CN103747682A - Ester compound and use thereof - Google Patents
Ester compound and use thereof Download PDFInfo
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- CN103747682A CN103747682A CN201280040921.XA CN201280040921A CN103747682A CN 103747682 A CN103747682 A CN 103747682A CN 201280040921 A CN201280040921 A CN 201280040921A CN 103747682 A CN103747682 A CN 103747682A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/31—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing rings other than six-membered aromatic rings
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
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Abstract
An ester compound represented by formula (1): wherein R1 represents hydrogen atom, halogen atom, methyl group, methoxy group or methoxymethyl group; R2 represents a C1-C3 alkyl group; and a relative configuration between the substituent at the 1-position of the cyclopropane ring and the substituent at the 3-position of the cyclopropane ring is a trans configuration, has an excellent pest control effect. (The formula is shown in the specification)
Description
Technical field
The present invention relates to ester compounds and application thereof.
Background technology
Up to now, synthesized multiple compounds with pest control (referring to < < pharmacy research and development second series (The Second series of pharmaceutical research and development) > >, the 18th volume, < < agricultural chemicals development III (Development ofagrochemicals III) > >, the 493rd page, Hirokawa Shoten, 1993).
For example, certain esters compound has been described in JP-A-60-16962.
Summary of the invention
(inventing problem to be solved)
The object of this invention is to provide a kind of noval chemical 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 compounds being represented by formula as follows (1) has outstanding pest controling effect, and obtains the present invention.
In other words, the present invention relates to following invention:
[1] a kind of ester compounds being represented by formula (1):
Wherein
R
1represent hydrogen atom, halogen atom, methyl, methoxyl group or methoxy;
R
2represent C1-C3 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 anti-configuration,
(hereinafter, being called compound of the present invention);
[2] according to the ester compounds [1] described, wherein, in formula (1), the absolute configuration on the 1-position of cyclopropane ring is R configuration;
[3] according to the ester compounds [1] or [2] described, wherein, in formula (1), the two keys that exist on the substituting group on the 3-position of described cyclopropane ring are in E configuration or the mix-configuration in E configuration and Z configuration, and the ratio of described E configuration is more than 50%;
[4] according to the ester compounds [1] or [2] described, wherein, in formula (1), the two keys that exist on the substituting group on the 3-position of described cyclopropane ring are in E configuration;
[5] ester compounds according to [1] or [2], wherein in formula (1), R
2represent methyl;
[6] ester compounds according to [1] or [2], wherein in formula (1), R
2represent ethyl;
[7] ester compounds according to [1] or [2], wherein in formula (1), R
2represent isopropyl;
[8] ester compounds according to [3], wherein in formula (1), R
2represent methyl;
[9] ester compounds according to [3], wherein in formula (1), R
2represent ethyl;
[10] ester compounds according to [3], wherein in formula (1), R
2represent isopropyl;
[11] ester compounds according to [4], wherein in formula (1), R
2represent methyl;
[12] ester compounds according to [4], wherein in formula (1), R
2represent ethyl;
[13] ester compounds according to [4], wherein in formula (1), R
2represent isopropyl;
[14] according to the ester compounds described in any one in [1] to [13], wherein in formula (1), R
1represent fluorine atom;
[15] according to the ester compounds described in any one in [1] to [13], wherein in formula (1), R
1represent methyl;
[16] according to the ester compounds described in any one in [1] to [13], wherein in formula (1), R
1represent methoxyl group;
[17] according to the ester compounds described in any one in [1] to [13], wherein in formula (1), R
1represent methoxy;
[18] pest control agent, described pest control agent comprises according to ester compounds and inert carrier described in any one in [1] to [17]; With
[19] method for pest control, described method comprises: the step that the ester compounds according to described in any one in [1] to [17] of effective dose is applied to insect or insect habitat.
(invention effect)
Compound of the present invention has outstanding pest controling effect, therefore can be used as the active component for pest control agent.
Invention embodiment
Hereinafter, specific explanations the present invention.
The substituting group example of using is in the present invention as follows:
The example of the halogen atom using in this article comprises fluorine atom, chlorine atom, bromine atoms and iodine atom.
The example of the C1-C3 alkyl group using in this article comprises methyl, ethyl, propyl group and isopropyl.
In compound of the present invention, exist to be derived from the 1-position of cyclopropane ring and the isomer of two asymmetric carbon atoms on 3-position, and the isomer that is derived from the two keys that exist on the substituting group on the 3-position of cyclopropane ring.The present invention comprises that each has the mixture of the isomer of control of insect activity or the arbitrary proportion of these isomers.
The example of compound of the present invention comprises following compound.
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration;
The compound being represented by formula (1), wherein, the ratio of the two keys that exist on the substituting group on the 3-position of cyclopropane ring in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50%;
The compound being represented by formula (1), wherein, the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration;
The compound being represented by formula (1), wherein, the absolute configuration of the 1-position of cyclopropane ring be two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring in E configuration or the mix-configuration in E configuration and Z configuration, and the ratio of E configuration is more than 50%;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is that two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring are in E configuration;
The compound being represented by formula (1), wherein, R
1represent hydrogen atom;
The compound being represented by formula (1), wherein, R
1represent halogen atom;
The compound being represented by formula (1), wherein, R
1represent fluorine atom;
The compound being represented by formula (1), wherein, R
1represent methyl;
The compound being represented by formula (1), wherein, R
1represent methoxyl group;
The compound being represented by formula (1), wherein, R
1represent methoxy;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration and R
1represent fluorine atom;
The compound being represented by formula (1), wherein, the ratio of the two keys that exist on the substituting group on the 3-position of cyclopropane ring in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50%, and R
1represent fluorine atom;
The compound being represented by formula (1), wherein, the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration and R
1represent fluorine atom;
The compound being represented by formula (1), wherein, the absolute configuration of the 1-position of cyclopropane ring is that two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring ratio in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50%, and R
1represent fluorine atom;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring be two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring in E configuration, and R
1represent fluorine atom;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration and R
1represent methyl;
The compound being represented by formula (1), wherein, the ratio of the two keys that exist on the substituting group on the 3-position of cyclopropane ring in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50%, and R
1represent methyl;
The compound being represented by formula (1), wherein, the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration and R
1represent methyl;
The compound being represented by formula (1), wherein, the absolute configuration of the 1-position of cyclopropane ring be two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring in E configuration or the mix-configuration in E configuration and Z configuration and the ratio of E configuration be more than 50%, and R
1represent methyl;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is that two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring are in E configuration and R
1represent methyl;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration and R
1represent methoxyl group;
The compound being represented by formula (1), wherein, the ratio of the two keys that exist on the substituting group on the 3-position of cyclopropane ring in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50%, and R
1represent methoxyl group;
The compound being represented by formula (1), wherein, the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration and R
1represent methoxyl group;
The compound being represented by formula (1), wherein, the absolute configuration of the 1-position of cyclopropane ring is that two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring ratio in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50%, and R
1represent methoxyl group;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring be two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring in E configuration, and R
1represent methoxyl group;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration and R
1represent methoxy;
The compound being represented by formula (1), wherein, the ratio of the two keys that exist on the substituting group on the 3-position of cyclopropane ring in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50%, and R
1represent methoxy;
The compound being represented by formula (1), wherein, the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration and R
1represent methoxy;
The compound being represented by formula (1), wherein, the absolute configuration of the 1-position of cyclopropane ring is that two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring ratio in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50%, and R
1represent methoxy;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring be two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring in E configuration, and R
1represent methoxy;
The compound being represented by formula (1), wherein, R
2represent methyl;
The compound being represented by formula (1), wherein, R
2represent ethyl;
The compound being represented by formula (1), wherein, R
2represent isopropyl;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration and R
2represent methyl;
The compound being represented by formula (1), wherein, the ratio of the two keys that exist on the substituting group on the 3-position of cyclopropane ring in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50%, and R
2represent methyl;
The compound being represented by formula (1), wherein, the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration and R
2represent methyl;
The compound being represented by formula (1), wherein, the absolute configuration of the 1-position of cyclopropane ring is that two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring ratio in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50%, and R
2represent methyl;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring be two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring in E configuration, and R
2represent methyl;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration and R
2represent ethyl;
The compound being represented by formula (1), wherein, the ratio of the two keys that exist on the substituting group on the 3-position of cyclopropane ring in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50%, and R
2represent ethyl;
The compound being represented by formula (1), wherein, the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration and R
2represent ethyl;
The compound being represented by formula (1), wherein, the absolute configuration of the 1-position of cyclopropane ring be two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring in E configuration or the mix-configuration in E configuration and Z configuration and the ratio of E configuration be more than 50%, and R
2represent ethyl;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring be two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring in E configuration, and R
2represent ethyl;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration and R
2represent isopropyl;
The compound being represented by formula (1), wherein, the ratio of the two keys that exist on the substituting group on the 3-position of cyclopropane ring in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50%, and R
2represent isopropyl;
The compound being represented by formula (1), wherein, the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration and R
2represent isopropyl;
The compound being represented by formula (1), wherein, the absolute configuration of the 1-position of cyclopropane ring is that two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring ratio in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50%, and R
2represent isopropyl;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring be two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring in E configuration, and R
2represent isopropyl;
The compound being represented by formula (1), wherein, R
2represent methyl and R
1represent fluorine atom;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration and R
2represent methyl, and R
1represent fluorine atom;
The compound being represented by formula (1), wherein, the ratio of the two keys that exist on the substituting group on the 3-position of cyclopropane ring in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50% and R
2represent methyl, and R
1represent fluorine atom;
The compound being represented by formula (1), wherein, the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration and R
2represent methyl, and R
1represent fluorine atom;
The compound being represented by formula (1), wherein, the absolute configuration of the 1-position of cyclopropane ring is that two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring ratio in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50% and R
2represent methyl, and R
1represent fluorine atom;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is that two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring are in E configuration and R
2represent methyl, and R
1represent fluorine atom;
The compound being represented by formula (1), wherein, R
2represent ethyl and R
1represent fluorine atom;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration and R
2represent ethyl, and R
1represent fluorine atom;
The compound being represented by formula (1), wherein, the ratio of the two keys that exist on the substituting group on the 3-position of cyclopropane ring in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50% and R
2represent ethyl, and R
1represent fluorine atom;
The compound being represented by formula (1), wherein, the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration and R
2represent ethyl, and R
1represent fluorine atom;
The compound being represented by formula (1), wherein, the absolute configuration of the 1-position of cyclopropane ring be two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring in E configuration or the mix-configuration in E configuration and Z configuration, and the ratio of E configuration is more than 50%, and R
2represent ethyl, and R
1represent fluorine atom;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is that two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring are in E configuration and R
2represent ethyl, and R
1represent fluorine atom;
The compound being represented by formula (1), wherein, R
2represent isopropyl and R
1represent fluorine atom;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration and R
2represent isopropyl, and R
1represent fluorine atom;
The compound being represented by formula (1), wherein, the ratio of the two keys that exist on the substituting group on the 3-position of cyclopropane ring in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50% and R
2represent isopropyl, and R
1represent fluorine atom;
The compound being represented by formula (1), wherein, the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration and R
2represent isopropyl, and R
1represent fluorine atom;
The compound being represented by formula (1), wherein, the absolute configuration of the 1-position of cyclopropane ring is that two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring ratio in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50%, and R
2represent isopropyl, and R
1represent fluorine atom;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is that two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring are in E configuration and R
2represent isopropyl, and R
1represent fluorine atom;
The compound being represented by formula (1), wherein, R
2represent methyl and R
1represent methyl;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration and R
2represent methyl, and R
1represent methyl;
The compound being represented by formula (1), wherein, the ratio of the two keys that exist on the substituting group on the 3-position of cyclopropane ring in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50%, and R
2represent methyl, and R
1represent methyl;
The compound being represented by formula (1), wherein, the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration and R
2represent methyl, and R
1represent methyl;
The compound being represented by formula (1), wherein, the absolute configuration of the 1-position of cyclopropane ring is that two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring ratio in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50%, and R
2represent methyl, and R
1represent methyl;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is that two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring are in E configuration and R
2represent methyl, and R
1represent methyl;
The compound being represented by formula (1), wherein, R
2represent ethyl and R
1represent methyl;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration and R
2represent ethyl, and R
1represent methyl;
The compound being represented by formula (1), wherein, the ratio of the two keys that exist on the substituting group on the 3-position of cyclopropane ring in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50%, and R
2represent ethyl, and R
1represent methyl;
The compound being represented by formula (1), wherein, the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration and R
2represent ethyl, and R
1represent methyl;
The compound being represented by formula (1), wherein, the absolute configuration of the 1-position of cyclopropane ring is that two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring ratio in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50%, and R
2represent ethyl, and R
1represent methyl;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is that two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring are in E configuration and R
2represent ethyl, and R
1represent methyl;
The compound being represented by formula (1), wherein, R
2represent isopropyl and R
1represent methyl;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration and R
2represent isopropyl, and R
1represent methyl;
The compound being represented by formula (1), wherein, the ratio of the two keys that exist on the substituting group on the 3-position of cyclopropane ring in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50%, and R
2represent isopropyl, and R
1represent methyl;
The compound being represented by formula (1), wherein, the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration and R
2represent isopropyl, and R
1represent methyl;
The compound being represented by formula (1), wherein, the absolute configuration of the 1-position of cyclopropane ring is that two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring ratio in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50%, and R
2represent isopropyl, and R
1represent methyl;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring be two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring in E configuration, and R
2represent isopropyl, and R
1represent methyl;
The compound being represented by formula (1), wherein, R
2represent methyl and R
1represent methoxyl group;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration and R
2represent methyl, and R
1represent methoxyl group;
The compound being represented by formula (1), wherein, the ratio of the two keys that exist on the substituting group on the 3-position of cyclopropane ring in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50%, and R
2represent methyl, and R
1represent methoxyl group;
The compound being represented by formula (1), wherein, the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration, and R
2represent methyl, and R
1represent methoxyl group;
The compound being represented by formula (1), wherein, the absolute configuration of the 1-position of cyclopropane ring is that two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring ratio in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50%, and R
2represent methyl, and R
1represent methoxyl group;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is that two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring are in E configuration and R
2represent methyl, and R
1represent methoxyl group;
The compound being represented by formula (1), wherein, R
2represent ethyl and R
1represent methoxyl group;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration and R
2represent ethyl, and R
1represent methoxyl group;
The compound being represented by formula (1), wherein, the ratio of the two keys that exist on the substituting group on the 3-position of cyclopropane ring in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50%, and R
2represent ethyl, and R
1represent methoxyl group;
The compound being represented by formula (1), wherein, the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration and R
2represent ethyl, and R
1represent methoxyl group;
The compound being represented by formula (1), wherein, the absolute configuration of the 1-position of cyclopropane ring be two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring in E configuration or the mix-configuration in E configuration and Z configuration, and the ratio of E configuration is more than 50% and R
2represent ethyl, and R
1represent methoxyl group;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is that two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring are in E configuration and R
2represent ethyl, and R
1represent methoxyl group;
The compound being represented by formula (1), wherein, R
2represent isopropyl and R
1represent methoxyl group;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration and R
2represent isopropyl, and R
1represent methoxyl group;
The compound being represented by formula (1), wherein, the ratio of the two keys that exist on the substituting group on the 3-position of cyclopropane ring in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50% and R
2represent isopropyl, and R
1represent methoxyl group;
The compound being represented by formula (1), wherein, the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration and R
2represent isopropyl, and R
1represent methoxyl group;
The compound being represented by formula (1), wherein, the absolute configuration of the 1-position of cyclopropane ring is that two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring ratio in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50% and R
2represent isopropyl, and R
1represent methoxyl group;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is that two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring are in E configuration and R
2represent isopropyl, and R
1represent methoxyl group;
The compound being represented by formula (1), wherein, R
2represent methyl and R
1represent methoxy;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration and R
2represent methyl, and R
1represent methoxy;
The compound being represented by formula (1), wherein, the ratio of the two keys that exist on the substituting group on the 3-position of cyclopropane ring in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50% and R
2represent methyl, and R
1represent methoxy;
The compound being represented by formula (1), wherein, the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration and R
2represent methyl, and R
1represent methoxy;
The compound being represented by formula (1), wherein, the absolute configuration of the 1-position of cyclopropane ring is that two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring ratio in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50%, and R
2represent methyl, and R
1represent methoxy;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is that two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring are in E configuration and R
2represent methyl, and R
1represent methoxy;
The compound being represented by formula (1), wherein, R
2represent ethyl and R
1represent methoxy;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration and R
2represent ethyl, and R
1represent methoxy;
The compound being represented by formula (1), wherein, the ratio of the two keys that exist on the substituting group on the 3-position of cyclopropane ring in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50% and R
2represent ethyl, and R
1represent methoxy;
The compound being represented by formula (1), wherein, the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration and R
2represent ethyl, and R
1represent methoxy;
The compound being represented by formula (1), wherein, the absolute configuration of the 1-position of cyclopropane ring is that two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring ratio in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50% and R
2represent ethyl, and R
1represent methoxy;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is that two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring are in E configuration and R
2represent ethyl, and R
1represent methoxy;
The compound being represented by formula (1), wherein, R
2represent isopropyl and R
1represent methoxy;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is R configuration and R
2represent isopropyl, and R
1represent methoxy;
The compound being represented by formula (1), wherein, the ratio of the two keys that exist on the substituting group on the 3-position of cyclopropane ring in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50% and R
2represent isopropyl, and R
1represent methoxy;
The compound being represented by formula (1), wherein, the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration and R
2represent isopropyl, and R
1represent methoxy;
The compound being represented by formula (1), wherein, the absolute configuration of the 1-position of cyclopropane ring is that two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring ratio in E configuration or the mix-configuration in E configuration and Z configuration and E configuration is more than 50% and R
2represent isopropyl, and R
1represent methoxy;
The compound being represented by formula (1), wherein, the absolute configuration on the 1-position of cyclopropane ring is that two keys of existing on the substituting group on the 3-position of R configuration and cyclopropane ring are in E configuration and R
2represent isopropyl, and R
1represent methoxy;
The compound being represented by formula (1), wherein, R
1represent hydrogen atom, methyl or methoxy methyl;
The compound being represented by formula (1), wherein, R
1absolute configuration on the 1-position of expression hydrogen atom, methyl or methoxy methyl and cyclopropane ring is R configuration;
The compound being represented by formula (1), wherein, R
1the two keys that exist on substituting group on the 3-position of expression hydrogen atom, methyl or methoxy methyl and cyclopropane ring are in E configuration;
The compound being represented by formula (1), wherein, R
1absolute configuration on the 1-position of expression hydrogen atom, methyl or methoxy methyl and cyclopropane ring is R configuration, and the two keys that exist on the substituting group on the 3-position of cyclopropane ring are in E configuration.
Method for the preparation of compound of the present invention is below described.
Compound of the present invention can for example be prepared by the following method.
(preparation method 1)
A kind of alcoholic compound that formula (2) is represented:
R wherein
1represent identical meanings as above,
Carboxylic acid compound with formula (3) expression:
R wherein
2represent identical meanings as above, and the substituting group on the 1-position of cyclopropane ring with
Relative configuration between substituting group on the 3-position of cyclopropane ring is anti-configuration,
Or the method for its reactive derivatives reaction.
The example of reactive derivatives comprises the carboxylic acid halides of the carboxylic acid compound being represented by formula (3), the ester of the acid anhydrides of the carboxylic acid that represented by formula (4), the carboxylic acid that represented by formula (4) etc.The example of carboxylic acid halides comprises chloride compounds and acylbromide compound, and the example of ester comprises methyl esters, ethyl ester etc.
This reaction is carried out conventionally under the existence of condensing agent or alkali in solvent.
The example of the condensing agent using in this reaction comprises dicyclohexylcarbodiimide and 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride.
The example of the alkali using in this reaction comprises organic base, as triethylamine, pyridine, N, and N-diethylaniline, 4-dimethylaminopyridine and diisopropylethylamine.
The example of the solvent using in this reaction comprises hydrocarbon, as benzene, toluene and hexane; Ether, as Anaesthetie Ether and oxolane; Halogenated hydrocarbons, as chloroform, carrene, 1,2-dichloroethane and chlorobenzene; And the mixture of these solvents; Etc..
The reaction time of this reaction is conventionally in the scope of 5 minutes to 72 hours.
The reaction temperature of this reaction conventionally in the scope of-20 ℃ to 100 ℃ (in the situation that the boiling point of the solvent using is lower than 100 ℃,-20 ℃ of boiling points to solvent), and preferably-5 ℃ to 100 ℃ (in the situation that the boiling point of the solvent using lower than 100 ℃ ,-5 ℃ of boiling points to solvent).
In this reaction, the alcoholic compound being represented by formula (2) of use can at random be set with the carboxylic acid compound being represented by formula (3) or the mol ratio of its reactive derivatives, and is preferably equimolar ratio or the ratio approaching with equimolar ratio.
The alcoholic compound being represented by formula (2) based on 1mol, condensing agent or alkali conventionally can be to use to the arbitrary proportion in excessive scope at 0.25mol, and preferred 0.5mol to 2mol.These condensing agents or alkali depend on by the carboxylic acid compound of formula (3) expression or the kind of its reactive derivatives suitably to be selected.
After reaction completes, conventionally reactant mixture is carried out to postprocessing working procedures, for example, reactant mixture is filtered and subsequently filtrate concentrated, or reactant mixture is poured into water and is used the solution of organic solvent extraction gained subsequently that organic layer is concentrated, can obtain compound of the present invention thus.Can be by the compound of the present invention of gained being purified as operations such as chromatography and distillations.
The alcoholic compound being represented by formula (2) is commercially available product, or the mixture of explaining in JP-A-2000-63329, and can therefore as commercially available product, buy, or can be according to the method preparation of describing in these are open.
Intermediate of the present invention can for example be prepared by method as follows.
(with reference to preparation method 1)
The carboxylic acid compound being represented by formula (3) can for example be prepared by method as follows.
That is, make carane aldehydo-ester (caronaldehyde ester) derivative by formula (6) expression:
Wherein R represents C1-C5 alkyl, and substituting group and cyclopropane ring on the 1-position of cyclopropane ring
3-position on substituting group between relative configuration be anti-configuration,
With the phosphate compound being represented by formula (7):
R wherein
2represent identical meanings as above,
The compound of reaction to obtain being represented by formula (8) under the existence of alkali:
Wherein R and R
2represent respectively identical meanings as above, and on the 1-position of cyclopropane ring
Relative configuration between substituting group on the 3-position of substituting group and cyclopropane ring is anti-configuration, the reaction that is further hydrolyzed under the existence of alkali, to prepare the carboxylic acid compound being represented by formula (3):
R wherein
2represent identical meanings as above, and the relative configuration between the substituting group on the 3-position of the substituting group on the 1-position of cyclopropane ring and cyclopropane ring is anti-configuration.
Conventionally, the carane aldehydo-ester derivative being represented by formula (6) based on 1mol, the phosphate compound being represented by formula (7) of the ratio of use in 1.0 to 1.5mol proportions and the alkali of the ratio within the scope of 1 to 10mol, and make they 0 ℃ to 80 ℃ and preferably the scope of 0 ℃ to 30 ℃ in polar solvent or non-polar solven, react, and can obtain thus the compound being represented by formula (8).The example of the alkali using in reaction comprises: alkali metal compound is as sodium methoxide and tert-butoxy potassium, metal hydride compound is as sodium hydride and hydrofining, and alkali metal amino compound is as two (TMS) Sodamide, two (TMS) lithium amide and lithium diisopropylamine.
The example of the polar solvent using in reaction comprises: ether is as diethyl ether and oxolane, and acid amides is as N, N-dimethylformaldehyde, and sulfoxide is as methyl-sulfoxide.The example of the non-polar solven using in reaction comprises: hydrocarbon is as benzene, toluene and hexane.
After reaction completes, reactant mixture is carried out to postprocessing working procedures, for example, reactant mixture is added to the water and is used the solution of organic solvent extraction gained, and subsequently organic layer is dried and is concentrated, and can obtain thus the compound being represented by formula (8).
In addition, in the step of reaction that the compound being represented by formula (8) is hydrolyzed, conventionally, the compound being represented by formula (8) based on 1mol, the alkali of the ratio of use within the scope of 1 to 10mol, and make subsequently they 0 ℃ to 80 ℃ and preferably the scope of 0 ℃ to 30 ℃ in solvent, react, and can obtain thus the carboxylic acid compound being represented by formula (3).The example of the alkali using in reaction comprises that alkali metal compound is as potassium hydroxide and sodium hydroxide.The embodiment of the solvent using in reaction comprises: ether is as Isosorbide-5-Nitrae-bis-
alkane, oxolane, ethylene glycol dimethyl ether, alcohol is as methyl alcohol, ethanol, propyl alcohol, and the mixture of water and these solvents.
After reaction completes, reactant mixture is carried out to postprocessing working procedures, for example, reaction solution acidifying is also used to organic solvent extraction subsequently, and subsequently organic layer is dried and is concentrated, and can obtain subsequently the carboxylic acid compound being represented by formula (3).
The carane aldehydo-ester derivative being represented by formula (5) can be according to Tetrahedron45, describing method preparation in 3039-3052 (1989).
The example that compound of the present invention has the insect of control efficiency to it comprises harmful arthropod, as harmful insect and harmful acarid, and following insect more specifically.
Semiptera (Hemiptera): Delphacidae (Planthoppers) is (as small brown rice planthopper (Laodelphax striatellus), brown planthopper (Nilaparvata lugens) and white back of the body rice fulgorid (Sogatella furcifera)), angle top Cicadidae (Leafhoppers) (as rice leafhopper (Nephotettix cincticeps) and nephotettix bipunctatus (Nephotettix virescens)), Aphidiadae (Aphids) (as cotten aphid (Aphis gossypu) and black peach aphid (Myzus persicae)), Miridae (Plant bugs) (the green stinkbug Nezara of Ru Huajiao antennata), beans honeybee coried (Riptortus clavetus), Japan two star stinkbugs (Eysarcoris lewisi), wedge angle two star stinkbugs (Eysarcoris parvus), Si Shi amber stinkbug (Plautia stali) and mixed tea wing stinkbug (Halyom orpha mista)), Aleyrodidae (White flies) is (as greenhouse whitefly (Trialeurodes vaporariorum), sweet potato whitefly (Bemisia tabaci) and Bemisia argentifolii (Bemisia argentifo) lii)), 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 cottonycushion scale (Icerya purchasi)), Tingidae (Lace bugs), Cimicidae (Bed bugs) (as bed bug (Cimex lectularius)), Psyllidae (Jumping plantlice) etc.,
Lepidoptera (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 imported cabbageworm (Pieris rapae)), Tortricidae (Tortricidae) is (as Adoxophyes spp belongs to (Adoxopheys spp.), oriental fruit moth (Grapholita molesta), adoxophyes moth (Adoxophy ex orana fasciata) and apple skin steinernema (Cydia pomonella)), Carposinidae (Carposinidae) (such as peach post fruit moth (Carposma mponensis)), 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 diamond-back moth (Plutella Xylostella)), Gelechidae (Gelechiidae) (as Pectinophora gossypiella (Pectinophora gossypiella)), Arctiidae (Arctiidae) (as fall webworm (Hyphantria cunea)), rain moth section (Tineidae) (as casemaking clothes moth (Tinea translucens) and curtain rain moth (Tineola bisselliella)) etc.,
Diptera (Diptera): Culex (Culex spp.) is (such as Culex pipiens pallens (Culex pipiens pallens), Culex tritaeniorhynchus (Culex tritaeniorhynchus) and Culex quinquefasciatus (Culex quinquefasciatus)), Aedes (Aedes spp.) (such as Aedes aegypti (Aedes aegypti) and aedes albopictus (Aedes albopictus)), Anopheles (Anopheles spp.) (such as Anopheles sinensis (Anopheles sinensis) with just than sub-anopheles (Anopheles gambiae)), Chironomidae (Chironomidae), Nuscidae (Muscidae) (as housefly (Musca domestica) and false stable fly (Muscina stabulans)), Calliphoridae (Calliphoridae), Flesh flies (Sarcophagidae), Fannia canicularis (little housefly), Anthomyiidae (Anthomyiidae) (such as delia platura (Delia platura) and green onion ground kind fly (Delia antiqua)), Tephritidae (Tephritidae), Drosophilidae (Drosophilidae), Phoridae (Phoridae) (such as the different eye fly in East Asia (Megaselia spiracularis)), Phlebotominae (phlebotominae) (such as moth fly (Clogmia albipunctata)), Moth files (Psychodidae), Simulidae (Simuliidae), Tabanidae (Tabanidae), sting Nuscidae (Stomoxyidae), Agromyzidae (Agromyzidae) etc.,
Coleoptera (Coleoptera): root Galeruca (Diabrotica spp.) (as chrysomelid in corn root firefly (Diabrotica virgifera virgifera) and cucumber 11 asterophyllite first food root subspecies (Diabrotica undecimpunctaca howardi)), Scarabaeidae (Scarabaeidae) (as bronze different beetle (Anomala cuprea) and polychrome different beetle (Anomala rufocuprea)), Curculionidae (Curculionidae) is (such as corn weevil (Sitophilus zeamais), rice water resembles (Lissorhoptrus oryzophilus) and adzuki bean weevil (Callosobruchuys chienensis)), TRenebrionidae (Tenebrionidae) (such as bloom first (Tenebrio molitor) and red flour beetle (Tribolium castaneum)), Chrysomelidae (Chrysomelidae) is (such as Oulema oryzae (Oulemaoryzae), 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), poison rove beetle (Paederus fuscipes) etc.,
Blattaria (Blattodea): Groton bug (Blattella germanica), Peroplaneta fluligginosa (Periplaneta fuliginosa), American cockroach (Periplaneta americana), the large Lian of foxiness (Periplaneta brunnea), oriental cockroach (Blatta orientalis) etc.;
Thrips (Thysanoptera): southern golden thistle horse (Thripspalmi), onion thrips (Thrips tabaci), Frankliniella occidentalis (Frankliniella occidentalis), beautiful flower thrips (Frankliniella intonsa) etc.;
Hymenoptera (Hymenoptera): Formicidae (Formicidae) is (such as MonomoriumMayr (Monomorium pharaosis), black ant (Formica fuscajaponica), without hair recessed smelly ant (Qchetellus glaber), crosspointer ant (Prtstomyrmex pungens), wide knot major part ant (Pheidole noda) and Argentine ant (Linepithema humile)), Ma Fengke (Long-legged wasps) is (such as the long pin hornet of China (Polistes chinensis antennalis), family hornet (Polistes jadwigae) and land hornet (Polistes rothneyi)), Vespidae (Vespidae) is (such as Japanese hornet (Vespa mandariniajaponica), yellowjacket (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 Ying section (mason wasp) etc.,
Orthoptera (Orthoptera): Gryllotalpidae (Mole crickets), locust Superfamily (Grasshoppers) etc.;
Siphonaptera (Shiphonaptera): ctenocephalides felis (Ctenocephalides felis), ctenocephalides canis (Ctenocephalides cams), Pulex irritans (Pulex irritants), Xanthopsyllacheopis (Xenopsylla cheopis) etc.;
Anoplura (Anoplura): body louse (Pediculus humanus corporis), hair lice (Phthirus pubis), haematopinus eurysternus (Haematopinus eurysternus), sheep lice (Dalmalinia ovis) etc.;
Isoptera (Isoptera): Reticulitermes (Reticulitermes spp.) is (such as eastern subterranean termite (Reticulitermes speratus), Workers of Coptotermes formosanus Shiraki (Coptotermes formosanus), American-European reticulitermes flavipe (Reticulitermes flavipes), U.S. reticulitermes flavipe (Reticulitermes hesperus), Reticulitermes virginicus (Reticulitermes virgmicus), 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 (Inctsttermes minor)), and moving Cryptotermes (Zootermopsis spp.) (such as the ancient termite (Zootermopsis nevadensis) in Nevada) etc.,
Acarina (Acarina): Tetranychidae (Tetranychidae) is (as Tetranychus urticae (Tetranychus urticae), god Ze Shi tetranychid (Tetranychus kanzawai), panonychus citri (Panonychus cttrt), panonychus ulmi (Panonychus ulmi) and Oligonychus (Oligonychus spp.)), Eriophyidae (Eriophyidae) (as tangerine peronium goitre mite (Aculops pelekassi) and steinman pin thorn goitre mite (Aculus schlechtendali)), Tarsonemidae (Tarsonemidae) (as Polyphagotarsonemus latus Banks (Polyphagotarsonemus latus)), Tenuipalpidae (Tenuipalpidae), Tuckerellidae (Tuckerellidae), Ying Pi section (Ixodxdae) is (such as haemaphysalis longicornis (Haemaphysalis longicornis), haemaphysalis flava (Haemaphysalis flava), Dermacentor variabilis (Dermacentor variabilis), ixodes ovatus (Ixodes ovatus), ixodes persulcatus (Ixodes persulcatus), the hard tick of black leg (Ixodes scapularis), boophilus microplus (Boophilus microplus), lone star tick (Amblyomma americanum) and brown dog tick (Rhipicephalus sangumeus)), 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 (Dermanyssus gallinae)), Trombidiidae (Trombiculidae) (as leptotrombidium akamushi (Leptotrombidium akamushi)) etc.,
Araneida (Araneae): Japanese red is bitten spider (Chiracanthium japonicum), redback spider (Latrodectus hasseltii), Tetragnathidae section (Tetragnathidae), eight knurl Chinese mugwort spiders (Cyclosa octotuberculata), Argiope amoena (Argiope amoena), argiope bruennichii (Argiope bruennichii), large abdomen circle spider (Araneus ventricosus), forest Atrax robustus (Agelena silvatica), black panther spider (Pardosa astrtgera), yellowish-brown crafty spider (Dolomedes sulfurous), black panther spider (Pardosa astrtgera), 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 rubigmosus) 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 prumosus (Brandt)) and smooth pillworm (Porcellio scaber Latreille)), 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 (Limax flavus) etc.
Pest control agent of the present invention comprises compound of the present invention and inert carrier.Conventionally pest control agent of the present invention is mixed with to the preparation the following describes.The example of preparation comprises oily solution, emulsifiable concentrates, wetting powder, can flow preparation (for example, waterborne suspension, or water-based emulsion), microcapsules, powder agent, granula, aerosol, carbonic acid gas preparation, hot flashing preparation (for example, insecticidal incense coil, electricity pesticide tablet or imbibition core pattern hot flashing insecticide), piezoelectricity insecticidal preparation, hot smoking agent (for example, self-ignition type fumigant, chemical reaction type fumigant or porous ceramic plate fumigant), that does not heat (for example evapotranspires preparation, the resin preparation that evapotranspires, the paper preparation that evapotranspires, the adhesive-bonded fabric preparation that evapotranspires, knit goods evapotranspire preparation or distillation tablet), aerosol formulation (for example, atomization preparation), directly contact preparation (for example, sheet shape contact preparation, band shape contact preparation or net form contact preparation), ULV preparation and poison bait.
The example of the method for preparation comprises following methods.
(1) comprise compound of the present invention is mixed with solid carrier, liquid-carrier, gaseous carrier, poison bait etc., if need to add afterwards surfactant and other auxiliary agents for preparation, and the method being further processed.
(2) comprise and will not contain the method for the base material of active component with compound dipping of the present invention.
(3) comprise compound of the present invention is mixed with base material, afterwards mixture is carried out the method for mold treatment.
Depend on dosage form, these preparations contain the compound of the present invention of 0.001 to 98 % by weight conventionally.
The example of the inert carrier using in preparation comprises inert solid carrier, inertia liquid carrier and inertia gaseous carrier.
The example of the solid carrier using in preparation comprises: clay (for example, kaolinton, diatomite, bentonite, Fubasami clay or acid kaolin), synthetic oxidizing aqueous silicon, talcum, pottery, other inorganic minerals are (for example, sericite, quartz, sulphur, activated carbon, calcium carbonate or aqueous silicon dioxide) or fine powder or the particle of chemical fertilizer (for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ammonium chloride or urea) etc.; Material in room temperature in solid form (for example, 2,4,6-triisopropyl-1,3,5-tri-
alkane, naphthalene, paracide, camphor or adamantane); And the felt, fiber, fabric, braid, thin slice, paper, line, foam, porous material and the multifilament that comprise one or more materials in the group of selecting free the following composition: (for example, polyvinyl resin is as low density polyethylene (LDPE), straight-chain low density polyethylene and high density polyethylene (HDPE) for wool, silk, cotton, fiber crops, paper pulp, synthetic resin; Ethylene-vinyl ester copolymer is as vinyl-vinyl acetate copolymer; Ethylene-methyl acrylate copolymer is as ethylene-methyl methacrylate methyl terpolymer and ethylene-methyl methacrylate ethyl ester copolymer; Vinyl-acrylate copolymer is as ethylene-methyl acrylate copolymer and ethylene-ethyl acrylate copolymer; Vinyl-vinyl polymers of carboxylic acid is as ethylene-acrylic acid copolymer; Ethene-tetracyclododecane copolymer; Acrylic resin is as Noblen and propylene-ethylene copolymers; Poly-_ 4-methylpentene-1, PB Polybutene-1, polybutadiene, polystyrene; Acrylonitrile-styrene resin; Acrylonitrile-butadiene-styrene resin; Styrenic elastomer is as styrene-conjugated diene block copolymer and hydrogenated styrene-conjugated diene block copolymer; Fluororesin; Acrylic resin is as polymethyl methacrylate; Polyamide is as nylon 6 and nylon 66; Mylar is as PETG, PEN, polybutylene terephthalate (PBT) and poly-cyclohexene-terephthalic acid (TPA) two methylene esters (polycyclohexylene dimethylene terephthalate); Or porous resin is as Merlon, polyacetals, polypropylene acyl group sulfone, polyarylate, hydroxybenzoic acid polyester, polyimide, polyestercarbonate, polyhenylene ether resin, polyvinyl chloride, polyvinylidene chloride, polyurethane, foamed polyurethane, foam polypropylene and foam ethene), glass, metal and pottery.
The example of liquid-carrier comprises aromatic series or aliphatic hydrocarbon (for example, dimethylbenzene, toluene, Fluhyzon, phenyl xylyl ethane, kerosene, light oil, hexane or cyclohexane), halogenated hydrocarbons (for example, chlorobenzene, carrene, dichloroethane or trichloroethanes), alcohol (for example, methyl alcohol, ethanol, isopropyl alcohol, butanols, hexanol, benzylalcohol or ethylene glycol), ether (for example, diethyl ether, glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, oxolane Huo diox), ester (for example, ethyl acetate or butyl acetate), ketone (for example, acetone, methyl ethyl ketone, methylisobutylketone or cyclohexanone), nitrile (as, acetonitrile or isobutyronitrile), sulfoxide (for example, methyl-sulfoxide), acid amides (for example, DMF, DMA or N-methyl-pyrrolidones), alkylene carbonates (for example, propylene carbonate), vegetable oil (for example, soybean oil or cottonseed oil), plants essential oil (for example, orange oil, oil of hyssop or lemon oil) and water.
The example of gaseous carrier comprises butane gas, Chlorofluorocarbons (CFCs), liquefied petroleum gas (LPG), dimethyl ether and carbonic acid gas.
The example of surfactant comprises alkyl aryl ether, polyglycol ether, polyol ester and the sugar alcohol derivant of alkyl sulfate, alkylsulfonate, alkylaryl sulfonates, alkyl aryl ether, polyoxyethylene.
The example of other auxiliary agents that preparation is used comprises adhesive, dispersant and stabilizing agent.Instantiation comprises: casein, gelatin, polysaccharide are (for example, starch, gum Arabic, cellulose derivatives or alginic acid), lignin derivative, bentonite, carbohydrate, synthetic polymer (for example, polyvinyl alcohol or PVP(polyvinyl pyrrolidone)), polyacrylic acid, BHT (2,6-, bis--tert-butyl group _ 4-cresols) and BHA (mixture of the 2-tert-butyl group _ 4-metoxyphenol and the 3-tert-butyl group _ 4-metoxyphenol).
Example for the base material of insecticidal incense coil comprises: plant powder is if wood powder and vinasse powder and adhesive are as the mixture of stacte material powder, starch and glutelin.
Example for the base material of electric pesticide tablet comprises: the sheet that the fibril of the sheet obtaining by sclerosis velveteen and the mixture by sclerosis velveteen and paper pulp obtains.
The example that is used for the base material of self-ignition type fumigant comprises that flammable heat release reagent is as nitrate, nitrite, guanidinesalt, potassium chlorate, NC Nitroncellulose, ethyl cellulose and wood powder; Thermolysis stimulant is as alkali metal salt, alkali salt, bichromate and chromate; The carrier of oxygen is as potassium nitrate; Burning supporting agent is as melamine and powdered starch; Incremental agent is as diatomite, and adhesive is as rubber polymer.
The example that is used for the base material of chemical reaction type fumigant comprises that heat release reagent is as alkali metal sulphide, polysulfide, sulfhydrate and calcium oxide; Catalytic reagent is as carbonaceous material, cementite and alukalin; Organic foam agent is as Celogen Az, benzene sulfonyl hydrazide, dinitropentamethylenetetramine, polystyrene and polyurethane; And filler is as native fiber bar and synthetic fibre strip.
As the evapotranspire example of the resin that the base material of agent uses of resin, comprise that polyvinyl resin is as low density polyethylene (LDPE), straight-chain low density polyethylene and high density polyethylene (HDPE); Ethylene-vinyl ester copolymer is as vinyl-vinyl acetate copolymer; Ethylene-methyl acrylate copolymer is as ethylene-methyl methacrylate methyl terpolymer and ethylene-methyl methacrylate ethyl ester copolymer; Vinyl-acrylate copolymer is as ethylene-acrylic acid methyl ester copolymer and ethylene-ethyl acrylate copolymer; Vinyl-vinyl polymers of carboxylic acid is as ethylene-acrylic acid copolymer; Ethene-tetracyclododecane copolymer; Acrylic resin is as propylene copolymer and propylene-ethylene copolymers; Poly-_ 4-methylpentene-1, PB Polybutene-1, polybutadiene, polystyrene, acrylonitrile-styrene resin; Acrylonitrile-butadiene-styrene resin; Styrenic elastomer is as the styrene-conjugated diene block copolymer of styrene-conjugated diene block copolymer and hydrogenation; Fluororesin; Acrylic resin is as polymethyl methacrylate; Polyamide is as nylon 6 and nylon 66; Mylar is as PETG, PEN, poly butylene succinate (polybutylene butalate) and poly-cyclohexene-terephthalic acid (TPA) two methylene esters; Merlon, polyacetals, polypropylene acyl group sulfone, polyarylate, hydroxybenzoic acid polyester, PEI, polyestercarbonate, polyhenylene ether resin, polyvinyl chloride, polyvinylidene chloride and polyurethane.These base materials can be used separately or being used in combination with two or more types.If needed, plasticizer for example, can be added in these base materials as phthalic acid ester (, repefral, dioctyl phthalate etc.), adipate ester and stearic acid.The resin agent of evapotranspiring can be prepared in the following manner: compound of the present invention is mixed with above-mentioned base material, mixture is mediated, afterwards it undertaken molded by injection moulding, extrusion molding or compression moulding.If needed, can carry out further molded or cutting step to resulting resin formulation, to be processed as sheet shape, film shape, with shape, net form or linear and so on shape.These resin formulation can be processed as to Animal neck ring, animal ear tag, sheet product, trap strips, gardening support and other products.
The example that is used for the base material of poison bait comprises that bait composition is as flour, vegetable oil, sugar and avicel cellulose, antioxidant is as dibutyl hydroxy toluene and nordihydroguaiaretic acid, preservative is as dehydroactic acid, for the unexpected food rcstriction agent of children and pet as chilli powder; Attract insects spices is as cheese spices, onion spice and peanut oil.
Insect pest control method of the present invention for example, is undertaken by the compound of the present invention of effective dose is applied to insect or its habitat (plant corpus, soil, indoor, animal body, Che Nei or outdoor open space) with the form of pest control agent of the present invention conventionally.
For the method that applies pest control agent of the present invention, comprise following methods, and depend on pest control agent of the present invention form, apply area etc. and suitably select.
(1) comprise the method that pest control agent former state of the present invention is applied to the habitat of insect or insect.
(2) comprise pest control agent of the present invention with solvent as water dilutes, afterwards dilution is sprayed to the method for the habitat of insect or insect.
In this case, conventionally pest control agent of the present invention is configured to emulsifiable concentrates, wetting powder, preparation, microcapsules etc. can flow.Conventionally said preparation is diluted so that the concentration of compound of the present invention can be in 0.1 to 10,000ppm scope.
(3) comprise pest control agent of the present invention is heated in the habitat of insect, thus the method that makes active component volatilize and spread from pest control agent.
In this case, the applied amount of compound of the present invention and any of concentration can depend on pest control agent of the present invention formulation, apply the cycle, apply area or applying method, or the kind of insect, the destruction of causing etc. and suitably determine.
When pest control agent of the present invention is during for the prevention of epidemic disease, be in application to the amount that applies in the situation in space conventionally 0.0001 to 1,000mg/m
3the scope of compound of the present invention in, and be in application in the situation of plane 0.0001 to 1 000mg/m
2the scope of compound of the present invention in.The form that depends on preparation, insecticidal incense coil or electric pesticide tablet etc. volatilizees active component and is spread by heating, to reach application.Make resin agent, paper agent, adhesive-bonded 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 standing, and place 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 during as the epizoon of dog, cat, rat and mouse, can be applied to these animals by the known method in veterinary applications as ox, horse, pig, sheep, goat and chicken and small animal by pest control agent of the present invention for preventing and treating domestic animal.Particularly, when needs system is prevented and treated, using pest control agent of the present invention as tablet, with mixture or the suppository of feed, or (comprise muscle, subcutaneous, vein and peritonaeum injection) by injecting and be administered to animal.On the other hand, 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 processing, or with hair washing preparation washing animal, or necklace or ear tag that the agent of being evapotranspired by resin is made are placed to animal.In the situation that being administered to animal body, the dosage of compound of the present invention is conventionally in the weight of animals of every 1kg is 0.01 to 1,000mg scope.
When pest control agent of the present invention is used for preventing and treating the insect in farmland, the example of applying method comprises spraying processing, soil treatment, seed treatment and immersion treatment.
When pest control agent of the present invention is when preventing and treating the insect in farmland, consumption can depend on the cycle of applying, applies area, applying method and other factors and vary widely, and with every 10,000m
2compound meter of the present invention is conventionally in 1 to 10,000g scope.When pest control agent of the present invention being configured to emulsifiable concentrates, wetting powder, the preparation that can flow etc.; conventionally by pest control agent at dilute with water so that the concentration of active component becomes 0.01 to 10; after the scope of 000ppm, apply, and conventionally particle or pulvis are in statu quo applied.
Can by the water dilution Direct spraying of these preparations or preparation insect maybe to protect its be not subject to plant that insect affects as crop plants on, or it can be used in soil treatment with control and perch the insect on the soil of ploughing.
Apply also and can carry out by the following method: directly the resin formulation that is configured as sheet or wire or rope form preparation is twisted in around plant, preparation is placed near plant, or preparation is dispersed on the soil surface at root place.
Compound of the present invention can be used as and plough as farm, rice field, lawn or orchard, or the pest control agent in untilled ground.Compound of the present invention can be below plantation be prevented and treated in the arable land etc. of " plant crop " and is perched the insect in arable land.
Crops: corn, rice, wheat, barley, rye, oat, Chinese sorghum, cotton, soybean, peanut, buckwheat, sugar beet, rape seed, sunflower, sugar are used sugarcane, tobacco etc.;
Vegetables: Solanaceae (Solanaceae) plant (eggplant, tomato, green pepper, capsicum, potato etc.), Curcurbitaceae (Cucurbitaceae) plant (cucumber, pumpkin, custard squash, watermelon, muskmelon etc.), Cruciferae (Cruciferae) plant (ternip (Japanese radish), turnip, horseradish, thumb dish, Chinese cabbage, wild cabbage, leaf mustard, broccoli, cauliflower etc.), composite family (Compositae) plant (burdock, crowndaisy chrysanthemum, arithoke, lettuce etc.), Liliaceae (Liliaceae) plant (shallot, onion, garlic, asparagus etc.), Umbelliferae (Umbelliferae) plant (carrot, parsley, celery, parsnip etc.), Chenopodiaceae (Chenopodiaceae) plant (spinach, chard etc.), Labiatae (Labiatae) plant (Japanese purple perilla, peppermint, sweet basil etc.), strawberry, sweet potato, Chinese yam, aroid etc.,
Fruit tree: pomaceous fruits (apple, European pear, sand pear, pawpaw, Quinces Quince etc.), drupe class (peach, plum, peach are refuted Lee, Japanese plum, cherry, apricot, Lee etc.), hesperidium aurantium class (satsuma mandarin, tangerine, lemon, come lemon, grapefruit etc.); Nut fruits (chestnut, English walnut, hazel, almond, pistachio, cashew nut, macadamia nut etc.), soft fruits (cowberry, Cranberry, blackberry, blueberry, red raspberry etc.), grape, persimmon, olive, loquat, banana, coffee, nipa palm, coconut, oil palm etc.;
Other trees except fruit tree: tea, mulberry, woody plant (azalea, camellia, silk ball, tea plum, Chinese anise (Illicium religiosum), cherry tree, Chinese tulip tree, crape myrtle, sweet-scented osmanthus etc.), street tree (Ash, birch, Lai wood, eucalyptus, ginkgo, cloves, maple, oak, poplar, cercis, sweetgum, plane tree, beech tree, Japanese arbor-vitae, fir, siebold hemlock, Chinese juniper, pine, dragon spruce, Chinese yew, elm, horse chestnut etc.), Jia Opulus, podocarpus (Podocarpus macrophyllus), Japanese cedar, Japanese cypress, crotons, winged euonymus, hawthorn (Chinease howthorn) etc.,
Lawn: Korea lawn grass (Japanese lawn grass, manilagrass etc.), Bermuda grass (honeysuckle Bermuda grass (Cynodon dactylon) etc.), bent grass (common bent grass, the bent grass of crawling (Agrostis stolonifera), thin and delicate bent grass (Agrostis tenuis) etc.), annual bluegrass (kentucky blue grass, rough stalked blue grass etc.), fescue grass (huge fescue grass, chewing fescue, chewing fescue etc. crawls), perennial ryegrass (lolium temulentum, perennial ryegrass etc.), orchardgrass, timothy grass etc.;
Other: flower (rose, carnation, chrysanthemum, Lisianthus (purple Lisianthus), silk China pink, African daisy, marigold, Salvia japonica, green winter eggplant, Verbena officinalis, tulip, aster, rough gentian, lily, pansy, ivyleaf cyclamen, orchis, the lily of the valley, lavender, violet stock violet (stock), rape, common primrose, poinsettia sword lily, Bowring cattleya, daisy, Verbena officinalis, blue, begonia etc.), biofuel plant (manioca, red blue flower, flax shepherd's purse, switchgrass, awns (Miscanthus), Phalaris grass, giantreed, hibiscus cannabinus, cassava, willow etc.), ornamental foliage plant, Deng.
" plant crop " comprises genetically modified plants crop above.
Compound of the present invention can mix or be used in combination with other insecticides, miticide, nematocide, soil pests control agent, fungicide, weed killer herbicide, plant growth regulator, repellant, synergist, fertilizer or soil modifier.
The example of this insecticide and acaricidal active component comprises:
(1) synthetic pyrethroid compound:
Acrinathrin (acrinathrin), allethrin (allethrin), betacyfluthrin (beta-cyfluthrin), Biphenthrin (bifenthrin), cycloprothrin (cycloprothrin), cyfloxylate (cyfluthrin), cyhalothrin (cyhalothrin), cypermethrin (cypermethrin), empenthrin (empenthrin), decis (deltamethrin), S-sumicidin (esfenvalerate), ether chrysanthemum ester (ethofenprox), fenpropathrin (fenpropathrin), sumicidin (fenvalerate), flucythrinate (flucythrinate), trifluoro chrysanthemum ester (flufenoprox), flumethrin (flumethrin), taufluvalinate (fluvalinate), halfenprox (halfenprox), Imiprothrin (imiprothrin), permethrin (permethrin), prallethrin (prallethrin), pyrethrin (pyrethrins), resmethrin (resmethrin), beta-cypermethrin (sigma-cypermethrin), silafluofene (silafluofen), tefluthrin (tefluthrin), tralomethrin (tralomethrin), transfluthrin (transfluthrin), tetramethrin (tetramethrin), phenothrin (phenothrin), cyphenothrin (cyphenothrin), alpha-cypermethrin (alpha-cypermethrin), zeta-cypermethrin (zeta-cypermethrin), gamma cyhalothrin (lambda-cyhalothrin), essence gamma cyhalothrin (gamma-cyhalothrin), PH (furamethrin), taufluvalinate (tau-fluvalinate), methoxy benzyl Flumethrin (metofluthrin), 2,2-dimethyl-3-(1-acrylic) cyclopropane-carboxylic acid [2,3,5,6-tetrafluoro _ 4-methyl-benzyl] ester, 2,2-dimethyl-3-(2-methyl-1-propylene base) cyclopropane-carboxylic acid [2,3,5,6-tetrafluoro _ 4-(methoxy) benzyl] ester, 2,2,3,3-tetramethyl cyclopropane-carboxylic acid [2,3,5,6-tetrafluoro _ 4-(methoxy) benzyl] ester etc.,
(2) organic phosphorus compound:
Orthene (acephate), aluminum phosphate (Aluminum phosphide), demethylation fourth Diothyl (butathiofos), cadusafos (cadusafos), chlorethoxyfos (chlorethoxyfos), chlorfenviphos (chlorfenvinphos), chlopyrifos (chlorpyrifos), chlorpyrifos-methyl (chlorpyrifos-methyl), cynock (cyanophos (abbreviation CYAP)), diazinon (diazinon), DCIP (dichlorodiisopropyl ether), dichlofenthion (dichlofenthion (abbreviation ECP)), dichlorvos (dichlorvos (abbreviation DDVP)), Rogor (dimethoate), dimethylvinphos (dimethylvinphos), disulfoton (disulfoton), EPN (EPN), ethion (ethion), phonamiphos (ethoprophos), etrimfos (etrimfos), fenthion (fenthion (abbreviation MPP)), sumithion (fenitrothion (abbreviation MEP)), lythidathion (fosthiazate), formothion (formothion), phosphine (hydrogen phosphide), isofenphos (isofenphos), oxazole phosphorus (isoxathion), malathion (malathion), fenthion sulfoxide (mesulfenfos), methidathion (methidathion (abbreviation DMTP)), nuvacron (monocrotophos), 2-dichloroethylk dimethyl phosphate (naled (abbreviation BRP)), thiometan (oxydeprofos (abbreviation ESP)), parathion (parathion), Phosalone (phosalone), phosmet (phosmet (abbreviation PMP)), pirimiphos-methyl (pirimiphos-methyl), pyridaphethione (pyridafenthion), quinalphos (quinalphos), phenthoate dimephenthoate cidial (phenthoate (abbreviation PAP)), Profenofos (profenofos), Kayaphos (propaphos), Toyodan (prothiofos), pyraclofos (pyraclorfos), salithion (salithion), sulprofos (sulprofos), butyl pyrimidine phosphorus (tebupirimfos), Swebate (temephos), Ravap (tetrachlorvinphos), terbufos (terbufos), thiometon (thiometon), chlorophos (trichlorphon (abbreviation DEP)), vamidothion (vamidothion), thimet (phorate), cadusafos (cadusafos) etc.,
(3) carbamate compounds:
Alanycarb (alanycarb),
worm prestige (bendiocarb), Benfuracard micro (benfuracarb), Bassa (BPMC), carbaryl (carbaryl), carbofuran (carbofuran), carbosulfan (carbosulfan), cloethocarb (cloethocarb), ethiofencarb (ethiofencarb), Bassa (fenobucarb), fenothiocarb (fenothiocarb), fenoxycarb (fenoxycarb), furathiocarb (furathiocarb), Mobucin (isoprocarb (abbreviation MIPC)), meta-tolyl-N-methylcarbamate (MTMC) (metolcarb), Methomyl (methomyl), methiocarb (methiocarb), carbaryl (NAC), oxamyl (oxamyl), Aphox (pirimicarb), unden (propoxur (abbreviation PHC)), XMC (xMC), thiodicarb (thiodicarb), Meobal (xylylcarb), Aldicarb (aldicarb) etc.,
(4) nereistoxin (Nereistoxin) compound:
Cartap (cartap), bensultap (bensultap), thiocyclam (thiocyclam), desinsection list (monosultap), dimehypo (bisultap) etc.;
(5) anabasine compound:
Imidacloprid (imidacloprid), Nitenpyram (nitenpyram), Acetamiprid (acetamiprid), Diacloden (thiamethoxam), thiacloprid (thiacloprid), MTI-446 (dinotefuran), clothianidin (clothianidin) etc.;
(6) benzoyl carbamide compound:
Fluorine pyridine urea (chlorfluazuron), two two flufenoxurons (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), triaguron (triazuron) etc.,
(7) phenyl pyrazole compounds:
Acetyl worm nitrile (acetoprole), second worm nitrile (ethiprole), ethiprole (fipronil), methylene ethiprole (vaniliprole), pyridine ethiprole (pyriprole), pyrazine ethiprole (pyrafluprole) etc.;
(8) Bt toxin insecticide:
Derive from the spore alive of bacillus thuringiensis,Bt (Bacillus thuringiesis) and the crystal toxin of being prepared by bacillus thuringiensis,Bt, 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 (dieldrin), gram (dienochlor), 5a,6,9,9a-hexahydro-6,9-methano-2,4 (endosulfan), methoxychlor (methoxychlor) etc. everywhere;
(11) natural insecticide:
Machine oil, nicotine sulphate (nicotine-sulfate);
(12) other insecticides:
Avermectin (avermectin-B), fenisobromolate (bromopropylate), Buprofezin (buprofezin), capillary (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), multiple killing teichomycin (spinosad), sulfluramid (sulfluramid), Tolfenpyrad (tolfenpyrad), triaguron (triazamate), Flubendiamide (flubendiamide), woods skin does not have fourth (lepimectin), arsenic acid, different thiophene worm azoles (benclothiaz), nitrolim, calcium polysulfide, Niran (chlordane), dichlorodiphenyl trichloroethane (DDT), DSP, phonetic worm amine (flufenerim), flonicamid (flonicamid), phonetic worm amine (flurimfen), Carzol (formetanate), Carbam NCS (metam-ammonium), metham-sodium (metam-sodium), Celfume (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 active component of repellant comprises N, N-diethyl-m-toluamide, limonene, linalool, citronellal, menthol, menthones, hinokitiol, citronellol, cineole, indoxacarb (indoxacarb), carane-3,4-glycol, MGK-R-326, MGK-R-874 and BAY-KBR-3023.
The example of the active component of synergist comprises 5-[2-(2-butoxy ethyoxyl) ethoxyl methyl] _ 6-propyl group-1,3-benzo dioxole (benzodioxol), N-(2-ethylhexyl) dicyclo [2.2.1] heptan-5-alkene-2,3-dicarboximide, eight chlorine dipropyl ethers, sulfo-cyanoacetic acid isobornyl and N-(2-ethylhexyl)-1-isopropyl _ 4-methyl bicycle [2.2.2] be pungent-5-alkene-2, and 3-dicarboximide.
Embodiment
Below by preparation example, describe in more detail the present invention with reference to preparation example, formulation example and test case, but the invention is not restricted to these embodiment.
First, the preparation example of compound of the present invention is as follows.?
1in H-NMR, for example, the description list of " 1.18+1.19 (s+s, 3H) " is shown in the peak that 1.18ppm and 1.19ppm exist substance, and that the integrated value at these two peaks is totally 3H.
Preparation example 1
4-methoxy-2,3,5,6-ptfe benzyl alcohol (0.30g, 1.34mmol) and in pyridine (0.2mL), add toluene (5mL), and add wherein (1R)-trans-3_[(E)-2-cyano group-2-methoxy] _ 2, the toluene of 2-dimethylcyclopropane formyl chloride (0.28g, 1.31mmol) (2mL) solution.By reactant mixture after stirring at room 12 hours, reaction solution is poured in the mixture being comprised of 5% hydrochloric acid of 5mL and the frozen water of 30mL, and is extracted with ethyl acetate the solution of gained.The saturated brine of 20mL and the washing of the saturated sodium bicarbonate aqueous solution of 5mL for reactant mixture, and by organic layer process dried over mgso.Concentrated solution under reduced pressure, and residue is carried out to silica gel column chromatography, obtain (1R)-trans-3-[(E of 0.46g)-2-cyano group-2-methoxy-ethylene base]-2,2-dinethyl cyclopropane carboxylic acid 4-methoxy-2,3,5,6-ptfe benzyl ester (hereinafter, be called compound of the present invention (1)), it is expressed from the next:
Weak yellow liquid:
1h-NMR (CDCl
3, TMS) δ (ppm): 1.19 (s, 3H), 1.32 (s, 3H), 1.59 (d, 1H), 2.29 (m, 1H), 3.40 (s, 3H), 3.62 (s, 3H), 4.59 (s, 2H), 5.25 (s, 2H), 5.26 (d, 1H)
Preparation example 2
To 4-methoxy-2,3,5,6-tetrafluorobenzyl alcohol (550mg, 2.46mmol) with (1R)-trans-3-[(1E)-2-cyano group-2-ethoxy ethylene base]-2, in the chloroformic solution of 2-dinethyl cyclopropane carboxylic acid (508mg, 2.43mmol) (5mL), add 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (610mg, 3.18mmol) and 4-dimethylaminopyridine (20mg).By reactant mixture after stirring at room 12 hours, in reaction solution, pour water into, and be extracted with ethyl acetate solution.By organic layer process dried over mgso, and under reduced pressure concentrated subsequently, and residue is carried out to silica gel column chromatography, to obtain (1R)-trans-3_[(E of 940mg)-2-cyano group-2-ethoxy ethylene base]-2,2-dinethyl cyclopropane carboxylic acid 4-methoxy-2,3,5,6-ptfe benzyl ester (hereinafter, being called compound of the present invention (2)), it is expressed from the next:
compound of the present invention (2)
Colourless liquid:
1h-NMR (CDCl
3, TMS) δ (ppm): 1.18 (s, 3H), 1.28 (t, 3H), 1.32 (s, 3H), 1.59 (d, 1H), 2.29 (m, 1H), 3.41 (s, 3H), 3.85 (q, 2H), 4.59 (s, 2H), 5.25 (s, 2H), 5.30 (d, 1H)
Preparation example 3
Except using (1R)-trans-3-[(1E)-2-cyano group-2-(isopropoxy) vinyl]-2,2-dinethyl cyclopropane carboxylic acid replaces (1R)-trans-3_[(E)-2-cyano group-2-ethoxy ethylene base]-2, outside 2-dinethyl cyclopropane carboxylic acid, in the mode identical with preparation example 2, operate, obtain (1R)-trans-3-[(E)-2-cyano group-2-(isopropoxy) vinyl]-2,2-dinethyl cyclopropane carboxylic acid 4-methoxy-2,3,5,6-ptfe benzyl ester (hereinafter, be called compound of the present invention (3)), it is expressed from the next:
compound of the present invention (3)
Colourless liquid:
1h-NMR (CDCl
3, TMS) δ (ppm): 1.18 (s, 3H), 1.24-1.28 (m, 6H), 1.31 (s, 3H), 1.61 (d, 1H), 2.30 (m, 1H), 3.41 (s, 3H), 4.28 (m, 1H), 4.59 (s, 2H), 5.25 (s, 2H), 5.43 (d, 1H)
Preparation example 4
Except using (1R)-trans-3-[(1E)-2-cyano group-2-(methoxyl group) vinyl] _ 2,2-dinethyl cyclopropane carboxylic acid replaces (1R)-trans-3_[(E)-2-cyano group-2-ethoxy ethylene base] _ 2, outside 2-dinethyl cyclopropane carboxylic acid, in the mode identical with preparation example 2, operate, obtain (1R)-trans-3-[(E)-2-cyano group-2-(methoxyl group) vinyl]-2,2-dinethyl cyclopropane carboxylic acid 4-methyl-2,3,5,6-ptfe benzyl ester (hereinafter, be called compound of the present invention (4)), it is expressed from the next:
1H-NMR(CDCl
3，TMS)δ(ppm)：1.18(s，3H)，1.31(s，3H)，1.60(d，1H)，2.29(m，4H)，3.62(s，3H)，5.23(s，2H)，5.26(d，1H)
Preparation example 5
Except using (1R)-trans-3-[(E)-2-cyano group-2-(methoxyl group) vinyl]-2, 2-dinethyl cyclopropane carboxylic acid replaces (1R)-trans-3_[(1E)-2-cyano group-2-ethoxy ethylene base]-2, 2-dinethyl cyclopropane carboxylic acid, with use 4-methoxyl group-2, 3, 5, 6-tetrafluorobenzyl alcohol replaces 4-methoxy-2, 3, 5, outside 6-tetrafluorobenzyl alcohol, in the mode identical with preparation example 2, operate, obtain (1R)-trans-3-[(E)-2-cyano group-2-(methoxyl group) vinyl]-2, 2-dinethyl cyclopropane carboxylic acid 4-methoxyl group-2, 3, 5, 6-ptfe benzyl ester (hereinafter, be called compound of the present invention (5)), it is expressed from the next:
1H-NMR(CDCl
3，TMS)δ(ppm)：1.18(s，3H)，1.32(s，3H)，1.60(d，1H)，2.29(dd，1H)，3.62(s，3H)，4.10(s，3H)，5.20(s，2H)，5.27(d，1H)
Preparation example 6
Except using (1R)-trans-3-[(E)-2-cyano group-2-(methoxyl group) vinyl]-2, 2-dinethyl cyclopropane carboxylic acid replaces (1R)-trans-3_[(1E)-2-cyano group-2-ethoxy ethylene base]-2, 2-dinethyl cyclopropane carboxylic acid, with use 2, 3, 4, 5, 6-five fluoro benzyl alcohols replace 4-methoxy-2, 3, 5, outside 6-tetrafluorobenzyl alcohol, in the mode identical with preparation example 2, operate, obtain (1R)-trans-3-[(E)-2-cyano group-2-(methoxyl group) vinyl]-2, 2-dinethyl cyclopropane carboxylic acid 2, 3, 4, 5, 6-PFBBR ester (hereinafter, be called compound of the present invention (6)), it is expressed from the next:
1H-NMR(CDCl
3，TMS)δ(ppm)：1.18(s，3H)，1.31(s，3H)，1.59(d，1H)，2.28(m，1H)，3.62(s，3H)，5.22(s，2H)，5.27(d，1H)
Show the particular compound different from above-claimed cpd below.
(example compound 1)
(1R)-trans-3-[(1EZ)-2-cyano group-2-methoxy-ethylene base] _ 2,2-dinethyl cyclopropane carboxylic acid 4-methoxy-2,3,5,6-ptfe benzyl ester (E: Z=2: 1), 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 4-methoxy-2,3,5,6-ptfe benzyl ester (E: Z=1: 1), it is expressed from the next:
(example compound 3)
(1R)-trans-3-[(1EZ)-2-cyano group-2-ethoxy ethylene base] _ 2,2-dinethyl cyclopropane carboxylic acid 4-methoxy-2,3,5,6-ptfe benzyl ester (E: Z=2: 1), it is expressed from the next:
(example compound 4)
(1R)-trans-3-[(1EZ)-2-cyano group-2-ethoxy ethylene base] _ 2,2-dinethyl cyclopropane carboxylic acid 4-methoxy-2,3,5,6-ptfe benzyl ester (E: Z=1: 1), it is expressed from the next:
(example compound 5)
(1R)-trans-3-[(1EZ)-2-cyano group-2-isopropoxy vinyl]-2,2-dinethyl cyclopropane carboxylic acid 4-methoxy-2,3,5,6-ptfe benzyl ester (E: Z=2: 1), it is expressed from the next:
(example compound 6)
(1R)-trans-3-[(1EZ)-2-cyano group-2-isopropoxy vinyl] _ 2,2-dinethyl cyclopropane carboxylic acid 4-methoxy-2,3,5,6-ptfe benzyl ester (E: Z=1: 1), it is expressed from the next:
(example compound 7)
(1R)-trans-3-[(E)-2-cyano group-2-propoxyl group vinyl] _ 2,2-dinethyl cyclopropane carboxylic acid 4-methoxy-2,3,5,6-ptfe benzyl ester, it is expressed from the next:
(example compound 8)
(1R)-trans-3-[(E)-2-cyano group-2-ethoxy ethylene base] _ 2,2-dinethyl cyclopropane carboxylic acid 2,3,5,6-ptfe benzyl ester, it is expressed from the next:
Then, show the reference preparation example about the preparation of intermediate (it is for the preparation of the compound of the invention described above) below.
With reference to preparation example 1
Sodium hydride (55.2%, oil dispersion) (0.42g, 9.7mmol) is added in round-bottomed flask, and add wherein the anhydrous tetrahydro furan of 15mL.Under ice-cooled, under blanket of nitrogen, drip wherein the solution that is dissolved in methoxyl group (cyano group) the methyl acid phosphate diethylester (2.0g, 9.7mmol) in anhydrous tetrahydro furan (5mL).Under ice-cooled, stirred reaction mixture 30 minutes, and stir again 1 hour at 25 ℃.Drip and be dissolved in (1R)-trans-3-formoxyl-2 in anhydrous tetrahydro furan (5mL), the solution of 2-dinethyl cyclopropane carboxylic acid methyl esters (1.40g, 9.0mmol) wherein.After mixture being stirred to 2 hours at 25 ℃, reaction solution is joined in the mixed solution being comprised of 5% hydrochloric acid of 10mL and the frozen water of 30mL, and use the ethyl acetate of 50mL by reactant mixture extracting twice at every turn.The ethyl acetate layer of gained is merged, and with the saturated brine of saturated sodium bicarbonate aqueous solution and 30mL, wash successively, and through dried over mgso.The solution of gained is under reduced pressure concentrated, and residue is carried out to silica gel column chromatography, obtain 480mg as (1R)-trans-3-[(1E with the cut of high polarity)-2-cyano group-2-methoxy-ethylene base]-2,2-dinethyl cyclopropane carboxylic acid methyl esters, it is expressed from the next:
Colourless liquid:
1h-NMR (CDCl
3, TMS) 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 with the cut of lower polarity)-2-cyano group-2-methoxy-ethylene base]-2,2-dinethyl cyclopropane carboxylic acid methyl esters, it is expressed from the next:
Colourless liquid:
1h-NMR (CDCl
3, TMS) δ (ppm): 1.31 (s, 3H), 1.35 (s, 3H), 1.66 (m, 1H), 2.46 (m, 1H), 3.69 (s, 3H), 3.77 (s, 3H), 5.21 (d, 1H)
(with reference to preparation example 2)
By (1R)-trans-3-[(1E)-2-cyano group-2-methoxy-ethylene base]-2,2-dinethyl cyclopropane carboxylic acid methyl esters (463mg, 2.2mmol) be dissolved in the mixture solution being formed by the methyl alcohol of 1.5mL and the water of 0.5mL, and add wherein subsequently potassium hydroxide (200mg, 3.6mmol), and by reactant mixture stirring at room 12 hours.Reaction solution is added in the frozen water of 20mL, and with the ethyl acetate extractive reaction mixture of 20mL.In the water layer of gained, adding hydrochloric acid, is pH2 until make water layer, and subsequently with twice, the mixture of 20mL ethyl acetate extraction gained.The ethyl acetate layer of gained is merged, and by the saturated brine washed twice of 20mL, and pass through subsequently dried over mgso.Solution is under reduced pressure concentrated, obtain 336mg (1R)-trans-3_[(1E)-2-cyano group-2-methoxy-ethylene base] _ 2,2-dinethyl cyclopropane carboxylic acid, it is expressed from the next:
Light yellow crystal:
1h-NMR (CDCl
3, TMS) δ (ppm): 1.22 (s, 3H), 1.36 (s, 3H), 1.62 (d, 1H), 2.32 (m, 1H), 3.64 (s, 3H), 5.29 (d, 1H)
(with reference to preparation example 3)
Sodium hydride (50.0%, oil dispersion) (1.56g, 32.5mmol) is added in 200mL round-bottomed flask, and add wherein the anhydrous tetrahydro furan of 43mL.Under ice-cooled, under blanket of nitrogen, drip wherein the solution that is dissolved in ethyoxyl (cyano group) the methyl acid phosphate diethylester in anhydrous tetrahydro furan (11mL).Ice-cooled lower to reactant mixture stirring 40 minutes, and stir again one hour at 25 ℃.Drip and be dissolved in (1R)-trans-3-formoxyl-2 in anhydrous tetrahydro furan (11mL), the solution of 2-dinethyl cyclopropane carboxylic acid methyl esters (3.17g, 20.3mmol) wherein.After reactant mixture being stirred to 12 hours at 25 ℃, reaction solution is joined in the mixed solution being comprised of 5% hydrochloric acid of 10mL and the frozen water of 100mL, and with the ethyl acetate of 100mL, extract twice, the mixture of gained at every turn.The ethyl acetate layer of gained is merged, and with the saturated brine of saturated sodium bicarbonate aqueous solution and 50mL, wash successively, and pass through subsequently dried over mgso.The mixture of gained is under reduced pressure concentrated, and residue is carried out to silica gel column chromatography, obtain 6.00g (1R)-trans-3-[(1EZ)-2-cyano group-2-ethoxy ethylene 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) 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 obtaining with reference to preparation example 3)-2-cyano group-2-ethoxy ethylene base] _ 2,2-dinethyl cyclopropane carboxylic acid methyl esters (E: Z=2: 1) carry out silica gel column chromatography (eluent: hexane/ethyl acetate=10: 1), obtain 2.91g as (1R)-trans-3-[(1E with the cut of high polarity)-2-cyano group-2-ethoxy ethylene base]-2,2-dinethyl cyclopropane carboxylic acid methyl esters, it is expressed from the next:
Colourless liquid:
1h-NMR (CDCl
3, TMS) 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-ethoxy ethylene base]-2,2-dinethyl cyclopropane carboxylic acid methyl esters (2.91g, 13.0mmol) be dissolved in the mixed solution being formed by the methyl alcohol of 17mL and the water of 6mL, and add wherein subsequently potassium hydroxide (1.56g, 27.9mmol), and by reactant mixture stirring at room 12 hours.The reaction solution of gained is joined in the frozen water of 45mL, and with the ethyl acetate of 45mL, extract the mixture of gained.In the water layer of gained, adding hydrochloric acid, is pH2 until make water layer, and subsequently with twice, the mixture of the ethyl acetate extraction gained of 45mL.The ethyl acetate layer of gained is merged, and by the saturated brine washed twice of 50mL, and pass through subsequently dried over mgso.The solution of gained is under reduced pressure concentrated, (1R)-trans-3_[(1E of acquisition 2.64g)-2-cyano group-2-ethoxy ethylene base]-2,2-dinethyl cyclopropane carboxylic acid, it is expressed from the next:
White crystal:
1h-NMR (CDCl
3, TMS) 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-ethoxy ethylene base] _ 2,2-dinethyl cyclopropane carboxylic acid (E: Z=2: 1) (500mg, 2.39mmol) in, the toluene that adds 3mL, add subsequently thionyl chloride (370mg, 3.11mmol), and further add the N of 10mg, dinethylformamide, and at the internal temperature of 60 to 70 ℃, reactant mixture is stirred 4 hours.By the standing room temperature that is cooled to of reaction solution, and under reduced pressure concentrated, (1R)-trans-3-[(1EZ of acquisition 550mg)-2-cyano group-2-ethoxy ethylene base]-2,2-dimethylcyclopropane formyl chloride (E: Z=2: 1), it is expressed from the next:
With reference to preparation example 7
Except using isopropoxy (cyano group) methyl acid phosphate diethylester to replace ethyoxyl (cyano group) methyl acid phosphate diethylester, with with reference to the identical mode of preparation example 3, react, 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) 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-ethoxy ethylene base] _ 2, outside 2-dinethyl cyclopropane carboxylic acid methyl esters, with with reference to the identical mode of preparation example 5, react, 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) δ (ppm): 1.20-1.36 (m, 12H), 1.62 (d, 0.8H), 1.66 (d, 0.2H), 2.31 (m, 0.8H), 2.48 (m, 0.2H), 4.30 (q, 0.8H), 4.39 (q, 0.2H), 5.29 (d, 0.2H), 5.46 (d, 0.8H)
Then, the method for the preparation of the phosphate compound being represented by formula (7) is below described:
R wherein
2represent identical meanings as above.
According in J.Org.Chem. (1976), 41 volumes, the method described in 2846-2849 page, synthetic by R wherein
2the compound that represents formula (7) expression of methyl, that is, and methoxyl group (cyano group) methyl acid phosphate diethylester.Also according at J.Org.Chem. (1976) 41 volumes, the method described in 2846-2849 page, except using ethyoxyl acetonitrile, propoxyl group acetonitrile or isopropoxy acetonitrile to replace methoxyacetonitrile, synthetic by R wherein similarly
2the compound that represents formula (7) expression of ethyl, propyl group or isopropyl, that is, and ethyoxyl (cyano group) methyl acid phosphate diethylester, propoxyl group (cyano group) methyl acid phosphate diethylester or isopropoxy (cyano group) methyl acid phosphate diethylester.
Show formulation example below.Umber in mass.
Formulation example 1
The compound of the present invention (1) of 20 (20) parts is dissolved in separately to (6) in the dimethylbenzene of 65 parts, and by the SOLPOL3005X of 15 parts (TOHO Chemical Industry Co., Ltd. registration mark) add wherein, and thoroughly mix to obtain emulsifiable concentrates by stirring.
Formulation example 2
The SORPOL3005X of five (5) parts is added in each of compound of the present invention (1) to (6) of 40 parts, and mixture is thoroughly mixed, and by the CARPLEX#80 of 32 parts (synthetic oxidizing aqueous silicon, SHIONOGI & CO., LTD. registration mark) and the 300 order diatomite of 23 parts add wherein, by being uniformly mixed of blender, obtain wetting powder afterwards.
Formulation example 3
By the compound of the present invention (1) to (6) of 1.5 parts separately with TOKUSIL GUN (the synthetic oxidizing aqueous silicon of 1 part, by Tokuyama Corporation, produced), the REAX85A (sodium lignosulfonate of 2 parts, by West Vaco Chemicals, produced), the BENTONITE FUJI (bentonite of 30 parts, by Houjin, produced) and the SHOUKOUZAN A clay (kaolinton of 65.5 parts, by Shoukouzan Kougyousho, produced) mixture thoroughly clay into power and mix, and water is added wherein.Mixture is thoroughly mediated, by extruding granulator granulation, dry afterwards, obtain 1.5% granule.
Formulation example 4
To the compounds of the present invention (1) to (6) of 10 parts separately with the phenyl xylyl ethane of 10 parts and the SUMIDUR L-75 (toluene di-isocyanate(TDI) of 0.5 part, by Sumitomo Bayer Urethane Co., Ltd. in mixture production), 10% Arabic gum aqueous solution that adds 20 parts, and mixture is stirred with homogenizer, obtain the emulsion of the average grain diameter with 20 μ m.To emulsion, add 2 parts of ethylene glycol and mixture is further stirred in the temperature of 60 ℃ of temperature is bathed to 24 hours to obtain microcapsule slurry.On the other hand, the VEEGUM R of the xanthans of 0.2 part and 1.0 parts (aluminium-magnesium silicate, by Sanyo Chemical Industries, Ltd. produces) is dispersed in the ion exchange water of 56.3 parts to obtain thickening fluid.Afterwards, the above-mentioned thickening fluid of the above-mentioned microcapsule slurry of 42.5 parts and 57.5 parts mixed and obtain microcapsules.
Formulation example 5
The compound of the present invention (1) to (6) 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 blender, obtain the emulsion of the average grain diameter with 3 μ m.On the other hand, the VEEGUM R of the xanthans of 0.2 part and 1.0 parts (Magnesiumaluminumsilicate, by Sanyo Chemical Industries, Ltd. produces) is dispersed in the ion exchange water of 58.8 parts to obtain thickening fluid.Afterwards, the above-mentioned thickening fluid of the above-mentioned emulsion solution of 40 parts and 60 parts mixed and obtain the preparation that can flow.
Formulation example 6
In each of the compounds of the present invention (1) to (6) of 5 parts, CARPLEX#80 (the synthetic oxidizing aqueous silicon that adds 3 parts, SHIONOGI & CO., LTD. registration mark), the PAP (mixture of mono phosphoric acid ester isopropyl ester and diisopropyl phosphate) of 0.3 part and the talcum (300 order) of 91.7 parts, mixture is stirred and is obtained pulvis by blender.
Formulation example 7
The compound of the present invention (1) of 0. 1 (0.1) parts is dissolved in separately to (6) in the carrene of 10 parts, and solution is mixed and obtains oily solution with the deodorized kerosine of 89.9 parts.
Formulation example 8
The compound of the present invention (1) to (6) of 0. 1 (0.1) parts is mixed and dissolved with the deodorized kerosine of 39.9 parts separately, and solution is filled in aerosol container, and mounted valve part.Afterwards, the energy propellant (liquefied petroleum gas) of 60 parts is partly filled in wherein by valve under pressure, to obtain oil base aerosol formulation.
Formulation example 9
By the compound of the present invention (1) to (6) of 0. 6 (0.6) parts separately with the dimethylbenzene of 5 parts, the deodorized kerosine of 3.4 parts and the Reodol MO-60 (emulsifier of 1 part, the registration mark 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) of 40 parts is partly inserted wherein by valve under pressure, obtained waterborne aerosol agent formulation.
Formulation example 10
The compound of the present invention (1) of 0. 3 (0.3) g is dissolved in the acetone of 20mL separately to (6), and the solution of gained is under agitation evenly mixed with the base material for incense coil (by Tabu powder, Dalmatian chrysanthemum slag (mark) and wood powder are mixed to acquisition with the ratio of 4: 3: 3) of 99.7g.Afterwards, the water of 100mL is added wherein, and by mixture thoroughly mediate, dry and molded, obtain insecticidal incense coil.
Formulation example 11
The compound of the present invention (1) to (6) of 0.8g is dissolved in acetone with the mixture of the piperonyl butoxide of 0.4g separately, and cumulative volume is adjusted to 10ml.Afterwards, this solution of 0.5mL is flooded equably to the base material for electrical heating pesticide tablet with the size of 2.5cm * 1.5cm and the thickness of 0.3cm (sheet that the fibril sclerosis of the mixture of velveteen and paper pulp is obtained), obtain electrical heating insecticidal mat.
Formulation example 12
The compounds of this invention by by 3 parts (1) is dissolved in separately to the solution obtaining in the deodorized kerosine of 97 parts is poured in the container of being made by vinyl chloride to (6).The liquid-sucking core that its top can be heated by heater (with the inorganic flour of adhesive sclerosis sintering) inserts wherein, obtains the parts that use for imbibition core pattern heat evaporating device.
Formulation example 13
The compounds of this invention of 100 (100) mg (1) is dissolved in the acetone of appropriate amount separately to (6), and the solution of gained is soaked into and to having in the size of 4.0cm * 4.0cm and the porous ceramic plate of 1.2cm thickness, obtains hot smoking agent.
Formulation example 14
The compounds of this invention of 100 (100) μ g (1) is dissolved in the acetone of appropriate amount separately to (6), and the solution of gained is applied to equably and has the size of 2cm * 2cm and the filter paper of 0.3mm thickness, and air is dry to remove acetone, thereby obtain the volatile reagent for using in room temperature.
Formulation example 15
The compounds of this invention (1) to (6) of ten (10) parts separately with 35 parts of white carbons (the polyoxyethylene alkyl ether ammonium sulfate that contains 50 parts), and the water of 55 parts mixes, levigate by wet grinding afterwards, obtains 10% mobility preparation.
Then, following test case has illustrated that compound of the present invention is effective as the active component of pest control agent.
Test case 1
By compound of the present invention (1) to (4) each each 0.00625 part be dissolved in 10 parts of isopropyl alcohols, and the solution of gained is mixed with 89.994 parts of deodorized kerosines, to prepare the oily solution of 0.00625% (w/v).
By ten (10) only adult Groton bug (Blattella germanica, 5 male and 5 female) be discharged into (diameter 8.75cm in the test container that is coated with butter on its inner surface, height 7.5cm, lower surface is made by 16 order metal wires), and by container be placed on test cabinet bottom (lower surface: 46cm * 46cm, highly: 70cm).Use spray gun with 0.42kg/cm
2pressure from the high 60cm of container end face, spray compound of the present invention (1) to (4) each 1.5mL of oily solution separately.After spraying 30 seconds, container is pulled out in test cabinet, and cockroach is transferred in clean polyethylene cup.After official hour, number and the definite rate of knockdown (repeating twice) of the cockroach that number goes out to knock down.By following formula, calculate rate of knockdown.
Rate of knockdown (%)=(number of number/test cockroach of the cockroach of knocking down) * 100
Result (spraying 2.0 minutes afterwards) is shown in Table 1.
Table 1
| Test compounds | The rate of knockdown (%) of 2 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) | 70 |
Test case 2
Each each 0.00625 part of the compound of the present invention (2) of preparing in above-mentioned preparation example, (3) or (5) is dissolved in 10 parts of isopropyl alcohols, and the solution of gained is mixed with 89.994 parts of deodorized kerosines, to prepare the oily solution of 0.00625% (w/v).
By ten (10) only grow up houseflies (Musca domestica, 5 male and 5 female) be covered with bottom being discharged in the polyethylene cup of 650ml volume of filter paper, and cover this cup with 16 order nylon gauzes.By this glass be placed on test cabinet bottom (lower surface: 46cm * 46cm, highly: 70cm).Use spray gun with 0.9kg/cm
2pressure from the high 30cm of container end face, spray compound (2), (3) or (5) each 0.5mL of oily solution separately.After spraying, at once cup is pulled out in test cabinet.After official hour, number and the definite rate of knockdown (repeating twice) of the housefly that number goes out to knock down.By following formula, calculate rate of knockdown.
Rate of knockdown (%)=(number of number/test cockroach of the cockroach of knocking down) * 100
Result (spraying 2.0 minutes afterwards) provides in table 2.
Result is presented in table 2.
Table 2
| Test compounds | The rate of knockdown (%) of 2 minutes after spraying |
| Compound of the present invention (2) | 100 |
| Compound of the present invention (3) | 100 |
| Compound of the present invention (5) | 90 |
Test case 3
By compound of the present invention (1) to (6) each each 1 part be dissolved in 10 parts of isopropyl alcohols, and the solution of gained is mixed with 89 parts of deodorized kerosines, to prepare one (1) part of (w/v) oily solution.
Ten (10) only 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.By this glass be placed on test cabinet bottom (lower surface: 46cm * 46cm, highly: 70cm).Use spray gun with 0.4kg/cm
2pressure from the high 30cm of container end face, spray each each 0.5mL of compound of the present invention (1) to (6) oily solution separately.After spraying, at once cup is pulled out in test cabinet, and in sprinkling latter two minutes, number and definite rate of knockdown (repeating twice) of the common house mosquitos that number goes out to knock down.
Industrial applicibility
Compound of the present invention has outstanding pest controling effect, therefore can be used as the active component of pest control agent.
Claims (19)
1. the ester compounds being represented by formula (1):
Wherein
R
1represent hydrogen atom, halogen atom, methyl, methoxyl group or methoxy;
R
2represent C1-C3 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 anti-configuration.
2. ester compounds according to claim 1, wherein, in formula (1), the absolute configuration on the 1-position of described cyclopropane ring is R configuration.
3. ester compounds according to claim 1 and 2, wherein in formula (1), the two keys that exist on substituting group on the 3-position of described cyclopropane ring are in E configuration or the mix-configuration in E configuration and Z configuration, and the ratio of described E configuration is more than 50%.
4. ester compounds according to claim 1 and 2, wherein, in formula (1), the two keys that exist on the substituting group on the 3-position of described cyclopropane ring are in E configuration.
5. ester compounds according to claim 1 and 2, wherein in formula (1), R
2represent methyl.
6. ester compounds according to claim 1 and 2, wherein in formula (1), R
2represent ethyl.
7. ester compounds according to claim 1 and 2, wherein in formula (1), R
2represent isopropyl.
8. ester compounds according to claim 3, wherein in formula (1), R
2represent methyl.
9. ester compounds according to claim 3, wherein in formula (1), R
2represent ethyl.
10. ester compounds according to claim 3, wherein in formula (1), R
2represent isopropyl.
11. ester compounds according to claim 4, wherein in formula (1), R
2represent methyl.
12. ester compounds according to claim 4, wherein in formula (1), R
2represent ethyl.
13. ester compounds according to claim 4, wherein in formula (1), R
2represent isopropyl.
14. according to the ester compounds described in any one in claim 1 to 13, wherein in formula (1), and R
1represent fluorine atom.
15. according to the ester compounds described in any one in claim 1 to 13, wherein in formula (1), and R
1represent methyl.
16. according to the ester compounds described in any one in claim 1 to 13, wherein in formula (1), and R
1represent methoxyl group.
17. according to the ester compounds described in any one in claim 1 to 13, wherein in formula (1), and R
1represent methoxy.
18. 1 kinds of pest control agents, described pest control agent comprises according to the ester compounds described in any one in claim 1 to 17 and inert carrier.
The method of 19. 1 kinds of pest controls, described method comprises: the step that the ester compounds according to described in any one in claim 1 to 17 of effective dose is applied to insect or insect habitat.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4602038A (en) * | 1983-06-14 | 1986-07-22 | Roussel Uclaf | Insecticidal cyclopropane carboxylates |
| CN1451650A (en) * | 2002-04-12 | 2003-10-29 | 住友化学工业株式会社 | Ester compound and use thereof |
| CN101437401A (en) * | 2006-05-11 | 2009-05-20 | 住友化学株式会社 | Ester compound and pest-controlling application thereof |
| CN101636382A (en) * | 2007-03-07 | 2010-01-27 | 住友化学株式会社 | A cyclopropane carboxylic acid ester compound and its use in pest control |
| CN101880243A (en) * | 2010-06-04 | 2010-11-10 | 贵阳柏丝特化工有限公司 | Fluorocyanogen-containing pyrethroid compound and synthesis method and application thereof |
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| JP3728967B2 (en) | 1998-02-26 | 2005-12-21 | 住友化学株式会社 | Ester compound |
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- 2012-08-23 WO PCT/JP2012/071938 patent/WO2013027865A1/en active Application Filing
- 2012-08-23 TW TW101130651A patent/TW201326098A/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4602038A (en) * | 1983-06-14 | 1986-07-22 | Roussel Uclaf | Insecticidal cyclopropane carboxylates |
| CN1451650A (en) * | 2002-04-12 | 2003-10-29 | 住友化学工业株式会社 | Ester compound and use thereof |
| CN101437401A (en) * | 2006-05-11 | 2009-05-20 | 住友化学株式会社 | Ester compound and pest-controlling application thereof |
| CN101636382A (en) * | 2007-03-07 | 2010-01-27 | 住友化学株式会社 | A cyclopropane carboxylic acid ester compound and its use in pest control |
| CN101880243A (en) * | 2010-06-04 | 2010-11-10 | 贵阳柏丝特化工有限公司 | Fluorocyanogen-containing pyrethroid compound and synthesis method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| AR087651A1 (en) | 2014-04-09 |
| JP2013060436A (en) | 2013-04-04 |
| TW201326098A (en) | 2013-07-01 |
| WO2013027865A1 (en) | 2013-02-28 |
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Application publication date: 20140423 |