JPH013184A - Nitro-substituted heterocyclic compounds and pesticides - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel nitro-substituted heterocyclic compounds, their preparation and use as insecticides.

Chema Ber, (Hemisieperichte), 1 volume, 220 g to 22 pages, known before the filing date of the present application.

/Ri O♂ year, the following ceremony will be held. A compound represented by

Similarly, J, Chem, Soe, + Per
Kin Trans, I (Journal of
Chemical Society Perkin Translation I), 1979.

23 Otsu pages 1 to 2363 contain compounds represented by the following formula, as well as J, Hetrocyelle Chew,
(Journal of Heterocyclic Chemistry).

/7 volume, /41-/3 pages, /rego year, the following formula,
A compound represented by: Also, Heteroeyeleg (Hetep Cycles).

/! Volume 1/-37, i9go, compounds represented by the following formulas are described.

The present inventors have now discovered a nitro-substituted heterocyclic compound represented by the following formula (1).

formula: In the formula, R represents a hydrogen atom or an alkyl group.

2 represents an optionally substituted aryl group or a heterocyclic group, where the cyclic group is N, 0. B represents an optionally substituted ethylene or trimethylene group containing at least / optionally selected heteroatoms; indicates 2 to 3 residues in the hetero atom formed, and the residues may be at least / or heteroatoms, and may be optionally substituted, provided that the residues are 3, If the moss is a carbon atom and the remaining one is a nitrogen atom, and the nitrogen atom is located in the middle of the three carbon atoms, at least / of the two carbon atoms are keto U) Substituted with a group.

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

Manufacturing method a) Formula: %Formula%) In the formula, R and 2 are the same as above, and M represents a halogen atom or -0802-L, where L represents an alkyl group or an optionally substituted aryl group .

A compound represented by formula: In the formula, A and B are the same as above.

characterized by reacting with a compound represented by
A method for producing a nitro-substituted heterocyclic compound of formula (1).

■ Manufacturing method b): [In formula (I), B is 10M2-C= (
Here, R1 represents alkyl or aryl), ←CH
2-C+.

←C-CH=C- (here, R2 represents alkyl), and "←" represents the bond between B and the adjacent nitrogen atom)
, then let B be B'] Formula: %Formula% In the formula, R, Z and A are the same as above, and a compound represented by Formula: %Formula%() In the formula, R1 is the same as above, A compound represented by the formula: or glyoxal represented by the formula: where R is the same as above; or glyoxylic acid represented by the formula: % chlorothioformyl chloride represented by the formula %(); or the formula: Oxolyl chloride represented by the formula: or malonyl chloride represented by the formula: or ≠-chlorobenzenesulfonyl azide represented by the formula: %Formula%() In the formula, R is the same as above.

Alkyl acrylate, represented by the formula: %Formula% [), where R is the same as above, or alkyl propiolate, represented by the formula: %Formula%), where R is the same as above, represented by Dialkyl acetylene dicarboxylate, or halopropionic acid represented by the formula: %formula%() where Hal represents a halogen atom) ') /', or i'l: the formula: %formula%() A method for producing a nitro-substituted heterocyclic compound represented by the formula: wherein R, Z, A and B' are the same as above.

The nitro-substituted heterocyclic compounds of formula (I) of the present invention exhibit strong insecticidal activity.

According to the present invention, the nitro-substituted heterocyclic compound of formula (I) surprisingly has a structure similar to that of the above-mentioned compounds of the present invention, as shown in the Examples below. In fact, it exhibits an outstanding insecticidal effect.

In the compound of formula (1) of the present invention, preferably R is
2 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and 2 includes an aryl group having 6 to IO carbon atoms and a heteroatom of 1 to moss selected from 0°S, N, etc., and at least one of them is Indicates a heterocyclic group with s to m members which is a nitrogen atom, where the aryl group and the cyclic group include halogen, alkyl having 1 to ≠ carbon atoms, alkoxy having 1 to 5 carbon atoms, and 1 to 1 carbon atoms. ≠ haloalkyl, carbon number 1 -41
' may be substituted with any one selected from alkylthio, haloalkoxy having 1-7 carbon atoms, haloalkylthio having 1 to ≠ carbon atoms, nitro, and cyano, and A is ethylene, which may be substituted with methyl. or trimethylene group, and B represents 2 to 3 residues in the heterocycle formed by trapping it with its adjacent carbon atoms and nitrogen atoms, where at least / is N.

It may be a heteroatom selected from S, or I. Rodan, alkyl having 1 to 2 carbon atoms, alkoxy having 1 to ≠ carbon atoms, alkoxycarbonyl having 1 to ≠ carbon atoms, even if substituted. Good aryl having 6 to 10 carbon atoms, keto, imino, phenoxy, alkylthio having 1 to μ carbon atoms, alkoxycarbonylimino having alkyl having 1 to ≠ carbon atoms, phenoxycarbonylimino, benzoylimino, benzyl, cyano, thioketo, benzyl , hydroxy, and alkylizo having 1 to 2 carbon atoms, with the proviso that there are 3 residues, of which 2 are carbon atoms and the remaining 1 is a nitrogen atom. and when the nitrogen atom is located between the three carbon residues, at least / of the λ carbon residues
Ke is substituted with a keto group.

Furthermore, in formula (I), particularly preferred.

R represents a hydrogen atom or methyl, 2 is selected from a phenyl group and N, O, S/-,
Contains 2 heteroatoms, and at least /
represents a j-6-membered heterocyclic group in which ke is a nitrogen atom, where the phenyl group and the cyclic group include bafluoro, chlor, bromo, methyl, ethyl, methoxy, trifluoromethyl, methylthio, trifluoromethoxy, It may be substituted with any one to λ selected from trifluoromethylthio, nitro and cyano, A represents an ethylene group or trimethylene group which may be substituted with methyl, and B represents its adjacent 2 to 3 residues in the heterocycle formed together with carbon atoms and nitrogen atoms, where at least / is N.

It may be a hetero atom selected from S, or an alkoxycarous atom having an alkyl having 1 to 2 carbon atoms such as fluoro, chloro, bromo, methyl, methoxy, nyl, phenyl, keto, imino, phenoxy, or 1-2 carbon atoms. may be substituted with at least one selected from alkoxycarbonylimino, phenoxycarbonylimino, benzoylimino, benzyl, cyano, thioketo, benzyl, hydroxy, and alkylidene having 1 to 7 carbon atoms, provided that the remaining is 3, of which 2 are carbon atoms and the remaining 1 is a nitrogen atom, and when the nitrogen atom is located in the middle of the 3 carbon atoms, at least / of the 2 carbon atoms Ke is substituted with a keto group.

As specific examples of the compound of formula (I) of the present invention, the following compounds can be particularly exemplified.

In manufacturing method B), 5 as raw materials, for example,! -Chloroyochloromethylpyridine, ethyl/, 2,3.3
-tetrahydro- and -nitroimizo[/,,2-a
:]] Pyridine! -One-B-Carpoxyle is expressed by the following reaction formula.

(Left below) (/ri) In production method b), if, for example, nitromethylene-3-C2-chloro-terpyridylmethyl)imidazolidine and methyl propionate are used as raw materials, the following reaction will occur. It is expressed by the formula.

(The following is a blank space) (7/) (,20) H-No2 In the above production method a), the compound of the formula (IQ) which is a raw material means a compound based on the definitions of R, Z and M above.

In formula QI)K, R and 2 preferably have the same meanings as the preferred definitions above, and M represents chloro or tosyloxy.

The compound of formula (II) has already been disclosed in JP-A-62-73g2.
A specific example is 2-chloro-j-chloromethylpyridi7.2-
Examples include chloro-chloromethylthiazole.

Similarly, the compound of formula (Iff) which is a raw material is the above-mentioned A and (
d) Means what is based on the definition of B.

In formula (I[l), A and B preferably have the same meanings as the preferred definitions above.

The compound of formula ([1)] is, for example, J e ch em
a So e.

Perkin (Journal Otsu Chemical Society Perkin) ■, / 7 years, 23 pages/page, J.

Heterocylie m Chem ++ (Journal of Heterocyclic Chemistry)
, 77 volumes.

/≠/3 pages, Chem, Ber, (Hemisie perichte).

This includes the compounds already described in Vol.

Formula: %Formula% In the formula, A is the same as above, and the compound represented by the above 2M1 formula (■), formula (■)
, formula (su, formula (■), formula (X), formula (X), formula (Xff
), formula (XI[r), formula (XI), formula CXV) or formula (xvI).

The compound of the above formula (■) is JP-A Sho tO-2/DO, 311
It may be a known compound already described in No. 2, etc., and specific examples thereof include 2-nitromethyleneimidazolidine, 2-nitromethylenetetrahydropyrimidine, and the like.

In addition, formula (b), formula (■), formula (■), formula (■), formula (■), formula (X), formula (X), formula [ ), formula (XII[), formula (XI),
Compounds of formula (XV) and formula (XVI) are well known in the field of organic chemistry.

In addition, for example, in the following two formulas corresponding to formula (I[I),
A is the same as above, and n is 2 or 3.

Formula: Where A and n are the same as above, it can be obtained by decomposing a compound represented by the following with an acid and then cyclizing it.

Further, the compound of the above formula (XIX) can be obtained by reacting a compound represented by the formula: %formula%() where A and n are the same as above, and l-nitro-2,2-bis(methylthio)ethylene. It can be obtained by

Further, the compound of the above formula (XX) is a compound represented by the formula: %Formula%([) where A is the same as above, and a compound represented by the formula: %Formula%() where n is the same as above, Hal is a halogen atom and can be obtained by reacting with a compound represented by:

The compounds of formula (XX[) and formula (XXII) above are known compounds.

In production method b), the compound 2〇V) which is a raw material means a compound based on the definitions of R, Z and A above.

In formula (IV), 'R, Z and A preferably have the same meanings as the above preferred definitions.

The compound of formula (IV) has already been disclosed in JP-A-1.0-. 2/g
, No. 311°, No. 3, No. 3, 27/, etc., and specific examples thereof include -nitromethylenetetone hydrobilimidun.

When carrying out process a) above, all inert solvents may be mentioned as suitable diluents.

Examples of such diluents include water: aliphatic, aliphatic and aromatic hydrocarbons (optionally chlorinated) such as hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, Methylene chloride, chloroform, carbon tetrachloride, ethylene chloride and hydrochloroethylene, chlorobenzene;
In addition to these, ethers such as diethyl ether, methyl ethyl ether, 1so-7'robyl ether, dibutyl ether, tetrapyrene oxide, dioxane,
Tetrahydrone: Nitriles such as acetonitrile, propionitrile, acrylonitrile; Alcohols such as methanol, ethanol, 1so-7' lovanol, butanol, ethylene glycol; Acid amides such as dimethylformamide, dimethylacetamide; Sulfones, sulfoxides such as , dimethyl sulfoxide, sulfolane: and bases such as hydrides such as sodium hydride and potassium hydride, alkali metal hydroxides, carbonates, and tertiary amines such as triethylamine.

Process a) above can be carried out within a wide temperature range, generally between about θ<0>C and about /θ0<0>C, preferably between about 0<0>C and about KO<0>C.

Further, although the reaction is preferably carried out under normal pressure, it can also be carried out under conditions of increased pressure or reduced pressure.

In carrying out the above production method a), for example, formula (II
For 1 mole of compound I), sodium hydride is used as a base in about 7.7 to 7.2 times the molar amount, and the compound of formula The desired compound can be obtained by reacting a molar amount to about /,/fold molar amount in an inert solvent, such as dimethyl sulfoxide.

When carrying out process b), all inert solvents similar to those exemplified in process &) can be used as suitable diluents.

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

Further, such a reaction is preferably carried out under normal pressure, but it can also be carried out under conditions of increased pressure or reduced pressure.

The reaction between the compound of formula (IV) and the compound of formula (VI) or formula (■) in production method b) is described in U.S. Patent No. ≠, 033
．． rij4 No. ≠, 033. It can be carried out similarly to the reaction described in No. 3s.

Moreover, the compound of formula (R'), formula (MID), formula (■)
Or the reaction with the compound of formula (X) is J a Pr ak
t a ch am *(Journal of practice),? It can be carried out using a similar reaction described in Volume 1, Page 4L.

Still, the compound of formula (IV) and the compound of formula (XII)
The reaction with the compound of [) or formula (ff) can be carried out according to the well-known Mickle reaction.

The reaction between the compound of formula (mV) and the compound of formula (Xv) is
By carrying out the reaction in the presence of a base, the desired nitro-substituted heterocyclic compound of formula (IB) can be obtained.

Apart from the above production method &), b), when the compound of formula (I) of the present invention is represented by the following formula: where R, Z, A and R are the same as above, the compound of formula (Ib) is , by reacting the compound of the formula (F/) with a compound represented by the formula: %formula%[), where R1 is the same as above, and then reacting with chromium), It will be done.

Such a reaction is known as Tetrahedron.

Volume 33, page 1037, Volume 37, /! 70 pages, India
It can be carried out according to the method described in ianJ, Chem, (Indian Journal Otsuka Mistry>, /!; B, f♂ page O).

Furthermore, by gently hydrolyzing the compound of the above formula (Ib), a compound corresponding to the formula (1) of the present invention represented by the following formula: where -R, Z and A are the same as above, can be obtained. Obtainable. Further, the compound of the formula (F/) and the formula (
In a reaction in which XXI [[ is the same as above, and it is possible to obtain a compound corresponding to the formula (1) of the present invention represented by:

When the compound of formula (1) of the present invention is represented by the following formula: where R, Z, A and R1 are the same as above, R1 may be the same or different, ) is a compound represented by the formula: where R, Z, A and R are the same as above, and a compound represented by the formula: %formula%() where R is the same as above. The reaction is described in US Patent No. 3 βg! ;, No. 733.

The compound of the above formula (XXIV) is JP-A-62-♂/31
．． The compound described in No. 2 can be obtained by the method described in the same publication.

The compounds of formula (I) of the present invention exhibit strong insecticidal activity.

Therefore, they can be used as insecticides. The active compound of formula (I) of the present invention exerts an accurate control effect against harmful insects without causing phytotoxicity to cultivated plants. Furthermore, the compounds of the present invention can be used to control a wide variety of pests, such as harmful sap-sucking insects, biting insects, and other plant-parasitic pests, storage pests, sanitary pests, etc., and can be applied to exterminate them.

Examples of such pests include the following. Insects include Coleoptera pests, such as the bean weevil (Calloaobruchus ch.
inensis), brown weevil (5itophilu
s zeamais), Trib.
olium eastaneum), Epilachna viginti
oetomaculata), Agriotes fusci-eollii
, Anomala rufoeuprea
), Colorado potato beet/1/ (Leptino
tarIlgdecemlineata), Diabrotieaspp-, Monochamu salt
ernatug), rice weevil (Lisso
rhoptrugoryzophilus), Lyetus bruneus: Lepidoptera 1 For example, the gypsy moth (Lymantria di
spar), Malaeosoma n.
eustrla), Pisrisrap
lLe), Spodoptera spp.
a11tura), armyworm (Mamegtra br)
assieae ), = Kameichiniu (Chilo)
5uppressalis), Py
rausta nubilalis), Ephestia eautella, Adoxophyes orana
), codling moth (Carpoea-111!IJL p
omonella), Cabra Yaga (Agrotis)
fueosa), honey hemlock (Ga1leria)
mellonella), diamondback moth (Plutella
maculipennis ), Citrus leafminer moth (
Phyllocnistis eitrella)
: Hemiptera insects, such as Nephotettix cinc
tieeps).

Brown planthopper (Ni1aparvata lugen)
s), Pseudoeoe
cus comitoeki ), Unaspis yanonensis , green peach aphid ( Myzus persicae ), apple aphid ( Aphis pomi ), cotton aphid ( Aphis gossypii ), and Japanese radish aphid ( Rh opalogiphum pgeu
dobrassieas), Nasi Gunpai (5te
phanitis nashi), red stink bug (
Nezara spp, ), ) louse (C
imex 1ectnlarius).

Trialeurodea va
porari-orutn), Pheasant 2mi (Psyll)
a spp, ); Orthoptera insects, such as the German cockroach (Blatella germani);
ca ), American cockroach (Periplaneta
americana), Gryllota
lpa afrieana), 7< ivy (Loe
ustamigratoria migratoria
des): Isopteran insects, such as the Japanese termite (Deucotermes 5pera)
tus), Coptotermes
formosanus): Diptera insects, such as Masca domestica, Aedes aegypti, Seed/? Engineering (Hylemia pla-tura),
Culex pipiens, Anopbeles 5lnens+i
s ), Culex tritae
niorhynchus), etc.

Furthermore, in the field of veterinary medicine, the novel compounds of the present invention can be used to treat a large number of harmful animal parasites (internal and external parasites).
, the analogy is valid for use against insects and helminths. Examples of such animal parasites include the following pests.

Examples of insects include Ga5trophilus gpp,
), Stable fly (Stomoxys spp, )
, Trichodectes 8PP -,
Examples include Rhodnius spp - and Ctenocephalidea eanlg.

In the present invention, a substance having an insecticidal action against all of these insects may be referred to as an insecticide.

The active compounds of formula (I) according to the invention can be put into customary pharmaceutical forms. and such forms include solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active compound infiltration - natural and synthetic, microcapsules, seed coatings, preparations with combustion devices. (For example, combustion devices include fumigation and fume cartridges, cans and coils), ULV (: cold mist (co
ld m1st), warm mist (warm m1
st)].

These formulations can be manufactured by known methods. Such a method comprises, for example, combining the active compound with a vehicle, i.e. a liquid diluent; a liquefied gas diluent; a solid diluent; or a carrier, optionally a surfactant, i.e. an emulsifier and/or a dispersant and/or This can be done by using a foam-forming agent and mixing. When using water as a developing agent, for example, organic solutions can also be used as co-solvents.

Examples of liquid diluents or carriers include, for example, aromatic hydrocarbons (e.g. xylene, toluene, alkylnaphthalenes, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (e.g. chlorobenzenes, ethylene chlorides, etc.). , methylene chloride, etc.), aliphatic hydrocarbons [e.g., cyclohexane, etc., gouphines (e.g., mineral oil fractions, etc.)], alcohols (e.g., butanol, glycol, and their ethers and esters, etc.), ketones ( For example, acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, etc.), strong polar solvents (eg dimethylformamide, dimethyl sulfoxide, etc.) and water may also be mentioned.

The liquefied gas diluent or carrier is a gas at room temperature and pressure, examples of which include butane, propane, nitrogen gas, carbon dioxide, and aerosol propellants such as halogenated hydrocarbons. .

Solid diluents include soil natural minerals (e.g. kaolin, clay, talc, chalk, quartz, attapulgite,
montmorillonite, diatoms, etc.), and soil synthetic minerals (for example, highly dispersed silicic acid, alumina, silicates, etc.).

Solid carriers for the granule reservoir include crushed and fractionated rocks (e.g. calcite, marble, pumice, sepiolite, dolomite, etc.), synthetic granules of inorganic and organic powders, and fine granules or organic substances (e.g. , sawdust, coconut shells, corncobs and tobacco stalks).

Emulsifiers and/or foaming agents include nonionic and anionic emulsifiers [e.g., polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (e.g., alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfones); salts, etc.)] and albumin hydrolysis products.

Dispersants include, for example, lignin sulfide waste liquor and methyl cellulose.

Adhesives can also be used in the formulations (powders, granules, emulsions), such adhesion agents include carboxymethylcellulose and natural and synthetic polymers (e.g. eba, gum arabic, polyvinyl alcohol and polyvinyl acetate, etc.). be able to.

Colorants may also be used, including inorganic pigments (e.g. iron oxide, titanium oxide and zolcyano blue), and organic dyes such as alizarin dyes, azo dyes or metal phthalocyanine dyes, and dyes. Trace elements such as iron, manganese, iron, copper, cobalt, molybdenum, and their salts of zinc can be mentioned.

The formulation contains, for example, 0.1 to 23% by weight of the active ingredient.
, preferably 0.3° to 0% by weight.

The active compounds of formula (I) according to the invention, in their commercially useful formulations and the use forms prepared by them, may be used in combination with other active compounds, such as insecticides, baits, fungicides,
As a mixture with acaricides, centinicides, fungicides, growth regulators or herbicides.

You can also use it. Here, the above insecticides include:
Examples include organic phosphorus agents, carbamate agents, carpoquinate agents, chlorinated hydrocarbon agents, and insecticidal substances produced by microorganisms.

Furthermore, the active compound of formula (1) of the present invention can be used as a mixture with a synergist, and such formulations and usage forms include those that are commercially useful. The synergist need not be active itself, but is a compound that amplifies the action of the active compound.

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

The concentration for use of the active compounds of formula (I) according to the invention is, for example, from 0.0000001 to 100% by weight, preferably from 0.0001 to 1% by weight.

The compound of formula (1) of the present invention can be used in a conventional manner depending on the usage form.

When used against sanitary pests and stored pests, the active compounds are distinguished by their good stability against alkalis on limestone materials, as well as their excellent residual activity in wood and soil. .

Next, the content of the present invention will be specifically explained with reference to Examples.
The present invention should not be limited to this only.

Synthesis Examples: Example/ (Compound Jf62) 2-nitromethylene-3-(2-chloro-3-pyridylmethyl)imidazolidine (/2.71!), Methyl propiolate (≠,, 2 g), Methanol Cl
A mixed solution of 00ml) was heated under reflux for about 20 hours. Next, methanol is distilled off under reduced pressure, and the residue is purified by silica dull column chromatography to obtain the desired product 2.3. ．．
3--tetrahydro-/-(,2-chloro-3-pyridylmethyl)-t-ditorimidazo(/,,2-a)pyridin-3-one (Zg) is obtained.

mpa 727-203°C Example 2 (Compound JFL≠) Ethyl/,2,3.3-tetrahydro-d-nitro!
- Oxymidazo [/, 2-a) Pyridine-O-Cal xylene] (/2.79) was dissolved in dry dimethyl sulfoxide Cl, Owg'), and Otsu0tin sodium hydride C, 21'') was added little by little. was added at room temperature in a stream of nitrogen gas, followed by stirring at room temperature for 1 hour to form the sodium salt.Next, 11C12-chloro!-chlorov methylpyridine (♂, /g) was added at room temperature, and the contents were stirred at room temperature. Stir for a day. Carefully pour the entire mixture into ice water at 100 °C. The target product will crystallize and precipitate. Wash this several times with ethanol to obtain the target ethyl /, 2,3.j-tetrahydro-7. -(,2-10roj-hiIJdylmethyl)- and -nitro-imidazoCI, 2-a)-3-one-o-carpoxylate (/coI) are obtained.

mp, 2j - 21.3°C Example 3 (Compound A Otsu 3) 2-nitromethylene-3-(2-chloro-!-thiazolylmethyl)-imidazolidine C/39') was dissolved in dry acetonitrile (100 yd). Suspend in In this solution,
Ethoxylic isothiocyanate (Otsu, Otsug) is added at room temperature, followed by heating to reflux for 10 minutes. When the contents are returned to room temperature and further stirred for 7 hours, crystals are precipitated, and these are separated.

Next, the crystals are suspended in acetic acid (Otsu θgo), and while stirring at 70° C., gypsum is added dropwise little by little.

After completion of the dropwise addition, stirring was continued for an additional 7 hours to complete the reaction. Acetic acid is distilled off under reduced pressure, water is added to the residue to dissolve it, sodium bicarbonate is added little by little to make it alkaline, and the mixture is extracted twice with dichloromethane.

After drying the dichloromethane layer with sodium sulfate, the solvent was distilled off and the residue was reconsolidated with ethanol to obtain the desired ethyl λ,≠,3. B - Tetrahydro ≠ - (2
-chloro-j-thiazolylmethyl)-3-nitroimidazo[/,,2-b]]isothiazole-2-ylidenecarpamet(/,l!,l) is obtained.

mp, /76~/10°C Compounds obtained by the same method as in Examples 1 to 3 above are shown in Table 1 below, together with the compounds of Examples 1 to 3.

(Leaving space below) Biological test example Knee comparative compound C-/: C-,2: Example 1A (biological test) Preparation of test sample solution against organic phosphorus agent-resistant black leafhopper Solvent: 3 parts by weight of xylol Emulsifier: polyoxy Ethylene alkylphenyl ether/parts by weight To prepare a suitable active compound formulation, the active compound/parts by weight are mixed with the amount of solvent containing the amount of emulsifier and the mixture is diluted with water to the desired concentration. did.

Test method: Diameter/2cm? The rice, about 10 cm tall, was planted in a pot.
A water dilution of the active compound prepared as described above at a predetermined concentration was sprinkled 10 times per pot. After drying the sprayed chemical solution, the diameter is 7 cm, and the height is 11. The cage was covered with a cFn wire mesh, and 30 adult female leafhoppers of a strain showing resistance to organic phosphorus agents were released into the mesh.The cage was placed in a thermostatic chamber, and two days later, the number of dead insects was counted and the killing rate was calculated.

The results are shown in Table 2 with representative examples.

(Left below) Table 2 Examples! Test against organic phosphorus agent and carbamate agent resistant peach aphid Test method: Approximately 20 cm tall eggplant seedlings planted on unglazed needles with diameter/j cm
Approximately 200 peach aphids/seedlings resistant to organic phosphorus agents and carbamate agents were inoculated into reared deep-black long eggplants, and 7 days after inoculation, a predetermined concentration of the active compound prepared in the same manner as in Example ≠ was inoculated. A sufficient amount of the water diluted solution was sprayed using a spray gun. After spraying, 2. ! It was left in a greenhouse at i''C, and the insect killing rate was calculated 2≠hours after spraying.The test was repeated once.

The results are shown in Table 3.

Table 3 (2ri)

Claims (4)

[Claims] (1) Formula: ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the formula, R represents a hydrogen atom or an alkyl group, and Z represents an optionally substituted aryl group or heterocyclic group, where , the cyclic group contains at least one heteroatom arbitrarily selected from N, O, and S, A represents an optionally substituted ethylene group or trimethylene group, and B represents that it is an adjacent represents two to three residues in the heterocycle formed together with carbon atoms and nitrogen atoms, at least one of which may be a heteroatom, and optionally substituted. However, if the number of remaining atoms is three, two of which are carbon atoms, and the remaining one is a nitrogen atom, and the nitrogen atom is located between the three remaining atoms, A nitro-substituted heterocyclic compound, wherein at least one of the two carbon residues is substituted with a keto group. (2) R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Z represents an aryl group having 6 to 10 carbon atoms, or O, S, N
A 5- to 6-membered heterocyclic group containing 1 to 2 heteroatoms selected from the following, and at least one of which is a nitrogen atom, where the aryl group and the cyclic group are halogen, Alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, haloalkoxy having 1 to 4 carbon atoms, haloalkylthio having 1 to 4 carbon atoms, optionally substituted with one selected from nitro and cyano, A represents an ethylene group or trimethylene group optionally substituted with methyl, and B together with its adjacent carbon atoms and nitrogen atoms At least one of the residues may be a hetero atom selected from N, S, or a halogen, a carbon atom having 1 to 6 carbon atoms. alkyl having 1 to 4 carbon atoms, alkoxycarbonyl having alkyl having 1 to 4 carbon atoms, optionally substituted aryl having 6 to 10 carbon atoms, keto, imino, phenoxy, alkylthio having 1 to 4 carbon atoms , alkoxycarbonylimino having alkyl having 1 to 4 carbon atoms, phenoxycarbonylimino, benzoylimino, benzyl,
Cyano, thioketo, benzyl, hydroxy and 1 carbon number
may be substituted with at least one member selected from alkylidene of ~2, provided that the remainder is 3 members, 2 of which are carbon atoms, and the remaining 1 member is a nitrogen atom,
and when the nitrogen atom is located between the three residues,
2. A compound according to claim 1, wherein at least one of the two carbon residues is substituted with a keto group. (3) R represents a hydrogen atom or methyl, and Z is a phenyl group and 1 to 2 selected from N, O, and S
represents a 5- to 6-membered heterocyclic group containing 6 heteroatoms, at least one of which is a nitrogen atom, where the phenyl group and the cyclic group are fluoro, chloro, bromo, methyl, ethyl. , methoxy, trifluoromethyl,
Optionally substituted with 1 to 2 members selected from methylthio, trifluoromethoxy, trifluoromethylthio, nitro and cyano, A represents an ethylene group or trimethylene group which may be methyl-substituted, and B represents 2 to 3 residues in the heterocycle formed together with its adjacent carbon atoms and nitrogen atoms, and at least one of the residues is a heteroatom selected from N and S. It may also be fluor, chloro, bromine,
Methyl, methoxy, alkoxycarbonyl having an alkyl having 1 to 2 carbon atoms, phenyl, keto, imino, phenoxy, alkoxycarbonylimino having an alkyl having 1 to 2 carbon atoms, phenoxycarbonylimino, benzoylimino, benzyl, cyano, thioketo, Optionally substituted with at least one member selected from benzyl, hydroxy, and alkylidene having 1 to 2 carbon atoms, provided that
There are 3 residues, 2 of which are carbon atoms, and the remaining 1
Claim 1, in which ke is a nitrogen atom, and when the nitrogen atom is located between the 3 carbon residues, at least one of the 2 carbon residues is substituted with a keto group. Compounds described in Section. (4) Formula: ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the formula, R represents a hydrogen atom or an alkyl group, and Z represents an optionally substituted heterocyclic group, where the ring The formula group is at least one arbitrarily selected from N, O, and S.
A represents an optionally substituted ethylene group or trimethylene group, and B represents 2 in the heterocycle formed when it is taken together with adjacent carbon atoms and nitrogen atoms. ~3 residues, at least one of which may be a hetero atom, or may be optionally substituted, provided that there are 3 residues, two of which are carbon atoms. When the remaining one is a nitrogen atom and the nitrogen atom is located between the three remaining carbon atoms, at least one of the two carbon residues is substituted with a keto group. An insecticide containing a nitro-substituted heterocyclic compound represented by , as an active ingredient.