in the mix-configuration of E and Z configuration, and the ratio of E is more than 50%;
The compound 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 double bond that substituting group on the 3-position of cyclopropane ring exists is in E;
The compound represented by formula (1), wherein, R 3represent C1-C3 alkyl;
The compound represented by formula (1), wherein, R 3represent methyl;
The compound represented by formula (1), wherein, R 3represent ethyl;
The compound represented by formula (1), wherein, R 3represent sec.-propyl;
The compound represented by formula (1), wherein, R 3represent the tertiary butyl;
The compound represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration and R 3represent methyl;
The compound represented by formula (1), wherein, the double bond that the substituting group on the 3-position of cyclopropane ring exists is in E or is in the mix-configuration of E and Z configuration and the ratio of E is more than 50%, and R 3represent methyl;
The compound represented by formula (1), wherein, the double bond that the substituting group on the 3-position of cyclopropane ring exists is in E and R 3represent methyl;
The compound represented by formula (1), wherein, absolute configuration on the 1-position of cyclopropane ring is R configuration and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E or is in the mix-configuration of E and Z configuration and the ratio of E is more than 50%, and R 3represent methyl;
The compound represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E, and R 3represent methyl;
The compound represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration and R 3represent ethyl;
The compound represented by formula (1), wherein, the double bond that the substituting group on the 3-position of cyclopropane ring exists is in E or is in the mix-configuration of E and Z configuration and the ratio of E is more than 50%, and R 3represent ethyl;
The compound represented by formula (1), wherein, the double bond that the substituting group on the 3-position of cyclopropane ring exists is in E and R 3represent ethyl;
The compound represented by formula (1), wherein, absolute configuration on the 1-position of cyclopropane ring is R configuration and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E or is in the mix-configuration of E and Z configuration and the ratio of E is more than 50%, and R 3represent ethyl;
The compound represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E, and R 3represent ethyl;
The compound 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 represented by formula (1), wherein, the double bond that the substituting group on the 3-position of cyclopropane ring exists is in E or is in the mix-configuration of E and Z configuration and the ratio of E is more than 50%, and R 3represent sec.-propyl;
The compound represented by formula (1), wherein, the double bond that the substituting group on the 3-position of cyclopropane ring exists is in E, and R 3represent sec.-propyl;
The compound represented by formula (1), wherein, absolute configuration on the 1-position of cyclopropane ring is R configuration and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E or is in the mix-configuration of E and Z configuration and the ratio of E is more than 50%, and R 3represent sec.-propyl;
The compound represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E, and R 3represent sec.-propyl;
The compound 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 represented by formula (1), wherein, the double bond that the substituting group on the 3-position of cyclopropane ring exists is in E or is in the mix-configuration of E and Z configuration and the ratio of E is more than 50%, and R 3represent the tertiary butyl;
The compound represented by formula (1), wherein, the double bond that the substituting group on the 3-position of cyclopropane ring exists is in E, and R 3represent the tertiary butyl;
The compound represented by formula (1), wherein, absolute configuration on the 1-position of cyclopropane ring is R configuration and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E or is in the mix-configuration of E and Z configuration and the ratio of E is more than 50%, and R 3represent the tertiary butyl;
The compound represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E, and R 3represent the tertiary butyl;
The compound represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-CH 2-C *(=O) and R 3represent methyl;
The compound 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 R 3represent methyl;
The compound represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-CH 2-C *(=O) and the double bond that substituting group on the 3-position of cyclopropane ring exists are in E or are in the mix-configuration of E and Z configuration and the ratio of E is more than 50%, and R 3represent methyl;
The compound represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-CH 2-C *(=O) and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E, and R 3represent methyl;
The compound represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-CH 2-C *(=O), and the absolute configuration on the 1-position of cyclopropane ring is R configuration, and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E or is in the mix-configuration of E and Z configuration, and the ratio of E is more than 50%, and R 3represent methyl;
The compound 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 are R configuration and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E, and R 3represent methyl;
The compound represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-CH 2-C *(=O) and R 3represent ethyl;
The compound 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 R 3represent ethyl;
The compound represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-CH 2-C *(=O) and the double bond that substituting group on the 3-position of cyclopropane ring exists are in E or are in the mix-configuration of E and Z configuration and the ratio of E is more than 50%, and R 3represent ethyl;
The compound represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-CH 2-C *(=O) and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E and R 3represent ethyl;
The compound 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 are R configuration and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E or is in the mix-configuration of E and Z configuration and the ratio of E is more than 50%, and R 3represent ethyl;
The compound 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 are R configuration and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E, and R 3represent ethyl;
The compound represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-CH 2-C *(=O) and R 3represent sec.-propyl;
The compound 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 R 3represent sec.-propyl;
The compound represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-CH 2-C *(=O) and the double bond that substituting group on the 3-position of cyclopropane ring exists are in E or are in the mix-configuration of E and Z configuration and the ratio of E is more than 50%, and R 3represent sec.-propyl;
The compound represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-CH 2-C *(=O) and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E, and R 3represent sec.-propyl;
The compound 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 are R configuration and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E or is in the mix-configuration of E and Z configuration and the ratio of E is more than 50%, and R 3represent sec.-propyl;
The compound 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 are R configuration and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E, and R 3represent sec.-propyl;
The compound represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-CH 2-C *(=O) and R 3represent the tertiary butyl;
The compound 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 R 3represent the tertiary butyl;
The compound represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-CH 2-C *(=O) and the double bond that substituting group on the 3-position of cyclopropane ring exists are in E or are in the mix-configuration of E and Z configuration and the ratio of E is more than 50%, and R 3represent the tertiary butyl;
The compound represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-CH 2-C *(=O) and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E, and R 3represent the tertiary butyl;
The compound 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 are R configuration and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E or is in the mix-configuration of E and Z configuration and the ratio of E is more than 50%, and R 3represent the tertiary butyl;
The compound 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 are R configuration and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E, and R 3represent the tertiary butyl;
The compound represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-C (CH 3)=N *and R 3represent methyl;
The compound 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 represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-C (CH 3)=N *and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E or is in the mix-configuration of E and Z configuration and the ratio of E is more than 50%, and R 3represent methyl;
The compound represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-C (CH 3)=N *and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E, and R 3represent methyl;
The compound 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 double bond that substituting group on the 3-position of cyclopropane ring exists is in E or is in the mix-configuration of E and Z configuration and the ratio of E is more than 50%, and R 3represent methyl;
The compound 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 double bond that substituting group on the 3-position of cyclopropane ring exists is in E, and R 3represent methyl;
The compound represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-C (CH 3)=N *and R 3represent ethyl;
The compound 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 represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-C (CH 3)=N *and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E or is in the mix-configuration of E and Z configuration and the ratio of E is more than 50%, and R 3represent ethyl;
The compound represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-C (CH 3)=N *and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E, and R 3represent ethyl;
The compound 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 double bond that substituting group on the 3-position of cyclopropane ring exists is in E or is in the mix-configuration of E and Z configuration and the ratio of E is more than 50%, and R 3represent ethyl;
The compound 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 double bond that substituting group on the 3-position of cyclopropane ring exists is in E, and R 3represent ethyl;
The compound represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-C (CH 3)=N *and R 3represent sec.-propyl;
The compound 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 represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-C (CH 3)=N *and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E or is in the mix-configuration of E and Z configuration and the ratio of E is more than 50%, and R 3represent sec.-propyl;
The compound represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-C (CH 3)=N *and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E, and R 3represent sec.-propyl;
The compound 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 double bond that substituting group on the 3-position of cyclopropane ring exists is in E or is in the mix-configuration of E and Z configuration, and the ratio of E is more than 50%, and R 3represent sec.-propyl;
The compound 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 double bond that substituting group on the 3-position of cyclopropane ring exists is in E, and R 3represent sec.-propyl.
The compound represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-C (CH 3)=N *and R 3represent the tertiary butyl;
The compound 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 represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-C (CH 3)=N *and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E or is in the mix-configuration of E and Z configuration, and the ratio of E is more than 50%, and R 3represent the tertiary butyl;
The compound represented by formula (1), wherein, Q represents N (CH 2c ≡ CH)-C (CH 3)=N *and the double bond that substituting group on the 3-position of cyclopropane ring exists is in E, and R 3represent the tertiary butyl;
The compound 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 double bond that substituting group on the 3-position of cyclopropane ring exists is in E or is in the mix-configuration of E and Z configuration, and the ratio of E is more than 50%, and R 3represent the tertiary butyl;
The compound 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 double bond that substituting group on the 3-position of cyclopropane ring exists is in E, 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 such as 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,
The carboxylic acid cpd represented with formula (4):
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 carboxylic acid halides that the example of reactive derivatives comprises the carboxylic acid cpd represented by formula (4), acid anhydrides, the ester etc. of carboxylic acid that represented by formula (4) of carboxylic acid that are 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 in a solvent usually under the existence of condensing agent or alkali.
The example of the condensing agent used in the reaction comprises dicyclohexylcarbodiimide and 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride.
The example of the alkali used in the reaction comprises organic bases, as triethylamine, pyridine, N, N-diethyl-aniline, 4-dimethylaminopyridine and diisopropylethylamine.
The example of the solvent used in the 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 usually in the scope of 5 minutes to 72 hours.
The temperature of reaction of this reaction usually in the scope of-20 DEG C to 100 DEG C (when the boiling point of the solvent used is lower than 100 DEG C,-20 DEG C of boiling points to solvent), and preferably-5 DEG C to 100 DEG C (when the boiling point of the solvent used is lower than 100 DEG C ,-5 DEG C of boiling points to solvent).
In the reaction, the alkylol cpd represented by formula (3) used can at random set with the mol ratio of the carboxylic acid cpd represented by formula (4) or its reactive derivatives, and is preferably equimolar ratio or the ratio close with equimolar ratio.
Based on the alkylol cpd represented by formula (3) of 1mol, condensing agent or alkali can use with the arbitrary proportion in 0.25mol to excessive scope usually, and preferred 0.5mol to 2mol.These condensing agents or alkali depend on that the kind of carboxylic acid cpd or its reactive derivatives represented by formula (4) is suitably selected.
After the reaction was completed, usually postprocessing working procedures is carried out to reaction mixture, such as, reaction mixture is filtered and subsequently filtrate is concentrated, or reaction mixture be poured into water and use the solution of organic solvent extraction gained and subsequently organic layer concentrated, compound of the present invention can be obtained thus.Can be purified by such as the compound of the present invention of the operation such as chromatography and distillation by gained.
The alkylol cpd represented by formula (3) is commercially available product, or the mixture of stating in JP-A-05-255271, JP-A-57-158765, and can therefore buy as commercially available product, or can according to the method preparation described in these are open.
Intermediate of the present invention can such as be prepared by method as follows.
(with reference to preparation method 1)
The carboxylic acid cpd represented by formula (4) can such as be prepared by method as follows.
That is, carane aldehydo-ester (caronaldehyde ester) derivative represented by formula (5) is made:
Wherein R represents C1-C5 alkyl, and the 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 the phosphate compound represented by formula (6):
Wherein R 3represent identical meanings as above,
React the compound obtaining being represented by formula (7) in the presence of base:
Wherein R and R 3represent identical meanings as above respectively, and the relative configuration between substituting group on the 3-position of substituting group on the 1-position of cyclopropane ring and cyclopropane ring is transconfiguration,
Be hydrolyzed reaction further in the presence of base, to prepare the carboxylic acid cpd represented by formula (4):
Wherein R 3represent identical meanings as above, and the relative configuration between substituting group on the 3-position of substituting group on the 1-position of cyclopropane ring and cyclopropane ring is transconfiguration.
Usually, based on the carane aldehydo-ester derivative that 1mol is represented by formula (5), be used in the alkali of the phosphate compound represented by formula (6) of the ratio in 1.0 to 1.5mol proportional range and the ratio in 1 to 10mol scope, and make they 0 DEG C to 80 DEG C and preferably the scope of 0 DEG C to 30 DEG C react in polar solvent or non-polar solvent and react, and the compound represented by formula (7) can be obtained thus.The example of the alkali used in the reaction comprises: alkali metal compound is as sodium methoxide and potassium t-butoxide, metal hydride compound is as sodium hydride and potassium hydride KH, and alkali metal amide is as two (TMS) sodium amide, two (TMS) Lithamide and lithium diisopropylamine.
The example of the polar solvent used in the 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 used in the reaction comprises: hydrocarbon is as benzene, toluene and hexane.
After the reaction was completed, postprocessing working procedures is carried out to reaction mixture, such as, reaction mixture is added to the water and uses the solution of organic solvent extraction gained, and subsequently that organic layer is dry and concentrated, and the compound represented by formula (7) can be obtained thus.
In addition, in the step compound represented by formula (7) being hydrolyzed to reaction, usually, based on the compound that 1mol is represented by formula (7), be used in the alkali of the ratio in 1 to 10mol scope, and make subsequently they 0 DEG C to 80 DEG C and preferably the scope of 0 DEG C to 30 DEG C react in a solvent, and the carboxylic acid cpd represented by formula (4) can be obtained thus.The example of the alkali used in the reaction comprises alkali metal compound as potassium hydroxide and sodium hydroxide.The embodiment of the solvent used in the reaction comprises: ether is as Isosorbide-5-Nitrae-two alkane, tetrahydrofuran (THF), ethylene glycol dimethyl ether, alcohol is as methyl alcohol, ethanol, propyl alcohol, and the mixture of water and these solvents.
After the reaction was completed, postprocessing working procedures is carried out to reaction mixture, such as, by reaction soln acidifying use organic solvent extraction subsequently, and subsequently that organic layer is dry and concentrated, and the carboxylic acid cpd represented by formula (4) can be obtained subsequently.
The carane aldehydo-ester derivative represented by formula (5) can according to described method preparation in Tetrahedron45,3039-3052 (1989).
Compound of the present invention comprises harmful arthropod to the example that it has the insect of prevention effect, as harmful insect and harmful acarid, and insect following more specifically.
Hemiptera (Hemiptera): Delphacidae (Planthoppers) is (as small brown rice planthopper (Laodelphax striatellus), brown paddy plant hopper (Nilaparvata lugens) and carry on the back planthopper (Sogatella furcifera) in vain), 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) (Ru Huajiao green stinkbug Nezara antennata), beans honeybee coried (Riptortus clavetus), Japan two star stinkbugs (Eysarcoris lewisi), wedge angle two star stinkbug (Eysarcoris parvus), Si Shi amber stinkbug (Plautia stali) and mixed eating attraction (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 scale (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), the wild snout moth's larva (Notarcha derogata) of lap leaf 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 codling moth (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.) (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) and 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) (fly (Delia antiqua) is planted on such as delia platura (Delia platura) and green onion ground), Tephritidae (Tephritidae), Drosophilidae (Drosophilidae), Phoridae (Phoridae) (the different eye fly in such as 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) (such as sitophilus zea-mais (Sitophilus zeamais), rice water resembles (Lissorhoptrus oryzophilus) and Callosobruchus chinensis (Callosobruchuys chienensis)), TRenebrionidae (Tenebrionidae) (such as Cabot's Tragopan (Tenebrio molitor) and red flour beetle (Tribolium castaneum)), Chrysomelidae (Chrysomelidae) (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) (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) (such as Chinese long pin hornet (Polistes chinensis antennalis), family hornet (Polistes jadwigae) and land hornet (Polistes rothneyi)), Vespidae (Vespidae) (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.) (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 dynamic Cryptotermes (Zootermopsis spp.) (the ancient termite (Zootermopsis nevadensis) in such as Nevada) etc.,
Acarina (Acarina): Tetranychidae (Tetranychidae) is (as Tetranychus urticae (Tetranychus urticae), Shenmu-Yanan railway (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) (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 bites spider (Chiracanthium japonicum), redback spider (Latrodectus hasseltii), Tetragnathidae section (Tetragnathidae), eight knurls Chinese mugwort spider (Cyclosa octotuberculata), Argiope amoena (Argiope amoena), golden spider (Argiope bruennichii), araneus ventricosu (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.Usually pest control agent of the present invention is mixed with preparation described below.The example of preparation comprises oily solution, emulsifiable concentrates, wettable powder, preparation can be flowed (such as, waterborne suspension, or water-based emulsion), microcapsule, powder agent, granula, aerosol, carbon dioxide formulation, hot flashing preparation (such as, insecticidal incense coil, electricity pesticide tablet or wick type hot flashing sterilant), piezoelectricity pesticide preparation, hot smoking agent (such as, self-ignition type fumigant, chemical reaction type fumigant or porous ceramic plate fumigant), that does not heat evapotranspires preparation (such as, resin evapotranspires preparation, paper evapotranspires preparation, nonwoven fabric evapotranspires preparation, knit goods evapotranspire preparation or distillation tablet), aerosol formulation (such as, atomization preparation), direct contact preparation (such as, 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 afterwards to add tensio-active agent and other auxiliary agents for preparation, and the method be further processed.
(2) method of being flooded with compound of the present invention by the base material not containing activeconstituents is comprised.
(3) comprise compound of the present invention is mixed with base material, afterwards mixture is carried out to 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 usually.
The example of the inert support used in the formulation comprises inert solid carrier, inertia liquid carrier and inert gaseous carrier.
The example of the solid carrier used in the formulation comprises: clay (such as, kaolinton, diatomite, wilkinite, Fubasami clay or acid kaolin), synthesize oxidizing aqueous silicon, talcum, pottery, other inorganic minerals (such as, sericite, quartz, sulphur, activated carbon, calcium carbonate or aqueous silicon dioxide) or the fine powder of chemical fertilizer (such as, ammonium sulfate, ammonium phosphate, ammonium nitrate, ammonium chloride or urea) etc. or particle; Material (such as, 2,4, the 6-triisopropyl-1,3,5-tri-of solid form is in room temperature alkane, naphthalene, santochlor, camphor or diamantane); And comprising the felt of one or more materials in the group that is selected from and is made up of the following, fiber, fabric, cloth, thin slice, paper, line, foam, porous material and multifilament: (such as, 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 multipolymer and ethylene-ethyl methacrylate multipolymer; Ethylene-acrylate copolymer is as ethylene-methyl acrylate copolymer and ethylene-ethyl acrylate copolymer; Ethylene-vinyl carboxylic acid copolymer 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 nylon66 fiber; Vibrin is as polyethylene terephthalate, PEN, polybutylene terephthalate and polycyclic hexene-terephthalic acid two methylene ester (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 foamed ethylene), glass, metal and pottery.
The example of liquid vehicle comprises aromatic series or aliphatic hydrocrbon (such as, dimethylbenzene, toluene, alkylnaphthalene, phenyl xylyl ethane, kerosene, light oil, hexane or hexanaphthene), halohydrocarbon (such as, chlorobenzene, methylene dichloride, ethylene dichloride or trichloroethane), alcohol (such as, methyl alcohol, ethanol, Virahol, butanols, hexanol, benzylalcohol or ethylene glycol), ether (such as, diethyl ether, glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, tetrahydrofuran (THF) or two alkane), ester (such as, ethyl acetate or butylacetate), ketone (such as, acetone, methyl ethyl ketone, mibk or pimelinketone), nitrile (such as, acetonitrile or isopropyl cyanide), sulfoxide (such as, methyl-sulphoxide), acid amides (such as, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE or N-methyl-pyrrolidon), alkylene carbonates (such as, propylene carbonate), vegetables oil (such as, soybean oil or Oleum Gossypii semen), plants essential oil (such as, 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-sulphate, alkylsulfonate, alkylaryl sulphonate, alkyl aryl ether, polyoxyethylated alkyl aryl ether, polyglycol ether, polyol ester and sugar alcohol derivant.
The example of other auxiliary agents of preparation comprises tackiness agent, dispersion agent and stablizer.Specific examples comprises: casein, gelatin, polysaccharide are (such as, starch, Sudan Gum-arabic, derivatived cellulose or Lalgine), lignin derivative, wilkinite, carbohydrate, synthetic polymer (such as, 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 obtained by sclerosis velveteen and the sheet obtained by the fibril of the mixture of harden velveteen and paper pulp.
Example for the base material of self-ignition type fumigant comprises flammable heat release reagent 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.
Example for the base material of chemical reaction type fumigant comprises heat release reagent 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.
The example of resin that the base material that evapotranspire agent as resin uses comprises polyvinyl resin 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 multipolymer and ethylene-ethyl methacrylate multipolymer; Ethylene-acrylate copolymer is as ethylene-methyl acrylate copolymer and ethylene-ethyl acrylate copolymer; Ethylene-vinyl carboxylic acid copolymer 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 styrene-conjugated diene segmented copolymer and hydrogenation; Fluoro-resin; Acrylic resin is as polymethylmethacrylate; Polyamide resin is as nylon 6 and nylon66 fiber; Vibrin is as polyethylene terephthalate, PEN, poly butylene succinate (polybutylene butalate) and polycyclic hexene-terephthalic acid two methylene ester; 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 be used alone or combinationally using with two or more type.If needed, can by softening agent as phthalic ester (such as, dimethyl phthalate, dioctyl phthalate (DOP) etc.), adipic acid ester and stearic acid be added in these base materials.Resin agent of evapotranspiring can be prepared in the following manner: mixed with above-mentioned base material by compound of the present invention, mediated by mixture, it be molded by injection moulding, extrusion molding or compression moulding afterwards.If needed, can be molded further or cutting step obtained resin formulation, to be processed as sheet shape, film shape, band shape, net form or linear and so on shape.These resin formulation can be processed as Animal neck ring, animal ear tag, sheet product, trap strips, gardening support and other products.
Example for the base material of poison bait comprises bait composition as flour, vegetables oil, sugar and crystalline cellulose, antioxidant is as butylated hydroxytoluene and nordihydroguaiaretic acid, sanitas 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 usually by being applied to insect or its habitat (such as 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.
Method for applying pest control agent of the present invention comprises following methods, and depends on the form, applying area etc. of pest control agent of the present invention and suitably select.
(1) method pest control agent former state of the present invention being applied to the habitat of insect or insect is comprised.
(2) comprise pest control agent solvent such as water of the present invention is diluted, afterwards dilution is sprayed to the method for the habitat of insect or insect.
In this case, usually pest control agent of the present invention is configured to emulsifiable concentrates, wettable powder, can flow preparation, microcapsule etc.Usually by said preparation dilution to make the concentration of compound of the present invention can in the scope of 0.1 to 10,000ppm.
(3) comprise pest control agent of the present invention is heated in the habitat of insect, thus activeconstituents is volatilized and the method spread from pest control agent.
In this case, any one of the applied amount of compound of the present invention and concentration can depend on pest control agent of the present invention formulation, applying 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 used for the prevention of epidemic disease, the amount applied when being in application to space usually 0.0001 to 1,000mg/m 3compound of the present invention scope in, and 0.0001 to 1,000mg/m when being in application to plane 2compound of the present invention scope in.Depend on the form of preparation, insecticidal incense coil or electric pesticide tablet etc. make activeconstituents volatilize by heating and spread, 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 places under air blows.
When 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 is for preventing and treating domestic animal as epizoon as dog, cat, rat and mouse of ox, horse, pig, sheep, goat and chicken and animalcule, pest control agent of the present invention can be applied to these animals by the currently known methods in veterinary applications.Particularly, when needs systemic control, using pest control agent of the present invention as tablet, with the mixture of feed or suppository, or (comprise muscle, subcutaneous, vein and peritonaeum to inject) by injecting and be administered to animal.On the other hand, when 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 process, or washs animal with washing preparations, or necklace agent of being evapotranspired by resin made or ear tag are placed to animal.When being administered to animal body, the dosage of compound of the present invention is in the scope of 0.01 to 1,000mg at the weight of animals of every 1kg usually.
When pest control agent of the present invention is for preventing and treating the insect in farmland, the example of applying method comprises spraying process, soil treatment, seed treatment and immersion treatment.
When pest control agent of the present invention is for preventing and treating the insect in farmland, consumption can depend on the applying cycle, applies area, applying method and other factors and vary widely, and with every 10,000m 2compound meter of the present invention usually 1 to 10, in the scope of 000g.When pest control agent of the present invention being configured to emulsifiable concentrates, wettable powder, the preparation that can flow etc.; usually pest control agent is become 0.01 to 10 at dilute with water to make the concentration of activeconstituents; the scope of 000ppm after-applied, and usually particle or pulvis are in statu quo applied.
Can the plant of its not affected by pests maybe to be protected as on crop plants insect the water dilution Direct spraying of these preparations or preparation, or it can be used in soil treatment prevent and treat the insect perched on the soil of ploughing.
Apply also can carry out by the following method: directly the resin formulation being configured as sheet or wire or rope form preparation is twisted in surrounding plants, preparation is placed on vicinity of plants, or preparation is dispersed on the soil surface at root place.
Compound of the present invention can be used as to plough as farm, rice field, lawn or orchard, or the pest control agent in untilled ground.Compound of the present invention can be prevented and treated and perch the insect in arable land in the arable land of plantation following " plant crop " etc.
Farm crop: corn, rice, wheat, barley, rye, oat, Chinese sorghum, cotton, soybean, peanut, buckwheat, sugar beet, Semen Brassicae campestris, Sunflower Receptacle, sugar use 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.), kernel approaches (peach, plum, peach refute 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 is set, Liriodendron, crape myrtle, sweet-scented osmanthus etc.), shade tree (Ash, birch, Lai wood, eucalyptus, ginkgo, cloves, maple, oak, poplar, cercis, sweetgum, plane tree, beech are set, 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, creeping bentgrass (Agrostis stolonifera), thin and delicate bent grass (Agrostis tenuis) etc.), annual bluegrass (English grass, rough stalked blue grass etc.), fescue grass (huge fescue grass, red fescue, crawl red fescue etc.), rye grass (lolium temulentum, rye grass etc.), orchardgrass, thimothy grass etc.,
Other: flower (rose, carnation, chrysanthemum, Lisianthus (purple Lisianthus), G. paniculata, 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 indigo plant flower, False flax, 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 with other insecticides, miticide, nematocides, soil pests control agent, mycocide, weedicide, plant-growth regulator, repellent, synergistic agent, fertilizer or soil modifier or combinationally use.
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), metofluthrin (metofluthrin), 2,2-dimethyl-3-(1-propenyl) cyclopropane-carboxylic acid [the fluoro-4-methyl-benzyl of 2,3,5,6-tetra-] ester, 2,2-dimethyl-3-(2-methyl-1-propylene base) cyclopropane-carboxylic acid [the fluoro-4-of 2,3,5,6-tetra-(methoxymethyl) benzyl] ester, 2,2,3,3-tetramethyl-cyclopropane-carboxylic acid [the fluoro-4-of 2,3,5,6-tetra-(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), Cupric sulfate (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:
Chlorfluazuron (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:
The spore alive deriving from Bacillus thuringiensis (Bacillus thuringiesis) and the crystal toxin 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), everywhere gram (dienochlor), 5a,6,9,9a-hexahydro-6,9-methano-2,4 (endosulfan), methoxychlor (methoxychlor) etc.;
(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-Butoxyethoxy) ethoxyl methyl]-6-propyl group-1,3-benzodioxole (benzodioxol), N-(2-ethylhexyl) dicyclo [2.2.1]-5-in heptan alkene-2,3-dicarboximide, eight chlorine dipropyl ethers, thiocyano isobomyl base and N-(2-ethylhexyl)-1-isopropyl-4-methyl dicyclo [2.2.2] pungent-5-alkene-2,3-dicarboximide.
Embodiment
Below by way of preparation example, describe the present invention in more detail with reference to preparation example, formulation example and test case, but the invention is not restricted to these embodiments.
First, the preparation example of compound of the present invention is as follows.? 1in H-NMR, such as, the description list of " 1.17+1.18 (s+s, 3H) " is shown in the peak that 1.17ppm and 1.18ppm exists 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 through dried over mgso, and under reduced pressure concentrate subsequently, and silica gel column chromatography is carried out to resistates, 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 referred to as 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 the pyridine of 0.15mL wherein.Under ice-cooling,-trans-3-[(1EZ)-2-cyano group-2-vinyl ethyl ether base]-2 is added (1R) in this solution, 2-dimethylcyclopropane formyl chloride (250mg, 1.10mmol, E: tetrahydrofuran solution (1mL) Z=2: 1).By reaction mixture after stirring at room temperature 12 hours, water is poured in reaction soln, and is extracted with ethyl acetate solution.Successively with 5% hydrochloric acid, saturated sodium bicarbonate aqueous solution and saturated brine washing organic layer, subsequently through dried over mgso.After under reduced pressure organic layer being concentrated, silicagel column column chromatography is carried out to resistates, obtain (1R)-trans-3-[(1EZ)-2-cyano group-2-vinyl ethyl ether base]-2 of 261mg, 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)-2-cyano group-2-(oxyethyl group) vinyl]-2 obtained in preparation example 2, 2-dinethyl cyclopropane carboxylic acid 2, 5-dioxy-3-(2-propynyl) imidazolidyl methyl esters (E: Z=2: 1) carries out silica gel column chromatography (elutriant: hexane/ethyl acetate=2: 1), obtain (1R)-trans-3-[(1E)-2-cyano group-2-vinyl ethyl ether base]-2 as the cut with high polarity, 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) replaces (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)-2-cyano group-2-(isopropoxy) vinyl]-2 obtained in preparation example 5, 2-dinethyl cyclopropane carboxylic acid 2, 5-dioxy-3-(2-propynyl) imidazolidyl methyl esters (E: Z=78: 22) carries out silica gel column chromatography (elutriant: hexane/ethyl acetate=2: 1), obtain (1R)-trans-3-[(1E)-2-cyano group-(isopropoxy) vinyl]-2 as the cut with high polarity, 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) replaces (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) carries out silica gel column chromatography (elutriant: hexane/ethyl acetate=2: 1), obtain cut (1R)-trans-3-[(1E)-2-cyano group-(tert.-butoxy) vinyl]-2 with high polarity, 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)
The particular compound that display is 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-dioxies-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-dioxies-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-dioxies-3-(2-propynyl) imidazolidyl methyl esters (E: Z=2: 1), it is expressed from the next:
Then, the reference preparation example of the preparation about intermediate (it is for the preparation of the compound of the invention described above) is shown below.
With reference to preparation example 1
Sodium hydride (55.2%, oil dispersion) (0.42g, 9.7mmol) is added in round-bottomed flask, and adds the anhydrous tetrahydro furan of 15mL wherein.Under ice-cooling, under nitrogen atmosphere, the solution of the methoxyl group (cyano group) methyl acid phosphate diethyl ester (2.0g, 9.7mmol) be dissolved in anhydrous tetrahydro furan (5mL) is dripped wherein.Under ice-cooling, stirred reaction mixture 30 minutes, and stir 1 hour again at 25 DEG C.Drip the solution of (1R)-trans-3-formyl radical-2,2-dinethyl cyclopropane carboxylic acid methyl esters (1.40g, 9.0mmol) be dissolved in anhydrous tetrahydro furan (5mL) wherein.After mixture stirs 2 hours by 25 DEG C, reaction soln is joined in the mixing solutions be made up of 5% hydrochloric acid of 10mL and the frozen water of 30mL, and the ethyl acetate of each 50mL is by reaction mixture extracting twice.The ethyl acetate layer of gained is merged, and washs 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 silica gel column chromatography is carried out to resistates, obtain 480mg as (1R)-trans-3-[(1E)-2-cyano group-2-methoxy-ethylene base]-2 of cut with high polarity, 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)-2-cyano group-2-methoxy-ethylene base]-2, the 2-dinethyl cyclopropane carboxylic acid methyl esters of cut with lower polarity, 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 be made up of the methyl alcohol of 1.5mL and the water of 0.5mL, and subsequently to wherein adding 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 extraction into ethyl acetate reaction mixture of 20mL.In the water layer of gained, add hydrochloric acid, until make water layer be pH2, and use twice, the mixture of 20mL extraction into ethyl acetate gained subsequently.The ethyl acetate layer of gained is merged, and washes twice with the saturated brine of 20mL, and subsequently through dried over mgso.Under reduced pressure concentrated by solution, obtain 336mg (1R)-trans-3-[(1E)-2-cyano group-2-methoxy-ethylene base]-2,2-dinethyl cyclopropane carboxylic acids, 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 adds the anhydrous tetrahydro furan of 43mL wherein.Under ice-cooling, under nitrogen atmosphere, the solution of oxyethyl group (cyano group) the methyl acid phosphate diethyl ester be dissolved in anhydrous tetrahydro furan (11mL) is dripped wherein.Under ice-cooling reaction mixture is stirred 40 minutes, and stir one hour again at 25 DEG C.Drip the solution of (1R)-trans-3-formyl radical-2,2-dinethyl cyclopropane carboxylic acid methyl esters (3.17g, 20.3mmol) be dissolved in anhydrous tetrahydro furan (11mL) wherein.After reaction mixture stirs 12 hours by 25 DEG C, reaction soln is joined in the mixing solutions be made up of 5% hydrochloric acid of 10mL and the frozen water of 100mL, and twice, the mixture of the extraction into ethyl acetate gained of each 100mL.The ethyl acetate layer of gained is merged, and washs with the saturated brine of saturated sodium bicarbonate aqueous solution and 50mL successively, and subsequently through dried over mgso.The mixture of gained is under reduced pressure concentrated, and silica gel column chromatography is carried out to resistates, 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)-trans-3-[(1EZ)-2-cyano group-2-vinyl ethyl ether base]-2 obtained with reference to preparation example 3,2-dinethyl cyclopropane carboxylic acid methyl esters (E: Z=2: 1) carries out silica gel column chromatography (elutriant: hexane/ethyl acetate=10: 1), obtain 2.91g as (1R)-trans-3-[(1E)-2-cyano group-2-vinyl ethyl ether base]-2 of cut with high polarity, 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 be made up of the methyl alcohol of 17mL and the water of 6mL, and subsequently to wherein adding 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 the mixture of extraction into ethyl acetate gained with 45mL.In the water layer of gained, add hydrochloric acid, until make water layer be pH2, and use twice, the mixture of the extraction into ethyl acetate gained of 45mL subsequently.The ethyl acetate layer of gained is merged, and washes twice with the saturated brine of 50mL, and subsequently through dried over mgso.Under reduced pressure concentrated by the solution of gained, obtain (1R)-trans-3-[(1E)-2-cyano group-2-vinyl ethyl ether base]-2, the 2-dinethyl cyclopropane carboxylic acids of 2.64g, 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 thionyl chloride (370mg, 3.11mmol) subsequently, and add the N of 10mg further, dinethylformamide, and at the internal temperature of 60 to 70 DEG C, reaction mixture is stirred 4 hours.Reaction soln is left standstill and is cooled to room temperature, and under reduced pressure concentrate, obtain (1R)-trans-3-[(1EZ)-2-cyano group-2-vinyl ethyl ether base]-2, the 2-dimethylcyclopropane formyl chlorides (E: Z=2: 1) of 550mg, it is expressed from the next:
With reference to preparation example 7
Replace except oxyethyl group (cyano group) methyl acid phosphate diethyl ester except using isopropoxy (cyano group) methyl acid phosphate diethyl ester, react in the mode identical with reference to 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, react in the mode identical with reference to 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 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, synthesizes by wherein R 3represent the compound that the formula (6) of methyl represents, that is, methoxyl group (cyano group) methyl acid phosphate diethyl ester.Also according at J.Org.Chem. (1976) 41 volume, the method described in 2846-2849 page, except using oxyethyl group acetonitrile, propoxy-acetonitrile or isopropoxy acetonitrile to replace except methoxyacetonitrile, synthesizes similarly by wherein R 3represent the phosphate compound that the formula (6) of ethyl, propyl group or sec.-propyl represents, that is, 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.Number in mass.
Formulation example 1
The compound of the present invention (1) of 20 (20) parts is dissolved in the dimethylbenzene of 65 parts to (8) separately, and by the SOLPOL3005X of 15 parts (TOHO Chemical Industry Co., Ltd. registered trademark) add wherein, and by stirring thoroughly mixing to obtain emulsifiable concentrates.
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 (the oxidizing aqueous silicon of synthesis, SHIONOGI & CO., LTD. registered trademark) and the 300 order diatomite of 23 parts add wherein, being uniformly mixed afterwards by mixing tank, obtains wettable powder.
Formulation example 3
By the compound of the present invention (1) to (8) of 1.5 parts separately with TOKUSIL GUN (the oxidizing aqueous silicon of synthesis 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 to be added wherein.Mixture is thoroughly mediated, by extruding granulator granulation, dry afterwards, obtain the granule of 1.5%.
Formulation example 4
Respective and the phenyl xylyl ethane of 10 parts and the SUMIDUR L-75 (tolylene diisocyanate of 0.5 part to the compounds of the present invention (1) to (8) of 10 parts, by Sumitomo Bayer Urethane Co., Ltd. produce) mixture in, add 10% Arabic gum aqueous solution of 20 parts, and by mixture homogenizer, obtain the emulsion with the median size of 20 μm.Add 2 parts of ethylene glycol to emulsion and mixture is stirred 24 hours further to obtain microcapsule slurry in the temperature bath of 60 DEG C of temperature.On the other hand, the VEEGUM R (neusilin is produced by Sanyo Chemical Industries, Ltd.) of the xanthan gum of 0.2 part and 1.0 parts is dispersed in the ion exchanged water of 56.3 parts to obtain thickening fluid.Afterwards, the above-mentioned thickening fluid mixing of the above-mentioned microcapsule slurry of 42.5 parts and 57.5 parts is obtained 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, obtains the emulsion with the median size of 3 μm.On the other hand, the VEEGUM R (magnesium aluminum silicate is produced by Sanyo Chemical Industries, Ltd.) of the xanthan gum of 0.2 part and 1.0 parts is dispersed in the ion exchanged water of 58.8 parts to obtain thickening fluid.Afterwards, the above-mentioned thickening fluid mixing of the above-mentioned emulsion solution of 40 parts and 60 parts is obtained the preparation that can flow.
Formulation example 6
To the compounds of the present invention (1) to (8) of 5 parts each in, add CARPLEX#80 (the oxidizing aqueous silicon of synthesis 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 by mixing tank and obtains pulvis.
Formulation example 7
The compound of the present invention (1) of 0. 1 (0.1) parts is dissolved in the methylene dichloride of 10 parts separately to (8), and the deodorized kerosine of solution with 89.9 parts is mixed and obtain oily solution.
Formulation example 8
The compound of the present invention (1) to (8) of 0. 1 (0.1) parts is mixed with the deodorized kerosine of 39.9 parts and dissolves separately, and solution is filled in aerosol container, and mounted valve part.Afterwards, the energy propellant of 60 parts (liquefied petroleum gas (LPG)) are partially fill in wherein by valve under stress, to obtain oil-based aerosol preparation.
Formulation example 9
By the compound of the present invention (1) to (8) of 0. 6 (0.6) parts separately with the Reodol MO-60 (emulsifying agent of the dimethylbenzene of 5 parts, the deodorized kerosine of 3.4 parts and 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 propellant (liquefied petroleum gas (LPG)) of 40 parts is inserted wherein by valve part under stress, obtain 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 by the solution of gained under agitation with 99.7g be used for incense coil base material (by by Tabu powder, pyrethrum slag (mark) and wood powder with 4: 3: 3 ratio mix obtain) Homogeneous phase mixing.Afterwards, the water of 100mL is added wherein, and mixture is thoroughly mediated, dry and molded, obtain insecticidal incense coil.
Formulation example 11
By the compound of the present invention (1) to (8) of 0.8g separately and the mixture of the piperonyl butoxide of 0.4g dissolve in acetone, and cumulative volume is adjusted to 10ml.Afterwards, this dissolution homogeneity of 0.5mL is flooded in the base material for electrically heated pesticide tablet (sheet sclerosis of the fibril of the mixture of velveteen and paper pulp obtained) of the thickness to the size and 0.3cm with 2.5cm × 1.5cm, obtains electrically heated insecticidal mat.
Formulation example 12
The solution obtained in deodorized kerosine by be dissolved in 97 parts separately to (8) by the compounds of this invention (1) of 3 parts is poured in the container be made up of vinylchlorid.Its top can be inserted wherein by the wick of heater heats (hardening with tackiness agent and the inorganic flour sintered), obtain the parts being used for wick type heat evaporating device and using.
Formulation example 13
The compounds of this invention (1) of 100 (100) mg is dissolved in the acetone of appropriate amount separately to (8), and obtains hot smoking agent by the solution saturates of gained to the porous ceramic plate of the size and 1.2cm thickness with 4.0cm × 4.0cm.
Formulation example 14
The compounds of this invention (1) of 100 (100) μ g is dissolved in the acetone of appropriate amount separately to (8), and the dissolution homogeneity of gained is applied to the filter paper of size and the 0.3mm thickness with 2cm × 2cm, and dry air is to remove acetone, thus obtain the volatile reagent being used 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 sulfates containing 50 parts), and the water mixing of 55 parts, levigate by wet milling process afterwards, obtain the mobility preparation of 10%.
Then, following test case describes compound of the present invention as the activeconstituents of pest control agent is effective.
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) the little Lian of adult German (Blattella germanica, 5 male and 5 female) be discharged on its internal surface and be coated with (diameter 8.75cm in the test container of butter, height 7.5cm, lower surface is made up of 16 order metal wires), and container is placed on the bottom (lower surface: 46cm × 46cm, highly: 70cm) of test cabinet.Use fog gun with 0.42kg/cm 2pressure from container end face height 60cm spray compound of the present invention (1) to each 1.5mL of the oily solution that (5) are respective.Spraying after 30 seconds, container is pulled out from test cabinet, and cockroach is transferred in clean polyethylene cup.After specific time, count the number of the cockroach knocked down and determine rate of knockdown (repeating twice).By following formulae discovery rate of knockdown.
Rate of knockdown (%)=(number of the number/test cockroach of the cockroach knocked down) × 100
As the contrast for comparing, to test with mode identical above, 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 described 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 described 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 described in JP-A-57-158765, hereinafter referred to as comparative compound (3)), it is expressed from the next:
Result (after spraying 0.7 minute) 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) the little Lian of adult German (Blattella germanica, 5 male and 5 female) be discharged on its internal surface and be coated with (diameter 8.75cm in the test container of butter, height 7.5cm, lower surface is made up of 16 order metal wires), and container is placed on the bottom (lower surface: 46cm × 46cm, highly: 70cm) of test cabinet.Use fog gun with 0.42kg/cm 2pressure from container end face height 60cm spray compound of the present invention (1) to each 1.5mL of the oily solution that (8) are respective.Spraying after 30 seconds, container is pulled out in test cabinet, and cockroach is transferred in clean polyethylene cup.After specific time, count the number of the cockroach knocked down and determine rate of knockdown (repeating twice).By following formulae discovery rate of knockdown.
Rate of knockdown (%)=(number of the number/test cockroach of the cockroach knocked down) × 100
Result (after spraying 0.7 minute) 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).
Only grow up six (6) periplaneta americana (Periplaneta americana, 3 male and 3 female) be discharged into test container (the diameter 12.5cm its internal surface being coated with butter, height 10cm, lower surface is made up of 32 order metal wires) in, and container is placed on the bottom (lower surface: 46cm × 46cm, highly: 70cm) of test cabinet.Use fog gun with 0.42kg/cm 2pressure from container end face height 60cm spray compound of the present invention (1) to each 1.5mL of the oily solution that (8) are respective.Spraying after 30 seconds, container is pulled out in test cabinet, and cockroach is transferred in clean polyethylene cup.After specific time, count the number of the cockroach knocked down and determine rate of knockdown (repeating twice).By following formulae discovery rate of knockdown.
Rate of knockdown (%)=(number of the number/test cockroach of the cockroach knocked down) × 100
Result (after spraying 5 minutes) 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).
Only grow up ten (10) 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 the bottom (lower surface: 46cm × 46cm, highly: 70cm) of test cabinet.Use fog gun with 0.9kg/cm 2pressure spray compound of the present invention (1) to each 1.5mL of the oily solution that (7) are respective from the end face height 30cm than cup.After spraying, at once cup is pulled out from test cabinet.After specific time, count the number of the housefly knocked down and determine rate of knockdown (repeating twice).
Result is 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) Adult female common house mosquitos (Culex pipens pallens) 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 the bottom (lower surface: 46cm × 46cm, highly: 70cm) of test cabinet.Use fog gun with 0.4kg/cm 2pressure spray compound of the present invention (1) to each 1.5mL of the oily solution that (7) are respective from the end face height 30cm than cup.After spraying, at once cup is pulled out from test cabinet, and after the specified time, count the number of the common house mosquito knocked down and determine rate of knockdown (repeating twice).
Result is 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 (12)

1. the ester cpds be expressed from the next:
Wherein
R 3represent methyl, ethyl or sec.-propyl.
2. ester cpds according to claim 1, wherein in formula, R 3represent methyl.
3. ester cpds according to claim 1, wherein in formula, R 3represent ethyl.
4. ester cpds according to claim 1, wherein in formula, R 3represent sec.-propyl.
5. a pest control agent, described pest control agent comprises ester cpds according to any one of claim 1 to 4 and inert support.
6. a method for pest control, described method comprises: the step ester cpds according to any one of claim 1 to 4 of significant quantity being applied to insect or insect habitat.
7. a method for pest control, described method comprises: the step ester cpds according to any one of claim 1 to 4 of significant quantity being applied to cockroach or cockroach habitat.
8. method according to claim 7, wherein, described cockroach is periplaneta americana.
9. method according to claim 7, wherein, described cockroach is Groton bug.
10. a method for pest control, described method comprises: the step ester cpds according to any one of claim 1 to 4 of significant quantity being sprayed to cockroach or cockroach habitat.
11. methods according to claim 10, wherein, described cockroach is periplaneta americana.
12. methods according to claim 10, wherein, described cockroach is Groton bug.
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US4602038A (en) * 1983-06-14 1986-07-22 Roussel Uclaf Insecticidal cyclopropane carboxylates

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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
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
JP2010173951A (en) * 2009-01-28 2010-08-12 Sumitomo Chemical Co Ltd Cyclopropanecarboxylic acid ester and use thereof
AR080192A1 (en) * 2010-02-25 2012-03-21 Sumitomo Chemical Co ESTER COMPOUNDS AND ITS USE IN PEST CONTROL

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US4176189A (en) * 1977-06-20 1979-11-27 Sumitomo Chemical Company, Limited Insecticidal and acaricidal hydantoin N-methylol esters
US4602038A (en) * 1983-06-14 1986-07-22 Roussel Uclaf Insecticidal cyclopropane carboxylates

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