JPH07196653A - New heterocyclic compound - Google Patents

Abstract

PURPOSE:To obtain a new heterocyclic compound of a specific formula useful for exterminating and destroying various insect pests exhibiting proper control effects without providing cultured plants with phytotoxicity. CONSTITUTION:The compound of formula I [R<1> is H or an alkyl; A is an (alkyl- substituted) ethylene or trimethylene; X is S; Z is a (1-4C alkyl-substituted) 3- or 4-pyridyl], to be concrete, 1(2-chlori-5-pyridylmethyl)-2- cyanoiminoimidazoline. The compound, for example, is preferably obtained by reacting a compound of formula II with a compound of formula III [M<1> is a halogen, OSO2-M<2> (M<2> is a lower alkyl or aryl)] to be concrete 2- nitroiminothiazolidine, etc., with 2-chloro-5-pyridylmethyl chloride, etc.

Description

Detailed Description of the Invention

The present invention relates to novel heterocyclic compounds useful, for example, as insecticides.

More specifically, the present invention relates to a novel heterocyclic compound represented by the formula below. formula:

[0003]

[Chemical 3]

In the formula, R ¹ represents a hydrogen atom or an alkyl group, A represents an optionally substituted ethylene group or an optionally substituted trimethylene group, An atom, an optionally substituted alkyl group, an alkenyl group, an alkynyl group, or an acyl group, R ³ represents a hydrogen atom or an alkyl group, and Z is the same or selected from an oxygen atom, a sulfur atom and a nitrogen atom. 5 represents an optionally substituted 5- or 6-membered heterocyclic group containing at least two different heteroatoms or an optionally substituted 3- or 4-pyridyl group.

The compound of the above formula (I) can be produced, for example, by the following method.

Manufacturing method a) Formula:

[0007]

[Chemical 4]

In the formula, A and X are the same as defined above, and a compound of the formula:

[0009]

[Chemical 5]

In the formula, R ¹ and Z are the same as defined above, M ¹ is a halogen atom or a group —OSO ₂ —M ² , and M ² is a lower alkyl group or an aryl group. The method for producing the compound of formula (I), wherein

Formula b) Formula

[0012]

[Chemical 6]

Wherein R ¹ , A and Z are the same as defined above, An optionally represented alkyl group, an alkenyl group or an alkynyl group, and a compound of the formula: (R′-S) ₂ C═N-CN (V) where R ′ is a lower alkyl group or a benzyl group. Or two R's together represent a C ₂ or higher lower alkylene group which may form a ring with the adjacent sulfur atom. Characterized expressions:

[0014]

[Chemical 7]

Wherein R ¹ , A, X ¹ and Z are the same as defined above,
A method for producing the compound represented by.

Manufacturing method c)

[0017]

[Chemical 8]

In the formula, R ¹ , A and Z are the same as defined above, and a compound of the formula: R ⁵ -Hal (VI) wherein R ⁵ represents an acyl group and Hal represents a halogen atom. , Characterized by reacting with a compound represented by:

[0019]

[Chemical 9]

Wherein R ¹ , A, Z and R ⁵ are the same as defined above,
A method for producing the compound represented by.

The novel heterocyclic compound of formula (I) of the present invention has, for example, high insecticidal activity, and the present invention also relates to an insecticide containing the compound as an active ingredient.

Japanese Patent Application Laid-Open No. 48-9106, which is known before the filing date of the present application
No. 4 discloses a compound represented by the following general formula, which is useful as an intermediate in the production of bactericidal, antidiabetic, virus-sedative and diuretic active substances. Has been done.

[0023]

[Chemical 10]

(Wherein the groups R ₁ and R ₂ are a hydrogen atom or a linear or branched lower alkyl group having 1 to 4 carbon atoms, ..., R ₃ and R ₄ Is a hydrogen atom, a linear or branched lower alkyl group having 1 to 4 carbon atoms, ..., R ⁵ is a hydrogen atom,
Linear or branched lower alkyl group having 1 to 6 carbon atoms, hydroxyalkyl group having 2 to 3 carbon atoms, halogen atom, lower alkyl or alkoxy having 1 or 2 carbon atoms Represents a phenyl group optionally mono- or di-substituted by a group, a benzyl or phenethyl group optionally mono-substituted by a halogen atom ..., X is an oxygen or sulfur atom or a nitrogen atom thereof Is a linear or branched lower alkyl group having 1 to 4 carbon atoms or benzyl or an optionally substituted imino group, and n
However, from the definition of R ⁵ and X in the above formula [W], the compound of the above formula (I) of the present invention cannot be included, and the publication discloses that the insecticidal activity is Is neither mentioned nor suggested.

Similarly, Japanese Patent Application Laid-Open No. 59-196877, which is publicly known prior to the filing date of the present application, discloses the following formula:

[0026]

[Chemical 11]

A thiazolidine derivative represented by the formula is described, and it is described that the compound of the formula (Q) has an antitumor activity against gastrointestinal ulcer. Then, in the formula (Q), Ar is 2-
Furyl, phenyl, naphthyl or pyridyl groups [these are optionally one or more C _1-4 alkyl, C
_1-6 alkoxy, halogen-C _1-4 alkoxy, di- or trihalomethyl, hydroxy and / or nitro groups or of the formula

[0028]

[Chemical 12]

May be substituted by
Y = indicating nitrogen or CH, and when Y = nitrogen, Z = cyano or carbamoyl; when Y = CH, Z =
It is a nitro group. And in the specification, for example, 2-cyanoimino-3- (6-methyl-
2-Pyridylmethyl) -thiazolidine is described.

[0030]

[Chemical 13]

The definition of the group Ar of the compound of the formula (A) in the above-mentioned Japanese Patent Application Laid-Open No. 59-196877 and the portion "corresponding to the group Z corresponding to the group Z specified in the compound of the formula (I) of the present invention. As is clear from the comparison with “optionally 3- or 4-pyridyl group”, in the compound of the formula (I) of the present invention, some compounds can be included in the general concept of the above-mentioned general formula (Q).

However, the proposal is based on the formula (I) of the present invention.
Compounds that overlap with compounds are not specifically described at all.

The above-mentioned formula (I) is included in the general formula (Q) proposed in JP-A-59-196877, including some compounds which are not specifically described in the proposal. The invention compound was successfully synthesized. Then, it has been discovered that the compound represented by the formula (I) which has not been described in any conventionally known document is a very useful compound for solving a new technical problem of pest control which the publication does not mention at all. . According to the study of the present inventors, as shown later for many example compounds in comparison with the related comparative compounds described in the above publications, the compound of the formula (I) of the present invention has an insecticidal activity. In addition, it was discovered that it has a totally unexpected and extremely excellent action effect.

Furthermore, in addition to the above-mentioned strong insecticidal activity, the compound of the formula (I) of the present invention is resistant to these insecticides resulting from the use of organophosphorus and carbamate insecticides for many years. Pests, especially Hemiptera (Hemi
It has been discovered that it exerts a remarkable control effect on pricking and absorption pests represented by ptera) such as aphids, planthoppers and leafhoppers.

Therefore, the object of the present invention is to provide a novel heterocyclic compound having an insecticidal activity.

The above objects and many other objects and advantages of the present invention will become more apparent from the following description.

In the formula (I) of the compound of the present invention, preferably R ¹ represents a hydrogen atom or a methyl group, A represents an optionally substituted ethylene group or a trimethylene group, Child, optionally substituted alkyl group having 1 to 4 carbon atoms
(Wherein the substituent is any selected from halogen, alkoxy having 1 to 4 carbons, alkylthio having 1 to 4 carbons and cyano), alkenyl having 2 to 4 carbons, alkynyl having 2 to 4 carbons. Group, halogen and / or pyridylmethyl group optionally substituted with methyl, halogen and / or
Or a benzyl group optionally substituted with methyl, a formyl group, an alkylcarbonyl group having an alkyl having 1 to 2 carbon atoms optionally substituted with halogen, a phenyl optionally substituted with halogen and / or methyl. A carbonyl group, an alkoxy- or alkylthio-carbonyl group having an alkyl group having 1 to 4 carbon atoms, a phenoxycarbonyl group, an alkylsulfonyl group having 1 to 2 carbon atoms which may be substituted with halogen, or substituted with methyl. Represents a phenylsulfonyl group, R ³ represents a hydrogen atom,
And Z contains 2-3 same or different heteroatoms selected from oxygen atom, sulfur atom and nitrogen atom, and at least one of them is a nitrogen atom.
Or 6-membered heterocyclic group or 3-pyridyl group, wherein the heterocyclic group and 3-pyridyl group are a halogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. Group, alkylthio group having 1 to 4 carbon atoms, 1 to carbon atoms
It may be substituted with at least one selected from a haloalkyl group having 4 carbon atoms, a haloalkoxy group having 1 to 4 carbon atoms, an alkylsulfonyl group having 1 to 4 carbon atoms, a cyano group and a nitro group.

Further, in the formula (I), particularly preferably, R ¹ represents a hydrogen atom, A represents an ethylene group or trimethylene group, Z is a 5-membered or 6-membered heterocyclic group containing two identical or different heteroatoms selected from an oxygen atom, a sulfur atom and a nitrogen atom, and at least one of which is a nitrogen atom, or 3- Represents a pyridyl group, wherein the heterocyclic group and the 3-pyridyl group are a fluorine atom, a chlorine atom, a bromine atom, a methyl group, a methoxy group, a methylthio group, trifluoromethyl, trifluoromethoxy,
It may be substituted with at least one selected from a methylsulfonyl group, a cyano group and a nitro group.

Incidentally, 3-pyridyl in the definition of Z is
Structurally, it has the same meaning as 5-pyridyl.

The following compounds may be mentioned as specific examples of the compound of the formula (I) of the present invention. That is, 1- (2-chloro-5-pyridylmethyl) -2-
Cyanoimino imidazolidine, 1- (2-fluoro-5
-Pyridylmethyl) -2-cyanoiminoimidazolidine, 1- (2-chloro-5-pyridylmethyl) -2-cyanoiminotetrahydropyrimidine, 1- (2-methyl-
5-pyridylmethyl) -2-cyanoiminoimidazolidine, 1- (2-chloro-5-thiazolylmethyl) -2-cyanoiminoimidazolidine, 1- (2-chloro-5-thiazolylmethyl) -2-cyanoiminotetrahydropyrimidine , 1- (2-methyl-5-pyrazinylmethyl) -2
-Cyanoiminoimidazolidine, 1- (2-chloro-5
-Pyridylmethyl) -2-cyanoiminothiazolidine,
1- (2-chloro-5-pyridylmethyl) -2-cyanoiminotetrahydro-2H-1,3-thiazine, 1- (2-
Chloro-5-thiazolylmethyl) -2-cyanoiminothiazolidine, 1- (2-methyl-5-pyrazinylmethyl)
-2-cyanoiminothiazolidine, 1- (2-methyl-
5-thiazolylmethyl) -2-cyanoiminothiazolidine, 1- (1,2,5-thiadiazol-3-yl) -2-
Cyanoimino thiazolidine. When 2-nitroiminothiazolidine and 2-chloro-5-pyridylmethyl chloride are used as the raw materials in the above-mentioned production method a) of the compound of the formula (I) of the present invention, they are represented by the reaction formulas shown below.

[0041]

[Chemical 14]

In the above-mentioned production method b) of the compound of the formula (I) of the present invention, when N- (2-chloro-5-pyridylmethyl) ethylenediamine and dimethylcyanodithioimide carbonate are used as raw materials, the reaction shown below is carried out. It is represented by a formula.

Manufacturing method b):

[0044]

[Chemical 15]

In the above-mentioned production method c) of the compound of the formula (I) of the present invention, when 1- (2-chloro-5-pyridylmethyl) -2-cyanoiminoimidazolidine and acetyl chloride are used as raw materials, It is represented by the reaction formula shown below.

Manufacturing method c)

[0047]

[Chemical 16]

In the above production method a), the compound of the formula (II) as a raw material is meant to be based on the above definition of each of A and X. Each of A and X preferably has the same meaning as the above-mentioned preferable definition.

Compounds of formula (II) include known compounds.

2-cyanoiminoimidazolidine and 2-
Cyanoiminotetrahydropyridine is described in J. Org. Che
m. (Journal Organic Chemistry), 38
Vol., Pp. 155-156, and is easily obtained by the reaction of dimethylcyanodithioimide carbonate with ethylenediamine or trimethylenediamine. Similarly, by reacting with N-substituted ethylenediamine other than an acyl group or trimethylenediamine, the corresponding 3-substituted-2-cyanoiminoimidazolidine or 3
A -substituted-2-cyanoiminotetrahydropyrimidine is obtained.

If an aminoalkanol is used instead of the alkylenediamine, the corresponding oxazolidine or 1,3-oxazine derivative can be obtained (JP-A 48-48).
91064).

2-Cyanoiminothiazolidine is available as Arc
h. Pharm. (Architecture Pharmacology), 3
Vol. 05, pp. 731-737.
Reaction of aminopropanethiol with dimethylcyanodithioimide carbonate gives 2-cyanoiminotetrahydro-1,3-thiazine.

2-Cyanoiminopyrrolidine is described in Khim.
Farm. Zh. Vol. 19, pp. 154-158, and is easily obtained by the reaction of 2-methoxypyrroline-2 with cyanoamide. Similarly, 2-methoxy-3,4,
From 5,6-tetrahydropyridine and cyanoamide, 2
A cyanoiminopiperidine is obtained.

Similarly, the compound of the formula (III) as a raw material means a compound based on the above-mentioned definitions of R ¹ , Z and M ¹ . R ¹ and Z each preferably have the same meaning as defined above, and M ¹ preferably represents a chloro atom or a bromine atom.

The compound of the formula (III) can be obtained by the same applicant as that of the present application, for example, in Japanese Patent Application Laid-Open No. 61-189881 (Japanese Patent Application No. 60-18627) and Japanese Patent Application No. 61-18628 (Japanese Patent Application No. Sho 61-18628). 60-18628), JP-A-61-267.
No. 561 (Japanese Patent Application No. 60-10267561), and specific examples thereof include:
2-Fluoro-5-pyridylmethyl chloride, 2-chloro-5-pyridylmethyl chloride, 2-bromo-5
-Pyridylmethyl chloride, 2-methyl-5-pyridylmethyl chloride, 2-chloro-5-thiazolylmethyl chloride, 2-methyl-5-pyrazinylmethyl chloride, 2-methyl-5-oxazolylmethyl chloride Examples include 1,2,5-thiadiazol-3-ylmethyl chloride, 3-methyl-5-isoxazolylmethyl chloride and 2-chloro-5-pyrimidinylmethyl chloride.

In the above-mentioned production method b), the compound of the formula (IV) as a raw material means the compound based on the definition of each of R ¹ , A and Z described above. R ¹ , A and Z each preferably have the same meaning as defined above.

The compound of the formula (IV) is disclosed in Japanese Patent Application Laid-Open No. 61-189881 (Japanese Patent Application No. 60-18627) and Japanese Patent Application Laid-Open No. 61-18628 (Japanese Patent Application No. JP-A-60-18628), JP-A-61-18332.
71 (Japanese Patent Application No. 60-23683, Japanese Patent Laid-Open No. 61-
267561 (Japanese Patent Application No. 60-106853) and Japanese Patent Laid-Open No. 62-81382 (Japanese Patent Application 60-219).
No. 082), and specific examples thereof include N- (2-chloro-5-pyridylmethyl).
-, N- (2-fluoro-5-pyridylmethyl)-, N-
Examples include (2-methyl-5-pyridylmethyl)-, N- (2-methyl-5-thiazolylmethyl) -N- (2-methyl-5-pyrazinylmethyl) -ethylenediamine, trimethylenediamine, and the like, and 2- (2-chloro-
5-pyridylmethyl) aminoethanethiol, 3- (2-
Examples include chloro-5-pyridylmethyl) aminopropanethiol, 2- (2-chloro-5-thiazolylmethyl) aminoethanethiol, and 2- (2-methyl-5-pyrazinylmethyl) aminoethanethiol.

The compound of the formula (V) as the raw material was prepared according to J. Org. Che
m. , 32, pp. 1566-1572.

In the above production method c), the compound of the formula (Ib) as a raw material is included in the formula (I) of the present invention which can be produced by the above production method a) or b).

Similarly, the compound of the formula (VI) which is the starting material is a compound well known in the field of organic chemistry, and specific examples thereof include, for example, propionyl chloride, acetyl chloride, chloroacetyl chloride, methylsulfonyl chloride, tosyl. Examples thereof include chloride and methoxycarbonyl chloride.

In carrying out the process a) mentioned above, use may be made, as suitable diluent, of any inert solvent.

Examples of such diluents are aliphatic, cycloaliphatic and aromatic hydrocarbons, which may optionally be chlorinated, for example 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; ketones such as acetone,
Methyl ethyl ketone, methyl-iso-propyl ketone,
Methyl-iso-butyl ketone; Nitriles such as acetonitrile, propionitrile, acrylonitrile; Esters such as ethyl acetate, amyl acetate; Acid amides such as dimethylformamide, dimethylacetamide;
Sulfones and sulfoxides, such as dimethyl sulfoxide and sulfolane, can be mentioned.

Further, the production method a) can react in the presence of a base, and examples of such a base include alkali metal hydrides such as sodium hydride and potassium hydride, and alkali metal hydroxides and carbonates. Can be mentioned.

The above-mentioned production method a) can be carried out within a wide temperature range. For example, it can be carried out at a temperature of about 0 to about 100 ° C, preferably about 10 to about 80 ° C. Further, the reaction is preferably carried out under normal pressure, but it is also possible to operate under increased pressure or reduced pressure. In carrying out the above-mentioned production method a), for example, 1 mol of the compound of the formula (II) is used,
By reacting the compound of I) in an equimolar amount to about 1.2-fold molar amount, preferably an equimolar amount to about 1.1-fold molar amount in an inert solvent such as dimethylformamide in the presence of a base. Thus, the desired compound of the general formula (I) can be obtained.

In carrying out the above-mentioned production method b), suitable diluents include all inert organic solvents exemplified in the production method a), as well as water and alcohols.

Process b) above can be carried out within a wide temperature range, for example between 0 ° C. and the boiling point of the mixture, preferably between about 0 ° C. and about 100 ° C.

The reaction is preferably carried out under normal pressure, but it may be carried out under pressure or reduced pressure.

In carrying out the above-mentioned production method b), for example, 1 mol of the compound of the formula (IV) is used, and an equimolar amount to about 1.2 times the molar amount of the compound of the formula (V) is used. Molar amount to about 1.
A one-fold molar amount, an inert solvent such as an alcohol (eg,
(Methanol, ethanol) in a solvent until the generation of mercaptan is stopped, by reacting the target general formula
The novel compound of (I) can be obtained.

In carrying out the above-mentioned production method c), as a suitable diluent, the same solvent as in the production method a) can be mentioned, and further, the reaction can be carried out in the presence of a base. Examples thereof include the same alkali metal hydrides as in a).

Process c) above can be carried out within a wide temperature range, for example between 0 ° C. and the boiling point of the mixture, preferably between about 0 ° C. and about 100 ° C.

The reaction is preferably carried out under normal pressure, but it may be carried out under pressure or reduced pressure.

The compound of the formula (I) of the present invention may exist in the form of a salt, and examples of the salt include inorganic acid salts, sulfonic acid salts, organic acid salts, metal salts and the like. Therefore, in the present invention, the novel heterocyclic compound of the formula (I) is a name including its salt form.

The compounds of formula (I) according to the invention exhibit a strong insecticidal action. Therefore, they can be used as insecticides. And the formula (I) active compound of the present invention,
It exerts an accurate control effect against harmful insects without giving any 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.

Examples of such pests include the following pests. Examples of insects include Coleoptera pests such as azuki bean weevils (Callosobruchus chinensis), weevil (Sitophilus zeamais), and stag beetles (Tr
obolium castaneum), Red-tailed tentacle (E)
pilachna vigintioctomaculata), Red-eye squirrel (Agriotes fuscicollis), Red beetle (Anomala)
rufocuprea), Colorado potato beetle (Leptinotars)
a decemlineata), Diabrotica (Diabrotica sp.
p.), pinewood chamomile (Monochamus alternatus),
Rice weevil (Lissorhoptrus oryzophilus), flat beetle (Lyctus bruneus); Lepidoptera, for example,
Maiga (Lymantria dispar), Umebu (Malaco)
soma neustria), caterpillar (Pieris rapae), Spodoptera litura (Spodoptera litura), Spodoptera litura (Mamestra b)
rassicae), Nikameichiyu (Chilo suppressalis),
Red corn borer (Pyrausta nubilalis), Black-necked moth (Ephestia cautella), Red beetle (Adoxophya)
es orana), codling moth (Carpocapsa pomonella), turnip moth (Agrotis fucosa), honey moth (Galleria)
mellonella), diamondback moth (Plutella maculipennis), citrus fruit moth (Phyllocnistis citrella); hemiptera, for example, leafhopper leafhopper (Nephotettix cincticeps),
Black planthopper (Nilaparvatalugens), scale insect (Pseudococcus comstocki), scale insect (Unaspis yanonensis), green peach aphid (Myzu)
persicae), apple aphid (Aphis pomi), cotton aphid (Aphis gossypii), radish aphid (Rhopalosiphum pseudobrassicas), nasi-gumbai
(Stephanitisnashi), Blue bug (Nazara spp.),
Whitefly (Cimex lectularius), Whitefly (Trial eurodes vaporariorum), Whitefly (Psylla)
spp. ); Orthoptera, for example, the German cockroach (Blate)
Lla germanica), American cockroach (Periplaneta amer)
icana), kerula (Gryllotalpa africana), and locust (Locu)
sta migratoria migratoriodes); Isoptera, for example,
Yamato termites (Deucotermes speratus), house termites (Coptotermes formosanus); Diptera, such as house flies (Musca domestica), netted mosquitoes (Aedes)
aegypti), Fly (Hylemia platura), Culex pipiens
(Culex pipiens), Sinama Daraka (Anopheles slne
nsis), Culex tritaeniorhynchu
s), etc. can be mentioned.

Furthermore, in the field of veterinary medicine, the novel compounds of the present invention are effective for use against various harmful animal parasites (internal and ectoparasites) such as insects and helminths. . Examples of such animal parasites include the following pests.

Examples of insects include the horsefly (Gastro)
pholus spp. ), Horn flies (Stomoxys spp.), Lice
(Trichodectes spp.), Triatomine (Rhodnius spp.)
p. ), Dog flea (Ctenocephalide scanis) and the like.

The active compounds of formula (I) according to the invention can be in the usual pharmaceutical forms. And as such a form, liquid agent, emulsion, suspension agent, powder agent, foam agent, paste,
Granules, aerosols, active compound-soaked lubricants-natural and synthetic, microcapsules, seed coatings, formulations with combustion devices (for example fumigation and fumes cartridges, cans and coils), and ULV [cold Mist (cold mist, warm mist).

These formulations can be manufactured by a known method. Such a process comprises, for example, applying an active compound to a developing agent, ie a liquid diluent; a liquefied gas diluent; a solid diluent, or a carrier, and optionally a surfactant, ie an emulsifier and / or a dispersant and And / or by using a foam forming agent and mixing. When water is used as the developing agent, for example, an organic solvent can also be used as an auxiliary solvent.

Liquid diluents or carriers generally include aromatic hydrocarbons (eg, xylene, toluene, alkylnaphthalene, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (eg, chlorobenzenes, ethylene chloride). , Methylene chloride etc.), aliphatic hydrocarbons [eg cyclohexane etc., paraffins (eg mineral oil fraction etc.)], alcohols (eg butanol, glycol and their ethers, esters etc.), ketones (eg , Acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone), a strong polar solvent (eg dimethylformamide, dimethylsulfoxide etc.) and water.

The liquefied gas diluent or carrier is a gas at normal temperature and pressure, and examples thereof include butane, propane, and the like.
There may be mentioned aerosol propellants such as nitrogen gas, carbon dioxide, and halogenated hydrocarbons.

As the solid diluent, soil natural minerals (for example, kaolin, clay, talc, chiyoke, quartz, attapal guide, montmorillonite, diatomaceous earth, etc.), soil synthetic minerals (for example, highly dispersed silicic acid, alumina, silicate). etc)
Can be mentioned.

Solid carriers for granules include ground and fractionated rocks (eg, calcite, marble, pumice, sepiolite, dolomite, etc.), synthetic particles of inorganic and organic powders, and organic materials (eg, , Sawdust, coconut coconut, corn cob, tobacco stem, etc.).

Examples of the emulsifier and / or foaming agent include nonionic and anionic emulsifiers [eg, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid alcohol ether (eg, alkylaryl polyglycol ether, alkyl sulfonate, alkyl sulfate). , Aryl sulfonates, etc.)], and albumin hydrolysis products.

Examples of the dispersant include lignin sulfite waste liquor and methylcellulose.

Adhesives may also be used in the formulation (powder, granules, emulsions) such as carboxymethylcellulose and natural and synthetic polymers (eg gum arabic, polyvinyl alcohol and polyvinyl acetate). Can be mentioned.

It is also possible to use colorants, which include inorganic pigments (for example iron oxide, titanium oxide and Prussian blue) and organic dyes such as alizarin dyes, azo dyes or metal phthalocyanine dyes, and In addition, trace elements such as salts of iron, manganese, boron, copper, cobalt, molybdenum, zinc can be mentioned.

The formulations generally contain 0.
It may be contained in an amount of 1 to 95% by weight, preferably 0.5 to 90% by weight.

The active compounds of formula (I) according to the present invention are in their commercially useful formulations and in the use forms prepared according to these formulations, other active compounds, such as insecticides, baits, fungicides. It can also be present as a mixture with agents, acaricides, centrifuges, fungicides, growth regulators or herbicides. Here, examples of the insecticide include organic phosphorus agents, carbamate agents, carboxylate agents, chlorinated hydrocarbon agents, and insecticidal substances produced by microorganisms.

Further, the active compound of formula (I) of the present invention can be present as a mixture with a synergist, and such preparations and usage forms include those which are commercially useful. it can. The synergist need not itself be active,
A compound that amplifies the action of an active compound.

The content of the active compounds of the formula (I) according to the invention in the commercially useful use forms can be varied within wide limits.

The concentration of the active compounds of formula (I) of the present invention in use is, for example, 0.000001 to 100% by weight, preferably 0.0001 to 1% by weight.

The compound of the formula (I) of the present invention can be used in a usual manner adapted to the use form.

When used in insect pests against hygiene pests, the active compounds are notable for their good residual stability on lime substances, as well as their excellent residual efficacy in wood and soil. Has been done.

Next, the contents of the present invention will be specifically described with reference to examples, but the present invention should not be limited to these.

[0095]

【Example】

 Manufacturing Example: Example 1

[0096]

[Chemical 17]

3.7 g of N- (2-chloro-5-pyridylmethyl) ethylenediamine and 1.3 g of dimethylcyanodithioimide carbonate are added to 50 ml of ethanol and the mixture is heated slowly with stirring and subsequently refluxed for 3 hours. After the reaction, ethanol is distilled off under reduced pressure to solidify the residue, which is crushed and washed with a mixed solution of ether and a small amount of ethanol. Yield after drying 3.5 g mp. 167 to 170 ° C. Example 2

[0098]

[Chemical 18]

2.0 g of N- (2-chloro-5-pyridylmethyl) cysteamine and 1.3 g of dimethylcyanodithioimide carbonate are added to 50 ml of ethanol, and the mixture is stirred and refluxed for 8 hours in a nitrogen gas stream. The approximately _^2/3 of the reaction after ethanol was distilled off under reduced pressure the residue was collected by filtration since the desired product if allowed to stand at room temperature come precipitates Te summer and crystals are washed and dried with ether. Yield 2.4 g mp. 128-129 ° C Example 3

[0100]

[Chemical 19]

A mixture of 2.5 g of 2-cyanoiminothiazolidine, 3.0 g of anhydrous potassium carbonate, 3.3 g of 2-chloro, 5-chloromethylthiazole and dry acetonitrile is refluxed for 3 hours with good stirring. After the reaction, acetonitrile was distilled off under reduced pressure, dichloromethane was added to the residue, and water and 1%
Wash with caustic soda solution. If the dichloromethane layer is dried and then concentrated, the desired product will be precipitated, so it is filtered and dried. Yield 3.3 g mp. 145 to 146 ° C. Example 4

[0102]

[Chemical 20]

2.2 g of 2-cyanoiminoimidazolidine was dissolved in 25 ml of dry dimethylformamide, 1 g of sodium hydride was added little by little at 10 ° C. or lower, and the mixture was stirred at 10 ° C. until the generation of hydrogen ceased. Then 2-chloromethyl 5
-Methylpyrazine 2.8g dimethylformamide 10ml
The solution is added dropwise at 10 ° C. After the dropping, the mixture is stirred for 1 hour at room temperature, then the content is added to ice water, and then the pH of the aqueous solution is adjusted to 7. The aqueous layer is extracted with dichloromethane, the dichloromethane layer is washed with water and dried. 1.8 g of the desired product is obtained by reconstituting the solid remaining after the concentration of dichloromethane with dilute ethanol. mp. 144-147 ° C

[0104]

[Chemical 21]

1- (2-chloro-5-pyridylmethyl)-
2.4 g of 2-cyanoiminoimidazolidine is dissolved in 30 ml of dry dimethylformamide, 0.26 g of sodium hydride is added at 10 ° C., and the mixture is stirred at room temperature until hydrogen evolution stops. Next, add 1.4 g of benzoyl chloride and add 4 parts to the contents.
After stirring at 0 ° C for 30 minutes, pour into ice water. The aqueous layer is extracted with dichloromethane, the dichloromethane layer is washed with water, and the dichloromethane is concentrated. The desired product can be obtained by purifying the residue by silica gel column chromatography. Yield 1.3g m
p. 158 to 161 ° C The compounds shown in Table 1 below were obtained in the same manner as in Examples 1 to 5 above. In addition, the compounds obtained in Examples 1 to 5 are also shown in Table 1.

[0106]

[Table 1]

[0107]

[Table 2]

[0108]

[Table 3]

[0109]

[Table 4]

[0110]

[Table 5]

[0111]

[Table 6]

[0112]

[Table 7]

[0113]

[Table 8]

[0114]

[Table 9]

[0115]

[Table 10]

[0116]

[Table 11]

[0117]

[Table 12]

[0118]

[Table 13]

[0119]

[Table 14]

[0120]

[Table 15]

[0121]

[Table 16]

Biological test:-

[0123]

[Chemical formula 22]

Example 6 (Biological test) Test against organophosphorus drug-resistant leafhoppers Preparation of reagent solution Solvent: 3 parts by weight of xylol Emulsifier: 1 part by weight of polyoxyethylene alkylphenyl ether A formulation of a suitable active compound was prepared. To make 1 part by weight of the active compound, the abovementioned amount of solvent containing the abovementioned amount of emulsifier is mixed and the mixture is 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 as above at a predetermined concentration was sprayed per pot. After spraying the chemical solution, cover it with a wire net with a diameter of 7 cm and a height of 14 cm. Release 30 female adults of the leafhopper leafhopper, which is a strain that is resistant to organophosphorus agents, and place it in a temperature-controlled room for 2 days. Insect kill rates were calculated.

The results are shown in Table 2 with a representative example.

[0127]

[Table 17]

Example 7 (Biological test) Test for planthoppers Test method: To a rice plant planted in a pot having a diameter of 12 cm and having a plant height of about 10 cm, 1 water dilution of the active compound prepared in the same manner as in the above Example was prepared. 10 ml was applied per pot. After spraying the chemical solution, cover it with a wire net with a diameter of 7 cm and a height of 14 cm, and release 30 female adult planthoppers of the strain that are resistant to the organophosphorus agent, and place them in a temperature-controlled room for 2 days. Insect kill rates were calculated.

In the same manner as the above method, the insecticidal rate for the sedge loach and the organophosphorus-resistant Himetobibunka were calculated. The results are shown in Table 3 with a representative example.

[0130]

[Table 18]

Example 8 (Biological test) Test for organophosphorus agent and carbamate resistance peach aphid Test method: Eggplant seedlings (genuine long eggplants) having a height of about 20 cm planted in a clay pot having a diameter of 15 cm were bred. Organophos and carbamate-resistant peach aphids about 200 per seedling
Head inoculation was performed, and one day after the inoculation, a water dilution of the active compound prepared as in Example 6 at a predetermined concentration was used using a spray gun.
Sprayed a sufficient amount. After spraying, leave in a greenhouse at 28 ° C and spray 2
The insecticidal rate was calculated after 4 hours. The test was repeated twice.

The results are shown in Table 4 with a representative example.

[0133]

[Table 19]

The above Examples 6, 7 and 8 exemplify the usefulness of the compound of the present invention. The compounds of the present invention exemplified therein are also representative examples, and the usefulness of the compound of the present invention is only for these. It should not be limited.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07D 417/06 261 263 273 275 277 279 A01N 47/40 (72) Inventor Koichi Morie Hachioji, Tokyo 39-15 Namiki-cho, Japan (72) Inventor Yumi Hattori 598 Kobiki-cho, Hachioji-shi, Tokyo

Claims (2)

[Claims] 1. The formula: In the formula, R ¹ represents a hydrogen atom or an alkyl group, A represents an alkyl-substituted ethylene group or an alkyl-substituted trimethylene group, X represents a sulfur atom, and Z represents a carbon number of 1 A heterocyclic compound represented by, which represents a 3- or 4-pyridyl group optionally substituted with an alkyl group of -4. 2. Formula: In the formula, R ¹ represents a hydrogen atom or an alkyl group, A represents an alkyl-substituted ethylene group or an alkyl-substituted trimethylene group, X represents a sulfur atom, and Z represents a carbon number of 1 An insecticide characterized by containing as an active ingredient a heterocyclic compound represented by 3 or 4-pyridyl group which may be substituted with an alkyl group of -4.