Patent Grant
7153815
The present invention to insecticides containing hydrazone derivatives as active ingredient, specifically insecticides for agricultural and horticultural use, clothing, food and housing-related use, or livestock and pet use, and to novel hydrazone derivatives useful as the insecticide.
There are many researches for insecticides having hydrazone skeleton, and some hydrazone derivatives are put in practical use as insect pest control agents. However, they are insufficient in control effect, limited in use due to appearance of insects with resistance thereto, occur chemical injury to plants or pollution, or have a strong toxicity to man and beast, and to fishes. Therefore, there are few control agents to be satisfied. Consequently, it has been strongly demanded to overcome these defects and to provide novel agents that can be safely used.
On the other hand, it is disclosed in Japanese Patent Laid-open Nos. Hei 5-32603, Hei 5-262712 and 2001-72516 that hydrazono acetic acid amide derivatives represented by the compound indicated below have an insecticidal activity. However, they are compounds which a substituent on the nitrogen atom of the amide group is a phenyl group, and insufficient in insecticidal spectrum.
In addition, Japanese Patent Laid-open No. Hei 11-503134 discloses that hydrazono phenylacetic acid amide derivatives represented by the compound indicated below are useful as fungicides, but does not disclose at all insecticidal activity of these compounds.
Consequently, it is demanded to successively provide insecticides having a new structure in the field of insecticides because of acquisition of resistance to insecticides. Thus, it is an object of the present invention to find compounds with a stable effect as insecticide and to find compounds with a high safety to mammals and fishes.
The present inventors have conducted extensive studies with the aim of solving the problems mentioned above to find that hydrazone derivatives having specific structure have broad insecticidal spectrum and excellent insecticidal activity, and are extremely high in safety to mammals and fishes. Based on this finding, the present invention has been accomplished.
That is, the gist of the resides in an insecticide characterized by containing as active ingredient a hydrazone derivative of formula (I)
Hereinafter, the present invention will be described in detail.
The hydrazone derivatives which are active ingredients in the insecticides of the present invention are represented by the formula (I).
In the formula (I), A and Q independently of the other are an aryl such as phenyl or naphthyl; or a heterocyclic group such as tetrahydrofuranyl, furyl, thienyl, pyrrolyl, oxazolyl, oxazolinyl, isoxazolyl, isoxazolinyl, thiazolyl, thiazolinyl, isothiazolyl, isothiazolinyl, imidazolyl, imidazolinyl, pyrazolyl, pyrazolinyl, oxadiazolyl, ozadiazolinyl, thiadiazolyl, thiadizolinyl, oxadiazolonyl, pyridyl, pyrazyl, pyrimidyl, pyridazyl, triazyl, benzoxazolyl or benzothiazolyl. They may be substituted by arbitrary substituents.
Substituents on the above-mentioned A and Q are not specifically limited so long as the compound has an insecticidal activity. Concretely, they include the groups of G1.
The groups of G1 include a halogen atom such as fluorine atom, chlorine atom or bromine atom; hydroxy; cyano; nitro; a linear, branched or cyclic alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl; a linear, branched or cyclic haloalkyl such as trifluoromethyl, pentafluoroethyl, difluoromethyl, trichloromethyl or dichlorodifluoroethyl; a linear, branched or cyclic alkenyl such as vinyl, propenyl, butenyl, or hexenyl; a linear, branched or cyclic haloalkenyl such as difluorovinyl or trifluorovinyl; an alkynyl such as ethynyl, butynyl or pentynyl; a haloalkynyl such as fluorobutynyl or chlorobutynyl; amino; an alkylamino such as methylamino or ethylamino: a linear or cyclic dialkylamino such as dimethylamino, diethylamino, ethylmethylamino or piperidyl; an alkoxy such as methoxy, ethoxy or n-butoxy; a haloalkoxy such as trifluoromethoxy, difluoromethoxy or trifluoroethoxy; formyl; an acyl such as acetyl, trifluoroacetyl, benzoyl or phenylacetyl; an acyloxy such as acetoxy or propanoyloxy; an alkoxycarbonyl such as methoxycarbonyl or ethoxycarbonyl; an alkylthio such as methylthio, ethylthio, n-propylthio, iso-propylthio or n-butylthio; a haloalkylthio such as trifluoromethylthio or trifluoroethylthio; an alkylsulfinyl such as methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, iso-propylsulfinyl or n-butylsulfinyl; a haloalkylsulfinyl such as trifluoromethylsulfinyl or trifluoroethylsulfinyl; an alkylsulfonyl such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, iso-propylsulfonyl or n-butylsulfonyl; a haloalkylsulfonyl such as trifluoromethylsulfonyl or trifluoroethylsulfonyl; or an aryl such as phenyl or naphthyl; an aryloxy such as phenoxy or naphthyloxy; an arylthio such as phenylthio; a heterocyclic group such as pyridyl; heterocyclic oxy such as pyridyloxy; or a heterocyclic thio such as pyridylthio.
The above-mentioned alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkylamino, dialkylamino, alkoxy, haloalkoxy, alkylthio haloalkylthio, alkylsulfinyl, haloalkylsufinyl, alkylsulfonyl and haloalkylsulfonyl of G1 contain preferably carbon atom of 1 to 6, and the acyl, acyloxy and alkoxycarbonyl contain preferably carbon atom of 2 to 10.
The above-mentioned aryl, aryloxy, arylthio, heterocyclic group, heterocyclic oxy and heterocyclic thio of G1 may be further substituted by a substituent selected from the group consisting of a halogen atom, hydroxy, cyano, nitro, an alkyl, a haloalkyl, an alkenyl, a haloalkenyl, an alkynyl, a haloalkynyl, amino, an alkylamino, a dialkylamino, an alkoxy, a haloalkoxy, formyl, an acyl, an acyloxy, an alkoxycarbonyl, an alkylthio, a haloalkylthio, an alkylsulfinyl, a haloalkylsulfinyl, an alkylsulfonyl and a haloalkylsulfonyl. Among them, the alkyl, haloalkyl, alkylamino, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsufinyl, alkylsulfonyl and haloalkylsulfonyl contain preferably carbon atom of 1 to 10, and the alkenyl, haloalkenyl, alkynyl, haloalkynyl, dialkylamino, acyl, acyloxy and alkoxycarbonyl contain preferably carbon atom of 2 to 10.
Further, in G1 a substituent together with the adjacent substituent may form methylenedioxy, ethylenedioxy or the like, or it may form a fused ring together with the aryl or heterocyclic group of Q or A.
Among them, substituent A is preferably an unsubstituted or substituted aryl or nitrogen-containing heterocycle, more preferably an unsubstituted or substituted aryl, and particularly preferably an unsubstituted or substituted phenyl.
In A, G1 which is a substituent of the aryl or heterocyclic group is preferably a halogen atom, cyano, nitro, an alkyl, a haloalkyl, an alkoxy, a haloalkoxy, alkylthio or a haloalkylthio, more preferably a halogen atom, an alkyl, a haloalkyl, an alkoxy or a haloalkoxy, further preferably a halogen atom, an alkyl, a haloalkyl or a haloalkoxy, and particularly preferably fluorine atom, a chlorine atom, bromine atom or trifluoromethyl. It is most preferable that the substituent at the 4-position on the benzene ring is trifluoromethyl. Further, one having at least a fluorine atom and trifluoromethyl is preferable.
In addition, in case where the aryl or heterocyclic group of A is substituted by a substituent selected from the above-mentioned G1, the number of the substituents is preferably 1 to 3.
Q is preferably an unsubstituted or substituted phenyl or heterocyclic group, more preferably an unsubstituted or substituted nitrogen-containing heterocyclic group, particularly preferably unsubstituted or substituted pyridyl or thiazolyl.
In Q, G1 which is a substituent of the aryl or heterocyclic group is preferably a halogen atom, an alkyl, a haloalkyl, an alkylamino, a dialkylamino, an alkoxy, a haloalkoxy, alkylthio and a haloalkylthio, more preferably a halogen atom, an alkyl, a haloalkyl or an alkoxy, and particularly preferably fluorine atom, a chlorine atom, bromine atom or trifluoromethyl.
In addition, in case where the aryl or heterocyclic group of Q is substituted by substituents selected from the above-mentioned G1, the number of the substituents is preferably 1 to 3.
W is oxygen atom; aminylene; an alkylene such as methylene, ethylene or propylene; an oxyalkylene such as oxymethylene or oxyethylene; or an alkyleneoxy such as ethyleneoxy or propyleneoxy.
The above-mentioned aminylene, alkylene, oxyalkylene and alkyleneoxy may be arbitrarily substituted. The substituents are not specifically limited as long as the compound has an insecticidal activity. Concretely, they include for example a monovalent group of hydrocarbon.
Among them, W is preferably oxygen atom, —(C(R1)(R2))n—, or —N(R3)—.
The above-mentioned n is an integer of 1 to 5, preferably 1 to 3 and particularly preferably 1.
R1 and R2 independently of the other are hydrogen atom; a linear, branched or cyclic alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl; a linear, branched or cyclic alkenyl such as vinyl, propenyl, butenyl, or hexenyl; an alkynyl such as ethynyl, butynyl or pentynyl. In addition, R1 together with R2 may form an alkylidene such as ethylidene or propylidene.
In addition, in case where n is 2 or more, the plural R1s or R2s bonded to each carbon atom may be same or different each other.
R3 is hydrogen atom; a linear, branched or cyclic alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl; a linear, branched or cyclic alkenyl such as vinyl, propenyl, butenyl or hexenyl; an alkynyl such as ethynyl, butynyl or pentynyl.
Further preferably, W is oxygen atom, —CH2— or —NH—, and particularly preferably —CH2— or —NH—.
X1 and X2 independently of the other are hydrogen atom; formyl; a linear, branched or cyclic alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl; a linear, branched or cyclic alkenyl such as vinyl, propenyl, butenyl, or hexenyl; an alkynyl such as ethynyl, butynyl or pentynyl; an aryl such as phenyl or naphthyl; a heterocyclic group such as tetrahydrofuranyl, furyl, thienyl, pyrrolyl, oxazolyl, oxazolinyl, isoxazolyl, isoxazolinyl, thiazolyl, thiazolinyl, isothiazolyl, isothiazolinyl, imidazolyl, imidazolinyl, pyrazolyl, pyrazolinyl, oxadiazolyl, ozadiazolinyl, thiadiazolyl, thiadiazolinyl, oxadiazolonyl, pyridyl, pyrazyl, pyrimidyl, pyridazyl, triazyl, benzoxazolyl or benzothiazolyl; an acyl such as acetyl, benzoyl or phenylacetyl; an alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl or t-butoxycarbonyl; an aryloxycarbonyl such as phenyloxycarbonyl; heterocyclic oxycarbonyl such as pyridyloxycarbonyl; an alkylsulfinyl such as methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, iso-propylsulfinyl or n-butylsulfinyl; an arylsulfinyl such as phenylsulfinyl or naphthylsulfinyl; a heterocyclic sulfinyl such as pyridylsulfinyl; an alkylsulfonyl such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, iso-propylsulfonyl or n-butylsulfonyl; an arylsulfonyl such as phenylsulfonyl or naphthylsulfonyl; a heterocyclic sulfonyl such as pyridylsulfonyl.
Among X1 and X2, the alkyl, alkenyl, alkynyl, aryl, heterocyclic group, acyl, alkoxycarbonyl, aryloxycarbonyl, heterocyclic oxycarbonyl, alkyksulfinyl, arylsulfinyl, heterocyclic sulfinyl, alkylsulfonyl, arylsulfonyl and heterocyclic sulfonyl may be substituted by arbitrary substituents. The substituents are not specifically limited so long as the compound has an insecticidal activity. Concretely, they include the groups of G2.
The groups of G2 include a halogen atom such as fluorine atom, chlorine atom or bromine atom; hydroxy; cyano; a linear, branched or cyclic alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl; a linear, branched or cyclic haloalkyl such sd trifluoromethyl, pentafluoroethyl, difluoromethyl, trichloromethyl or dichlorodifluoroethyl; a linear, branched or cyclic alkenyl such as vinyl, propenyl, butenyl or hexenyl; a linear, branched or cyclic haloalkenyl such as difluorovinyl or trifluorovinyl; an alkynyl such as ethynyl, butynyl or pentynyl; a haloalkynyl such as fluorobutynyl or chlorobutynyl; an alkoxy such as methoxy, ethoxy, iso-propoxy, iso-butoxy or n-butoxy; a haloalkoxy such as trifluoromethoxy, difluoromethoxy or trifluoroethoxy; alkoxyalkoxy such as methoxyethoxy; formyl; an acyl such as acetyl, trifluoroacetyl, benzoyl or phenylacetyl; an acyloxy such as acetoxy or propanoyloxy; an alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl or t-butoxycarbonyl; an alkylthio such as methylthio, ethylthio, n-propylthio, iso-propylthio or n-butylthio; a haloalkylthio such as trifluoromethylthio or trifluoroethylthio; an alkylsulfinyl such as methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, iso-propylsulfinyl or n-butylsulfinyl; a haloalkylsulfinyl such as trifluoromethylsulfinyl or trifluoroethylsulfinyl; an alkylsulfonyl such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, iso-propylsulfonyl or n-butylsulfonyl; a haloalkylsulfonyl such as trifluoromethylsulfonyl or trifluoroethylsulfonyl; or an aryl such as phenyl or naphthyl; an aryloxy such as phenoxy or naphthyloxy; an arylthio such as phenylthio; a heterocyclic group such as pyridyl; heterocyclic oxy such as pyridyloxy; or a heterocyclic thio such as pyridylthio.
The above-mentioned alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkoxy, haloalkoxy, alkoxyalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsufinyl, alkylsulfonyl and haloalkylsulfonyl of G2 contain preferably carbon atom of 1 to 6, and the acyl, acyloxy and alkoxycarbonyl contain preferably carbon atom of 2 to 10.
The above-mentioned aryl, aryloxy, arylthio, heterocyclic group, heterocyclic oxy and heterocyclic thio of G2 may be further substituted by a substituent selected from the group consisting of a halogen atom, hydroxy, cyano, an alkyl, a haloalkyl, an alkenyl, a haloalkenyl, an alkynyl, a haloalkynyl, an alkoxy, a haloalkoxy, formyl, an acyl, an acyloxy, an alkoxycarbonyl, an alkylthio, a haloalkylthio, an alkylsulfinyl, a haloalkylsulfinyl, an alkylsulfonyl and a haloalkylsulfonyl. Among them, the alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsufinyl, alkylsulfonyl and haloalkylsulfonyl contain preferably carbon atom of 1 to 10, and the alkenyl, haloalkenyl, alkynyl, haloalkynyl, acyl, acyloxy and alkoxycarbonyl contain preferably carbon atom of 2 to 10.
X1 is preferably hydrogen atom, an alkenyl having 1 to 4 carbon atoms, an acyl having 1 to 10 carbon atoms, or an alkyl having 1 to 10 carbon atoms which is unsubstituted or substituted by a substituent selected from the group consisting of a halogen atom, cyano, an alkoxy, an alkylthio, an alkoxycarbonyl and an unsubstituted or substituted aryl, and more preferably hydrogen atom, an alkenyl having 1 to 4 carbon atoms or an alkyl having 1 to 4 carbon atoms.
X2 is preferably hydrogen atom, an alkyl or an alkoxycarbonyl, more preferably hydrogen atom or an alkyl having 1 to 4 carbon atom, and particularly preferably hydrogen atom.
Y is oxygen atom or sulfur atom, and preferably oxygen atom.
Z is hydrogen atom; a halogen atom such as fluorine atom, chlorine atom or bromine atom; cyano; a linear, branched or cyclic alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl; a linear, branched or cyclic alkenyl such as vinyl, propenyl, butenyl or hexenyl; an alkynyl such as ethynyl, butynyl or pentynyl; amino; an alkoxy such as methoxy, ethoxy, iso-butoxy or n-butoxy; an alkylthio such as methylthio, ethylthio, n-propylthio, iso-propylthio or n-butylthio.
The alkyl, alkenyl, alkynyl, alkoxy and alkylthio of the above-mentioned Z are preferably ones having carbon atoms of 6 or less. The alkyl, alkenyl, alkynyl, amino, alkoxy and alkylthio of the above-mentioned Z may be arbitrarily substituted. The substituents are not specifically limited as long as the compound has an insecticidal activity. Concretely, the substituents of the alkyl, alkenyl, alkynyl, alkoxy and alkylthio include the groups of G3, and the substituents of the amino include the groups of G4.
The groups of G3 include a halogen atom such as fluorine atom, chlorine atom or bromine atom; hydroxy; cyano; nitro; a haloalkyl such as trifluoromethyl, pentafluoroethyl, difluoromethyl, trichloromethyl or dichlorodifluoroethyl; a linear, branched or cyclic alkenyl such as vinyl, propenyl, butenyl or hexenyl; a linear, branched or cyclic haloalkenyl such as difluorovinyl or trifluorovinyl; an alkynyl such as ethynyl, butynyl or pentynyl; a haloalkynyl such as fluorobutynyl or chlorobutynyl; an alkoxy such as methoxy, ethoxy, iso-propoxy, iso-butoxy or n-butoxy; a haloalkoxy such as trifluoromethoxy, difluoromethoxy or trifluoroethoxy; an alkylthio such as methylthio, ethylthio, n-propylthio, iso-propylthio or n-butylthio; or a haloalkylthio such as trifluoromethylthio or trifluoroethylthio.
The alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkoxy, haloalkoxy, alkylthio and haloalkylthio of G3 include preferably carbon atoms of 3 or less.
The groups of G4 include hydroxy; cyano; a linear, branched or cyclic alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl; a linear, branched or cyclic haloalkyl such as trifluoromethyl, pentafluoroethyl, difluoromethyl, trichloromethyl or dichlorodifluoroethyl; a linear, branched or cyclic alkenyl such as vinyl, propenyl, butenyl or hexenyl; a linear, branched or cyclic haloalkenyl such as difluorovinyl or trifluorovinyl; an alkynyl such as ethynyl, butynyl or pentynyl; a haloalkynyl such as fluorobutynyl or chlorobutynyl; an alkoxy such as methoxy, ethoxy, is-propoxy, iso-butoxy or n-butoxy; or a haloalkoxy such as trifluoromethoxy, difluoromethoxy or trifluoroethoxy.
The alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, alkoxy and haloalkoxy of G4 include preferably carbon atoms of 3 or less.
In addition, in case where the above-mentioned amino is substituted by two substituents selected from G4, the G4s may be same or different each other, and further two G4s together form a ring such as pyrrolidinyl, piperidyl, piperadinyl or morphoryl.
Z is preferably hydrogen atom, cyano, an amino unsubstituted or substituted by one or two alkyl groups having 1 to 4 carbon atoms, or an alkyl unsubstituted or substituted by a substituent selected from the group consisting of a halogen atom, an alkoxy and an alkylthio, more preferably a halogen atom, an alkyl, cyano or amino, further preferably an alkyl or cyano, and particularly preferably methyl or ethyl.
Although the hydrazone derivatives of the formula (I) have geometrical isomers (E/Z) based on the double bond C═N, both ingredients are effective and can be used as the insecticide of the present invention. Preferably, the E form is effective as the insecticide of the present invention.
The hydrazone derivatives of the formula (I) have generally a molecular weight of 1000 or less, and more preferably a molecular weight of 750 or less.
Further, the compounds of the formula (II) are a group of particularly preferable novel compounds among the hydrazone derivatives used as the insecticides of the present invention.
The aryl and heterocyclic group unsubstituted or substituted by a substituent selected from G5 which are A′ and Q′ in the formula (II) include groups similar to ones exemplified for A and Q in the formula (I).
G5 is a halogen atom, hydroxy, cyano, an alkyl, a haloalkyl, an alkenyl, a haloalkenyl, an alkynyl, a haloalkynyl, amino, an alkylamino, a dialkylamino, an alkoxy, a haloalkoxy, formyl, an acyl, an acyloxy, an alkoxycarbonyl, an alkylthio, a haloalkylthio, an alkylsulfinyl, a haloalkylsulfinyl, an alkylsulfonyl, a haloalkylsulfonyl, an aryl, an aryloxy, an arylthio, a heterocyclic group, a heterocyclic oxy or a heterocyclic thio, and the aryl, aryloxy arylthio, heterocyclic group, heterocyclic oxy and heterocyclic thio are optionally substituted by a halogen atom, hydroxy, cyano, nitro, an alkyl, a haloalkyl, an alkenyl, a haloalkenyl, an alkynyl, a haloalkynyl, amino, an alkylamino, a dialkylamino, an alkoxy, a haloalkoxy, formyl, an acyl, an acyloxy, an alkoxycarbonyl, an alkylthio, a haloalkylthio, an alkylsulfinyl, a haloalkylsulfinyl, an alkylsulfonyl or a haloalkylsulfonyl.
The halogen atom, alkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, amino, alkylamino, dialkylamino, alkoxy,haloalkoxy, acyl, acyloxy, alkoxycarbonyl, alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, aryl, aryloxy, arylthio, heterocyclic group, heterocyclic oxy and heterocyclic thio that are substituent G5, include groups similar to ones exemplified for G1 in the formula (I).
The A′ is preferably phenyl or a nitrogen-containing heterocyclic group unsubstituted or substituted by a substituent selected from the group consisting of a halogen atom, an alkyl, a haloalkyl, an alkoxy, a haloalkoxy, an alkylthio and a haloalkylthio, more preferably phenyl unsubstituted or substituted by a substituent selected from the group consisting of a halogen atom, an alkyl, a haloalkyl and a haloalkoxy.
The Q′ is preferably an aryl or a heterocyclic group unsubstituted or substituted by a substituent selected from the group consisting of a halogen atom, an alkyl, a haloalkyl, an alkylamino, a dialkylamino, an alkoxy, a haloalkoxy; an alkylthio and a haloalkylthio, more preferably a heterocyclic group unsubstituted or substituted by a substituent selected from the group consisting of a halogen atom, an alkyl and a haloalkyl.
W′ is oxygen atom, —(C(R1)(R2))n—, —O(C(R1)(R2))n—, or —(C(R1)(R2))nO— wherein n is an integer of 1 to 5, and R1 and R2 independently of the other are hydrogen atom, an alkyl, an alkenyl or alkynyl, or R1 and R2 together form an alkylidene group, or —N(R3)— wherein R3 is hydrogen atom, an alkyl, an alkenyl or an alkynyl.
The groups —(C(R1)(R2))n—, —O(C(R1)(R2))n—, —(C(R1)(R2))nO— and —N(R3)— in the W′ include groups similar to ones exemplified for W in the formula (I).
The W′ is preferably oxygen atom, —(C(R1)(R2))n—, —(C(R1)(R2))nO— or —N(R3)—, more preferably oxygen atom, —CH2— or —NH— and particularly preferably —CH2— or —NH—.
X1′ and X2′ independently of the other are hydrogen atom, formyl, or an alkyl, an alkenyl, an alkynyl, an aryl, a heterocyclic group, an acyl, an alkoxycarbony, an aryloxycarbonyl, a heterocyclic oxycarbonyl, an alkylsulfinyl, an arylsulfinyl, a heterocyclic sulfinyl, an alkylsulfonyl, an arylsulfonyl or a heterocyclic sulfonyl which is unsubstituted or substituted by a substituent selected from G2.
The alkyl, alkenyl, alkynyl, aryl, heterocyclic group, acyl, alkoxycarbony, aryloxycarbonyl, heterocyclic oxycarbonyl, alkylsulfinyl, arylsulfinyl, heterocyclic sulfinyl, alkylsulfonyl, arylsulfonyl or heterocyclic sulfonyl which is unsubstituted or substituted by a substituent selected from G2 in the X1′ and X2′, include groups similar to ones exemplified for X1 and X2 in the formula (I).
Further, the substituent G2 also include groups similar to ones exemplified in the formula (I).
The X1′ is preferably hydrogen atom, an alkenyl having 1 to 4 carbon atoms, an acyl having 1 to 10 carbon atoms, or an alkyl having 1 to 10 carbon atoms which is unsubstituted or substituted by a substituent selected from the group consisting of a halogen atom, cyano, an alkoxy, an alkylthio, an alkoxycarbonyl and an unsubstituted or substituted aryl, and X2′ is preferably hydrogen atom, an alkyl or an alkoxycarbonyl.
Y′ is oxygen atom or sulfur atom, and preferably oxygen atom.
Z′ is a linear or branched alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, n-pentyl or n-hexyl; a linear or branched alkenyl such as vinyl, propenyl, butenyl or hexenyl; or a linear or branched alkynyl such as ethynyl, butynyl or pentynyl, and the alkyl, alkenyl and alkynyl may be substituted by a substituent selected from G6.
The alkyl, alkenyl and alkynyl of the above-mentioned Z′ are preferably ones having carbon atoms of 6 or less.
The groups of G6 include a halogen atom such as fluorine atom, chlorine atom or bromine atom; an alkoxy such as methoxy, ethoxy, iso-propoxy, iso-butoxy or n-butoxy; a haloalkoxy such as trifluoromethoxy, difluoromethoxy or trifluoroethoxy; an alkylthio such as methylthio, ethylthio, n-propylthio, iso-propylthio or n-butylthio; or a haloalkylthio such as trifluoromethylthio or trifluoroethylthio. The alkoxy, haloalkoxy, alkylthio and haloalkylthio of G6 include preferably carbon atoms of 1 to 3.
Z′ is preferably a linear or branched alkyl unsubstituted or substituted by a substituent selected from the group consisting of a halogen atom, an alkoxy and an alkylthio, more preferably a linear or branched alkyl, and particularly preferably methyl or ethyl.
Although the hydrazone derivatives of the formula (II) have geometrical isomers (E/Z) based on the double bond C═N, both ingredients are effective and can be used as the insecticide of the present invention. Preferably, the E form is effective as the insecticide of the present invention.
The hydrazone derivatives of the formula (I) have generally a molecular weight of 1000 or less, and more preferably a molecular weight of 750 or less.
The compounds of the formulae (I) and (II) that can be used as the insecticide of the present invention can be produced by a combination of the known reactions. For example, the production processes indicated in Schemes 1–7 described below can efficiently afford the compounds.
In the schemes described below, L is a leaving group, for example a halogen atom such as chlorine atom, bromine atom or iodine atom; an alkylsulfonyloxy such as methanesulfonyloxy or ethanesulfonyloxy; a haloalkylsulfonyloxy such as trifluoromethylsulfonyloxy or chloromethylsulfonyloxy; or an arylsulfonyloxy such as benzenesulfonyloxy or p-toluenesulfonyloxy, and preferably chlorine atom, bromine atom, methanesulfonyloxy, p-toluenesulfonyloxy or trifluoromethylsulfonyloxy.
L1 is a halogen atom such as chlorine atom, bromine atom or iodine atom, and preferably chlorine atom.
R is a linear, branched or cyclic alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
A, Q, W, X1, X2, Z and G4 are the same groups as ones defined for the above-mentioned formula (I).
The hydrazone derivative of formula (Ia) is obtained by reacting carboxylic acid derivative (III) with amine derivative or hydrazine derivative (IV) in the presence of a condensation agent as indicated in Scheme 1.
The amount of amine derivative or hydrazine derivative (IV) used is generally 0.7 to 1.5 equivalent to the carboxylic acid derivative (III). In addition, the reaction temperature is 0 to 150° C. and preferably 10 to 100° C.
The condensation agent used is not specifically limited if it is a condensation agent generally used for a condensation reaction of a carboxylic acid with an amine, and concretely include a carbodiimide condensation agent such as dicyclohexylcarbodiimide (DCC) or 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC.HCl); a dehydration condensation agent such as carbonyldiimidazole (CDI), BOP-Cl, HATU or diphenylphosphoryl azide (DPPA); sulfonylchloride such as methane sulfonylchloride or p-toluene sulfonylchloride; a halogenation agent such as thionyl chloride or oxazaryl chloride; acid chloride such as 2,4,6-trichlorobenzoyl chloride, pivalic acid chloride, isobutyloxycarbonyl chloride or ethyl chloroformate.
The amount of the condensation agent used is generally 0.5 to 10 times, preferably 1 to 3 times that of carboxylic acid derivative (III).
In addition, if necessary, an alkaline metal alkoxide such as sodium methoxide; an alkaline metal carbonate such as potassium carbonate; an alkaline metal carboxylate such as sodium acetate; an alkaline metal hydroxide such as potassium hydroxide; a tertiary amine such as N-methylmorpholine or triethylamine; an aromatic base such as pyridine or picoline may be added in an amount 0.01 to 1 time that of the condensation agent.
Further, if necessary, 1-hydroxybenzotriazole; N-hydroxysuccinimide; pentafluorophenol; a sulfonic acid such as methanesulfonic acid, p-toluenesulfonic acid or camfor sulfonic acid may be added in an amount 0.01 to 1 time that of the condensation agent.
The reaction is carried out by optionally using solvents. The solvent used is selected depending on reagents used, and includes for example aromatic hydrocarbons such as benzene, toluene or xylene; halogenated hydrocarbons such as dichloromethane, chloroform or 1,2-dichloroethane; ethers such as diethyl ether, tetrahydrofuran or dioxane; esters such as ethyl acetate; alcohols such as methanol, ethanol or propanol; ketones such as acetone or methyl ethyl ketone; aprotic polar solvents such as N,N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide or acetonitrile; or water, which is used as a single solvent or a mixed solvent. Among them, toluene, dichloromethane or N,N-dimethylformamide is preferable.
The amount of the solvent used is generally 1 to 100 times by weight, preferably 4 to 40 times by weight of that carboxylic acid derivative (III).
The hydrazone derivative of formula (Ia) is obtained by reacting carboxylic acid halide derivative (V) with amine derivative or hydrazine derivative (IV) in the presence of a base as indicated in Scheme 2.
The amount of amine derivative or hydrazine derivative (IV) used is generally 0.7 to 1.5 equivalent to the carboxylic acid halide derivative (V). In addition, the reaction temperature is 0 to 150° C. and preferably 10 to 100° C.
Examples of the base used include an alkaline metal alkoxide such as sodium methoxide; an alkaline metal carbonate such as potassium carbonate; an alkaline metal carboxylate such as sodium acetate; an alkaline metal hydroxide such as potassium hydroxide; a tertiary amine such as N-methylmorpholine or triethylamine; and an aromatic base such as pyridine or picoline.
The amount of the base used is generally 0.5 to 10 times, preferably 1 to 3 times that of carboxylic acid halide derivative (V) or amine derivative or hydrazine derivative derivative (IV).
The reaction is carried out by optionally using solvents. The solvent used includes for example aromatic hydrocarbons such as benzene, toluene or xylene; halogenated hydrocarbons such as dichloromethane, chloroform or 1,2-dichlroethane; ethers such as diethyl ether, tetrahydrofuran or dioxane; esters such as ethyl acetate; ketones such as acetone or methyl ethyl ketone; aprotic polar solvents such as N,N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide or acetonitrile; or water, which is used as a single solvent or a mixed solvent. Among them, toluene or dichloromethane is preferable.
The amount of the solvent used is generally 1 to 100 times by weight, preferably 4 to 40 times by weight of that carboxylic acid halide derivative (V).
The hydrazone derivative of formula (Ia) is obtained by reacting carboxylic acid ester derivative (VI) with amine derivative or hydrazine derivative (IV) as indicated in Scheme 3.
The amount of amine derivative or hydrazine derivative (IV) used is generally 0.7 to 1.5 equivalent to the carboxylic acid ester derivative (VI). In addition, the reaction temperature is 0° C. to a boiling point of the solvent used and preferably 10 to 150° C.
The reaction is optionally carried out by using solvents, for example aromatic hydrocarbons such as benzene, toluene or xylene; halogenated hydrocarbons such as dichloromethane, chloroform or 1,2-dichlroethane; ethers such as diethyl ether, tetrahydrofuran or dioxane; alcohols such as methanol, ethanol or propanol; aprotic polar solvents such as N,N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide or acetonitrile; or water, which is used as a single solvent or a mixed solvent. Among them, aromatic hydrocarbon solvents such as toluene or xylene are preferable.
The amount of the solvent used is generally 1 to 100 times by weight, preferably 4 to 40 times by weight of that carboxylic acid ester derivative (VI).
The hydrazone derivative of formula (Ia) is obtained by reacting hydrazone derivative (Ib) with halogen derivative or sulfonate derivative (VII) in the presence of a base as indicated in Scheme 4.
The amount of halogen derivative or sulfonate derivative (VII) used in the reaction is generally 0.5 to 10 times equivalent to that of the chydrazone derivative (Ib). In addition, the reaction temperature is −70 to 150° C. and preferably −20 to 100° C.
Examples of the base used include an alkyl lithium reagent such as butyl lithium; an alkaline metal hydride such as sodium hydride; an alkaline metal alkoxide such as sodium methoxide; and an alkaline metal carbonate such as sodium carbonate;.
The amount of the base used is generally 0.5 to 10 times equivalent, preferably 1 to 3 times equivalent to that of hydrazone derivative (Ib).
In addition, if necessary, a catalyst for example quaternary ammonium salt such as tetra-n-butyl ammonium bromide, or crown ether such as 18-crown-6-ether may be added in an amount of 0.01 to 1 time equivalent to that of hydrazone derivative (Ib).
The reaction is carried out by optionally using solvents. The solvent used includes for example aromatic hydrocarbons such as benzene, toluene or xylene; halogenated hydrocarbons such as dichloromethane, chloroform or 1,2-dichlroethane; ethers such as diethyl ether, tetrahydrofuran or dioxane; or aprotic polar solvents such as N,N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide or acetonitrile, which is used as a single solvent or a mixed solvent. Among them, a polar solvent such as N,N-dimethylformamide or tetrahydrofuran is preferable.
The amount of the solvent used is generally 1 to 100 times by weight, preferably 4 to 40 times by weight of that compound (Ib).
The hydrazone derivative of formula (Id) is obtained by halogenating hydrazone derivative (Ic) with a halogenation agent generally at a reaction temperature of 0 to 150° C., preferably 0 to 80° C. as indicated in Scheme 5.
Examples of the halogenation agent used include chlorine, bromine, N-chlorosuccinic acid imide, N-bromosuccinic imide and sulfuryl chloride.
The amount of the halogenation agent is generally 0.5 to 10 times equivalent, preferably 1 to 3 times equivalent to that of the hydrazone derivative (Ic).
The reaction is carried out by optionally using solvents. The solvent used includes for example aromatic hydrocarbons such as benzene, toluene or xylene; halogenated hydrocarbons such as dichloromethane, chloroform or 1,2-dichlroethane; ethers such as diethyl ether, tetrahydrofuran or dioxane; esters such as ethyl acetate; alcohols such as methanol, ethanol or propanol; ketones such as acetone or methyl ethyl ketone; aprotic polar solvents such as N,N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide or acetonitrile; or water, which is used as a single solvent or a mixed solvent. Among them, N,N-dimethylformamide, tetrahydrofuran or toluene is preferable.
The amount of the solvent used is generally 1 to 100 times by weight, preferably 4 to 40 times by weight of that compound (Ib).
The amidine derivative of formula (Ie) is obtained by reacting hydrazone derivative (Id) with amine derivative (VIII) in the presence of a base generally at a reaction temperature of 0 to 150° C., preferably 10° C. to a boiling point of the solvent used as indicated in Scheme 6.
The amount of amine derivative (VIII) is generally 0.5 to 10 times equivalent, preferably 1 to 3 times equivalent to that of the hydrazone derivative (Id).
Examples of the base used include an alkaline metal hydride such as sodium hydride; an alkaline metal alkoxide such as sodium methoxide; an alkaline metal carbonate such as potassium carbonate; an alkaline metal carboxylate such as sodium acetate; an alkaline metal hydroxide such as potassium hydroxide; a tertiary amine such as N-methylmorpholine or triethylamine; an aromatic base such as pyridine or picoline.
The amount of the base used is generally 0.5 to 10 times equivalent, preferably 1 to 3 times equivalent to that of the hydrazone derivative (Id).
In addition, if necessary, a catalyst for example quaternary ammonium salt such as tetra-n-butyl ammonium bromide, or crown ether such as 18-crown-6-ether may be added in an amount of 0.01 to 1 time equivalent to that of hydrazone derivative (Ib) to the reaction system.
Examples of the solvent used include for example aromatic hydrocarbons such as benzene, toluene or xylene; halogenated hydrocarbons such as dichloromethane, chloroform or 1,2-dichlroethane; ethers such as diethyl ether, tetrahydrofuran or dioxane; esters such as ethyl acetate; alcohols such as methanol, ethanol or propanol; aprotic polar solvents such as N,N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide or acetonitrile; or a protic polar solvent such as water or acetic acid, which is used as a single solvent or a mixed solvent. Among them, ethers such as dietheylether, tetrahydrofuran or dioxane are preferable.
The amount of the solvent used is generally 1 to 100 times, preferably 4 to 40 times by weight of that compound (Id).
The hydrazone derivative of formula (If) is obtained by reacting diazonium salt derivative prepared by subjecting aniline derivative or heterocyclic amine (X) to diazotization with cyanoacetic acid amide (IX) in the presence of a base at a reaction temperature of 0 to 100° C., preferably 10° C. to a boiling point of the solvent used as indicated in Scheme 7.
Diazotization agents used for the diazotization of the aniline derivative or heterocyclic amine are not specifically limited if it is a diazotization agent that is generally used, and concretely include a metal nitrite such as sodium nitrite; and a nitrite such as isoamyl nitrite.
The amount of the diazotization agent is generally 0.5 to 10 times equivalent, preferably 1 to 3 times equivalent to that of the aniline derivative or heterocyclic amine (X).
The diazotization is generally carried out in the presence of an acid at a reaction temperature of −70 to 100° C., preferably −50 to 20° C.
Acids used are not specifically limited if it is an acid generally used in diazotization, and concretely include hydrochloric acid; sulfuric acid; sulfonic acid such as methanesulfonic acid or p-toluene sulfonic acid; carboxylic acid such as acetic acid or trifluoro acetic acid; Lewis acid such as boron trifluoride ether complex, and preferably hydrochloric acid, sulfuric acid or acetic acid.
The amount of the acid is generally 0.5 to 100 times equivalent, preferably 1 to 50 times equivalent to that of the aniline derivative or heterocyclic amine (X).
Examples of the base used for the reaction between diazonium salt derivative and cyanoacetic acid amide derivative (IX) are not specifically limited if it is a base generally used for coupling between diazonium salt and cyanoacetic acid derivative, and include an alkaline metal hydride such as sodium hydride; an alkaline metal alkoxide such as sodium methoxide; an alkaline metal carbonate such as potassium carbonate or sodium carbonate; an alkaline metal carboxylate such as sodium acetate; an alkaline metal hydroxide such as potassium hydroxide; a tertiary amine such as N-methylmorpholine or triethylamine; an aromatic base such as pyridine or picoline.
The amount of the base is generally 0.5 to 100 times equivalent, preferably 1 to 20 times equivalent to that of the cyanoacetic amide derivative (IX).
The reaction is generally carried out in the presence of solvent. Examples of the solvent used include for example aromatic hydrocarbons such as benzene, toluene or xylene; halogenated hydrocarbons such as dichloromethane, chloroform or 1,2-dichlroethane; esters such as ethyl acetate; alcohols such as methanol, ethanol or propanol; ketones such as acetone or methyl ethyl ketone; aprotic polar solvents such as N,N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide or acetonitrile; or a protic polar solvent such as water or acetic acid, which is used as a single solvent or a mixed solvent. Among them, water, acetic acid and alcohols such as methanol, ethanol or propanol are preferable, and they may be mixed in an arbitrary proportion.
The amount of the solvent used is generally 1 to 100 times, preferably 4 to 40 times by weight of that compound (IX) or compound (X).
The insecticide containing the compound of the present invention as active ingredient has a control effect against insects or other pests, and is effective for repelling, exterminating or controlling pests in a wide range of scenes, such as agriculture, forestry, livestock industry, fishery and conservation scene of products in these industries, or public hygiene.
In particular, the compound of the present invention exerts an excellent effect in repellent, extermination and control of pests causing harm in agriculture or forestry, concretely in cultivation of agricultural crops or to harvest, trees or ornamental plants, etc., or pests in public hygiene scene.
Hereinafter, concrete application scenes, targeted pests, application method and the like are described, but the present invention is not limited thereto. Further, pests concretely exemplified are not limited as targeted pests, and the exemplified pests include adults, larvae, eggs and the like.
(A) Agriculture or Forestry Scene
The compounds of the present invention are effective for repellent or control of pests such as arthropods, molluscs or nematodes, or several fungi, particularly arthropods such as insects, which cause harm to agricultural crops such as food crops (rice, wheat, barley, rye or oats, corn, potato, sweet potato, leguminous plants, etc.), vegetables (rapes, cucumbers, egg plant, tomato, spring onions, etc.), fruit trees (oranges, apple, grape, peach, etc.), industrial crops (tobacco, tea, sugar beet, sugarcane, cotton, olive, etc.), forage crops and grasses (sorghums, gramineous forage grasses, leguminous forage grasses, etc.) or ornamental plants (herbaceous plants, flowers and ornamental plants, garden plants, etc) in the culturing scene thereof. In addition, the compounds of the present invention are effective also for repellent or extermination of pests in storage of harvests from the above-mentioned crops, such as cereals, fruits, nuts, spices or tobacco, or storage of the products prepared by subjecting the harvests to a process such as drying, disintegration or the like. Further, the compounds are effective for protecting standing trees, fallen trees, modified woods, stored woods or the like from harm by pests such as termites or beetles.
For example, concrete pests include the followings belonging to the phylum Arthropoda, Mollusca or Nematoda. The followings can be exemplified as pests belonging to the class Insecta in the phylum Arthropoda.
Pests of the order Lepidoptera include for example
Pests of the order Coleoptera include for example
Pests of the order Hemiptera include for example
Pests of the order Thysanoptera include for example
Pests of the order Hymenoptera include for example
Pests of the order Diptera include for example
Pests of the order Orthoptera include for example
Pests of the order Collembola include for example
Pests of the order Isoptera include for example the family Termitidae such as Odontotermes formosanus and pests of the order Dermaptera include for example the family Labiduridae such as Labidura riparia and the like.
The followings can be exemplified as pests belonging to the classes Crustacea and Arachnida in the phylum Arthropoda.
Pests of the order Isopoda in the class Crustacea include for example the family Armadillidae such as pillbug (Armadillidium vulgare).
Pests of the order Acarina in the class Arachnida include for example
Pests of the class Gastropoda in the phylum Mollusca include the order Mesogastropoda such as apple snail (Pomacea canaliculata), the order Stylommatophora such as giant African snail (Achatina fulica), Incilaria bilineata, Milax gagates, giant garden slug (Limax marginatus) or Acusta despecta; and the like.
The followings can be exemplified as pests belonging to the classes Secernentea and Adenophorea in the phylum Nematoda.
Pests of the order Tylenchida in the class Secernentea include for example
Pests of the order Dorylaimida in the class Adenophorea include for example
The compounds of the present invention are effective for repellent, control or extermination of pests that injure natural forests, artificial forests and trees in city green space or have an effect on vital force of these trees. In such a scene concrete pests include the followings.
The followings can be exemplified as pests belonging to the classes Insecta and Arachnida in the phylum Arthropoda.
Pests of the order Lepidoptera include for example
Pests of the order Coleoptera include for example
Pests of the order Hemiptera include for example
Pests of the order Hymenoptera include for example
Pests of the order Diptera include for example
Pests of the order Acarina in the class Arachnida include for example spruce spider mite (Oligonychus ununguis).
Pests of the order Tylenchida in the class Secernentea in the phylum Nematoda include for example the family Philomycidae such as pine wood nematode (Bursaphelenchus lignicolus); and the like.
The insecticide containing the compound of the present invention as active ingredient can be used as a formulation effective in the above-mentioned scene of agriculture or forestry, or in any arbitrary application form prepared from the formulation, alone or by a simultaneous use of other active compounds such as an insecticide, acaricide, nematicide, fungicide, synergist, plant growth regulator, herbicide or poison bait, etc., or in an admixture therewith. More concrete active compounds include for example the followings to Which the present invention is not limited.
Active Compounds of Insecticides or Acaricides:
Organophosphorus compounds include for example dichlorvos, fenitrothion, malathion, naled, chlorpyrifos, diazinon, tetrachlorvinphos, fenthion, isoxathion, methidathion, salithion, acefate, dimeton-S-methyl, disulfoton, monocrotophos, azinphos-methyl, parathion, phosalone, pirimiphos-methyl, prothiofos and the like.
Carbamate compounds include for example metolcarb, fenocarb, propoxur, carbaryl, ethiofencarb, pirimicarb, bendiocarb, carbosulfan, carbofuran, methomyl, thiodicarb and the like.
Organochlorine compounds include for example lindane, DDT, endosulfan, aldrin, chlordane and the like.
Pyrethroids include for example permethrin, cypermethrin, deltamethrin, cyhalothrin, cyfluthrin, acrinathrin, fenvalerate, etofenprox, silafluofen, fluvalinate, flucythrinate, bifenthrin, allethrin, phenothrin, fenpropathrin, cyphenothrin, furamethrin, resmethrin, transfluthrin, prallethrin, flufenprox, halfenprox, imiprothrin and the like.
Neonicotinoids include for example imidacloprid, nitenpyram, acetamiprid, dinotefuran, thiamethoxam, thiacloprid, clothianidin and the like.
Insect growth regulators such as phenyl benzoyl ureas include for example diflubenzuron, chlorfluazuron, triflumuron, flufenoxuron, hexaflumuron, lufemuron, teflubenzuron, novaluron, buprofezin, tebufenozide, chromafenozide, methoxy fenozide, cyromazine and the like.
Juvenile hormone mimics include for example pyriproxyfen, fenoxycarb, methoprene, hydroprene and the like.
Insecticidal materials produced by microorganisms include for example abamectin, milbemectin, nikkomycins, emamectin benzoate, ivermectin, spinosad and the like.
Other insecticides include for example cartap, bensultap, chlorfenapyr, diafenthiuron, nicotine sulfate, metaldehyde, fipronil, ethiprole, pymetrozin, indoxacarb, tolfenpyrad, pyridalyl, flurimfen, BT agents and the like.
Active compounds of acaricides include for example dicofol, phenisobromolate, benzomate, tetradifon, polynactin-complex, amitraz, propargite, fenbutatin oxide, tricyclohexyltin hydroxide, tebufenpyrad, pyridaben, fenpyroximate, pyrimidifen, fenazaquin, clofentezine, hexythiazox, acequinocyl, quinomethionat, fenothiocarb, etoxazole, bifenazate, fluacrypyrim and the like.
Active compounds of nematicides include for example methyl isocyanate, fosthiazate, cadusafos, oxamyl, mesulfenfos and the like.
Poison baits include for example monofluoroacetate, warfarin, coumatetralyl, diphacin and the like.
Active compounds of fungicides include for example an inorganic copper, an organic copper, sulfur, maneb, thiuram, thiadiazine, captan, chlorothalonil, iprobenfos, thiophanata-methyl, benomyl, thiabendazole, iprodione, procymidone, pencycuron, metalaxyl, sandofan, baileton, triflumizole, fenarimol, triforine, dithianon, triazine, fluazinam, probenazole, diethofencarb, isoprothiolane, pyroquilon, iminoctadine acetate, echlomezol, dazomet, kresoxim-methyl and the like.
Active compounds of herbicides include for example bialaphos, sethoxydim, trifluralin, mefenacet and the like.
Active compounds of plant growth regulators include for example indoleacetic acid, ethephon, 4-CPA and the like.
Active compounds of repellents include for example carane-3,4-diol, N,N-diethyl-m-triamide (Deet), limonene, linalool, citronellal, menton, hinokitiol, menthol, graniol, eucalyptole and the like.
Active compounds of synergists include for example bis-(2,3,3,3-tetrachloropropyl) ether, N-(2-ethylhexyl)bicyclo[2.1.1]hept-5-en-2,3-dicarboxy imide, α-[2-(2-butoxyethoxy)ethoxy]-4,5-methylenedioxy-2-propyl toluene and the like.
The insecticide of the present invention can be used in any arbitrary application form, and be formulated for example in a form of wettable powders, water dispersible granules, water soluble powders, emulsifiable concentrates, liquid formulations, flowables such as suspension concentrate in water or emulsifiable concentrate in water, encapsulations, dusts, granules, aerosols and the like, after adding any auxiliary substances to the compound of the present invention. These formulations may contain the active ingredients such as the compounds of the present invention, etc. in any arbitrary amount, and generally the total amount of the active ingredients is selected from a range of 0.001 to 99.5% by weight depending on several conditions such as a formulation form or application method, etc. For example, it is suitable to prepare formulations so as to contain the active ingredients in an amount of about 0.01 to 90% by weight, preferably 1 to 50% by weight in case of wettable powders, water dispersible granules, water soluble powders, emulsifiable concentrates, liquid formulations, flowables, encapsulations or the like, in an amount of 0.1 to 50% by weight, preferably 1 to 10% by weight in case of dusts, granules or the like, and in an amount of about 0.001 to 20% by weight, preferably 0.01 to 2% by weight in case of aerosols or the like.
As the auxiliary substance, for example a carrier (diluent), a spreader, an emulsifier, a wetting agent, a dispersing agent, a disintegrator or the like may be used in order to improve repellent effect, control effect or extermination effect of pests and improve stability or dispersibility.
Liquid carriers include water, aromatic hydrocarbons such as toluene or xylene, alcohols such as methanol, butanol or glycol, ketones such as acetone, amides such as dimethylformamide, sulfoxides such as dimethylsulfoxide, methyl naphthalene, cyclohexane, animal and vegetable oils, fatty acids and the like. In addition, solid carriers include clay, kaolin, talc, diatomaceous earth, silica, calcium carbonate, montmorillonite, bentonite, feldspar, quartz, alumina, sawdust, nitrocellulose, starch, gum arabic and the like.
As the emulsifier or dispersing agent, surfactants can be generally used. The surfactants include for example anionic, cationic, non-ionic oramphoteric surfactants such as higher alcohol sodium sulfate, stearyl trimethyl ammonium chloride, polyoxyethylene alkyl phenyl ethers or lauryl betaine.
The followings may be used: a spreader such as polyoxyethylene nonyl phenyl ether or polyoxyethylene lauryl phenyl ether; a wetting agent such as dialkylsulfosuccinate; an adhesive agent such as carboxymethyl cellulose or polyvinyl alcohol; a disintegrator such as sodium lignin sulfonate or sodium lauryl sulfonate.
For example, in case of wettable powders, raw powders are prepared by mixing the compound of formula (I) as active ingredient, a solid carrier and a surfactant, etc. Further, the raw powders can be applied by diluting it with water to a prescribed concentration when it is used.
In case of emulsifiable concentrates, they can be prepared by mixing a solvent and a surfactant to the active ingredient. Further, the concentrate can be applied by diluting it with water to a prescribed concentration when it is used.
In case of dusts, they can be applied as such after mixing the active ingredient, a solid carrier and the like. In case of granules, they can be applied as such after mixing and granulating the active ingredient, a solid carrier, a surfactant and the like.
In the meanwhile, the preparation method of each of the above-mentioned formulations is not limited to the above-mentioned ones, and those skilled in the art can select suitably depending on the kind of active ingredient, the object of application or the like.
The application method is selected depending on the kind or population of pests, or the kind, cultivating form or growth condition of crops or trees to be objected, and for example in case where pests to be controlled are arthropods, gastropods or nematodes, etc., generally the area where injury due to the pests occurs or the area where such an injury is predicted is treated with the insecticide in an active ingredient amount of 0.1 to 1000 g, preferably 1 to 100 g per 10 are (a).
A concrete application method comprise diluting for example the above-mentioned wettable powders, water dispersible granules, water soluble powders, emulsifiable concentrates, liquid formulations, flowables such as suspension concentrate in water or emulsifiable concentrate in water, encapsulations, or the like with water, and spraying it to crops or trees to be objected in an amount of 10 to 1000 liter per 10 a depending on the kind, cultivating form or growth condition of the crops or trees. In addition, in case of dusts, granules or aerosols, they may be applied to crops or trees in a form of the formulations in the above-mentioned application rate.
In case where pests to be objected injure crops or trees mainly in soil, for example wettable powders, water dispersible granules, water soluble powders, emulsifiable concentrates, liquid formulations, flowables such as suspension concentrate in water or emulsifiable concentrate in water, encapsulations, or the like are diluted with water to obtain a diluted formulation, and the diluted formulation is sprayed in an application rate of 5 to 500 liter per 10 a. In this case, the diluted formulation may be sprayed on the surface of soil in a manner that it is dispersed evenly on the whole application area or drenched in soil. In case where formulations are dusts or granules, the formulation may be sprayed as such on the surface of soil in a manner that it is dispersed evenly on the whole application area. When spraying or drench is carried out, the formulation may be applied only the periphery of seeds, crops, trees or the like to be protected from the injury of pests, or during or after spraying the soil is cultivated thereby dispersing the active ingredients mechanically.
Further, the insecticide containing the compound of the present invention as active ingredient may be adhered on plant seeds by any known methods. Such a treatment provides not only a protection from injury by pests in soil after sowing the seeds but also a protection of stems or flowers of plants or fruits after growing from injury by pests,
In case where the above-mentioned trees or fallen trees, processed woods, stored woods or the like are protected from injury by termites or beetles, application methods include spraying, injection, drench or coating of an oil solution, an emulsifiable concentrate, a wettable powder or a sol, or spraying of a dust or granule to the periphery soil of trees or woods. In such a scene, the pest control agent containing the compound of the present invention as active ingredient may be used alone or by a simultaneous use of other active compounds such as insecticides, acaricides, nematicides, fungicides, repellents, synergists or the like, or in an admixture therewith.
These formulations may contain the active ingredients such as the compounds of the present invention, etc. in any arbitrary amount, and generally the amount of the active ingredients is selected from a range of 0.0001 to 95% by weight, preferably 0.005 to 10% by weight in oil solutions, dusts or granules, or 0.01 to 50% by weight in emulsifiable concentrates, wettable powders or sols. Concretely, in case where for example termites or beetles are exterminated or controlled, the formulation is sprayed on soil or the surface of woods at 0.01 to 100 g of the active ingredients per 1 m2.
(B) Livestock Industry, Fishery Scene
The insecticides containing the compounds of the present invention are effective for repellent, extermination or control of pests such as arthropods, nematodes, trematodes, tapeworms, protozoans or the like which parasitize internally or externally animals fed in livestock industry or fishery, or house such as pets, or household, and do a direct harm, such as skin-eating or blood-sucking or do an injury, such as spreading of diseases. They can be also used for prevention and treatment diseases in related with the pests. Animals to be objected include vertebrates, for example livestock such as cattle, sheep, goat, horses, pigs that are warm-blood vertebrates, cultured fishes; further domestics, dogs or cats or rodents such as mice, rats, hamsters or squirrels; and pets or laboratory animals that are carnivores such as ferrets and fishes.
Among the pests, the followings can be exemplified as ones belonging to the classes Insecta and Arachnida in the phylum Arthropoda.
Pests of the order Diptera include for example
In addition, pests of the order Siphonaptera include for example the family Pulicidae such as Ctenocephalides felis or Ctenocephalides canis; and the like.
Pests of the order Anoplura include for example the family Echinophthiriidae such as Haematopinus suis or Haematopinus eurysternus;
Pests of the order Acarina in the class Arachnida in the phylum Arthropoda include for example
The followings can be exemplified as pests of the class Secernentea in the phylum Nematoda.
The order Strongylida include for example cattle hookworm (Bunostomum phlebotomum), Stephanurus dentatus, Metastrongylus apri, Trichostrongylus colubriformis or Oesophagostomum radiatum.
The order Ascaridida include for example Toxocara suum or Ascaridia galli, etc.
The class Trematoda in the phylum Plathelminthes include for example oriental blood fluke (Schistosoma japonicum), liver fluke (Fosciola hepatica), Paramphistomum cervi, Paragonimus westermanii or Prosthogonimus ovatus, etc.
The class Cestoda include for example Anoplocephala perfoliata, Moniezia expansa, Moniezia benedeni, Raillietina tetragona or Raillietina cesticillus, etc.
The class Mastigophorea in the phylum Protozoa include the order Rhizomastigida such as Histomonas, the order Protomastigida such as Leishmania or Trypanosoma, the order Polymastigida such as Giardia, the order Trichomonadida such as Trichomonas, and the like.
The order Amoebida in the class Sarcodinea include for example Entamoeba and the like, the subclass Piroplasmia in the class Sporozoea include for example Theilaria, Babesia and the like, and the subclass Telosporidia such as Eimeria, Plasmodium, Toxoplasma and the like.
The insecticide containing the compound of the present invention as active ingredient can be used as a formulation effective in the above-mentioned livestock industry or fishery scene, or in any arbitrary application form prepared from the formulation, alone or by a simultaneous use of other active compounds such as an insecticide, acaricide, nematicide, fungicide, synergist, plant growth regulator, herbicide or poison bait, etc., or in an admixture therewith. More concrete active compounds include for example the compounds listed in the item “(A) Agriculture or forestry scene” to which the present invention is not limited.
Concrete application methods comprise for example blending the insecticide in feeds for livestock or pets, or orally administrating a medical preparation that can be orally ingested, such as tablets, balls, capsules, paste, gel, beverage, medicinal feeds, medicinal drinking water, medicinal additional feeds, gradual-releasing large balls or other gradual-releasing devices prepared in such a manner to be stayed in the intestine, for example containing pharmaceutically acceptable carriers or coating materials, or percutaneously administrating in a form of a spray, a powder, grease, cream, ointment, emulsifiable concentrate, lotion, spot-on, pour-on, shampoo, etc.
The percutaneous or topical administration can be carried out by use of a device (for example a collar, a medallion, an ear-tag, etc.) attached to animals so that arthropods should be controlled locally or systematically.
Although concrete methods for oral or percutaneous administration in case where the insecticide of the present invention is used as antiparasitic agent will hereinafter be described, the present invention is not limited to these methods. In case where a medicinal beverage preparation is orally administered, the preparation is prepared by dissolving the active ingredient together with a suspending agent such as bentonite, a moistening agent or other excipients in a non-poisonous solvent or water to obtain a suspension or a dispersion. The preparation contains optionally an antifoaming agent. The beverage preparations generally contain the active ingredient in an amount of 0.01 to 1.0% by weight, preferably 0.01 to 0.1% by weight.
In case where the insecticide is orally administered in a form of dried solid unit, generally capsules, balls or tablets containing a prescribed amount of the active ingredient are used. They are prepared by homogeneously mixing the active component with suitably milled diluents, fillers, disintegrators or binders, such as starch, lactose, talc, magnesium stearate, plant gum or the like. For the prescription of the unit, the weight and content of antiparasitic agents may be determined depending on the kind of host animals to be treated, the level of infection, the kind of parasites and the body weight of the hosts.
In case where an active compound is administered, through a feed, the active compound may be used by homogeneously dispersing it in the feed, or be used as top-dressing or in a form of pellet. In order to accomplish antiparasitic effect, the active compound is contained in an amount of 0.0001 to 0.05% by weight, preferably 0.0005 to 0.01% by weight in the final feed.
In case where an active compound is dissolved or dispersed in a liquid excipient, the insecticide may be parenterally administered by intraproventriculus, intramuscular, endotracheal or subcutaneous injection. As it is parenterally administrated, it is preferable to mix the active compound with vegetable oil such as peanut oil or cotton seed oil. The formulation generally contains the active compound in an amount of 0.05 to 50% by weight, preferably 0.1 to 0.2% by weight. The formulation in which a carrier such as dimethylsulfoxide or hydrocarbon solvent, etc. is mixed can be administered directly or locally to the outer surface of livestock or pets by a spray or direct pouring.
(C) Public Hygiene Scene, etc.
Also, the insecticides of the present invention are effective for repellent, extermination or control of pests in public hygiene scene which exert an adverse effect on the environment of clothing, food and housing, cause harm to human body or transport or mediate pathogens, or the like, in order to maintain good public hygiene state. Concretely, the pesticides of the present invention are effective for repellent, extermination or control of pests belonging to Lepidoptera, Coleoptera, Thysanura, Blattariae, Cyclorhapha and Acarina. The pests in the public hygiene scene concretely include the followings.
The followings can be exemplified as the class Insecta in the phylum Arthropoda.
The pests of the order Lepidoptera include for example
The pests of the order Coleoptera include for example the family Oedemeridae such as Xanthochroa waterhousei;
The pests of the order Hymenoptera include for example
The pests of the order Diptera include for example
The pests of the order Siphonaptera include for example
The pests of the order Collembola include for example
The pests of the order Blattaria include for example
The pests of the order Orthoptera include for example
The pests of the, order Anoplura include for example
The pests of the order Hemiptera include for example
The pests of the order Isoptera include for example
The pests of the order Thysanura include for example
The followings can be exemplified as the class Arachnida in the phylum Arthropoda.
The pests of the order Acarina include for example
The pests of the order Araneae include for example
The pests of the order Scoriones include for example
Other pests belonging to the phylum Arthropoda include
In addition, the pests belonging to the order Polydesmida in the class Diplopoda in the phylum Arthropoda include for example the family Paradoxosomatidae such as Oxidus gracilis; and the pests belonging to the order Isopoda in the class Crustacea in the phylum Athropoda include for example the family Porcellionidae such as Porcellio sp.; and the like.
Further, the pests belonging to the order Gnathobdellida in the class Hirudinea in the phylum Annelida include for example the family Haemadipsidae such as Haemadipsa zeylanica; and the like.
The insecticide containing the compound of the present invention as active ingredient can be used as a formulation effective in the above-mentioned public hygiene scene, or in any arbitrary application form prepared from the formulation, alone or by a simultaneous use of other active compounds such as an insecticide, acaricide, nematicide, fungicide, synergist, plant growth regulator, herbicide or poison bait, etc., or in an admixture therewith. More concrete active compounds include for example the compounds listed in the item “(A) Agriculture or forestry scene” to which the present invention is not limited.
The insecticide of the present invention can be used in any arbitrary application form, and for example in case where the above-mentioned animal or plant products are protected, the pests can be controlled by spraying the oil solution, emulsifiable concentrate, wettable powder or dust of the insecticide, by setting a resin transpiration agent, by treating with the smoking pesticide or fogging agent of the insecticide, by setting the granule, tablet or poison bait of the insecticide, or by atomizing the aerosol of the insecticide. These formulations preferably contain the active ingredients in an amount of 0.0001 to 95% by weight.
The application is carried out as follows, for example. When pests are arthropods which directly cause damage or are mediators of diseases, the application comprises spraying, injecting, pouring or coating an oil solution, emulsifiable concentrate, wettable powder or the like in the periphery where the arthropods may be present, spraying a dust there, or treating there with a fumigant, a heat-fogging agent such as a mosquito coil, a self-combustion type smoking agent or chemical reaction type fogging agent, a smoking agent such as a fogging, or a formulation such as ULV formulation. Alternatively, the application may be carried out by setting other types of formulations, such as a granule, tablet or poison bait, or adding dropwise a floating dust formulation or granule in a water channel, well, water reservoir or other flowing or retained water.
Further, the pests belonging to tussock moths that are pests also in agriculture or forestry can be controlled in a similar way as the methods described in the item “(A) Agriculture or forestry scene”. In addition, for flies it is effective to mix the insecticide in the feed of livestock so that the active ingredient could be introduced into the feces, and for mosquitos it is effective to transpire the active ingredient in the air with an electric mosquito-repellent apparatus.
The formulations of these application types may be present as an admixture with other active compounds as mentioned above, such as an insecticide, acaricide, nematicide, fungicide, repellent or synergist, and it is preferable to contain the active compounds in an total amount of 0.0001 to 95% by weight in total therein. In the meanwhile, when the formulation is used, it may be simultaneously used with other active compounds.
In case where houses or wooden furnishings are protected against pests such as termites or beetles, the application comprises spraying, injecting, pouring or coating an oil solution, emulsifiable concentrate, wettable powder, sol agent or the like in the periphery where the pests are present, or spraying a formulation in a form of dust there. Also in such a scene, the compound of the present invention may be simultaneously used with other active compounds such as an insecticide, acaricide, nematicide, fungicide, repellent or synergist, etc., or be used in an admixture therewith.
The total content of the active compounds such as the compound of the present invention in these formulations is arbitrary, and generally is 0.0001 to 95% by weight. It is preferable to contain the active compounds in an amount of 0.005 to 10% by weight in an oil solution, dust or granule, etc. and in an amount of 0.01 to 50% by weight in an emulsifiable concentrate, wettable powder or sol agent. Concretely, for example in case where termites or beetles are exterminated or controlled, the formulation is sprayed in the periphery or directly the surface thereof at 0.01 to 100 g of the active ingredients per 1 m2.
In repellent, extermination or control of pests that cause damage to human body or transport or mediate pathogen, in addition to the above-mentioned applications, it is able to orally administrate a medical preparation that can be orally ingested, such as tablets, balls, capsules, paste, gel, beverage, medicinal feeds, medicinal drinking water, medicinal additional feeds, gradual-releasing large balls or other gradual-releasing devices prepared in such a manner to be stayed in the intestine, for example containing pharmaceutically acceptable carriers or coating materials, or to percutaneously administrate in a form of a spray, a powder, grease, cream, ointment, emulsifiable concentrate, lotion, spot-on, pour-on, shampoo, etc.
Concrete prescriptions of the formulation and the like are similar to those described in the item “(B) Livestock industry, fishery scene”.
Next, the present invention will be more concretely described based on examples. However, the present invention is not limited to them unless it is beyond the gist of the present invention.
4-Trifluoromethylphenyl hydrazine (8.40 g, 47.7 mmol) was suspended in 1 N hydrochloric acid (130 ml) and fully stirred with a mechanical stirrer to obtain a suspension. A aqueous solution (50 ml) of pyruvic acid (4.20 g, 47.7 mmol) was added to the suspension and vigorously stirred to a mixture. 6 hours later, the mixture was extracted with ethyl acetate and washed with a saturated brine. The washed mixture was dried on sodium sulfate and then filtered. The residue obtained by concentrating the resulting filtrate was washed with a mixed solvent of hexane and chloroform (1:1) to obtain 2-(4-trifluoromethylphenyl hydrazono) propionic acid (10.47 g, 42.52 mmol, 89%). mp 190–191° C.; 1H NMR (400 MHz, CDCl3) δ 2.19 (3H, s), 7.23 (2H, d), 7.60 (2H, d), 7.87 (1H, brs).
2-(4-Trifluoromethylphenyl hydrazono) propionic acid (0.74 g, 3.0 mmol) was dissolved in dichloromethane (15 ml), and 4-chlorobenzyl amine (0.42 g, 3.0 mmol) and 1-[3-(dimethylamino) propyl]-3-ethylcarbodiimide hydrochloric acid salt (0.58 g, 3.0 mmol) were added thereto. 20 hours later, the mixture was washed with 1N hydrochloric acid, a saturated sodium bicarbonate water and a saturated brine, and dried on sodium sulfate and then filtrated. The residue obtained by concentrating the resulting filtrate was suspended in a mixed solvent of hexane and chloroform (1:1) and filtered to obtain N-(4-chlorobenzyl)-2-(4-trifluoromethylphenyl hydrazono) propionic acid amide (Compound No. 62) (0.83 g, 2.2 mmol, 75%).
Compound No. 62: mp 124–125° C.; 1H NMR (400 MHz, CDCl3) δ 2.16 (3H, s), 4.55 (2H, d), 7.15 (2H, d), 7.27 (2H, d), 7.32 (2H, d), 7.53 (2H, d), 7.69 (1H, brs).
2-(4-Chlorophenyl hydrazono) propionic acid (0.64 g, 3.0 mmol) was dissolved in tetrahydrofuran (3 ml), and carbonyl diimidazole (0.49 g, 3.0 mmol) was added under cooling with ice. After stirring at room temperature for 1 hour, a solution of 4-methoxybenzyl amine (0.41 g, 3.0 mmol) in tetrahydrofuran (3 ml) was added thereto. 15 hours later, the mixture was washed with 6N hydrocloric acid, 1N aqueous solution of sodium hydroxide and a saturated brine, dried on sodium sulfate and then filtered. The residue obtained by concentrating the resulting filtrate was suspended in a mixed solvent of hexane and chloroform (1:1) and filtered to obtain N-(4-methoxybenzyl)-2-(4-chlorophenyl hydrazono) propionic acid amide (Compound No. 93) (0.76 g, 2.3 mmol, 76%).
Compound No. 93: mp 156–158° C.; 1H NMR (400 MHz, CDCl3) δ 2.13 (3H, s), 3.8 (3H, s), 4.50 (2H, d), 6.88 (2H, d), 7.00 (2H, d), 7.23 (2H, d), 7.26 (2H, d), 7.44 (1H, brs).
2-(4-Trifluoromethylphenyl hydrazono) propionic acid (12.31 g, 50.0 mmol) was dissolved in dichloromethane (250 ml) and N,N-dimethylformamide (25 ml), and 5-aminomethyl-2-chloropyridine (7.13 g, 50.0 mmol) and 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloric acid salt (9.59 g, 50.0 mmol) were added thereto. 30 hours later, the mixture was washed with 1N hydrochloric acid, a saturated sodium bicarbonate water and a saturated brine, and dried on sodium sulfate and then filtrated. The residue obtained by concentrating the resulting filtrate was purified with a silica gel chromatography to obtain N-(6-chloro-3-pyridylmethyl)-2-(4-trifluoromethylphenyl hydrazono) propionic acid amide (Compound No. 63) (14.47 g, 39.02 mmol, 78%).
Compound No. 63: mp 184° C.; 1H NMR (400 MHz, CDCl3) δ 2.16 (3H, s), 4.57 (2H, d), 7.15 (2H, d), 7.31 (2H, d), 7.35 (1H, brt), 7.54 (2H, d), 7.64 (1H, s), 7.66 (1H, dd), 8.38 (1H, d).
Pyruvic acid (0.88 g, 10.0 mmol) was dissolved in tetrahydrofuran (20 ml), and carbodiimidazole (1.62 g, 10 mmol) was added under colling with ice. After stirring at room temperature for 1 hour, 4-chlorophenyl hydrazine hydrochloric acid salt (3.94 g, 22.0 mmol) and triethylamine (2.53 g, 25 mmol) were added thereto. 6 hours later, 1N hydrochloric acid was added, and the organic phase was extracted with ethyl acetate, and washed with a saturated sodium bicarbonate water and a saturated brine, dried on sodium sulfate and then filtered. The residue obtained by concentrating the resulting filtrate was purified with a silica gel chromatography to obtain (E)-N′-(4-chlorophenyl)-2-(4-chlorophenyl hydrazono) propionic acid hydrazide (Compound No. 104) (0.63 g, 1.9 mmol, 14%) and (Z)-N′-(4-chlorophenyl)-2-(4-chlorophenyl hydrazono) propionic acid hydrazide (Compound No. 105) (0.06 g, 0.44 mmol, 4%).
Compound No. 104: mp 169–171° C.; 1H NMR (400 MHz, CDCl3) δ 2.09 (3H, s), 6.10 (1H, brs), 6.80 (2H, d, J=8.8 Hz), 7.08 (2H, d, J=8.8 Hz), 7.16 (2H, d, J=8.8 Hz), 7.28 (2H, d, J=8.8 Hz), 7.67 (1H, brs), 8.55 (1H, brs).
Compound No. 105: mp 160–162° C.; 1H NMR (400 MHz, CDCl3) δ 2.27 (3H, s), 6.13 (1H, brs), 6.82 (2H, d, J=8.4 Hz), 7.05 (2H, d, J=8.8 Hz), 7.20 (2H, d, J=8.4 Hz), 7.22 (2H, d, J=8.8 Hz), 7.46 (1H, brs), 12.66 (1H, brs).
60% sodium hydride (0.060 g, 1.5 mmol) was added to a solution of N-(6-chloro-3-pyridylmethyl)-2-(4-trifluoromethylphenyl hydrazono) propionic acid amide (0.4 g, 1 mmol) in N,N-dimethylformamide (3 ml) and stirred for 10 minutes. Ethoxy methyl chloride (0.14 g, 1.5 mmol) was added thereto, and stirred at room temperature for 1 hour. The reaction mixture was purified with a silica gel chromatography to obtain N-(6-chloro-3-pyridylmethyl)-2-[N-ethoxymethyl-N-(4-trifluoromethylphenyl hydrazono) propionic acid amide (Compound No. 127) (0.24 g, 0.56 mmol, 56%).
Compound No. 127: mp 90–91° C.; 1H NMR (400 MHz, CDCl3) δ 1.21 (3H, t), 1.96 (3H, s), 3.55 (2H, q), 4.55 (2H, d), 5.01 (2H, s), 7.04 (2H, d), 7.32 (1H, d), 7.55 (2H, d), 7.68 (2H, dd), 8.38 (1H, s).
A mixture of ethyl pyruvate (3.3 g, 28 mmol), 4-trifluoromethylphenyl hydrazine (5.0 g, 28 mmol) and ethanol (50 ml) was refluxed under heating for 5 hours. After cooling to room temperature, the solvent was distilled off, and ethyl acetate and water were added to the residue, and then the mixture was subjected to extraction. The organic phase was washed with a saturated brine, and then dried on anhydrous sodium sulfate. Filtration and next concentration gave crude ethyl 2-(4-trifluoromethylphenyl hydrazono) propionate (4.7 g, 17 mmol, 61%).
1H NMR (400 MHz, CDCl3) δ 1.39 (3H, t), 2.14 (3H, s), 4.33 (2H, q), 7.27 (2H, d), 7.55 (2H, d), 7.78 (1H, s).
60% sodium hydride (0.2 g, 5 mmol) was gradually added to a solution of ethyl 2-(4-trifluoromethylphenyl hydrazono) propionate (1.37 g, 5.00 mmol) in tetrahydrofuran (10 ml) and stirred for 30 minutes. Methyl iodide (0.85 g, 5.0 mmol) was gradually added, and stirred further for 1 hour. The solvent was distilled off, and ethyl acetate and water were added to the residue, and then the mixture was subjected to extraction. The organic phase was washed with a saturated brine, and then dried on anhydrous sodium sulfate. After filtrating and then concentrating, the residue was purified with a silica gel chromatography to obtain ethyl 2-[N-methyl-N-(4-trifluoromethylphenyl) hydrazono]propionate (1.0 g, 3.6 mmol, 72%).
mp 71–72° C.; 1H NMR (400 MHz, CDCl3) δ 1.40 (3H, t), 2.22 (3H, s), 3.40 (3H, s), 4.36 (2H, q), 7.18 (2H, d), 7.54 (2H, d).
Ethyl 2-[N-methyl-N-(4-trifluoromethylphenyl) hydrazono]propionate (0.94 g, 3.3 mmol) was dissolved in tetrahydrofuran (10 ml), 1N aqueous solution of sodium hydroxide (6.5 ml, 6.6 mmol) was added thereto, and the resulting mixture was left at room temperature overnight. When the mixture was acidified with 1N hydrochloric acid, crystals were separated out. The crystals were dissolved in ethyl acetate and extracted therewith. The organic phase was washed with a saturated brine, and then dried on anhydrous sodium sulfate. Filtration and next concentration gave 2-[N-methyl-N-(4-trifluoromethylphenyl hydrazono) propionic acid (0.6 g, 2.4 mmol, 72%). mp 53–54° C.; 1H NMR (400 MHz, CDCl3) δ 2.49 (3H, s), 3.54 (3H, s), 7.17 (2H, d), 7.61 (2H, d).
A mixture of 2-[N-methyl-N-(4-trifluoromethylphenyl hydrazono) propionic acid (0.59 g, 2.3 mmol), 4-chlorobenzyl amine (0.33 g, 2.3 mmol), 1-[3-(dimethylamino) propyl]-3-ethylcarbodiimide hydrochloric acid salt (0.44 g, 2.3 mmol) and dichloromethane (10 ml) was left at room temperature overnight. The mixture was extracted with chloroform, washed 1N hydrochloric acid, a saturated sodium bicarbonate water and a saturated brine, dried on sodium sulfate and then filtered. The residue obtained by concentrating the resulting filtrate was purified with a silica gel chromatography to obtain N-(4-chlorobenzyl)-2-[N-methyl-N-(4-trifluoromethylphenyl) hydrazono]propionic acid amide (Compound No. 109) (0.30 g, 0.78 mmol, 34%).
Compound No. 109: mp 112–113° C.; 1H NMR (400 MHz, CDCl3) δ 2.24 (3H, s), 3.31 (3H, s), 4.53 (2H, d), 7.02 (2H, d), 7.30 (4H, m), 7.54 (2H, d).
60% sodium hydride (0.12 g, 3.0 mmol) was added to a solution of N-(6-chloro-3-pyridylmethyl)-2-(4-trifluoromethylphenyl hydrazono) propionic acid amide (Compound No. 63) (1.0 g, 2.7 mmol) in N,N-dimethylformamide (5 ml) and stirred for 10 minutes. Methyl iodide (0.40 g, 2.8 mmol) was gradually added thereto, and stirred at room temperature for 2 hours. To the reaction mixture, ice water and ethyl acetate were added, and subjected to extraction. The organic phase was washed with a saturated brine, then dried on anhydrous sodium sulfate and concentrated. The resulting residue was purified with a silica gel chromatography to obtain N-(6-chloro-3-pyridylmethyl)-2-[N-methyl-N-(4-trifluoromethylphenyl) hydrazono]propionic acid amide (Compound No. 110) (0.80 g, 2.1 mmol, 77%).
Compound No. 110: mp 141–142° C.; 1H NMR (400 MHz, CDCl3) δ 2.23 (3H, s), 3.32 (3H, s), 4.55 (2H, d), 7.03 (2H, d), 7.31 (1H, d), 7.55 (2H, d), 7.60 (1H, brs), 7.67 (2H, dd), 8.37 (1H, s).
4-Trifluoromethylphenyl hydrazine (1.76 g, 10.0 mmol) was gradually added to a mixture of ethyl bromopyruvate (1.95 g, 10.0 mmol) and ethanol (2 ml) under cooling with water. The mixture was stirred at room temperature for 1 hour. The resulting solution was added dropwise under cooling with water to a solution obtained by gradually adding 60% sodium hydride (0.4 g, 10.0 mmol) to ethanol (20 ml). The resulting mixture was left at room temperature overnight, then the solvent was distilled off, and ethyl acetate and water were added to the residue, and then the mixture was subjected to extraction. The organic phase was washed with a saturated brine, and then dried on anhydrous sodium sulfate. After filtrating and then concentrating, the residue was purified with silica gel chromatography to obtain ethyl 3-ethoxy-2-(4-trifluoromethylphenyl hydrazono) propionate (0.57 g, 1.8 mmol, 18%).
nD25 1.5250; 1H NMR (400 MHz, CDCl3) δ 1.24 (3H, t), 1.38 (3H, t), 3.59 (2H, q), 4.32 (4H, m), 7.27 (2H, d), 7.54 (2H, d), 12.38 (1H, s).
Ethyl 3-ethoxy-2-(4-trifluoromethylphenyl hydrazono) propionate (0.5 g, 1.6 mmol) was dissolved in tetrahydrofuran (2 ml), 1N aqueous solution of sodium hydroxide (3.2 ml, 3.2 mmol) was added thereto, and the resulting mixture was left at room temperature overnight. The mixture was acidified with 1N hydrochloric acid, and then subjected to extraction by adding ethyl acetate and water. The organic phase was washed with a saturated brine, and then dried on anhydrous sodium sulfate. Filtration and next concentration gave 3-ethoxy-2-(4-trifluoromethylphenyl hydrazono) propionic acid (0.3 g, 1.0 mmol, 65%).
mp 96–99° C.; 1H NMR (400 MHz, CDCl3) δ 1.31 (3H, t), 3.70 (2H, q), 4.46 (2H, s), 7.28 (2H, d), 7.56 (2H, d), 12.42 (1H, s).
A mixture of 3-ethoxy-2-(4-trifluoromethylphenyl hydrazono) propionic acid (0.3 g, 1 mmol), 5-aminomethyl-2-chloropyridine (0.21 g, 1.5 mmol), 1-[3-(dimethylamino) propyl]-3-ethylcarbodiimide hydrochloric acid salt (0.29 g, 1.5 mmol) and chloroform (10 ml) was left at room temperature overnight. The mixture was extracted with chloroform, washed 1N hydrochloric acid, a saturated sodium bicarbonate water and a saturated brine, dried on anhydrous sodium sulfate and then filtered. The residue obtained by concentrating the resulting filtrate was purified with a silica gel chromatography to obtain N-(6-chloro-3-pyridylmethyl)-3-ethoxy-2-(4-trifluoromethylphenyl hydrazono) propionic acid amide (Compound No. 170) (0.3 g, 0.72 mmol, 72%).
Compound No. 170: mp 98–99° C.; 1H NMR (400 MHz, CDCl3) δ 1.20 (3H, t), 3.57 (2H, q), 4.36 (2H, s), 4.51 (2H, d), 6.22 (2H, d), 7.33 (1H, d), 7.37 (1H, d), 7.52 (2H, d), 7.52 (2H, d), 7.64 (1H, dd), 7.85 (1H, brt).
4-Trifluoromethylphenyl hydrazine (4.1 g, 23 mmol) was gradually added to a solution of concentrated hydrochloric acid (5 ml) in water (120 ml). 40% aqueous solution (4.3 g, 23 mmol) of glyoxylic acid was gradually added, and stirred at room temperature for 5 hours. After leaving it overnight, the mixture was extracted with ethyl acetate. The organic phase was washed with a saturated brine, and dried on anhydrous sodium sulfate. The solvent was distilled off, and the resulting crystals were washed with hexane and a little amount of ethyl acetate to obtain (4-trifluoromethylphenyl hydrazono) acetic acid (4.7 g, 20 mmol, 88%).
mp 125° C.; 1H NMR (400 MHz, DMSO-d6) δ 7.21 (1H, s), 7.25 (2H, d), 7.62 (2H, d), 11.45 (1H, s), 12.55 (1H, s).
(4-Trifluoromethylphenyl hydrazono) acetic acid (2.3 g, 10 mmol), 5-aminomethyl-2-chloropyridine (1.4 g, 10 mmol) and 1-[3-(dimethylamino) propyl]-3-ethylcarbodiimide hydrochloric acid salt were added to dichloromethane (30 ml), and stirred at room temperature for 8 hours. After leaving it overnight, 1N hydrochloric acid and chloroform were added thereto, but they were not dissolved therein, and then crystals were filtered off. The resulting crystals were dried to obtain N-(6-chloro-3-pyridylmethyl)-4-trifluoromethylphenylhydrazono acetic acid amide (2.1 g, 5.9 mmol). Further, the filtrate was subjected to extraction, the organic phase was washed with a saturated brine and then dried on anhydrous sodium sulfate. The solvent was distilled off, and the resulting crystals were washed with hexane and a little amount of ethyl acetate to obtain N-(6-chloro-3-pyridylmethyl)-4-trifluoromethylphenyl hydrazono acetic acid amide (0.4 g, 1.1 mmol, 70%).
1H NMR (400 MHz, DMSO-d6) δ 4.41 (2H, d), 7.22 (1H, s), 7.34 (2H, d), 7.49 (1H, d), 7.58 (2H, d), 7.77 (1H, dd), 8.36 (1H, d), 8.81 (1H, t).
N-chlorosuccinimide (0.53 g, 4.0 mmol) was added to a solution of N-(6-chloro-3-pyridylmethyl)-4-trifluoromethylphenyl hydrazono acetic acid amide in N,N-dimethylformamide (6 ml), and left at room temperature overnight. To the reaction mixture, ice water and ethyl acetate were added, and subjected to extraction. The organic phase was washed with an aqueous solution of sodium thiosulfate and a saturated brine, then dried on anhydrous sodium sulfate. After concentrating it, hexan and a little amount of ethyl acetate were added thereto, and the resulting crystals were washed and filtered to obtain N-(6-chloro-3-pyridylmethyl)-2-chloro-2-(4-trifluoromethylphenyl hydrazono) acetic acid amide (Compound No. 5) (1.15 g, 2.95 mmol, 82%).
Compound No. 5: mp 172–173° C.; 1H NMR (400 MHz, CDCl3) δ 4.61 (2H, d), 7.10 (1H, brs), 7.20 (2H, d), 7.33 (1H, d), 7.58 (2H, d), 7.70 (1H, dd), 8.33 (1H, s), 8.38 (1H, d).
40% aqueous solution of methylamine (78 mg, 1.0 mmol) was gradually added to a solution of N-(6-chloro-3-pyridylmethyl)-2-chloro-2-(4-trifluoromethylphenyl hydrazono) acetic acid amide (Compound No. 5) (0.4 g, 1 mmol) and triethylamine (0.1 g, 1 mmol) in tetrahydrofuran (10 ml) and left at room temperature overnight. Further, 40% aqueous solution of methylamine (10 mg, 0.13 mmol) was added and stirred at room temperature for 1 hour, and thereafter subjected to extraction by adding ethyl acetate and water. The organic phase was washed with a saturated brine, and then dried on anhydrous sodium sulfate. The resulting residue was purified with a silica gel chromatography to obtain N-(6-chloro-3-pyridylmethyl)-2-methylamino-2-(4-trifluoromethylphenyl hydrazono) acetic acid amide (Compound No. 191) (0.13 g, 0.34 mmol, 34%).
Compound No. 191: mp 156° C.; 1H NMR (400 MHz, CDCl3) δ 2.96 (3H, d), 4.54 (2H, d), 5.11 (1H, brd), 7.05 (2H, d), 7.13 (1H, s), 7.32 (1H, d), 7.50 (2H, d), 7.65 (1H, dd), 8.37 (1H, d).
Cyanoacetic acid (2.6 g, 0.030 mmol), 5-aminomethyl-2-chloropyridine (4.3 g, 0.030 mmol) and 1-[3-(dimethylamino) propyl]-3-ethylcarbodiimide hydrochloric acid salt (5.8 g, 0.030 mol) were added to dichloromethane (50 ml), and stirred overnight. Chloroform and 1N hydrochloric acid were added thereto, and crystals were separated out. The crystals were filtered off, dissolved in ethyl acetate, and water was added thereto and subjected to extraction. The organic phase was washed with a saturated sodium bicarbonate and a saturated brine, and then dried anhydrous sodium sulfate. The residue obtained by filtrating and concentrating was washed with hexane and a little amount of ethyl acetate to obtain N-(6-chloro-3-pyridylmethyl)-2-cyanoacetic acid amide (6.1 g, 0.029 mmol, 97%).
mp 119° C.; 1H NMR (400 MHz, DMSO-d6) δ 3.72 (2H, s), 4.32 (2H, d), 7.50 (1H, d), 7.75 (1H, dd), 8.33 (1H, d), 8.80 (1H, brs).
4-Trifluoromethyl aniline (0.97 g, 6.0 mmol) was gradually added to acetic acid (3.5 ml), water (1.7 ml) and concentrated hydrochloric acid (1.7 ml) and dissolved, and cooled to 5° C. A solution of sodium nitrate (0.5 g, 7.2 mmol) in water (2 ml) was gradually added thereto at a temperature of 10° C. or less. The resulting solution was gradually added to a mixture of N-(6-chloro-3-pyridylmethyl)-2-cyanoacetic acid amide (1.3 g, 6.0 mmol), sodium acetate (1.23 g, 15.0 mmol), ethanol (30 ml) and 1N aqueous solution of sodium carbonate (40 ml). After stirring at room temperature for 5 hours, water and ethyl acetate were added thereto and subjected to extraction. The organic phase was washed with a saturated brine, and dried on anhydrous sodium sulfate. The residue obtained by filtering and concentrating was purified with a silica gel chromatography to obtain N-(6-chloro-3-pyridylmethyl)-2-cyano-2-(4-trifluoromethylphenyl hydrazono) acetic acid amide (Compound No. 184) (0.12 g, 0.30 mmol, 5%) (Compound No. 185) (1.15 g, 3.00 mmol, 50%). Geometrical isomerism (E/Z) was not determined.
Compound No. 184: mp 204–205° C.; 1H NMR (400 MHz, DMSO-d6) δ 4.43 (2H, d), 7.53 (1H, d), 7.63 (2H, d), 7.74 (2H, d), 7.85 (1H, dd), 8.43 (1H, d), 9.23 (1H, t).
Compound No. 185: mp 205–206° C.; 1H NMR (400 MHz, DMSO-d6) δ 4.46 (2H, d), 7.50 (1H, d), 7.72 (2H, d), 7.82 (3H, m), 8.39 (1H, d), 9.04 (1H, t), 12.04 (1H, s).
Compounds listed in the Tables 1 to 8 below were synthesized in a similar manner as the above-mentioned Synthetic Examples 1 to 11.
In case where Z is CN, geometrical isomerism (E/Z) was not determined.
In case where Z is CN, geometrical isomerism (E/Z) was not determined.
In case where Z is CN, geometrical isomerism (E/Z) was not determined.
Hereinafter, formulation example and test examples of the pesticides according to the present invention will be described. In the meanwhile, Compound No. indicated in each of the tests corresponds to Compound No. in Tables 1 to 8.
A wettable powder containing 20% by weight of an active ingredient was prepared by homogeneously mixing and milling 20 parts by weight of a compound of the present invention, 20 parts by weight of Carplex #80 (white carbon, Shionogi & Co., Ltd., trade name), 52 parts by weight of ST Kaolincray (kaolinite, Tsuchiya Kaolin Co., Ltd., trade name), 5 parts by weight of Sorpol 9047K (anionic surfactant, Toho Chemical Industry Co., Ltd., trade name), and 3 parts by weight of Lenox P65L (an anionic surfactant, Toho Chemical Industry Co., Ltd., trade name).
A dust containing 2% by weight of an active ingredient was prepared by homogeneously mixing and milling 2 parts by weight of a compound of the present invention, 93 parts by weight of cray (manufactured by Nippon Talc Co., Ltd.), and 5 parts by weight of Carplex #80 (white carbon, Shionogi & Co., Ltd., trade name).
A emulsifiable concentrate containing 20% by weight of an active ingredient was prepared by dissolving 20 parts by weight of a compound of the present invention in a mixed solvent of 35 parts by weight of xylene and 30 parts by weight of dimethylformamide, and adding 15 parts by weight of Sorpol 3005X (mixture of nonionic surfactant and anionic surfactant, Toho Chemical Industry Co., Ltd., trade name).
A flowable agent containing 20% by weight of an active ingredient was prepared by wet-milling 30 parts by weight of a compound of the present invention with 5 parts by weight of Sorpol 9047K (ditto), 3 parts by weight of SorbonT-20 (nonionic surfactant, Toho Chemical Industry Co., Ltd., trade name), 8 parts by weight of ethylene glycol and 44 parts by weight of water by means of Dyno-Mill (manufactured by Shinmaru Enterprises Corporation) to obtain a slurry mixture, adding 10 parts by weight of 1% by weight aqueous solution of xanthane gum (natural polymer) to the slurry mixture, and fully mixing and milling.
A piece of cabbage leaf (diameter: 6 cm) was immersed for 1 minute in a water-diluted solution of the insecticide (wettable powder) of the present invention prepared according to the prescription of Formulation Example 1. After immersion, the cabbage was air-dried and placed in a plastic cup (inner diameter: 7 cm), and then inoculated with 5 larvae of cabbage moth in the third stage therein (1-concentration, 2-repetion). The cup was allowed to stand in a room thermostated at 25° C. Four days after the inoculation, dead or alive larvae or suffuring larvae were counted, and mortality (%) was calculated wherein a suffering larva was regarded as 0.5 dead larva. When compounds of Compound Nos. described below were subjected to the test, the mortality was 100% in a compound concentration of 500 ppm. In the meanwhile, the Compounds Nos. correspond to ones in Tables 1 to 8.
Compounds Nos. 1, 5, 7, 8, 9, 10, 11, 12, 13, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 38, 42, 43, 44, 45, 47, 49, 50, 51, 52, 53, 54, 55, 59, 60, 61, 62, 63, 64, 65, 66, 68, 69, 70, 71, 72, 73, 74, 75, 78, 79, 81, 82, 85, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 102, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 134, 136, 137, 139, 140, 141, 142, 143, 144, 145, 146, 147, 149, 150, 151, 152, 153, 155, 156, 157, 158, 159, 160, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 175, 177, 181, 182, 184, 185, 191, 192, 194, 195, 196, 197, 199, 200, 201, 202, 203, 204, 205, 206, 207, 208, 209, 210, 211, 212, 214, 215, 216, 217, 218, 219, 220, 221, 225, 226, 227, 230, 232, 233, 234, 235, 236, 237, 238, 239, 240, 241, 242, 243, 245, 246, 247, 248, 249, 250, 251, 252, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 269, 270, 272, 275, 276, 284, 285, 286, 287, 288, 289, 290, 291, 292, 293, 294, 295, 296, 297, 298, 299, 300, 301, 302, 304, 305, 306, 307, 308, 309, 318, 319, 320, 321, 322, 323, 324, 325, 326, 328, 329, 330, 331, 332, 333, 334, 335, 336, 337, 338, 339, 340, 341, 342, 343, 344, 345, 346 and 347.
A piece of cabbage leaf (diameter: 6 cm) was immersed for 1 minute in a water-diluted solution of the insecticide (wettable powder),of the present invention prepared according to the prescription of Formulation Example 1. After immersion, the cabbage was air-dried and placed in a plastic cup (inner diameter: 7 cm), and then inoculated with 5 larvae of common cutworm in the third stage therein (1-concentration, 2-repetion). The cup was allowed to stand in a room thermostated at 25° C. Four days after the inoculation, dead or alive larvae or suffuring larvae were counted, and mortality (%) was calculated wherein a suffering larva was regarded as 0.5 dead larva. When compounds of Compound Nos. described below were subjected to the test, the mortality was 100% in a compound concentration of 500 ppm. In the meanwhile, the Compounds Nos. correspond to ones in Tables 1 to 8.
Compounds Nos. 6, 7, 8, 9, 11, 12, 13, 15, 16, 17, 19, 20, 21, 22, 23, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 38, 39, 42, 43, 44, 45, 47, 49. 50, 51, 52, 53, 54, 59, 60, 61, 62, 63, 64, 65, 69, 70, 71, 72, 73, 74, 75, 78, 79, 81, 82, 85, 87, 88, 89, 90, 91, 92, 94, 95, 96, 97, 98, 99, 104, 105, 106, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 139, 140, 141, 143, 144, 145, 146, 147, 152, 153, 155, 157, 158, 159, 160, 161, 162, 165, 166, 167, 168, 171, 174, 175, 176, 177, 180, 182, 184, 185, 188, 189, 190, 191, 192, 194, 195, 196, 197, 199, 200, 201, 205, 206, 207, 208, 209, 210, 211, 212, 215, 216, 217, 219, 220, 221, 225, 226, 227, 230, 232, 235, 236, 237, 238, 239, 240, 241, 242, 243, 245, 246, 247, 248, 249, 250, 251, 255, 256, 257, 258, 259, 262, 263, 264, 265, 266, 267, 269, 270, 272, 275, 276, 284, 287, 288, 289, 290, 291, 292, 293, 294, 295, 296, 297, 298, 299, 300, 301, 302, 303, 304, 307, 308, 309, 318, 319, 320, 321, 322, 323, 324, 325, 326, 327, 328, 329, 330, 331, 332, 333, 334, 335, 336, 337, 338, 339, 340, 341, 342, 343, 344, 345, 346 and 347.
A piece of artificial feed (diameter: ca. 5 cm; one eighth of a circle; thickness: 0.5 cm) was immersed for 10 seconds in a water-diluted solution of the insecticide (wettable powder) of the present invention prepared according to the prescription of Formulation Example 1. After immersion, the feed was placed in a plastic cup (inner diameter: 4 cm), and then inoculated with 5 larvae of smaller tea tortrix in the third stage therein (1-concentration, 2-repetion). The cup was allowed to stand in a room thermostated at 25° C. Four days after the inoculation, dead or alive larvae or suffuring larvae were counted, and mortality (%) was calculated wherein a suffering larva was regarded as 0.5 dead larva. When compounds of Compound Nos. described below were subjected to the test, the mortality was 100% in a compound concentration of 500 ppm. In the meanwhile, the Compounds Nos. correspond to ones in Tables 1 to 8.
Compounds Nos. 8, 11, 12, 13, 16, 17, 20, 21, 22, 24, 26, 27, 28, 29, 30, 31, 34, 35, 37, 38, 39, 43, 44, 45, 47, 49, 52, 53, 54, 59, 60, 63, 64, 65, 68, 69, 71, 72, 73, 74, 75, 78, 79, 82, 85, 90, 91, 92, 93, 94, 95, 97, 99, 100, 104, 106, 107, 109, 110, 111, 113, 115, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 131, 134, 136, 137, 139, 144, 145, 146, 147, 152, 153, 155, 157, 159, 160, 162, 163, 166, 168, 171, 174, 175, 176, 177, 178, 182, 184, 185, 189, 190, 191, 192, 194, 195, 196, 197, 201, 207, 208, 209, 210, 211, 212, 215, 216, 217, 219, 220, 225, 226, 227, 230, 235, 236, 237, 238, 240, 241, 242, 243, 246, 247, 248, 249, 250, 251, 255, 256, 257, 258, 259, 262, 263, 264, 265, 266, 267, 270, 272, 275, 284, 287, 288, 289, 290, 292, 294, 295, 296, 297, 298, 299, 300, 302, 303, 304, 307, 309, 318, 320, 321, 322, 323, 324, 325, 326, 327, 328, 329, 330, 331, 332, 333, 334, 335, 336, 337, 338, 339, 340, 342, 343, 344, 345, 346 and 347.
The insecticides containing hydradine derivatives as active ingredient according to the present invention exert an extremely excellent control effect against pests such as arthropods (insects), nematodes, worms or protozoans in the agriculture and horticulture field, clothing, food and housing-related field, or livestock and pet field, in particular against harmful insects in the agriculture and horticulture field, and therefore the insecticides are useful as controller against these pests.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2002-003830 | Jan 2002 | JP | national |
| 2002-198275 | Jul 2002 | JP | national |
| 2002-262256 | Sep 2002 | JP | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP03/00152 | 1/10/2003 | WO | 00 | 7/27/2004 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO03/059064 | 7/24/2003 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 5304573 | Hino et al. | Apr 1994 | A |
| 5358965 | Hino et al. | Oct 1994 | A |
| 5990171 | Seitz et al. | Nov 1999 | A |
| Number | Date | Country |
|---|---|---|
| 05-262712 | Oct 1993 | JP |
| 2001-072516 | Mar 2001 | JP |
| WO 0101781 | Jan 2001 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20050203149 A1 | Sep 2005 | US |
