JPH06172342A - New hydrazine derivative and insecticide composition containing the same as active ingredient - Google Patents

Abstract

PURPOSE:To obtain a new compound capable of exhibiting high insecticidal effects, especially on insect pests of Lepidoptera as an insecticide. CONSTITUTION:A compound of formula I [A is OCH2CH2O, OCH2O, CH=CHO, etc.; R<1> is H, 1-4C alkyl or halogen; R<2> to R<4> are H, halogen, 1-4C alkyl, nitro, etc.; R<5> is 3-8C branched alkyl; R<6> is di-(1-6C alkyl)amino, N-(1-6C alkyl) substituted anilino, etc.; (n) is 0-2], e.g. N-5-methyl-benzodioxane-6-carbo-N-(N''- isopropyl-N'-isopropoxycarbonylaminouslphenyl)-N'-tert-butyl-N'-3,5- dimethylbenzoylhydrazine. The compound of formula I is obtained by reacting a compound of formula II with a compound of the formula X-S(O)n-R<6> (X is halogen) in the presence of a base (e.g. sodium hydroxide) in a solvent (e.g. THF) at -10-50 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel hydrazine derivative, which is a paddy field, upland field, orchard,
It can be used as an insecticide in forest or environmental hygiene situations. Further, the derivative can be used as a parasite control agent for protecting humans or animals from parasite damage.

[0002]

2. Description of the Related Art JP-A-62-167747 and JP-A-6-167747
2-263150, JP-A-2-295963 and JP-A-3-141245 disclose N-substituted-N'-substituted-N,
It has been described that N'-diacylhydrazine derivatives have insecticidal activity. However, these patents do not describe the derivative of the present invention described later.

[0003]

[Problems to be Solved by the Invention] Paddy fields, uplands, orchards,
In pest control scenes in forests or in environmental hygiene scenes, compounds with greater insecticidal activity and properties that do not harm beneficial insects, the environment, etc. and that are low in toxicity are required. Further, recently, harmful insects such as organophosphorus agents, carbamate agents, pyrethroid agents and the like have increased in number, and it has become difficult to control them, so that a new type of agent is required.

The present invention provides a new type of insecticidal compound which is substantially harmless to beneficial insects, environment, etc., has low toxicity and is effective against drug-resistant pests, and an insecticidal composition containing the compound as an active ingredient. The purpose is to provide things.

[0005]

Means for Solving the Problems The present inventor has conducted extensive studies as a result of the general formula

[0006]

[Chemical 14]

[In the formula, A is --OCH ₂ CH ₂ O--, --O
_{CH 2 O -, - CH 2} CH 2 CH 2 O- or -CH =
CHO-, R ¹ represents a hydrogen atom, a (C ₁ -C ₄ ) alkyl group, or a halogen atom, and R ² , R ³ , R ⁴
Are each independently a hydrogen atom, a halogen atom, or (C ₁ -C
₄ ) alkyl group, nitro group, (C ₁ -C ₄ ) haloalkyl group, (C ₁ -C ₄ ) alkoxy group, or (C ₁ -C)
₄ ) represents a haloalkoxy group, and R ⁵ represents a (C ₃ -C ₈ ) branched alkyl group. R ⁶ is ^{-N (R 7) R 8,} -N
^{(R 7) COR 8, -N} (R 7) COOR 8, -N (R
⁷ ) COSR ⁸ , -N (R ⁷ ) SO ₂ R ⁸ , -N
(R ⁷ ) SO ₂ N (R ⁸ ) ₂ or formula

[0008]

[Chemical 15]

And R ⁷ and R ⁸ are independently (C
₁ -C ₆₎ alkyl group, (C ₁ -C ₆₎ haloalkyl group, (C ₃ -C ₆₎ alkenyl, (C ₃ -C ₆₎ haloalkenyl, (C ₃ -C ₆₎ alkynyl, ( C ₃ −
C ₇₎ cycloalkyl group or a halogen atom, (C ₁ -
C ₄₎ alkyl group, (C ₁ -C ₄₎ alkoxy, (C
₁ -C ₄₎ a haloalkyl group or a nitro group or a phenyl group or benzyl group which may be substituted with a cyano group. n is 0, 1 or 2, m is 0 or 1
Indicates. However, the case where A is —OCH ₂ O— and R ¹ is hydrogen is excluded. ] It was found that the hydrazine derivative represented by the formula [4] has excellent insecticidal activity, and the present invention has been completed.

In the general formula (1), examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms, and examples of the (C ₁ -C ₄ ) alkyl group include methyl, ethyl, n-propyl and isopropyl. , N-butyl, isobutyl, sec-butyl or tert-butyl, and examples of the (C ₁ -C ₆ ) alkyl group include a pentyl or hexyl group in addition to the (C ₁ -C ₄ ) alkyl group described above. Examples of the (C ₁ ~C ₆₎ haloalkyl group, such as chloromethyl, 2-bromoethyl, fluoromethyl, difluoromethyl, trifluoromethyl or 2-chloro-hexyl group and the like, (C ₃ -C
₆ ) Examples of the alkenyl group include allyl, 1-propenyl and 2-butenyl groups, and (C ₁ -C ₄ ).
Examples of the alkoxy group include methoxy, ethoxy, n
-Propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy groups, and the (C ₃ -C ₆ ) alkynyl groups include, for example, propynyl or butynyl groups, and (C _1-
C ₄ ) haloalkyl groups include, for example, 1- or 2
-Chloroethyl, chloromethyl, dichloromethyl, bromomethyl, 1- or 2-bromoethyl, fluoromethyl, difluoromethyl or trifluoromethyl group and the like, and the (C ₁ -C ₄ ) haloalkoxy group includes, for example, 1- or A 2-bromoethoxy, 3-bromo-n-propoxy, 2,2,2-trifluoroethoxy or trifluoromethoxy group may be mentioned, (C _3-
C ₆₎ The haloalkenyl group, for example 3,3-dichloroacetophenone allyl and the like, (as a C ₃ -C ₆₎ cycloalkyl, for example cyclohexyl, include cyclopentyl or cyclopropyl group, (C ₃ ~ C ₈ )
Examples of the branched alkyl group include tert-butyl, 1,
2,2-trimethylpropyl, 2,2-dimethylpropyl, or 1,2,2-trimethylbutyl may be mentioned.

The preferred hydrazine derivative of the present invention is that in the general formula (1), A is -OCH ₂ CH.
_{2 O -, - OCH 2 O} -, - CH 2 CH 2 CH 2 O- or indicates -CH = CHO-, R ¹ represents a (C ₁ -C ₄₎ alkyl group, R ^2, R ^3, R ⁴ each independently represent a hydrogen atom, a halogen atom, a (C ₁ -C ₄ ) alkyl group or a nitro group, R ⁵ represents a (C ₃ -C ₈ ) branched alkyl group, and R ⁶ represents —N (R ^{7 ) R 8, -N (R 7} ) CO
^{R 8, -N (R 7)} COOR 8, -N (R 7) SO 2 R
^{8, -N (R 7) SO} 2 N (R 8) 2 or formula

[0012]

[Chemical 16]

And R ⁷ and R ⁸ are independently (C
₁ -C ₆₎ an alkyl group, (C ₁ -C ₆₎ haloalkyl group or a halogen atom or (C ₁ -C ₄₎ alkyl optionally substituted phenyl or benzyl group optionally in radical, n represents 0, m is a hydrazine derivative showing 1.

A more preferred hydrazine derivative of the present invention is that in the general formula (1), A is -OCH _{2
CH 2 O -, - CH 2} CH 2 CH 2 O- or -CH =
CHO-, R ¹ represents a (C ₁ -C ₂ ) alkyl group, R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom or a (C ₁ -C ₄ ) alkyl group, R ⁵
Represents a (C ₃ -C ₈₎ branched alkyl group, R ⁶ is -N
^{(R 7) R 8, -N} (R 7) COOR 8 or formula,

[0015]

[Chemical 17]

And R ⁷ and R ⁸ are independently (C
₁ -C ₆₎ represents an alkyl radical, n is 0, m is a hydrazine derivative that shows a 1.

The compound of the general formula (1) of the present invention can be produced by the following method. Ie the formula,

[0018]

[Chemical 18]

[In the formula, A, R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the same meanings as described above. ] The compound shown by
Formula in the presence of a base such as an alkali metal hydride (sodium hydride, etc.) in an inert solvent such as tetrahydrofuran, dioxane, ether, N, N'-dimethylformamide, dimethylsulfoxide, toluene, etc.

[0020]

Embedded image X—S (O) _n —R ⁶ (4) [X represents a halogen atom, and R ⁶ and n have the same meanings as described above. ] It can be obtained by reacting with a corresponding halide represented by, for example, N-methyl-Nn-butoxycarbonylaminosulfenyl chloride, N-isopropyl-N-isopropoxycarbonylaminosulfenyl chloride and the like.

In the reaction, the compound of the general formula (3) and the compound of the general formula (4) can be used in arbitrary ratios, but preferably in equimolar ratio or almost equimolar ratio. The base can be used in stoichiometric amount or in excess,
Preferably, a stoichiometric amount or a 1.0 to 5.0-fold excess amount is used. The reaction can be carried out usually in the temperature range of -20 ° C to the boiling point of the solvent, but preferably -10.
It is in the range of ℃ to 50 ℃.

The compound represented by the general formula (1) can also be produced by the method described below. Ie the formula,

[0023]

[Chemical 20]

[In the formula, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and n have the same meanings as described above. ] An acyl hydrazide represented by the formula in the presence of a base in an inert solvent,

[0025]

[Chemical 21]

[Wherein X is a halogen atom, A, R
¹ has the same meaning as above], and can also be produced by a method comprising reacting with benzoyl halide.

In the reaction, the compounds represented by the general formula (6) and the compound represented by the general formula (7) can be used in an arbitrary ratio, but they are preferably used in an equimolar ratio or an approximately equimolar ratio. As the solvent, a solvent inert to the reaction product can be used. For example, hexane, heptane and other aliphatic hydrocarbons,
Examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as chloroform, dichloromethane and chlorobenzene, ethers such as diethyl ether and tetrahydrofuran, nitriles such as acetonitrile and propionitrile. If necessary, a mixed solvent of these and a mixed solvent of these and water can also be used. As the base, for example, an inorganic base such as potassium hydroxide or sodium hydroxide, an organic base such as triethylamine or pyridine, or an organic metal base such as n-butyllithium can be used.
When an organic base such as triethylamine or pyridine is used, it can be used in a large excess and used as a solvent.
The amount of the base may be stoichiometric or may be used in excess, but is preferably stoichiometric or 1.0 to 5.0.
Use a fold excess. The reaction can be carried out usually in the temperature range from -20 ° C to the boiling point of the solvent, preferably -10 ° C to 50 ° C. A catalyst such as N, N'-dimethylaminopyridine may be added to the reaction system.

The compound of the general formula (6) used for producing the compound represented by the general formula (1) is represented by the general formula (5).
It can be obtained by reacting the hydrazide represented by the formula (4) with a halogen compound represented by the general formula (4) in the presence of a base in an inert solvent. The reaction is illustrated below.

[0029]

[Chemical formula 22]

[Wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ ,
X and n have the same meanings as described above. In the reaction, the compound of the general formula (5) and the compound of the general formula (4) can be used in an arbitrary ratio, but they are preferably used in an equimolar ratio or an approximately equimolar ratio. Examples of the inert solvent include tetrahydrofuran, dioxane, ether, N, N'-dimethylformamide, dimethyl sulfoxide, toluene and the like. As the base, for example, an alkali metal hydride such as sodium hydride or the like is used. The base can be used in a stoichiometric amount or an excess amount, but preferably, a stoichiometric amount or a 1.0 to 5.0-fold excess amount is used. The reaction can be carried out usually in the temperature range of -20 ° C to the boiling point of the solvent, but preferably -10 ° C to 5 ° C.
It is in the range of 0 ° C.

Further, the compound represented by the general formula (1) can also be produced by the method described below. Ie the formula,

[0032]

[Chemical formula 23]

[Wherein A, R ¹ , R ⁵ , R ⁶ , and n
Has the same meaning as above. ] The compound represented by the formula in the presence of a base in an inert solvent,

[0034]

[Chemical formula 24]

[In the formula, R ² , R ³ , R ⁴ and X have the same meanings as described above. ] It can manufacture also by the method which consists of making it react with the benzoyl halide shown.

The reaction conditions, such as the solvent and the reaction temperature, are the same as those used for the reaction between the compounds of the general formulas (6) and (7).

The compound of the general formula (10) used for producing the compound of the general formula (1) is obtained by first protecting the acyl hydrazide of the general formula (8) with a protecting group. A compound represented by the general formula (9) can be obtained by reacting with a halogen compound represented by the general formula (4) in the presence of a base in an inert solvent, followed by deprotection. The reaction is illustrated below.

[0038]

[Chemical 25]

[In the formula, A, R ¹ , R ⁵ , R ⁶ , X, B and n have the same meanings as described above. As B, for example, a protecting group for an amino group such as a formyl group or a tert-butoxycarbonyl group can be used. As a method for introducing the protecting group, a generally known method can be used.For example, in the case of a formyl group, acetic anhydride is reacted with formic acid, and in the case of a tert-butoxycarbonyl group, a general formula is used. It can be obtained by reacting the acyl hydrazide represented by (8) with di-tert-butyl dicarbonate in the presence of a base in an inert solvent. Also, as a method for removing the protecting group, a generally known method can be used. For example, methanol, alcohol such as ethanol, or hydrochloric acid in a solvent such as dioxane,
The protecting group can be removed by acting an acid such as trifluoroacetic acid. In the reaction of the compound of the general formula (9) with the compound of the general formula (4), each compound can be used in an arbitrary ratio, but is preferably used in an equimolar ratio or almost an equimolar ratio. Examples of the inert solvent include tetrahydrofuran, dioxane, ether, N,
N'-dimethylformamide, dimethyl sulfoxide,
Toluene and the like can be mentioned. As the base, an alkali metal hydride such as sodium hydride is used. The base can be used in a stoichiometric amount or an excess amount, but preferably, a stoichiometric amount or a 1.0 to 5.0-fold excess amount is used. The reaction can be carried out usually in the temperature range of -20 ° C to the boiling point of the solvent, but preferably -10 ° C.
Is in the range of -50 ° C.

The reaction mixture at the time of producing the compound of the general formula (1) is stirred for a sufficient time and the desired product is recovered by the usual post-treatments such as extraction, washing with water, drying and solvent removal. In many cases, simple solvent washing is sufficient, but if necessary, purification can be performed by recrystallization or column chromatography.

When the compound of the general formula (1) of the present invention is used, it is generally carried out in the field of pesticide manufacturing, either as it is or according to the purpose of use, or an agrochemical auxiliary is mixed in order to promote or stabilize the effect. Depending on the method used, powders, fine granules, granules, wettable powders, flowables, emulsions, microcapsules, oils, aerosols, fumigants for heating (mosquito coils, electric mosquito coils, etc.), fog and other fog agents. , A non-heated fumigant, a poison bait, and the like can be used as a composition in any formulation form.

In actual use, these various preparations can be used directly as they are or diluted with water to a desired concentration for use.

Examples of the agricultural chemical auxiliary agent include carriers (diluents) and other auxiliary agents such as spreading agent, emulsifying agent, wetting agent, dispersing agent, fixing agent and disintegrating agent. As the liquid carrier, toluene, aromatic hydrocarbons such as xylene, butanol, octanol, alcohols such as glycols, ketones such as acetone, amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, methylnaphthalene, cyclohexanone,
Examples thereof include animal and vegetable oils, fatty acids, fatty acid esters, petroleum fractions such as kerosene and light oil, and water.

Examples of solid carriers include clay, kaolin, talc, diatomaceous earth, silica, calcium carbonate, montmorillonite, bentonite, feldspar, quartz, alumina and sawdust.

A surfactant is usually used as the emulsifier or dispersant, and examples thereof include higher alcohol sodium sulfate, stearyl trimethyl ammonium chloride,
Examples thereof include anionic surfactants such as polyoxyethylene alkylphenyl ether and lauryl betaine, cationic surfactants, nonionic surfactants, and zwitterionic surfactants.

Examples of the spreading agent include polyoxyethylene nonylphenyl ether and polyoxyethylene lauryl ether, and examples of the wetting agent include polyoxyethylene nonylphenyl ether dialkylsulfosuccinate and the fixing agent. Examples include carboxymethyl cellulose and polyvinyl alcohol, and examples of the disintegrator include sodium lignin sulfonate and sodium lauryl sulfate.

Further, these compounds of the present invention can express more excellent insecticidal activity by using two or more kinds of them in combination, and other physiologically active substances such as allethrin, phthalthrin, permethrin, deltamethrin, fenvalerate, Pyrethroids such as cycloprothrin and various isomers, pyrethrum extract, DDVP (dichlorvos), fenitrothion, diazinon, organophosphorus insecticides such as temefos, NAC (carbaryl), PHC
(Propoxur), BPMC (fenbucarb), pirimicarb, carbamate insecticides such as carbosulfan, other insecticides, acaricides or fungicides, nematicides, herbicides, plant growth regulators, fertilizers, BT agents It is also possible to prepare a multipurpose composition having more excellent efficacy by mixing it with an insect hormone agent or other pesticide, and it is expected that a multiplicative effect will be obtained.

Further, for example, piperonyl butoxide, sulphoxide, safloxane, NIA-16824
(O-sec-butyl-O-propargyl phenylphosphonate), DEF (S, S, S-tributylphosphotrithioate), and other known synergists for pyrethrins are added to enhance this effect. You can also

Further, the compound of the present invention is highly stable to light, heat, oxidation, etc., but if necessary, an antioxidant or an ultraviolet absorber, for example, phenols such as BHT and BHA, aryl such as α-naphthylamine, etc. By appropriately adding amines or benzophenone compounds as stabilizers, a composition with more stable effects can be obtained.

The content of the active ingredient in the composition of the present invention varies depending on the formulation form, application method and other conditions. In some cases, only the active ingredient compound is necessary, but usually 0.02 to 9
5% (weight) It is preferably in the range of 0.05 to 80% (weight).

The amount of the composition of the present invention to be used varies depending on the dosage form, the method of application, the time of application, and other conditions. Agro-horticultural agents, agents for forest pests and agents for pests of makino are usually used as active ingredients per 10 ares. 0.5-300 g, preferably 2-2 in amount
00g is used, sanitary anti pests for agents 1~200mg a normal 1 m ² per effective component amount, preferably 1~100mg use. For example, a powder is an active ingredient of 1 to 120 g per 10 are, a granule is an active ingredient of 5 to 300 g, an emulsion, a wettable powder, a flowable powder, a wettable granule, and EW (emulsi).
On in water) agent is an active ingredient in the range of 0.5 to 100 g. However, in special cases it is possible, and sometimes even necessary, to exceed or fall below these ranges.

When the compound of the general formula (1) of the present invention is used for the control of parasites, the body weight is 0.
It can be used in doses corresponding to 1 to 200 mg / kg. The exact dosage for a given condition can be routinely determined and depends on various factors such as the substance used, the type of parasite, the formulation used and the condition of the human or animal affected by the parasite. Dependent.

Specific names of pests to which the insecticidal composition of the present invention can be applied are listed below.

From the order of the Hemiptera, for example, Nephotettix cin.
cticeps), sedge loacher (Sogatella)
furcifera), brown planthopper (Nilap
arvata lugens), Little brown planthopper (La)
odephax striatellus), Rabbit bug (Riptortus clavatu)
s), Southern green stink bug (Nezara virid)
ula), Nasigumbai (Stephanitisna)
shi), Whitefly Whitefly (Trialeurod)
From es vaporiorum, cotton aphid (Aphis gossypii), green peach aphid (Myzus persicae), scale insect (Unasquis yanonensis), lepidoptera (Lepidoptera), for example, P. serrata
eella), diamondback moth (Plutella xylos)
tella), Watamiga (Promalactis i)
nonisema), Scutellaria palustris (Adoxop)
hyes orana), bean squid (Legum)
inivora glycinivorella), Cnaphalocrosis medi
nalis), Nikameiga (Chirolo super)
essalis), Awanomeiga (Ostrinia)
furnacalis), Spodoptera frugiperda (Mamestra)
brassicae), armyworm (Pseudal)
etia separa), Hasmonyoto (Sp)
odoptera litura), rice beetle (P
arnara guttata, Pieris brassicae (P
ieris rapae-crucivora), Heliothis spp., aga (Ag)
rotisspp. ), Helicoverpa sp
p. From the order of the Coleoptera, for example, Anomala cuprea, Poplaria japonica, Weevil Weevil (Echinocnemus soqame)
us), rice weevil (Lissorhoptru)
s oryzophilus), rice muzzle (O)
ulema oryzae), Anthrenus verbasic, Tenebroides mauritanicu
s), weevil (Sitophilus zeam)
is), Red-tailed Ladybird (Henosepil)
achna vicintiocttopuncat
a), Azuki bean weevils (Callosobruchus)
chinensis), Matsunomadara Kamikiri (Mo
nochamus alternatus), succulent beetle (Aulacophora femorialis),
Leptino Tulsa Tesemulineata (Leptionta)
rsa decemlineta), Phedon cochlearia
s), Diaprotica sp.
p. ), As a Hymenoptera, for example, the turnip bee (Athalia rosae j)
aponensis), Rurichu Range Habachi (Ar
gesimilis) and diptera [Diptera] include, for example, Culex pipe.
ns fatigans, Aedes aegypti
s aegypti), soybean fly (Asph)
ondylls sp. ), Fly (Hylemya)
platter), housefly (Muscadomes)
tica viclna), fruit fly (Dacus)
cucurcitae), rice leafhopper (Agro)
myza oryzae), fruit fly (Luclia)
spp. ), As an Aphaniptera, a human flea (Pulex irritans), and a Xenopsylla cheopi.
s), dog flea (Ctenocephalides c)
anis), as a Thysanoptera, as a thrips thrombus (Sirtotrips)
Dorsalls), Thrips negra (Thrips)
tabaci), Thrips palmi Thrips (Thri
ps palmi), rice thrips (Balioth)
rips biformis), lice [Anopl
ura], for example, white lice (Pedicu)
ls humanus corporis, lice (Pthirus pubis), Chaptoptera [P
Socopter], for example, cochate (T
rodium pulsatorium), hiratachatate (Liposcelisbostrychophi)
lus), as an orthoptera [Orthoptera], kerula (Gryllottalpa africana), locust migratory locust (Locusta migratori)
a), Kobaneago (Oxya yezoensi)
s), German cockroach (Blattella ger)
manlica), Black cockroach (Periplane)
ta fuliginosa).

Further, the insecticidal composition of the present invention can be applied.
The most important parasites and their associated diseases that afflict humans are summarized below, but are not limited thereto.

Disease product Bilharzosis or Schistosoma mansoni Schistosomiasis S. Japanicum S. Haematobium (schistosomiasis, fluke) Ancyclostomiasis Necator americanus, Ancyclostoma duode- nale (hookworm, nematode) Ascariasis Ascaris lumbricold- es (roundworm, C. elegans) Filariasis or Wuchereria bancrof- elephantiasis ti Brugia malayi (nematode) Onchoceriasis or Onchocerrca volvul- river blindus us (nematode) Loisis Loa loa (eye filamentous nematode, nematode)

[0057]

The present invention will be described below with reference to examples.
The present invention is not limited to these.

Production Example 1 N-5-methyl-benzodioxane-6-carbo-N-
(N "-isopropyl-N" -isopropoxycarbonylaminosulfenyl) -N'-tert-butyl-N'-
3,5-Dimethylbenzoylhydrazine (Compound No.
1-5) Preparation: 60% sodium hydride 45 mg T
To the HF suspension (5 ml) was added N-5-methyl-benzodioxane-6-carbo-N'-tert-butyl-N'-3,5.
-A solution of 300 mg of dimethylbenzoylhydrazine in THF (5 ml) was added dropwise under ice cooling. After stirring for 1 hour,
176 mg of N-isopropyl-N-isopropoxycarbonylaminosulfenyl chloride was added dropwise, and the mixture was stirred for 2 hours. Water was added to the reaction solution, extracted with ethyl acetate, dried over magnesium sulfate, and the solvent was evaporated under reduced pressure to give a yellow oil. This oil was purified by silica gel column chromatography to obtain 95 mg of a white solid. (Mp:
152-155 ° C) ¹ H-NMR (CDCl ₃ ) δ (ppm) 0.30 to 1.17 (6H), 1.20 to 1.52 (6
H), 1.55 to 1.80 (11H), 2.09 (3
H, s), 2.27 (6H, s), 4.25 (4H,
s), 5.08 (1H, brs), 6.53 (1H, b)
rs), 7.03 (3H, s).

Production Example 2 N-5-methylchroman-6-carbo-N- (N "-isopropyl-N" -isopropoxycarbonylaminosulfenyl) -N'-tert-butyl-N'-3,5- Preparation of dimethylbenzoylhydrazine (Compound No. 2-2): N-5-methylchroman-6-carbo-N'-tert
1.0 g of -butyl-N'-3,5-dimethylbenzoylhydrazine was dissolved in 20 ml of anhydrous THF, 0.15 g of 60% sodium hydride was added, and the mixture was heated until no bubbles were generated. Then, in an ice bath, N-isopropyl-
1.1 g of N-isopropoxycarbonylaminosulfenyl chloride was added dropwise, and the mixture was stirred at room temperature for 2 hours. Next, the reaction solution was poured into ice water and extracted with ethyl acetate. The obtained organic layer was washed with 5% hydrochloric acid, water and saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a yellow oil. This oil was purified by silica gel column chromatography and then recrystallized from hexane-ethyl acetate to give the desired N-5-methylchroman-6-.
206 mg of white crystals of carbo-N- (N "-isopropyl-N" -isopropoxycarbonylaminosulphenyl) -N'-tert-butyl-N'-3,5-dimethylbenzoylhydrazine were obtained. (Mp: 132-13
4 ° C.) ¹ H-NMR (CDCl ₃ ) δ (ppm) 0.45 to 1.00 (6H), 1.00 to 1.50 (8
H), 1.70 (9H, s), 1.90 to 2.20 (5
H), 2.27 (6H, s), 2.50 to 2.76 (2
H), 4.12 (2H, t), 5.05 (1H, br
s), 6.50 (1H, brs), 7.05 (3H,
s).

Production Example 3 N-5-methylbenzodioxane-6-carbo-N-
(N ", N" -di-n-butylaminosulfenyl)-
N'-tert-butyl-N'-3,5-dimethylbenzoylhydrazine (Compound No. 1-1) and di (N-5)
-Methylbenzodioxane-6-carbo-N'-tert-
Production of butyl-N'-3,5-dimethylbenzoylhydrazino) disulfide (Compound No. 5-1): N-
5-Methylbenzodioxane-6-carbo-N'-tert
0.5 g of -butyl-N'-3,5-dimethylbenzoylhydrazine was dissolved in 10 ml of anhydrous THF, 76 mg of 60% sodium hydride was added, and the temperature was raised to 40 ° C. Then, in an ice bath, di-n-butylamine and S ₂ Cl ₂
0.2 g of di-n-butylaminosulfenyl chloride adjusted by was added dropwise and stirred for 3 hours. The reaction solution was added to water and extracted with ethyl acetate, the obtained organic phase was washed with water and then with brine, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a yellow oil. This oil was purified by silica gel column chromatography to give N-5-methylbenzodioxane-6-carbo-N-di-n-butylaminosulphenyl-N'-tert-butyl-N'-3,5.
-Dimethylbenzoylhydrazine (amorphous) 60
mg and di (N-5-methylbenzodioxane-6-carbo-N'-tert-butyl-N'-3,5-dimethylbenzoylhydrazino) disulfide (mp: 149-
152 ° C.) 160 mg was obtained.

¹ H-NMR (CDCl ₃ ) δ (ppm) Compound No. 1-1. 0.60 to 1.20 (14H), 1.68 (9H,
s), 1.99 (3H, s), 2.29 (6H, s),
2.50-3.20 (4H), 4.21 (4H, s),
5.85 (1H, m), 6.48 (1H, d), 7.0
2 (1H, s), 7.11 (2H, s). -Compound No. 5-1. 1.51 (18H, s), 1.91 (6H, s), 2.
22 (12H, s), 4.24 (8H, s), 5.60
(2H, m), 6.44 (2H), 6.90 to 7.10
(6H).

Next, representative examples of the compounds according to the present invention are shown in Tables 1 to 5 together with their general formulas.

[0063]

[Chemical formula 26]

[0064]

[Table 1]

[0065]

[Chemical 27]

[0066]

[Table 2]

[0067]

[Chemical 28]

[0068]

[Table 3]

[0069]

[Chemical 29]

[0070]

[Table 4]

[0071]

[Chemical 30]

[0072]

[Table 5]

Next, the insecticidal composition will be specifically described with reference to formulation examples.

Formulation Example 1. Emulsion To 5 parts of the compound No. 1-1, 80 parts of a mixed solution of xylene-DMSO was added and dissolved, and then 15 parts of a mixture of an ethylenephenol condensate of alkylphenol oxide and calcium alkylbenzenesulfonate was mixed to prepare an emulsion. This product is diluted with water and used as a spray solution.

Formulation Example 2. Wettable powder 20 parts of compound No. 1-1, 20 parts of kaolin, 30 parts of clay, 7.5 parts of diatomaceous earth are mixed, and a mixture of sodium laurate and sodium dinaphthylmethanesulfonate (1: 1) 7. 5 parts were mixed and pulverized to obtain a powder. This product is diluted with water and used as a spray solution.

Formulation Example 3. Dust agent: To 1 part of compound Nos. 1-5, 97 parts of a mixture of talc and calcium carbonate (1: 1) was added, mixed and ground, and sufficiently evenly dispersed and mixed, and then 2 parts of silicic anhydride was further added and mixed and ground. Made into a powder. Disperse this product as it is before use.

Formulation Example 4. Granules Compound No. 1-5 2 parts Bentonite fine powder 4
8 parts, talc 48 parts, sodium lignin sulfonate 2
After mixing with the parts, add water and knead until uniform. Next, the mixture was granulated through an injection molding machine and passed through a sizing machine and a dryer screen to obtain granules having a particle size of 0.6 to 1 mm. This product is used by spraying directly on the paddy field surface and the soil surface.

Formulation Example 5. Oil agent Compound No. 1-1 Compound (0.1 parts) To which 0.5 part of piperonyl butoxide was added and dissolved in white kerosene,
An oil solution was obtained by setting the amount to 00 parts. This product is used as it is.

Formulation Example 6. Flowable agent 5 parts of compound No. 1-5, 5 parts of Newkalgen (dispersing agent manufactured by Takemoto Yushi Co., Ltd.), 0.2 parts of Antifoam 422 (antifoaming agent manufactured by Rhone-Poulin) and 74.6 parts of distilled water. After mixing and milling at 1,000 rpm for 45 minutes, 8 parts of propylene glycol, 2 parts of xanthan gum and 1% Pro
7 parts of xcel GXL solution was added and mixed. This agent (5% flowable agent) is diluted with water and used as a spray solution.

Next, the biological effects of the compounds represented by the general formula (1) and the general formula (2) according to the present invention will be specifically described with reference to test examples.

The following compounds were used as the comparison agents in the following test examples.

A: Japanese Patent Laid-Open No. 62-167747 (No. 2)
00)

[0083]

[Chemical 31]

B: JP-A-2-295963 (No. 1.
10)

[0085]

[Chemical 32]

Test Example. 1 Effect on diamondback moth (stem and leaf dipping method) A 20% wettable powder or a 5% emulsion of the compound of the present invention was produced according to Formulation Examples 1 and 2 and used as a reagent.

Test method: The middle leaf of cabbage, which had grown to about 10 cabbage true leaves, was cut off, and 20 times was added to the treatment solution diluted with water so that the active ingredient of each reagent became 12.5 ppm.
Soaked for 2 seconds. After air-drying, it was placed in a plastic container having a diameter of 9 cm, and 10 third-instar larvae of diamondback moth were released. The container was covered with a lid having 5 to 6 small holes and allowed to stand in a constant temperature room at 25 ° C. The number of live and dead insects was investigated 4 days after the treatment and release.
Mortality was calculated. The results are shown in Table 6 as an average value of duplicates.

[0088]

[Table 6]

Test Example 2. Effect on Spodoptera litura A 20% wettable powder or a 5% emulsion of the compound of the present invention was produced according to Formulation Examples 1 and 2 and used as a reagent.

Test method: The middle leaf of cabbage, which had grown to about 10 cabbage true leaves, was cut out and immersed in a treatment solution diluted with water so that the active ingredient of each reagent was 3 ppm. After air-drying, two treated leaves were placed in a plastic container having a diameter of 9 cm, and 5 third-instar larvae of Spodoptera litura were released into the container. Cover the container with a lid that has 5 to 6 small holes 2
It was left standing in a constant temperature room at 5 ° C. The number of live and dead insects was investigated 4 days after the treatment and release, and the death rate was calculated. The results are shown in Table 7 as an average value of duplicates.

[0091]

[Table 7]

Test Example 3. Effect on Cobb Noumea 20% wettable powder or 5% emulsion of the compound of the present invention was produced according to Formulation Examples 1 and 2 and used as a reagent.

Test method: 10 rice plants at the 3-leaf stage were immersed in a treatment solution diluted with water so that the active ingredient of each reagent was 1 ppm for 20 seconds. After air-drying, the rice was wrapped with urethane and fixed in a glass cylinder (inner diameter 44 mm, height 140 mm), and 5 third instar insects of Cobnomaiga were released, and the upper portion of the glass cylinder was covered with a medicine wrapping paper. The glass cylinder was allowed to stand in a constant temperature room at 25 ° C. for 16 hours in a light period. Five days after treatment and release, the number of live and dead insects was investigated and the death rate was calculated. In addition, the test was conducted in a double system, and the Cobno meiga tested the susceptible strain. The results are shown in Table 8.

[0094]

[Table 8]

[0095]

Since the present invention is configured as described above with reference to the embodiments, it has the following effects.

The hydrazine derivative of the present invention exhibits an excellent insecticidal activity against harmful insects which are resistant to known insecticides such as organophosphorus agents and pyrethroid agents,
It is effective in pest control scenes in orchards, forests or environmental hygiene scenes.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification number Internal reference number for FI Technical indication location A01N 51/00 9159-4H C07D 307/79 311/58 7252-4C 317/68 (72) Inventor Kato Yasuhito 1090 Kamiochiai, Yono-shi, Saitama Nikkasha Housing B431 (72) Inventor Hidetoshi Shirakura 1039 Kamiochiai, Yono-shi, Saitama Nikka Dormitory (72) Inventor Akio Masui 1-14 Minaminakano, Omiya-shi, Saitama (72) Inventor Tetsuo Watanabe 880-33 Okubo, Koshigaya, Ageo City, Saitama Prefecture (72) Inventor Seiichiro Kodama 1039 Kamiochiai, Yono City, Saitama Nikka Dormitory (72) Inventor Toshiaki Yanai 1041, Yasu Town, Yasu Town, Shiga Prefecture In-house (72) Inventor Yoshihisa Tsukamoto 1041 Yasu-cho, Yasu-machi, Yasu-gun, Shiga Prefecture In-house (72) Inventor Yoshihiro Sawada 1041 Yasu-cho, Yasu-cho, Yasu-gun, Shiga Prefecture In-house (72) Inventor Yokoi Two Shiga Prefecture Yasu-gun, Yasu-cho, Yasu 1041 Sankyo shares meeting house

Claims (6)

[Claims] 1. A compound represented by the general formula (1): [In the formula, A _{-OCH 2 CH 2 O -, -} OCH 2 O-,
—CH ₂ CH ₂ CH ₂ O— or —CH═CHO—, R ¹ represents a hydrogen atom, a (C ₁ -C ₄ ) alkyl group, or a halogen atom, and R ² , R ³ , and R ⁴ are each Independently, a hydrogen atom, a halogen atom, a (C ₁ -C ₄ ) alkyl group, a nitro group, a (C ₁ -C ₄ ) haloalkyl group, (C ₁
-C ₄₎ alkoxy group, or, (C ₁ -C ₄₎ shows a haloalkoxy group, R ⁵ represents a (C ₃ -C ₈₎ branched alkyl group. R ⁶ is ^{-N (R 7) R 8,} -N (R 7) COR
^{8, -N (R 7) COOR} 8, -N (R 7) COS
^{R 8, -N (R 7)} SO 2 R 8, -N (R 7) SO 2 N
(R ⁸ ) ₂ or the formula: R ⁷ and R ⁸ are each independently a (C ₁ -C ₆ ) alkyl group, a (C ₁ -C ₆ ) haloalkyl group, and a (C ₃ -C ₆ ).
₆ ) alkenyl group, (C ₃ -C ₆ ) haloalkenyl group,
(C ₃ -C ₆₎ alkynyl, (C ₃ -C ₇₎ cycloalkyl group or a halogen atom, (C ₁ -C ₄₎ alkyl group, (C ₁ -C ₄₎ alkoxy, (C ₁ -C ₄ ) A phenyl group or a benzyl group which may be substituted with a haloalkyl group, a nitro group or a cyano group. n is 0, 1
Or 2 is shown, and m is 0 or 1. However, the case where A is —OCH ₂ O— and R ¹ is hydrogen is excluded. ] The hydrazine derivative shown by these. 2. An insecticide containing the hydrazine derivative according to claim 1 as an active ingredient. 3. An insecticidal method, which comprises applying the hydrazine derivative according to claim 1 to a pest. 4. A method for producing a hydrazine derivative represented by the general formula (1) according to claim 1, which comprises the formula: [Wherein A, R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the same meanings as in claim 1. A compound represented by the formula: embedded image in the presence of a base in an inert solvent: embedded image wherein: X—S (O) _n —R ⁶ (4) [wherein, X is a halogen atom, R ⁶ And n have the same meaning as in claim 1. ] The method of reacting with the halogen compound shown by these. 5. A method for producing a hydrazine derivative represented by the general formula (1) according to claim 1, which comprises the formula: [Wherein R ² , R ³ , R ⁴ and R ⁵ have the same meanings as in claim 1. ] In the presence of a base in an inert solvent, a compound represented by the formula: X-S (O) _n -R ⁶ (4) [wherein X is a halogen atom] , R ⁶ and n have the same meaning as in claim 1. ] The halogen compound represented by the formula [Wherein R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and n have the same meanings as in claim 1. ] In the presence of a base in an inert solvent, an acyl hydrazide represented by the formula: [Wherein, X is a halogen atom, and A and R ¹ have the same meanings as in claim 1]. 6. A method for producing a hydrazine derivative represented by the general formula (1) according to claim 1, which is represented by the formula: [In the formula, A, R ¹ and R ⁵ have the same meanings as in claim 1. ] The acyl hydrazide represented by the above formula is first protected with a protecting group, and then the following formula: [In the formula, A, R ¹ and R ⁵ have the same meanings as in claim 1, and B represents a protecting group. A compound represented by the formula: embedded image in the presence of a base in an inert solvent, wherein: X—S (O) _n —R ⁶ (4) [wherein, X is a halogen atom, R ⁶ and n has the same meaning as in claim 1. ] The resulting compound of the following formula: [In the formula, A, R ¹ , R ⁵ , R ⁶ and n have the same meanings as in claim 1. ] In the presence of a base in an inert solvent, a compound represented by the formula: [In the formula, R ² , R ³ and R ⁴ have the same meanings as in claim 1, and X represents a halogen atom. ] The method which consists of making it react with the benzoyl halide shown by these.