JP2764784B2 - New heterocyclic compounds and insecticides - 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 SC known before the filing date of the present application
IENCE Part 2 (July 24-28, 1978)
(Symposium of the International Congress of Pesticides and Chemistry, Zurich, Switzerland, Japan), pages 206 to 217, pages 206 to 217, describe insecticidal activities of 2- (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)
-3 pieces including shows a 5- or 6-membered heteroaryl group ring, the heteroaryl group may be substituted by a halogen atom or an alkyl group having a carbon number of 1-4.

[0003] Z represents a linear three-membered member arbitrarily selected from the group consisting of CH ₂ , O, S and NR ² , wherein Z
At least one of O, 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 compounds of the formula (I) according to the invention exhibit a strong insecticidal action. According to the present invention, the heterocyclic compound of the formula (I) is, for example, the aforementioned ADVANCES IN
Compared with the compound similar to the compound of the present invention described in PESTICIDE SCIENCE, it shows substantially extremely excellent insecticidal action. In the formula (I) of the present invention, A preferably represents 2-chloropyridin-5-yl or 2-chlorothiazol-5-yl, and Z represents CH ₂ , O, S
And N—R ² , wherein at least one of Z is O, S or N—R
² is shown. E represents CH ₂ , O, S or NR ² ,
R ² represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms or 2-chloropyridin-5-ylmethyl, X represents N, and Y 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 Is obtained by reacting 3-morpholinone represented by the formula with a compound represented by the formula (R ⁴ O) ₂ SO ₂ (V) (wherein R ⁴ is the same as described above).

3-Morpholinone is already available from Chemic
al Abstract (Chemical Abstract) 4
7-2761e, and the compound represented by the formula (V) is 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 those 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 such as methanol, ethanol, iso-propanol, butanol, ethylene glycol; esters such as ethyl acetate, amyl acetate; acid amide Such as dimethylformamide and dimethylacetamide; sulfones and sulfoxides such as
Dimethyl sulfoxide, sulfolane; and bases such as pyridine.

Process a) can be carried out in the presence of an acid binder, such as, for example, alkali metal hydroxides, carbonates, bicarbonates and alcoholates; 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 moles relative to 1 mole of the compound of the formula (III) in an inert solvent such as acetonitrile.
By reacting in the presence of equimolar amount to 1.2 times molar amount of potassium carbonate, the target compound can be obtained.

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 (Callosobru)
chus chinensis) and weevil (Si)
tophilus zemais), Tribium castaneum, and Epilachna vig
intictomaculata, Agriotes fusicocolli
s), Anemona rufocupr
ea), Colorado potato beetle (Leptinota)
rs decemlineata), diabloteica (Diabrotica spp.), pine beetle (Monochamus alternata)
s), rice weevil (Lissorhoptrus)
oryzophilus, Flycatcher beetle (Ly)
ctus bruneus);

Lepidoptera, for example, Lymantria dispar, and Malacosoma neustra
a), Caterpillar (Pieris rapae), Spodoptera litura, Spodoptera (Mamestra brassicae), Chilo suppressali
s), Awanomeiga (Pyrausta nubila)
lis), E. kestura (Ephesia ca)
utella), Scarlet Monamaki (Adoxophy)
es orana), codling moth (Carpocaps)
a pomonella), Kaburaya (Agroti)
s fucosa) and honeybee (Galleria)
mellonella), Konaga (Plutella)
maculipennis), Citrus scuttlefish (Ph)
yllocnistis citellla);

[0016] Hemiptera, for example, Leafhopper, Nephotettix cinc
ticeps), brown planthopper (Nilaparva)
talugens) and the stag beetle (Pseu)
dococcus comsticki), Unabis yanonensis,
Green peach aphid (Myzus persica)
e), apple aphids (Aphis pomi), cotton aphids (Aphis gossypii), and radish aphids (Rhopalosiphum p.
sedobrassicas, Nashigumbai (Steel)
phanitis nashi, green stink bug (Ne)
zara spp. ), Bed Bug (Cimex le)
ctularius), Whitefly on whitefly (Tria)
leurodes vapororium, psyllium (Psylla spp.);

Orthoptera, for example, German cockroaches (Blatella germani)
ca), American cockroach (Periplaneta a
meriana, Kera (Grylotalpa)
africana), grasshopper (Locusta mig)
ratomiamigratorodes); Isoptera, for example, the termite (Deucotermes spera)
tus), House termites (Copterotermes f)
ormosanus); Diptera, for example, house fly (Musca domestica), nettle sea mosquito (Aedesegypti),
ylemia plateura, Culex pipiens (Cul)
ex pipiens), Anopheles sinensis (Anoph)
eles slnensis) and Culex pipiens (C)
ulex tritaeniorhynchus).

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.), And whiteflies (T
richodictes spp. ), Assassin turtle (Rh
odnius spp. ), Dog flea (Ctenose)
pharidescanis) 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 (warm mist)
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 the solid diluent include soil natural minerals (eg, kaolin, clay, talc, chalk, quartz, attapull guide, montmorillonite, or diatomaceous earth), soil synthetic minerals (eg,
Highly dispersed silicic acid, alumina, silicate, etc.). Solid carriers for granules include ground and fractionated rocks (eg, calcite, marble, pumice, sepiolite,
Dolomite), synthetic particles of inorganic and organic flours, and fine granules or organic substances (eg, sawdust, coconut, corn cob, 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, carbamate agents, 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 product of 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), 2-chloro-5-chloromethylpyridine (1.62 g) and anhydrous potassium carbonate (1.4 g) were 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, the desired 4- (2-chloro-5-pyridylmethyl) -3-cyanoiminomorpholine (0.9 g) was obtained.
I got mp. 97-98.5 ° C

Embodiment 2

Embedded image 5-methyl-2-nitroimino-hexahydro-1,
3,5-Triazine (3.0 g) was added to DMF (20 ml).
And sodium hydride (950 mgo) at 0-5 ° C.
il free) was added in small portions. After stirring at 0 to 5 ° C. for 1 hour, DMF (dimethylformamide) (20
ml), 2-chloro-5-chloromethylpyrimidine (3.1 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, the solvent was distilled off, and the obtained residue was subjected to silica gel chromatography (eluent: ethanol: chloroform =
1:20) to give the desired 1- (2-chloro-5-pyridylmethyl) -5-methyl-2-nitroimino-hexahydro-1,3,5-triazine (3.7 g). mp. 160-161 ° 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 potassium (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 =
1:20) to obtain 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 g oil free) was added little by little. 0-5 ° C
After stirring for 1 hour, 2-chloro-5-chloromethylpyridine (7.7 g) dissolved in DMF (20 ml) 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. 159-16
At 3 ° C. in Table 1, compounds which can be synthesized in the same manner as in the above Examples
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 consisting 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 was reconstituted from ethanol to give 5-methyl-2-nitroimino-hexahydro-.
1,3,5-Triazine (2.6 g) is obtained. m
p. 206-210 ° 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: Rice plant of about 10cm height planted in a pot of 12cm in diameter,
A 10 ml water dilution of the active compound prepared as described above having a predetermined concentration was sprayed per pot. After drying the spray liquid,
A 14-cm-high wire mesh was covered with a wire mesh, and 30 female adults of the leafhopper leafhopper, which showed resistance to the organic phosphorus agent, were released in the wire mesh. The insects were placed in a constant temperature room, the number of dead insects was checked two days later, and the insecticidal rate was calculated. . As a result, Compound No. 2,3,1
1,12,14,15,16,17,40 showed 100% insecticidal rate at 200 ppm of the active ingredient.

Example 9 Test for Organic Phosphorus and Carbamate-Resistant Peach Aphid Test Method: Organophosphorus raised in about 20 cm-high eggplant seedling (maeguro long eggplant) planted in a clay pot having a diameter of 15 cm; Approximately 200 carbamate-resistant peach aphids were inoculated per seedling, and one day after the inoculation, a sufficient amount of a water dilution of the active compound prepared in the same manner as in Example 8 and having a predetermined concentration was sprayed using a spray gun. . After spraying, leave at a temperature of 28 ° C and spray.
After time, the mortality was calculated. The test was repeated twice. As a result, Compound No. 2,3,11,12,1
4,15,16,17,40 compounds have an active ingredient content of 5
At 100 ppm, the insecticidal rate was 100%.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI A01N 43/88 102 A01N 43/88 102 47/40 47/40 C07D 401/14 213 C07D 401/14 213 403/06 241 403 / 06 241 405/06 251 405/06 251 409/06 251 409/06 251 413/06 251 413/06 251 417/06 251 417/06 251 265 265 419/06 419/06 (72) Katsuhiko Shibuya Tokyo 39-15 Namiki-cho, Hachioji-shi, Tokyo (58) Fields investigated (Int. Cl. ⁶ , DB name) CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] [Claim 1] The formula: (Wherein A is a heteroatom 1 selected from S, O or N)
Including to three to indicate a 5- or 6-membered heteroaryl group ring, the heteroaryl group may be substituted by a halogen atom or an alkyl group having 1 to 4 carbon atoms, X is, CH ₂ Or N; Y represents a nitro group or a cyano group; Z ¹ represents O or S; and R ¹ represents a hydrogen atom or a methyl group). Wherein A is 2-chloropyridin-5-yl or 2-chloro indicates 5-yl, X is, shows a CH ₂ or N, Y is a nitro group or a cyano group, Z ¹ represents O or S, and R ¹ represents a hydrogen atom
To, at the compound according to claim 1. 3. An insecticide containing the heterocyclic compound according to claim 1 as an active ingredient.