JP3352082B2 - New heterocyclic compounds - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to novel heterocyclic compounds, their preparation and use as insecticides. ADVANCES IN PESTICIDE SCIENCE Part 2 (published on July 24-28, 1978 in Zurich, Switzerland, International Symposium on Pesticide Chemistry, Pergamon Press Publishing), pages 206 to 217, published on the date of filing of the present application. Describes insecticidal activity of-(nitromethylene) oxazolidine and the like.

The present inventors have now found a novel heterocyclic compound of the following formula (I).

Embedded image (Wherein A is a heteroatom 1 selected from S, O or N)
Represents a 5-membered or 6-membered heteroaryl group containing -3, and the heteroaryl group may be substituted with a halogen atom or an alkyl group having 1 to 4 carbon atoms.

[0003] Z represents a linear three-membered member arbitrarily selected from the group consisting of CH ₂ , O, S and NR ² , wherein Z represents
At least one of O, S, and N—R ² ;
Represents CH ₂ , O, S or NR ² , wherein R ² is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or

Embedded image (Where R ³ represents a hydrogen atom or a halogen atom), X represents CH or N, Y represents a nitro group or a cyano group, and R ¹ represents a hydrogen atom or a methyl group. )

The compound of the formula (I) of the present invention can be synthesized, for example, by the following method. Production method a)

Embedded image Wherein A and R ¹ are the same as described above, and Hal represents a halogen atom.

Embedded image (Wherein Z, E, X and Y are the same as defined above), which is reacted with a compound represented by the formula (I).

The heterocyclic compound of the formula (I) of the present invention
Shows powerful insecticidal action. According to the present invention, there is provided a compound of formula (I)
B cyclic compounds, for example, the ADVANCES INPESTICIDE S
Comparison with compounds similar to the compounds of the present invention described in CIENCE
In effect, they exhibit an extremely excellent insecticidal action. The present invention
In the formula (I), preferably, A is 2-chloropyri
Zin-5-yl or 2-chlorothiazol-5-yl
And Z is CH_Two, O, S and NR ^Two Group consisting of
A linear three member selected from the group consisting of at least Z
One is O, S or NR^Two Is shown. E is CH_Two,
O, S or NR^Two And R^Two Is an atom having 1-3 carbon atoms.
Alkyl group, alkoxy group having 1-3 carbon atoms or 2-chloro
X represents N; Y represents pyridin-5-ylmethyl;
Represents a nitro group or a cyano group.

In the production method a), for example, 2-
When chloro-5-chloromethylpyridine and 3-cyanoiminomorpholine are used, they are represented by the following reaction formula.

Embedded image In the above-mentioned production method a), the compound of the formula (II) as a raw material means a compound based on the definition of A, R ¹ and Hal, and A and R ¹ are preferably the same as those defined above. Has the same meaning as Hal preferably represents a chlorine atom.

The compounds of the formula (II) are already known, representative examples of which are, for example, 2-chloro-5-chloromethylpyridine, 5-chloromethyl-3-methylisoxazole, 5-chloromethyl-2 -Chlorothiazole, 5-chloromethyl-2-methylthiazole, 5-chloromethyl-2-fluoropyridine, 2-bromo-5
Chloromethylpyridine, 5-chloromethyl-2-methylpyridine and the like can be exemplified. The compound of the formula (III) as a raw material in the above-mentioned production method a) means a compound based on the definition of Z, E, X and Y, and preferably has the preferable definition.

The compounds of formula (III) include novel compounds, for example, 3-cyanoiminomorpholine has the formula

Embedded image (Wherein R ⁴ represents lower alkyl) and a cyanamide. The compounds of formula (IV) are novel compounds, for example

Embedded image In represented by 3-morpholinone and the formula ^{_{(R 4 O) 2 SO 2}} (V) ( wherein R ⁴ is as defined above) is obtained by reacting a compound represented by.

3-Morpholinone is already available from Chemical Ab
Stract (Chemical Abstract), vol. 47-2762e, and the like, and the compound represented by the formula (V) is also well known in the field of organic chemistry. Further, 3-nitroiminomorpholine included in the formula (III) is represented by the formula

Embedded image By reacting 3-amino-2H-1,4-dihydrooxazine represented by the following formula with fuming nitric acid.
The compound of the above formula (VI) is a novel compound and is obtained, for example, by reacting the compound of the above formula (IV) with ammonia.

The 3-nitromethylene morpholine included in the formula (III) can be obtained by reacting the compound represented by the formula (IV) with nitromethane. The compound of formula (III) has the formula

Embedded image (Wherein R ² and Y are the same as described above) is a compound represented by the formula R ² —NH ₂ (VII) (wherein R ² is the same as described above) and formalin and nitroguanidine Or it is obtained by reacting with cyanoguanidine.

In carrying out process a) above, suitable inert diluents include all inert solvents. Examples of such diluents are water; aliphatic, cycloaliphatic and aromatic hydrocarbons (optionally chlorinated) such as hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene Methylene chloride, chloroform, carbon tetrachloride, ethylene chloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene; and 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; alcohols For example, methanol, ethanol, iso-propanol, butanol, ethylene glycol; esters such as ethyl acetate, amyl acetate; acid amides such as dimethylformamide, dimethylacetamide; sulfones and sulfoxides such as dimethyl sulfoxide, sulfolane; and bases such as , Pyridine and the like.

Process a) can be carried out in the presence of an acid binder, such as hydroxides, carbonates, bicarbonates and alcoholates of alkali metals, tertiary alcohols and the like. Secondary amines include, for example, triethylamine, diethylaniline, pyridine and the like. Process a) can be carried out within a substantially wide temperature range. Generally, it can be carried out between about 0 and about 100 ° C, preferably between about 30 and about 80 ° C. The various reactions are desirably performed under normal pressure, but can be performed under increased or reduced pressure. In carrying out the process a), for example, the compound of the formula (II) is equimolar to 1.1-fold molar quantity per 1 mol of the compound of the formula (III), and is equimolar in an inert solvent such as acetonitrile. The target compound can be obtained by reacting in the presence of about 1.2-fold molar amount of potassium carbonate.

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

[0014] Examples of such pests include the following pests. As insects, Coleoptera pests, for example, Azuki weevil (Callosobruchus chinen)
sis), Sitophilus zeamais, Tribolium castaneum, Epilachna vigintioctomaculata, Agriotes fuscicollis, Anomala ruforea
ptinotarsa decemlineata, Diabrotheica (Diabro)
tica spp.), Monochamus alternatus (Monochamus alt)
ernatus, rice weevil (Lissorhoptrus oryzop)
hilus), Flycatcher beetle (Lyctus bruneus);

Lepidoptera, such as the gypsy moth (Lymantria)
dispar), Pterodactyla (Malacosoma neustria), Caterpillar (Pieris rapae), Spodoptera (Spodoptera l)
itura), armyworm (Mamestra brassicae), Nikameichiniu (Chilo suppressalis), Awanomeiga (Pyrausta nub)
ilalis), Elephalia cautella (Ephestia cautella), Oleander (Adoxophyes orana), Codling moth (Ca)
rpocapsa pomonella, Kaburayaga (Agrotis fucosa)
), Honeybee (Galleria mellonella), diamondback moth (Plut
ella maculipennis), Citrus leaf moth (Phyllocnisti)
s citrella);

[0016] Hemiptera, for example, leafhopper (Neph)
otettix cincticeps, brown planthopper (Nilaparvatal)
ugens), Pseudodococcus comste
cki), the wild insect scale (Unaspis yanonensis),
Peach aphid (Myzus persicae), apple aphid (Aphis pomi), cotton aphid (Aphis gossypi
i), radish aphid (Rhopalosiphum psedobr
assicas), Stephanitis nashi, Green stink bug (Nezara spp.), Bed bug (Cimex lectular)
ius), Whitefly (Trialeurodes vaporarior)
um), psyllium (Psylla spp.);

Orthoptera, such as the cockroach (Bl)
atella germanica), American cockroach (Periplaneta am)
ericana), Kera (Gryllotalpa africana), Grasshopper (Locusta migratoria migratoriodes); Isoptera, for example, Yamato termite (Deucotermes speratus), Housewort (Coptotermes formosanus); Diptera, for example, Musca domestica, Musca domestica (Aed
es aegypti), Musca domestica (Hylemia platura), Culex pipiens, and Anopheles slne
nsis) and Culex tritaeniorhynchu
s), and the like.

Furthermore, in the field of veterinary medicine, the novel compounds of the present invention are effective against various harmful animal parasites (endo and ectoparasites) such as insects and helminths. . Examples of such animal parasites include the following pests. Examples of insects include horse flies (Gastrophilus spp.), Sand flies (Stomoxys spp.), Lice (Trichodectes spp.),
Red turtle (Rhodnius spp.), Dog flea (Ctenocephalide)
scanis) and the like.

In the present invention, a substance having an insecticidal action on insects including all of them is sometimes referred to as an insecticide. The active compounds of the formula (I) according to the invention can be formulated in the customary formulations. And such forms include solutions, emulsions, suspensions, powders, foams, pastes, granules,
Aerosols, active compound infiltration-natural and synthetic, microcapsules, seed coatings, formulations with combustion equipment (for example, fumigation and fume cartridges as combustion equipment,
Cans and coils), and ULV (cold mist, warm mist).

These preparations can be manufactured by a known method. Such methods include, for example, converting the active compound into a developing agent, ie, a liquid diluent; a liquefied gas diluent; a solid diluent,
Alternatively, it can be carried out by mixing with a carrier, optionally a surfactant, ie, an emulsifier and / or a dispersant and / or a foam-forming agent. When water is used as the developing agent, for example, organic solutions can also be used as auxiliary solvents. Examples of liquid diluents or carriers include, for example, aromatic hydrocarbons (eg, xylene, toluene, alkylnaphthalene, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (eg, chlorobenzenes, ethylene chlorides) , Methylene chloride, etc.), aliphatic hydrocarbons [eg, cyclohexane, etc., paraffins (eg, mineral oil fractions, etc.)], alcohols (eg, butanol, glycol and their ethers, esters, etc.), ketones (eg, Mention may also be made of acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone), strong polar solvents (eg dimethylformamide, dimethylsulfoxide, etc.) and water.

The liquefied gas diluent or carrier is a gas at normal temperature and normal pressure, for example, butane, propane,
Aerosol propellants such as nitrogen gas, carbon dioxide, and halogenated hydrocarbons can be mentioned. Examples of solid diluents include soil natural minerals (eg, kaolin, clay, talc, chalk, quartz, attapull guide, montmorillonite, or diatomaceous earth), and soil synthetic minerals (eg, highly dispersed silicic acid, alumina, silicate, etc.). Can be mentioned. Solid carriers for granules include crushed and fractionated rocks (e.g., calcite, marble, pumice, sepiolite, dolomite, etc.), synthetic granules of inorganic and organic powders, and fine or organic materials ( For example, from sawdust, coconut,
Corn cobs and tobacco stems). Examples of the emulsifier and / or foaming agent include nonionic and anionic emulsifiers [for example, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid alcohol ether (for example, alkylaryl polyglycol ether, alkyl sulfonate, alkyl sulfate, aryl sulfone). Acid salt)] and albumin hydrolysis products.

The dispersants include, for example, lignin sulfite waste liquor and methylcellulose. Fixatives can also be used in formulations (powder, granules, emulsions)
Such fixatives include carboxymethylcellulose and natural and synthetic polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate. Coloring agents can also be used, such as inorganic pigments (eg, iron oxide, titanium oxide and Prussian blue), and organic dyes such as alizarin dyes, azo dyes or metal phthalocyanine dyes,
And furthermore, trace elements such as iron, manganese, boron, copper, cobalt, molybdenum, zinc salts thereof can be mentioned. The preparation may, for example, contain the active ingredient in an amount of 0.
It can be contained in an amount of 1 to 95% by weight, preferably 0.5 to 90% by weight.

The active compounds of the formula (I) according to the invention can be used in their commercially useful preparations and in the use forms prepared by these preparations in the form of other active compounds such as insecticides, baits, fungicides, It can also be used as a mixture with acaricide, centrifugal killer, fungicide, growth regulator or herbicide. Here, examples of the insecticide include organophosphorus agents, carbamates, carboxylates, chlorinated hydrocarbons, and insecticides produced by microorganisms. Further, the active compound of the formula (I) of the present invention can be used also as a mixture with a synergist, and such preparations and forms of use include those which are commercially useful. The synergist itself need not be active, but is a compound that amplifies the action of the active compound.

The content of the active compounds of the formula (I) according to the invention in commercially useful forms can vary within wide limits. The working concentrations of the active compounds of the formula (I) according to the invention are, for example, from 0.0000001 to 100% by weight, preferably from 0.0001 to 1% by weight. The compound of the formula (I) of the present invention can be used in a usual manner suitable for the use form. When used in sanitary pests, pests on stored products, the active compounds are distinguished by a good stability against alkali on lime substances, as well as excellent residual action in wood and soil . Next, the content of the present invention will be specifically described with reference to examples, but the present invention should not be limited to these.

Production Example Example 1

Embedded image 3-morpholinone (10.1 g) was added to toluene (100 m
l) and heated to 70 ° C.
2.6 g) were added dropwise over 30 minutes. Thereafter, the mixture was heated and refluxed for 6 hours. After cooling, anhydrous potassium carbonate (13.8 g) was added little by little while cooling in an ice bath. After stirring for 1 hour, the precipitated salt was filtered and the filtrate was concentrated to obtain a crude 3-methoxy-5,6-dihydro-2H-oxazine (8 g). This was dissolved in 30 ml of anhydrous THF (tetrahydrofuran), 2.9 g of cyanamide was added, and the mixture was heated under reflux for 3 hours. The THF was distilled off under reduced pressure, and the residue was recrystallized from chloroform to obtain 2 g of 3-cyanoiminomorpholine (mp. 169 ° C to 170 ° C). This 3-cyanoiminomorpholine (1.25 g) was dissolved in acetonitrile (50 ml), and 2-chloro-5-chloromethylpyridine (1.62 g) and anhydrous potassium carbonate (1.4) were dissolved.
g) was added and the mixture was heated under reflux for 5 hours. After allowing to cool, the reaction solution is poured into ice water and extracted with dichloromethane. The organic layer treated in a conventional manner was further purified by silica gel chromatography (eluent: chloroform: ethanol 95:
5) Then, desired 4- (2-chloro-5-pyridylmethyl) -3-cyanoiminomorpholine (0.9 g) was obtained. mp. 97-98.5 ° C

Embodiment 2

Embedded image 5-methyl-2-nitroimino-hexahydro-1,
3,5-Triazine (3.0 g) was dissolved in DMF (20 ml), and sodium hydride (950 mg oil fr
ee) was added little by little. After stirring at 0-5 ° C for 1 hour, 2-chloro-5-chloromethylpyridine (3.1 ml) dissolved in DMF (dimethylformamide) (20 ml).
g) was slowly added dropwise while maintaining this temperature, and 5 g was further added.
Stirred for hours. The reaction mixture was poured into ice water, extracted several times with methylene chloride, dried over anhydrous magnesium sulfate, and the solvent was distilled off. The resulting residue was purified by silica gel chromatography (eluent: ethanol: chloroform = 1: 20). 1- (2-chloro-5-pyridylmethyl)-
5-methyl-2-nitroimino-hexahydro-1,
3,5-Triazine (3.7 g) was obtained. mp. 1
60-161 ° C

Embodiment 3

Embedded image 5-methyl-2-cyanoimino-hexahydro-1,
A mixture of 3,5-triazine (6.0 g), 5-chloro-2-chloromethylpyridine (7.0 g), anhydrous potassium carbonate (6.6 g) and acetonitrile (80 ml) was heated under reflux for 10 hours. After cooling, the solid was filtered off, the filtrate was concentrated under reduced pressure, and the resulting residue was subjected to column chromatography (eluent ethanol: chloroform = 1: 1).
Purification by 20) gave the desired 1- (2-chloro-5-pyridylmethyl) -5-methyl-2-cyanoimino-hexahydro-1,3,5-triazine (7.9 g). mp. 198-202 ° C

Embodiment 4

Embedded image 5-methoxy-2-nitroimino-hexahydro-1,
3,5-Triazine hydrochloride (10 g) was added to DMF (18
0 ml) and sodium hydride (3.4 ml) at 0-5 ° C.
g oil free) was added little by little. After stirring at 0-5 ° C for 1 hour, 2-chloro-dissolved in DMF (20 ml).
5-Chloromethylpyridine (7.7 g) was slowly added dropwise while maintaining the temperature, and the mixture was further stirred for 5 hours. The reaction mixture was poured into ice water, extracted several times with methylene chloride, dried over anhydrous magnesium sulfate, and the solvent was distilled off. The resulting residue was purified by silica gel chromatography (eluent: ethanol: chloroform = 1: 20). 1- (2-chloro-5-pyridylmethyl) -5-methoxy-2-nitroimino-hexahydro-1,3,5-triazine (8.5 g) was obtained. mp. 159-163 ° C first
In the table, compounds that can be synthesized in the same manner as in the above Examples are shown together with the above compounds.

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

[Table 3]

[0032]

[Table 4]

[0033]

[Table 5]

[0034]

[Table 6]

[0035]

[Table 7]

[0036]

[Preparation of Intermediate] Example 5

Embedded image Nitroguanidine (10 g), methoxyamine hydrochloride (9.6 g), 75% paraformaldehyde (11.5 g)
g), a mixture of toluene (80 ml) and a catalytic amount of concentrated hydrochloric acid was heated to reflux for 3 hours while removing water. The solvent was distilled off under reduced pressure to obtain white crystals of 5-methoxy-2-nitroimino-hexahydro-1,3,5-triazine hydrochloride (16.2 g). mp. 160-170 ° C

Embodiment 6

Embedded image A mixture of nitroguanidine (21 g), 40% aqueous methylamine solution (15.7 g) and formalin (40 ml) is stirred at 50-60 ° C. for 1 hour. The residue obtained by evaporating the solvent under reduced pressure is reconstituted from ethanol,
5-methyl-2-nitroimino-hexahydro-1,
3,5-Triazine (2.6 g) is obtained. mp. 2
06-210 ° C (decomposition)

[0038]

Embedded image A mixture of cyanoguanidine (21 g), 40% aqueous methylamine solution (19.4 g) and formalin (40 ml) is stirred at 50-60 ° C. for 1 hour. The residue obtained by distilling off the solvent under reduced pressure was recrystallized from ethanol to give 5-methyl-2-cyanoimino-hexahydro-.
1,3,5-Triazine (24 g) is obtained. mp.
170-173 ℃ Biological test example-

Example 8 Test on Organophosphorus Resistant Leafhoppers Preparation of Reagent Solution Solvent: 3 parts by weight of Xylol Emulsifier: 1 part by weight of polyoxyethylene alkyl phenyl ether Active compound for preparing a suitable active compound formulation One part by weight was mixed with the above amount of the solvent containing the above amount of the emulsifier, and the mixture was diluted with water to a predetermined 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 water dilution of the active compound prepared as described above having a predetermined concentration was sprayed per pot. After drying the sprayed drug solution, cover it with a wire mesh of 7 cm in diameter and 14 cm in height, and release 30 female adults of the leafhopper leafhopper, which is resistant to the organophosphorus agent, in the constant temperature room. The insecticidal rate was calculated. As a result, Compound Nos. 2, 3, 11,
12, 14, 15, 16, 17, and 40 represent the amount of active ingredient 2
At 100 ppm, the insecticidal rate was 100%.

Example 9 Test for Organic Phosphorus and Carbamate-Resistant Peach Aphid Test Method: Organophosphorus raised in about 20 cm-high eggplant seedling (Meguro long eggplant) planted in a clay pot having a diameter of 15 cm; About 200 mosquito aphids resistant to carbamate per seedling
The head was inoculated, and one day after the inoculation, a sufficient amount of a diluted water solution of the active compound prepared in the same manner as in Example 8 was sprayed using a spray gun. After spraying, the mixture was allowed to stand at a temperature of 28 ° C., and 24 hours after spraying, the insecticidal rate was calculated. The test was repeated twice. As a result, Compound Nos. 2, 3, 11, 12,
Compounds 14, 15, 16, 17, and 40 showed 100% insecticidal rate at 500 ppm of active ingredient.

────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI A01N 43/836 A01N 43/84 101 43/84 101 43/88 43/88 101 101 102 102 102 47/40 47/40 51/00 51/00 C07D 405/06 C07D 405/06 409/06 409/06 417/06 417/06 A01N 43/82 104 (72) Inventor Ikuo Honda 3-17-7, Minamimachi, Tanashi-shi, Tokyo (72) Inventor Katsuhiko Shibuya 39-15 Namiki-cho, Hachioji-shi, Tokyo (56) References JP-A-2-235881 (JP, A) JP-A-6-316572 (JP, A) JP-A 8-277286 (JP, A) ( 58) Field surveyed (Int. Cl. ⁷ , DB name) C07D 401/14 C07D 405/06 C07D 409/06 C07D 417/06 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A compound of the formula (I) (Wherein, A represents a heteroaryl group selected from the group consisting of furyl, thiadiazolyl, thienyl or pyrimidinyl, wherein the heteroaryl group is optionally halogen or C ₁ -C ₄
E represents NR ² , R ² is hydrogen, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ alkoxy group or (Wherein R ₃ represents hydrogen or a halogen atom), Y represents NO ₂ or CN, and R ¹ represents hydrogen or CH ₃ . 2. An insecticide comprising the heterocyclic compound according to claim 1 as an active ingredient.