JP3209649B2 - Production intermediate of insecticidal nitroimino or cyanoimino compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to an insecticidal nitroimino or
The present invention relates to a method for producing a cyanoimino compound. For more information, see the book
The invention relates to an insecticidal nitroi represented by the following formula (I).
The present invention relates to a method for producing a mino or cyano imino compound. [0002] Embedded image In the formula, R represents a hydrogen atom or an alkyl group.
And W is selected from heteroatoms consisting of N, O and S
Represents a 5- or 6-membered heterocyclic group containing at least one
Wherein the ring is optionally substituted, Y is
A represents a nitro group or a cyano group, and A is an optionally substituted
An optionally substituted ethylene group or an optionally substituted
Denotes a limethylene group, and Z is optionally substituted
Alkyl group, optionally substituted alk
An optionally substituted alkynyl group,
An optionally substituted aryl group, optionally substituted
An optionally substituted alkoxy group, which may be optionally substituted
Alkylthio group, optionally substituted aryl
Luthio group, optionally substituted cycloalkyl
Group, cyano group, formyl group, aryloxy group, alk
Heterogen optionally selected from Nyloxy group, N, O, S
A heterocyclic group containing a ring, wherein the ring is optionally substituted
An optionally substituted acyl group,
An optionally substituted alkoxycarbonyl group,
Optionally substituted cycloalkoxycarbonyl
Group, an optionally substituted aryloxycarbo
Nyl group, optionally substituted alkylthiocar
Bonyl group, arylthioca optionally substituted
Rubonyl group, optionally substituted alkenyl
Xycarbonyl group, optionally substituted alkyl
Nyloxycarbonyl group, optionally substituted
Carbamoyl group, thiocarb optionally substituted
Bamoyl group, optionally substituted alkylsul
Honyl group, arylsulfo optionally substituted
Nyl group, optionally substituted alkoxysulfo
Nyl group, optionally substituted cycloalkoxy
Sulfonyl group, aryloxysulfonyl group, optional
Optionally substituted sulfamoyl groups, phosphate esters
Residue, thiophosphate residue, amidothiophosphate
Ter residue, optionally substituted alkoxalyl
Group, optionally substituted aryloxalyl
Group, [0004] Embedded image Where Q is more arbitrary than N, O, and S
Optionally containing a heteroatom selected in
Shows a good heterocyclic group, or [0006] Embedded image The insecticidal nitroimino or shea represented by
To produce a neumino compound, [0008] Embedded image Wherein Y, A and Z are the same as above.
With the compound being an intermediate, [0010] Embedded image Wherein R and W are the same as above, and M is
Halogen atom or [0012] Embedded image Wherein L is an alkyl group or an aryl
Reacting with a compound represented by
Wherein the insecticidal nitroimino of the formula (I) or
A method for producing a cyanoimino compound. Published prior to the filing date of the application
The Canadian Journal of Chemist
Li (Can. J. Chem), 39, 1787-1.
On page 796, the following formula: [0014] Embedded image 1-benzyl-2-nitroi represented by the formula
Minoimidazolidines have been described. However,
There is no description of the compound of formula (I).
The publication also describes the insecticidal action of the compound of formula [D].
It is not mentioned at all. Similarly, this application
Japanese Patent Application Laid-Open No. 48-91064, which is well-known before
A compound represented by the general formula is described.
But bactericidal, antidiabetic, viral sedative and diuretic
That it is useful as an intermediate in the production of active substances
Has been described. [0016] Embedded image Wherein the group R₁And R_TwoIs a hydrogen atom or
Is a straight or branched chain having 1 to 4 carbon atoms
Lower alkyl group,..., R_ThreeAnd R_FourIs hydrogen field
Child, straight-chain or branched having 1 to 4 carbon atoms
Lower alkyl group,..., R^FiveIs a hydrogen atom,
Linear or branched lower having 6 carbon atoms
Alkyl groups, hydroxy having 2 to 3 carbon atoms
Cycloalkyl group, halogen atom, 1 or 2 carbon atoms
Optionally with a lower alkyl or alkoxy group having
A mono- or di-substituted phenyl group, a halogen atom
Benzyl or phenene optionally monosubstituted by
X represents an oxygen or sulfur atom;
Has 1 to 4 carbon atoms in its nitrogen atom. straight
A chain or branched lower alkyl group or benzyl
Or an optionally substituted imino group, and n is 0 or
Is equal to 1). However, in the above formula [E], R^FivePassing
From the definitions of X and X, the compounds of formula (I) of the present invention
And the publication discloses that the insecticidal activity
And no further suggestion. And the details
In the description, for example, a compound corresponding to the following formula is described.
ing. [0018] Embedded image The present inventors have now proposed a novel technique not described in a known document.
The nitroimino or cyanoimino compound of the formula (I) is
Have been found to exhibit insecticidal action, and
In addition, a production method for obtaining the active compound has been found. The present invention
According to the above formula obtained by the production method of the present invention
The nitroimino or cyanoimino compounds of (I) are potent
Shows insecticidal action. Nitroimino or cyano of formula (I)
Imino compounds are surprisingly surprising, for example,
A compound similar to the compound of formula (I) of the present invention described in the known publication
Practically extremely excellent insecticidal action compared to
You. Further, the compound of the formula (I) of the present invention has the above-mentioned strong insecticidal properties.
In addition to the activity, organophosphorus and
This resulted from the use of carbamate pesticides
Pests that are resistant to insecticides, especially Hemiptera (Hemip
puncture-absorbing insect pests, such as
Has a remarkable control effect on bugs, planthoppers, leafhoppers, etc.
It was discovered that I forgot. Therefore, the object of the present invention is
Provided is a method for producing a nitroimino or cyanoimino compound
To be. The above and other objects and advantages of the present invention.
The points will become more apparent from the following description. In the compound of the formula (I) of the present invention,
R represents a hydrogen atom or a methyl group, and W represents N,
One or two selected from heteroatoms consisting of O and S
Containing terrorism atoms, at least one of which is an N-atom
A 5- or 6-membered heterocyclic group which is
The ring is, for example, halogen, alkyl having 1 to 6 carbons, carbon number
2-4 alkenyl, 2-4 carbon alkynyl, carbon
Haloalkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms,
C1-6 alkylthio, C1-6 alkyl
Sulfonyl, alkylsulfinyl having 1 to 6 carbon atoms, charcoal
Haloalkoxy, nitro, cyano, and amino having 1 to 6 prime numbers
Mono-substituted or by any substituent selected from
Poly-substituted, for example, di- or tri-substituted
And Y represents a nitro group or a cyano group, and A represents
An ethylene group or a trimethylene group.
And the trimethylene group is, for example, halogen,
Alkyl, hydroxy and alkoxy having 1 to 4 carbon atoms
Mono-substituted or any substituent selected from
Poly-substituted, for example di-, tri-substituted
And Z is an alkyl group having 1 to 6 carbon atoms, wherein
The alkyl group is, for example, halogen and / or C 1 -C 1.
C 3-7 alkyl optionally substituted by alkyl
Chloroalkyl, halogen, alkoxy having 1 to 4 carbon atoms,
C1-C4 alkoxyethoxy, optionally substituted
Phenoxy which may be substituted (for example, ha
Logene, nitro, alkyl having 1 to 4 carbons, 1 to 1 carbon
From haloalkyl of 4 and haloalkoxy having 1 to 4 carbon atoms
Indicates any one selected)), even if optionally substituted
A good benzyloxy group (for the substituent,
The same as in the case of xy) is shown.
Killsulfonyl, alkylsulfini having 1 to 4 carbon atoms
And optionally substituted phenylthio (the substituted
As the group, for example, those similar to those of the above phenoxy
), Optionally substituted pyridyloxy
(As the substituent, for example, halogen);
Optionally substituted pyridylthio (as the substituent
Represents, for example, halogen), optionally substituted
Thioazolylthio (as the substituent, for example, halo
Represents alkylene), alkylthio having 1 to 4 carbon atoms, thiocyanate
Nato, dialkylamino having 2 to 6 carbon atoms, optionally substituted
Anilino (optional as the substituent, for example,
Any selected from halogen, alkyl having 1 to 4 carbon atoms
), Optionally substituted pyridylua
Mino (the substituents are the same as those of the above anilino
), Cyano, optionally substituted charcoal
Alkylcarbonyl having an alkyl having a prime number of 1 to 4
The substituent is, for example, halogen), optionally substituted
Having an aryl group having 6 to 10 carbon atoms which may be
Arylcarbonyl (as the substituent, for example, halogen
Substituted with pyridylcarbonyl and halogen
Having an optionally substituted alkoxy having 1 to 4 carbon atoms
Xycarbonyl, optionally substituted phenoxy
Cicarbonyl (as the substituent, for example, halogen, charcoal
Represents any one selected from alkyls having a prime number of 1 to 4
Benzyloxycarbonyl, optionally substituted
Carbamoyl which may be substituted (for example, charcoal
Any one selected from alkyl of 1 to 4 primes and phenyl
), Hydroxy, optionally substituted
Alkylcarbonyloxy having alkyl having 1 to 4 carbon atoms
Xy (as the substituent, for example, halogen);
Optionally substituted benzoyloxy (substituent
As, for example, halogen, alkyl having 1 to 4 carbon atoms,
Any one selected from haloalkyl having 1 to 4 carbon atoms
Shown), alkylsulfonyloxy having 1 to 4 carbon atoms,
Optionally substituted phenylsulfonyloxy
(As the substituent, for example, halogen, having 1 to 4 carbon atoms)
Any one selected from alkyl), total carbon number 2
Dialkylaminocarbonyl having from 6 to 6 dialkyls
Oxy, optionally substituted phenyl (the substituted
Examples of the group include halogen, alkyl having 1 to 4 carbon atoms.
, Alkoxy having 1 to 4 carbon atoms, haloa having 1 to 4 carbon atoms
Any selected from alkyl, nitro, methylenedioxy
O, O-dialkylphospho having 2 to 6 carbon atoms
Suhono, O, O-dialkylthiophos having 2 to 6 total carbon atoms
Holylthio, O, S-dialkylthio having 2 to 6 total carbon atoms
Phosphoryloxy, trialkylsilyl having 3 to 6 carbon atoms
And a small atom selected from heteroatoms consisting of N, O, S
Contains at least one and may be arbitrarily substituted
5- or 6-membered heterocyclic group or 9- or 10-membered condensation
Heterocyclic group (for example, halogen, carbon
Alkyl having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms,
Phenyl, nitroimino, cyanoimino, keto, carbon number
From alkylthio having 1 to 4 carbon atoms and alkoxy having 1 to 4 carbon atoms
Arbitrarily selected from the group consisting of:
Having 2 to 6 carbon atoms which may be substituted by
An alkenyl group, wherein the alkenyl group is
, C 1-4 alkoxy, also alkylthio
Charcoal, optionally substituted by
An alkynyl group having a prime number of 2 to 6, wherein the alkynyl group is
For example, carbon number 6 which may be substituted by halogen.
To 10 aryl groups, wherein the aryl group is, for example, ha
Logen, alkyl having 1 to 4 carbons, nitro, 1 to 1 carbons
4 haloalkyl and optionally substituted
Nonoxy (as the substituent, for example, halogen,
Any one selected from haloalkyls of ~ 4)
Substituted by any member selected from the group consisting of
A C 1-6 alkoxy group, wherein the alcohol
Xyl groups are more commonly found than halogen, phenyl and pyridyl, for example.
Carbon number which may be substituted by a group of choice
1-6 alkylthio groups, wherein the alkylthio group is
Halogen, optionally substituted phenyl (the
As the substituent, for example, halogen))
Fe, which may be substituted by
A nilthio group, wherein the phenylthio group is, for example, a halogeno
Arbitrarily selected from alkyl having 1 to 4 carbon atoms
A cycloalkyl having 3 to 7 carbon atoms which may be more substituted
Alkyl, wherein the cycloalkyl group is, for example,
4 optionally substituted with alkyl
No group, formin group, phenoxy group, allyloxy group,
At least one selected from heteroatoms consisting of N, O, S
5 or 6 membered heterocyclic group including 1 or 9 or 1
A 0-membered fused heterocyclic group, wherein said heterocyclic group and
The heterocyclic group is, for example, an alkyl having 1 to 4 carbons,
Rogen, nitro, haloalkyl having 1 to 4 carbon atoms and carbon
Arbitrarily selected from the group consisting of haloalkoxys of Formulas 1 to 4
Having 1 to 6 carbon atoms which may be substituted by
An alkylcarbonyl group having an alkyl, wherein the alkyl
A carbonyl group is, for example, a halogen, an alkyl group having 1 to 4 carbon atoms.
Lucoxy, alkylthio having 1 to 4 carbon atoms, 1 to 4 carbon atoms
An alkoxyethoxy having an alkoxy of 1 to 1 carbon atoms
Alkylcarbonyloxy having 4 alkyls, optional
Optionally substituted phenyl, optionally substituted
Phenoxy (substituents of phenyl and phenoxy
As, for example, halogen, alkyl having 1 to 4 carbon atoms,
C1-C4 alkoxy, C1-C4 haloalkyl
, Nitro, hydroxy, phenoxy
), Cyano, and alkyl having 1 to 4 carbon atoms.
Alkylcarbonyl, hydroxy, total carbon number 2-6
May be substituted with dialkylamino and halogen
Arbitrarily selected from the group consisting of benzyloxy
Optionally substituted cycloalkyl having 3 to 6 carbon atoms
Carbonyl group, wherein the cycloalkylcarbonyl group
Are, for example, halogen, alkoxy having 1 to 4 carbon atoms and carbon
Arbitrarily selected from the group consisting of alkyl having a prime number of 1 to 4
A benzoyl group optionally substituted by
The benzoyl group is, for example, halogen, an alkyl having 1 to 4 carbon atoms.
Kill, alkoxy having 1 to 4 carbon atoms, nitro, cyano, charcoal
Haloalkyl having 1 to 4 carbon atoms, haloalkco having 1 to 4 carbon atoms
Xy, hydroxy, alkylthio having 1 to 4 carbon atoms, carbon
Alkylsulfinyl having 1 to 4 carbon atoms, alkyl having 1 to 4 carbon atoms
Alkylsulfonyl, alkyl having 1 to 4 carbon atoms
Kill carbonyl, optionally substituted phenoxy
(The substituent may be, for example, halogen, 1-4 carbon atoms.
Represents any one selected from alkyl of
Optionally substituted pyridyloxy (as the substituent
Indicates the same as in the case of the above phenoxy)), carbon
Alkylcarbonylamido having alkyl of formula 1-4
, Dialkylamino having 2 to 4 carbon atoms and 2 total carbon atoms
Arbitrarily selected from the group consisting of
Having 2 to 4 carbon atoms which may be substituted by
An alkenyl-containing alkenylcarbonyl group, wherein
An alkenylcarbonyl group is, for example, halogen and having 1 carbon atom
Substituted by an arbitrarily selected from alkoxy of
Optionally having an alkynyl having 2 to 4 carbon atoms
A alkynylcarbonyl group, wherein the alkylnylcarbo is
The nyl group is substituted in the same manner as in the case of the alkenylcarbonyl.
May be replaced, [0022] Embedded image Here, U is a hetero element composed of N, O and S.
5- or 6-membered hete, including at least one selected from offspring
A cyclic group or a 9- or 10-membered fused heterocyclic group
The cyclic group is, for example, halogen, having 1 to 4 carbon atoms.
Alkyl, haloalkyl having 1 to 4 carbon atoms, 1 to 4 carbon atoms
Alkoxy, haloalkoxy having 1 to 4 carbon atoms, carbon number
1-4 haloalkylthio, phenyl, nitro, carbon number
Arbitrarily selected from the group consisting of 1-4 alkylthio and keto
1 to 6 carbon atoms which may be substituted by
An alkoxycarbonyl group having an alkyl
The alkoxycarbonyl group is, for example, an alkyl group having 1 to 4 carbon atoms.
Coxy, phenoxy optionally substituted (the
Examples of the substituent include halogen, alkyl having 1 to 4 carbon atoms.
Dialkylamino having 2 to 6 carbon atoms, carbon
Alkylthio of formulas 1-4, halogen, hydroxy, optional
Optionally substituted phenyl (as the substituent,
For example, halogen, haloalkyl having 1 to 4 carbon atoms, carbon number
Selected from alkyl of 1-4, alkoxy of 1-4 carbon
Phenoxyphenyl)
Even if substituted by an arbitrarily selected from the group consisting of
Cycloa having cycloalkyl having 3 to 7 carbon atoms
A alkoxycarbonyl group, wherein the cycloalkoxycar
The bonyl group is substituted with, for example, an alkyl having 1 to 4 carbon atoms.
A phenoxycarbonyl group, wherein
The nonoxycarbonyl group is, for example, halogen, having 1 to 4 carbon atoms.
Alkyl, nitro, haloalkyl having 1 to 4 carbon atoms,
Dialkylamino having 2 to 6 carbon atoms, alalkyl having 1 to 4 carbon atoms
Kirthio, C 1-4 alkylsulfinyl, shea
And pyridyloxy optionally substituted
(As the substituent, halogen, halo having 1 to 4 carbon atoms)
From the group consisting of:
Fe, which may be substituted by
Nylthiocarbonyl group, having alkyl having 1 to 4 carbon atoms
Alkylthiocarbonyl group, alkenyl having 2 to 4 carbon atoms
An alkenyloxycarbonyl group having
The alkenyloxycarbonyl group is substituted with, for example, halogen.
Having alkynyl having 2 to 4 carbon atoms which may be
An alkynyloxycarbonyl group, wherein the alkynyloxy
The oxycarbonyl group is, for example, substituted with halogen.
Carbamoyl group, thiocarbamoyl group, where
The carbamoyl group and thiocarbamoyl group are, for example,
Alkenyl having 2 to 4 carbon atoms, cycloalkyl having 3 to 7 carbon atoms
Optionally substituted phenyl (the substituent and
For example, for example, halogen, hydroxy, having 1 to 4 carbon atoms
Alkyl, alkoxy having 1 to 4 carbons, 1 to 4 carbons
Haloalkyl, haloalkoxy having 1 to 4 carbon atoms, carbon number
Any one selected from haloalkylthio of 1-4
), An optionally substituted alkyl having 1 to 6 carbon atoms
Kill (as the substituent, for example, halogen, carbon number 1
Alkoxy having 4 to 4, alkylthio having 1 to 4 carbons, and cyan
R, dialkylamino having 2 to 4 carbon atoms, optionally substituted
Optionally consisting of phenyl and N, O, S
5 or 6 membered members including at least one member selected from
Selected from an optionally substituted heterocyclic group
And heterogeneous N, O, S
Contains at least one atom selected from atoms, and
Optionally substituted 5- or 6-membered heterocyclic group,
Is a 9- or 10-membered fused heterocyclic group (as the substituent
Is halogen, alkyl having 1 to 4 carbons, 1 to 4 carbons
Alkoxy, haloalkyl having 1 to 4 carbons, 1 carbon
Any one selected from alkylsulfonyls of
) Is replaced by any selected from the group consisting of
An alkylsulfonyl group having 1 to 4 carbon atoms, which may be
An alkenylsulfonyl group having 2 to 4 carbon atoms, wherein
A killsulfonyl group and the alkenylsulfonyl group are, for example,
For example, phenylsulfo which may be substituted with halogen
Phenyl, wherein the phenylsulfonyl is, for example, halo
Group consisting of gen, alkyl having 1 to 4 carbon atoms, and nitro
May be substituted by those arbitrarily selected from
An alkoxysulfonyl group having 1 to 4 carbon atoms, 3 to 7 carbon atoms
Cycloalkoxysulfonyl group, phenoxysulfonyl
, A sulfamoyl group, wherein the sulfamoyl group
Is composed of, for example, alkyl having 1 to 4 carbon atoms and phenyl.
May be replaced by any one selected from the group
O, O-di- (C.sub.1-4 alkyl) phosphono
Group, O, O-di- (alkyl having 1 to 4 carbon atoms) thiophos
Hono group, O, S-di- (alkyl having 1 to 4 carbon atoms) thio
Phosphono group, O- (alkyl having 1 to 4 carbon atoms) -O-
(Optionally substituted phenyl) thiophosphono
Group, O, N-di- (alkyl having 1 to 4 carbon atoms) amido
Ophosphono group, C1-C4 alkoxalyl group, here
Wherein the alkoxalyl group is substituted with, for example, phenyl
A phenoxalyl group, wherein the phenoxali
The group may be substituted with, for example, a halogen, [0024] Embedded image Where Q¹Is a heterogeneous N, O, S
5- or 6-membered containing at least one selected from atoms
A telocyclic group or a 9 or 10 membered fused heterocyclic group
Shows, wherein the heterocyclic group or fused heterocyclic group is
For example, halogen, alkyl having 1 to 4 carbons, phenyl,
From the group consisting of keto and haloalkyl having 1 to 4 carbon atoms
May be substituted by an arbitrarily selected one, or [0026] Embedded image Furthermore, the compounds of the formula (I) are particularly preferred.
More preferably, R represents a hydrogen atom and W represents N, O, S
One or two heteroatoms selected from heteroatoms
And at least one of them is an N-atom
Represents a 5- or 6-membered heterocyclic group, wherein the ring is an example
For example, halogen, alkyl having 1 to 2 carbons, 1 to 2 carbons
Haloalkyl, C 1-2 alkoxy, C 1
Alkylthio of 1-2, alkylsulfonyl of 1-2 carbon
Alkylsulfinyl having 1 to 2 carbons, 1 to 2 carbons
2 selected from haloalkoxy, nitro and cyano
Mono- or di-substituted by any substituents
Y represents a nitro group or a cyano group, and A represents
Represents a ethylene group or a trimethylene group, wherein the ethylene
Groups and the trimethylene group are, for example, halogen and carbon
With an optional substituent selected from alkyls of the formulas 1 and 2,
May be mono-substituted or di-substituted; Z is an alkyl group having 1 to 4 carbon atoms, wherein
The alkyl group can be substituted, for example, by halogen and / or methyl.
Optionally substituted cycloalkyl having 3 to 6 carbon atoms, ha
Rogen, C 1-2 alkoxy, optionally substituted
Phenoxy (optionally, for example, halo
Gen, nitro, methyl, halomethyl, halomethoxy
Indicates any one selected)), benzyloxy, carbon number
Alkylthio having 1 to 2 alkylsulfo having 1 to 2 carbon atoms
Nil, alkylsulfinyl having 1 to 2 carbon atoms, optionally
Optionally substituted phenylthio (as the substituent,
For example, any one selected from halogen, methyl, and nitro
), Optionally substituted pyridyloxy
C (for the substituent, for example, halogen), optional
Optionally substituted pyridylthio (as the substituent
Represents, for example, halogen), even if optionally substituted
Good thiazolylthio (for the substituent, for example, halogen
), Thiocyanato, dialkyl having 2 to 4 carbon atoms in total
Amino, optionally substituted anilino (the
Examples of the substituent include halogen, alkyl having 1 to 2 carbon atoms.
Optional), optionally substituted
Pyridylamino which may be present (for the substituent,
Similar to Nirino), Cyano, Aceti
2,2-dimethylpropionyl, optionally substituted
Benzoyl (optionally, for example, halo
A) having 1 to 2 carbon atoms.
Alkoxycarbonyl with alkyl, optionally substituted
Optionally substituted phenoxycarbonyl (as the substituent
Is, for example, any one selected from halogen and methyl
), Benzyloxycarbonyl, optionally substituted
Carbamoyl which may be present (for the substituent, for example,
Any one selected from alkyl and phenyl having 1 to 2 carbon atoms
), Hydroxy, optionally substituted
Having alkyl having 1 to 2 carbon atoms
Oxy (as the substituent, for example, halogen);
Benzoyloxy, alkylsulfonyl having 1-2 carbon atoms
Oxy, phenylsulfonyloxy, having 2 to 4 carbon atoms
Dialkylaminocarbonyloxy having alkyl,
Optionally substituted phenyl (as the substituent
Is, for example, halogen, methyl, methoxy, halomethyl,
Indicates any one selected from nitro and methylenedioxy
), O, O-dimethylphosphono, O, O-diethylthio
Ophosphorylthio, O-ethyl-S-propylthiophos
From holyloxy, trimethylsilyl, and N, O, S
At least one selected from heteroatoms comprising
Optionally substituted 5- or 6-membered heterocyclic
Or a 9- or 10-membered fused heterocyclic group (the substituent
As, for example, halogen, alkyl having 1 to 2 carbon atoms,
Halomethyl, phenyl, keto, alkyl having 1-2 carbon atoms
Thio, any one selected from alkoxy having 1 to 2 carbon atoms
Arbitrarily selected from the group consisting of
May be substituted, may be substituted with halogen
2-propenyl group, a group which may be substituted with halogen
Lopardyl group, phenyl group, wherein the phenyl group is an example
For example, halogen, methyl, nitro, trifluoromethyl and
And optionally substituted phenoxy (with the substituent
For example, selected from halogen, trifluoromethyl
Arbitrarily selected from the group consisting of:
An alkyl having 1 to 4 carbon atoms which may be substituted by
A oxy group, an alkylthio group having 1 to 4 carbon atoms,
The alkylthio group is substituted by halogen or phenyl
A phenylthio group, wherein the phenylthio group
Is, for example, arbitrarily selected from halogen and methyl
A cycloalkyl having 3 to 6 carbon atoms which may be more substituted
Alkyl, wherein the cycloalkyl group is, for example, methyl.
Optionally substituted cyano group, formyl
Group, phenoxy group, allyloxy group, N, O, S
5 containing at least one selected from hetero atoms
6 membered heterocyclic group or 9 or 10 membered fused hetero
Cyclic groups, wherein said heterocyclic groups and fused heterocyclic groups
Is, for example, methyl, halogen, halomethyl and carbon number 1
Arbitrarily selected from the group consisting of
An alkyl having 1 to 4 carbon atoms which may be substituted by
An alkylcarbonyl group having
The rubonyl group is, for example, halogen, methoxy, methylthio.
E, acetoxy, chloro and / or methyl substituted
Phenoxy, phenyl, cyano and acetyl
Substituted by any member selected from the group consisting of
A cycloalkyl having a cycloalkyl having 3 to 6 carbon atoms
Alkylcarbonyl, wherein the cycloalkyl carbonyl
The chloro radical is, for example, substituted by chloro and / or methyl.
A benzoyl group, wherein the benzoyl group is an example
For example, halogen, methyl, alkoxy having 1 to 2 carbon atoms,
Arbitrarily selected from the group consisting of toro and halomethyl
Alkenyl having 2 to 3 carbon atoms which may be more substituted
An alkenylcarbonyl group having the formula:
The carbonyl group may be substituted with, for example, a halogen.
Alkynylcal having alkynyl having 2 to 3 carbon atoms
Bonyl group, [0029] Embedded image Where U¹Is a heterogeneous N, O, S
5- or 6-membered containing at least one selected from atoms
A telocyclic group or a 9- or 10-membered fused heterocyclic group
Wherein the heterocyclic group and the fused heterocyclic group are, for example,
Halogen, methyl, halomethyl, phenyl, nitro,
Selected from the group consisting of alkylthio having 1 to 2 carbon atoms and keto
Carbon number which may be substituted by a group of choice
An alkoxycarbonyl group having 1 to 4 alkyls,
Here, the alkoxycarbonyl group is, for example, one having 1 to 2 carbon atoms.
Of the alkoxy, optionally substituted phenoxy
(As the substituent, for example, halogen);
Dialkylamino having 2 to 4 carbon atoms, alkyl having 1 to 2 carbon atoms
Thio, halogen, optionally substituted phenyl
(As the substituent, for example, halogen, halomethyl,
Any one selected from alkoxy having 1 to 2 tyl carbon atoms
And phenoxyphenyl)
Having 3 carbon atoms which may be substituted by
Cycloalkoxycarbo having cycloalkyl of from 6 to 6
Nil group, wherein the cycloalkoxycarbonyl group is an example
For example, phenoxycarbo which may be substituted with methyl
A phenyl group, wherein the phenoxycarbonyl group is, for example, ha
Logen, methyl, nitro, halomethyl, cyano, and ha
Consisting of pyridyloxy optionally substituted by a logen
May be substituted by any selected from the group
Phenylthiocarbonyl group, alkyl having 1 to 4 carbon atoms
Alkylthiocarbonyl group containing allyloxyca
A rubonyl group, wherein the allyloxycarbonyl group is an example
For example, propargylo, which may be substituted with halogen
An oxycarbonyl group, where the propargyloxycarbo
A nyl group is, for example,
A rubamoyl group, wherein the carbamoyl group is, for example, an ant
, Cycloalkyl having 3 to 6 carbon atoms, optionally substituted
Phenyl which may be present (for example, halogen
, Alkyl having 1 to 2 carbon atoms, alkoxy having 1 to 2 carbon atoms
Arbitrarily selected from halomethoxy), any
Alkyl having 1 to 4 carbon atoms which may be substituted
As the substituent, for example, halogen, alk having 1 to 2 carbon atoms
Represents any one selected from coxy and phenyl),
And at least one selected from heteroatoms consisting of N, O, and S
And one that is optionally substituted and optionally substituted
Is a 6-membered heterocyclic group or a 9- or 10-membered fused
A cyclic group (as the substituent, halogen, methyl, halo
Methoxy, halomethyl, alkylsulfo having 1-2 carbon atoms
An optional member selected from nil).
Carbon number which may be substituted by a group of choice
1-2 alkylsulfonyl groups, wherein the alkylsulfonyl group
A honyl group may be substituted with, for example, a halogen,
A phenylsulfonyl group, wherein the phenylsulfonyl group
Is, for example, from the group consisting of halogen, methyl and nitro
A carbon optionally substituted by one selected
An alkoxysulfonyl group of the formula 1-2, phenoxysulfo
Nyl group, sulfamoyl group, wherein the sulfamoyl group
Is composed of, for example, alkyl having 1 to 3 carbon atoms and phenyl.
May be replaced by any one selected from the group
O, O-di- (C 1-3) alkylphosphono
Group, O, O-di- (C 1-3) alkylthiophospho
Group, O, S-di- (C 1-3) alkylthiophos
Hono group, O- (C 1-3) alkyl-O- (optionally
Phenylthiophosphono group, which may be substituted), O,
N-di- (C 1-3) alkylamidothiophosphono
Group, or [0031] Embedded image In the production method of the present invention, for example,
For example, 1-isopropyl-2-nitroiminoimidazolide
And 2-chloro-5-chloromethylpyridine
Then, it is represented by the following reaction formula. [0033] Embedded image In the production method of the present invention, the starting material represented by the formula (I)
The compound of I) is based on the definition of Y, A and Z described above.
Means things. In the formula (II), Y, A and Z are
Preferably, the definition is as defined above. Formula (II)
Compounds include both known and novel compounds,
And as a novel compound, for example, a compound of the following formula (IIa)
Can be suggested. [0035] Embedded image In the formula, Y represents a nitro group or a cyano group;
A¹Represents an ethylene group or a trimethylene group, where
Each group is, for example, halogen or alkyl having 1 to 4 carbon atoms.
Mono- or poly-substituted, depending on the optional substituents selected
(Eg di-, tri-substituted), Z¹Is
Cycloalkyl having 3 to 7 carbon atoms which may be methyl-substituted
Kill group, haloalkyl group having 1 to 4 carbon atoms, total 2 to 2 carbon atoms
6 alkoxyalkyl groups, alkyl having 2 to 6 carbon atoms in total
Thioalkyl group, alkylsulfini having 2 to 6 carbon atoms in total
Alkyl group, alkylsulfonylus having 2 to 6 carbon atoms in total
Alkyl group, alkyl group having a substituent having 1 to 3 carbon atoms
(Where the substituent is, for example, optionally substituted
Phenoxy, optionally substituted phenoxy
Phenylthio, an optionally substituted pyridyloxy
C, an optionally substituted cycloalkyl having 3 to 6 carbon atoms
Alkyl, optionally substituted pyridylthio,
Thiazolylthio, benzyloxy, thiocyanato, total coal
Dialkylamino having 2 to 6 primes, and alkyl having 2 to 4 carbons in total
Coxyalkoxy, optionally substituted anili
No, optionally substituted pyridylamino, shea
(H) alkyl carbonyl having alkyl having 2 to 4 carbon atoms
Benzoyl, optionally substituted benzoyl, carbon number 1
Haloalkylcarbonyl having ハ ロ 3 haloalkyl,
Pyridylcarbonyl, having alkyl having 1 to 4 carbon atoms
Alkoxycarbonyl, optionally substituted
Phenoxycarbonyl, benzyloxycarbonyl, cal
Bamoyl, alkylaminocarbonyl having 1 to 3 carbon atoms,
Dialkylaminocarbonyl having 2 to 6 carbon atoms, optionally
Optionally substituted phenylaminocarbonyl, hydr
Roxy, halogen-substituted alkyl having 1 to 3 carbon atoms
Alkylcarbonyloxy, benzoy
Roxy, alkylsulfonyloxy having 1 to 4 carbon atoms,
Tosyloxy, a dial having 1 to 3 carbon atoms
Killaminocarbonyloxy, phosphate ester residue,
Phosphoric acid ester residue, amide thiophosphoric acid ester residue
Groups, trimethylsilyl having 4 to 5 carbon atoms in total, and N, O,
Including at least one selected from heteroatoms consisting of S
9- or 10-membered optionally substituted
Arbitrarily selected from the group consisting of heterocyclic groups
), Optionally substituted phenyl (wherein
Examples of the substituent include halogen, alkyl having 1 to 3 carbon atoms.
And nitro).
At least one selected from heteroatoms consisting of O and S
Optionally substituted 5- or 6-membered hete
Or a 9- or 10-membered fused heterocyclic group (this
Here, the cyclic group has the same substituent as in the case of the phenyl.
May be present), the number of carbon atoms which may be substituted by halogen
3 to 4 alkenyl groups, which may be halogen-substituted
Propargyl group, alkoxy group having 1 to 4 carbon atoms, cyano
Group, phenoxy group, benzyloxy group, having 2 to 3 carbon atoms
Alkenyloxy group, halogen-substituted with 1 to 4 carbon atoms
Alkylthio group, halogen and / or carbon
A phenylthio group substituted with an alkyl of the formulas 1-4, halo
Benzylthio group, dialkylamino having 2 to 6 carbon atoms
Carbonyl having an alkyl group having 2 to 6 carbon atoms
Having an alkyl group having 1 to 4 carbon atoms and having a substituent.
Alkylcarbonyl group (wherein the substituent is
For example, halogen, alkoxy having 1 to 4 carbon atoms, 1 carbon atom
Having up to 4 alkylthio, alkyl having 1 to 4 carbon atoms
Alkylcarbonyloxy, halophenoxy, pheny
And alkyl having 1 to 2 carbon atoms.
Arbitrarily selected from kill carbonyl), halo
Substituted by an alkyl having 1 to 4 carbon atoms and / or
Optionally having 3 to 6 carbon atoms
A benzoyl group which may be substituted
Examples of the group include halogen, alkyl having 1 to 4 carbon atoms.
, Alkoxy having 1 to 4 carbon atoms, nitro, 1 to 4 carbon atoms
Haloalkyl, alkyl having 1 to 4 carbon atoms
Killcarbonylamino and alkoxy having 2 to 4 carbon atoms
Arbitrarily selected from alkoxy), halogen
Having an optionally substituted alkenyl having 2 to 4 carbon atoms
Alkenylcarbonyl group having 2 to 3 carbon atoms
An alkynylcarbonyl group having [0038] Embedded image (Where U^TwoIs a hete consisting of N, O, S
5 or 6 membered members including at least one member selected from
Heterocyclic group or 9- or 10-membered fused heterocyclic group
And the cyclic group is, for example, halogen, having 1 to 4 carbon atoms.
Alkyl, haloalkyl having 1 to 4 carbon atoms, phenyl,
Toro, haloalkyl having 1 to 4 carbon atoms, phenyl, nitro
(B) a group consisting of alkylthio having 1 to 4 carbon atoms and keto
May be substituted by those arbitrarily selected from
A having a substituent and having an alkyl having 1 to 3 carbon atoms;
Alkoxycarbonyl group (where the substituent is, for example,
Halogen, alkoxy having 1 to 2 carbon atoms, 1 to 2 carbon atoms
Alkylthio, dialkylamino having 2 to 4 carbon atoms in total,
Hydroxy, alkylthio having 1 to 2 carbon atoms, halopheno
Arbitrarily selected from xy), having 1 to 4 carbon atoms
C3-C7 cyclo which may be substituted by alkyl
Cycloalkoxycarbonyl group having alkyl, substitution
A phenoxycarbonyl group (wherein said substituent and
For example, halogen, alkyl having 1 to 4 carbons, charcoal
Haloalkyl having 1 to 4 carbon atoms, cyano, and 1 to 4 carbon atoms
Alkylthio, alkoxy having 1 to 4 carbon atoms, nitro, carbon
Alkylsulfinyl having 1 to 4 carbon atoms, alkyl having 1 to 4 carbon atoms
Alkoxycarbonyl, halogen and / or
Is pyridyloxy substituted by trihaloalkyl
Arbitrarily selected from the group consisting of
A benzyloxycarbonyl group (wherein
Examples of the substituent include a halogen and a halo having 1 to 2 carbon atoms.
From alkyl, alkoxy with 1 to 4 carbon atoms and phenoxy
Phenylthiocarbonyl
Having an alkyl group having 1 to 4 carbon atoms
Bonyl group, C2-4 which may be halogen-substituted
An alkenyloxycarbonyl group having an alkenyl of
C2-C4 alkynyl optionally substituted with halogen
An alkynyloxycarbonyl group having [0040] Embedded image (Where Q¹Is a heterogeneous N, O, S
5- or 6-membered containing at least one selected from atoms
A telocyclic group or a 9 or 10 membered fused heterocyclic group
Wherein the cyclic group is, for example, halogen, having 1 to 4 carbon atoms.
Alkyl, phenyl, keto and halo with 1 to 4 carbon atoms
Replaced by any selected from the group consisting of
A carbamoyl group, an alkyl group having 1 to 4 carbon atoms.
Alkylaminocarbonyl group having alkyl, carbon number 3
Cycloalkylaminoca having cycloalkyl of from 6 to 6
Rubonyl group, phenylaminocarb which may be substituted
A bonyl group (where the substituent is, for example, halogen
, Alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms
Any one selected from the group consisting of
A dialkylaminocarbonyl group having an alkyl, [0042] Embedded image (Where G is a heterogeneous N, O, S
5- or 6-membered containing at least one selected from atoms
A telocyclic group or a 9 or 10 membered fused heterocyclic group
And the cyclic group is halogen, alkyl having 1 to 4 carbons,
C1-C4 alkoxy, C1-C4 haloalkyl
Selected from alkylsulfonyl having 1 to 2 carbon atoms
N is 0 or 1 which may be substituted by
And R 'is a hydrogen atom or an alkyl having 1 to 4 carbon atoms.
Represents an optionally substituted piperidinocarboni
(Herein, examples of the substituent include those having 1 to 4 carbon atoms)
Alkyl)), morpholinoca which may be substituted
Rubonyl group (here, the substituent may be, for example,
To 4), a pyrrolidinocarbonyl group,
Benzylaminocarbonyl optionally substituted with tyl
Group, mono- or di- having alkenyl having 2 to 3 carbon atoms
Alkenylaminocarbonyl group, alkyl having 2 to 3 carbon atoms
Alkynylaminocarbonyl group having nil, halogen
C1-C4 alkylsulphoni which may be substituted
A phenylsulfonyl group which may be substituted
Here, as the substituent, for example, halogen, having 1 to 4 carbon atoms
Represents any one selected from alkyl and nitro), An alkoxysulfonyl group having 1 to 4 carbon atoms,
A cycloalkoxysulfonyl group having 3 to 6 carbon atoms, mono-
Or di- (alkyl having 1 to 4 carbon atoms) aminosulfonyl
Group, phenylaminocarbo which may be methyl-substituted
Nyl group, O, O-di- (alkyl having 1 to 4 carbon atoms) phos
Hono group, O, O-di- (alkyl having 1 to 4 carbon atoms) thio
Phosphono group, O, S-di- (alkyl having 1 to 4 carbon atoms)
Thiophosphono group, O- (alkyl having 1 to 4 carbon atoms) -O
-(Phenyl optionally substituted with halogen) thiophos
Hono group, O, N-di- (alkyl having 1 to 4 carbon atoms) amido
Dothiophosphono group, an alkoxyl group having 1 to 4 carbon atoms,
Phenoxalyl group which may be halogen-substituted, ben
A dioxalyl group, or [0045] Embedded image A heterocyclic compound represented by the formula: Further, the above proposed formula included in the formula (II)
Novel compounds other than (IIa) are represented by the formula (IIa)
This is illustrated together with specific examples of the compound of the above. Of the above formula (IIa)
The compounds are, for example, prepared according to process a): Embedded imageWherein Y and A are the same as defined above, Z¹− M¹                      (V) Where Z¹Is the same as above, M¹Is a halogen atom, preferred
Or chromium or bromo.
Is reacted, or production method b): H_TwoNA-NH-Z¹            (VI) Where A and Z¹Is the same as above
When, Embedded image Wherein Y is the same as above, M^TwoIs amino group, alkylthio
A compound represented by the formula or a benzylthio group:
It is obtained by a method of reacting. In the formula (IIa), Y is a cyano group
In some cases, the compound of formula (IIa) is further prepared in process c):
A compound of the above formula (VI), (M^Three-S)_TwoC = N-CN (VIII) Where M^ThreeRepresents alkylthio or benzylthio, and
Two M^ThreeTogether with the sulfur atom to which they bind
And a compound represented by the formula:
It is easily obtained by the method of reacting. In the above process a), the compound of the formula (IV)
Include known compounds. Am. Chem.
Soc. (Journal American Chemical Sosae
Tee), Vol. 73, pp. 2201-2205, UK Patent No.
2,055,796 and the like. Similarly above
In the process a), most of the compounds of the formula (V) are
It is well known in the field of organic chemistry. The above manufacturing method
In b), the compounds of formula (VI) include known compounds
But generally H_TwoNA-NH_Two                (IX) In the formula, A is the same compound as defined above,
By reacting with the compound of (V), the compound is easily obtained.
It is. The compound of the above formula (IX) is a known compound
For example, West German Patent Publication No. 2,732,660
The ethylene diamine described in French Patent No. 1,499,785
And trimethylenediamine. For example, J.
A. C. S. (Journal American Chemical So
Society), vol. 76, p.
In this, the compounds of the formula (VII) include known compounds.
In process c) above, the compound of formula (VIII) is Or
g. Chem. (Journal Organic Chemist
Li), Vol. 32, pp. 1566-1572.
It is. The compound of formula (II) in the process of the present invention
Specific examples include those described below. As well
In the production method of the present invention, the starting compound of the formula (III)
Means those based on the definitions of R, W and M.
In the formula (III), R and W are preferably the same as defined above.
And M is preferably chromium,
Shows a rom or tosyloxy group. The compound of formula (III) is
It is known, for example, Japanese Patent Application Laid-Open No. 61-12682
No. 61-183, 271.
I do. Specific examples of the formula (III) include, for example,
Can be exemplified. 2-methyl-5-chloromethylpyridi
2-chloro-5-chloromethylthiazole, 2-butane
Lomo-5-chloromethylpyridine, 2-trifluoromethyl
Tyl-5-chloromethylpyridine, 2-bromo-5-c
Loromethylthiazole, 3-chloromethylpyridine, 2
-Fluoro-5-bromomethylpyridine, 2-chloro-
5-chloromethylpyridine, 2-methoxy-5-pyridi
Methyl tosylate, 2-chloro-5-bromomethylo
Xazole. In carrying out the production method of the present invention, an appropriate dilution
Excipients include all inert solvents.
You. Examples of such diluents are water; aliphatic, cycloaliphatic
And aromatic hydrocarbons (even if chlorinated
Good) For example, hexane, cyclohexane, petroleum ether
, Ligroin, benzene, toluene, xylene, methyl
Len chloride, chloroform, carbon tetrachloride, ethylene
Chloride and trichlorethylene, chlorobenze
Ethers such as diethyl ether,
Tyl ethyl ether, di-iso-propyl ether,
Dibutyl ether, propylene oxide, dioxa
, Tetrahydrofuran; nitriles such as acetonitrile
Tolyl, propionitrile, acrylonitrile; Alco
Tools such as methanol, ethanol, iso-pro
Panol, butanol, ethylene glycol; acid amide
Such as dimethylformamide, dimethylacetamide
Sulfones, sulfoxides such as dimethyl sulfo
Oxide, sulfolane and the like can be exemplified. The production method of the present invention
Further, sodium hydride, potassium
Hydroxide, carbonic acid of hydride alkali metal such as idolide
It can be performed in the presence of a salt or the like. The production method of the present invention
It can be performed over a wide temperature range and generally
Is from about 0 ° C to about 100 ° C, preferably from about 10 ° C to about 80 ° C.
C. can be carried out. The reaction should be performed under normal pressure.
It is preferable to perform under pressure or reduced pressure
Can also. In carrying out the production method of the present invention, for example,
For example, with respect to 1 mol of the compound of the formula (II),
About 1.1 to 1.2 times molar amount of ium hydride;
The compound of the formula (III) is used in an equimolar amount to about 1.2-fold molar amount,
Preferably an equimolar amount to about 1.1 times the molar amount is added to the inert solvent,
For example, by reacting in dimethylformamide
Thus, the desired compound can be obtained. In the above manufacturing method
The compound of formula (II) into sodium hydride
It is better to prepare the sodium salt in advance
Above, preferred, and such reaction is sodium hydra
It is desirable to perform in a nitrogen gas atmosphere
New Also, the processes a) and b) for producing the compound of the formula (IIa)
And when carrying out c), the above-mentioned production method of the present invention
The same inert solvents as mentioned above can be exemplified. Method a)
The method can be performed in the presence of the same base as described above.
Wear. The process a) has the same temperature range as the process of the present invention.
Can be done within In carrying out process a)
Is, for example, the presence of a base per mole of the compound of the formula (IV).
In the presence, from about 0.9 mole to about 1.1 mole of the compound of formula (V)
By reacting the amounts in an inert solvent, the compound of formula (IIa)
Can be obtained. Process b) generally comprises from about 0 ° C. to about 120 ° C.
C., preferably between about 30 C. and about 100 C.,
The reaction is preferably carried out under normal pressure,
Alternatively, the reaction can be performed under reduced pressure conditions. Production method b)
In carrying out, for example, 1 mole of the compound of formula (VI)
On the other hand, the compound of the formula (VII) is equimolar to about 1.2-fold molar.
Amount, preferably equimolar to about 1.1 times the molar amount, e.g.
Easily by reacting while heating in
The following compound of formula (IIa) can be obtained. Production method c)
Is, for example, between about 0 ° C. and the boiling point of the mixture, preferably 0 ° C.
~ 100 ° C, and the reaction is carried out under normal pressure.
Although it is preferable to use
You can also. In carrying out the production method c), for example,
For example, 1 mole of the compound of the formula (VI) is
Is equimolar amount to about 1.2 times molar amount, preferably equimolar amount
About 1.1 times the molar amount of an inert solvent such as an alcohol (meth
(E.g., ethanol, ethanol)
Until life stops, the corresponding formula
Compound (IIa) can be obtained. The compound of formula (I) produced by the process of the present invention
Nitroimino or cyanoimino compounds are powerful insecticides
Show your business. Therefore, they can be used as insecticides.
Can be And, the activity of the formula (I) in the present invention
Compounds can be used without harm to cultivated plants.
Exhibits an effective control effect on insect pests. The present invention
The compound is a wide variety of pests, harmful sucking insects, chewing insects
And other plant parasitic pests, storage pests, sanitary pests, etc.
Can be used for control and applied for their eradication
it can. In addition, the formula (I) which is a raw material in the production method of the present invention.
In I), the compound of the formula (IIa) is, as described above,
A novel compound which is of the formula (I)
Industrially useful as an intermediate for the production of anoimino compounds
In addition, the compound of formula (IIa) itself is an insecticide
It is useful as an indicator. Next, according to the embodiment,
The content of the present invention will be specifically described, but the present invention
It should not be limited to. [0055] 【Example】 Production Example:- Example 1 Embedded image 1- {2- (3,5-dichloropyridyl-2-yloxy)
B) 3.2 g of ethyl @ 2-nitroiminoimidazolidine
Was dissolved in 20 ml of dimethylformamide, and
% Of sodium hydride and stop generating hydrogen
And stir. Next, 2-chloro-5-chloromethylthiazo
1.7 g at room temperature followed by 40 minutes at room temperature for 1 hour.
Stir at 30 ° C for 30 minutes. After the reaction, pour the contents into ice water,
Extract with chloromethane. Dichloromethane from extract
After concentration and addition of ether to the residue, the target product becomes crystals
And washed with ether and dried. 2.7 g yield,
mp. 77-80 ° C Embodiment 2 Embedded image1- (3,3-dimethyl-2-butan-1-yl)-
2-cyano imino imidazolidine 2.1 g, 2-chloro
1.6 g of -5-chloromethylpyridine, anhydrous potassium carbonate
And stirred a mixture of 1.4 g of acetonitrile and 30 ml of acetonitrile.
While refluxing for 8 hours. Reduce acetonitrile after reaction
After distilling off under reduced pressure, dichloromethane is added to the residue and washed with water. The
After concentrating chloromethane, a silica gel column (chloroform
Colorless viscous object when purified by using
0.9 g are obtained. n_D ²⁰1.5446 According to the same method as in Example 1, the synthesis
Representative examples of the compounds of the formula (I) which can be
Are shown in Table 1. Embedded image In Table 1, “←” in the column of “← A-” represents the above formula.
(I) Naka group: Embedded image Shows a bond to the N-atom to be 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]Example of intermediate synthesis: Example 3 Embedded image 2.6 g of 2-nitroiminoimidazolidine, anhydrous carbonic acid
A mixture of 3.0 g of dry acetonitrile and 30 ml of dry acetonitrile.
Stirred at room temperature for 30 minutes, then 1-chloro-3,3-dimethyl
2.7 g of 2-butanone are added at room temperature with stirring.
Subsequently, the contents are heated and refluxed for 1 hour. Acetonit
Lil was distilled off under reduced pressure, water was added to the residue, and the desired product was collected by filtration.
The crystals are washed with ether and dried to give 1- (3,3-dimethyl).
Ru-2-butan-1-yl) -2-nitroiminoimi
3.5 g of dazolidine are obtained. mp. 158-159
° C Embodiment 4 Embedded image 2.2 g of 2-cyanoiminoimidazolidine was dried with
Dissolved in 20 ml of formamide and 60%
1.7 g of sodium hydride are added in small portions. Hydrogen emission
After stirring at 0 ° C until the mixture stops growing, propionyl chloride
1.9 g is added dropwise while maintaining the temperature at 0 ° C. or lower. Room after dripping
Stir for a while at room temperature, add the contents to ice water and neutralize with hydrochloric acid
I do. Then extract with dichloromethane and concentrate the extract.
If the desired product crystallizes out and precipitates, it is collected by filtration and washed with ether.
If washed, 2-cyanoimino-1-propionylimidazoly
1.4 g of gin are obtained. mp. 208-210 ° C Embodiment 5 Embedded image2.6 g of 2-nitroiminoimidazolidine,
60% sodium hydride in room temperature
And the mixture is stirred until hydrogen evolution stops. Continued
And add 3.6 g of 2,3,5-trichloropyridine
Stir at 100-120 ° C. for 7 hours. After cooling to room temperature
Pour into ice water, filter off the desired crystals, and add a small amount of ethanol.
Wash with knol and ether. Yield 2.2 g mp. Fifteen
1 to 155 ° C Embodiment 6 Embedded image N-allylethylenediamine [Journal American
  Chemical Society (J. Am. Chem. Sc)
i. ), Vol. 67, pp. 1581-1582] 2 g, N
-Nitro S-methylisothiourea 2.7 g, ethanol
Is stirred at 60 ° C. for 3 hours. room temperature
After cooling to room temperature, the resulting crystals were collected by filtration, and a small amount of ethanol
And then dry. Yield 1.4 g mp. 86-90
° C Embodiment 7 Embedded image 3.6 g of N-2-phenoxyethylethylenediamine,
Dimethyl N-cyanodithioimino carbonate 2.9
g, and a solution of 50 ml of ethanol was gradually added with stirring.
Heat, then reflux until methyl mercaptan generation stops
Let it. After the reaction, about 2/3 of the ethanol was distilled off, and the remaining liquid was removed.
If the target is cooled, the target product precipitates as crystals.
dry. Yield 3.6 g mp. 93-95 ° C According to the same method as in the above intermediate synthesis example,
Representative examples of the compounds of the formula (II) that can be synthesized are described in Examples 3 to
The results are shown in Table 2 together with the compound No. 7. Embedded image In Table 2, “←” in the column of “← A-” indicates the above equation.
As shown, the bond between the hydrogen atom and the N atom
You. [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 on organic phosphorus resistant leafhopper leafhopper Preparation of reagent solution Solvent: 3 parts by weight of xylol Emulsifier: polyoxyethylene alkyl phenyl ether
1 part by weight Single unit active compound (s) to form an appropriate active compound formulation
Mix the parts by weight with the amount of solvent containing the amount of emulsifier
Then, the mixture was diluted with water to a predetermined concentration. Test method: planted in a 12 cm diameter pot
Activated compound prepared as above on rice with plant height of about 10cm
Spray 10ml per pot of water dilution of specified concentration
Was. After drying the spray liquid, gold 7cm in diameter and 14cm in height
Cover the net with a system that is resistant to organophosphates.
Release 30 female adults of the black leafhopper, placed in a constant temperature room
After 24 hours, the number of dead insects was examined and the mortality was calculated. Embodiment 9 Tests against stag beetle To rice of about 10cm in height planted in a 12cm diameter pot,
A predetermined concentration of the active compound prepared in the same manner as in Example 8
10 ml of the water dilution was sprayed per pot. Spray medicinal solution
After drying, cover with a wire mesh of 7cm in diameter and 14cm in height.
Females of the brown planthopper, strains showing resistance to organophosphates in the soil
Release 30 adults and place them in a constant temperature room. After 2 days, count the number of dead insects.
In addition, the insecticidal rate was calculated. In the above biological test,
The compounds of formula (I) exemplified in Table 1 are, for example,
With a concentration of 200 ppm, it shows an accurate insecticidal effect
Even at lower concentrations, it shows excellent insecticidal effects.
You.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C07D 233/20 C07D 233/20 233/22 233/22 401/04 401/04 401/06 401/06 401/12 401/12 403/04 403/04 403/06 403/06 403/12 403/12 405/04 405/04 405/06 405/06 405/12 405/12 409/04 409/04 409/06 409/06 409 / 12 409/12 411/06 411/06 413/04 413/04 413/06 413/06 417/04 417/04 417/06 417/06 417/12 417/12 (72) Inventor Katsuhiko Shibuya Hachioji, Tokyo 39-15 Ichinamiki-cho (56) Reference European publication 192060 (EP, A1) German publication 2205745 (DE, A1)

Claims (1)

(57) [Claims] Embedded image [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 mono-substituted by any substituent selected from halogen and 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 C2 to C6 alkoxyalkyl group, C2 to C6 alkylthioalkyl group, C2 to C6 alkylsulfinylalkyl group, C2 to C6 alkylsulfonylalkyl group, C1 to C3 (Wherein the substituent is selected from halogen, nitro, alkyl having 1 to 4 carbons, haloalkyl having 1 to 4 carbons, and haloalkoxy having 1 to 4 carbons) Phenoxy, halogen, nitro, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 haloalkoxy which may be substituted Good phenylthio, halogen-substituted pyridyloxy, halogen and / or cycloalkyl having 3 to 6 carbons which may be substituted by alkyl having 1 to 4 carbons, pyridylthio optionally substituted with halogen, thiazolylthio, Benzyloxy, thiocyanato, dialkylamino having 2 to 6 total carbon atoms, alkoxyalkoxy having 2 to 4 total carbon atoms, anilino which may be substituted by halogen and / or 1 to 4 carbon atoms, halogen and / or carbon number Pyridylamino, cyano, which may be substituted by 1-4 alkyl, C2-C2 Alkyl carbonyl, halogen-substituted benzoyl, haloalkyl carbonyl having 1 to 3 carbon atoms, pyridyl carbonyl, alkoxycarbonyl having 1 to 4 carbon alkyl, halogen and / or 1 carbon atom Phenoxycarbonyl, benzyloxycarbonyl, carbamoyl, alkylaminocarbonyl having 1 to 3 carbons, dialkylaminocarbonyl having 2 to 6 carbons, phenylaminocarbonyl, hydroxy, 1 to 4 carbons which may be substituted by Alkylcarbonyloxy having 3 alkyl and optionally substituted halogen, benzoyloxy, alkylsulfonyloxy having 1 to 4 carbon atoms, tosyloxy,
Dialkylaminocarbonyloxy having alkyl having 1 to 3 carbon atoms, phosphate residue, thiophosphate residue, amide thiophosphate residue, total carbon number of 4 to
5, optionally selected from the group consisting of a 9- or 10-membered fused heterocyclic group containing at least one selected from tolumethylsilyl and a heteroatom consisting of N, O, S and which may be substituted. Wherein the substituent for the 9- or 10-membered fused heterocyclic group is halogen, alkyl having 1 to 4 carbons, haloalkyl having 1 to 4 carbons, phenyl, nitroimino, keto, An alkylthio having 4 carbon atoms or an alkoxy having 1 to 4 carbon atoms), or a phenyl group which may be substituted (here, the substituent is optionally selected from halogen, alkyl having 1 to 3 carbon atoms and nitro) Or an optionally substituted 5- or 6-membered heterocyclic group or 9- or 10-membered heterocyclic group containing at least one selected from heteroatoms consisting of N, O and S (Wherein the cyclic group may have the same substituent as in the case of the above-mentioned phenyl), an alkenyl group having 3 to 4 carbon atoms which may be substituted by halogen, halogen Optionally substituted propargyl group, alkoxy group having 1 to 4 carbon atoms, cyano group, phenoxy group, benzyloxy group, 2 carbon atoms
Alkenyloxy group having 1 to 3 carbon atoms, alkylthio group which may be substituted with halogen 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 of 2 A dialkylamino group having 6 to 6 carbon atoms; an alkylcarbonyl group having 2 to 6 carbon atoms; an alkylcarbonyl group having 1 to 4 alkyl atoms and having a substituent (where the substituent is halogen, Arbitrary from alkoxy having 1 to 4 carbons, alkylthio having 1 to 4 carbons, alkylcarbonyloxy having 1 to 4 alkyls, halophenoxy, phenyl, cyano, and alkylcarbonyl having 1 to 2 carbons Selected from the group consisting of :), halogen and / or carbon number which may be substituted by alkyl having 1 to 4 carbons 6 cycloalkyl group, the optionally substituted benzoyl group (wherein the substituent, halogen, alkyl of 1 to 4 carbon atoms, atoms 1
Which is arbitrarily selected from alkoxy, nitro, haloalkyl having 1 to 4 carbon atoms, alkylcarbonylamino having alkyl having 1 to 4 carbon atoms, and alkoxyalkoxy having 2 to 4 carbon atoms). An alkenylcarbonyl group having an alkenyl having 2 to 4 carbon atoms, an alkynylcarbonyl group having an alkynyl having 2 to 3 carbon atoms, (Where U ² represents a 5- or 6-membered heterocyclic group or a 9- or 10-membered condensed heterocyclic group containing at least one member selected from the group consisting of N, O, and S). Is halogen, alkyl having 1 to 4 carbons, 1 to carbons
4 haloalkyl, phenyl, nitro, alkylthio having 1 to 4 carbon atoms and keto), which may have a substituent and having 1 to 3 carbon atoms. Wherein the substituent includes halogen, alkoxy having 1 to 2 carbons, alkylthio having 1 to 2 carbons, dialkylamino having 2 to 4 carbons, hydroxy, alkylthio having 1 to 2 carbons , Halophenoxy), a cycloalkoxycarbonyl group having a cycloalkyl having 3 to 7 carbon atoms which may be substituted by an alkyl having 1 to 4 carbon atoms, a phenoxycarbonyl group having a substituent ( Here, examples of the substituent include halogen, alkyl having 1 to 4 carbons, haloalkyl having 1 to 4 carbons, cyano, and 1 to 4 carbons. From alkylthio, alkoxy having 1 to 4 carbons, nitro, alkylsulfinyl having 1 to 4 carbons, alkoxycarbonyl having an alkyl having 1 to 4 carbons, pyridyloxy substituted by halogen and / or trihaloalkyl. A benzyloxycarbonyl group which may be substituted, wherein the substituent is any of halogen, haloalkyl having 1 to 2 carbon atoms, alkoxy having 1 to 4 carbon atoms, and phenoxy A phenylthiocarbonyl group, an alkylthiocarbonyl group having an alkyl having 1 to 4 carbons, an alkenyloxycarbonyl group having an alkenyl having 2 to 4 carbons which may be halogen-substituted, Having optionally substituted alkynyl having 2 to 4 carbon atoms Leoxycarbonyl group (Where Q ¹ represents a 5- or 6-membered heterocyclic group or a 9- or 10-membered condensed heterocyclic group containing at least one heteroatom selected from N, O and S, wherein the ring is The formula group may be substituted by any selected from the group consisting of halogen, alkyl having 1 to 4 carbons, phenyl, keto and haloalkyl having 1 to 4 carbons), carbamoyl group, 1 to 4 carbons An alkylaminocarbonyl group having an alkyl of 3; a cycloalkylaminocarbonyl group having a cycloalkyl having 3 to 6 carbon atoms; a phenylaminocarbonyl group which may be substituted (here, the substituent includes halogen, And any one selected from alkoxy having 1 to 4 carbon atoms and alkoxy having 1 to 4 carbon atoms), dialkylaminocarboni having alkyl having 2 to 8 carbon atoms in total Group, (Where G represents a 5- or 6-membered heterocyclic group or a 9- or 10-membered condensed heterocyclic group containing at least one heteroatom selected from N, O, and S), Is halogen, alkyl having 1 to 4 carbons, 1 to 4 carbons
Alkoxy, haloalkyl having 1 to 4 carbons, 1 carbon
N is 0 or 1, and R 'is a hydrogen atom or an alkyl having 1 to 4 carbons), which may be substituted. A good piperidinocarbonyl group (here, the substituent represents alkyl having 1 to 4 carbon atoms); a morpholinocarbonyl group which may be substituted (here, the substituent has 1 to 4 carbon atoms). Alkyl), a pyrrolidinocarbonyl group, a benzylaminocarbonyl group which may be methyl-substituted, a mono- or di-alkenylaminocarbonyl group having 2 to 3 carbon atoms, and an alkynyl having 2 to 3 carbon atoms. Alkynylaminocarbonyl group, halogen-substituted alkylsulfonyl group having 1 to 4 carbon atoms, phenyls which may be substituted Honyl group (here, the substituent is any selected from halogen, alkyl having 1 to 4 carbon atoms and nitro), alkoxysulfonyl group having 1 to 4 carbon atoms, cycloalkoxysulfonyl having 3 to 6 carbon atoms A mono- or di- (alkyl having 1 to 4 carbon atoms) aminosulfonyl group, a phenylaminocarbonyl group which may be substituted with methyl, an O, O-di- (alkyl having 1 to 4 carbon atoms) phosphono group, O, O-di- (alkyl having 1 to 4 carbon atoms) thiophosphono group, O, S-di- (alkyl having 1 to 4 carbon atoms) thiophosphono group, O- (alkyl having 1 to 4 carbon atoms) -O- (Phenyl which may be substituted by halogen) thiophosphono group, O, N-di- (alkyl having 1 to 4 carbon atoms) amide thiophosphono group, alkoxyxaryl group having 1 to 4 carbon atoms, halogen-substituted There may be Fenokisariru group, a benzyl oxalyl group, or ## STR5 ## Wherein Y represents a cyano group, and A ¹ represents trimethylene.
And except when Z ¹ represents hydroxypropyl,
Further , except for the case where Y represents a cyano group and Z ¹ represents a phenyl group which may be substituted as defined above,
Represents a nitro group, and Z ¹ is a haloalkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 2 to 6 total carbon atoms, an alkylthioalkyl group having 2 to 6 total carbon atoms, a total carbon number of 2 Dialkylamino-substituted carbon atoms of 1-3
An alkyl group, a halogen-substituted alkenyl group having 3 to 4 carbon atoms, a halogen-substituted propargyl group, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group, an alkyl group having 2 to 6 carbon atoms alkylcarbonyl group having, having an alkyl of 1 to 4 carbon atoms, and an alkylcarbonyl group having a substituent, an optionally substituted benzoyl group, -CO-U ^{2 (U} 2 is as defined above), halogen Substituted alkoxycarbonyl group having 1 to 3 carbon atoms, substituted phenoxycarbonyl group, optionally substituted benzyloxycarbonyl group, phenylthiocarbonyl group, alkylthiocarbonyl group having 1 to 4 carbon atoms An alkylsulfonyl group having 1 to 4 carbon atoms which may be halogen-substituted, -Di- (C1-4 alkyl) phosphono group, O, O-di- (C1-4 alkyl) thiophosphono group, O, S-di- (C1-4 alkyl) thiophosphono group An O- (alkyl having 1 to 4 carbons) -O- (phenyl which may be substituted by halogen) thiophosphono group, or O,
Excluding the case of showing an N-di- (alkyl having 1 to 4 carbon atoms) amidothiophosphono group. ] The heterocyclic compound represented by these.