JPH07278140A - Intermediate for producing insecticidal nitroimino or cyanoimino compound - Google Patents

Abstract

PURPOSE:To obtain a new intermediate for producing a compound useful for controlling, exterminating and eradicating noxious insects such as liquid-sucking insects, biting insects, insects pests parasitic on plants, storage insect pests and sanitary insect pests without exerting phytotoxicity on cultivated plants. CONSTITUTION:This intermediate is expressed by formula I (Y is nitro or cyano; A<1> is ethylene or trimethylene which may respectively be mono- or polysubstituted with a halogen and a 1-4C alkyl; Z<1> is 3-7C cyloalkyl, a 1-4C haloalkyl, etc., which may be substituted with methyl), e.g. 1-isopropyl-2- nitroiminoimidazolidine expressed by formula II. The intermediate is obtained by reacting, e.g. a compound expressed by formula III (A is ethylene or trimethylene which may respectively be substituted) with a compound expressed by the formula, Z<1>-M<1> (M<1> is a halogen) in the presence of a base such as sodium hydride in an inert solvent such as dimethylformamide.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing an insecticidal nitroimino or cyanoimino compound. More specifically, the present invention relates to a method for producing an insecticidal nitroimino or cyanoimino compound represented by the formula (I) shown below.

[0002]

[Chemical 6]

In the formula, R represents a hydrogen atom or an alkyl group, and W represents a 5- or 6-membered heterocyclic group containing at least one hetero atom consisting of N, O and S, wherein The ring is optionally substituted, Y represents a nitro group or a cyano group, A represents an optionally substituted ethylene group or an optionally substituted trimethylene group, and Z is an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted aryl group, an optionally substituted Optionally substituted alkoxy group, optionally substituted alkylthio group, optionally substituted arylthio group, optionally substituted cycloalkyl group, cyano group, formy Group, an aryloxy group, an alkenyloxy group, a heterocyclic group containing a heteroatom arbitrarily selected from N, O and S, wherein the ring may be optionally substituted, or optionally substituted A good acyl group, an optionally substituted alkoxycarbonyl group, an optionally substituted cycloalkoxycarbonyl group, an optionally substituted aryloxycarbonyl group, an optionally substituted Alkylthiocarbonyl group, optionally substituted arylthiocarbonyl group, optionally substituted alkenyloxycarbonyl group, optionally substituted alkynyloxycarbonyl group, optionally substituted Good carbamoyl group, optionally substituted thiocarbamoyl group, optionally substituted Alkylsulfonyl group, optionally substituted arylsulfonyl group, optionally substituted alkoxysulfonyl group, optionally substituted cycloalkoxysulfonyl group, aryloxysulfonyl group, optionally substituted Optionally sulfamoyl group, a phosphoric acid ester residue, a thiophosphoric acid ester residue, an amidothiophosphoric acid ester residue, an optionally substituted alcoxalyl group, an optionally substituted aryloxalyl group,

[0004]

[Chemical 7]

Wherein Q is an optionally substituted heterocyclic group containing a heteroatom arbitrarily selected from N, O and S, or

[0006]

[Chemical 8]

To produce an insecticidal nitroimino or cyanoimino compound represented by

[0008]

[Chemical 9]

In the formula, Y, A and Z are the same as defined above, and the compound represented by

[0010]

[Chemical 10]

Wherein R and W are as defined above, and M is a halogen atom or

[0012]

[Chemical 11]

Wherein L is an alkyl group or an aryl group, and a compound of the formula (I) is reacted with the compound of formula (I) to produce the insecticidal nitroimino or cyanoimino compound. A publication known before the filing date of the present application, Canadian Day of Chemistry (Can. J. Chem), 39, 1787-1.
On page 796, the following formula:

[0014]

[Chemical 12]

1-benzyl-2-nitroiminoimidazolidine of the formula: has been described. However,
No mention is made of the compound of formula (I).
Further, the publication does not mention the insecticidal action of the compound of the above formula [D] at all. Similarly, Japanese Patent Application Laid-Open No. 48-91064, which is known before the filing date of the present application, describes compounds represented by the following general formula, which compounds have bactericidal, antidiabetic, virus-sedative and diuretic activities. The fact that it is useful as an intermediate substance in the production of substances,
Have been described.

[0016]

[Chemical 13]

(In the formulae, the groups R ₁ and R ₂ are hydrogen atoms or a straight-chain or branched lower alkyl group having 1 to 4 carbon atoms, ..., R ₃ and R ₄ are hydrogen. Atom, a straight-chain or branched lower alkyl group having 1 to 4 carbon atoms, ..., R ⁵ is a hydrogen atom, a straight-chain or branched chain having 1 to 6 carbon atoms Lower alkyl group, hydroxyalkyl group having 2 to 3 carbon atoms, halogen atom, phenyl group optionally mono- or di-substituted by lower alkyl or alkoxy group having 1 or 2 carbon atoms, halogen Represents a benzyl or phenethyl group optionally mono-substituted by an atom ... X is an oxygen or sulfur atom or its nitrogen atom has 1 to 4 carbon atoms. A lower alkyl group or benzyl or an optionally substituted imino group, and n equals 0 or 1.) However, in the above formula [E], from the definition of R ⁵ and X, the compound of the above formula (I) of the present invention cannot be included, and the publication also describes the insecticidal activity, It has not been suggested. And in the specification, for example, a compound corresponding to the following formula is described.

[0018]

[Chemical 14]

The present inventors have now found that the novel nitroimino or cyanoimino compounds of the above formula (I), which have not been described in the known literature, exhibit an insecticidal action, and as mentioned above, a preparation for obtaining the active compound is obtained. I found a way. According to the invention, the nitroimino or cyanoimino compound of formula (I) obtained by the process of the invention exhibits a strong insecticidal action. Surprisingly and surprisingly, the nitroimino or cyanoimino compounds of the formula (I) have a substantially very excellent insecticidal action as compared with compounds similar to the compounds of the formula (I) of the invention described, for example, in the publications mentioned above. Shows up. Furthermore, the compound of formula (I) of the present invention is, in addition to the above-mentioned strong insecticidal activity, pests resistant to these insecticides resulting from the use of organophosphorus and carbamate insecticides for many years than before. In particular, hemiptera (Hemip
It has been discovered that puncture-absorptive pests typified by tcra) such as aphids, planthoppers, leafhoppers, etc. exhibit a remarkable control effect. Therefore, an object of the present invention is to provide a method for producing an insecticidal nitroimino or cyanoimino compound. The above and other objects and advantages of the present invention will be more apparent from the following description.

In the compound of the formula (I) of the present invention, R is preferably a hydrogen atom or a methyl group, W is N,
A 5- or 6-membered heterocyclic group containing 1-2 heteroatoms selected from heteroatoms consisting of O and S, and at least one of which is an N-atom, wherein the ring is For example, halogen, alkyl having 1 to 6 carbons, alkenyl having 2 to 4 carbons, alkynyl having 2 to 4 carbons, haloalkyl having 1 to 6 carbons, alkoxy having 1 to 6 carbons,
With an arbitrary substituent selected from alkylthio having 1 to 6 carbons, alkylsulfonyl having 1 to 6 carbons, alkylsulfinyl having 1 to 6 carbons, haloalkoxy having 1 to 6 carbons, nitro, cyano, amino and the like, Mono-substituted or poly-substituted, for example, may be di- to tri-substituted, Y represents a nitro group or a cyano group, A represents an ethylene group or trimethylene group, wherein the ethylene group and the The trimethylene group is, for example, halogen or 1 to 1 carbon atoms.
4 alkyl, hydroxy and alkoxy having 1 to 4 carbons may be mono-substituted or poly-substituted, for example, di- or tri-substituted, by any substituent selected from the group consisting of:

Z is an alkyl group having 1 to 6 carbon atoms, wherein the alkyl group is, for example, halogen and / or 1 to 6 carbon atoms.
A cycloalkyl having 3 to 7 carbon atoms which may be substituted with an alkyl having 4 to 4 carbon atoms, a halogen, an alkoxy having 1 to 4 carbon atoms,
Alkoxyethoxy having 1 to 4 carbon atoms, optionally substituted phenoxy (as the substituent, for example, halogen, nitro, alkyl having 1 to 4 carbons, 1 to 1 carbon atoms)
4 is a haloalkyl, or any one selected from a haloalkoxy having 1 to 4 carbon atoms) and an optionally substituted benzyloxy group (the substituents are the same as those in the case of the above phenoxy. ), An alkylsulfonyl group having 1 to 4 carbon atoms, an alkylsulfinyl group having 1 to 4 carbon atoms, and optionally substituted phenylthio (as the substituent, for example, the same groups as those of the above-mentioned phenoxy) are optionally used. Optionally substituted pyridyloxy (wherein the substituent represents, for example, halogen), optionally substituted pyridylthio (wherein the substituent represents, for example, halogen), optionally substituted May also be thiazolylthio (the substituent is, for example, halogen), alkylthio having 1 to 4 carbons, thiocyanato, and 2 to 6 total carbons. Dialkylamino, optionally substituted anilino (the substituent is, for example, any selected from halogen and alkyl having 1 to 4 carbon atoms), optionally substituted pyridylamino (wherein As the substituent, the same as those of the above-mentioned anilino are shown), cyano, alkylcarbonyl having an optionally substituted alkyl having 1 to 4 carbon atoms (as the substituent, for example, halogen is shown), Arylcarbonyl having an aryl group having 6 to 10 carbon atoms which may be optionally substituted (the substituent is, for example, halogen), pyridylcarbonyl, and 1 to 4 carbon atoms which may be substituted with halogen. Alkoxycarbonyl having alkoxy, optionally substituted phenoxycarbonyl (as the substituent, for example, Halogen, any one selected from alkyl having 1 to 4 carbons), benzyloxycarbonyl, optionally substituted carbamoyl (as the substituent, for example, alkyl having 1 to 4 carbons, phenyl Selected from the group), hydroxy, alkylcarbonyloxy having an optionally substituted alkyl having 1 to 4 carbon atoms (the substituent is, for example, halogen), optionally substituted Optionally benzoyloxy (as the substituent, for example, halogen, alkyl having 1 to 4 carbon atoms,
An arbitrary one selected from haloalkyl having 1 to 4 carbon atoms), alkylsulfonyloxy having 1 to 4 carbon atoms, and phenylsulfonyloxy optionally substituted (as the substituent, for example, halogen, carbon number 1 to 4 is arbitrary), and the total number of carbon atoms is 2
Dialkylaminocarbonyloxy having a dialkyl of 6 to 6, optionally substituted phenyl (as the substituent, for example, halogen, alkyl having 1 to 4 carbons, alkoxy having 1 to 4 carbons, 1 to 1 carbons) 4 is any one selected from haloalkyl, nitro and methylenedioxy), O, O-dialkylphosphono having 2 to 6 carbon atoms, O, O-dialkylthiophosphorylthio having 2 to 6 carbon atoms, At least one selected from the group consisting of O, S-dialkylthiophosphoryloxy having 2 to 6 carbon atoms, trialkylsilyl having 3 to 6 carbon atoms, and hetero atom consisting of N, O, S, and optionally substituted. Optionally substituted 5- or 6-membered heterocyclic group or 9- or 10-membered fused heterocyclic group (as the substituent, for example, halogen, an alkyl group having 1 to 4 carbon atoms) , Haloalkyl of 1 to 4 carbon atoms,
A phenyl, a nitroimino, a cyanoimino, a keto, an alkylthio having 1 to 4 carbons, or an alkoxy having 1 to 4 carbons), which may be substituted with a carbon selected from the group consisting of An alkenyl group having 2 to 6 carbon atoms, and the alkenyl group having 2 to 6 carbon atoms, which may be optionally substituted by, for example, halogen, alkoxy having 1 to 4 carbon atoms, or alkylthio. , Wherein the alkynyl group is
6 carbon atoms, which may be substituted by, for example, halogen
An aryl group having 10 to 10 carbon atoms, wherein the aryl group is, for example, halogen, alkyl having 1 to 4 carbons, nitro, or 1 to 1 carbon
4 haloalkyl and optionally substituted phenoxy (as the substituent, for example, halogen, carbon number 1)
To C4 haloalkyl) and optionally substituted by a group selected from the group consisting of (1) to (4) haloalkyl, an alkoxy group having 1 to 6 carbon atoms, wherein the alkoxy group is, for example, halogen or phenyl. , An alkylthio group having 1 to 6 carbon atoms, which may be substituted with one selected from pyridyl, wherein the alkylthio group is
Halogen, optionally substituted phenyl (wherein the substituent represents, for example, halogen), a phenylthio group optionally substituted by one selected from the group consisting of, wherein the phenylthio group is For example, cycloalkyl having 3 to 7 carbon atoms, which may be substituted with one selected from halogen and alkyl having 1 to 4 carbon atoms, wherein the cycloalkyl group has, for example, 1 to 1 carbon atoms.
A cyano group, a formin group, a phenoxy group, an allyloxy group, which may be optionally substituted with alkyl of 4;
5- or 6-membered heterocyclic group containing at least one hetero atom selected from N, O and S, or 9 or 1
A 0-membered fused heterocyclic group, wherein the heterocyclic group and the fused heterocyclic group are, for example, alkyl having 1 to 4 carbons, halogen, nitro, haloalkyl having 1 to 4 carbons and 1 to 4 carbons. Alkylcarbonyl group having an alkyl having 1 to 6 carbon atoms, which may be optionally substituted by a group selected from the group consisting of haloalkoxy, wherein the alkylcarbonyl group is, for example, halogen, or having 1 to 4 carbon atoms. Alkoxy, alkylthio having 1 to 4 carbons, 1 to 4 carbons
Alkoxy ethoxy with 1 to 3 carbon atoms
Alkylcarbonyloxy having 4 alkyl, optionally substituted phenyl, optionally substituted phenoxy (phenyl and phenoxy substituents include, for example, halogen, alkyl having 1 to 4 carbon atoms,
(Any one selected from alkoxy having 1 to 4 carbons, haloalkyl having 1 to 4 carbons, nitro, hydroxy and phenoxy), cyano, alkylcarbonyl having an alkyl having 1 to 4 carbons, hydroxy, total carbon number 2-6
And a cycloalkylcarbonyl group having 3 to 6 carbon atoms, which may be substituted by any one selected from the group consisting of dialkylamino and optionally substituted benzyloxy. A benzoyl group optionally substituted with one selected from the group consisting of halogen, alkoxy having 1 to 4 carbons and alkyl having 1 to 4 carbons, wherein the benzoyl group is, for example, halogen or 1 carbon. ~ 4 alkyl, C1-4 alkoxy, nitro, cyano, C1-4 haloalkyl, C1-4 haloalkoxy, hydroxy, C1-4 alkylthio, C1-4 Alkylsulfinyl, alkylsulfonyl having 1 to 4 carbons, alkylcarbonyl having alkyl having 1 to 4 carbons, As good phenoxy (wherein the substituents may be substituted in the meaning, for example, halogen, carbon atoms 1-4
An optionally selected from the above alkyls), optionally substituted pyridyloxy (the substituents are the same as in the case of the above phenoxy), and an alkyl group having 1 to 4 carbon atoms. Alkylcarbonylamino, dialkylamino having 2 to 4 carbon atoms and 2 carbon atoms in total
Alkenylcarbonyl group having alkenyl having 2 to 4 carbon atoms, which may be substituted by any one selected from the group consisting of alkoxyalkoxy having 4 to 4 carbon atoms, wherein the alkenylcarbonyl group is, for example, halogen or 1 carbon atom.
Alkynylcarbonyl group having an alkynyl having 2 to 4 carbon atoms, which may be substituted by any one selected from alkoxy of 4 to 4, wherein the alkylnylcarbonyl group is substituted in the same manner as in the case of the above alkenylcarbonyl. May have been

[0022]

[Chemical 15]

U is a 5- or 6-membered heterocyclic group containing at least one heteroatom selected from N, O and S, or a 9- or 10-membered fused heterocyclic group, The cyclic group is, for example, halogen, alkyl having 1 to 4 carbons, haloalkyl having 1 to 4 carbons, or 1 to 4 carbons.
Of alkoxy, C1-4 haloalkoxy, C1-4 haloalkylthio, phenyl, nitro, C1-4 alkylthio, and keto. , Carbon number 1-6
An alkoxycarbonyl group having an alkyl, wherein the alkoxycarbonyl group is, for example, an alkoxy having 1 to 4 carbon atoms, or an optionally substituted phenoxy (as the substituent, for example, halogen, having 1 to 4 carbon atoms). Alkyl), dialkylamino having 2 to 6 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogen, hydroxy, optionally substituted phenyl (as the substituent,
For example, halogen, haloalkyl having 1 to 4 carbons, alkyl having 1 to 4 carbons, alkoxy having 1 to 4 carbons), and substituted with one arbitrarily selected from the group consisting of phenoxyphenyl. Optionally, a cycloalkoxycarbonyl group having a cycloalkyl having 3 to 7 carbons, wherein the cycloalkoxycarbonyl group may be substituted with, for example, an alkyl having 1 to 4 carbons, a phenoxycarbonyl group, Here, the phenoxycarbonyl group is, for example, halogen or a carbon number of 1 to 4
Alkyl, nitro, haloalkyl having 1 to 4 carbon atoms, dialkylamino having 2 to 6 carbon atoms, alkylthio having 1 to 4 carbon atoms, alkylsulfinyl having 1 to 4 carbon atoms, cyano, and optionally substituted. A phenylthiocarbonyl group, which may be optionally substituted with a group selected from the group consisting of good pyridyloxy (wherein the substituent is any selected from halogen and haloalkyl having 1 to 4 carbon atoms), Alkylthiocarbonyl group having alkyl having 1 to 4 carbon atoms, alkenyloxycarbonyl group having alkenyl having 2 to 4 carbon atoms, wherein the alkenyloxycarbonyl group has 2 to 2 carbon atoms which may be substituted with, for example, halogen. An alkynyloxycarbonyl group having 4 alkynyl, wherein the alkynyloxycarbonyl group is For example, a carbamoyl group, a thiocarbamoyl group, which may be substituted with halogen, wherein the carbamoyl group and the thiocarbamoyl group are, for example, alkenyl having 2 to 4 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, and optionally substituted. Optionally substituted phenyl (as the substituent, for example, halogen, hydroxy, alkyl having 1 to 4 carbons, alkoxy having 1 to 4 carbons, haloalkyl having 1 to 4 carbons, haloalkoxy having 1 to 4 carbons, It represents any one selected from haloalkylthio having 1 to 4 carbon atoms, and optionally substituted alkyl having 1 to 6 carbon atoms (as the substituent, for example, halogen, carbon number 1)
At least 1 selected from alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, cyano, dialkylamino having 2 to 4 carbon atoms, phenyl optionally substituted, and hetero atom consisting of N, O and S. And optionally at least one selected from the group consisting of heteroatoms consisting of 5 or 6-membered optionally substituted heterocyclic groups) and N, O, S, And optionally substituted 5- or 6-membered heterocyclic group, or 9- or 10-membered condensed heterocyclic group (as the substituent, halogen, alkyl having 1 to 4 carbons, carbon number 1) ~ 4
Alkoxy, C1-4 haloalkyl, C1
To an alkylsulfonyl group of 4 to 4), which may be substituted with one selected from the group consisting of:
An alkenylsulfonyl group having 2 to 4 carbon atoms, wherein the alkylsulfonyl group and the alkenylsulfonyl group may be substituted with, for example, halogen, a phenylsulfonyl group, wherein the phenylsulfonyl group is, for example, halogen, the number of carbon atoms. Optionally substituted by any one selected from the group consisting of 1-4 alkyl and nitro,
Alkoxysulfonyl group having 1 to 4 carbon atoms, 3 to 7 carbon atoms
A cycloalkoxysulfonyl group, a phenoxysulfonyl group, a sulfamoyl group, wherein the sulfamoyl group may be optionally substituted with one selected from the group consisting of alkyl having 1 to 4 carbon atoms and phenyl, O, O -Di- (C1-4 alkyl) phosphono group, O, O-di- (C1-4 alkyl) thiophosphono group, O, S-di- (C1-4 alkyl) thiophosphono group , O- (alkyl having 1 to 4 carbon atoms) -O-
(Phenyl which may be optionally substituted) thiophosphono group, O, N-di- (alkyl having 1 to 4 carbons) amidothiophosphono group, alcoxaryl group having 1 to 4 carbon atoms, wherein the alkoxyl group is A phenoxalyl group, which may be substituted, for example with phenyl, wherein the phenoxalyl group is optionally substituted, for example with halogen,

[0024]

[Chemical 16]

Wherein Q ¹ is a 5- or 6-membered heterocyclic group containing at least one heteroatom selected from N, O and S, or a 9- or 10-membered fused heterocyclic group, wherein And the heterocyclic group or fused heterocyclic group is
For example, halogen, alkyl having 1 to 4 carbons, phenyl,
Optionally substituted by a group selected from the group consisting of keto and haloalkyl having 1 to 4 carbon atoms, or

[0026]

[Chemical 17]

Further, in the compound of formula (I), it is particularly preferable that R represents a hydrogen atom and W represents 1 to 2 heteroatoms selected from the heteroatoms consisting of N, O and S. And a 5- or 6-membered heterocyclic group in which at least one is an N-atom, wherein the ring is, for example, halogen, alkyl having 1 to 2 carbons, or 1 to 2 carbons.
Haloalkyl, alkoxy having 1 to 2 carbons, 1 carbon
~ 2 alkylthio, alkylsulfonyl having 1-2 carbons, alkylsulfinyl having 1-2 carbons, 1-carbon
2, which may be mono-substituted or di-substituted by any substituent selected from haloalkoxy, nitro and cyano, Y represents a nitro group or a cyano group, and A represents an ethylene group or a trimethylene group. The ethylene group and the trimethylene group are represented by, for example, an arbitrary substituent selected from halogen and alkyl having 1 to 2 carbon atoms,
May be mono-substituted or di-substituted,

Z is an alkyl group having 1 to 4 carbon atoms, wherein the alkyl group is, for example, cycloalkyl having 3 to 6 carbon atoms which may be substituted with halogen and / or methyl, halogen, 1 to 1 carbon atoms. 2 alkoxy, optionally substituted phenoxy (as the substituent, for example, any selected from halogen, nitro, methyl, halomethyl and halomethoxy), benzyloxy, alkylthio having 1 to 2 carbon atoms , Alkylsulfonyl having 1 to 2 carbons, alkylsulfinyl having 1 to 2 carbons, phenylthio which may be optionally substituted (as the substituent,
For example, any one selected from halogen, methyl, and nitro is shown), optionally substituted pyridyloxy (wherein the substituent is, for example, halogen), optionally substituted pyridylthio (wherein As the substituent, for example, halogen is shown), optionally substituted thiazolylthio (as the substituent is, for example, halogen), thiocyanato, dialkylamino having 2 to 4 carbon atoms, and optionally substituted. Optionally anilino (the substituent is, for example, any selected from halogen and alkyl having 1 to 2 carbon atoms), and optionally substituted pyridylamino (the substituent is the above-mentioned anilino). And the like), cyano, acetyl, 2,2-dimethylpropionyl, optionally substituted benzoyl (As the substituent, for example, halogen is shown.), Pyridylcarbonyl, alkoxycarbonyl having an alkyl having 1 to 2 carbon atoms, and optionally substituted phenoxycarbonyl (as the substituent, for example, halogen, methyl Selected is selected), benzyloxycarbonyl, optionally substituted carbamoyl (the substituent is, for example,
Alkyl having 1 to 2 carbon atoms, any selected from phenyl), hydroxy, alkylcarbonyloxy having optionally substituted alkyl having 1 to 2 carbons (as the substituent, for example, halogen) ),
Benzoyloxy, alkylsulfonyloxy having 1 to 2 carbon atoms, phenylsulfonyloxy, dialkylaminocarbonyloxy having alkyl having 2 to 4 carbon atoms,
Optionally substituted phenyl (as the substituent, for example, halogen, methyl, methoxy, halomethyl,
Nitro, methylenedioxy), O, O-dimethylphosphono, O, O-diethylthiophosphorylthio, O-ethyl-S-propylthiophosphoryloxy, trimethylsilyl, and N, O, A 5- or 6-membered heterocyclic group or a 9- or 10-membered fused heterocyclic group, which contains at least one selected from the heteroatoms consisting of S, and is optionally substituted (as said substituents, For example, halogen, alkyl having 1 to 2 carbon atoms,
Substituted with halogen, which may be substituted with any one selected from the group consisting of halomethyl, phenyl, keto, alkylthio having 1 to 2 carbons, and alkoxy having 1 to 2 carbons). Optionally substituted 2-propenyl group, optionally halogen substituted propargyl group, phenyl group, wherein said phenyl group is, for example, halogen, methyl, nitro, trifluoromethyl and optionally substituted. Alkoxy group having 1 to 4 carbon atoms, carbon, which may be substituted with one selected from the group consisting of phenoxy (the substituent represents any selected from halogen and trifluoromethyl) An alkylthio group of the formulas 1 to 4, wherein the alkylthio group may be substituted with halogen or phenyl, A ruthio group, wherein the phenylthio group may be substituted with, for example, any one selected from halogen and methyl, a cycloalkyl having 3 to 6 carbon atoms, wherein the cycloalkyl group is optionally substituted with, for example, methyl. 5- or 6-membered heterocyclic group or 9- or 10-membered optionally containing at least one hetero atom selected from a cyano group, a formyl group, a phenoxy group, an allyloxy group and a hetero atom consisting of N, O and S. A fused heterocyclic group, wherein said heterocyclic group and fused heterocyclic group are, for example, methyl, halogen, halomethyl and C 1
To an alkylcarbonyl group having an alkyl having 1 to 4 carbon atoms, which may be optionally substituted with one selected from the group consisting of haloalkoxy, wherein the alkylcarbonyl group is, for example, halogen, methoxy, methylthio, Cycloalkylcarbonyl having a cycloalkyl having 3 to 6 carbon atoms, which may be substituted by any one selected from the group consisting of phenoxy optionally substituted with acetoxy, chloro and / or methyl, phenyl, cyano and acetyl. , Wherein the cycloalkylcarbonyl group may be substituted with, for example, chloro and / or methyl, a benzoyl group, wherein the benzoyl group is, for example, halogen, methyl, alkoxy having 1 to 2 carbon atoms, nitro, halomethyl. Substituted by any one selected from the group consisting of Good, alkenylcarbonyl group having an alkenyl having 2 to 3 carbon atoms, wherein the alkenyl group, for example halogen may be substituted, alkynyl group having alkynyl of 2-3 carbon atoms,

[0029]

[Chemical 18]

U ¹ represents a 5- or 6-membered heterocyclic group containing at least one heteroatom selected from N, O and S, or a 9- or 10-membered fused heterocyclic group, The heterocyclic group and the fused heterocyclic group are, for example, halogen, methyl, halomethyl, phenyl, nitro,
Alkoxycarbonyl group having an alkyl of 1 to 4 carbon atoms, which may be substituted with one selected from the group consisting of alkylthio having 1 to 2 carbon atoms and keto, wherein the alkoxycarbonyl group is, for example, 1-2
Alkoxy, optionally substituted phenoxy (as the substituent, for example, halogen), dialkylamino having 2 to 4 carbon atoms, alkylthio having 1 to 2 carbon atoms, halogen, optionally substituted. Optionally substituted phenyl (wherein the substituent is, for example, any selected from halogen, halomethyl, and alkoxy having 1 to 2 carbon atoms) and phenoxyphenyl. May have 3 carbons
A cycloalkoxycarbonyl group having 6 to 6 cycloalkyl, wherein the cycloalkoxycarbonyl group is optionally substituted with, for example, methyl, a phenoxycarbonyl group, wherein the phenoxycarbonyl group is, for example, halogen, methyl, nitro, A phenylthiocarbonyl group optionally substituted with one selected from the group consisting of halomethyl, cyano, and pyridyloxy optionally substituted with halogen, an alkylthiocarbonyl group having an alkyl group having 1 to 4 carbon atoms, An allyloxycarbonyl group, wherein the allyloxycarbonyl group may be substituted with, for example, halogen, a propargyloxycarbonyl group, wherein the propargyloxycarbonyl group may be substituted with, for example, halogen. Good, carbamoyl group, here The carbamoyl group is, for example, allyl, cycloalkyl having 3 to 6 carbon atoms, or phenyl which may be optionally substituted (as the substituent, for example, halogen, alkyl having 1 to 2 carbons, alkyl having 1 to 2 carbons). Optionally selected from alkoxy and halomethoxy), and optionally substituted alkyl having 1 to 4 carbons (as the substituent, for example, selected from halogen, alkoxy having 1 to 2 carbons, and phenyl). Any of the following),
And a 5- or 6-membered heterocyclic group containing at least one heteroatom selected from N, O and S, and optionally substituted, or a 9- or 10-membered fused heterocyclic group ( The substituent may be any one selected from the group consisting of halogen, methyl, halomethoxy, halomethyl, and alkylsulfonyl having 1 to 2 carbon atoms), and may be substituted with one selected from the group consisting of 1 carbon atoms ~ 2 alkylsulfonyl group, wherein the alkylsulfonyl group may be substituted, for example with halogen,
Phenylsulfonyl group, wherein the phenylsulfonyl group may be substituted with, for example, any one selected from the group consisting of halogen, methyl and nitro, an alkoxysulfonyl group having 1 to 2 carbon atoms, a phenoxysulfonyl group, sulfamoyl A group, wherein the sulfamoyl group is optionally substituted by, for example, one selected from the group consisting of alkyl having 1 to 3 carbon atoms and phenyl, O, O-di- (alkyl having 1 to 3) alkyl Phosphono group, O, O-di- (C1-3) alkylthiophosphono group, O, S-di- (C1-3) alkylthiophosphono group, O- (C1-3) alkyl -O- (optionally substituted) phenylthiophosphono group, O,
N-di- (C1-C3) alkylamidothiophosphono group, or

[0031]

[Chemical 19]

In the production method of the present invention, when 1-isopropyl-2-nitroiminoimidazolidine and 2-chloro-5-chloromethylpyridine are used as raw materials, they are represented by the following reaction formula.

[0033]

[Chemical 20]

In the production method of the present invention, the raw material represented by the formula (I
The compound of I) is based on the definition of Y, A and Z above. In the formula (II), Y, A and Z are
Preferably, it has the same meaning as the above preferred definition. Formula (II)
The compounds of (1) include both known compounds and novel compounds, and as the novel compounds, for example, compounds of the following formula (IIa) can be proposed.

[0035]

[Chemical 21]

In the formula, Y represents a nitro group or a cyano group,
A ¹ represents an ethylene group or a trimethylene group, wherein each group is mono- or poly-substituted (for example, di-, tri-substituted by an arbitrary substituent selected from halogen and alkyl having 1 to 4 carbon atoms). ) Which may be substituted, Z ¹ may be a methyl-substituted cycloalkyl group having 3 to 7 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, or 2 to total carbon atoms.
An alkoxyalkyl group having 6 carbon atoms, an alkylthioalkyl group having 2 to 6 carbon atoms, an alkylsulfinylalkyl group having 2 to 6 carbon atoms, an alkylsulfonylalkyl group having 2 to 6 carbon atoms, and a substituent having 1 to 3 carbon atoms. An alkyl group having (wherein, as the substituent, for example, optionally substituted phenoxy, optionally substituted phenylthio, optionally substituted pyridyloxy, optionally substituted Optionally cycloalkyl having 3 to 6 carbon atoms, optionally substituted pyridylthio,
Thiazolylthio, benzyloxy, thiocyanato, dialkylamino having 2 to 6 total carbon atoms, alkoxyalkoxy having 2 to 4 total carbon atoms, optionally substituted anilino, optionally substituted pyridylamino, cyano, carbon Alkylcarbonyl having 2-4 alkyl, benzoyl optionally substituted, carbon number 1
A haloalkylcarbonyl having haloalkyl of 3 to 3,
Pyridylcarbonyl, alkoxycarbonyl having 1 to 4 carbon atoms, phenoxycarbonyl which may be optionally substituted, benzyloxycarbonyl, carbamoyl, alkylaminocarbonyl having 1 to 3 carbon atoms,
Dialkylaminocarbonyl having 2 to 6 carbon atoms in total, phenylaminocarbonyl which may be optionally substituted, hydroxy, halogen having alkyl having 1 to 3 carbon atoms, optionally substituted alkylcarbonyloxy, benzoyloxy, carbon number 1-4 alkylsulfonyloxy,
Tosyloxy, dialkylaminocarbonyloxy having alkyl having 1 to 3 carbon atoms, phosphoric acid ester residue, thiophosphoric acid ester residue, amidothiophosphoric acid ester residue, trimethylsilyl having 4 to 5 carbon atoms, and N, O,
And at least one selected from the heteroatoms consisting of S, and optionally selected from the group consisting of optionally substituted 9- or 10-membered fused heterocyclic groups),

Optionally substituted phenyl (wherein the substituent is, for example, any one selected from halogen, alkyl having 1 to 3 carbon atoms and nitro), N,
An optionally substituted 5- or 6-membered heterocyclic group or 9- or 10-membered fused heterocyclic group containing at least one hetero atom consisting of O and S (wherein the cyclic group is The group may have the same substituents as in the case of phenyl), an alkenyl group having 3 to 4 carbon atoms which may be halogen substituted, a propargyl group which may be halogen substituted, and a carbon number of 1 to 1. 4 alkoxy group, cyano group, phenoxy group, benzyloxy group, alkenyloxy group having 2 to 3 carbon atoms, alkylthio group having 1 to 4 carbon atoms which may be substituted with halogen, halogen and / or 1 to 4 carbon atoms Phenylthio group substituted by alkyl, halobenzylthio group, dialkylamino group having 2 to 6 carbon atoms, alkylcarbonyl group having 2 to 6 carbon alkyl, 1 to 4 carbon atoms Alkylcarbonyl group and having a substituent having an alkyl (wherein examples of the substituent,
For example, halogen, alkoxy having 1 to 4 carbons, 1 carbon
~ 4 alkylthio, alkylcarbonyloxy having 1 to 4 carbon alkyl, halophenoxy, phenyl, cyano, and alkylcarbonyl having 1 to 2 carbon alkyl), halogen and / Or a cycloalkylcarbonyl group having 3 to 6 carbon atoms which may be substituted by alkyl having 1 to 4 carbon atoms, a benzoyl group which may be substituted (wherein, as the substituent, for example, halogen, 1 to 1 carbon atoms) 4 alkyl, C 1-4 alkoxy, nitro, C 1-4
Of haloalkyl, alkylcarbonylamino having alkyl having 1 to 4 carbons and alkoxyalkoxy having 2 to 4 carbons in total), and alkenyl having 2 to 4 carbons which may be halogen-substituted. Having an alkenylcarbonyl group, an alkynylcarbonyl group having an alkynyl having 2 to 3 carbon atoms,

[0038]

[Chemical formula 22]

(Wherein U ² represents a 5- or 6-membered heterocyclic group containing at least one heteroatom consisting of N, O and S, or a 9- or 10-membered fused heterocyclic group, Examples of the cyclic group include halogen, alkyl having 1 to 4 carbons, haloalkyl having 1 to 4 carbons, phenyl, nitro, haloalkyl having 1 to 4 carbons, phenyl, nitro, alkylthio having 1 to 4 carbons, and keto. Optionally substituted from the group consisting of),
Alkoxycarbonyl group having a substituent and an alkyl having 1 to 3 carbon atoms (wherein, as the substituent, for example, halogen, alkoxy having 1 to 2 carbon atoms, or 1 to 2 carbon atoms)
Alkylthio, dialkylamino having 2 to 4 carbon atoms,
Hydroxy, alkylthio having 1 to 2 carbon atoms, and optionally selected from halophenoxy), and cycloalkoxycarbonyl group having 3 to 7 carbon atoms, which may be substituted with alkyl having 1 to 4 carbon atoms. A phenoxycarbonyl group having a substituent (as the substituent, for example, halogen, alkyl having 1 to 4 carbons, haloalkyl having 1 to 4 carbons, cyano, alkylthio having 1 to 4 carbons, 1 to 1 carbons 4 is optionally selected from the group consisting of alkoxy, nitro, alkylsulfinyl having 1 to 4 carbons, alkoxycarbonyl having 1 to 4 carbons alkyl, pyridyloxy substituted with halogen and / or trihaloalkyl. ), An optionally substituted benzyloxycarbonyl group (wherein the substituent is, for example, For example, halogen, haloalkyl having 1 to 2 carbon atoms, alkoxy having 1 to 4 carbon atoms, phenoxy), phenylthiocarbonyl group, alkylthiocarbonyl group having alkyl having 1 to 4 carbon atoms, halogen substitution 2 to 4 carbon atoms that may be included
An alkenyloxycarbonyl group having an alkenyl of
An alkynyloxycarbonyl group having an optionally substituted alkynyl having 2 to 4 carbon atoms,

[0040]

[Chemical formula 23]

(Wherein Q ¹ represents a 5- or 6-membered heterocyclic group containing at least one hetero atom consisting of N, O and S, or a 9- or 10-membered fused heterocyclic group, And the cyclic group is, for example, halogen, having 1 to 4 carbon atoms.
Of Alkyl, phenyl, keto and haloalkyl having 1 to 4 carbon atoms), carbamoyl group, alkylaminocarbonyl group having 1 to 4 carbon alkyl, carbon Number 3
A cycloalkylaminocarbonyl group having cycloalkyl of 6 to 6, an optionally substituted phenylaminocarbonyl group (wherein, as the substituent, for example, halogen, alkyl having 1 to 4 carbons, alkyl having 1 to 4 carbons) An arbitrary one selected from alkoxy), a dialkylaminocarbonyl group having an alkyl having a total of 2 to 8 carbon atoms,

[0042]

[Chemical formula 24]

(Here, G represents a 5- or 6-membered heterocyclic group containing at least one heteroatom selected from N, O and S, or a 9- or 10-membered fused heterocyclic group, The cyclic group is halogen, alkyl having 1 to 4 carbons,
It may be substituted with any one selected from alkoxy having 1 to 4 carbons, haloalkyl having 1 to 4 carbons, and alkylsulfonyl having 1 to 2 carbons, n represents 0 or 1, and R'is Hydrogen atom or an alkyl group having 1 to 4 carbon atoms), an optionally substituted piperidinocarbonyl group (wherein the substituent group represents, for example, an alkyl group having 1 to 4 carbon atoms), or substituted May also be a morpholinocarbonyl group (wherein the substituent has, for example, 1 carbon atom).
~ 4 alkyl), a pyrrolidinocarbonyl group, a methyl-substituted benzylaminocarbonyl group, a mono- or di- having an alkenyl of 2 to 3 carbon atoms.
Alkenylaminocarbonyl group, alkynylaminocarbonyl group having alkynyl of 2 to 3 carbon atoms, alkylsulfonyl group of 1 to 4 carbon atoms which may be halogen substituted, phenylsulfonyl group which may be substituted (wherein the substituted Examples of the group include halogen, alkyl having 1 to 4 carbon atoms, and any selected from nitro),

An alkoxysulfonyl group having 1 to 4 carbon atoms,
C3-C6 cycloalkoxysulfonyl group, mono-
Or, a di- (alkyl having 1 to 4 carbons) aminosulfonyl group, a phenylaminocarbonyl group optionally substituted with methyl, O, O-di- (alkyl having 1 to 4 carbons) phosphono group, O, O- Di- (C1-4 alkyl) thiophosphono group, O, S-di- (C1-4 alkyl)
Thiophosphono group, O- (C1-4 alkyl) -O
-(Phenyl optionally substituted by halogen) thiophosphono group, O, N-di- (alkyl having 1 to 4 carbons) amidothiophosphono group, alcoxaryl group having 1 to 4 carbons,
A halogen-substituted phenoxalyl group, a benzyloxalyl group, or

[0045]

[Chemical 25] A heterocyclic compound represented by.

Further, new compounds other than the above-mentioned proposed formula (IIa) included in the formula (II) are represented by the formula (IIa) in Table 2 below.
Examples of the compound will be illustrated. The compound of the above formula (IIa) can be produced, for example, by the production method a):

[Chemical formula 26] In the formula, Y and A are the same as the above, and Z ¹ -M ¹ (V) in the formula, Z ¹ is the same as the above, M ¹ is a halogen atom, preferably chromium or bromine. A method of reacting a compound represented by the above, or a production method b): H ₂ N—A—NH—Z ¹ (VI), wherein A and Z ¹ are the same as the above, and

[Chemical 27] In the formula, Y is the same as above, and M ² is an amino group, an alkylthio group or a benzylthio group, and a compound represented by

In the formula (IIa), when Y is a cyano group, the compound of the formula (IIa) can be produced by the process c):
The compound of the above formula (VI) and (M ³ —S) ₂ C═N—CN (VIII) In the formula, M ³ represents alkylthio or benzylthio, and two M ³ are sulfur atoms to which these are bonded. It is easily obtained by a method of reacting with a compound represented by which may form a ring together with

In the above production method a), the compound of the formula (IV) includes known compounds, for example, J. Am. Chem.
Soc. (Journal American Chemical Society), Volume 73, pages 2201-2205, British Patent No. 2,055,796, and the like. Similarly, in the above production method a), most of the compounds of the formula (V) are well known in the field of organic chemistry. In the above production method b), the compound of the formula (VI) includes a known compound, but in general, H ₂ N—A—NH ₂ (IX) wherein A is the same as the above, Can be easily obtained by reacting with the compound of the formula (V).

The compound of the above formula (IX) is a known compound, and examples thereof include ethylenediamine and trimethylenediamine described in West German Patent Publication No. 2,732,660 and French Patent No. 1,499,785. For example, J.
A. C. S. (Journal American Chemical Society), Vol. 76, page 1877, the above-mentioned production method b), the compound of the formula (VII) includes known compounds.
In the above production method c), the compound of the formula (VIII) is a compound of J. Or
g. Chem. (Journal Organic Chemistry), 32, 1566-1572.

Specific examples of the compound of the formula (II) in the production method of the present invention include those shown below. Similarly, in the manufacturing method of the present invention, the compound of formula (III) as a raw material is based on the above definitions of R, W and M.
In formula (III), R and W preferably have the same meanings as defined above, and M preferably represents a chromium, bromine or tosyloxy group. The compound of the formula (III) is known, and is disclosed in, for example, JP-A-61-212682.
No. 61-183,271. Specific examples of the formula (III) include the followings. 2-methyl-5-chloromethylpyridine, 2-chloro-5-chloromethylthiazole, 2-bromo-5-chloromethylpyridine, 2-trifluoromethyl-5-chloromethylpyridine, 2-bromo-5-chloromethyl Thiazole, 3-chloromethylpyridine, 2
-Fluoro-5-bromomethylpyridine, 2-chloro-
5-chloromethylpyridine, 2-methoxy-5-pyridylmethyl tosylate, 2-chloro-5-bromomethyloxazole.

In carrying out the process according to the invention, suitable diluents can include all inert solvents. Examples of such diluents are water; aliphatic, cycloaliphatic and aromatic hydrocarbons (optionally chlorinated) such as hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, Methylene chloride, chloroform, carbon tetrachloride, ethylene chloride and trichloroethylene, chlorobenzene; other ethers such as diethyl ether, methyl ethyl ether, di-iso-propyl ether,
Dibutyl ether, propylene oxide, dioxane, tetrahydrofuran; nitriles such as acetonitrile, propionitrile, acrylonitrile; alcohols such as methanol, ethanol, iso-propanol, butanol, ethylene glycol; acid amides such as dimethylformamide, dimethylacetamide; Sulfones and sulfoxides, such as dimethyl sulfoxide and sulfolane, can be exemplified. The manufacturing method of the present invention is
Further, it can be carried out in the presence of a hydroxide or carbonate of an alkali metal hydride such as sodium hydride or potassium hydride as a base. The manufacturing method of the present invention is
It can be carried out within a wide temperature range, generally from about 0 ° C to about 100 ° C, preferably from about 10 ° C to about 80 ° C.
It can be carried out between ° C. Further, the reaction is preferably carried out under normal pressure, but it may be carried out under pressure or reduced pressure.

In carrying out the process of the present invention, for example, sodium hydride as a base is used in an amount of about 1.1 to 1.2 times the molar amount of the compound of the formula (II).
An equimolar amount to about 1.2 times the molar amount of the compound of the formula (III), preferably an equimolar amount to about 1.1 times the molar amount of an inert solvent,
For example, the desired compound can be obtained by reacting in dimethylformamide. In the above-mentioned production method, it is preferable in view of the reaction that the compound of the formula (II) is previously formed into a sodium salt form with sodium hydride, and the reaction is carried out in a nitrogen gas atmosphere from the characteristics of sodium hydride. It is desirable to do it below. In addition, the production methods a) and b) of the compound of the above formula (IIa)
In carrying out step (c) and (c), the same inert solvents as mentioned above in the production method of the present invention can be exemplified. The method of the production method a) can be carried out in the presence of the same base as described above. The production method a) can be carried out within the same temperature range as the production method of the present invention. In carrying out the production method a), for example, with respect to 1 mol of the compound of the formula (IV), about 0.9 mol to about 1.1 mol of the compound of the formula (V) is inactive in the presence of a base. By reacting in a solvent, the compound of formula (IIa)
Can be obtained.

Process b) is generally about 0 ° C to about 120 ° C.
C., preferably between about 30.degree. C. and about 100.degree. C.,
Further, the reaction is preferably carried out under normal pressure, but it may be carried out under pressure or reduced pressure. In carrying out the production method b), for example, with respect to 1 mol of the compound of the formula (VI), the compound of the formula (VII) is equimolar to about 1.2 times, preferably equimolar to about 1 times. The corresponding compound of formula (IIa) can be easily obtained by reacting while heating a 1-fold molar amount in, for example, water. Manufacturing method c)
Is, for example, between about 0 ° C. and the boiling point of the mixture, preferably 0 ° C.
It can be carried out at a temperature of from about 100 ° C., and the reaction is preferably carried out under normal pressure, but it can also be carried out under elevated or reduced pressure. In carrying out the production method c), for example, with respect to 1 mol of the compound of the formula (VI), the compound of the formula (VIII) is equimolar to about 1.2 times the molar amount, preferably the equimolar amount to.
The corresponding compound of formula (IIa) can be obtained by reacting about 1.1 times the molar amount in an inert solvent such as an alcohol (methanol, ethanol, etc.) solvent until the generation of mercaptan is stopped.

The nitroimino or cyanoimino compound of formula (I) produced by the process of the present invention exhibits a strong insecticidal action. Therefore, they can be used as insecticides. Then, the active compound of formula (I) in the present invention exerts a proper controlling effect against harmful insects without giving phytotoxicity to cultivated plants. Further, the compound of the present invention can be used for controlling a wide variety of pests, harmful sucking insects, biting insects and other plant parasitic pests, storage pests, sanitary pests and the like, and can be applied for exterminating and eradicating them. In addition, the formula (I
In the above I), the compound of the formula (IIa) is as described above.
INDUSTRIAL APPLICABILITY The present invention is a novel compound, which is industrially useful as an intermediate for producing an insecticidal nitroimino or cyanoimino compound of the formula (I), and is also useful as a compound of the formula (IIa) itself showing an insecticidal action. . Then, according to the example,
Although the content of the present invention will be specifically described, the present invention should not be limited thereto.

[0055]

【Example】

 Manufacturing Example: -Example 1

[Chemical 28] 3.2 g of 1- {2- (3,5-dichloropyridyl-2yloxy) ethyl} 2-nitroiminoimidazolidine
Is dissolved in 20 ml of dimethylformamide and the mixture is stirred at room temperature for 60 minutes.
0.4 g of sodium hydride is added and the mixture is stirred until generation of hydrogen stops. Next, 1.7 g of 2-chloro-5-chloromethylthiazole was added at room temperature, followed by 40 hours at room temperature.
Stir for 30 minutes at ° C. After the reaction, the contents are poured into ice water and extracted with dichloromethane. When dichloromethane is concentrated from the extract and ether is added to the residue, the desired product becomes crystals, which are collected by filtration, washed with ether and dried. Yield 2.7g,
mp. 77-80 ° C

Example 2

[Chemical 29] 1- (3,3-dimethyl-2-butanone-1-yl)-
A mixture of 2.1 g of 2-cyanoiminoimidazolidine, 1.6 g of 2-chloro-5-chloromethylpyridine, 1.4 g of anhydrous potassium carbonate and 30 ml of acetonitrile is refluxed for 8 hours while stirring. After the reaction, acetonitrile is distilled off under reduced pressure, dichloromethane is added to the residue, and the mixture is washed with water. After dichloromethane is concentrated, it is purified by a silica gel column (chloroform: ethanol = 9: 1) to obtain 0.9 g of a colorless viscous target substance. n _D ²⁰ 1.5446

Representative examples of compounds of formula (I) that can be synthesized according to the same method as in Example 1 above are shown in Table 1 together with the compounds of the above Examples.

[Chemical 30] In Table 1, "←" in the column of "← A-" is a group in the above formula (I):

[Chemical 31] Shows a bond with the N-atom to which is bonded.

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

[Table 3]

[0061]

[Table 4]

[0062]

[Table 5]

[0063]

[Table 6]

[0064]

[Table 7]

[0065]

[Table 8]

[0066]

[Table 9]

[0067]

[Table 10]

[0068]

[Table 11]

Intermediate Synthesis Example: -Example 3

[Chemical 32] A mixture of 2.6 g of 2-nitroiminoimidazolidine, 3.0 g of anhydrous potassium carbonate and 30 ml of dry acetonitrile was stirred at room temperature for 30 minutes, and then 2.7 g of 1-chloro-3,3-dimethyl-2-butanone was stirred at room temperature. Add with stirring.
Subsequently, the contents are heated and refluxed for 1 hour. Acetonitrile is distilled off under reduced pressure, water is added to the residue, and the desired product is collected by filtration.
The crystals are washed with ether and dried to obtain 3.5 g of 1- (3,3-dimethyl-2-butanone-1-yl) -2-nitroiminoimidazolidine. mp. 158-159
℃

Example 4

[Chemical 33] 2.2 g of 2-cyanoiminoimidazolidine are dissolved in 20 ml of dry dimethylformamide, and 1.7 g of 60% sodium hydride is added little by little at 0 ° C or lower. After stirring at 0 ° C. until generation of hydrogen stopped, 1.9 g of propionyl chloride was added dropwise while keeping the temperature at 0 ° C. or lower. After dropping, the mixture is stirred at room temperature for a while, the contents are added to ice water, and the mixture is neutralized with hydrochloric acid. Then, the product is extracted with dichloromethane and the extract is concentrated. The target substance crystallizes and precipitates. It is collected by filtration and washed with ether to obtain 1.4 g of 2-cyanoimino-1-propionylimidazolidine. mp. 208-210 ° C

Example 5

[Chemical 34] To a solution of 2-nitroiminoimidazolidine (2.6 g) and dimethylformamide (20 ml) was added 60% sodium hydride (0.8 g) at room temperature, and the mixture was stirred until generation of hydrogen stopped. Subsequently, 3.6 g of 2,3,5-trichloropyridine is added and the content is stirred at 100 to 120 ° C. for 7 hours. After cooling to room temperature, the mixture is poured into ice water, the produced crystals of interest are collected by filtration, and washed with a small amount of ethanol and ether. Yield 2.2 g mp. 15
1-155 ° C

Example 6

[Chemical 35] N-allylethylenediamine [Journal American Chemical Society (J. Am. Chem. Sc
i. ), 67, pp. 1581-1582] 2 g, N
A mixture of 2.7 g of -nitro S-methylisothiourea and 20 ml of ethanol is stirred at 60 ° C for 3 hours. After cooling to room temperature, the target crystals formed are collected by filtration, washed with a small amount of ethanol and dried. Yield 1.4 g mp. 86-90
℃

Example 7

[Chemical 36] 3.6 g of N-2-phenoxyethylethylenediamine,
Dimethyl N-cyanodithioiminocarbonate 2.9
g, 50 ml of ethanol is gradually heated with stirring and then refluxed until the generation of methyl mercaptan ceases. After the reaction, about 2/3 of ethanol is distilled off, and the residual liquid is cooled to precipitate the desired product as crystals, which is collected by filtration and dried. Yield 3.6 g mp. 93-95 ° C

According to a method similar to the above-mentioned intermediate synthesis example,
Representative examples of compounds of formula (II) that can be synthesized are described in Examples 3 to above.
It is shown in Table 2 together with 7 compounds.

[Chemical 37] In Table 2, "←" in the column of "← A-" indicates a bond with a N atom to which a hydrogen atom is bonded, as shown in the above formula.

[0075]

[Table 12]

[0076]

[Table 13]

[0077]

[Table 14]

[0078]

[Table 15]

[0079]

[Table 16]

[0080]

[Table 17]

[0081]

[Table 18]

[0082]

[Table 19]

[0083]

[Table 20]

[0084]

[Table 21]

[0085]

[Table 22]

[0086]

[Table 23]

[0087]

[Table 24]

[0088]

[Table 25]

[0089]

[Table 26]

[0090]

[Table 27]

[0091]

[Table 28]

[0092]

[Table 29]

[0093]

[Table 30]

[0094]

[Table 31]

[0095]

[Table 32]

Biological test example: Example 8 Test against organophosphorus agent resistant green leafhopper Preparation of reagent solution Solvent: 3 parts by weight of xylol Emulsifier: 1 part by weight of polyoxyethylene alkyl phenyl ether A formulation of a suitable active compound is prepared. For this purpose, 1 part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emulsifier and the mixture was diluted with water to the given concentration.

Test method: To a rice plant having a plant height of about 10 cm planted in a pot having a diameter of 12 cm, 10 ml of a diluted solution of the active compound prepared above having a predetermined concentration was sprayed per pot. After drying the spray solution, cover the wire net with a diameter of 7 cm and a height of 14 cm, release 30 female adults of the leafhopper leafhopper, a strain that is resistant to organophosphorus agents, and place it in a temperature-controlled room for 24 hours to determine the number of dead insects. The mortality rate was calculated.

Example 9 Test against Cedrus planta For a rice plant having a plant height of about 10 cm planted in a pot having a diameter of 12 cm,
10 ml of a potted solution of the active compound diluted with water prepared in the same manner as in Example 8 was sprayed. After the sprayed drug solution was dried, it was covered with a wire net with a diameter of 7 cm and a height of 14 cm, and 30 female adults of the sedge loach that were resistant to the organophosphorus agent were released in the wire net and placed in a temperature-controlled room for 2 days to determine the number of dead insects. It investigated and calculated the insecticidal rate. In the above-mentioned biological test, the compounds of formula (I) exemplified in Table 1 above show an appropriate insecticidal effect at an active ingredient concentration of 200 ppm, and are excellent even at concentrations lower than that. It has an insecticidal effect.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C07D 413/06 233 413/14 213 417/06 233 239 417/14 213 // A01N 43/50 Q 43/54 F 47/40 Z 51/00

Claims (1)

[Claims] Claims: In the formula, Y represents a nitro group or a cyano group, A ¹ represents an ethylene group or a trimethylene group, wherein each group is, for example, a halogen atom or an optionally substituted substituent selected from alkyl having 1 to 4 carbon atoms. - or poly - substituted (for example, di -, tri - substituted) assessment may be, Z ¹ is cycloalkyl group having 3 to 7 carbon atoms which may optionally be methyl substituted, a haloalkyl group having 1 to 4 carbon atoms, the total Alkoxyalkyl group having 2 to 6 carbon atoms, alkylthioalkyl group having 2 to 6 carbon atoms, alkylsulfinylalkyl group having 2 to 6 carbon atoms, alkylsulfonylalkyl group having 2 to 6 carbon atoms, 1 to 3 carbon atoms An alkyl group having a substituent of (wherein, as the substituent, for example, optionally substituted phenoxy, optionally substituted phenylthio,
Optionally substituted pyridyloxy, optionally substituted cycloalkyl having 3 to 6 carbons, optionally substituted pyridylthio, thiazolylthio, benzyloxy, thiocyanato, total carbon number 2 6 dialkylamino, alkoxyalkoxy having a total of 2 to 4 carbon atoms, optionally substituted anilino, optionally substituted pyridylamino, cyano, carbon number 2
Alkylcarbonyl having an alkyl of 4 to 4, optionally substituted benzoyl, haloalkylcarbonyl having a haloalkyl of 1 to 3 carbons, pyridylcarbonyl, alkoxycarbonyl having an alkyl of 1 to 4 carbons, optionally substituted Optionally, phenoxycarbonyl, benzyloxycarbonyl, carbamoyl, alkylaminocarbonyl having 1 to 3 carbon atoms, 2 to total carbon atoms
6 dialkylaminocarbonyl, optionally substituted phenylaminocarbonyl, hydroxy, optionally halogen substituted alkylcarbonyloxy, benzoyloxy, alkyl having 1 to 4 carbons Sulfonyloxy, tosyloxy, dialkylaminocarbonyloxy having an alkyl of 1 to 3 carbon atoms, a phosphoric acid ester residue, a thiophosphoric acid ester residue, an amidothiophosphoric acid ester residue, a total carbon number of 4 to 5 tolmethylsilyl, and N, O, S is at least one selected from a heteroatom, and optionally selected from the group consisting of optionally substituted 9- or 10-membered fused heterocyclic group), Optionally substituted phenyl (wherein the substituent is, for example, halogen, carbon number Optionally selected from alkyl of 1 to 3 and nitro), optionally substituted 5- or 6-membered heterocycle containing at least one heteroatom consisting of N, O and S Formula group or 9- or 10-membered condensed heterocyclic group (wherein the cyclic group may have the same substituent as in the case of the above-mentioned phenyl), optionally halogen-substituted 3 carbon atoms To alkenyl group, optionally substituted halogen-containing propargyl group, alkoxy group having 1 to 4 carbon atoms, cyano group, phenoxy group, benzyloxy group, and 2 carbon atoms
To alkenyloxy group having 3 to 4 carbon atoms, optionally substituted alkylthio group having 1 to 4 carbon atoms, phenylthio group substituted with halogen and / or alkyl having 1 to 4 carbon atoms, halobenzylthio group, total carbon number 2 A dialkylamino group having 6 to 6 carbon atoms, an alkylcarbonyl group having 2 to 6 carbon alkyls, an alkylcarbonyl group having 1 to 4 carbon alkyls and having a substituent (wherein the substituent is, for example, halogen. From alkoxy having 1 to 4 carbons, alkylthio having 1 to 4 carbons, alkylcarbonyloxy having alkyl having 1 to 4 carbons, halophenoxy, phenyl, cyano, and alkylcarbonyl having alkyl having 1 to 2 carbons. Which is arbitrarily selected), and may be substituted with halogen and / or alkyl having 1 to 4 carbon atoms. Cycloalkylcarbonyl group having a prime number of 3 to 6, optionally substituted benzoyl group (as the substituent, for example, halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, nitro, carbon number 1 to 4 haloalkyl, alkylcarbonylamino having 1 to 4 carbon alkyl, and alkoxyalkoxy having 2 to 4 carbon atoms are shown), and optionally halogen substituted 2 to 4 carbon atoms An alkenylcarbonyl group having an alkenyl, an alkynylcarbonyl group having an alkynyl having 2 to 3 carbon atoms, (Wherein U ² represents a 5- or 6-membered heterocyclic group containing at least one member selected from the heteroatoms consisting of N, O and S, or a 9- or 10-membered condensed heterocyclic group; Is, for example, halogen, alkyl having 1 to 4 carbons, haloalkyl having 1 to 4 carbons, phenyl, nitro, or 1 carbon.
To 4 optionally substituted by a group consisting of alkylthio and keto), an alkoxycarbonyl group having a substituent and having an alkyl of 1 to 3 carbon atoms (wherein the substituent is Is, for example, halogen, alkoxy having 1 to 2 carbons, or 1 to 2 carbons.
Alkylthio, dialkylamino having 2 to 4 carbon atoms,
Hydroxy, alkylthio having 1 to 2 carbon atoms, and optionally selected from halophenoxy), and cycloalkoxycarbonyl group having 3 to 7 carbon atoms, which may be substituted with alkyl having 1 to 4 carbon atoms. A phenoxycarbonyl group having a substituent (as the substituent, for example, halogen, alkyl having 1 to 4 carbons, haloalkyl having 1 to 4 carbons, cyano, or 1 to 1 carbons
4 alkylthio, alkoxy having 1 to 4 carbons, nitro, alkylsulfinyl having 1 to 4 carbons, 1 to carbon
An alkoxycarbonyl having an alkyl of 4, a pyridyloxy substituted by halogen and / or a trihaloalkyl, and an optionally substituted benzyloxycarbonyl group (wherein the substituent is substituted). Are, for example, halogen, carbon number 1 to
2 is a haloalkyl, an alkoxy having 1 to 4 carbons, or a phenoxy), a phenylthiocarbonyl group, an alkylthiocarbonyl group having an alkyl having 1 to 4 carbons, and an optionally halogen-substituted carbon Alkenyloxycarbonyl group having 2 to 4 alkenyl, alkynyloxycarbonyl group having optionally halogen substituted alkynyl having 2 to 4 carbon atoms (Wherein Q ¹ represents a 5- or 6-membered heterocyclic group containing at least one member selected from the heteroatoms consisting of N, O and S, or a 9- or 10-membered condensed heterocyclic group, wherein the ring is The formula group is, for example, halogen, alkyl having 1 to 4 carbons,
Phenyl, keto and optionally selected from the group consisting of haloalkyl having 1 to 4 carbon atoms), carbamoyl group, alkylaminocarbonyl group having 1 to 4 carbon alkyl, 3 to 3 carbon atoms A cycloalkylaminocarbonyl group having 6 cycloalkyl, an optionally substituted phenylaminocarbonyl group (wherein, as the substituent, for example, halogen, carbon number 1 to
4 alkyl, an arbitrary one selected from alkoxy having 1 to 4 carbon atoms), a dialkylaminocarbonyl group having an alkyl having 2 to 8 carbon atoms in total, (Here, G represents a 5- or 6-membered heterocyclic group containing at least one member selected from the heteroatoms consisting of N, O and S, or a 9- or 10-membered fused heterocyclic group, Is halogen, alkyl having 1 to 4 carbons, 1 to 4 carbons
Alkoxy, C1-4 haloalkyl, C1
~ 2 may be substituted by any selected from alkylsulfonyl, n represents 0 or 1, and R'represents a hydrogen atom or alkyl having 1 to 4 carbon atoms), Good piperidinocarbonyl group (wherein the substituent is, for example, alkyl having 1 to 4 carbon atoms), optionally substituted morpholinocarbonyl group (wherein the substituent is, for example, 1 to 4 carbon atoms) 4 alkyl), a pyrrolidinocarbonyl group, an optionally substituted benzylaminocarbonyl group, a mono- or di-alkenylaminocarbonyl group having an alkenyl group having 2 to 3 carbon atoms, and an alkynyl group having 2 to 3 carbon atoms. An alkynylaminocarbonyl group having: an optionally substituted halogen-substituted alkylsulfonyl group having 1 to 4 carbon atoms, optionally substituted Phenylsulfonyl group (wherein the substituent is, for example, any one selected from halogen, alkyl having 1 to 4 carbons and nitro), alkoxysulfonyl group having 1 to 4 carbons, cyclo having 3 to 6 carbons Alkoxysulfonyl group, mono- or di- (C1-4 alkyl) aminosulfonyl group, phenylaminocarbonyl group which may be substituted with methyl, O, O-di- (C1-4 alkyl) phosphono Group, O, O-di- (C1-4 alkyl) thiophosphono group, O, S-di- (C1-4 alkyl) thiophosphono group, O- (C1-4 alkyl)- O- (phenyl which may be substituted with halogen) thiophosphono group, O, N-
Di- (C1-4 alkyl) amidothiophosphono group, C1-4 alcoxaryl group, optionally halogen-substituted phenoxalyl group, benzyloxalyl group, or A heterocyclic compound represented by.