JPH0892204A - Dithiocarbonimide derivative and its use - Google Patents

Abstract

PURPOSE: To provide a new dithiocarbonimide derivative having excellent microbicidal activity against various kinds of plant blight and exhibiting excellent insecticidal and miticidal activities. CONSTITUTION: This dithiocarbonimide derivative is expressed by formula I [X is O or NH; Y is N or CH; (a) A is an alkyl, an alkenyl, an alkynyl, a cycloalkyl, a cycloalkenyl, a cycloalkyl or a tricycloalkyl and B is an alkyl when X is NH and Y is N or (b) Y is N or CH, A is group of formula II (R is t-butyl, isopropyl or phenyl) and B is methyl when X is O], e.g. N-(3,3- dimethylbutyl)-S-methyl-S-[2-[α-methoxyimino-α-(N-methylcarbamoyl)methyl] phenylmethyl ]dithiocarbonimide. The compound of formula I can be produced by reacting a compound of formula III with a compound of formula IV (L is an eliminable group). The compound of formula I is useful as a microbicide, insecticide and miticide for agricultural and horticultural use.

Description

Detailed Description of the Invention

[0001]

OBJECT OF THE INVENTION The present invention relates to a dithiocarbonimide derivative and its use.

[0002]

The present inventors have conducted extensive studies to develop an excellent agricultural and horticultural fungicide, and as a result, the dithiocarboximide derivative represented by the following general formula (3) has an excellent bactericidal effect against various plant diseases. The present invention has been completed by finding out that it has an activity and further has an excellent insecticidal and acaricidal activity. That is, the present invention has the general formula

[Chemical 3] [Wherein, X represents an oxygen atom or an NH group, Y represents a nitrogen atom or a CH group, (a) when X represents an NH group and Y represents a nitrogen atom, A is substituted. Optionally an alkyl group (usually C _{1 to} C ₂₀ , for example C ₁ to
C ₁₀ ), an optionally substituted alkenyl group (usually C ₂
-C _20, for example C ₃ ~C _10), an optionally substituted alkynyl group (usually C ₃ -C _20, for example C ₃ ~C _10), an optionally substituted cycloalkyl group (usually C ₃ ~
C _20, for example C ₃ ~C _10), an optionally substituted cycloalkenyl group (typically C ₅ -C _20, for example C ₅ ~
C _10), optionally substituted bicycloalkyl groups (typically C ₄ -C _20, for example C ₇ -C ₁₀₎ or optionally substituted tricycloalkyl group (typically C ₄ -C _20, for example C ₈ To C ₁₀ ), B represents a C _{1 to} C ₆ alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, etc.), and (b) when X represents an oxygen atom, Y represents a nitrogen atom or CH. Represents a group, A is a general formula 4

## STR00004 ## R--CH ₂ CH ₂ (wherein R represents a tert-butyl group or an isopropyl group, or a halogen atom (eg, chlorine atom, bromine atom, fluorine atom, etc.), C ₁ -C ₄ Alkyl group (eg, methyl group, ethyl group, isopropyl group, te
rt- butyl group, C ₁ -C ₄ alkoxy group (e.g.,
Methoxy group, ethoxy group, isopropoxy group, tert
-Butoxy group, etc.), C ₁ -C ₄ alkylthio group (eg, methylthio group, ethylthio group, etc.), C ₁ -C ₄ haloalkyl group (eg, trifluoromethyl group, etc.), C ₁
~ C ₄ substituted with a haloalkoxy group (eg, trifluoromethoxy group, difluoromethoxy group, 2,2,2-trifluoroethoxy group, 1,1,2,2-tetrafluoroethoxy group) or cyano group Represents a phenyl group which may be present. ) Is shown, B represents a methyl group. The present invention provides a dithiocarbonimide derivative (hereinafter referred to as the compound of the present invention) and an agricultural and horticultural fungicide containing the same as an active ingredient; insecticides and acaricides. .

In the present invention, the alkyl group in the optionally substituted alkyl group represented by A is
For example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1,1-dimethylethyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, 3-methylbutyl group, 2,
3-dimethylbutyl group, 1,3-dimethylbutyl group,
3,3-dimethylbutyl group, 1-methylpentyl group, 1
-Ethylpentyl group, 1-methylhexyl group, 2-ethylhexyl group, 1,5-dimethylhexyl group, and the like, and examples of the alkenyl group in the optionally substituted alkenyl group include allyl group and 2-methylallyl group. Examples of the alkynyl group in the optionally substituted alkynyl group include a propargyl group and the like, and examples of the cycloalkyl group in the optionally substituted cycloalkyl group include a cyclopropyl group. , A cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, and the like. Examples of the cycloalkenyl group in the optionally substituted cycloalkenyl group include a cyclopentenyl group and a cyclohexenyl group. Such Examples of the bicycloalkyl group in the optionally substituted bicycloalkyl group include, for example, an exo-2-norbornyl group, an endo-2-norbornyl group, and the like in the optionally substituted tricycloalkyl group. Examples of the tricycloalkyl group include a 1-adamantyl group and a 2-adamantyl group.

In the present invention, a substituted, designated A
Optionally substituted alkyl group, optionally substituted alkyl group
Nyl group, optionally substituted alkynyl group, substituted
Optionally substituted cycloalkyl group, optionally substituted
Cycloalkenyl group, optionally substituted bicycloar
Alkyl group and optionally substituted tricycloalkyl
The same or different substituents for the
For example, C₁~ C₆Alkoxy group (for example, methoxy group,
Toxy group, n-propoxy group, isopropoxy group, n-
Butoxy group, t-butoxy group, etc.), C₁~ C₆Haloa
Lucoxy group (eg, trifluoromethoxy group, 2,
2,2-trifluoroethoxy group, 2,2,2,2 ',
2 ', 2'-hexafluoroisopropoxy group, etc.),
Halogen atom (fluorine atom, chlorine atom, bromine atom, iodine
Elementary atom), cyano group, C₁~ C₆Alkylthio group
(Eg methylthio group, ethylthio group, etc.), or
Are each, for example, 3 or less substituents [substituents are the same.
Or differently, C ₁~ C_FourAlkyl groups (eg methyl
Group, ethyl group, n-propyl group, isopropyl group
DO), C₁~ C_FourHaloalkyl groups (eg trifluoro)
Methyl group, etc.), C₁~ C_FourAn alkoxy group (eg
Methoxy group, ethoxy group, n-propoxy group, isoprop
Poxy group, etc.), C₁~ C_FourHaloalkoxy group (even if
For example, trifluoromethoxy group), halogen atom (fluorine
Elementary atom, chlorine atom, bromine atom, iodine atom, etc.), shear
No group, nitro group, C₁~ C_FourAlkylthio groups (eg
Methylthio group, ethylthio group, etc.)
Phenyl group, phenoxy group, phenylthio
Group, aromatic heterocyclic group (for example, 2-furyl group, 2-thiene group
Nyl group, 1-imidazolyl group, 2-imidazolyl group, 3
-Imidazolyl group, 2-pyridyl group, 3-pyridyl group,
4-pyridyl group), C₃~ C_TenCycloalkyl group
(Cyclopropyl group, cyclobutyl group, cyclopentyl
Group, cyclohexyl group, etc.), having 3 to 10 ring atoms
Aliphatic heterocyclic group (oxynyl group, oxonyl group, tetra
Hydrofuryl group, tetrahydropyranyl group, 4-morpho
Nyl group) and the like.

Of the compounds of the present invention, when X is an NH group,
Preferred as A is C optionally substituted with a phenyl group (the phenyl group may be substituted).
_{1 to} C ₁₀ alkyl groups can be mentioned, among which the general formula

Embedded image R—CH ₂ CH ₂ (wherein R represents a tert-butyl group or an isopropyl group, or a halogen atom (eg, chlorine atom, bromine atom, fluorine atom, etc.), C ₁ -C ₄ Alkyl group (eg, methyl group, ethyl group, isopropyl group, te
rt- butyl group, C ₁ -C ₄ alkoxy group (e.g.,
Methoxy group, ethoxy group, isopropoxy group, tert
-Butoxy group, etc.), C ₁ -C ₄ alkylthio group (eg, methylthio group, ethylthio group, etc.), C ₁ -C ₄ haloalkyl group (eg, trifluoromethyl group, etc.), C ₁
~ C ₄ substituted with a haloalkoxy group (eg, trifluoromethoxy group, difluoromethoxy group, 2,2,2-trifluoroethoxy group, 1,1,2,2-tetrafluoroethoxy group) or cyano group Represents a phenyl group which may be present. ) Are preferred, and as B, a C ₁ -C ₃ alkyl group, especially a methyl group, is preferred.

The compounds of the present invention have the general formula

[Chemical 6] [In formula, A and B represent the same meaning as the above. ] And the compound represented by the general formula:

[Chemical 7] [In the formula, L is a leaving group (for example, chlorine atom, bromine atom, iodine atom, mesyloxy group or tosyloxy group, etc.)
And X and Y have the same meanings as described above. ] It can manufacture by reacting with the compound shown by these. The reaction temperature can range from 0 ° C or the freezing point of the solvent used to the boiling point of the solvent or 150 ° C, but is usually 10 ° C to 30 ° C. The reaction time range is
Usually 0.5 to 24 hours. The reaction is usually carried out in the presence of a base, and examples of the base used include hydroxides of alkali metals such as sodium hydroxide, carbonates of alkali metals such as potassium carbonate, hydrogens of alkali metals such as sodium hydride. Compounds. The amount of the reagent to be used in the reaction is usually 0.5 to 2 mol per 1 mol of the compound represented by the general formula 6 with respect to the compound represented by the general formula 7 and a base used if necessary. It is a ratio. As the solvent that can be used in the reaction, hexane,
Aliphatic hydrocarbons such as heptane, ligroin, petroleum ether, aromatic hydrocarbons such as benzene, toluene, xylene, halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloromethane and chlorobenzene, diethyl ether, diisopropyl ether, Dioxane, tetrahydrofuran, ethers such as ethylene glycol dimethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone and other ketones, ethyl formate, ethyl acetate, butyl acetate, diethyl carbonate and other esters, nitromethane, nitrobenzene and other nitro Compounds, nitriles such as acetonitrile and isobutyl nitrile, amides such as formamide, N, N-dimethylformamide and N, N-dimethylacetamide, dimethylsulfate Kishido, sulfur compounds such as sulfolane, and the like. Water may be used as a solvent when a water-prohibiting base such as sodium hydride is not used. Further, the above solvents may be mixed and used. After completion of the reaction, usual post-treatments such as extraction with an organic solvent, washing with water and concentration are carried out, and if necessary, further purification is carried out by operations such as chromatography and recrystallization to isolate the desired compound.

Among the compounds of the present invention, the compound in which X is an NH group can also be produced by reacting the corresponding compound in which X is an oxygen atom with methylamine. The reaction temperature range is usually 0 ° C. to 30 ° C., and the reaction time range is usually 0.5 hour to 24 hours. The amount of the reagent used in the reaction is 1 mol to a large excess of methylamine with respect to 1 mol of the compound in which X is an oxygen atom. As the solvent that can be used, for example, alcohols such as methanol, ethanol, isopropanol, hexane, heptane, ligroin, aliphatic hydrocarbons such as petroleum ether, benzene, toluene, aromatic hydrocarbons such as xylene, chloroform, Halogenated hydrocarbons such as carbon tetrachloride, dichloromethane and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran and ethylene glycol dimethyl ether, formamide, N, N-
Examples thereof include amides such as dimethylformamide and N, N-dimethylacetamide, sulfur compounds such as dimethyl sulfoxide and sulfolane, water and the like, and mixtures thereof. After completion of the reaction, usual post-treatment such as concentration is performed,
If desired, the desired compound can be isolated by further purification by operations such as chromatography and recrystallization.

The compound represented by the general formula (6), which is a starting compound for producing the compound of the present invention, can be prepared by, for example, March,
Jerry, Advanced Organic Chemistry, 4th Ed., P891 (19
90) and the like. The compound represented by the general formula 7 which is a starting compound for producing the compound of the present invention is described in, for example, JP-A-3-246268.
It can be produced by the method described in Japanese Patent Publication No. DE-4030038, German Patent Application DE-4030038, International Patent Application WO-9307116, Japanese Patent Application Laid-Open No. 63-30463, and the like.

When the compound of the present invention is used as an active ingredient of an agricultural and horticultural fungicide, it may be used as it is without adding any other ingredients, but it is usually used for solid carriers, liquid carriers, surfactants and other formulations. Mixed with auxiliary agents, emulsions, wettable powders,
Used as a suspension, powder, granule and the like. In this case, the content of the active ingredient in the preparation is 0.1 to 99.9% by weight, preferably 1 to 90%. Examples of solid carriers that can be used include kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn cob powder, walnut shell powder, urea, ammonium sulfate, synthetic hydrous silicon oxide and the like. Examples of the liquid carrier include fine powders or granules of
For example, xylene, aromatic hydrocarbons such as methylnaphthalene, alcohols such as isopropanol, ethylene glycol, cellosolve, acetone, cyclohexanone, ketones such as isophorone, soybean oil, vegetable oil such as cottonseed oil,
Examples include dimethyl sulfoxide, acetonitrile, water and the like. Examples of surfactants used for emulsification, dispersion, wet extension, etc. include alkyl sulfate ester salts, alkyl (aryl) sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkyl aryl ether phosphate ester salts, and naphthalene sulfone. Examples thereof include anionic surfactants such as acid formalin condensates, nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl polyoxypropylene block copolymers and sorbitan fatty acid esters. Examples of the auxiliaries for formulation include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose), PAP (isopropyl acid phosphate) and the like.

When the compound of the present invention is used as an active ingredient of a plant disease controlling agent, its application methods include foliar application, soil treatment, seed disinfection, etc., but any application method usually used by those skilled in the art can be used. Can be used, the application rate of the active ingredient, the target crop type, target disease type, disease occurrence degree, formulation form, application method, application time,
It is usually 0.01 per are although it depends on weather conditions.
˜50 g, preferably 0.05 to 10 g, and when the emulsion, wettable powder, suspending agent, etc. are diluted with water and applied, the application concentration is 0.0001 to 0.5%, preferably 0.0005 to 0.2%. %, And powders, granules, etc. are applied as they are without any dilution. The compound of the present invention is used in upland fields, paddy fields, orchards, tea fields,
It can be used as an agricultural and horticultural fungicide for pastures, lawns and the like, and when used in combination with other agricultural and horticultural fungicides, it can be expected to enhance the bactericidal effect. In addition, insecticides,
It can also be used as a mixture with acaricide, nematicide, herbicide, plant growth regulator, and fertilizer.

Examples of plant diseases which can be controlled by the compound of the present invention include the following diseases. Rice blast (Pyricularia oryaze), sesame leaf blight (Cochliobolus miyabeanus), and blight (Rhizoc)
tonia solani), powdery mildew of wheat (Erysiphe grami
nis), Fusarium head blight (Gibberella zeae), Rust (Puccinia)
striiformis P. graminis, P. recondita, P. horde
i), snow rot (Typhula sp., Micronectriella nivalis),
Bare smut (Ustilago tritici, U. unda), linseed scab (Tilletia caries), eye spot (Pseudocercosporella)
herpotrichoides), cloud disease (Rhynchosporium secalis)
, Leaf blight (Septoria tritici), Blight (Leptosphaeri)
a nodorum), citrus black spot (Diaporthe citri),
Scab (Elsinoe fawcetti), fruit rot (Penicill
ium digitatum. P. italicum), Monilia disease in apple
(Sclerotinia mail), rot (Valsa mali), powdery mildew (Podosphaera leucotricha), leaf spot disease (Alte)
rnaria mali), scab (Venturia inaequalis), pear scab (Venturia nashicola, V. pirina), black spot (Al)
ternaria kikuchiana), scab (Gymnosporangium hara)
eanum), peach scab (Sclerotinia cinerea), scab
(Cladosporium carpophilum), Phomopsis rot
(Phomopsis sp.), Black wilt of grape (Elsinoe ampelin
a), late rot (Glomerella cingulata), powdery mildew (U
ncinula necator), rust (Phakopsora ampelopsidi)
s), black lotus disease (Guignardia bidwellii), downy mildew (Plasmopara viticola), oyster anthracnose (Gloeospori)
um kaki), leaf blight (Cercospora kaki, Mycosphaerella
nawae), anthracnose of cucumber (Colletotrichum lagenariu
m), powdery mildew (Sphaerotheca fuliginea), vine wilt
(Mycosphaerella melonis), Fusarium oxy
sporum), downy mildew (Pseudoperonospora cubensis), plague (Phytophthora sp.), seedling wilt (Pythium sp.), tomato ring spot (Alternaria solani), leaf mold (Clados)
porium fulvum), plague (Phytophthora infestans), brown leaf spot of eggplant (Phomopsis vexans), powdery mildew (Erysip)
he cichoracearum), black spot of cruciferous vegetables (Altern
aria japonica), white spot (Cercosporella brassicae),
Green onion rust (Puccinia allii) and soybean purpura (Ce
rcosporera kikuchii), black spot (Elsinoe glycines)
, Black spot (Diaporthe phaseolorum var. Sojae), Bean anthracnose (Colletotrichum lindemthianum), Peanut black spot (Mycosphaerella personatum), Brown spot
(Cercospora arachidicola), powdery mildew of pea
(Erysiphe pisi), potato summer blight (Alternaria so
lani), plague (Phytophthora infestans), powdery mildew of strawberry (Sphaerotheca humuli), net blast of Chu (Exob)
asidium reticulatum), white scab (Elsinoe leucospila)
, Tobacco scab (Alternaria longipes), powdery mildew (Erysiphe cichoracearum), anthracnose (Colletotrichu)
m tabacum), downy mildew (Peronospora tabacina), plague
(Phytophthora nicotianae), brown leaf spot of sugar beet (Cerco
spora beticola), rose scab (Diplocarpon rosa)
e), powdery mildew (Sphaerotheca pannosa), brown spot of chrysanthemum (Septoria chrysanthemi-indici), white rust (Pucc)
inia horiana), gray mold of various crops (Botrytis c
inerea), sclerotinia sclerotiorum, etc.

When the compound of the present invention is used as an active ingredient for insecticides and acaricides, it may be used as it is without adding any other ingredients, but it is usually a solid carrier, liquid carrier, gaseous carrier, Oil, emulsion, wettable powder, flowable agent, granule, powder, aerosol, fumes (fogging etc.), poison bait, mixed with bait etc. and added surfactants and other auxiliary agents for formulation if necessary. It is used after being formulated. These formulations usually contain the compound of the present invention as an active ingredient in a weight ratio.
Contains 0.01% to 95%. Examples of solid carriers used for formulation include clays (kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide, bentonite, fubasami clay, acid clay, etc.), talcs, ceramics, and other inorganic minerals (sericite, quartz, Sulfur, activated carbon, calcium carbonate, hydrated silica, etc., chemical fertilizers (ammonium sulfate, ammonium phosphorus, ammonium nitrate,
Examples of the liquid carrier include water, alcohols (methanol, ethanol, etc.), ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (urea, ammonium chloride, etc.) and the like. Benzene, toluene, xylene, ethylbenzene, methylnaphthalene, etc.), aliphatic hydrocarbons (hexane, cyclohexane,
Kerosene, light oil, etc.), esters (ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), ethers (diisopropyl ether, dioxane, etc.), acid amides (N, N-dimethylformamide, N, N-dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), dimethyl sulfoxide, soybean oil, vegetable oils such as cottonseed oil, and the like, and a gaseous carrier, that is, a propellant, Examples thereof include CFC gas, butane gas, LPG (liquefied petroleum gas), dimethyl ether, carbon dioxide gas and the like. Examples of the surfactant include alkyl sulfate salts, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylenated products thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives and the like. can give. Examples of formulation adjuvants such as sticking agents and dispersants include casein, gelatin, polysaccharides (starch powder, gum arabic, cellulose derivatives, alginate sugars), lignin derivatives, bentonites, sugars, synthetic water-soluble polymers (polyvinyl alcohol). , Polyvinylpyrrolidone, polyacrylic acids, etc., and examples of the stabilizer include PAP (isopropyl acid phosphate) and BH.
T (2,6-di-tert-butyl-4-methylphenol), BHA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oil, mineral oil , Surfactants, fatty acids or esters thereof, and the like. As a base material for poison bait, for example, grain flour, vegetable oil, sugar, bait components such as crystalline cellulose, antioxidants such as dibutylhydroxytoluene, nordihydroguaiaretic acid, and preserved amount of dehydroacetic acid,
Examples include an accidental food ingestion agent such as pepper powder, a cheese flavor, and an attractive flavor such as onion flavor. The preparation thus obtained is used as it is or after diluted with water or the like. Also, other insecticides, nematicides, acaricides, fungicides,
Herbicide, plant growth regulator, synergist, fertilizer, soil conditioner,
It can be used simultaneously with or without mixing with animal feed or the like. When the compound of the present invention is used as an agricultural insecticide or acaricide, the application rate is usually 0.1 g to 100 g per 10 ares, and the emulsion, wettable powder, flowable agent, etc. are diluted with water before use. In this case, the application concentration is usually 0.1 ppm to 500 ppm, and granules, powders and the like are applied as the preparation without any dilution. When used as an insecticidal or acaricidal agent for epidemic prevention, emulsions, wettable powders, flowable agents, etc. are usually 0.1 ppm to 500 pp in water.
Apply it after diluting it to m, and apply as it is to oils, aerosols, fumes, poison baits, etc. The application amount and application concentration depend on the type of formulation, application time, application site, application method, pest type, degree of damage, etc., and may be increased or decreased without regard to the above range. can do.

Examples of harmful insects and harmful mites which the compound of the present invention has a controlling effect on include the following. Hemiptera small brown planthopper (Laodelphax striatellus), brown planthopper (Nilaparvatalugens), Sejirounka (Sogatel
l furcifera ), such as planthoppers, leafhopper leafhoppers ( N
ephotettix cincticeps )
( Nephotettixvirescens ) and other leafhoppers, aphids, stink bugs, whiteflies, scale insects, gum beetles, white lice , etc. Lepidoptera pests Chilo suppressalis , Cobnomeiga ( Cn )
aphalocrocis medinalis ), European corn borer ( Ostrinia nubilalis ), Shibattoga ( Parpediasia )
teterrella ), cotton bollworm ( Notarcha nubilalis )
, Phytolacca punctata ( Plodia interpunctella )
Greater moths , such as the common cutworm ( Spodoptera litura)
), Armyworm ( Pseudalitia separata ), armyworm
(Mamestra brassicae ), Tamanayaga ( Agotis ipsilon )
, Trichopurcia, Heliotis, Helicoverpa, and other moths, Pieris rapae cruci
vora ) and other white butterflies, Adoxophyes, Nasihimesinkii ( Grapholita molesa ), Kodling moss
( Cydia pomonella ) and other tortoises , peach squid ( Carposia niponensis ) and other squid moths, such as Rionetia spp., Remantoria spp., And Euproclutis spp., Plutella xyl
Stag beetles such as ostella ), and the cotton bollworm ( Pectinopho
Rhizobium species such as ra gossipiella )
(Hyphantria cunea) Hidoriga such as clothes moth (Tinea tra
Nslucens), webbing clothes moth (Tineola bisselliela) Hirozukoga such like Diptera Culex (Culex pipiens pallens such), Culex such as Culex (Cules tritaeniorhynchus), Ae
Ades, such as des aegypti , Aedes albopictus , An
Anopheles genus, such as opheles sinensis , chironomids,
Housefly ( Musca domestica ), Housefly ( Muscin
a stabulans ), such as house flies, blow flies, flesh flies, light flies, and sand flies ( Delia platura ),
Onion flies ( Delia antigua ) and other fruit flies, fruit flies, fruit flies, butterfly flies, gnats,
Western corn rootworm ( Diabrotica virgifer)
a ) the Southern corn rootworm ( Diabrotica undecimp
unctata ) and other corn rootworms, Rana buoy ( Anomala cuprea ), and Scutellaria ( Anomala rufocu )
prea ) and other chafers , Maize Weevil ( Sitoph
ilus zeamais ), rice weevil ( Lissorhoptrus or
yzophilus ), alfalfa weevil ( Hypera p
astica ), adzuki bean weevil ( Calosobruchys chienensi)
s) weevil such as, chai loco Meno garbage Shi damascene (T
enebrio molitor ), Tricium cas ( Tribolium cas)
Taneum ) and other beetles
ophora femoralis ), Phyllotreta
striolata ), Colorado potato beetle ( Lepitinotarsa decem)
lineata ) and other beetle beetles, beetles, Epilachna vigintioctopunctata ) and other epilacunas, flat beetles, long beetles, long-tailed beetles, long-horned beetles, blue-spotted beetles ( Paed)
erus fuscipes ), etc., Orthoptera pests Blattella germanica ), Black cockroach ( Periplaneta fuliginosa ), American cockroach ( Pe
roplaneta americana ), Black-tailed Cockroach ( Periplan)
eta brunnca ), North American cockroach ( Blatta orientali
s) Thysanoptera South kilometers thrips such as (Thrips palmi), green onion thrips (Thrips tabaci), Hana thrips (Thrips hawaii
Ensis) etc. Hymenoptera ants, wasps, Arigatabachi acids, sawfly, etc. Orthoptera pests eclipse such Kaburahabachi, grasshoppers, etc. Siphonaptera pests human flea (Purex irritans), etc. Anoplura body lice, crab louse (Phthirus pubis), etc. Pests of the order Homoptera, Reticulitermes spentus , harmful termites, such as Coptermes formosanus , and mites, Tetranychus uriticae
( Tetranychus cinnabarinus ), Kanzawa mites ( Tetr
anychus kazawai ), mandarin orange mites ( Panonychus citr
i ), apple spider mite (Panonychus ulmi ), spider mites such as oligonicus, citrus rust mite ( Aculops peleka)
ssi ), phytoseiid mite ( Calacarus carinatus ), and phytoseiid mite ( Polyphaqotarsonemu)
s latus ), dust mites such as slatus), tick mites, mosquito mites, ticks such as Boophilus microplus , spider mites, harmful mites such as house dust mites such as Pyroglyphidae, claw mites, and black mites, and existing insecticides and acaricides It is also effective against pests that have developed resistance to the agents.

[0014]

EXAMPLES The present invention will be described in more detail below with reference to production examples, formulation examples and test examples, but the present invention is not limited to these examples. First, production examples of the compound of the present invention will be shown. Production Example 1 A solution of S-methyl-N- (3,3-dimethylbutyl) dithiocarbamate (4.2g, 22mmol) in DMF (50ml) was added with sodium hydride (60% oil dispersion) (0.8g, 20m).
mol) was added. After stirring for 15 minutes at room temperature, methyl (E) -3-methoxy-2- (2-bromomethylphenyl) propenoate
(5.7 g, 20 mmol) was added. After stirring at room temperature for 1 hour, water was added to the reaction solution, extracted with ethyl acetate, and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was subjected to silica gel column chromatography (hexane / ethyl acetate = 6/1) to give N- (3,3-dimethylbutyl) -S-methyl-S-.
(2- (α-Methoxymethylene-α-methoxylcarbonylmethyl) phenylmethyl) dithiocarbonimide (Compound 390) (3.5 g, 8.7 mmol) was obtained as an oil. Production Example 2 S-methyl-N- (3,3-dimethylbutyl) dithiocar
Sodium hydride (60% oil dispersion) (0.8g, 20m) was added to a solution of bamate (4.2g, 22mmol) in DMF (50ml).
mol), and the mixture was stirred at room temperature for 15 minutes, then (E) -N-methyl-2
-(2-Bromomethylphenyl) -2-methoxyiminoacetamide (5.7g, 20mmol) was added. After stirring at room temperature for 1 hour, water was added to the reaction solution, extracted with ether, and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was subjected to silica gel column chromatography (hexane / ethyl acetate =
2/1), N- (3,3-dimethylbutyl) -S-methyl-S- (2- (α-methoxyimino-α- (N-methylcarbamoyl) methyl) phenylmethyl) dithiocarbonimide (Compound 61) (2.1 g, 5.3 mmol) was obtained as an oil. Production Example 3 S-methyl-N- (3,3-dimethylbutyl) dithiocar
Sodium hydride (60% oil dispersion) (0.8g, 20m) was added to a solution of bamate (4.2g, 22mmol) in THF (20ml).
mol) was added. After stirring for 15 minutes at room temperature, methyl (E) -2- (2-bromomethylphenyl) -2-methoxyiminoacetate
(5.7 g, 20 mmol) was added. After stirring at room temperature for 1 hour, water was added to the reaction solution, extracted with diethyl ether, and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was subjected to silica gel column chromatography (hexane / ethyl acetate = 5 /
1), N- (3,3-dimethylbutyl) -S-methyl-S- (2- (α-methoxyimino-α-methoxylvonylmethyl) phenylmethyl) dithiocarbonimide
(Compound 391) (6.7 g, 17 mmol) was obtained as an oil.

Production Example 4 A solution of S-methyl-N- (2-phenylethyl) dithiocarbamate (2.0 g, 9.5 mmol) in THF (30 ml) was added with sodium hydride (60% oil dispersion) (0.38 g, 9.5m
mol) was added. After stirring for 15 minutes at room temperature, methyl (E) -2- (2-bromomethylphenyl) -2-methoxyiminoacetate
(2.4g, 8.4mmol) was added. After stirring at room temperature for 1 hour, water was added to the reaction solution, extracted with ethyl acetate, and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was subjected to silica gel column chromatography (hexane / ethyl acetate = 5/1) to give N- (2-phenylethyl) -S-methyl-S-.
(2- (α-Methoxyimino-α-methoxycarbonylmethyl) phenylmethyl) dithiocarbonimide (Compound 393) (2.8 g, 6.7 mmol) was obtained as an oil. Production Example 5 N- (2-phenylethyl) -S-methyl-S- (2-
(Α-Methoxyimino-α-methoxycarbonylmethyl) phenylmethyl) dithiocarbonimide (2.6 g, 6.
To a solution of 3 mmol) in methanol (30 ml) was added methylamine methanol solution (40%) (5 ml). After stirring at room temperature for 3 hours, the reaction solution was concentrated under reduced pressure and subjected to silica gel column chromatography (hexane / ethyl acetate = 2/1) to give N-
(2-phenylethyl) -S-methyl-S- (2- (α
-Methoxyimino-α- (N-methylcarbamoyl) methyl) phenylmethyl) dithiocarbonimide (compound
193) (1.8 g, 4.3 mmol) was obtained as an oil. Production Example 6 A solution of S-methyl-N- (2-phenylethyl) dithiocarbamate (2.0 g, 9.5 mmol) in THF (30 ml) was added with sodium hydride (60% oil dispersion) (0.38 g, 9.5 m).
mol) was added. After stirring at room temperature for 15 minutes, methyl (E) -3-methoxy-2- (2-bromomethylphenyl) propenoate
(2.9 g, 10 mmol) was added. After stirring at room temperature for 1 hour, water was added to the reaction solution, extracted with diethyl ether, and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was subjected to silica gel column chromatography (hexane / ethyl acetate = 5/1).
N- (2-phenylethyl) -S-methyl-S
-(2- (α-methoxymethylene-α-methoxycarbonylmethyl) phenylmethyl) dithiocarbonimide
(Compound 392) (3.5 g, 8.4 mmol) was obtained as an oil.

Production Example 7 A solution of S-methyl-N- (3-methylbutyl) dithiocarbamate (1.7 g, 9.6 mmol) in THF (30 ml) was added to sodium hydride (60% oil dispersion) (0.4 g, 10 mmol). )
Was added. After stirring for 15 minutes at room temperature, (E) -3-methoxy-2
Methyl-(2-bromomethylphenyl) propenoate (2.
9 g, 10 mmol) was added. After stirring at room temperature for 1 hour, water was added to the reaction solution, extracted with ethyl acetate, and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was subjected to silica gel column chromatography (hexane / ethyl acetate = 5/1),
N- (3-methylbutyl) -S-methyl-S- (2-
(Α-Methoxymethylene-α-methoxycarbonylmethyl) phenylmethyl) dithiocarbonimide (Compound 38
9) (3.5 g, 9.2 mmol) was obtained as an oil. Production Example 8 A solution of S-methyl-N- (3-methylbutyl) dithiocarbamate (1.7 g, 9.6 mmol) in THF (30 ml) was added with sodium hydride (60% oil dispersion) (0.4 g, 10 mmol).
Was added. After stirring for 15 minutes at room temperature, methyl (E) -2- (2-bromomethylphenyl) -2-methoxyiminoacetate (2.
9 g, 10 mmol) was added. After stirring at room temperature for 1 hour, water was added to the reaction solution, extracted with diethyl ether, and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was subjected to silica gel column chromatography (hexane / ethyl acetate = 5/1) to give N- (3-methylbutyl) -S-methyl-S-.
(2- (α-Methoxyimino-α-methoxycarbonylmethyl) phenylmethyl) dithiocarbonimide (Compound 388) (3.4 g, 8.9 mmol) was obtained as an oil. Production Example 9 N- (3-methylbutyl) -S-methyl-S- (2-
(Α-Methoxyimino-α-methoxycarbonylmethyl) phenylmethyl) dithiocarbonimide (1.0 g, 2.
To a solution of 6 mmol) in methanol (10 ml) was added methylamine methanol solution (40%) (5 ml). After stirring at room temperature for 3 hours, the reaction solution was concentrated under reduced pressure, and the residue was subjected to silica gel column chromatography (hexane / ethyl acetate = 2/1),
N- (3-methylbutyl) -S-methyl-S- (2-
(Α-Methoxyimino-α- (N-methylcarbamoyl) methyl) phenylmethyl) dithiocarbonimide
(Compound 52) (0.6 g, 1.6 mmol) was obtained as an oil.

Next, examples of the compounds of the present invention are shown in Tables 1 to 10 together with the compound numbers. (In the definition of each substituent of the compound represented by the general formula: 2) In Tables 1 to 10, Me represents a methyl group, Et represents an ethyl group, i-Pr and “A” represents an isopropyl group, and “phenethyl” represents a 2-phenylethyl group.

[0018]

[Table 1]

[Table 2]

[Table 3]

[0019]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[0020]

[Table 8]

[Table 9]

[Table 10]

Next, some ¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) data of the compounds of the present invention shown in Tables 1 to 10 are shown. (13): 0.87 to 0.94 (3H, m), 1.31 to 1.67 (4H, m), 1.55 to
1.72 (2H, m), 2.36 (1.2H, s), 2.47 (1.8H, s), 2.92 (1.8H, s)
d, J = 5.0), 2.93 (1.2H, d, J = 5.0), 3.36-3.39 (2H, m), 3.
97 (1.8H, s), 3.98 (1.2H, s), 4.13 (1.2H, s), 4.18 (0.8H, s)
s), 6.75 (1H, br s), 7.12 ~ 7.49 (4H, m) (16): 0.86 ~ 0.93 (3H, m), 1.24 ~ 1.72 (8H, m), 2.36
(1.2H, s), 2.47 (1.8H, s), 2.93 (3H, t, J = 5.1), 3.39 (2H, s
t, J = 6.6), 3.97 (1.8H, s), 3.98 (1.2H, s), 4.12 (0.8H, s)
s), 4.20 (1.2H, s), 6.76 (1H, br, s), 7.11-7.50 (4H, m) (19): 0.85-0.92 (3H, m), 1.22-1.41 (6H, m), 1.53 ~
1.72 (2H, m), 2.36 (1.2H, s), 2.47 (1.8H, s), 2.93 (3H, d,
J = 5.0), 3.38 (0.8H, t, J = 6.8), 3.39 (1.2H, t, J = 6.8), 3.
97 (1.8H, s), 3.98 (1.2H, s), 4.11 (0.8H, s), 4.18 (1.2H, s)
s), 6.76 (1H, br, s), 7.13 ~ 7.50 (4H, m) (22): 0.89 (3H, m), 1.20 ~ 1.72 (12H, m), 2.36 (1.2H,
s), 2.47 (1.8H, s), 2.93 (3H, d, J = 5.0), 3.33 to 3.41 (2H,
m), 3.97 (1.8H, s), 3.98 (1.2H, s), 4.11 (1.2H, s), 4.18
(0.8H, s), 7.1 to 7.5 (4H, m) (28): 0.88 (3H, t, J = 6.0), 1.22 to 1.71 (16H, m), 2.36
(1.2H, s), 2.47 (1.8H, s), 2.93 (3H, d, J = 5.0), 3.32-3.
41 (2H, m), 3.96 (1.2H, s), 3.98 (1.8H, s), 4.12 (1.2H, s)
s), 4.18 (0.8H, s), 7.1 to 7.5 (4H, m) (37): 0.92 (2.4H, d, J = 6.7), 0.97 (3.6H, d, J = 6.7), 1.
85 ~ 2.05 (1H, m), 2.37 (1.2H, s), 2.48 (1.8H, s), 2.93
(1.8H, d, J = 5.0), 2.94 (1.2H, d, J = 5.0), 3.17 (0.8H, d, J =
6.6), 3.18 (1.2H, d, J = 6.6), 3.97 (1.8H, s), 3.98 (1.2H,
s), 4.14 (0.8H, s), 4.18 (1.2H, s), 6.76 (1H, br, s), 7.
11 to 7.50 (4H, m) (43): 0.80 to 0.92 (3H, m), 1.02 (1.2H, d, J = 6.0), 1.10
(1.8H, d, J = 6.0), 1.15 ~ 1.62 (4H, m), 2.34 (1.2H, s), 2.
47 (1.8H, s), 2.92 (3H, d, J = 5.0), 3.68 ~ 3.82 (1H, m),
3.97 (3H, s), 4.11 (0.6H, s), 4.17 (0.4H, s), 6.75 (1H, br
s), 7.10 to 7.51 (4H, m) (52): 0.89 (2.4H, d, J = 6.6), 0.93 (3.6H, d, J = 6.6), 1.
44 to 1.81 (3H, m), 2.36 (1.2H, s), 2.48 (1.8H, s), 2.93 (3
H, d, J = 5.0), 3.39 (0.8H, t, J = 6.6), 3.42 (1.2H, t, J = 6.
6), 3.97 (1.8H, s), 3.98 (1.2H, s), 4.11 (1.2H, s), 4.18
(0.8H, s), 6.75 (1H, br s), 7.11 ~ 7.50 (4H, m) (61): 0.91 (3.6, s), 0.95 (5.4H, s), 1.48 ~ 1.64 (2H,
m), 2.35 (1.2H, s), 2.48 (1.8H, s), 2.93 (3H, d, J = 5.0),
3.39 to 3.49 (2H, m), 3.97 (1.8H, s), 3.98 (1.2H, s), 4.10
(1.2H, s), 4.19 (0.8H, s), 6.76 (1H, br s), 7.10 ~ 7.52
(4H, m) (145): 2.24 (0.4H, t, J = 2.6), 2.29 (0.6H, t, J = 2.6),
2.41 (1.2H, s), 2.50 (1.8H, s), 2.93 (1.8H, d, J = 5.0), 2.
94 (1.2H, d, J = 5.0), 3.98 (3H, s), 4.16-4.24 (4H, m), 6.
82 (1H, br, s), 7.09 to 7.55 (4H, m) (154): 2.37 (1.2H, s), 2.47 (1.8H, s), 2.91 (1.8H, d,
J = 5.0), 2.93 (1.2H, d, J = 5.0), 3.38 (1.2H, s), 3.42 (1.8
H, s), 3.57 to 3.72 (4H, m), 3.97 (1.8H, s), 3.98 (1.2H,
s), 4.14 (1.2H, s), 4.19 (0.8H, s), 6.82 (0.4H, br, s),
6.93 (0.6H, br, s), 7.08 to 7.47 (4H, m) (181): 1.00 to 1.36 (6H, m), 2.36 (1.2H, s), 2.48 (1.8
H, s), 2.53 to 2.68 (4H, m), 2.70 to 3.90 (2H, m), 2.92 (1.8
H, d, J = 5.0), 2.93 (1.2H, d, J = 5.0), 3.55 to 3.66 (2H, m),
3.97 (1.8H, s), 3.98 (1.2H, s), 4.12 (1.2H, s), 4.19 (0.8
H, s), 6.79 (1H, brs), 7.10 ~ 7.53 (4H, m) (184): 1.61 ~ 2.08 (4H, m), 2.37 (1.2H, s), 2.48 (1.8
H, s), 2.91 (1.8H, t, J = 5.0), 2.93 (1.2H, t, J = 5.0), 3.38
~ 3.58 (2H, m), 3.73 ~ 3.94 (2H, m), 3.96 (1.8H, s), 3.98
(1.2H, s), 4.06 to 4.37 (3H, m), 6.84 (0.4H, br s), 6.95
(0.6H, br s), 7.13 to 7.52 (4H, m) (193): 2.36 (1.2H, s), 2.45 (1.8H, s), 2.88 to 3.02 (5
H, m), 3.64 (0.8H, t, J = 7.6), 3.66 (1.2H, t, J = 7.6), 3.95
(1.2H, s), 3.96 (1.8H, s), 4.11 (1.2H, s), 4.16 (0.8H, s)
s), 6.76 (1H, br s), 7.08 ~ 7.48 (9H, m) (223): 2.40 (1.2H, s), 2.52 (1.8H, s), 2.90 (1.8H, d,
J = 5.0), 2.92 (1.2H, d, J = 5.0), 3.91 (1.8H, s), 3.98 (1.2
H, s), 4.16 (1.2H, s), 4.23 (0.8H, s), 4.56 (0.8H, s), 4.
59 (1.2H, s), 6.19 (0.4H, d, J = 3.1), 6.23 (0.6H, d, J = 3.
1), 6.32 (0.4H, dd, J = 3.1,1.9), 6.35 (0.6H, dd, J = 3.1,
1.9), 6.74 (0.6H, br, s), 6.82 (0.4H, br, s), 7.11 to 7.
51 (5H, m)

(388): 0.89 (2.4H, d, J = 6.6), 0.94 (3.6H,
d, J = 6.6), 1.46 ~ 1.81 (3H, m), 2.36 (1.2H, s), 2.48 (1.8
H, s), 3.40 (0.8H, t, J = 6.6), 3.44 (1.2H, t, J = 6.6), 3.70
(3H, s), 3.83 (1.8H, s), 3.84 (1.2H, s), 4.16 (1.2H, s),
4.22 (0.8H, s), 7.08 ~ 7.50 (4H, m), 7.58 (0.6H, s), 7.51
(0.4H, s) (389): 0.89 (2.4H, d, J = 6.6), 0.93 (3.6H, d, J = 6.6), 1.
30〜1.81 (3H, m), 2.35 (1.2H, s), 2.47 (1.8H, s), 3.38〜
3.46 (3H, m), 3.87 (3H, s), 4.05 (3H, s), 4.11 (1.2H, s),
4.17 (0.8H, s), 7.08 to 7.52 (4H, m) (390): 0.91 (3.6H, s), 0.96 (5.4H, s), 1.26 (2H, d, J = 7.
2), 2.36 (1.2H, s), 2.48 (1.8H, s), 3.43 (1.2H, d, J = 7.
2), 3.47 (0.8H, d, J = 7.2), 3.70 (3H, s), 3.83 (1.8H, s),
3.84 (1.2H, s), 4.15 (1.2H, S), 4.23 (0.8H, s), 7.08 ~ 7.
47 (4H, m), 7.57 (0.6H, s), 7.61 (0.4H, s) (391): 0.91 (3.6H, s), 0.96 (5.4H, s), 1.48 ~ 1.62 (2H,
m), 2.35 (1.2H, s), 2.47 (1.8H, s), 3.38-3.49 (2H, m),
3.87 (3H, s), 4.05 (1.8H, s), 4.07 (1.2H, S), 4.10 (1.2H, s)
S), 4.17 (0.8H, s), 7.09 to 7.55 (4H, m) (392): 2.37 (1.2H, s), 2.45 (1.8H, s), 2.91 (0.8H, t,
J = 7.4), 3.01 (1.2H, t, J = 7.4), 3.58-3.70 (2H, m), 3.67
(1.2H, s), 3.70 (1.8H, s), 4.16 (1.2H, s), 4.19 (0.8H, s)
s), 7.09 to 7.46 (9H, m), 7.57 (0.6H, s), 7.59 (0.4H, s)

(393): 2.36 (1.2H, s), 2.44 (1.8H, s),
2.90 (0.8H, t, J = 7.6), 2.99 (1.2H, t, J = 7.6), 3.65 (3H, t,
J = 7.6), 3.82 (1.2H, s), 3.87 (1.8H, s), 4.04 (1.2H, s),
4.06 (1.8H, s), 4.11 (1.2H, s), 4.14 (0.8H, s), 7.10 ~ 7.
50 (9H, m) (400): 2.35 (1.2H, s), 2.45 (1.8H, s), 3.06 (0.8H, t,
J = 7.2), 3.17 (1.2H, t, J = 7.2), 3.64 (1.2H, t, J = 7.2), 3.
65 (0.8H, t, J = 7.2), 3.67 (1.2H, s), 3.70 (1.8H, s), 3.80
(1.2H, s), 3.81 (1.8H, s), 4.15 (1.2H, s), 4.18 (0.8H, s)
s), 7.09 to 7.47 (8H, m), 7.57 (0.6H, s), 7.59 (0.4H, s) (414): 2.36 (1.2H, s), 2.46 (1.8H, s), 2.87 (0.8 H, t,
J = 2.1), 2.98 (1.2H, t, J = 7.1), 3.60 (0.8H, t, J = 7.1), 3.
64 (1.2H, t, J = 7.1), 3.67 (1.2H, s), 3.70 (1.8H, s), 3.80
(1.2H, s), 3.82 (1.8H, s), 4.14 (0.8H, s), 4.19 (1.2H, s)
s), 7.08 to 7.46 (8H, m), 7.57 (0.6H, s), 7.59 (0.4H, s) (428): 2.35 (1.2H, s), 2.45 (1.8H, s), 2.87 (0.8 H, t,
J = 7.2), 2.96 (1.2H, t, J = 7.0), 3.59 (0.8H, t, J = 7.2), 3.
62 (1.2H, t, J = 7.0), 3.67 (1.2H, s), 3.70 (0.8H, s), 3.80
(1.2H, s), 3.82 (1.8H, s), 4.13 (1.2H, s), 4.19 (0.8H, s)
s), 7.09 to 7.47 (8H, m), 7.57 (0.6H, s), 7.59 (0.4H, s)

Next, production examples of the compound represented by the general formula 5, which is a raw material compound for producing the compound of the present invention, will be shown. Reference Production Example 1 Triethylamine (9.1 g, 90 mmol) and carbon disulfide (6.5 g, 86) were added to a chloroform (120 ml) solution of 3,3-dimethylbutylamine (8.7 g, 85 mmol).
mmol) was added. After stirring for 30 minutes, methyl iodide (13
g, 92 mmol) was added. After 1 hour, add 0.1M hydrochloric acid,
It was extracted with diethyl ether. The extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to give S-methyl-N- (3,
3-Dimethylbutyl) dithiocarbamate (13 g, 6
8 mmol) was obtained as an oil. Reference Production Example 2 2-Phenylethyl isothiocyanate (4.1 g, 25
To a solution of (mmol) in THF (30 ml) was added methyl mercaptan sodium solution (15%) (13 ml, 28 mmol). After stirring for 1 hour, 30 ml of 1M hydrochloric acid was added, and the mixture was extracted with ethyl acetate. The extract was concentrated under reduced pressure, and the residue was subjected to silica gel column chromatography (hexane / ethyl acetate = 5 /
1), S-methyl-N- (2-phenylethyl)
Dithiocarbamate (3.7 g, 18 mmol) was obtained as an oil.

Next, formulation examples are shown. In addition, a part represents a weight part. Formulation Example 1 50 parts of each of the compounds (1) to (435) of the present invention, 3 parts of calcium ligninsulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrous silicon oxide are well pulverized and mixed to obtain each wettable powder. To get Formulation Example 2 25 parts of each of the compounds (1) to (435) of the present invention, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC and 69 parts of water are mixed and wet until the particle size of the active ingredient becomes 5 μm or less. Each suspension is obtained by crushing. Formulation Example 3 2 parts of each of the compounds (1) to (435) of the present invention, 88 parts of kaolin clay and 10 parts of talc are well pulverized and mixed to obtain each powder. Formulation Example 4 20 parts of each of the compounds (1) to (435) of the present invention, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 60 parts of xylene are mixed well to obtain each emulsion. . Formulation Example 5 2 parts of each of the compounds (1) to (435) of the present invention, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 65 parts of kaolin clay are well pulverized and mixed, and water is added. After thoroughly kneading, each granule is obtained by granulating and drying. Formulation Example 6 20 parts of each of the compounds (1) to (435) of the present invention and 1.5 parts of sorbitan trioleate were mixed with 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol, and finely pulverized with a sand grinder (particle size: 3 μm). After this), add 0.05 parts of xanthan gum and 0.
40 parts of an aqueous solution containing 1 part was added, 10 parts of propylene glycol was further added, and the mixture was stirred and mixed to obtain each 20% suspension in water. Formulation Example 7 0.1 parts of each of the compounds (1) to (435) of the present invention is dissolved in 5 parts of xylene and 5 parts of trichloroethane, and this is mixed with 89.9 parts of deodorized kerosene to obtain each 0.1% oil agent. .

Formulation Example 8 0.1 parts each of the compounds (1) to (435) of the present invention, 0.2 parts tetramethrin, 0.1 part d-phenothrin, 10 parts trichloroethane and 59.6 parts deodorizing kerosene were mixed and dissolved, After filling the aerosol container and attaching the valve portion, 30 parts of propellant (liquefied petroleum gas) is pressure filled through the valve portion to obtain each oil-based aerosol. Formulation Example 9 0.2 parts of each of the present compounds (1) to (435), 0.2 part of d-allethrin, 0.2 part of d-phenothrin, xylene 5
Parts, 3.4 parts of deodorized kerosene and 1 part of emulsifier {Atmos 300 (registered trademark name of Atlas Chemical Co.)} are mixed and dissolved, and 50 parts of pure water are filled in an aerosol container, the valve part is attached, and the valve is attached. 40 parts of propellant (liquefied petroleum gas) is charged under pressure through the part to obtain each aqueous aerosol. Formulation Example 10 To 0.3 g of each of the compounds (1) to (435) of the present invention, 0.3 g of d-allethrin was added and dissolved in 20 ml of acetone, and a carrier for mosquito coil (tab powder: lees powder: wood powder 4 After mixing uniformly with 99.4 g of the mixture, 120 ml of water was added, and the mixture was thoroughly kneaded and dried to obtain each mosquito coil. Formulation Example 11 Acetone is added to 0.4 g of each of the compounds (1) to (435) of the present invention, 0.4 g of d-allethrin and 0.4 g of pipenyl butoxide to dissolve them, and the total amount is 10 ml. 0.5 ml of this solution was evenly impregnated into a 2.5 cm x 1.5 cm, 0.3 cm thick base for an electric mat (a fibril mixture of cotton sillinter and pulp was solidified into a plate). , Get each electric mosquito mat. Formulation Example 12 100 mg of each of the compounds (1) to (435) of the present invention is dissolved in an appropriate amount of acetone and impregnated into a porous ceramic plate having a size of 4.0 cm × 4.0 cm and a thickness of 1.2 cm, and each of the heated smoke is smoked. Get the agent. Formulation Example 13 10 mg of each of the compounds (1) to (435) of the present invention was dissolved in acetone of
It is dissolved in 5 ml, and this solution is treated with 5 g of animal solid feed powder (solid feed powder for breeding and breeding CE-2, trade name of CLEA Japan, Inc.) and uniformly mixed. Then, it is air-dried with acetone to obtain each 0.5% poison bait.

Next, it is shown in Test Examples that the compound of the present invention is useful as an agricultural and horticultural fungicide. The control efficacy is "5" or 10% if the disease state of the test plant at the time of the survey, that is, the microflora of leaves, stems, and the extent of lesions is visually observed “4” if accepted, “3” if recognized by about 30%, “2”, 7 if recognized by about 50%.
If about 0% is found, it is evaluated as “1”, and if there is no difference with the disease state when the compound is not tested, it is evaluated as “0” and evaluated in 6 levels, 5, 4, 3, respectively.
Shown as 2,1,0. Test Example 1 Rice blast control test (preventive effect) Sand loam soil was filled in a plastic pot, rice (Nipponbare) was sown, and grown in a greenhouse for 20 days. Then, Formulation Example 1
The reagent solution made into a wettable powder according to the above was diluted with water to a predetermined concentration (500 ppm), and the foliage was sprayed so that it was sufficiently adhered to the rice leaf surface. After spraying, the plants were air-dried, and a spore suspension of blast fungus was sprayed and inoculated. After inoculation, the mixture was allowed to stand at 28 ° C. under high humidity for 6 days, and then the control efficacy was investigated. As a result, the compounds having the following compound numbers showed a control value of "5". Compound number: 1, 4, 10, 16, 19, 22, 25,
28, 31, 37, 43, 52, 61, 139, 14
5, 154, 157, 160, 181, 184, 19
0, 193, 223, 338, 389, 390, 39
1, 392, 393, 400, 414, 428 Test Example 2 Rice Leaf Spot Disease Control Test (Preventive Effect) Sand loam soil was filled in a plastic pot, and rice (Nihonbare) was sown and grown in a greenhouse for 20 days. According to Formulation Example 1, a wettable powder is diluted with water to give a predetermined concentration (500
ppm) and sprinkled it so that it adhered sufficiently to the leaf surface of the rice. After spraying, the plants were air-dried and inoculated with bran culture fungus hyphae of wilt fungus at the root. After inoculation, 28 ℃,
After being placed under high humidity for 4 days, the control efficacy was investigated. As a result, the compounds having the following compound numbers showed a control value of "5". Compound number: 1, 4, 10, 16, 19, 22, 25,
28, 31, 37, 43, 52, 61, 139, 14
5, 157, 160, 181, 184, 190, 19
3, 223, 338, 389, 390, 391, 39
2,393,400,414,428

Test Example 3 Wheat Powdery Mildew Control Test (Therapeutic Effect) A plastic pot was filled with sandy loam and wheat (Agriculture 73
No.) was sowed and grown in a greenhouse for 10 days. A wheat powdery mildew fungus was sprinkled on the wheat seedlings developed by the second leaf to inoculate. After inoculation, grow in a greenhouse at 23 ° C for 3 days,
A reagent solution made into a wettable powder according to Formulation Example 1 was diluted with water to a predetermined concentration (500 ppm) and sprayed on foliage so as to sufficiently adhere to the leaf surface of the wheat. After spraying, the seedlings were further grown for 7 days under illumination, and the control efficacy was investigated. As a result, the compounds having the following compound numbers showed a control value of "5". Compound number: 1, 4, 10, 16, 19, 22, 25,
28, 37, 43, 52, 61, 139, 145, 15
4, 157, 160, 181, 184, 190, 19
3, 223, 338, 389, 390, 391, 39
2,393,400,414,428 Test Example 4 Wheat rust control test (preventive effect) Sand loam soil was filled in a plastic pot, and wheat (Agriculture 73
No.) was sowed and grown in a greenhouse for 10 days. According to Formulation Example 1, a wettable powder is diluted with water to a predetermined concentration (500 ppm) so that it adheres sufficiently to the leaf surface of the wheat seedling in which the second to third true leaves have spread. Foliage was sprayed on. After air-drying, inoculate with spores of wheat rust disease, 23 ℃,
After left in the dark and humid for 1 day, it was further grown under illumination for 6 days, and the control efficacy was investigated. As a result, the compounds having the following compound numbers showed a control value of "5". Compound number: 1, 4, 10, 16, 19, 25, 28,
31, 37, 43, 52, 61, 139, 145, 15
4, 157, 160, 181, 184, 190, 19
3,338,389,390,391,392,39
3,400,414,428

Test Example 5 Grape downy mildew control test (treatment effect) A plastic pot was filled with sandy loam soil, inoculated with grape (berry A), and grown in a greenhouse for 40 days. The seedlings of the grape with about 3 leaves were spray-inoculated with a zoosporangium suspension of downy mildew. After inoculation, the mixture was left overnight at 23 ° C. and high humidity, and then the reagent solution made into a wettable powder according to Formulation Example 1 was diluted with water to a predetermined concentration (500 ppm), which was then applied to the leaf surface of the grape. The foliage was sprayed so as to adhere sufficiently. After spraying, the plants were further grown for 7 days, and the control efficacy was investigated. As a result, the compounds having the following compound numbers showed a control value of "5". Compound number: 4, 16, 19, 22, 25, 28, 3
7, 43, 52, 61, 139, 160, 181, 18
4, 193, 338, 389, 390, 391, 39
2,393,400,414,428 Test Example 6 Tomato Epidemic Control Test (Preventive Effect) A plastic pot was filled with sandy loam soil, inoculated with tomato (ponterosa), and grown in a greenhouse for 20 days. Formulation example 1
Dilute the reagent solution made into a wettable powder in accordance with the procedure above with water to a prescribed concentration (500ppm), and apply the foliage so that it adheres sufficiently to the leaf surface of the tomato seedlings on which the second and third true leaves have spread. did. After spraying, a spore suspension of Phytophthora infestans was sprayed and inoculated. After the inoculation, the plate was left at 20 ° C. and high humidity for 1 day, and further grown under illumination for 5 days, and the control efficacy was investigated. as a result,
The compounds having the following compound numbers showed a control value of "5". Compound number: 1, 10, 16, 19, 22, 31, 3
7, 43, 52, 61, 139, 145, 184, 19
0, 193, 338, 389, 390, 391, 39
2,393,400,414,428

Test Example 7 Cucumber Gray Mold Control Test (Preventive Effect) A plastic pot was filled with sandy loam soil, inoculated with cucumber (Shinjihaku white), and grown in a greenhouse for 12 days. A reagent solution made into a wettable powder according to Formulation Example 1 was diluted with water to a predetermined concentration (500 ppm), and the foliage was sprayed so that it adhered sufficiently to the leaf surface of the cucumber seedling. After spraying, a Botrytis spore suspension was inoculated. After inoculation, the plants were grown at 10 ° C, high humidity and in the dark for 4 days, and the control efficacy was investigated. As a result, the compounds having the following compound numbers showed a control value of "5". Compound number: 4, 10, 16, 19, 22, 25, 2
8, 31, 37, 43, 52, 61, 139, 145,
154, 160, 181, 184, 193, 223, 3
38, 389, 390, 391, 392, 393, 40
0, 414, 428 Test Example 8 Cucumber Powdery Mildew Control Test (Preventive Effect) A plastic pot was filled with sandy loam soil, inoculated with cucumber (Ajihanhanjiro), and grown in a greenhouse for 7 days. According to Formulation Example 1, a wettable powder is diluted with water to give a predetermined concentration (5
00 ppm), and the foliage was sprayed so that it would adhere sufficiently to the leaf surface of the cucumber seedling. After spraying, a spore suspension of cucumber powdery mildew was inoculated. After inoculation, the plant was grown in a greenhouse at 25 ° C for 14 days, and the control efficacy was investigated. As a result, the compounds having the following compound numbers showed a control value of "5". Compound number: 4, 16, 19, 22, 25, 28, 3
7, 52, 61, 139, 145, 184, 193, 3
38, 389, 390, 391, 392, 393, 40
0,414,428

Next, examples of insecticidal and acaricidal tests will be shown. Test Example 9 Test against cotton aphid Approximately 20 cotton aphid larvae per leaf are parasitized in potted cotton 7 days after sowing, and the reagent which has been emulsified according to Formulation Example 4 is diluted with water to a predetermined concentration ( 50 ppm). 15 ml of this solution was sprayed per pot on the turntable. After 7 days, the number of cotton aphids parasitizing was investigated, and the control value was calculated based on the number of surviving insects without treatment. As a result, compounds 16, 19, 22, 28, 19
3, 388, 389, 390, 391, 392, 39
3,400,414,428 showed the control value of 80 or more.

Test Example 10 Insecticidal test against Spodoptera litura A test compound was made into an emulsion according to Formulation Example 4, and 2 ml of its diluted solution (500 ppm) in water was preliminarily prepared in a polyethylene cup having a diameter of 11 cm. It was soaked in 13 g of artificial feed. Ten fourth-instar larvae of Spodoptera litura were released therein, and the life and death of the larvae were examined 6 days later to determine the mortality rate. As a result, compounds 392 and 40
0, 414, and 428 showed a mortality rate of 80% or more. The untreated plot had a mortality rate of 0%. Test Example 11 Insecticidal test against brown planthopper larvae Rice stems (about 5 cm in length) were immersed for 1 minute in a diluted solution (500 ppm) of the emulsion of the test compound obtained according to Formulation Example 4 in water. After air drying, a 5.5 cm diameter filter paper containing 1 ml of water was laid. Rice stalks were placed in a polyethylene cup having a diameter of 5.5 cm, and about 30 larvae of the brown planthopper were released therein, and their life and death were examined 6 days later. The criteria for effect evaluation are: a: No live insects are observed. b: Five or less surviving insects are recognized. c: Six or more live insects are recognized. As a result, the compounds 43, 390, 414 and 428 showed a. In addition, the untreated section showed c.

Test Example 12 Test against Culex pipiens The reagent reagent obtained according to Preparation Example 4 was diluted with water to a predetermined concentration (500 ppm). 0.7 ml of this solution was added to 100 ml of deionized water. (Active ingredient concentration 3.5 ppm). Twenty larvae of Culex pipiens were released into the larvae, and the rate of inhibition of emergence was investigated 8 days later. As a result, compounds 16, 22, 19
3, 388, 390, 392, 400, 414, 428
Showed an emergence inhibition rate of 90% or more.

Test Example 13 Test Against False Mites: 1 day after seeding, 7 days after sowing
Infested with 10 female adults of the spider mites,
It was placed in a constant temperature room at 25 ° C. After 6 days, the reagent that was made into an emulsion according to Formulation Example 4 was diluted with water to a predetermined concentration (500 ppm).
I made it. 15 per bowl of this solution on the turntable
ml was sprayed, and 2 ml of the same solution was simultaneously irrigated with soil. After 8 days, the degree of damage caused by the mites on the plants was investigated. The criteria for effectiveness are: -No damage is observed. +: Some damage is recognized. ++: The same damage as the untreated area is recognized. And As a result, compounds 22, 28, 61, 388,
The effect evaluation of 390, 391, 392, 400, 414, 428 was-.

[0035]

INDUSTRIAL APPLICABILITY The compound of the present invention exhibits excellent bactericidal activity and insecticidal and acaricidal activity.

Front page continuation (72) Inventor Makoto Fujimura 4-2-1 Takashi, Takarazuka-shi, Hyogo Sumitomo Kagaku Kogyo Co., Ltd. (72) Inventor Norio Kimura 4-2-1 Takashi, Takarazuka-shi, Hyogo Sumitomo Gaku Kogyo Co., Ltd. (72) Inventor Kimio Umeda 4-2-1 Takashi, Takarazuka-shi, Hyogo Sumitomo Chemical Gaku Kogyo Co., Ltd.

Claims (16)

[Claims] 1. A general formula: ## STR1 ## [Wherein, X represents an oxygen atom or an NH group, Y represents a nitrogen atom or a CH group, and (a) when X represents an NH group and Y represents a nitrogen atom, A is substituted. Optionally substituted alkyl group, optionally substituted alkenyl group, optionally substituted alkynyl group, optionally substituted cycloalkyl group, optionally substituted cycloalkenyl group, optionally substituted Represents a good bicycloalkyl group or an optionally substituted tricycloalkyl group, B represents a C _{1 to} C ₆ alkyl group, (b) when X represents an oxygen atom, Y represents a nitrogen atom or a CH group. A represents a compound of the general formula: embedded image R—CH ₂ CH ₂ (wherein R represents a tert-butyl group or an isopropyl group, or a halogen atom, a C ₁ -C ₄ alkyl group, C ₁ ~ C ₄ Arco A phenyl group which may be substituted with a xy group, a C ₁ -C ₄ alkylthio group, a C ₁ -C ₄ haloalkyl group, a C ₁ -C ₄ haloalkoxy group or a cyano group). B represents a methyl group. ) The dithiocarbonimide derivative shown by these. 2. The dithiocarbonimide derivative according to claim 1, wherein X is an NH group. 3. The dithiocarbonimide derivative according to claim 1, wherein X is an oxygen atom. 4. A is optionally substituted C₁~ C₂₀A
Rukyl group, optionally substituted C ₂~ C₂₀Alkenyl
Group, optionally substituted C₂~ C₂₀Alkynyl group, placement
C that may be replaced₃~ C₂₀Cycloalkyl group, substituted
May be C_Five~ C₂₀Cycloalkenyl group, substituted
May be C_Four~ C₂₀Bicycloalkyl group or
C which may be substituted_Four~ C₂₀Tricycloalkyl group
The dithiocarbonimide derivative according to claim 2. 5. A is optionally substituted C₁~ C_TenA
Rukyl group, optionally substituted C ₃~ C_TenAlkenyl
Group, optionally substituted C₃~ C_TenAlkynyl group, placement
C that may be replaced₃~ C_TenCycloalkyl group, substituted
May be C_Five~ C_TenCycloalkenyl group, substituted
May be C₇~ C_TenBicycloalkyl group or
C which may be substituted₈~ C_TenTricycloalkyl group
The dithiocarbonimide derivative according to claim 2. 6. An optionally substituted alkyl in A
Group, optionally substituted alkenyl group, substituted
Optionally substituted alkynyl group, optionally substituted cyclo
Alkyl group, optionally substituted cycloalkenyl
Group, optionally substituted bicycloalkyl group and group
The substituent of the optionally substituted tricycloalkyl group is
Up to 3 substituents (substituents being the same or different,₁
~ C₆Alkoxy group, C ₁~ C₆Haloalkoxy group, ha
Rogen atom, cyano group, C₁~ C₆Alkylthio group, placement
Optionally substituted phenyl group, optionally substituted
A phenoxy group, an optionally substituted phenylthio group,
Optionally substituted aromatic heterocyclic group, substituted
Good C₃~ C_TenCycloalkyl group or substituted
Or an aliphatic heterocyclic group (having 3 to 10 ring atoms)
is there. ) Is a dithiocarbonimide derivative according to claim 2.
conductor. 7. An optionally substituted alkyl group for A, an optionally substituted alkenyl group, an optionally substituted alkynyl group, an optionally substituted cycloalkyl group, and an optionally substituted. 3 is a preferable cycloalkenyl group, an optionally substituted bicycloalkyl group or an optionally substituted tricycloalkyl group.
Or less substituents (substituents are the same or different and are methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, t-butoxy group, trifluoromethoxy group, 2,2,2- Trifluoroethoxy group, 2,
2,2,2 ′, 2 ′, 2′-hexafluoroisopropoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, methylthio group or ethylthio group, or 3 or less each Substituents (substituents are the same or different and are methyl group, ethyl group, n-propyl group,
Isopropyl group, trifluoromethyl group, methoxy group,
Ethoxy group, n-propoxy group, isopropoxy group, trifluoromethoxy group, fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, nitro group, methylthio group or ethylthio group) , Phenyl group, phenoxy group, phenylthio group, 2-furyl group, 2-thienyl group, 1-imidazolyl group, 2-imidazolyl group, 3-imidazolyl group, 2-pyridyl group, 3-
It is a pyridyl group, 4-pyridyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, oxynyl group, oxonyl group, tetrahydrofuryl group, tetrahydropyranyl group or 4-morphonyl group. ] The dithiocarboximide derivative of Claim 2 which is these. 8. The dithiocarbonimide derivative according to claim 2, wherein A is a C ₁ -C ₁₀ alkyl group which may be substituted with a phenyl group (the phenyl group may be substituted). 9. A represents a general formula R—CH ₂ CH ₂ (wherein R represents a tert-butyl group or an isopropyl group, or a halogen atom, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ group). alkoxy groups, C ₁ -C ₄ alkylthio group, C ₁ -C ₄ haloalkyl groups, C ₁ -C ₄ haloalkoxy optionally substituted by a group or cyano group is a group which is also indicated by representing.) a phenyl group wherein Item 2. A dithiocarbonimide derivative according to item 2. 10. The dithiocarbonimide derivative according to claim 2, wherein B is a C ₁ -C ₃ alkyl group. 11. The dithiocarbonimide derivative according to claim 2, wherein B is a methyl group. 12. The dithiocarbonimide derivative according to claim 3, wherein Y is a CH group. 13. The dithiocarbonimide derivative according to claim 3, wherein Y is a nitrogen atom. 14. The dithiocarbonimide derivative according to claim 3, wherein R is a tert-butyl group, an isopropyl group or a phenyl group. 15. A fungicide for agricultural and horticultural use comprising the dithiocarbonimide derivative according to claim 1 as an active ingredient. 16. An insecticide comprising the dithiocarbonimide derivative according to claim 1 as an active ingredient,
Acaricide.