KR100225225B1 - Guanidine derivatives - Google Patents

Abstract

The present invention relates to novel guanidine derivatives of formula (1) and pesticide compositions containing the compound of formula (1) as active ingredient.

[Formula 1]

Where

Z represents a 2-chloro-5-pyridyl group, a 2-chloro-5-thiazolyl group, or a 3-chloro-5-isoxazolyl group,

R ¹ represents a hydrogen atom or a C _1-4 alkyl group,

R ² represents a hydrogen atom, a C _1-4 alkyl group, a C _3-4 alkynyl group, a C _3-4 alkenyl group or 2-chloro-5-pyridylmethyl,

R ³ and R ⁴ are each a hydrogen atom, a halogen atom, a C _1-4 alkyl group, a C _3-4 alkynyl group, a C _3-4 alkenyl group, a substituted benzyl, or ZC (R ¹ ) H— Group (wherein Z and R ¹ have the same meaning as mentioned above),

n represents an integer of 2 or 3,

Y represents nitro or cyano.

Description

Guanidine derivatives}

The present invention relates to novel guanidine derivatives, methods for their preparation, and their use as pesticides.

It is already known that certain groups of guanidine derivatives are useful as insecticides (Japanese Patent Application Laid-Open No. 10762/1988).

With the present invention, novel guanidine derivatives of the formula (1) have been found.

Where

Z represents a 2-chloro-5-pyridyl group, a 2-chloro-5-thiazolyl group, or a 3-chloro-5-isoxazolyl group,

R ¹ represents a hydrogen atom or a C _1-4 alkyl group,

R ² represents a hydrogen atom, a C _1-4 alkyl group, a C _3-4 alkynyl group, a C _3-4 alkenyl group or 2-chloro-5-pyridylmethyl,

R ³ and R ⁴ are each a hydrogen atom, a halogen atom, a C _1-4 alkyl group, a C _3-4 alkynyl group, a C _3-4 alkenyl group, a substituted benzyl, or ZC (R ¹ ) H— Group (wherein Z and R ¹ have the same meaning as mentioned above),

n represents an integer of 2 or 3,

Y represents nitro or cyano.

Guanidine derivatives of formula (1)

a) A compound of formula (2) is obtained by reaction with a compound of formula (3) in the presence of an inert solvent.

Where

R ¹ , R ² , R ³ , R ⁴ , n, Y and Z have the same meaning as mentioned above.

The novel guanidine derivatives of formula (1) exhibit potent pesticidal properties.

Surprisingly, the guanidine derivatives according to the present invention exhibit substantially greater pesticidal activity than the compounds known from the prior art of the above-mentioned Japanese Patent Application No. 10762/1988.

Preferred compounds among the guanidine derivatives of formula (1) according to the invention

Z represents a 2-chloro-5-pyridyl group or a 2-chloro-5-thiazolyl group,

R ¹ represents a hydrogen atom or a methyl group,

R ² represents a hydrogen atom, a methyl group, an allyl group, a propargyl group or 2-chloro-5-pyridylmethyl,

R ³ and R ⁴ each represent a hydrogen atom or a methyl group,

n represents an integer of 2 or 3,

Y is a compound representing nitro or cyano.

Very particularly preferred guanidine derivatives of formula (1) are

Z represents a 2-chloro-5-pyridyl group or a 2-chloro-5-thiazolyl group,

R ¹ represents a hydrogen atom,

R ² represents a hydrogen atom or a methyl group,

R ³ and R ⁴ each represent a hydrogen atom,

n represents an integer of 2 or 3,

Y is a compound representing nitro or cyano.

As specific examples of the compound represented by the formula (1) according to the present invention, the following compounds may be mentioned:

1- {2- (6-chloro-3-pyridylmethylamino) ethyl} -2-nitroguanidine,

1- {2- (6-chloro-3-pyridylmethylamino) propyl} -2-nitroguanidine and

1- {2- (2-chloro-5-thiazolylmethylamino) ethyl} -2-nitroguanidine.

For example, in the case of using N- (6-chloro-3-pyridylmethyl) -ethylenediamine and 3-nitro-2-methylisothio urea as starting materials, the reaction route may be represented by the following reaction formula (1). have:

Starting material of formula (2) in process (a) means a compound based on the above definitions for Z, R ¹ , R ² and n, preferably a compound based on said preferred definitions.

Starting materials of formula (2) are known compounds described in Japanese Patent Application Laid-Open Nos. 267561/1986 and 48680/1987, and specific examples thereof include

N- (6-chloro-3-pyridylmethyl) -ethylene diamine,

N- (6-chloro-3-pyridylmethyl) -propylene diamine, and

N- (2-chloro-5-thiazolyl) -ethylene diamine may be mentioned.

In process (a), the starting materials of formula (3) mean compounds based on the above definitions for R ³ , R ⁴ and Y, preferably compounds based on the above preferred definitions.

Compounds of formula (3) are well known in the field of organic chemistry, and specific examples are

3-nitro-2-methylisothiourea, and

3-cyano-2-methylisothiourea may be mentioned.

An inert solvent may be used as a diluent suitable for carrying out the above-mentioned method (a).

Examples of such diluents include water; Optionally chlorinated aliphatic, cycloaliphatic and aromatic hydrocarbons such as pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, ethylene chloride, chlorobenzene and dichlorobenzene; Ethers such as diethyl ether, methyl ethyl ether, diisopropyl ether, dibutyl ether, propyleneoxide, dimethoxyethane (DME), dioxane and tetrahydrofuran (THF) and the like; Nitriles such as acetonitrile, propionitrile and acrylonitrile; Alcohols such as methanol, ethanol, isopropanol, butanol and ethylene glycol and the like; Esters such as ethyl acetate and amyl acetate and the like; dimethyl formamide (DMF), diethyl acetamide (DMA), N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone and hexamethyl phosphate triamide ( Acid amides such as HMPA); Sulfones and sulfoxides such as dimethyl sulfoxide (DMSO) and sulfolane and the like; And bases such as pyridine.

In the above-mentioned method a) the reaction temperature can be varied within a fairly wide range. In general, the reaction is carried out at a temperature of about -20 ° C to about 100 ° C, preferably 10 ° C to about 80 ° C.

The reaction is also carried out at atmospheric pressure, but elevated or reduced pressure may be used.

In carrying out the above-mentioned method (a) according to the invention, for example, from 1.0 to 1.5 moles of the above-mentioned compound (3) per 1 mole of the above-mentioned compound (2), optionally in the presence of an inert solvent such as water, Preferably, the amount of 1.0 to 1.1 mole is used to obtain the desired compound of formula (1).

The active compounds of the formula (1) are well tolerated by plants, have a favorable toxicity level for warm-blooded animals, and can be used in arthropods, especially in the protection of arthropods, particularly in agriculture, forestry, storage and materials, and in animal hygiene. Can be used to rescue them. They are active against normally sensitive and resistant species and all or part of the growing season. The pests mentioned above include the following:

Neck of the Isopoda, such as Oniscus asellus, Armadillidium vulgare and Porcellio scaber.

Neck of Diloplopoda, for example, Blaniulus guttulatus.

From the neck of Chilopoda, such as Geophilus carpophagus and Scutigera spec.

From the order of the symphyla, for example Scutigerella immaculata.

Thysanura, for example Lepisma saccharina.

Neck of Collembola, for example Onychiurus armatus.

Orthoptera (e.g., Blata orientalis, Periplaneta americana, Leucophaea maderae, Blatella germanica, Arceta) Domestikus (Acheta domesticus), Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis and Schistoser Schistocerca gregaria.

From the order of the dermaptera, for example Porficula auricularia.

Termite (Isoptera), for example Reticulitermes spp.

Anoplura, for example, Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. .) And Linognathus spp.

Allophaga, for example Trichodectes spp. And Damaliane spp.

From the order of the Thysanoptera, for example Hercinothrips femoralis and Tripps tabaci.

From the order of the Heteroptera, for example Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and Triatoma spp.

The cicada (Homoptera), for example Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Apis gossypii, Bres Brevicoryne brassicae, Cryptomyzus ribis, Apis fabae, Doralis pomi, Eriosoma lanigerum, Hyaloptherus arundi Niceopterus arundinis, Macrorosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp. spp.), Eucelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Lao delfax stria Laodelphax striatellus, Nilaparva Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudodococcus spp., Psylla spp. .

The order of the Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Limantria spp. ), Buculatrix thurberiella, Phyloknistis citrella, Agrotis spp., Pediatric spp., Euxa spp., Feltia spp. .), Earias insulana, Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolis flammea ), Frodeny Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp. (Chilo spp.), Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Cacosia podana, Capua reticula Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, and Tortrix viridana.

Neck of Coleoptera, for example, Anobium punctatum, Rhizopertha dominica, Acanthoscelides obtectus, Hilotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Siliodes chrysepala Psylliodes chrysocephala), Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Antonomus spp. (Anthonomus spp.), Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Cethorthornchnch assimilis Hypera postica, Dermestes spp., Trogoderma spp., Antrenus spp., Athenus spp. ), Lyctus spp., Meligthes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides ), Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melonta Melonta melolontha, Amphimallon solstitialis and Costelitra zealandica.

The order of the Hymenopera, for example Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp.

Diptera, for example Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Pania spp., Califora erythrocephala, Lucilia spp., Chrysomyia spp., Couter Cuterebra spp., Gastrophilus spp., Hippobosca spp., Stommoxys spp., Oestrus spp. .), Hippoderma spp. (Hypoderma spp.), Tabanus spp., Taniaa spp., Bibio hortulanus, Oscinella frit, Forbia spp. ), Pegomia hyoscyami, Ceratitis capitata, Dacus oleae, and Tipula paludosa.

The active compounds are usually used as solutions, emulsions, aqueous powders, suspensions, powders, foams, pastes, granules, aerosols, microcapsules in coating compositions for natural and synthetic materials, polymers and seeds impregnated with the active compounds. And a formulation used with a combustion device, such as a fumigation cartridge, a fumigation can, a mixing coil, and the like, and a ULV coolant and warming agent.

These formulations may be prepared by known methods, for example, optionally using surfactants, ie emulsifiers and / or dispersants and / or foam-forming agents, to extend the active compounds with extenders, ie liquid solvents, pressurized liquefied gases or solid diluents or carriers. Prepare by mixing. When water is used as the extender, for example, an organic solvent can also be used as a cosolvent.

Liquid solvent diluents or carriers are mainly aromatic hydrocarbons such as xylene, toluene or alkylnaphthalene, chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride, cyclohexane or paraffins, for example aliphatic hydrocarbons such as mineral oil fractions. Alcohols such as butanol or glycol and ethers and esters thereof, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strong polar solvents such as dimethylformamide and dimethyl sulfoxide, and water are suitable . Liquefied gas diluent or carrier means a liquid that is gaseous at room temperature and atmospheric pressure, for example aerosol propellants such as butane, propane, nitrogen and carbon dioxide, as well as halogenated hydrocarbons.

Solid carriers include, for example, ground natural minerals such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and highly dispersed silicic acid, alumina and silicates; The same pulverized synthetic mineral is suitable. Solid carriers for granulation include, for example, pulverized and classified natural rocks such as calcite, marble, pumice, calcite and dolomite, and synthetic granules of inorganic and organic powders, and organic such as sawdust, coconut husks, corn cobs and tobacco stems. Granules of material are suitable.

Emulsifiers and / or foam-forming agents include nonionic and anionic emulsifiers, for example polyoxyethylene fatty alcohol ethers such as polyoxyethylene fatty acid esters, alkylaryl polyglycol ethers, alkylsulfonates, alkylsulphates, arylsulfonates And albumen hydrolysis products are suitable.

Suitable dispersants are, for example, lignin-sulphite waste liquors and methylcellulose.

Adhesives, for example natural and synthetic polymers in powder, granule or emulsion form, such as carboxymethylcellulose, gum arabic, polyvinyl alcohol and polyvinyl acetate can be used in the formulation.

Inorganic pigments such as iron oxide, titanium oxide and prussian blue, and colorants such as alizarin dyes, azo dyes and organic dyes such as metal phthalocyanine dyes and micronutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc You can also use

The formulations generally contain 0.1 to 95% by weight, preferably 0.5 to 90% by weight of active compound.

The active compounds according to the invention are commercially available formulations and uses made from these preparations in admixture with other active compounds such as insecticides, attractants, sterilizers, acaricides, nematicides, fungicides, growth-modulators or herbicides. May exist in the sentence. Pesticides include, for example, phosphates, carbamates, carboxylates, chlorinated hydrocarbons, phenylurea and substances produced by microorganisms.

The active compounds according to the invention may also be present in the commercial formulations and in the use forms prepared from these formulations in admixture with synergists. Synergists are compounds that increase the action of the active compound, but there is no need to add a substance that is active in itself.

The active compound content in the use forms prepared from commercial formulations can vary within wide ranges. The active compound concentration in the use form can be 0.0000001 to 100% by weight, preferably 0.0001 to 1% by weight.

The active compound is applied in a conventional manner suitable for the use form.

When the active compounds are used against hygienic pests and stored pests, they are characterized by excellent stability against alkali on calcareous material as well as excellent residual action on wood and clay.

Examples of the preparation and use of the active compounds according to the invention are described in the examples below.

Example 1

A mixture of N- (6-chloro-3-pyridylmethyl) ethylenediamine (3.7 g), 3-nitro-2-methylisothiourea (2.7 g) and ethanol (20 mL) was obtained from this methylmercaptan Stir at 30 ° C until generation stops. After cooling, the crystal separation is carried out under filtration to give the desired 1- {2- (6-chloro-3-pyridyl-methylamino) ethyl} -2-nitroguanidine having a melting point of 119 to 122 ° C.

According to the same method as used in the above-mentioned examples, a number of compounds specifically shown in Table 1 can be obtained, and Table 1 also shows the compounds prepared in the above-mentioned examples.

Biological Test Examples:

Example 2: Biological Tests Performed on Nephotettix cincticeps (Cicadas) Resistant to Organophosphorus and Carbamate Insecticides

Preparation of Test Formulations

Solvent: 3 parts by weight of xylene

Emulsifier: 1 part by weight of polyoxyethylene alkylphenyl ether

1 part by weight of each active compound is mixed with a specified amount of solvent containing a specified amount of emulsifier and the resulting mixture is diluted with water to a predetermined concentration to prepare a suitable formulation of the active compound.

Test Methods :

Plant rice of about 10 cm in height in several pots of 12 cm in diameter. To each of the rice plants planted in the pot is sprayed with 10 ml of an aqueous solution of the active compound prepared above and having a predetermined concentration. After drying the sprayed solution, each pot was covered with a metal net having a diameter of 7 cm and a height of 14 cm, and 30 adult female Nepotetics Scinticeps females resistant to organophosphorus and carbamate insecticides were released. Place in a chamber of temperature. After 2 days, the extinction degree of the pest is calculated by measuring the number of killed pests.

Example 3

Test for rice hoppers resistant to organophosphorus and carbamate insecticides

Plant rice of about 10 cm in height in several pots of 12 cm in diameter. Each of the rice planted in the pot is sprayed with 10 ml of an aqueous solution of the active compound prepared in a similar manner as in Example 2 above with a predetermined concentration. After drying the sprayed solution, each pot was covered with a metal net having a diameter of 7 cm and a height of 14 cm and 30 female adult Nilaparvate lugens resistant to organophosphorus and carbamate insecticides were released. Place in a chamber of temperature. After 2 days, the extinction degree of the pest is calculated by measuring the number of killed pests.

Sezirounka (white locust, Sogatella furcifera) and Himetobiunka (larvae, Lao delfax) resistant to organic phosphorus pesticides in a similar manner as mentioned above The mortality is measured for Laodelphax striate-llus, respectively.

In the above-mentioned Test Examples 2 and 3, as representative examples of the active compound represented by the formula (1), the compounds represented by Tables 1, 2 and 3 in Table 1 have an effective control effect against each pest, for example, an applied amount of 200 ppm. 100% control at

Claims (7)

Guanidine derivatives of formula (1). [Formula 1] Where Z represents a 2-chloro-5-thiazolyl group, R ¹ represents a hydrogen atom or a C _1-4 alkyl group, R ² represents a hydrogen atom, a C _1-4 alkyl group, a C _3-4 alkynyl group, a C _3-4 alkenyl group or 2-chloro-5-pyridylmethyl, R ³ is a hydrogen atom, a halogen atom, a C _1-4 alkyl group, a C _3-4 alkynyl group, a C _3-4 alkenyl group, benzyl, or a ZC (R ¹ ) H-group, wherein Z and R ¹ has the same meaning as mentioned above), R ⁴ is a hydrogen atom, a halogen atom, a C _1-4 alkyl group, a C _3-4 alkynyl group, a C _3-4 alkenyl group, benzyl, or a ZC (R ¹ ) H-group, wherein Z and R ¹ has the same meaning as mentioned above), n represents an integer of 2 or 3, Y represents nitro or cyano. The method of claim 1, Z represents a 2-chloro-5-thiazolyl group, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydrogen atom, a methyl group, an allyl group, a propargyl group or 2-chloro-5-pyridylmethyl, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a hydrogen atom or a methyl group, n represents an integer of 2 or 3, Y represents nitro or cyano. The method of claim 1, Z represents a 2-chloro-5-thiazolyl group, R ¹ represents a hydrogen atom, R ² represents a hydrogen atom or a methyl group, R ³ represents a hydrogen atom, R ⁴ represents a hydrogen atom, n represents an integer of 2 or 3, Y represents nitro or cyano. A process for preparing a guanidine derivative of formula (1) characterized by reacting a compound of formula (2) with a compound of formula (3) in the presence of an inert solvent. [Formula 1] [Formula 2] [Formula 3] Where Z represents a 2-chloro-5-thiazolyl group, R ¹ represents a hydrogen atom or a C _1-4 alkyl group, R ² represents a hydrogen atom, a C _1-4 alkyl group, a C _3-4 alkynyl group, a C _3-4 alkenyl group or 2-chloro-5-pyridylmethyl, R ³ and R ⁴ are each a hydrogen atom, a halogen atom, a C _1-4 alkyl group, a C _3-4 alkynyl group, a C _3-4 alkenyl group, benzyl, or a ZC (R ¹ ) H-group (here , Z and R ¹ have the same meaning as mentioned above), n represents an integer of 2 or 3, Y represents nitro or cyano. A pesticide composition, characterized in that it contains at least one guanidine derivative of formula (1). A method for combating pests, characterized by acting on guanidine derivatives of formula (1) to pests or their habitats. A process for preparing the pesticide composition, characterized in that the guanidine derivative of formula (1) is mixed with at least one substance selected from the group consisting of extenders and surfactants.