JP3114242B2 - N-substituted heterocyclic amidine derivative, method for producing the same and insecticide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an N-substituted heterocyclic amidine derivative, a method for producing the derivative and an insecticide containing the derivative as an active ingredient.

[0002]

BACKGROUND ART Over the years of research and development of insecticides, many drugs have been developed and put into practical use, for example, organophosphorus insecticides such as parathion and malathion, and carbamate insecticides such as carbaryl and mesomil. These insecticides have played an extremely important role in improving agricultural production.
Among these insecticides, those whose use has been restricted due to problems such as residue and accumulated environmental pollution, and those which have produced resistant pests as a result of long-term use have come out. Therefore, there is a demand for the development of a new drug that has excellent insecticidal properties against various pests including these resistant pests and can be used safely.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an agricultural chemical which can be synthesized industrially advantageously, has a certain effect and can be used safely.

[0004]

The present invention relates to a compound represented by the general formula [I]:

Embedded image [Wherein R ₁ is a halogen atom, a nitro group, a C _1-5 alkyl
Group, C _1-5 haloalkyl group, C _1-5 alkoxy group, C
_1-5 alkylthio group, phenoxy group or _C1-5 halo
Be substituted with an alkoxy group represents an heterocyclic group, wherein
Heterocyclic groups include pyridyl, thiazolyl, and pyrimidini
A pyridinyl or pyrazinyl group . X
Represents methylene or ethylene . R ₂ is a hydrogen atom,
C _1-5 alkyl group, C _2-5 alkenyl group, C _2-5 alkini
A C _1-5 haloalkyl group, a C _3-5 cycloalkyl group,
Benzyl group, C _1-5 alkoxy group, formyl group, C _1-5 A
Represents a carbonyl group or a C _1-5 alkylsulfonyl group .

R ₃ represents a hydrogen atom, a C _1-5 alkyl group,
_1-5 haloalkyl group, a cyano C _1-5 alkyl group, C _1-5 A
Alkoxy C _1-5 alkyl group, C _1-5 alkylthio C _1-5 A
Alkyl group, C _1-5 alkoxycarbonyl C _1-5 alkyl
Group, C _2-5 alkenyl group, —OR ₈ , —SR ₈ (where R ₈
Is, C _1-5 alkyl, C _2-5 alkenyl, C _2-5 Al
Represents a quinyl group or a benzyl group . ) Or -NR ₉ R
₁₀ (wherein R ₉ is a hydrogen atom or a C _1-5 alkyl group, R _{10
Represents} a hydrogen atom, a C _1-5 alkyl group, a C _1-5 haloalkyl
Group, cyano C _1-5 alkyl group, C _1-5 alkoxy carbonyl
C _1-5 alkyl group, phenyl C _1-5 alkyl group, C _2-5
Alkenyl group, C _2-5 alkynyl group, C _3-5 cycloalkyl
Group, C _1-5 alkylcarbonyl group or C _1-5 alkyls
Represents a rufonyl group , or R ₉ and R ₁₀ are taken together with N,
Represents morpholino or 4-methylpiperidino . Furthermore, R ₂ and R ₃ together form R ₂ -R ₃ , (CH ₂ )
mA or (CH ₂ ) m may form a ring.
No. (Where A represents O, S or NR ₁₅ and R ₁₅ is water
5-thiazolyl which may be substituted with a hydrogen atom or a methyl group
And m represents 2, 3 or 4. ) R
₄ represents a nitrogen-containing 5- or 6-membered heterocyclic group,
Are the same or different and are each a halogen atom, a C _1-5 alkyl
Or a phenyl group which may be substituted with a halogen atom or
It may be mono- or di-substituted by a nitro group. Or a salt thereof, a production method thereof, and an insecticide.

The compound of the present invention is produced as follows. (1) Production method:

Embedded imageWhere r₁Is a lower alkyl group, Q is an oxygen atom or sulfur
Represents a yellow atom, X, R ₁~ R_FourHas the same meaning as above
You. This reaction is carried out with an inert organic solvent, preferably ethanol.
Aromatic carbonization in alcohols or toluene, xylene, etc.
It is performed under reflux in a hydrogen-based solvent.
In the case of the agent, the reaction proceeds even at room temperature.

(2) When R ₃ is —NR ₉ R ₁₀ (production method):

Embedded image Here, r ₂ is a lower alkyl group, X, R ₁ , R ₂ , R
₄ , R ₉ and R ₁₀ have the same meaning as described above. The reaction is carried out in the same manner as in the production method.

(3) Production method:

Embedded image Here, Hal represents a halogen atom, and X, R ₁ , R ₄ ,
R ₈ has the same meaning as described above. This reaction is carried out in an inert organic solvent such as DMF, acetone, benzene, xylene, etc., in the presence of a deoxidizing agent, if necessary, at a temperature from room temperature to the boiling point of the solvent used. As the deoxidizing agent, potassium carbonate, sodium carbonate, triethylamine, DBU and the like can be used.

(4) When R ₃ is -SR ₈ (production method):

Embedded image Here, Hal represents a halogen atom, and R ₁ , R ₂ ,
R ₈ and X have the same meaning as described above. This reaction is carried out at room temperature in an inert organic solvent, preferably DMF, in the presence of a deoxidizing agent. Potassium carbonate, sodium carbonate, triethylamine, DBU and the like can be used as the deoxidizing agent.

(5) When R ₃ is -OR ₈ (production method):

Embedded image Here, r ₃ represents a lower alkyl group, and R ₁ , R ₂ ,
R ₄ , R ₈ and X have the same meaning as described above. This reaction is carried out in an inert organic solvent, preferably an alcohol such as methanol or ethanol, in the presence of a base such as DBU or sodium methylate at room temperature or under reflux with heating. The inert organic solvent is preferably used as a reaction reagent and a solvent, but xylene, toluene, benzene and the like may be used as the inert organic solvent.

(6) R ₂ is a C _1-5 alkylcarbonyl group or
Is a C _1-5 alkylsulfonyl group (production method)

Embedded image In an inert solvent, preferably in an aromatic hydrocarbon solvent such as benzene, toluene and xylene, a compound represented by the general formula [XIV] VR ₅ [XIV] (wherein R ₅ is a C _1-5 alkylcarbonyl group or a C _{1- 5} a
Represents a alkylsulfonyl group, and V represents a halogen atom.
You. Or a compound represented by the general formula [XV] (R ₅ 'CO) ₂ O [XV] (wherein R ₅ ' represents a C _1-5 alkyl group).
The target compound can be obtained by heating from -20 ° C to 200 ° C, preferably from room temperature to the boiling point of the solvent, using a compound or the like. This reaction is performed, if necessary, in the presence of a deoxidizing agent. Potassium carbonate, sodium carbonate, triethylamine, DBU and the like can be used as the deoxidizing agent.

(7) When R ₂ and R ₃ together form a ring: a.

Embedded image Here, m represents 2, 3 or 4, and Hal, X, R ₁ ,
R ₄ has the same meaning as described above. The reaction is carried out in the same manner as in the production method. b.

Embedded image Here, m is 2, 3 or 4, A is O, S or NH,
r ₄ represents a lower alkyl group, and X, R ₁ and R ₄ have the same meanings as described above. The reaction is carried out in the same manner as in the production method. After completion of the reaction, the target product can be obtained by performing ordinary post-treatment in any of the reactions.

The structure of the compound of the present invention is IR, NMR, M
Determined from ASS etc. When R ₂ is hydrogen in the compound of the present invention,

Embedded image May exist.

When R ₃ is —NR ₉ R ₁₀ and at least one of R ₉ and R ₁₀ is hydrogen,

Embedded image Such tautomers may exist.

The compound of the present invention may have a syn-anti isomer represented by the following formula:

Embedded image The ratio changes depending on the conditions of instrumental analysis.

[0016]

Examples-Compounds The compounds of the present invention are described in more detail with reference to the following examples. Reference Example 1 Methyl N- (2-thiazolyl) acetimidate

Embedded image 10 g of 2-aminothiazole and 13.4 g of orthoacetic acid methyl ester are charged and heated at about 100 ° C. for 1 hour while taking methanol out of the system. After completion of the reaction, the target product 13 was purified by distillation (95 to 96 ° C / 15 mmHg).
g was obtained.

Example 1 N- (2-chloro-5-pyridylmethyl) -N'-2-
Thiazolylacetoamidine (Compound No. 2):

Embedded image 1.0 g of methyl N- (2-thiazolyl) acetimidate and 0.9 g of 2-chloro-5-pyridylmethylamine in 20 ml of ethanol were charged and refluxed for 2 hours. After completion of the reaction, the product was purified and separated by column chromatography to obtain 1.3 g of the desired product. n _D ²⁵ 1.6275

Example 2 1- (2-Chloropyridylmethyl) -2- (thiazolyl-2-ylimino) imidazolidine (Compound No. 45)
5):

Embedded image 2.0 g of S, S'-dimethyl N-2-thiazolyldithioiminocarbonate and 2.0 g of 2-chloro-5-pyridylmethylaminoethylamine were charged in 20 ml of ethanol, and the mixture was refluxed for 18 hours. After completion of the reaction, 1.6 g of the desired product was obtained by purification and separation by column chromatography. mp134-135 ° C

Example 3 N-2-chloro-5-pyridylmethyl-N'-methyl-
N "-4-methyl-2-thiazolylguanidine (Compound No. 226):

Embedded image 1.1 g of N-2-chloro-5-pyridylmethyl-N'-4-methyl-2-thiazolyl-S-methylisothiourea and 0.6 g of 30% methylamine (ethanol solution) in 20 ml of ethanol were charged and refluxed overnight. did. After the completion of the reaction, the product was purified and separated by column chromatography to obtain 0.8 g of the desired product. mp 93-96 ° C. The compounds of the present invention including those in the above Examples are shown in Table 1.

[0020]

[Table 101]

[0021]

[Table 102]

[0022]

[Table 103]

[0023]

[Table 104]

[0024]

[Table 105]

[0025]

[Table 106]

[0026]

[Table 107]

[0027]

[Table 108]

[0028]

[Table 109]

[0029]

[Table 110]

[0030]

[Table 111]

[0031]

[Table 112]

[0032]

[Table 113]

[0033]

[Table 114]

[0034]

[Table 115]

[0035]

[Table 116]

[0036]

[Table 117]

[0037]

[Table 118]

[0038]

[Table 119]

[0039]

[Table 120]

[0040]

[Table 121]

[0041]

[Table 122]

[0042]

[Table 123]

[0043]

[Table 124]

[0044]

[Table 125]

[0045]

[Table 126]

[0046]

[Table 127]

[0047]

[Table 128]

[0048]

[Table 129]

[0049]

[Table 130]

[0050]

[Table 131]

[0051]

[Table 132]

[0052]

[Table 133]

[0053]

[Table 134]

[0054]

[Table 135]

[0055]

[Table 136]

[0056]

[Table 137]

[0057]

[Table 138]

[0058]

[Table 139]

[0059]

[Table 140]

[0060]

[Table 141]

[0061]

[Table 142]

[0062]

[Table 143]

[0063]

[Table 144]

[0064]

[Table 145]

[0065]

[Table 146]

[0066]

[Table 147]

[0067]

[Table 148]

[0068]

[Table 149]

[0069]

[Table 150]

[0070]

[Table 151]

[0071]

[Table 152]

The compounds of the present invention exhibit high insecticidal activity against various pests such as armyworm, moth, aphid, black leafhopper and brown planthopper. In recent years, many insect pests such as moth, planthopper, leafhopper, aphid and the like have developed resistance to organophosphates and carbamates, causing a problem of insufficient efficacy of those agents. Is desired. The compound of the present invention is an agent having an excellent insecticidal effect not only on susceptible strains but also on insect pests resistant to organophosphates and carbamate-resistant agents.

[0073]

Means for Solving the Problems-Insecticide The insecticide of the present invention contains a compound represented by the general formula [I] as an active ingredient, and can be used as a pure active ingredient compound. Usually, it is used in a form that can be taken by general pesticides, that is, a wettable powder, a water solvent, a powder, an emulsion, a granule, a flowable and the like. As an additive and a carrier, when a solid agent is intended, soybean flour, vegetable powder such as flour,
Mineral fine powders such as diatomaceous earth, apatite, gypsum, talc, bentonite, and clay, and organic and inorganic compounds such as sodium benzoate, urea, and sodium sulfate are used.

When a liquid dosage form is intended, vegetable oil,
Mineral oil, petroleum fractions such as kerosene, xylene and solvent naphtha, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, trichloroethylene, methyl isobutyl ketone, water and the like are used as solvents. In these formulations, a surfactant can be added if necessary to obtain a uniform and stable form. The wettable powder, emulsion, aqueous solution and flowable thus obtained are diluted with water to a predetermined concentration and used as a suspension or emulsion. Is done.

It goes without saying that the compound of the present invention is sufficiently effective alone, but it can also be used in combination with various insecticides, acaricides and fungicides. Representative examples of miticides and insecticides that can be used by mixing with the compound of the present invention are shown below.

Acaricides (fungicides): chlorbenzylate, chlorpropylate, proclonol, phenisopromolate, dicophor, dinobutone, binapacryl, chlorphenamide, amitraz, BPPS, PPPS,
Benzomate, Hexythiazox, Fenbutatin Oxide, Polynactin, Quinomethionate, Thioquinox, CPCBS, Tetradiphone, Kayaside, Avermectin, Polysulfide Lime, Clofenthedine, Flubenzmin, Flufenoxuron, BCPE, Cyhexatin, Pyridabene, Fenpyroximate, Thiophanate Methyl, Benomyl, Pthiram , EDDP, fusalide, probenazole, isoprothiolane, TPN, captan, polyoxin, blasticidin S, kasugamycin, validamycin, tricyclazole, pyroquilon, phenazine oxide, mepronil, flutranil,
Pencyclone, iprodione, himexazole, metalaxyl, triflumizole, diclomedine, teclophthalam,

Organophosphorus and carbamate insecticides (miticides): fenthion, fenitrothion, diazinon, chlorpyrifos, ESP, bamidione, fentoate, dimethoate, formothion, marathon, dipterex, thiometon, phosmet, menazone, dichlorvos, acephate, EPBP , Dialiphor, methyl parathion, oxydimetone methyl, ethion, pyraclophos, monocrotophos, aldicarp, propoxur, mesomil, BPMC, MTMC, Nack,
Cartap, Carbosulfan, Benftecarb, Pirimicarb, Ethiophenecarb, Fenoxycarb, Thiodicarb,

Pyrethroid insecticides (miticidal agents): permethrin, cypermethrin, decamesulin, fenvalerate, fenpropasulin, pyrethrin, arelesulin, tetramethrin, resmethrin, dimethrin, propasulin, bifensulin, prothrin, fluvalinate, cyfluthulin, cyhalothrin, flucilinate , Etofenprox, cycloprothrin, tralomethrin, silaneophan,

Benzoylphenylurea and other insecticides: diflubenzuron, chlorfluazuron, triflumuron, teflubenzuron, buprofezin, machine oil.

[0080]

Examples-Insecticides Examples of preparations are shown below, but the carriers, surfactants and the like to be added are not limited to these examples. Example 4 Emulsion 10 parts of the compound of the present invention 5 parts of alkylphenyl polyoxyethylene 5 parts of dimethylformamide 35 parts of xylene 35 parts of the above were mixed and dissolved, and diluted with water before use to spray as an emulsion.

Example 5 Water-dispersible compound 20 parts of the compound of the present invention 5 parts of higher alcohol sulfate ester 70 parts of diatomaceous earth 70 parts of silica 5 parts of the above were mixed, pulverized into fine powder, diluted with water before use, and dispersed as a suspension.

Example 6 Dusts 5 parts of the compound of the present invention 94.7 parts of talc 0.3 parts of silica The above components were mixed and pulverized.

Example 7 Granules 5 parts of the compound of the present invention 73 parts of clay 20 parts of bentonite 20 parts of sodium salt of dioctyl sulfosuccinate 1 part of sodium phosphate 1 part The above is granulated and used as it is when used.

[0084]

Test Example 1 Efficacy against Cotton Aphid Cotton aphids were inoculated into three-size pots of cucumber 10 days after germination, using a small brush with 30 to 50 heads per section. One day later, the injured insects were removed, and the compound concentration was 125 pp according to the emulsion formulation shown in Example 4 of the above drug.
m was diluted with water and sprayed. Temperature 25
The specimen was placed in a constant temperature chamber at 65 ° C. and a humidity of 65%, and after 7 days, the number of live insects was counted, and the control rate was determined by comparing with the untreated section. Second result
It is shown in the table.

[Table 201]

[0085]

[Table 202]

Test Example 2 Efficacy against black leafhopper Rice seedlings that had passed 7 days after germination were subjected to Example 4 of the above-mentioned agent.
According to the emulsion formulation shown in the above, the compound concentration was 125 ppm
Immersed in a chemical solution diluted with water for 30 seconds. After air-drying, the treated seedling was put into a test tube, and inoculated with 10 third-instar larvae of the leafhopper leafhopper, a strain resistant to an organophosphorus agent and a carbamate agent. It was covered with gauze and placed in a thermostatic chamber at a temperature of 25 ° C. and a humidity of 65%, and the insecticidal rate was examined after 5 days. The results are shown in Table 3.

[Table 301]

[0087]

[Table 302]

[Table 102]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI A01N 43/56 A01N 43/56 C 43/58 43/58 A 43/60 43/60 43/76 43/76 43/78 43 / 78 D 101 101 43/80 101 43/80 101 43/824 43/84 101 43/84 101 43/86 102 43/86 102 47/44 47/44 C07D 277/42 C07D 277/42 401/12 401 / 12 403/12 403/12 413/12 413/12 413/14 413/14 417/12 417/12 417/14 417/14 A01N 43/82 101C (72) Inventor Haruhito Oishi Character of Takada Odawara City, Kanagawa Prefecture Yanagimachi 345 Japan Soda Co., Ltd. Odawara Research Laboratories (72) Inventor Tomio Yamada Takada character Yanagimachi 345, Odawara-shi, Kanagawa Japan Soda Co., Ltd. Odawara Research Laboratories (72) Inventor Renpei Hatano 345 Takayanagi Yanagicho, Odawara-shi, Kanagawa Japan Japan Soda Shares (72) Inventor Nobuo Takakusa 345 Yanagimachi, Takada, Odawara-shi, Kanagawa Japan Soda Corporation Odawara Research Laboratories (56) References JP-A-49-102690 (JP, A) JP-A-62-226959 (JP, A) JP-A-55-38376 (JP) JP-A-52-73890 (JP, A) JP-A-50-38729 (JP, A) JP-A-50-29590 (JP, A) JP-B-51-8895 (JP, B1) UK patent application Publication 1028619 (GB, A) British Patent Application Publication 2031879 (GB, A) Indian J.C. Chemistry, Vol. 23B, p. 342-362 (1984) Eur. J. Chem. , Vol. 22, p. 369-371 (1987) The Chemical Society of Japan, Vol. 51, No. 2, p. 535-539 (1978) Justus Liebigs Ann. Chem. , No. 8, p. 1362-1371 (1973) Chemical Abstracts, Abstract No. 111: 112186 (1989) Phosphorus and Sulfer, Vol. 5, p. 189-190 (1978) Phosphorus and Sulfer, Vol. 11, p. 357-361 (1981) Indian J.C. Appl. Chem. , Vol. 31, No. 5-6, p. 202-206 (1968) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07D 213/00-213/74 C07D 277/00-277/42 C07D 401/00-401 / 12 C07D 403/00-403/12 C07D 413/00-413/14 C07D 417/00-417/14 CA (STN) REGISTRY (STN)

Claims (10)

(57) [Claims] 1. A compound of the general formula [I] Wherein R ₁ is a halogen atom, a nitro group, a C 1-5 alkyl
Group, C1-5 haloalkyl group, C1-5 alkoxy group, C1-
5 alkylthio group, phenoxy group or C1-5 haloa
Represents a heterocyclic group which may be substituted with a alkoxy group,
Telocyclic groups include pyridyl, thiazolyl, and pyrimidinyl
Group, pyridazinyl group or pyrazinyl group . X is
Represents methylene or ethylene . R ₂ is a hydrogen atom, C 1-5
Alkyl group, C2-5 alkenyl group, C2-5 alkynyl group,
C1-5 haloalkyl group, C3-5 cycloalkyl group, benzyl
Group, C1-5 alkoxy group, formyl group, C1-5 alkyl
Represents a carbonyl group or a C1-5 alkylsulfonyl group .
R ₃ is a hydrogen atom, a C 1-5 alkyl group, a C 1-5 haloalkyl
Group, cyano C1-5 alkyl group, C1-5 alkoxy C1-5
Alkyl group, C1-5 alkylthio C1-5 alkyl group, C1-
5 alkoxycarbonyl C1-5 alkyl group, C2-5 alk
Alkenyl group, -OR _8, -SR ₈ (wherein R ₈ is, C1-5 alkyl
Group, C2-5 alkenyl group, C2-5 alkynyl group or ben
Represents a jyl group . ) Or -NR ₉ R ₁₀ (where R ₉ is a hydrogen atom or a C 1-5 alkyl group , R ₁₀ is a hydrogen atom, a C 1-5
Alkyl group, C1-5 haloalkyl group, cyano C1-5 alkyl
Group, C1-5 alkoxycarbonyl C1-5 alkyl group,
Nyl C1-5 alkyl group, C2-5 alkenyl group, C2-5 alkyl
Kiniru groups, C3-5 a cycloalkyl group, C1-5 alkyl Cal
Represents a bonyl group or a C1-5 alkylsulfonyl group ,
R ₉ and R ₁₀ are taken together with N to form morpholino or 4
-Represents methylpiperazino . Further, R ₂ and R ₃ are combined to form R ₂ -R ₃ , wherein (CH 2) mA or (CH 2)
m may form a ring. (Where A is O,
Represents S or NR15, wherein R15 is a hydrogen atom or a methyl group
Represents an optionally substituted 5-thiazolylmethyl group, and m is
Represents 2, 3 or 4. ) R ₄ represents a nitrogen-containing 5 or 6 membered heterocyclic group, the heterocyclic group is the same or different, halo
Substituted with a gen atom, a C1-5 alkyl group, or a halogen atom
Mono or di substitution with phenyl or nitro group
It may be. Or a salt thereof. 2. A compound of the general formula [II] (In the formula, r ₁ represents a C _1-5 alkyl group, Q represents an oxygen atom or a sulfur atom, and R ₃ and R ₄ have the same meanings as described above.)
And a compound represented by the general formula [III]: (Wherein, X, R ₁ and R ₂ have the same meanings as described above) by reacting with a compound represented by the following general formula [I]: (Wherein, X and R _{1 to} R ₄ represent the same meaning as described above, provided that
Except when R ₂ and R ₃ together form a ring. )). 3. A compound of the general formula [IV] (Wherein, r ₂ is a lower alkyl group, X, R ₁ , R ₂ , R
₄ has the same meaning as described above. ) And a compound of the general formula [V] (Wherein R ₉ and R ₁₀ have the same meanings as described above) by reacting with a compound represented by the following general formula [I ′]: (Wherein, X, R ₁ , R ₂ , R ₄ , R ₉ and R ₁₀ have the same meanings as described above). 4. A compound of the general formula [VI] (Wherein X, R ₁ and R ₄ have the same meanings as described above) and a compound represented by the general formula [VII] Hal-R ₈ [VII] (where Hal represents a halogen atom and R ₈ Has the same meaning as described above.) The compound represented by the general formula [I ″] (Wherein, X, R ₁ , R ₄ and R ₈ have the same meanings as described above). 5. A compound of the general formula [VIII] (In the formula, R ₂ , R ₄ and R ₈ have the same meanings as described above.)
And a compound represented by the general formula [IX] R ₁ -X-Hal [IX] (wherein Hal represents a halogen atom, and R ₁ and X have the same meanings as described above). General formula [I ′ ″] (Wherein, X, R ₁ , R ₂ , R ₄ and R ₈ have the same meanings as described above). 6. A compound of the general formula [X] (Wherein, r ₃ is a lower alkyl group, X, R ₁ , R ₂ , R ₄
Has the same meaning as described above. Compound of the general formula [XI] R ₈ OH [XI] (wherein represented by), the general formula R ₈ consists of reacting a compound represented by.) Of the same meaning as defined above [I ^{4 ']} [ Formula 13 (Wherein, X, R ₁ , R ₂ , R ₄ and R ₈ have the same meanings as described above). 7. A compound of the general formula [XII] [XII] (wherein X, R ₁ , R ₃ and R ₄ have the same meanings as described above) and a compound represented by the general formula [XIV] VR ₅ [XIV] (wherein R ₅ is C _1-5 alkylcarbonyl or C _1-5 A
Represents an alkylsulfonyl group, V is a halogen atom. ) Or a compound represented by the general formula [XV] (R ₅ 'CO) ₂ O [XV] (wherein R ₅ ' represents a C _1-5 alkyl group). A general formula [I ⁵ '] consisting of [I ⁵ ′] (wherein, X, R ₁ , R ₃ , R ₄ and R ₅ have the same meanings as described above). 8. A compound of the general formula [XVI] (Wherein m represents 2, 3 or 4; Hal, X,
R ₁ and R ₄ have the same meaning as described above. The compound represented by the formula (I ^{6 ′} ) is obtained by subjecting the compound represented by the formula) to ring closure by heating, preferably in the presence of a deoxidizing agent. (Wherein, m, X, R ₁ and R ₄ have the same meanings as described above). 9. A compound of the general formula [XVII] (Wherein A represents O, S or NH, and m, X and R ₁ have the same meanings as described above) by converting a compound represented by the general formula [XVIII] (Wherein, r ₄ represents a lower alkyl group, and R ₄ has the same meaning as described above). The compound is reacted with a compound represented by the following general formula [I ^{7 ′} ]: (Wherein, m, X, A, R ₁ and R ₄ have the same meanings as described above). 10. A compound of the general formula [I] (Wherein X and R _{1 to} R ₄ have the same meanings as described above). An insecticide comprising as an active ingredient one or more compounds represented by the formula: