JPH08295663A - Aminoethylene derivative and its use - Google Patents

Abstract

PURPOSE: To obtain a new safe aminoethylene derivative low in human and livestock toxicity, fish toxicity and toxicity to the natural enemies against insect pests and having an excellent control effect on the insect pests and pathogenic microorganisms. CONSTITUTION: A compound of formula I [Ar<1> , Ar<2> are each a (substituted) aromatic group, a heterocyclic group; R<1> is H, a group intermediated with a carbon atom, a group intermediated with a sulfur atom; R<2> is a (substituted) alkyl; R<3> is an electron-attracting group). For example, 2-(2,4- dichlorophenyl)-3-(2,6-dichloro-4-trifluoromethylphenylamino)-4,4,4- trifluorocrotononitrile. The compound of formula I is obtained e.g. by reacting a compound of formula II with a compound of the formula: R<1c> -hal (R<1c> is a group intermediated with a carbon atom) in the presence of a base such as triethylamine in a solvent such as THF.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a novel aminoethylene derivative having excellent insecticidal or bactericidal activity or a salt thereof,
And an insecticidal or bactericidal composition containing the novel aminoethylene derivative or a salt thereof.

[0002]

2. Description of the Related Art Conventionally, many compounds having insecticidal and bactericidal activities have been synthesized and used as pesticides. However, it is well known that drug-resistant pests are generated and pose a problem because compounds in a limited range have been frequently used. For this reason, novel compounds having insecticidal and bactericidal activities are being sought. However, under the present circumstances, some of these compounds do not always have satisfactory effects in practical use, such as high toxicity to humans and too strong persistence in soil.

[0003]

DISCLOSURE OF THE INVENTION The present invention is directed to animal toxicity,
Provided are a novel aminoethylene derivative or salt thereof, which has low toxicity against fish and natural enemies of pests and is excellent in controlling pests and harmful microorganisms, and an insecticidal or bactericidal composition containing the same. The purpose is to do.

[0004]

Means for Solving the Problems In order to solve the above problems, the inventors of the present invention have been earnestly researching for many years in order to find a novel compound having an excellent insecticidal and bactericidal activity. As a result, it was discovered that the novel aminoethylene derivative or its salt surprisingly has extremely strong insecticidal and bactericidal activity,
Moreover, it was found that there is no phytotoxicity to plants and the toxicity to humans and fishes is low. As a result of further intensive research based on these, the present invention has been completed. That is, the present invention includes (1) the general formula [I]

[Chemical 9] [In the formula, Ar ¹ and Ar ² are an aromatic homo or heterocyclic group which may be substituted, R ¹ is a hydrogen atom, a group through a carbon atom or a group through a sulfur atom, and R ² is substituted. R ³ represents an electron-withdrawing group] or a salt thereof, (2) Ar ⁶ optionally substituted C _6-14 aryl group or nitrogen atom,
The compound according to (1) above, which is a 5- to 8-membered aromatic heterocyclic group containing 1 to 5 heteroatoms selected from oxygen atom or sulfur atom, and (3) C ₆ in which Ar ² may be substituted. _-14 The compound according to (1) above, which is an aryl group or a 5- to 8-membered aromatic heterocyclic group containing 1 to 5 heteroatoms selected from nitrogen atom, oxygen atom or sulfur atom, and (4) R ¹ is Hydrogen atom, C _1-6 alkyl group, C
_1-6 haloalkyl group, C _3-7 cycloalkyl group, C _2-6 alkenyl group, C _2-6 haloalkenyl group, C _2-6 alkynyl group, C _2-6 haloalkynyl group, C _1-6 alkanoyl group , C
_2-6 haloalkanoyl group, C _7-11 arylcarbonyl group, C _8-12 aralkylcarbonyl group, C _2-8 alkoxycarbonyl group, C _7-11 aryloxycarbonyl group, C
_8-12 aralkyloxycarbonyl group, C _1-6 alkylsulfonyl group, C _7-11 aralkylsulfonyl group, C _1-6
A haloalkylsulfonyl group, a _C6-10 arylsulfonyl group or a group represented by -SY, wherein Y is

[Chemical 10]

[Chemical 11]

[Chemical 12]

[Chemical 13]

Embedded image

[Chemical 15]

Embedded image Or a group represented by S—R ^4c , wherein R ^4a and R ^4e are C _1-6 alkyl group, C _1-6 haloalkyl group, C _3-7 cycloalkyl group, C _4-8 cycloalkylalkyl group, A phenyl group, a benzyl group, a phenethyl group, a C _2-6 cyanoalkyl group, a C _2-6 alkoxyalkyl group, a C _3-8 alkoxycarbonylalkyl group or a C _4-8 dialkylaminocarbonylalkyl group, each of which may be substituted. And an oxygen atom together with the adjacent nitrogen atom at R ^4a and R ^4e ,
A saturated 3- to 7-membered ring which may contain a sulfur atom or other nitrogen atom may be formed, and R ^4b is a fluorine atom,
C _1-6 alkyl group, C _3-7 cycloalkyl group, C _3-7 cycloalkyloxy group, C _2-8 dialkylamino group, C _1-6
Haloalkyl group, optionally substituted phenyl group or phenoxy group, C _1-6 alkoxy group, cyano group, nitro group, C _2-6 alkenyloxy group, C _4-8 alkoxyalkoxy group, C _1-4 alkylthio group Group, C _2-6 alkoxycarbonyl group, C _3-9 dialkylaminocarbonyl group, phenyl or C substituted with 1 to 6 halogens
_1-4 alkoxy group, morpholino group, piperidino group, pyrrolidino group, 1-naphthoxy group, 2,2-dimethyl-2,
3-dihydro-7-benzofuranoxy group or ON = C
(CH ₃ ) SCH ₃ group, R ^4c and R ^4d are C _1-4 alkyl group, C _1-4 haloalkyl group or an optionally substituted phenyl group, and R ^4c and R ^4d are (CH ₂ ) ₂ ,
(CH ₂ ) ₃ or CH ₂ C (CH ₃ ) ₂ CH ₂ may be formed, and Y ¹ , Y ² and Y ³ are an oxygen atom or a sulfur atom, (5) and R ² is is an optionally substituted C _1-6 alkyl group above (1) compounds described, (6) R ³ is optionally substituted C _7-11 arylcarbonyl group, optionally substituted A good C _8-12 aralkylcarbonyl group, a C _2-8 alkoxycarbonyl group, an optionally substituted C _7-11 aryloxycarbonyl group,
Optionally substituted C _8-12 aralkyloxycarbonyl group, cyano group, nitro group, C _1-6 alkylthio group, C
_1-6 alkylsulfinyl group, C _1-6 alkylsulfonyl group, C _1-6 haloalkylthio group, C _1-6 haloalkylsulfinyl group, C _1-6 haloalkylsulfonyl group, optionally C _6-10 arylthio which may be substituted Group, optionally substituted C _6-10 arylsulfinyl group, optionally substituted C _6-10 arylsulfonyl group, N-C _1-6 alkylcarbamoyl group, N, N-di (C _1-6 The above (1), which is an alkyl) carbamoyl group, an optionally substituted N- (C _6-10 aryl) carbamoyl group, or an optionally substituted N, N-di (C _6-10 arylcarbamoyl) group. And (7) an insecticidal composition or a bactericidal composition comprising the compound according to (1) or a salt thereof.

The aromatic homocyclic group represented by Ar ¹ and Ar ² which may be substituted includes, for example, phenyl, naphthyl, anthryl, phenanthryl, naphthacenyl and the like having 6 carbon atoms. To 18 aromatic hydrocarbon groups. Among these, carbon number 6 to 1
The aromatic hydrocarbon group of 4 is preferable, and the aromatic hydrocarbon group of 6 to 10 carbon atoms is particularly preferable. Examples of the substituent that the aromatic homocyclic group may have include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl,
t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl and the like having 1 to 15 carbon atoms (preferably 1 to 6 carbon atoms), for example Cycloalkyl groups having 3 to 10 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, such as vinyl, allyl, 2-methylallyl,
C2-C10 alkenyl groups such as 2-butenyl, 3-butenyl, 3-octenyl, etc., such as ethynyl, 2-propynyl, 2-hexynyl and other alkynyl groups, such as cyclopropenyl, cyclopentenyl, A cycloalkenyl group having 3 to 10 carbon atoms such as cyclohexenyl, an aryl group having 6 to 10 carbon atoms such as phenyl and naphthyl, and an aralkyl group having 7 to 10 carbon atoms such as phenylalkyl group such as benzyl and phenylethyl; Nitro group, hydroxyl group, mercapto group, oxo group, thioxo group,
A cyano group, an optionally esterified carboxyl group (eg, a carboxyl group, an alkoxycarbonyl group having 2 to 5 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, etc., an carbonyl group having 8 to 13 carbon atoms such as benzyloxycarbonyl, phenethyloxycarbonyl, etc. Aralkyloxycarbonyl group, etc.), for example, aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, etc., having 1 to 5 carbon atoms
An aminocarbonyl group, a sulfo group (—SO ₃ H), a halogen atom such as fluorine, chlorine, bromine and iodine, for example, methoxy, ethoxy, propoxy, isopropoxy,
Butoxy, isobutoxy, s-butoxy, t-butoxy and other alkoxy groups having 1 to 4 carbon atoms, such as phenoxy and other aryloxy groups having 6 to 10 carbon atoms, such as methylthio, ethylthio, n-propylthio, isopropylthio, butylthio, Isobutylthio, s-butylthio, t
-C1-4 alkylthio groups such as butylthio, for example, 1,3-dithian-2-yl, 1,3-dithiolane-
Cyclic 1,3-dithio-2-yl group such as 2-yl, for example, cyclic 1,3-dioxo-2-yl group such as 1,3-dioxan-2-yl, 1,3-dioxolan-2-yl An arylthio group having 6 to 10 carbon atoms such as phenylthio, an alkylsulfinyl group having 1 to 4 carbon atoms such as methylsulfinyl and ethylsulfinyl, an arylsulfinyl group having 6 to 10 carbon atoms such as phenylsulfinyl, such as methylsulfonyl. , An alkylsulfonyl group having 1 to 4 carbon atoms such as ethylsulfonyl, for example, an alkanesulfonyloxy group having 1 to 4 carbon atoms such as methanesulfonyloxy and ethanesulfonyloxy, and an arylsulfonyl group having 6 to 10 carbon atoms such as phenylsulfonyl. , Amino groups such as formylamino, acetylamino, propionylami Acylamino group having 1 to 6 carbon atoms such as alkanoylamino groups etc., e.g. methylamino,
An alkylamino group having 1 to 4 carbon atoms such as ethylamino, n-propylamino, isopropylamino, n-butylamino, dimethylamino, diethylamino and the like;
For example, a cycloalkylamino group having 3 to 6 carbon atoms such as cyclohexylamino, and 6 to 10 carbon atoms such as anilino.
Arylamino group, for example, formyl group, acyl group having 1 to 4 carbon atoms such as acetyl, for example, N-alkyliminoalkyl group having 1 to 5 carbon atoms such as N-methyliminomethyl,
Arylcarbonyl group having 7 to 11 carbon atoms such as benzoyl, for example, 2- or 3-thienyl, 2- or 3
-Furyl, 3-, 4- or 5-pyrazolyl, 2-, 4
-Or 5-thiazolyl, 3-, 4- or 5-isothiazolyl, 2-, 4- or 5-oxazolyl, 3-,
4- or 5-isoxazolyl, 2-, 4- or 5
-Imidazolyl, 1,2,3- or 1,2,4-triazolyl, 1H or 2H-tetrazolyl, 2-, 3-
Or 1 to 4 heteroatoms selected from oxygen atom such as 4-pyridyl, 2-, 4- or 5-pyrimidinyl, 3- or 4-pyridazinyl, quinolyl, isoquinolyl, indolyl, sulfur atom, nitrogen atom A 6-membered heterocyclic group, for example, a heterocyclicoxy group in which oxygen is bonded to the above heterocycle such as 2- or 3-thienyloxy, for example, alkylenedioxy having 1 to 3 carbon atoms such as methylenedioxy, ethylenedioxy and the like. Examples thereof include a haloalkylenedioxy group having 1 to 3 carbon atoms such as trifluoroethylenedioxy. The number of substitutions is 1 to the maximum number that can be substituted, preferably 1 to 5. The substituent that the aromatic homocyclic group may have is a C _6-10 aryl group, a C _7-10 aralkyl group, a C _3-10 cycloalkyl group, a C _3-10 cycloalkenyl group, C _{6 -10} aryloxy group, C _6-10 arylthio group, C _6-10 arylsulfinyl group, C _6-10 arylsulfonyl group, C _6-10 arylamino group, C _7-11 arylcarbonyl group, heterocyclic group, heterocycle When it is a ring oxy group or the like, a halogen atom, a hydroxyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
Alkyl groups having 1 to 4 carbon atoms such as s-butyl and t-butyl, for example, alkenyl groups having 2 to 4 carbon atoms such as vinyl, allyl, and 2-methylallyl, and 2 to 4 carbon atoms such as ethynyl and 2-propynyl. Alkynyl group having 6 to 10 carbon atoms
, An alkoxy group having 1 to 4 carbon atoms, a phenoxy group, an alkylthio group having 1 to 4 carbon atoms, a phenylthio group, for example, an alkylenedioxy group having 1 to 3 carbon atoms such as methylenedioxy and ethylenedioxy, It may be substituted with 1 to 5 haloalkylenedioxy having 1 to 3 carbon atoms such as trifluoroethylenedioxy. The substituents are C _1-15 alkyl group, C _2-10 alkenyl group, C _2-10 alkynyl group, C _1-4 alkoxy group, C _1-4 alkylthio group, C _1-4 alkylsulfinyl group, C _{1- 4} alkylsulfonyl group, C _1-4 alkanesulfonyloxy group, amino group, C _1-6 acylamino group, mono- or di-C _1-4 alkylamino group, C _3-6 cycloalkylamino group, C _6-10 arylamino group In the case of a group, a C _1-4 acyl group, etc., a halogen atom, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, an alkylamino group having 1 to 5 carbon atoms, carbon It may be substituted with 1 to 5 dialkylamino groups of 2 to 6 and the like. Preferred specific examples of the above C _1-15 alkyl group substituted with a halogen atom include C _1-6 substituted with 1 to 3 halogen atoms such as difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl and the like. Alkyl group (preferably C
_1-3 alkyl group) and the like. Specific examples of the alkoxy group having 1 to 4 carbon atoms substituted with a halogen atom include difluoromethoxy, difluoroethoxy,
Examples thereof include C _1-4 alkoxy groups substituted with 1 to 3 halogen atoms such as dichloromethoxy and dichloroethoxy. C1-C5 substituted with an alkylamino group having 1-5 carbon atoms or a dialkylamino group having 2-6 carbon atoms
Preferred specific examples of the alkyl group of 15 include mono- or di-C _1-4 such as methylaminomethyl, dimethylaminomethyl, methylaminoethyl, dimethylaminoethyl, ethylaminomethyl, diethylaminomethyl, ethylaminoethyl, diethylaminoethyl and the like. _Examples thereof include an alkylamino-C _1-3 alkyl group. The optionally substituted aromatic homocyclic group is a hydrocarbon group optionally substituted by halogen (eg, C _1-15 alkyl group, C _2-10
Alkenyl group, C _2-10 alkynyl group, C _6-10 aryl group, C _7-10 aralkyl group, C _3-10 cycloalkyl group, C
_3-10 cycloalkenyl group, etc.), halogen, nitro, hydrocarbon (eg C _1-15 alkyl group, C _2-10 alkenyl group, C
_2-10 alkynyl group, C _6-10 aryl group, C _7-10 aralkyl group, C _3-10 cycloalkyl group, C _3-10 cycloalkenyl group, etc.) oxy, formula —S (O) nA [in the formula, A is an alkyl group which may be substituted with halogen (eg, methyl, ethyl,
Propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, octyl etc. C _1-10 alkyl etc.)
Represents an integer of 0 to 2], and an optionally esterified carboxyl group is preferable.

The aromatic heterocyclic group in the optionally substituted aromatic heterocyclic group represented by Ar ¹ and Ar ² includes, for example, 1 to 5 heteroatoms such as oxygen atom, sulfur atom and nitrogen atom. Examples thereof include a 5- to 8-membered ring or a condensed ring thereof, and specific examples thereof include 2- or 3-
Thienyl, 2- or 3-furyl, 2- or 3-pyrrolyl, 2-, 3- or 4-pyridyl, 2-, 4- or 5-oxazolyl, 2-, 4- or 5-thiazolyl, 3-, 4 -Or 5-pyrazolyl, 2-, 4- or 5-imidazolyl, 3-, 4- or 5-isoxazolyl, 3-, 4- or 5-isothiazolyl, 3-or 5- (1,2,4-oxadiazolyl) , 1, 3,
4-oxadiazolyl, 3- or 5- (1,2,4-
Thiadiazolyl), 1,3,4-thiadiazolyl, 4-
Or 5- (1,2,3-thiadiazolyl), 1,2,
5-thiadiazolyl, 1,2,3-triazolyl, 1,
2,4-triazolyl, 1H or 2H-tetrazolyl, N-oxide-2-, 3- or 4-pyridyl, 2
-, 4- or 5-pyrimidinyl, N-oxide-2
-, 4- or 5-pyrimidinyl, 3- or 4-pyridazinyl, pyrazinyl, N-oxide-3- or 4-
Pyridazinyl, benzofuryl, benzothiazolyl, benzoxazolyl, triazinyl, oxotriazinyl,
Tetrazolo [1,5-b] pyridazinyl, triazolo [4,5-b] pyridazinyl, oxoimidazolinyl, dioxotriazinyl, pyrrolidinyl, piperidinyl, pyranyl, thiopyranyl, 1,4-oxazinyl, morpholinyl, 1, 4-thiazinyl, 1,3-thiazinyl, piperazinyl, benzimidazolyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, indolizinyl, quinolidinyl, 1,8
-Naphthyridinyl, purinyl, pteridinyl, dibenzofuranyl, carbazolyl, acridinyl, phenanthridinyl, phenazinyl, phenothiazinyl, phenoxazinyl and the like. Of these, 5 to 8 containing 1 to 5 heteroatoms such as oxygen atom, sulfur atom, and nitrogen atom
A member ring is preferable, and a 5- or 6-membered ring containing 1 to 3 hetero atoms such as oxygen atom, sulfur atom, and nitrogen atom is particularly preferable.
The substituent that the heterocyclic group may have has the same meaning as the substituent that the aromatic homocyclic group may have.

Ar ¹ and Ar ² are each an aromatic group 5 which may contain a nitrogen atom, an oxygen atom or a sulfur atom.
It is preferably a 6-membered ring group. Ar ¹ is particularly preferably phenyl which may be substituted or pyridyl which may be substituted. Ar ² is particularly preferably phenyl which may be substituted, pyridyl which may be substituted, and thienyl which may be substituted.

The group represented by R ¹ via a carbon atom includes all organic residues bonded via a carbon atom. Specifically, for example, alkyl (eg, C _1-6 alkyl such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, etc.) which may be each substituted, cycloalkyl (eg, cycloalkyl) C _3-6 cycloalkyl such as propyl, cyclopentyl, cyclohexyl), alkoxyalkyl (eg C _1-3 alkoxyC _1-6 alkyl such as methoxymethyl, ethoxymethyl, ethoxybutyl, propoxymethyl, propoxyhexyl), hydroxyalkyl (Eg hydroxymethyl,
C _1-6 alkyl such as hydroxyethyl, hydroxybutyl and hydroxypropyl, alkenyl (eg vinyl,
C _2-6 alkenyl such as butadienyl and hexatrienyl), formyl, carboxyl, alkoxycarbonyl (eg C _1-6 alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl),
Cyano, amide, mono, dialkylcarbamoyl (eg,
Methylcarbamoyl, ethylcarbamoyl, hexylcarbamoyl, dimethylcarbamoyl, mono- and methyl ethylcarbamoyl, di C _1-6 alkylcarbamoyl),
Amidino, aryl (eg, C _6-14 aryl such as phenyl, naphthyl, anthracenyl), aralkyl (eg, C _7-20 aralkyl such as benzyl, benzhydryl, trityl), and a heterocyclic group having a bond at a carbon atom. (Eg 2- or 3-thienyl, 2- or 3-furyl, 2- or 3-pyrrolyl, 2-, 3- or 4-pyridyl, 2-,
4- or 5-oxazolyl, 2-, 4- or 5-thiazolyl, 3-, 4- or 5-pyrazolyl, 2-, 4
-Or 5-imidazolyl, 3-, 4- or 5-isoxazolyl, 3-, 4- or 5-isothiazolyl,
3- or 5- (1,2,4-oxadiazolyl), 1,3,
4-oxadiazolyl, 3- or 5- (1,2,4-thiadiazolyl), 1,3,4-thiadiazolyl, 4-or 5- (1,2,3-thiadiazolyl), 1,2,5-thiadiazolyl, In addition to carbon atoms such as 1,2,3-triazolyl, 1,2,4-triazolyl, 1H- or 2H-tetrazolyl, etc., 1 to 4 heteroatoms selected from oxygen atom, sulfur atom, nitrogen atom and the like are included 5 Membered ring group; N-oxide-
2-, 3- or 4-pyridyl, 2-, 4- or 5-
Pyrimidinyl, N-oxide-2-, 4- or 5-pyrimidinyl, 2- or 3-thiomorpholinyl, 2- or 3-morpholinyl, oxoimidazolinyl, dioxotriazinyl, pyrrolidinyl, piperidinyl, pyranyl, thiopyranyl, 1,4-oxazinyl, 1,4-thiazinyl, 1,3-thiazinyl, 2- or 3-piperazinyl, triazinyl, oxotriazinyl, 3- or 4-pyridazinyl, pyrazinyl, N-oxide-3- or 4- 6-membered ring group containing 1 to 4 heteroatoms selected from oxygen atom, sulfur atom, nitrogen atom, etc. in addition to carbon atom such as pyridazinyl; benzofuryl, benzothiazolyl,
Benzoxazolyl, tetrazolo [1,5-b] pyridazinyl, triazolo [4,5-b] pyridazinyl, benzimidazolyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, indolizinyl, quinolidinyl, 1,8-naphthyridinyl, purinyl , Pteridinyl, dibenzofuranyl, carbazolyl, acridinyl, phenanthridinyl, chromanyl, benzoxazinyl, phenazinyl, phenothiazinyl, phenoxazinyl, and other carbon atoms, as well as hetero atoms selected from oxygen atom, sulfur atom, nitrogen atom, etc. 1
To a 5- to 8-membered ring containing 1 to 4 heteroatoms such as oxygen atom, sulfur atom, nitrogen atom, etc. in addition to carbon atoms such as bicyclic or tricyclic fused ring groups containing 4 to 4 or condensed rings thereof And so on. Examples of the substituent include (a) hydroxyl, (b) amino, (c) mono- or di-C _1-6 alkylamino (eg, methylamino, ethylamino, propylamino, dimethylamino, diethylamino, etc.), 1 selected from (d) C _1-6 alkoxy (eg, methoxy, ethoxy, propoxy, hexyloxy, etc.) and (e) halogen (fluorine, chlorine, bromine, iodine), etc.
To C _6-14 aryl optionally substituted with 4 to 4 (eg, phenyl, naphthyl, etc.); mono- or di-C
_1-6 alkylamino (eg, methylamino, ethylamino, propylamino, dimethylamino, diethylamino etc.); C _1-4 acylamino (eg, formylamino, acetylamino etc.); hydroxyl; carboxyl; nitro; C _1-6 Alkoxy (eg, methoxy, ethoxy, propoxy, isopropoxy, butoxy, etc.); C _1-6 alkyl-carbonyloxy (eg, acetoxy, ethylcarbonyloxy, etc.); Substituted with halogen (fluorine, chlorine, bromine, iodine) C _1-6 alkylthio (eg, methylthio, ethylthio, propylthio, butylthio, etc.); C _6-14 aryloxy (eg, phenyloxy, naphthyloxy, etc.); C _6-14 arylthio (eg, phenylthio, naphthylthio) Etc.) and halogens (eg, fluorine, chlorine, bromine, iodine), etc. It The number of substitutions is 1 to 6, preferably 1 within the range of substitutable numbers.
Or 3.

The group represented by R ¹ via a sulfur atom corresponds to all organic residues bonded via a sulfur atom. Specific examples include mercapto, and optionally substituted alkylthio, cycloalkylthio, arylthio, aralkylthio, heterocyclic thio, alkylsulfinyl, alkylsulfonyl, and arylsulfonyl groups. Each of which may be substituted,
Alkylthio, cycloalkylthio, arylthio, aralkylthio, heterocyclic thio, alkylsulfinyl, alkylsulfonyl, and alkyl in the arylsulfonyl group, cycloalkyl, aryl, aralkyl, and heterocyclic group have the same meanings as described above. Examples of the substituent include C _1-6 alkyl (eg, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, etc.), C _2-6 alkenyl (eg, vinyl, 1-methyl). Vinyl, 1-propenyl, allyl, etc.), C _2-6 alkynyl (eg, ethynyl, 1-propynyl, propargyl, etc.), C
_3-6 cycloalkyl (eg, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.), C _5-7 cycloalkenyl (eg, cyclopentenyl, cyclohexenyl, etc.), C _7-11 aralkyl (eg, benzyl, α-methylbenzyl) , Phenethyl etc.), C _6-14 aryl (eg phenyl, naphthyl etc.), C _1-6 alkoxy (eg methoxy, ethoxy, propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert. -Butoxy etc.), C _6-14 aryloxy (eg phenoxy etc.), C
_1-6 alkanoyl (eg, formyl, acetyl, propionyl, n-butyryl, iso-butyryl etc.), C _6-14 aryl
-Carbonyl (eg, benzoyl etc.), C _1-6 alkanoyloxy (eg, formyloxy, acetyloxy, propionyloxy, n-butyryloxy, iso-butyryloxy etc.), C _6-14 aryl-carbonyloxy (eg, benzoyloxy) Etc.), carboxyl, C _1-6 alkoxy-carbonyl (eg, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, iso-propoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl,
tert-butoxycarbonyl etc.), carbamoyl group, N-
Mono-C _1-4 alkylcarbamoyl (eg, N-methylcarbamoyl, N-ethylcarbamoyl, N-propylcarbamoyl, N-isopropylcarbamoyl, N-butylcarbamoyl, etc.), N, N-di-C _1-4 alkylcarbamoyl (Eg, N, N-dimethylcarbamoyl, N, N-diethylcarbamoyl, N, N-dipropylcarbamoyl, N, N-dibutylcarbamoyl, etc.), cyclic aminocarbonyl (eg, 1-aziridinylcarbonyl, 1- Azetidinyl carbonyl, 1-pyrrolidinyl carbonyl, 1-piperidinyl carbonyl, N-
Methylpiperazinylcarbonyl, morpholinocarbonyl, etc.), halogen (fluorine, chlorine, bromine, iodine), mono-, di- or tri-halogeno-C _1-4 alkyl (eg,
Chloromethyl, dichloromethyl, trifluoromethyl,
Trifluoroethyl, etc.), oxo group, amidino, imino group, alkylimino group (eg, methylimino, ethylimino, propylimino, butylimino, etc.), amino, mono- or di-C _1-4 alkylamino (eg, methylamino, ethyl Amino, propylamino, isopropylamino, butylamino, dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, etc.), carbon atom and one nitrogen atom, as well as oxygen atom, sulfur atom, nitrogen atom, etc. 1 to 3 heteroatoms
A 3- to 6-membered cyclic amino group which may contain one (eg,
Aziridinyl, azetidinyl, pyrrolidinyl, pyrrolinyl, pyrrolyl, imidazolyl, birazolyl, imidazolidinyl, piperidino, morpholino, dihydropyridyl,
Pyridyl, N-methylpiperazinyl, N-ethylpiperazinyl, etc.), C _1-6 alkanoylamino (eg, formamide, acetamide, trifluoroacetamide, propionylamide, butyrylamide, isobutyrylamide, etc.),
Benzamide, carbamoylamino, N-C _1-4 alkylcarbamoylamino (eg, N-methylcarbamoylamino, N-ethylcarbamoylamino, N-propylcarbamoylamino, N-isopropylcarbamoylamino, N-butylcarbamoylamino, etc.), N, N-di-C _1-4 alkylcarbamoylamino (eg, N, N-dimethylcarbamoylamino, N, N-diethylcarbamoylamino, N, N-dipropylcarbamoylamino, N, N-dibutylcarbamoylamino, etc.) , C _1-3 alkylenedioxy (eg, methylenedioxy, ethylenedioxy, etc.), —B (OH) ₂ , hydroxyl, epoxy (—O—), nitro, cyano, mercapto, sulfo, sulfino, phosphono, dihydroxy. Boriru, sulfamoyl, C _1-6 alkylsulfamoyl (e.g., N- methylsulfamoyl N-ethylsulfamoyl, N- propyl sulfamoyl, N- isopropyl sulfamoyl, N- butylsulfamoyl, etc.), di-C _1-6 alkylsulfamoyl (e.g., N, N- dimethylsulfamoyl , N, N-diethylsulfamoyl, N, N-dipropylsulfamoyl, N, N-dibutylsulfamoyl, etc.), C _1-6
Alkylthio (eg, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, tert-butylthio, etc.), phenylthio, C _1-6 alkylsulfinyl (eg, methylsulfinyl, ethylsulfinyl, propylsulfinyl, butylsulfinyl, etc.) ), Phenylsulfinyl, C _1-6 alkylsulfonyl (eg, methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, etc.), phenylsulfonyl and the like. The number of substitutions is 1 to 6, preferably 1 to 3, within the range of the number of substitutions.

The alkyl group in the optionally substituted alkyl group represented by R ² is, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl or heptyl. And straight-chain or branched alkyl groups having 1 to 10 carbon atoms such as octyl, nonyl, decanyl and the like. Among these, a linear or branched alkyl group having 1 to 6 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 3 carbon atoms is particularly preferable. The substituent which the alkyl group may have has the same meaning as the substituent in the above-mentioned group via a carbon atom.

The electron withdrawing group represented by R ³ is
Nitro, cyano, an optionally substituted carbonyl group,
Examples thereof include an optionally substituted carbamoyl group and a group via a sulfur atom. The substituent which the optionally substituted carbonyl group and the optionally substituted carbamoyl group may have has the same meaning as the substituent in the group through the carbon atom. The group via the sulfur atom has the same meaning as described above.

R ¹ is hydrogen atom, C _1-6 alkyl group, C _1-6
Haloalkyl group, C _3-7 cycloalkyl group, C _2-6 alkenyl group, C _2-6 haloalkenyl group, C _2-6 alkynyl group,
C _2-6 haloalkynyl group, C _1-6 alkanoyl group, C _2-6
Haloalkanoyl group, C _7-11 arylcarbonyl group, C
_8-12 aralkylcarbonyl group, C _2-8 alkoxycarbonyl group, C _7-11 aryloxycarbonyl group, C _8-12 aralkyloxycarbonyl group, C _1-6 alkylsulfonyl group, C _7-11 aralkylsulfonyl group, C _{A 1-6} haloalkylsulfonyl group, a _C6-10 arylsulfonyl group or a group represented by -SY, wherein Y is

[Chemical 17]

Embedded image

[Chemical 19]

Embedded image

[Chemical 21]

[Chemical formula 22]

[Chemical formula 23] Or a group represented by S—R ^4c , wherein R ^4a and R ^4e are C _1-6 alkyl group, C _1-6 haloalkyl group, C _3-7 cycloalkyl group, C _4-8 cycloalkylalkyl group, A phenyl group, a benzyl group, a phenethyl group, a C _2-6 cyanoalkyl group, a C _2-6 alkoxyalkyl group, a C _3-8 alkoxycarbonylalkyl group or a C _4-8 dialkylaminocarbonylalkyl group, each of which may be substituted. And an oxygen atom together with the adjacent nitrogen atom at R ^4a and R ^4e ,
A saturated 3- to 7-membered ring which may contain a sulfur atom or other nitrogen atom may be formed, and R ^4b is a fluorine atom,
C _1-6 alkyl group, C _3-7 cycloalkyl group, C _3-7 cycloalkyloxy group, C _2-8 dialkylamino group, C _1-6
Haloalkyl group, optionally substituted phenyl group or phenoxy group, C _1-6 alkoxy group, cyano group, nitro group, C _2-6 alkenyloxy group, C _4-8 alkoxyalkoxy group, C _1-4 alkylthio group Group, C _2-6 alkoxycarbonyl group, C _3-9 dialkylaminocarbonyl group, phenyl or C substituted with 1 to 6 halogens
_1-4 alkoxy group, morpholino group, piperidino group, pyrrolidino group, 1-naphthoxy group, 2,2-dimethyl-2,
3-dihydro-7-benzofuranoxy group or ON = C
(CH ₃ ) SCH ₃ group, R ^4c and R ^4d are C _1-4 alkyl group, C _1-4 haloalkyl group or an optionally substituted phenyl group, and R ^4c and R ^4d are (CH ₂ ) ₂ ,
(CH ₂ ) ₃ or CH ₂ C (CH ₃ ) ₂ CH ₂ may be formed, and Y ¹ , Y ² and Y ³ are preferably oxygen atoms or sulfur atoms.

R ² is halogen or the formula --X--A '[wherein
_A'is represented by a hydrocarbon group which may be substituted with halogen (eg, C _1-6 alkyl, C _6-14 aryl, C _7-15 aralkyl), and X represents an oxygen atom or a sulfur atom]. It is preferably a C _1-6 alkyl group which may be substituted with a group R ³ is a cyano group, a nitro group, a carboxyl group which may be esterified, a formula —S (O) n-A ′ [wherein A ′ is a hydrocarbon group which may be substituted with halogen (eg, C _1-6 alkyl, C _6-14 aryl, C _7-15 aralkyl), n is an integer of 0 to 2], and an optionally substituted carbamoyl group is preferable,
Further, optionally substituted C _7-11 arylcarbonyl group, an optionally substituted C _8-12 aralkyl group, C _2-8 alkoxycarbonyl group, an C _7-11 aryloxy which may be substituted Carbonyl group, optionally substituted C _8-12 aralkyloxycarbonyl group, cyano group, nitro group, C _1-6 alkylthio group, C _1-6 alkylsulfinyl group, C _1-6 alkylsulfonyl group, C _{1- 6} haloalkylthio group, C _1-6 haloalkylsulfinyl group, C _1-6 haloalkylsulfonyl group, an optionally substituted C _6-10 arylthio group, an optionally substituted C
_6-10 arylsulfinyl group, optionally substituted C
_6-10 arylsulfonyl group, N-C _1-6 alkylcarbamoyl group, N, N-di (C _1-6 alkyl) carbamoyl group, optionally substituted N- (C _6-10 aryl) carbamoyl group, Optionally substituted N, N-di (C _6-10
More preferably, it is an arylcarbamoyl) group.

The salt of compound [I] may be any salt that is acceptable in terms of agrochemical chemistry, and the acid addition salt may be an inorganic acid such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid or phosphoric acid. Salts such as salts with organic acids such as p-toluenesulfonic acid, methanesulfonic acid, formic acid and trifluoroacetic acid are used. Further, when the compound [I] has an acidic group such as a carboxyl group and a sulfo group, it may form a salt with a base. In this case, the base may be, for example, sodium,
Inorganic bases such as potassium, lithium, calcium, magnesium and ammonia, for example, organic bases such as pyridine, collidine, triethylamine and triethanolamine are used.

When the compound of the present invention or a salt thereof is used as an insecticidal composition or a bactericidal composition, it is used in a form known per se which can be taken by general agricultural chemicals. That is, one or more compounds [I] or salts thereof are dissolved or dispersed in an appropriate liquid carrier as an active ingredient or mixed or adsorbed with an appropriate solid carrier depending on the purpose of use, and an emulsion, an oil agent, Used as a wettable powder, powder, granule, tablet, spray, ointment and the like. If necessary, for example, an emulsifier, a suspension agent, a spreading agent, a penetrating agent, a wetting agent, a mucilage agent, a stabilizer and the like may be added to these preparations, and they can be prepared by a method known per se. Although the content ratio of the active ingredient in the insecticide and bactericide varies depending on the purpose of use, usually about 10 to 90% by weight, preferably about 5 to 70% by weight of emulsion, wettable powder, etc. About 0.1 to 10% by weight is suitable for powders and the like, and about 0.1 to 20% by weight, preferably about 0.1 to 1 for granules.
0% by weight is suitable, but these concentrations may be appropriately changed depending on the purpose of use. Emulsions, wettable powders, etc. are appropriately diluted with water before use (for example, about 100 to 10).
10,000 times) and spray. Examples of the liquid carrier (solvent) used include water, alcohols such as methanol, ethanol, n-propanol, isopropanol, and ethylene glycol, ketones such as acetone and methyl ethyl ketone, such as dioxane, tetrahydrofuran, and ethylene glycol monomethyl ether.
Ethers such as diethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc., aliphatic hydrocarbons such as kerosene, kerosene, fuel oil, machine oil, etc., aromatic hydrocarbons such as benzene, toluene, xylene, solvent naphtha, methylnaphthalene, etc. Halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, etc., acid amides such as N, N-dimethylformamide, N, N-dimethylacetamide, etc., esters such as ethyl acetate, butyl acetate, fatty acid glycerin ester, etc. Solvents such as nitriles such as acetonitrile and propionitrile are suitable, and one kind or a mixture of two or more kinds of these can be appropriately used by mixing them at a suitable ratio.

Examples of the solid carrier (diluting / expanding agent) are vegetable powders such as soybean powder, tobacco powder, wheat flour and wood powder, clays such as kaolin, bentonite and acid clay,
Talc powder, talc such as wax powder, diatomaceous earth, mineral powder such as silica such as mica powder, calcium carbonate, alumina, sulfur powder, activated carbon, etc. are used, and one kind or two or more kinds of these are used in an appropriate ratio. It can be mixed and used appropriately. Examples of ointment bases include polyethylene glycol, pectin, polyhydric alcohol esters of higher fatty acids such as glyceryl monostearate, cellulose derivatives such as methyl cellulose, sodium alginate, bentonite, higher alcohols such as glycerin. One or more of alcohol, petrolatum, white petrolatum, liquid paraffin, lard, various vegetable oils, lanolin, dehydrated lanolin, hydrogenated oil, resins, etc.,
Alternatively, those obtained by adding various kinds of surfactants shown below to these are appropriately used. As a surfactant used as an emulsifier, a spreading agent, a penetrating agent, a dispersant, etc., soaps, polyoxyethylene alkylaryl ethers [eg, Neugen ^TM , E-A142 (E ・ A142) ^TM ,
TM indicates a registered trademark. The same shall apply hereinafter); Dai-ichi Kogyo Seiyaku Co., Ltd., Nonal ^TM ; Toho Kagaku Co., Ltd.], alkylsulfates [eg, Emar 10 ^™ , Emar 4
0 ^TM ; manufactured by Kao Corporation], alkyl sulfonates [eg,
Neogen ^TM, Neogen T ^TM; Dai-ichi Kogyo Seiyaku Co., Ltd., Neoperex ^TM; manufactured by Kao Corporation], polyethylene glycol ethers [e.g., Nonipol 85 ^TM, Nonipol 1
Nonionic and anionic surfactants such as 00 ^™ , Nonipol 160 ^™ ; Sanyo Kasei Co., Ltd.], polyhydric alcohol esters [eg, Tween 20 ^™ , Tween 80 ^™ ; Kao Co., Ltd.] are suitable. Used. Further, the compound of the present invention or a salt thereof and, for example, another kind of insecticide (pyrroidoid insecticide, organophosphorus insecticide, carbamate insecticide, natural insecticide, etc.), acaricide, nematicide, herbicide , Phytohormonal agents, plant growth regulators, fungicides (for example, copper fungicides, organochlorine fungicides, organic sulfur fungicides, phenolic fungicides, etc.), synergists, attractants, repellents, pigments,
It is also possible to mix it with a fertilizer or the like and use them appropriately.

Typical examples of insecticides, acaricides and fungicides which can be used by mixing with the compound of the present invention or a salt thereof are shown below. Propoxur, isoprocarb
arb), BPMC, xylylcarb (xylylcarb), metolcarb (Xolyl), XMC, ethiophenecarb (ethi)
ofencarb, carbaryl, piricarb
micarb), bendiocarb, carbofuran
(carbofuran), flathiocarb (furathiocarb), carbosulfan (carbosulfan), aminosulfuran (aminosul)
fulan), methomyl, fenthione
n), fenitrothion, propaphos (pro)
paphos), cyanophos, prothiophos
iofos), sulprofos, profenofos (pr
ofenofos), EPN, cyanofenphos
s), acephate, oxydeprophos (oxyde)
profos), disulfoton, thiomethone (thio
meton), phenthoate, marathon
hion), dimethoate, vamidothione (vami
dothion), mecarbam, trichlorfon (tri
chlorphon), nailed, dichlorvs (dichlorv)
os), chlorofenvinphos, tetrachlorvihphos, monocrotophos, phosalone, dialyphos
(dialifos), chlorpyrifos-me
thyl), chlorpyrifos, pirimiphos-
Methyl (pirimiphos-methyl), diazinon (diazino
n), etrimfos, pyridafenthion (pyr
idaphenthion), quinalphos, isoxathion, isidathion, methidathion, salithion, cyfluthrin, permethrin, cypermethriin.
n), deltamethrin, cyhalothrin (cyh
alothrin), fenpropathrin, fenvalerate, flucytrinate (flucyt)
hrinate), flubalinate, cartap
(cartap), thiocyclam, buprofezin
(buprofezin), difulbenzuron, ethofenprox, fthalide
ide), validamycin A, mepronil, flutolanil, monguard (trade name monguard), pencicuron, edifenphos, isoprothiolane (isoprothi)
olane), tricyclazole, probenazole, kasugamycin, I
BP, bensultap, pyraclofos (pyra
clophos, ferimzone, imidacloprid, nitenpyram, sigma-cypermethrin, fipronil, silanophane, novaluron, hydroprene, hydroprene.
Flufenprox (flufenprox), fenpyrad or tebufenpyrad (fenpyrad or tebufenpyrad), phenoxycarb (fenoxycarb), fenazaquin (fenazaquin),
Chlorfluazuron, no malt (nom)
olt), hexaflumuron, flufenoxuron, alanicarb, diafenthiuron, clofentezine
(clofentezine), fenpropathri
n), tralomethrin, methoxadiazone
(methoxadiazone), fluazinam (fluazinam), ochimerinoure (okimeranolure), chlorthiophos (chlorthiop)
hos), fortress (fortress), levamis (levamis
ol), dienochlor, cloetocarb
thocarb), cycloprothrin, benfuracarb, isofenpho
s), avermectin, milbemycin (mil
bemycin), phenothiocarb (fenothiocarb), cyromazine, flucycloxuro
n), butathiofos (butathiofos), fenpyroximate (fenpyroximate), acrinathrin (acrinathrin), benfluthrin (benfluthrin), pyridaben (pyridaben),
Pyriproxyfen, hexithiazox
(hexythiazox), cycloprothrin, cherrytlure, sulframide (sulflurami)
d), diamolure, thiodicarb
carb), fenpropathrin, diafenthiuron, fenarimol
mol), flupyrimidol (flurprimidol), fluotrimazole, triadimafo (triadimafo)
n), triadimenol (triadimenol), diclobutazole (diclobutazol), paclobutazol (paclobutazol),
Diniconazole, uniconazole
nazole), triflumizole, propiconazole, flutriafol
l), flusilazole, penconazole (pe
nconazole), butiobate, prochloraz
(prochloraz), triapenthenol,
EDDP, pyroquilon, chlobenthiazone, zineb, mane
b), TPN, captan, captafol
tafol), folpet, dichlorfluanid (dic
hlorfluanid), carboxin, oxycarboxin, pyracarbolid
d), mebenil, furcarbani
l), cyclaframid, benodanil (benod)
anil), granovax (granovax), thiabendazole
(thiabendazole), fuberidazole, benomyl, thiophanate-methyl (thiptanate)
-methyl), cypendazole, carbendazine (carbendazin), diclozoline ((dichlozoline),
Iprodione, vinclozoli
n), procymidone (procymidone), microzoline (mycloz
olin), phthalaxyl (ftalaxyl), metalaxyl (metala
xyl), offrace (ofrace), benalaxyl (benalaxy
l), oxadixyl, cyprofuram
ram), tridemorph, fenpropimorph
(fenpropimorph), triforine (triforine), triarimol (triarimol), bietetanol (bitetanol), imazalil (imazalil), etaconazole (etaconazole), paclobutrazol (paclobutrazol), fenapronil (phen)
apronil), viniconazole, etirimol
(ehtirimol), dimethylmol (dimethirimol), fluoroimide (fluoroimide), hymexazol (hymexazol), ethazol (ethazol), proxychlor (proxychlor), pyrazophos (pyrazophos), prothiocarb (prothiocar)
b), ariette, fenpropidin
ropidin, flapenazole, pyrifenox, diethofencar
b), pipani pirim, clozylcon
acon), difenoconazole, dimethomorph, fenpiclonil
l), thicyofen, bromconazole (brom
uconazole), Ops (trade name, opus), ipconazole (i
pconazole), dimetconazole, microbutanil, myxothiaz
ol), thioimiconazole (thioimiconazole), zalilamide (zarilamid), metsulfovax (metsulfovax),
Hexaconazole, quinconazole (q
uinconazole), tecloftalam, triclofos-methyl, triclamide (tricl)
amide), fursulfamide, befuran (b
efran), cyproconazole, tecloftalam, fluconazole-cis (furconaz)
ole-cis), fenethanil, dimefluazole, ethyltriano
l), tebuconazole, oxolinic acid
(oxolinic acid) etc.

Examples of pests having a controlling effect on the compound of the present invention or a salt thereof include, for example, the turtle ( Eurydema rugosu).
m ), rice stink bug ( Scotinophara lurida ), Japanese beetle ( Riptortus clavatus ), nasi gumbai ( Steph
anitis nashi ), Greater Planthopper ( Laodelphax stritellu
s ), brown planthopper ( Nilaparvata lugens ), leafhopper leafhopper ( Nephotettix cincticeps ), scale bug
( Unaspis yanonensi s), Aphis glyci
nes), false radish aphid (Lipaphis er ysimi), radish aphid (Brevicoryne brassicae), cotton aphid (Aphisgossypii) Hemiptera such as, for example, common cutworm (Spodoptera litura), diamondback moth (Plutella Xylos
tella ), Pieris rapae crucivora ( Pieris rapae crucivora ), Nikamaiga ( Chilo supppressalis ), Tamanaginuwaba ( Au
tographa nigrisigna ), Tobacco moth ( Helicoverpa assult
a ), armyworm ( Pseudaletia separata ), armyworm ( Mam
e stra brassicae ), apple cockroach ( Adoxophye
s orana fasciata ), Watanameiga ( Notarcha derogat )
a ), Lepidoptera moth ( Cnaphalocrocis medinalis ), Potato moth ( Phthorimaea operculella ), and other lepidopteran pests, such as Epilachna vigintioctopu
nctata), cucurbit leaf beetle (Aulacophora femorali s), Kisujinomihamushi (Phyllotreta striolata), Imodorooimushi (Oulema ory zae), rice weevil (Echinocnemus squam
eus ) and other beetle pests such as the housefly ( Musca domestic
a), mosquito (Culex popiens pallens), gadfly (Ta
banus t rigonus), onion flies ( Delia antiqua ), and sand flies ( Delia platura ), and other dipteran pests, for example, Locusta migratoria locusts, Gryllotalpa afric
an a) and other orthoptera insects, such as the German cockroach ( Blattel
la germanica ), Black cockroach ( Periplaneta fuliginos)
a ) such as cockroaches pests, for example, Tetrany chus
urticae ), citrus spider mites ( Ponynychus citri ), kanzawa mites ( Tetranychu s kanzawai ), spider mites ( Tet
ranychus cinnabarinus ), apple spider mite ( Pano nychus ul
mi), mandarin orange rust mite (Aculops pelekassi) Acarina pests such as, for example, rice Shin Galle nematode (Aphelenchoides be
nematodes such as sseyi ), and termites ( Cop totermes formosa)
nus ), Yamato termites ( Reticulitermes speratus ), and the like termite pests, and the like, the diseases having a control effect are, for example, blast disease ( P yricularia oryzae ), sesame leaf blight ( Helminthosporium oryzae ), sickle seedling disease ( Gibber
ella fujikuroi ), White leaf blight ( Xanthomonas oryzae ), Seedling blight ( Rhizopus oryzae ), Leaf blight ( Pellicularia sasak)
ii , Rhizoctonia solani ) and other rice diseases, such as powdery mildew ( Erysiphe graminis ), and leaf blight ( Helminthosporium g )
ramineum , Pyrenoph ore gramineum ), naked smut ( Ustilag
o nuda ) and other diseases of barley, such as powdery mildew ( Erysiphe g
raminis ), black rust ( Puccinia graminis ), red rust ( Pu
ccinia reco ndita), netted smut ( Tilletia caries ) and other wheat diseases, such as powdery mildew ( Spha erotheca fuligine)
a ), downy mildew ( Pseudoperonospora cubensis ), gray mold
( Botr ytis cinerea ), anthracnose ( Colletotrichum lagenari
um ) and other diseases of cucumber, such as wilt disease ( Fusarium oxysp
orum), late blight (Phytophthora infestans), the black team's disease (Alter n
Tomato diseases such as aria tomato , such as downy mildew ( Plasmop)
ara viticola), gray mold (Botrytis cinerea) of grape, such as diseases, for example, scab (Venturia inaequalis), brown spot disease (Gymnosporangium yamadae), leaf spot (Alternar
ia mali ) and other apple diseases, corn, rye, potato, tobacco, sugar beet, capsicum, paprika, green beans, broad bean, groundnut, cabbage,
Diseases of cereal fruit and vegetable crops such as komatsuna, celery, radish, eggplant, Chinese cabbage, peppers, lettuce, citrus, pear and peach can be mentioned.

The compound [I] of the present invention has an insecticidal and bactericidal action, has very little toxicity, is safe, and can be used as an excellent insecticidal and bactericidal composition. The insecticidal and bactericidal composition of the present invention can be used as an insecticidal and bactericidal agent in the same manner as conventional insecticidal and bactericidal compositions, and as a result, can exhibit excellent effects as compared with conventional products. For example, the insecticide of the present invention, the fungicide, for example, nursery box treatment, foliage spray of crops,
It can be used by application of insect bodies, underwater application in paddy fields, seed treatment or soil treatment. The application rate can be varied over a wide range depending on the application time, application site, application method and the like, but generally, the active ingredient (the compound of the present invention or a salt thereof) is about 0.3 g to 3, per hectare.
It is desirable to apply it in an amount of 000 g, preferably about 50 g to 1,000 g. When the insecticidal and bactericidal agent of the present invention is a wettable powder, the final concentration of the active ingredient is about 0.
It may be used by diluting it in the range of 1 to 1,000 ppm, preferably about 10 to 500 ppm. The content ratio of the compound [I] or a salt thereof in the composition of the present invention is usually about 0.1 to 80% by weight, preferably about 1 to the total amount of the preparation.
It is about 20% by weight. Specifically, when it is used as an emulsion, a liquid preparation, a wettable powder (for example, a wettable granule), the amount is usually about 1 to 80% by weight, preferably about 1 to 20% by weight. When it is used as an oil or powder, the amount is usually about 0.1 to 50% by weight, preferably about 1 to 20% by weight. When it is used as a granule or the like, about 5 to 50% by weight, usually about 1 to 20% by weight is suitable. Other pesticidal active ingredients (eg, insecticides, herbicides, acaricides and / or fungicides) compounded in the composition of the present invention are usually about 1 to 8 relative to the total amount of the preparation.
It is used in the range of about 0% by weight, preferably about 1 to 20% by weight.

The content of additives other than the above-mentioned active ingredients varies depending on the kind or content of the agrochemical active ingredient, the dosage form of the preparation, etc., but is usually about 0.001 to 99.9% by weight, preferably about 1 to It is about 99% by weight. More specifically, the surfactant is usually used in an amount of about 1 to the total amount of the composition.
20% by weight, preferably about 1-15% by weight, a flow aid about 1-20% by weight, a carrier about 1-90% by weight,
It is preferable to add about 1 to 70% by weight.
Specifically, in the case of producing a liquid agent, it is preferable to add about 1 to 20% by weight of a surfactant, preferably about 1 to 10% by weight, and about 20 to 90% by weight of water. Emulsions, wettable powders (eg, granular wettable powders), etc. are appropriately diluted with water before use (for example, about 100 to 5.0).
00 times) and spray it.

The aminoethylene derivative [I] or a salt thereof of the present invention can be produced by combining reactions known per se used in synthetic organic chemistry. Specific preferred examples of the production method include the following method. When compound [I] is obtained as a free compound by the following production method, it can be converted into a salt as described above, or when it is obtained in the form of a salt, to a free compound, according to a conventional method. When the compound contained in the compound [I] is used as a raw material for producing another kind of compound [I], it may be used as a free form or as a salt. Similarly, when the other raw material can be a salt as described above, it can be used not only as a free salt but also as a salt. Therefore, the raw material compounds and products used in the following production methods also include salts thereof (for example, salts with acids as described in the above compound [I]). That is, a compound of the general formula [I] in which R ¹ is a group containing a carbon atom or a group containing a sulfur atom, or a salt thereof is a compound of the general formula [I] wherein R ¹ is hydrogen, or a salt thereof. It can be produced by reacting a salt with a compound represented by the general formula [IV] or a salt thereof.

[Chemical formula 24] Wherein, R ^1c represents a group bonded through a group or a sulfur atom through a carbon ^{atom, Ar 1, Ar 2, R} 2 and R ³ have the same meanings as defined above carbon atoms represented by R ^1c The intervening group and the group interposing the sulfur atom have the same meaning as described above. In this reaction, compound [Ic] or a salt thereof and compound [IV] or a salt thereof and a base may be added at the same time. The amount of base is about 0.8 to 5 equivalents, preferably about 1 to 3
The amount of the reaction reagent [IV] is about 0.8 to
It is 5 equivalents, preferably about 1 to 3 equivalents. The reaction is carried out in a solvent that does not adversely influence the reaction. As the solvent,
For example, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as chloroform, carbon tetrachloride and dichloromethane, ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran (THF), ketones such as acetone and methyl ethyl ketone. , Aliphatic amides such as dimethylformamide (DMF) and dimethylacetamide, dimethyl sulfoxide (D
Examples thereof include sulfoxides such as MSO), phosphoric acid amides such as hexamethylphosphoric triamide (HMPA), sulfones such as sulfolane, nitriles such as acetonitrile, and esters such as ethyl acetate. Examples of preferred bases used in this reaction include triethylamine, tri-n-propylamine, pyridine, dimethylaniline, dimethylaminopyridine, 1,8-diazabicyclo [5,4,0] -7-undecene (DB
U), organic bases such as 1,4-diazabicyclo [2,2,2] octane (DBO) and 1,5-diazabicyclo [4,3,0] non-5-ene (DBN); sodium hydroxide, water Alkali metal hydroxides such as potassium oxide, alkaline earth metal hydroxides such as calcium hydroxide, alkali metal hydrogencarbonates such as sodium hydrogencarbonate, inorganic bases such as alkaline earth metal carbonates such as calcium carbonate, n-butyllithium, Organic lithium compounds such as tert-butyllithium, phenyllithium, and methyllithium, lithium salts of secondary amines such as lithium diisopropylamide and lithium hexamethyldisilazane, and metal hydrides such as potassium hydride and sodium hydride are used. . The amount of the base used is about 0.8-5 equivalents, preferably about 1.0-1.2 equivalents, relative to compound [Ic]. Reaction temperature The reaction temperature varies depending on the base used and the reaction reagent [IV], etc., but generally the reaction temperature is about −100 to 200 ° C., preferably about −78 to 1
The reaction time is about 5 minutes to about 24 hours, preferably about 30 minutes to about 12 hours at 10 ° C.

The compound [Ic] or a salt thereof of the above general formula [I] in which R ¹ is hydrogen is represented by the general formula [II]

[Chemical 25] [In the formula, Ar ¹ , R ² and X have the same meanings as described above]
And an active methylene represented by the general formula [III] R ³ —CH ₂ —Ar ² [III] [wherein R ³ and Ar ² have the same meanings as described above] It can be produced by reacting the compound or a salt thereof, preferably in the presence of a base. In this reaction, compound [II] is compound [III]
In general, it is about 0.8 to 3 times mol, preferably about 0.9.
To 1.3 times the molar amount. This reaction is carried out in a solvent that does not adversely influence the reaction. Preferred solvents include, for example, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as chloroform, carbon tetrachloride and dichloromethane, diethyl ether, diisopropyl ether,
Ethers such as dioxane and tetrahydrofuran (THF), ketones such as acetone and methyl ethyl ketone, aliphatic amides such as dimethylformamide (DMF) and dimethylacetamide, dimethyl sulfoxide (DMS)
Sulfoxides such as O), phosphoric acid amides such as hexamethylphosphoric triamide (HMPA), sulfones such as sulfolane, and the like are used. Two or more kinds of these solvents may be mixed and used at an appropriate ratio.

The preferred base used in this reaction is
For example, triethylamine, tri-n-propylamine,
Pyridine, dimethylaniline, dimethylaminopyridine, 1,8-diazabicyclo [5,4,0] -7-undecene (DBU), 1,4-diazabicyclo [2,2,2]
2] Organic bases such as octane (DBO) and 1,5-diazabicyclo [4,3,0] non-5-ene (DBN); alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, calcium hydroxide, etc. Inorganic bases such as alkaline earth metal hydroxides, sodium hydrogen carbonates and other hydrogen carbonates, calcium carbonates and other alkaline earth metal carbonates,
Organolithium compounds such as n-butyllithium, tert-butyllithium, phenyllithium and methyllithium, lithium salts of secondary amines such as lithium diisopropylamide and lithium hexamethyldisilazane, hydrogenation of potassium hydride, sodium hydride and the like. Metal or the like is used.
The amount of base used is about 0.8 to 5 relative to compound [II].
It is an equivalent, preferably about 1.0 to 1.2 equivalents. The reaction temperature varies depending on the base used, but is generally about -100 to 2
The temperature is 00 ° C, preferably about -78 to 100 ° C. The reaction time varies depending on the reaction temperature, but is about 5 minutes to about 5 hours, preferably about 30 minutes to about 2 hours.

The salt of compound [Ic] can be prepared by a method known per se,
For example, the compound [Ic] is dissolved in a solvent such as alcohol,
It can be produced by adding the above-mentioned organic or inorganic salt to this. The above compound [II] or a salt thereof can be produced by the following formula.

[Chemical 25] [Wherein Ar ¹ , R ² and X have the same meanings as described above] The amide compound [V] is a known method or a method known per se (eg, J. O.
rg Chem., 44 , 2805 (1979), Tetrahedron Lett., 28 ,
4737 (1987)). [V]
The reaction of [II] can be carried out by a known method described in the literature or a method analogous thereto. As the document,
For example, J. Org Chem., 1959 , 2865, Chem. Ind. 1971 ,
175, Angew. Chem., 81 , 468 (1969), Tetrahedron
Lett., 1974 , 67 etc. can be mentioned. Examples of the halogenating agent include phosphorus pentachloride, phosphorus oxychloride, triphenylphosphine-carbon tetrachloride and the like. The amount of the halogenating agent can be usually about 0.8 to 10 times mol, preferably about 1.0 to 3.0 times mol, relative to 1 mol of the amide compound [V]. This reaction can be carried out using a solvent. As such a solvent, one that dissolves both the reaction substrate and the reaction reagent is desirable, and for example, aromatic hydrocarbons such as benzene, toluene, xylene, etc., aliphatic hydrocarbons such as pentane, hexane, heptane, etc., diethyl ether. , Ethers such as tetrahydrofuran, dioxane, acid amides such as dimethylformamide and dimethylacetamide, sulfoxides such as dimethylsulfoxide, sulfones such as sulfolane, phosphoramides such as hexamethylphosphoric triamide (HMPA), chloroform, Examples thereof include halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane and carbon tetrachloride, and mixed solvents thereof. The reaction temperature is usually about −30 to 200 ° C., preferably about 0 to 110.
° C. The reaction time varies depending on the reaction substrate, reaction reagent, reaction concentration and solvent used, but is generally about 1 to 24.
Time.

When R ³ is a cyano group or a C _1-6 alkylthio group, the compound represented by the above general formula [III], R ³ —CH ₂ —Ar ² [III] or a salt thereof is prepared by the following method. Can be manufactured.

[Chemical formula 26] [In the formula, M represents a chlorine atom, a hydroxyl group, a methoxy group or an ethoxy group, R ^3d represents a cyano group or a C _1-6 alkylthio group, Z represents an alkali metal, and Ar ² has the same meaning as above] The reaction [VI] → [VII] can be carried out by a method known per se or a similar method analogous thereto. As the known sentence method, for example, "Survey of Organic Syntheses", V
1 and vol. 2, Wiley-Interscience (1970 and 1977), Chapter 4 and the like. When M represents a chlorine atom, the reducing agent is preferably sodium borohydride or the like, and is used in an amount of about 0.25 to 5 equivalents, preferably about 0.5 to 2 equivalents, relative to compound [VI], and containing water. It is preferably carried out in a solvent. Such solvents include ethers such as THF and dioxane,
Examples thereof include nitriles such as acetonitrile, halogenated hydrocarbons such as chloroform, esters such as ethyl acetate, alcohols such as methanol and ethanol. The reaction temperature is about −50 to 100 ° C., preferably about −
20 to 50 ° C. The reaction time is about 5 minutes to 24 hours.

When M represents a hydroxyl group, lithium aluminum hydride, sodium borohydride, etc. can be used as the reducing agent. When using lithium aluminum hydride, it is desirable to carry out the reaction in an anhydrous solvent, and examples of such a solvent include ethers such as THF, dioxane, 1,2-dimethoxyethane (DME), and diethylene glycol dimethyl ether. You can The amount of lithium aluminum hydride used is
It is used in an amount of about 0.25 to 5 equivalents, preferably about 0.5 to 2 equivalents, relative to compound [VI]. The reaction temperature is about -78 to 15
It is 0 ° C, preferably about -50 to 100 ° C. The reaction time is about 10 minutes to 24 hours. When sodium borohydride is used as the reducing agent, for example, Journal of Organic Chemistry (Journal of Organic C
hemistry) 56, 5964 (1991). That is, it can be carried out in the presence of iodine. In such a case, ethers such as THF are used as the solvent, and the amount of sodium borohydride is about 0.8 to 5 equivalents, preferably about 1 to 5 equivalents to the compound [VI].
Use 2 equivalents. The amount of iodine used is about 0.3 to 2 equivalents, preferably about 0.4 to 1 equivalents, relative to compound [VI]. The reaction temperature is about -50 to 100 ° C, preferably about -30 to 50 ° C. Reaction time is about 10 minutes
It is about 24 hours. When M represents a methoxy group or an ethoxy group, for example, diisobutylaluminum hydride, lithium aluminum hydride, sodium borohydride, etc. can be used as the reducing agent. When diisobutylaluminum hydride or lithium aluminum hydride is used, It can be performed in the same manner as in the case where M represents a hydroxyl group as described above. When sodium borohydride is used as the reducing agent, for example, the Bulletin of Chemical Society of Japan (Bulletin of
Chemical Society of Japan) Volume 64, page 2730 (1991). That is, it can be carried out by coexisting with zinc chloride and, if necessary, a tertiary amine such as triethylamine, N, N-dimethylaniline or the like. The amount of sodium borohydride is about 0.5 to 5 equivalents, preferably about 1 to 3 equivalents, relative to compound [VI]. The amount of zinc chloride is about 0.5 to 3 equivalents, preferably about 0.7 to 2 equivalents, relative to compound [VI]. In this reaction, it is also effective to add about 0.5 to 3 equivalents of a tertiary amine to the compound [VI] if necessary. Examples of the solvent used include ethers such as THF and diethylene glycol dimethyl ether. The reaction temperature is about 0 to 150 ° C, preferably about 10 to 100 ° C
Is. The reaction time is about 0.5 to 24 hours. The compound [VIII] or a salt thereof thus obtained can be isolated and purified by the above-mentioned known means, or can be used as the reaction mixture as it is in the next reaction raw material.

The reaction [VII] → [VIII] can be carried out by a method known per se or an analogous method thereto. The known method includes, for example, "Survey of
Survey of Organic Synt
heses) ", Vol. 1 and vol. 2, Wiley-Interscience
(1970 and 1977), Chapter 7 can be mentioned. As a halogenating agent, hydrogen chloride,
Various agents such as chlorinating agents such as thionyl chloride, phosphorus oxychloride and phosphorus pentachloride, brominating agents such as hydrogen bromide, thionyl bromide, phosphorus oxybromide and phosphorus pentabromide are used. Of these, thionyl chloride is preferably used for chlorination. This reaction does not particularly require a solvent, but if necessary, halogenated hydrocarbons such as chloroform, methylene chloride and 1,2-dichloroethane, ethers such as THF and dioxane may be mixed alone or in an appropriate ratio. You can use it. The amount of thionyl chloride used is about 0.5 to a large excess, preferably about 0.8 to 5 equivalents, relative to compound [V11]. The thionyl chloride may be used as a solvent. Also,
By allowing a tertiary amine such as triethylamine, diisopropylethylamine, pyridine, and N, N-dimethylaniline to coexist in the reaction mixture, the reaction may be promoted and by-products may be suppressed. The reaction temperature is about 0 to 2
The temperature is 00 ° C, preferably about 20 to 150 ° C. The reaction time is about 10 minutes to 24 hours. The obtained [VIII] or a salt thereof can be isolated and purified by the above-mentioned known means, or can be directly used as a reaction mixture in the next reaction raw material.

The reaction of [VIII] → [III _a ] can be carried out by a method known per se or a similar method according thereto. Examples of the method include "Survey of Organic Synthese".
s) ”, Vol. 1 and vol. 2, Wiley-Interscience (197
0 and 1977), Chapter 19 can be mentioned. As the nitrileing agent, for example, sodium cyanide, potassium cyanide, etc., and as the alkylthioning agent, methyl mercaptan, an alkali metal salt of benzyl mercaptan, etc., are each used in an amount of about 0.5 to 10 equivalents, preferably about 10 equivalents to the compound [VIII]. 0.8 to 5 equivalents are used. This reaction can be promoted by allowing an alkali metal halide such as sodium iodide, potassium iodide, sodium bromide, or potassium bromide to coexist. The reaction is preferably carried out in a solvent that does not adversely influence the reaction. Examples of the solvent include alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile, DMF and DM.
Amides such as A, sulfoxides such as DMSO, HMP
Examples thereof include phosphoric acid amides such as A, mixed solvents thereof, and mixed solvents of these and water. The reaction temperature is about -20 to 200 ° C, preferably about 0 to 150 ° C.
The reaction time is about 10 minutes to about 24 hours. Obtained [II
_Ia ] or a salt thereof can be isolated and purified by the above-mentioned known means, or can be directly used as the reaction mixture in the next reaction raw material.

When R ³ is fluoroalkylsulfonyl in the compound [III], it can be produced by the method of the following formula.

[Chemical 28] [In the formula, R ^3e represents a fluoroalkyl group and Ar ² has the same meaning as described above.] The reaction [IX] → [X] can be carried out by a method known per se or a similar method according thereto. . Examples of the method include Tetrahedron Letter (Tetrahedron Le
tt.), 31 , 3579 (1990), Journal of American Chemical Society (J. Am. Chem. Soc.), 11
The method described in 5 , 2156 (1993) can be mentioned. The fluoroalkylating agent is, for example, S- (trifluoromethyl) dibenzothiophenium trifluoromethanesulfonate, S- (trifluoromethyl) 3,7-
Dinitrodibenzothiophenium trifluoromethanesulfonate and the like are preferable, and the compound [IX] is used in an amount of about 0.
75 to 5 equivalents, preferably about 0.95 to 3 equivalents are used. The solvent used in the reaction is preferably a solvent containing no water without adversely affecting the trifluoroalkylating agent. Examples of such a solvent include ethers such as tetrahydrofuran and dioxane, nitriles such as acetonitrile, halogenated hydrocarbons such as chloroform and dichloromethane, and amides such as dimethylformamide (DMF) and dimethylacetamide (DMA). This reaction is preferably carried out in the presence of a base, and preferred bases to be used include, for example, triethylamine and tri-n-
Organic salts such as propylamine, pyridine, dimethylaniline, dimethylaminopyridine, n-butyllithium, te
Organolithium compounds such as rt-butyllithium, phenyllithium and methyllithium, and metal hydrides such as potassium hydride and sodium hydride are used. The amount of the base used is about 0.75 to 5 equivalents, preferably about 0.95 to 3 equivalents, relative to compound [IX]. The reaction temperature varies depending on the base used, but generally about -100 to 100 ° C,
It is preferably about -78 to 50 ° C. The reaction time varies depending on the reaction temperature, but is about 10 minutes to about 8 hours, preferably about 30 minutes to about 3 hours. This reaction is preferably carried out in a non-aqueous system, and may be carried out in an atmosphere of an inert gas such as nitrogen or argon. The obtained [III _b ] or a salt thereof can be isolated and purified by the above-mentioned known means, or can be directly used as a reaction mixture in the next reaction raw material. The thus-obtained aminoethylene derivative [I] or a salt thereof is isolated and purified by known means, for example, concentration, vacuum concentration, vacuum distillation, liquid conversion, phase transfer, solvent extraction, crystallization, recrystallization, It can be isolated and purified by chromatography or the like. The compound [I] of the present invention has structural isomers of E type and Z type represented by the following formulas, but the present invention includes both isomers.

[Chemical 29]

Test Example 1 Hansmon Yote ( Spodoptera
Effect on litura ) To a soybean seedling (single leaf development stage), 0.5 mg of acetone containing 5 mg of a test compound (shown as No. of the compound obtained in the following examples) containing tween 20 (trade name). And dissolve it in 3000 times diluted Dyne water to a predetermined concentration (100
(20 ppm / pot) was sprayed with a spray gun. After the drug solution has dried, cut out two single soybean leaves,
It was placed in an ice cream cup, 10 third-instar larvae of Hansmon Yoto were released, and after the release, the cup was placed indoors (25 ° C.), and the number of dead insects was counted 5 days later. The mortality rate was calculated from the formula shown below, and the results are shown in [Table 1].

[Equation 1]

[Table 1]

Test Example 2 Chilo suppressal
is )) 5 mg of the test compound (indicated by the No. of the compound obtained in the following Examples) is added to the foliage of 3-4 leaf stage rice seedlings (6,7 plants / strain planted) grown in a nursery box. Tween 20
Dissolve with 0.5 ml of acetone containing (brand name), 300
20 ml / pot of chemical solution was sprayed with a spray gun to a predetermined concentration (100 ppm) with 0 times diluted dyne water. After the chemical solution has dried, rice seedlings are put into a tester (φ: 3 cm, h: 20 cm) with 5 ml of tap water, 10 third-instar larvae of Nikamaiga are released, and placed in an incubator (27 ° C). After a day, the number of dead insects was counted and the degree of feeding damage was observed. Mortality is test example 1
The degree of feeding damage was determined according to the following criteria, and the results are shown in [Table 2]. Eating damage degree 0: Almost no eating damage is observed 1: Very slight (less than about 1/10 of untreated area) eating damage is observed 2: Less than about 1/2 of untreated area is damaged 3: Untreated Approximately 1/2 or more of food damage is observed in the ward 4: The same level of food damage is observed as in the untreated ward

[Table 2]

Test Example 3 Pyudeletia sepa
Effect on rata ) Test compound (No. of compound obtained in the following Examples) is shown on the foliage of corn (2 plants / pot) in the 1.5 to 2 leaf stage planted in a Jiffy pot (φ: 6 cm). ) 5 mg
Was dissolved in 0.5 ml of acetone containing tween 20 (trade name), and a predetermined concentration (20 ppm) of 3000 times diluted dyne water was applied to spray 20 ml / 2 of the drug solution with a spray gun. After the drug solution has dried, two corn single leaves are cut out and placed in an ice cream cup, and 10 third-instar larvae of armyworm (2 repeats) are released. After the release, the cup is placed at room temperature (25 ° C) for 5 days. The dead insects were counted. The mortality rate was calculated from the formula shown in Test Example 1, and the results are shown in [Table 3].

[Table 3]

Test Example 4 Diamondback moth ( Pulutella xylostell)
Effect on a ) 5 mg of the compound to be tested (shown as No. of the compound obtained in the following Examples) is dissolved in 0.5 ml of acetone containing tween 20 (trade name), and diluted 3000 times with dyne water. To a specified concentration (20ppm) and cabbage leaves about 5c
Leaf pieces cut into m × 5 cm were immersed in the chemical solution for several seconds. After the drug solution dried, the leaf pieces were placed in an ice cream cup, 10 second-instar larvae of Plutella xylostella were released (2 repetitions), and after the release, the cup was placed at room temperature (25 ° C) and the dead insects were counted 5 days later. The mortality rate was calculated from the formula shown in Test Example 1, and the results are shown in [Table 4].
It was shown to.

[Table 4]

[0034] Test Example 5 beetle, Epilachna vigintioctopunctata (Heno
Effect on sepilachna rigintioctopunctata 5 mg of the test compound (denoted by the No. of the compound obtained in the following examples) was dissolved in 0.5 ml of acetone containing tween 20 (trade name), and diluted 3000 times with dyne. Potato tubers were cut to a thickness of about 5 mm with water to a predetermined concentration (20 ppm) and immersed in a chemical solution for several seconds. After the chemicals have dried, remove the potato tubers into a plastic petri dish (φ: 9c
m)), 10 second-instar larvae of Nitoya citrus ladybird / a petri dish (2 repetitions) were released, and after the release, the petri dish was placed at room temperature (25 ° C.) and the dead insects after 5 days were counted. The mortality was calculated from the formula shown in Test Example 1, and the results are shown in [Table 5].

[Table 5]

Test Example 6 Rhizoctonia sola
ni )) The test compound (indicated by the compound No. obtained in the following examples) is dissolved in dimethylformamide (final concentration 1% by weight), and further xylene (final concentration 0.02% by weight), Tween 20 (trade name) (final concentration: 0.02% by weight) was added, and the mixture was diluted with water to a predetermined active ingredient concentration (200 ppm). The spreading agent Dyne (trade name, manufactured by Takeda Pharmaceutical Co., Ltd., containing 20% by weight of polyoxyethylene nonylphenyl ether and 12% by weight of calcium lignin sulfonate) was added to this liquid in an amount of 0.05% by weight (final concentration). It was added in a ratio and sprayed on rice (about 5 weeks old seedlings) to the extent that it dripped. After air-drying, a 10 mm diameter flora block of rice wilt disease bacteria was inoculated to the edge of the soil at a rate of 1 per strain. After keeping the temperature at 25 to 30 ° C. for 7 days after the inoculation, the area ratio of diseased spots in the individual was investigated, and the results were shown in [Table 6] using the following control values. Control value 3: Disease area 0 to 5% Control value 2: Disease area 6 to 15% Control value 1: Disease area 16 to 30% Control value 0: Disease area 31% or more

[Table 6]

Test Example 7 Pyricularia or rice blast
Preventive effect against yzae ) In the same manner as in Test Example 6, a predetermined active ingredient concentration (200 pp
m) to the rice (approx. 5 weeks seedling)
It was sprayed so that it would drip. After air-drying, diseased rice was placed between the treated rice and inoculated for 2 days by natural infection from diseased leaves. After keeping the temperature at 25 to 30 ° C. for 7 days after inoculation, the area ratio of lesions occupying the individual was investigated, and the control values shown in Test Example 6 were used to show the results in [Table 7].

[Table 7]

Test Example 8 Barley powdery mildew ( Erysiphe
Preventive effect against graminis ) In the same manner as in Test Example 6, a predetermined active ingredient concentration (200 pp
The spray solution prepared so as to be m) was sprayed onto barley (cultivated for 8 days after sowing) to such an extent that it dripped. After air-drying, spores of diseased leaves were forcibly dropped and inoculated. After keeping the temperature at 20 ° C. for 8 days after the inoculation, the area ratio of lesions occupying the individual was investigated, and the results were shown in [Table 8] using the following control values. Control value 3: Disease area 0-10% Control value 2: Disease area 11-20% Control value 1: Disease area 21-50% Control value 0: Disease area 51% or less

[Table 8]

[0038]

The present invention will be described in more detail with reference to Examples and Reference Examples, but the present invention should not be construed as being limited to these Examples. Elution by column chromatography of Examples and Reference Examples was carried out under observation by TLC (Thin Layer Chromatograph). In TLC observation, as a TLC plate, Kesel gel 60F254 (70 to 230 mesh) manufactured by Merck
Was used as a developing solvent, and the solvent used as an elution solvent in column chromatography was used as a developing solvent, and a UV detector was used as a detection method. As the column silica gel, Kesel gel 60 (70 to 230 mesh) also manufactured by Merck & Co. was used. NM
R spectrum shows proton NMR, using tetramethylsilane as an internal standard, VARIAN EM390 (90MHz)
Type or Bruker AC-200P (200MHz) type spectrometer, and all δ values are shown in ppm. When a mixed solvent is used as the developing solvent, the numerical value shown in parentheses is the volume mixing ratio of each solvent. The abbreviations used in the following Examples, Reference Examples and Tables have the following meanings.
Me: methyl group, Et: ethyl group, Ph: phenyl group,
s: singlet, br: broad (wide), d: doublet, t: triplet, q: quartet, m:
Multiplet, dd: double doublet, J: coupling constant, Hz: Hertz, CDCl _3: deuterated chloroform, DMSO-d _6: heavy DMSO,%: weight%, mp: melting point, also Room temperature is about 15 Means 25 ° C.

Reference Example 1 2,6-Dichloro-4-trifluoromethylphenyl-2,2,2-trifluoroacetamide (Compound 1-1) 2,6-Dichloro-4-trifluoromethylaniline 2
3 g (0.1 mol) was dissolved in 100 ml dichloroethane,
Trifluoroacetic anhydride was added dropwise under ice cooling, and the mixture was stirred at room temperature for 5 hours. The reaction solution was concentrated under reduced pressure, petroleum ether was added to the residue, and the crystals were collected by filtration and dried to obtain 22.6 g (70.3%) of the title compound. mp 110-111 ° C NMR (CDCl ₃ ) δ: 7.70 (2H, s), 7.82 (1H, br) IR (Nujol) cm ⁻¹ : 3200, 1715, 1321, 1163, 1135, 880

Reference Example 2 Compound obtained in the same manner as in Reference Example 1, its melting point and NM
The R values are shown in [Table 9] and [Table 10].

[Table 9]

[Table 10]

Reference Example 3 N- {3,5-bis (trifluoromethyl) phenyl} -2,2-difluoro-2-methylthioacetamide (Compound 1-19) Methyl mercaptan sodium salt 4.09 under a nitrogen stream.
g (0.058 mol) was suspended in 20 ml of DMF, and N- {3,5-bis (trifluoromethyl) phenyl} was added at room temperature.
Add 2-chloro-2,2-difluoroacetamide (Compound 1-14) 5.0 g (0.014 mol) 115-
Heated at 120 ° C. for 6 hours. After cooling, the reaction solution was poured into water, neutralized with 10% hydrochloric acid, extracted with ethyl acetate, washed with water and dried, and then the solvent was distilled off. The residue was subjected to silica gel column chromatography, and hexane-ethyl acetate (7: 1).
By eluting with 2.54 g (49%) of the title compound.
%) Was obtained. NMR (CDCl ₃ ) δ: 2.43 (3H, s), 7.71 (1H, s), 8.13 (2H,
s), 8.34 (1H, brs)

Reference Example 4 N- {3,5-bis (trifluoromethyl) phenyl} -2-difluoromethylthioacetamide (Compound 1-20) (1) Thioglycolic acid 15.0 g (0.163 mol) was added to methanol 75 ml. 33% of a 40% sodium hydroxide aqueous solution was added, the mixture was heated to 60 ° C., and 104.25 g of chlorodifluoromethane gas was blown in for 6 hours. On the way
100 ml of 40% aqueous sodium hydroxide solution was added in 6 portions. After cooling, methanol was distilled off at room temperature, and the residue was adjusted to pH 1 with concentrated hydrochloric acid while cooling with ice. After extraction with dichloromethane and drying, the solvent was distilled off to obtain 16.77 g (72%) of an oily product of difluoromethylthioglycolic acid. NMR (CDCl ₃ ) δ: 3.61 (2H, s), 6.94 (1H, t, J = 56.2Hz),
10.61 (1H, brs) (2) 3.70 g (0.1%) of the substituted glycolic acid obtained above.
(026 mol) was dissolved in 50 ml of diethyl ether, 5.42 g (0.026 mol) of phosphorus pentachloride was added under ice cooling, and the mixture was stirred at the same temperature for 2 hours. Diethyl ether was distilled off under reduced pressure, carbon tetrachloride was added to the residue, and it was distilled off together with phosphorus oxychloride. 4.64 g of the obtained acid chloride (crude) is dissolved in 20 ml of acetonitrile, and under ice cooling, 3.77 g (0.02 mol) of 3,5-bistrifluoromethylaniline and 3.95 g (0.04 mol) of triethylamine in 30 ml of acetonitrile. Dropped into the solution. After stirring at the same temperature for 1 hour, the solvent was distilled off, and the residue was diluted with diisopropyl ether-
Recrystallized from hexane to give the title compound 4.1
g (45%) was obtained. mp 127-128 ° C NMR (CDCl ₃ ) δ: 3.71 (2H, s), 6.96 (1H, t, J = 55.5Hz),
7.66 (1H, s), 8.04 (2H, s), 8.43 (1H, brs)

Reference Example 5 N- {3,5-bis (trifluoromethyl) phenyl} -2-phenoxy-2,2-difluoroacetamide (Compound 1-21) (1) Sodium hydride (60% in oil) 5.2g
(0.13 mol) was suspended in 100 ml of dioxane, and 5.8 g (0.061 mol) of phenol was added little by little under ice cooling. Then, chlorodifluoroacetic acid 8.0 g (0.061
mol) was added and the mixture was heated to reflux (4 hours). After cooling, the reaction solution was poured into ice water, extracted with ethyl acetate, washed with water and dried, and then the solvent was distilled off. By distilling the residue under reduced pressure, bp
There was obtained 5.2 g (45.6%) of substituted phenoxydifluoroacetic acid (oil) at 93 ° C./0.2 mmHg. NMR (CDCl ₃ ) δ: 7.71 (4H, br), 8.12 (2H, s) (2) 5.2 g (0.027 mol) of the substituted phenoxydifluoroacetic acid obtained above was dissolved in 50 ml of dichloroethane, and thionyl chloride 6 was added. Add 0.6 g (0.055 mol),
It was heated to reflux (13 hours). After cooling, excess thionyl chloride was distilled off to obtain 3.2 g of the obtained acid chloride (crude).
Was dissolved in 20 ml of acetonitrile, and 2.3 g (0.01 mol) of 3,5-bistrifluoromethylaniline under ice cooling.
And triethylamine (2.1 ml, 0.015 mol) were added dropwise to a solution of 30 ml of acetonitrile. After stirring at room temperature for 1 hour,
The solvent was distilled off. A small amount of petroleum ether was added to the residue and the crystals were collected by filtration and dried to give 3.2 g (8%) of the title compound.
0.2%) was obtained. NMR (CDCl ₃ ) δ: 7.20-7.50 (5H, m), 7.73 (1H, s), 8.15
(2H, s), 8.42 (1H, br)

Reference Example 6 N- {3,5-bis (trifluoromethyl) phenyl} -2-phenylthio-2,2-
Difluoroacetamide (Compound 1-22) Sodium hydride (60% in oil) 0.26 g (0.0
(065 mol) was washed twice with hexane, suspended in DMF, and dissolved in 2 ml of DMF under ice cooling to give 0.71 thiophenol.
A solution of g (0.0064 mol) was added dropwise. After stirring at room temperature for 15 minutes, 1.0 g (0.0029 mol) of N- {3,5-bis (trifluoromethyl) phenyl} -2-chloro-2,2-difluoroacetamide (Compound 1-14) D
A 3 ml MF solution was added dropwise and reacted at 105 to 110 ° C for 5.5 hours. After cooling, the reaction solution was poured into ice water, extracted with ethyl acetate, washed with water and dried, the solvent was distilled off, and the residue was subjected to silica gel column chromatography and eluted with hexane-ethyl acetate (10: 1). This gave 1.14 g (94%) of the title compound. mp 111-113 ° C NMR (CDCl ₃ ) δ: 7.36-7.54 (3H, m), 7.64 (1H, s), 7.68
-7.70 (2H, m), 7.88 (1H, brs), 7.92 (2H, s)

Reference Example 7 N- (2,5-dichloro-4-
Trifluoromethylphenyl) -2,2,2-trifluoromethylacetamide (Compound 1-18) (1) 2,5-Dichlorobenztrifluoride 4.3
g (0.02 mol) was dissolved in 5.6 ml of concentrated sulfuric acid, and a mixture of 1.7 g of fuming nitric acid and 5.6 ml of concentrated sulfuric acid was added dropwise at 15 ° C. or lower, followed by stirring at 50 ° C. for 5 hours. After cooling, the reaction solution was poured into ice water, extracted with dichloromethane, washed with water, washed with aqueous sodium hydrogen carbonate, dried, and then the solvent was distilled off. The obtained oily substance (nitrobenzene) was mixed with 4.0 g of iron powder, 2.0 ml of acetic acid and 36 ml of water,
The mixture was stirred at an oil bath temperature of 120 ° C for 3 hours. After cooling, the insoluble matter was filtered off, washed with ethyl acetate, the filtrate was separated, the aqueous layer was extracted with ethyl acetate, the organic layers were combined, washed with water and dried,
The solvent was distilled off. The residue was subjected to silica gel column chromatography, and eluted with hexane-ethyl acetate (5: 1) to give 1.15 g (25.0%, oil) of 4-amino-2,5-dichlorobenztrifluoride. )
Obtained. NMR (CDCl ₃ ) δ: 3.71 (2H, s), 7.21 (1H, d), 7.52 (1H,
d) (2) 1.15 g (0.00) of the substituted aniline obtained above
(5 mol) was reacted in the same manner as in Reference Example 1 to obtain 1.5 g (92.0%) of the title compound. mp-74 ° C NMR (CDCl ₃ ) δ: 7.59 (1H, d), 8.60
(1H, brs), 8.64 (1H, d)

Reference Example 8 2,2,2-trifluoro-N
-(2,6-Dichloro-4-trifluoromethylphenyl) ethaneimidoyl chloride (Compound 2-1) 2,6-dichloro-4-trifluoromethylphenyl-
2,2,2-trifluoroacetanilide (Compound 1-
1) 22.5 g (0.069 mol) of dichloromethane 16
Dissolve in 0 ml, 27 g of triphenylphosphine at room temperature
(0.1 mol) and carbon tetrachloride (10.4 ml) were added, and the mixture was stirred at the same temperature for 16 hours. Then, the reaction solution was concentrated under reduced pressure. Hexane was added to the residue to remove insoluble crystals by filtration, and the filtrate was concentrated under reduced pressure. The residue was subjected to silica gel column chromatography and eluted with hexane-ethyl acetate (3: 1) to give 22.5 g (94.9%, oily substance) of the title compound. NMR (CDCl ₃ ) δ: 7.67 (2H, d, J = 0.6Hz) IR (Nujol) cm ^-1 : 1705, 1310, 1212, 1170, 1135, 957

Reference Example 9 Compounds obtained in the same manner as in Reference Example 8 and their NMR values are shown in [Table 11] to [Table 13].

[Table 11]

[Table 12]

[Table 13]

Reference Example 10 2-Methoxy-3,6-dichlorophenylacetonitrile (1) 2-Methoxy-3,6-dichlorobenzoic acid 5.0
g (0.023 mol) was suspended in 50 ml of dichloroethane, 3.3 ml (0.045 mol) of thionyl chloride was added, and the mixture was heated to reflux (5 hours). After cooling, excess thionyl chloride was distilled off, toluene was added to the residue, and the mixture was concentrated.
Methoxy-3,6-dichlorobenzoyl chloride was obtained. NMR (CDCl ₃ ) δ: 3.98 (3H, s), 7.16 (1H, d), 7.42 (1H,
d) (2) The acid chloride obtained above is suspended in 7.5 ml of isopropanol and 7.5 ml of water, and under cooling with water, 2.5 g (0.066 mol) of sodium borohydride is added little by little.
Stirred at room temperature for 1 hour. 50 ml of water was added to the reaction solution, extracted with diethyl ether, washed with water and dried, and then the solvent was distilled off.
4.1 g (87.6%) of 2-methoxy-3,6-dichlorobenzyl alcohol having an mp of 69 to 71 ° C. was obtained. (3) 4.1 g of the substituted benzyl alcohol obtained above
(0.02 mol) was dissolved in DMF, 2.6 g (0.022 mol) of thionyl chloride was added dropwise at room temperature (under water cooling), and the mixture was stirred at the same temperature for 1 hour. The reaction solution is poured into ice water and the precipitated crystals are collected by filtration, washed with water and dried to give 2-methoxy-3,6.
-4.3 g (95.3%) of dichlorobenzyl chloride
Obtained. NMR (CDCl ₃ ) δ: 3.99 (3H, s), 4.78 (2H, s), 7.14 (1H,
d), 7.31 (1H, d) (4) 0.5 g (0.01 mol) of sodium cyanide in D
Suspended in 10 ml of MSO, 2.25 g (0.01 mol) of the substituted benzyl chloride obtained above was added little by little at 30 ° C. or lower, and stirred at room temperature for 16 hours. The reaction solution was poured into ice water and the precipitated crystals were collected by filtration, washed with water and dried. The obtained crystals were subjected to silica gel column chromatography and eluted with hexane-ethyl acetate (3: 1) to give the title compound (2.1 g, 97.3%). _{mp: ~58 ℃ NMR (CDCl 3} ) δ: 3.87 (2H, s), 3.99 (3H, s), 7.17 (1H,
d), 7.34 (1H, d)

Reference Example 11 6-chloro-3-pyridylacetonitrile 2-chloro-5-pyridylmethanol 5.6 g (0.03)
4 mol) was reacted in the same manner as in Reference Examples 10- (3) and 10- (4) to give 3.0 g (57.
6%) was obtained. mp: 52 ° C. NMR (CDCl ₃ ) δ: 3.76 (2H, s), 7.39 (1H, d), 7.69 (1H, d)
d), 8.37 (1H, d)

Reference Example 12 4-Bromo-2-chlorophenylacetonitrile (1) 20 g (0.1 m) of 2-chloro-4-bromoaniline
ol), 30 ml of concentrated hydrochloric acid and 100 g of ice were added, and a solution prepared by dissolving 7.0 g (0.1 mol) of sodium nitrite in 24 ml of water was added dropwise under ice cooling. Further under ice cooling, sodium carbonate 9.0
g was added little by little to bring the pH to 7. Next, in another flask, 12.4 g (0.125 mol) of cuprous chloride was suspended in 90 ml of water, and 12.7 g (0.2
6 mol) was added little by little, and the mixture was stirred at the same temperature for 1 hour. Then, 50 g of ice was added, and the diazonium salt obtained above was added little by little over 1 hour. Ethyl acetate 10 in the reaction solution
After adding 0 ml and stirring, the insoluble matter was filtered off, the filtrate was separated,
After washing with water and drying, the solvent was distilled off. The residue was subjected to silica gel column chromatography, eluting with hexane-ethyl acetate (3: 1) to give 4-bromo-2-
Obtained 12.1 g (56.0%) of chlorobenzonitrile. mp: 73-75 ° C NMR (CDCl ₃ ) δ: 7.53 (2H, d), 7.71 (1H, t) (2) 12.0 g of the substituted benzonitrile obtained above
(0.055 mol) of monomethyl ethylene glycol 50
1 ml of potassium hydroxide (0.2mo)
A solution obtained by dissolving l) in 10 ml of water was added, and the mixture was heated to reflux (5 hours). After cooling, 50 ml of water was added to the reaction solution, washed with diethyl ether, the aqueous layer was neutralized with concentrated hydrochloric acid, and the precipitated crystals were collected by filtration, washed with water, and dried to give 4-bromo-2-
There was obtained 10.4 g (80.3%) of chlorobenzoic acid. mp: ~ 130 ° C (3) Lithium aluminum hydride 0.55 g (0.01
4 mol) was suspended in 100 ml of diethyl ether, and 30
Around 10.degree. C., 10.4 g (0.0) of the substituted benzoic acid obtained above.
(44 mol) was added little by little, and the mixture was refluxed under heating (0.5 hr) at room temperature for 1 hr. Under ice cooling, about 10 ml of water was added dropwise, and further 30 ml of 20% sulfuric acid was added dropwise to dissolve the crystals. The organic layer was separated, washed with 1N sodium hydroxide and water, dried, and then the solvent was distilled off to give 3.3 g (34.0 g) of 4-bromo-2-chlorobenzyl alcohol.
%) Was obtained. mp: 71 ° C NMR (CDCl ₃ ) δ: 4.73 (2H, s), 7.30-7.60 (3H, m) (4) 3.3 g of the substituted benzyl alcohol obtained above
By reacting (0.015 mol) in the same manner as in Reference Example 10- (3), 3.5 g of 4-bromo-2-chlorobenzyl chloride was obtained. NMR (CDCl ₃ ) δ: 4.64 (2H, s), 7.30-7.65 (3H, m) (5) 3.5 g of the substituted benzyl chloride obtained above
By reacting (0.015 mol) in the same manner as in Reference Example 10- (4), 2.38 g (68.8%) of the title compound was obtained. mp: 55 ° C NMR (CDCl ₃ ) δ: 3.79 (2H, s), 7.35-7.65 (3H, m)

Reference Example 13 2,5-Dichlorophenylacetonitrile (1) 10.0 g (0.062) of 2,5-dichlorotoluene
mol), N-bromosuccinimide 2.1 g (0.068 m)
ol) and dibenzoyl peroxide 0.6 g (0.002)
5 mol) was suspended in 80 ml of carbon tetrachloride and heated under reflux (1 hour). After cooling, the insoluble matter was filtered off, the filtrate was concentrated,
Distilled under reduced pressure to give 2,5-dichlorobenzyl bromide 7.
Obtained 9 g (53.1%) as an oil. bp: 80-85 ° C./0.8 mmHg NMR (CDCl ₃ ) δ: 4.52 (2H, s), 7.05-7.55 (3H, m) (2) 7.9 g of the substituted benzyl bromide obtained above.
By reacting (0.033 mol) in the same manner as in Reference Example 10- (4), 0.5 g (4.3%) of the title compound was obtained. mp: 91-94 ° C NMR (CDCl ₃ ) δ: 3.81 (2H, s), 7.20
-7.60 (3H, m)

Reference Example 14 2-chloro-4-fluorophenylacetonitrile (1) 10 g of 2-chloro-4-fluorotoluene (0.
069 mol) was reacted in the same manner as in Reference Example 13- (1) to obtain 11.1 g (72.0%) of 2-chloro-4-fluorobenzyl bromide. bp: 57-60 ° C./0.2 mmHg NMR (CDCl ₃ ) δ: 4.56 (2H, s) (2) Substituted benzyl bromide 11.1 obtained above.
2.7 g (23.0%) of the title compound was obtained by reacting g (0.05 mol) in the same manner as in Reference Example 10- (4). mp: 67-68 ° C NMR (CDCl ₃ ) δ: 3.80 (2H, s), 7.05 (1H, t), 7.15 (1H, d
d), 7.49 (1H, dd)

Reference Example 15 4-Trifluoromethylthiophenylacetonitrile (1) DM-ionated with 1.5 g (0.012 mol) of o-cresol.
Dissolve in F35 ml and cool with sodium hydride (60% i
n oil) 0.48 g (0.012 mol) was added. Then −
S- (trifluoromethyl) dibenzothiophenium trifluoromethanesulfonate [MEC-1 at 48 ° C.
1 (trade name)] was added little by little, and the temperature was gradually raised to room temperature. The reaction solution is poured into ice water, extracted with ethyl acetate, dried,
The solvent was distilled off. A small amount of hexane was added to the residue, and insoluble crystals were filtered off. By subjecting the residue to silica gel column chromatography and eluting with hexane,
4-trifluoromethylthiotoluene 0.5 g (21.7
%) As an oil. NMR (CDCl ₃ ) δ: 2.38 (3H, s), 7.22 (2H, d), 7.53 (2H,
d) (2) 0.5 g (0.00) of the substituted toluene derivative obtained above
By reacting 26 mol) in the same manner as in Reference Example 13- (1), 0.6 g (crude) of 4-trifluoromethylthiobenzyl bromide was obtained as an oil. NMR (CDCl ₃ ) δ: 4.47 (s) (3) 0.6 g of the substituted benzyl bromide obtained above
By reacting (0.0022 mol) in the same manner as in Reference Example 10- (4), 0.23 g (48.9) of the title compound was obtained.
%) As an oil. NMR (CDCl ₃ ) δ: 3.80 (2H, s), 7.41 (2H, d), 7.68 (2
H, d) Reference Example 16 5-chloro-2-thiopheneacetonitrile (1) 2-chlorothiophene (11.8 g, 0.1 mol) was dissolved in 9.35 g (0.13 mol) of DMF, and phosphorus oxychloride was added at 35 ° C or lower. 19.0 g (0.12 mol) was added dropwise,
The mixture was stirred at 100 ° C for 16.5 hours. After cooling, the reaction solution was poured into ice water, extracted with diethyl ether, washed with water, dried, and the solvent was distilled off to give 5-chloro-2-thiophene aldehyde 1.
3.1 g was obtained as an oil. NMR (CDCl ₃ ) δ: 7.05 (1H, d), 7.57 (1H, d), 9.87 (1H, d)
s) (2) 13.1 g of thiophene aldehyde obtained above
20 ml of isopropanol and 20 ml of water
The mixture was suspended in water, and under cooling (-40 ° C), 1.69 g (0.045 mol) of sodium borohydride was added little by little. After stirring at room temperature for 30 minutes, 50 ml of water and 5 ml of dichloromethane were added to the reaction solution.
After adding 0 ml, separating, washing with water and drying, the solvent was distilled off,
13.1 g of chloro-2-thiophenemethanol was obtained as an oil. NMR (CDCl ₃ ) δ: 1.88 (1H, t), 4.73 (2H, d), 6.77 (2H,
s) (3) Reference Example 10- was prepared by using 13.1 g (0.088 mol) of 5-chloro-2-thiophenemethanol obtained above.
By reacting in the same manner as in (3), 5-chloro-2
12.7 g of thiophene methyl chloride was obtained as an oil. NMR (CDCl ₃ ) δ: 4.68 (2H, s), 6.67 (1H, d), 6.85 (1H,
d), 4.82 (2H, s) (4) 12.7 g (0.076 mol) of 5-chloro-2-thiophenemethyl chloride obtained above was used in Reference Example 10
By reacting in the same manner as- (4), 6.05 g (38.5%) of the title compound was obtained as an oil. bp: 84-86 ° C / 0.2 mmHg NMR (CDCl ₃ ) δ: 3.82 (2H, d), 6.70-6.90 (2H, m)

Reference Example 17 4,5-Dichloro-2-thiopheneacetonitrile (1) 2-thiophenecarboxylic acid ethyl ester 12.
0 g (0.077 mol) and aluminum chloride 60 g (0.07 mol).
45 mol) was added to 200 ml of chloroform and cooled (~)
25 ℃) Carbon tetrachloride solution of chlorine (0.016mol) (18
0 ml) was added dropwise and the mixture was stirred at room temperature for 20 hours. After the reaction solution was poured into ice water and separated, the aqueous layer was extracted with chloroform, the organic layers were combined, washed with water and dried, and then the solvent was distilled off to give 4,5-dichloro-2-thiophenecarboxylic acid ethyl ester 11.
0 g (63.4%) was obtained as an oil. NMR (CDCl ₃ ) δ: 1.36 (3H, t), 4.34 (2H, q), 7.55 (1H,
s) (2) 15.0 g (0.049mo) of 4,5-dichloro-2-thiophenecarboxylic acid ethyl ester obtained above
l) suspended in 20 ml isopropanol and 20 ml water,
1.69 g (0.045 g) of sodium borohydride under ice cooling
mol) was added in small portions. After stirring at 50 ° C. for 6 hours, 50 ml of water was added to the reaction solution, extracted with diethyl ether, washed with water, dried and the solvent was distilled off to give 6.4 g of 4,5-dichloro-2-thiophenemethanol as an oil. Obtained. (3) Substituted thiophene methanol 6.4 obtained above
By reacting g (0.034 mol) in the same manner as in Reference Example 10- (3), 6.29 g (89.8%) of 4,5-dichloro-2-thiophenemethyl chloride was obtained as an oil. bp: 73-74 ° C./0.3 mmHg NMR (CDCl ₃ ) δ: 4.63 (2H, s), 6.87 (1H, d) (4) 6.29 g (0.031 mol) of the substituted 2-thiophenemethyl chloride obtained above. ) In Reference Example 10- (4)
By reacting in the same manner as in the above, the title compound (1.55 g)
(25.8%) was obtained as an oil. NMR (CDCl ₃ ) δ: 3.80 (2H, d), 6.88 (1H, d) Reference Example 18 5-chloro-2-pyridylacetonitrile (1) 2-picoline at room temperature in 71.6 g (0.53 mol) of aluminum chloride. 20 g (0.214 mol) was added dropwise.
Then bubbling chlorine gas at 80-90 ℃ (5 hours)
I let it. After cooling, the reaction solution was poured into ice water, neutralized with 30% sodium hydroxide (pH 7), extracted with diethyl ether, washed with water and dried, and then the solvent was distilled off. The residue was subjected to silica gel column chromatography, and eluted with hexane-ethyl acetate (3: 1) to divide into 3 sections, and 3 types of structures were determined by NMR measurement. From the first fraction, 1.1 g (3.1%) of crystals were obtained (3,5-dichloro-2-picoline). mp: 41-43 ° C NMR (CDCl ₃ ) δ: 2.59 (3H, s), 7.65 (1H, d), 8.35 (1H,
d) From the second fraction, 2.1 g (7.6%) of oil was obtained (5
-Chloro-2-picoline). NMR (CDCl ₃ ) δ: 2.53 (3H, s), 7.10 (1H, d), 7.54 (1H, d)
d), 8.45 (1H, d) From the 3rd section, 3.5 g (12.8%) of an oily substance was obtained (3-chloro-2-picoline). NMR (CDCl ₃ ) δ: 2.63 (3H, s), 7.10 (1H, d), 7.63 (1H, d)
d), 8.39 (1H, dd) (2) Dissolve 2.1 g of 5-chloro-2-picoline obtained in the above 2nd section in 40 ml of chloroform,
Chloroperbenzoic acid (3.45 g, 0.016 mol) was added little by little, and the mixture was stirred at 40 ° C for 30 minutes. The reaction solution was neutralized with an aqueous potassium carbonate solution, separated, washed with water and dried, and the solvent was evaporated to give 5-chloro-2-picoline-N-oxide (3.5 g).
I got NMR (CDCl ₃ ) δ: 2.49 (3H, s), 7.21 (2H, m), 8.34 (1H,
s) (3) 5-chloro-2-picoline-N-obtained above
Dissolve 3.5 g of oxide in 20 ml of acetic anhydride and heat at 100 ° C.
It was stirred for 1.5 hours. After cooling, the reaction solution was poured into ice water, neutralized with potassium carbonate, extracted with chloroform, washed with water and dried, and then the solvent was distilled off. The residue was subjected to silica gel column chromatography, and hexane-ethyl acetate (3: 1).
2-acetoxymethyl form 2.2 by eluting with
g was obtained as an oil. NMR (CDCl ₃ ) δ: 2.16 (3H, s), 5.19 (2H, s), 7.32 (1H,
d), 7.78 (1H, dd), 8.55 (1H, d) (4) 2.2 g of the 2-acetoxymethyl derivative obtained above
Was dissolved in 12 ml of concentrated hydrochloric acid and stirred at 100 ° C. for 1.5 hours. The reaction mixture was concentrated to dryness, 6 ml of thionyl chloride was added to the residue, and the mixture was stirred at room temperature for 18 hours. The reaction mixture was concentrated, water was added to the residue, the mixture was neutralized with aqueous sodium hydrogen carbonate, extracted with diethyl ether, washed with water, dried, and the solvent was distilled off to give 5-chloro-2-
1.3 g (50.1%) of pyridylmethyl chloride was obtained. NMR (CDCl ₃ ) δ: 4.65 (2H, s), 7.44 (1H, d), 7.70 (1H, d)
d), 8.53 (1H, d) (5) 1.3 g (0.008 mol) of 2-pyridylmethyl chloride obtained above was reacted in the same manner as in Reference Example 10- (4) to give the title compound 79 g (64.
7%) as an oil. NMR (CDCl ₃ ) δ: 3.93 (2H, s), 7.40 (1H, d), 7.73 (1H, d)
d)

Reference Example 19 3-chloro-2-pyridylacetonitrile (1) Reference Example 18- (3) Chloro-2-picoline (3.5 g, 0.028 mol) obtained in the third section of (1) was used as a reference example. By reacting in the same manner as 18- (2), 2.1 g (53.8%) of 3-chloro-2-picoline-N-oxide was obtained. mp: 92 ° C NMR (CDCl ₃ ) δ: 2.64 (3H, s), 7.07 (1H, t), 7.29 (1H,
d), 8.21 (1H, d) (2) 3-chloro-2-picoline-N-obtained above
Oxide 1.7 g (0.0118 mol) was used in Reference Example 18-
By reacting in the same manner as in (3), 1.4 g of 2-acetoxymethyl compound as an oily substance was obtained. NMR (CDCl ₃ ) δ: 2.17 (3H, s), 5.34 (2H, s), 7.23 (1H, d
d), 7.71 (1H, dd), 8.52 (1H, d) (3) 1.4 g of the 2-acetoxymethyl derivative obtained above
In the same manner as in Reference Example 18- (4),
3-chloro-2-pyridylmethyl chloride 0.9 g
(47.3%) was obtained. NMR (CDCl ₃ ) δ: 4.81 (2H, s), 7.25 (1H, dd), 7.73 (1H,
dd), 8.51 (1H, dd) (4) 0.9 g (0.0055 mol) of 3-chloro-2-pyridylmethyl chloride obtained above was used in Reference Example 10-
By reacting in the same manner as in (4), the title compound
Obtained 6 g (71.4%) as an oil. NMR (CDCl ₃ ) δ: 4.07 (2H, s), 7.28 (1H, dd), 7.75 (1H,
dd), 8.54 (1H, dd)

Reference Example 20 2,6-Dichloro-4-trifluoromethylphenylacetonitrile (1) 27.6 g of 2,6-dichloro-4-trifluoromethylaniline (purified crystals ground in a mortar)
(0.12 mol) was added little by little to 120 ml of concentrated hydrochloric acid at room temperature to suspend, and the mixture was stirred at the same temperature for 1 hour. After cooling to around -10 ° C, sodium nitrite 11.59 g (0.168 mol)
Aqueous solution (24 ml) was added dropwise over 2.5 hours, and the reaction solution was-
The mixture was stirred at 5 ° C to 10 ° C for 3 hours to obtain a suspension of diazonium salt. Separately, 120 ml of acetone was cooled to around -10 ° C, and an aqueous solution (12 ml) of 5.78 g (0.07 mol) of sodium acetate and 3.6 g (0.026 mol) of cupric chloride were added.
l) aqueous solution (6 ml) was added, and after confirming that the internal temperature was -5 ° C or lower, 18.6 ml of 1,3-butadiene (liquefied in a dry ice-acetone bath) was added. . The suspension of the diazonium salt obtained in the above reaction was added dropwise to the mixture containing butadiene over 70 minutes while the temperature was kept at -5 ° C with a cold addition funnel. The mixture was further stirred at -5 to 0 ° C for 2 hours and at room temperature overnight. Add 300 ml of water to the reaction mixture,
After extraction with diethyl ether, washing with water and drying, the solvent was distilled off. The residue was dissolved in 300 ml of hexane, treated with activated carbon, and the solvent was distilled off to give 1-chloro-
There was obtained 33.5 g (92%) of 4- (2,6-dichloro-4-trifluoromethylphenyl) -2-butene as a reddish brown oil. NMR (CDCl ₃ ) δ: 3.75 (2H, d, J = 5.9Hz), 4.02 (2H, d, J =
6.6Hz), 5.62-5.91 (2H, m), 7.57 (2H, s) (2) 1-chloro-4- (2,6-dichloro-4-trifluoromethylphenyl) -2-obtained above To 12.0 g (0.039 mol) of butene, 120 ml of dioxane and 40 ml of water were added, and 100 mg of osmium tetrachloride (0.03) was added at room temperature.
4 mmol) was added, and sodium metaperiodate 1 was added at room temperature.
9.43 g (0.09 mol) was divided into 10 equal parts and added at 15-minute intervals, and the mixture was stirred at the same temperature for 2 days. The precipitated crystals were filtered off and washed with about 300 ml of diethyl ether. The filtrate and the washing solution were combined and 200 ml of water was added to separate the layers. The aqueous layer was further extracted with diethyl ether and combined with the previous organic layer to form 5
% Sodium bisulfite aqueous solution (100 ml) was added, and 3
Stir for 0 minutes. The insoluble black precipitate was filtered off, the filtrate was separated, the aqueous layer was extracted with diethyl ether, the organic layers were combined, washed with water, dried and the solvent was distilled off. The residue was subjected to silica gel column chromatography and eluted with hexane-ethyl acetate (6: 1) to give 6.0 g (59%) of 2,6-dichloro-4-trifluoromethylphenylacetaldehyde. mp: 59-60 ° C NMR (CDCl ₃ ) δ: 4.20 (2H, s), 7.62 (2H, s), 9.77 (1H,
s) (3) 2.6 g of sodium acetate (anhydrous) in 30 ml of acetic acid
(0.032 mol) was dissolved, hydroxylamine hydrochloride (1.88 g, 0.027 mol) was added at room temperature, and the substituted phenylacetaldehyde (5.8 g, 0.02) obtained above was further added.
(22 mol) was added, and the mixture was reacted at 100 to 105 ° C for 1.5 hours. After cooling, 300 ml of water was added, the mixture was extracted with ethyl acetate, washed successively with water, aqueous sodium hydrogen carbonate and water and dried, and the solvent was evaporated. By washing the residue with a small amount of cold hexane,
5.01 g (82%) of 2,6-dichloro-4-trifluoromethylphenylacetaldehyde oxime was obtained.
The products were obtained as a mixture of E and Z, and subjected to silica gel column chromatography and eluted with hexane-ethyl acetate (6: 1) to give pure products. The absolute placement is unknown. Low polarity isomer mp: 123-125 ℃ NMR (CDCl ₃ ) δ: 3.91 (2H, d, J = 5.1Hz), 7.45 (1H, brd, J
= 2.0Hz), 7.52 (1H, t, J = 5.1Hz), 7.59 (1H, s) Highly polar isomer mp: 150-151 ℃ NMR (CDCl ₃ ) δ: 4.11 (2H, d, J = 4.6Hz ), 6.66 (1H, t, J =
4.6Hz), 7.60 (1H, s), 8.34 (1H, brd, J = 24Hz) (4) Oxime (E, Z mixture) 4.9 obtained above
5 g (0.018 mol) was dissolved in 50 ml DMF, 6.70 g (0.043 mol) phosphorus oxychloride was added at 0 ° C., and the mixture was stirred at the same temperature for 2 hours. Pour the reaction solution into 100 ml of ice water,
The precipitated crystals were collected by filtration, washed with water and dried. The obtained crystals are dissolved in hexane, the insoluble matter is filtered off, and the filtrate is concentrated,
Obtained 2.81 g (61.0%) of the title compound. mp: 50-53 ° C NMR (CDCl ₃ ) δ: 4.06 (2H, s), 7.66
(2H, s)

Reference Example 21 4-Chlorobenzyltrifluoromethylsulfone (1) Sodium hydride (60% in oil)
48 g (0.012 mol) was washed twice with a small amount of hexane, suspended in dry THF, and under ice cooling, 4-chlorobenzyl mercaptan (1.74 g, 0.011 mol) in dry THF.
The solution (10 ml) was added dropwise. After raising to room temperature once, -4
After cooling to 0 ° C., S- (trifluoromethyl) dibenzothiophenium trifluoromethanesulfonate [MEC
-11 (trade name)] 4.02 g (0.01 mol) was divided into 5 equal parts and added at 5-minute intervals. The reaction temperature was raised from -40 ° C to -5 ° C over about 2 hours, water was added at -5 ° C, the mixture was extracted with diethyl ether, washed with water, dried and the solvent was distilled off. The residue was subjected to silica gel column chromatography and isolated by eluting with hexane. The residue was further connected to a simple distillation apparatus for decompression, the receiver was cooled with dry ice acetone and decompression distillation was carried out at room temperature. 1.4 g (62.0%) of benzyl trifluoromethyl sulfide was obtained as an oil. ¹ H-NMR (CDCl ₃ ) δ: 4.08 (2H, s), 7.24-7.35 (4H, m) ¹⁹ F-NMR (CDCl ₃ ) δ: −42.05 (2) 1.38 g of the sulfide obtained above ( 0.006
mol) was dissolved in 15 ml of dichloromethane, 2.24 g (0.0012 mol) of m-chloroperbenzoic acid was added at room temperature, and the mixture was stirred at room temperature for 2 days. The crystals formed are filtered off and the filtrate is 5%
About 40 ml of an aqueous sodium hydrogen sulfite solution was added, and the mixture was stirred for 30 minutes. Add water to separate the layers, wash with sodium bicarbonate water and water,
After drying, the solvent was distilled off. The residue was subjected to silica gel column chromatography, and hexane-ethyl acetate (6:
Elution with 1) gave 1.37 g (8) of the title compound.
7.0%). mp: 98.0-98.5 ° C ¹ H-NMR (CDCl ₃ ) δ: 4.45 (2H, s), 7.34-7.46 (4H, m) ¹⁹ F-NMR (CDCl ₃ ) δ: −76.81 (3F, s) IR ( Nujol) cm ^-1 : 1354, 1344, 1222, 1194, 1122

Example 1 2- (2,4-Dichlorophenyl) -3- (2,6-dichloro-4-trifluoromethylphenylamino) -4,4,4-trifluorocrotononitrile (Compound No. 5) Sodium hydride (60% in oil) 0.08 g (0.0
(019mol) was washed twice with a small amount of hexane, and DMF 5m
l was added and suspended. Under ice cooling, 0.3 g (0.0016 mol) of 2,4-dichlorophenylacetonitrile was added little by little, and the mixture was once raised to room temperature and then cooled under ice cooling with 2,2,2-trifluoro-N obtained in Reference Example 8. A DMF solution (5 ml) of 0.5 g (0.0016 mol) of-(2,6-dichloro-4-trifluoromethylphenyl) ethaneimidoyl chloride was added dropwise and stirred at room temperature for 4 hours. The reaction solution was poured into ice water, and the precipitated crystals were collected by filtration, washed with water and dried. The obtained crystals were washed with a small amount of petroleum ether to obtain 0.54 g (68.3%) of the title compound. mp: 189-190 ° C NMR (CDCl ₃ ) δ: 6.28 (1H, brs), 6.95-7.54 (5H, m)

Example 2 2- (2,6-dichloro-4-
Trifluoromethylphenyl) -3- (2,6-dichloro-4-trifluoromethylphenylamino) -4,
4,4-trifluorocrotononitrile (Compound No.
45) 0.3 g (0.0012 mol) of 2,6-dichloro-4-trifluoromethylphenylacetonitrile in dry THF
After dissolving in 10 ml, 0.65 ml (0.0013 mol) of lithium diisopropylamide (2.0 M heptane, THF, ethylbenzene solution) was added dropwise at -78 ° C. After stirring for 30 minutes at the same temperature, 2,2,2-trifluoro-N- (2,6-dichloro-4-trifluoromethylphenyl) ethaneimidoyl chloride 0.41 obtained in Reference Example 8 was obtained.
A THF solution (2 ml) containing g (0.0012 mol) was added dropwise. After stirring at the same temperature for 30 minutes, the temperature was raised to 0 ° C over about 1 hour, and the mixture was stirred at the same temperature for 1 hour. Aqueous ammonium chloride was added to stop the reaction, water was added and the mixture was extracted with ethyl acetate, washed with diluted hydrochloric acid and water, respectively, dried, and then the solvent was distilled off. The residue was subjected to silica gel column chromatography and eluted with hexane-ethyl acetate (5: 1) to give 0.18 g (52.0%) of the title compound. mp: 192-193 ° C NMR (CDCl ₃ ) δ: 6.66 (1H, brs), 6.91 (4H, q, J = 8.8Hz),
7.30 (2H, s)

Example 3 The invention compound [I] obtained in the same manner as in Examples 1 and 2 was treated with [Table 14] to [Table 26].
The NMR is shown in [Table 27] to [Table 31].

[Table 14]

[0061]

[Table 15]

[0062]

[Table 16]

[0063]

[Table 17]

[0064]

[Table 18]

[0065]

[Table 19]

[0066]

[Table 20]

[0067]

[Table 21]

[0068]

[Table 22]

[0069]

[Table 23]

[0070]

[Table 24]

[0071]

[Table 25]

[0072]

[Table 26]

[0073]

[Table 27]

[0074]

[Table 28]

[0075]

[Table 29]

[0076]

[Table 30]

[0077]

[Table 31]

Example 4 2- (4-bromophenyl)-
3- (3,5-bistrifluoromethylphenylamino) -4- (difluoromethylsulfinyl) crotononitrile (Compound No. 79) 2- (4-bromophenyl) -3- (3,5-bistrifluoromethylphenyl Amino) -4- (difluoromethylsulfenyl) crotononitrile (Compound No. 8
0) 0.1 g (0.188 mol) of a dichloromethane solution (3 ml) was cooled with ice to give 41 mg (80 mg) of m-chloroperbenzoic acid.
% Eq) was added in small portions. below freezing,
The mixture was stirred for 1 hour and room temperature for 1.5 hours. Dichloromethane (20 ml) was added, the mixture was washed with aqueous sodium hydrogen carbonate and water, dried and then the solvent was distilled off. Hexane-isopropyl ether was added to the residue, and the crystals were collected by filtration to give 66 mg (64%) of the title compound.
I got mp: 135-137 ° C NMR (CDCl ₃ ) δ: 4.19-4.49 (2H, m), 6.62 (1H, t, J = 54.0H
z), 6.99-7.30 (6H, m), 7.39 (1H, s)

Example 5 2- (2,4,6-trichlorophenyl) -3- {3,5-bis (tolufluoromethyl) phenylamino} -4,4-difluoro-4-methylsulfinylcrotononitrile ( Compound No. 89) 2- (2,4,6-trichlorophenyl) -3- {3.
5-bis (trifluoromethyl) phenylamino}-
0.34 g (0.54 mmol) of 4,4-difluoro-4-methylthiocrotononitrile (Compound No. 85) was dissolved in 10 ml of dichloromethane, and at 0 ° C. 0.11 g of m-chloroperbenzoic acid (80% purity was obtained). 0.54 mmol) was added in small portions and the mixture was stirred at room temperature overnight. To the reaction mixture was added 5% aqueous sodium hydrogen sulfite solution (20 ml), the mixture was stirred for 30 minutes, water was added and the mixture was extracted with dichloromethane and washed with aqueous sodium hydrogen carbonate and water, respectively.
After drying, the solvent was distilled off. The residue was subjected to silica gel column chromatography and eluted with chloroform-ethyl acetate (5: 1) to give the title compound 0.2.
4 g (78%) were obtained. mp: 147-149 ° C NMR (CDCl ₃ ) δ: 3.05 (3H, s), 7.06 (2H, s), 7.30 (3H, s),
7.45 (1H, s)

Example 6 2- (2,4,6-trichlorophenyl) -3- {3,5-bis (tolufluoromethyl) phenylamino} -4,4-difluoro-4-methylsulfonylcrotononitrile ( Compound No. 90) 2- (2,4,6-trichlorophenyl) -3- {3
5-bis (trifluoromethyl) phenylamino}-
0.32 g (0.576 mmol) of 4,4-difluoro-4-methylthiocrotononitrile (Compound No. 85) was dissolved in 10 ml of dichloromethane, and 0.26 g of m-chloroperbenzoic acid was prepared at 0 ° C. (as 80% purity). (1.21 mmol) was added little by little, and the mixture was stirred at room temperature for 2 days. To the reaction solution was added 5% aqueous sodium hydrogen sulfite solution (20 ml), the mixture was stirred for 30 minutes, water was added, the mixture was extracted with dichloromethane, washed with aqueous sodium hydrogen carbonate and water, dried and the solvent was evaporated. The residue was subjected to silica gel column chromatography, and eluted with chloroform-ethyl acetate (6: 1) to give 0.26 g (77%) of the title compound. mp: 132-134 ° C NMR (CDCl ₃ ) δ: 3.33 (3H, s), 6.66 (1H, brs), 7.05 (2H,
s), 7.34 (2H, s), 7.48 (1H, s)

Example 7 2- (4-Bromophenyl)-
3- {N-acetyl-N- (2,6-dichloro-4-trifluoromethylphenyl) amino} -4,4,4-trifluorocrotononitrile (Compound No. 91) Sodium hydride (60% in oil ) 29 mg (1.2e
2- (4-bromophenyl) -3- (2,6-dichloro-4-trifluoromethylphenylamino) -4,4,4-trifluorocrotononitrile (compound No. 9) 0.3 g (0.059mo
l) was added in small portions. After the foaming stopped, 56 mg (1.2 eq) of acetyl chloride in THF (3 ml) was added dropwise, and the mixture was stirred at room temperature for 2.5 hours. THF was distilled off, the mixture was partitioned with dichloromethane-water, the dichloromethane layer was dried, and the solvent was distilled off. This was dissolved in 3 ml of THF and added to a suspension of 29 mg (1.2 eq) of sodium hydride in 3 ml of THF,
Acetyl chloride (0.1 ml, 2.4 eq) was added at 40 ° C., and the mixture was stirred at the same temperature for 30 minutes. The same operation was repeated again (since the reaction stopped as before). The reaction mixture was concentrated, water was added, the mixture was extracted with dichloromethane, washed with water, dried and the solvent was distilled off. The residue was subjected to silica gel column chromatography, eluted with hexane-acetone (6: 1), and recrystallized from hexane to give the title compound 0.115.
g (35%) were obtained. mp: 105-108 ° C NMR (CDCl ₃ ) δ: 2.07 (3H, s), 6.96 (2H, d, J = 8.2Hz), 7.4
1 (2H, d, J = 8.3Hz), 7.88 (1H, s)

Example 8 2- (4-Bromophenyl)-
3- {N-[(N'-ethoxycarbonyl-N'-isopropylamino) sulfenyl] -N- (2,6-dichloro-4-trifluoromethylphenyl) amino}-
4,4,4-Trifluorocrotononitrile (Compound N
o. 92) Sodium hydride (60% in oil) 48 mg (1.2e)
q) in a suspension of 5 ml of THF under ice-cooling 2- (4-bromophenyl) -3- (2,6-dichloro-4-trifluoromethylphenylamino) -4,4,4-trifluorocrotononitrile (compound No. 9) 0.5 g (0.99 mmo
l) was added in small portions. After the foaming subsides, N- at room temperature
A THF solution (5 ml) containing 0.24 g (1.2 eq) of ethoxycarbonyl-N-isopropylaminosulfenyl chloride was added dropwise. After stirring at room temperature for 0.5 hour, the solvent was distilled off. The residue was subjected to silica gel column chromatography and eluted with hexane-ethyl acetate (6: 1) to give 0.29 g (44%, amorphous) of the title compound. NMR (DMSO-d ₆ ) δ: 1.11-1.46 (9H, m), 4.11-4.57 (3H, m),
6.97 (2H, d, J = 8.4Hz), 7.26 (2H, d, J = 8.3Hz), 7.63 (2H,
s)

Example 9 Compound No. An emulsion was prepared by thoroughly mixing 1 (20% by weight), xylene (75% by weight) and polyoxyethylene glycol ether (Nonipol 85 (trade name)) (5% by weight). Example 10 Compound No. 1 (30% by weight), sodium lignin sulfonate (5% by weight), polyoxyethylene glycol ether (Nonipol 85 (trade name)) (5% by weight),
A wettable powder was prepared by thoroughly mixing white carbon (30% by weight) and clay (30% by weight). Example 11 Compound No. 1 (3% by weight), white carbon (3% by weight), and clay (94% by weight) were mixed well to produce a powder.

Example 12 Compound No. 1 (10% by weight), sodium ligninsulfonate (5% by weight) and clay (85% by weight) were well pulverized and mixed, water was added and the mixture was well kneaded, and then granulated and dried to produce granules. Example 13 Compound No. 1 (1.275% by weight), cartap (2.
2% by weight), white carbon (0.5% by weight) and clay (96.025% by weight) were mixed well to produce an insecticide powder. Example 14 Compound No. 1 (1.275% by weight), validamycin (0.33% by weight), white carbon (0.5% by weight), clay (97.895% by weight) were mixed well,
An insecticidal fungicide powder was produced.

[0085]

INDUSTRIAL APPLICABILITY The aminoethylene derivative [I] and its salt of the present invention have excellent insecticidal and bactericidal actions, and the composition containing the aminoethylene derivative [I] and its salt of the present invention is excellent insecticidal. It is useful as a composition or bactericidal composition and can contribute to the development of agriculture.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area A01N 47/02 A01N 47/02 C07C 255/43 C07C 255/43 317/28 317/28 317/48 317/48 323/58 323/58 323/63 323/63 C07D 213/57 C07D 213/57 213/61 213/61 333/24 333/24 333/28 333/28 521/00 521/00 (72) Inventor Isao Minami 4 Maikoponinomiya, No. 506, No. 4 Maikoponinomiya, 1-23, Sengen, Tsukuba-shi, Ibaraki Prefecture (72) Inventor Tetsuo Okauchi 10-11, Hidakata-cho, Hirakata-shi, Osaka

Claims (7)

[Claims] 1. A general formula: [In the formula, Ar ¹ and Ar ² are an aromatic homo or heterocyclic group which may be substituted, R ¹ is a hydrogen atom, a group through a carbon atom or a group through a sulfur atom, and R ² is substituted. R ³ represents an electron-withdrawing group, or a salt thereof. 2. A C _6-14 aryl group in which Ar ¹ may be substituted or a 5- to 8-membered aromatic heterocyclic group containing 1 to 5 heteroatoms selected from a nitrogen atom, an oxygen atom or a sulfur atom. The compound according to claim 1, which is 3. A C _6-14 aryl group in which Ar ² may be substituted or a 5- to 8-membered aromatic heterocyclic group containing 1 to 5 heteroatoms selected from nitrogen atom, oxygen atom or sulfur atom. The compound according to claim 1, which is 4. R ¹ is a hydrogen atom, C _1-6 alkyl group, C _1-6
Haloalkyl group, C _3-7 cycloalkyl group, C _2-6 alkenyl group, C _2-6 haloalkenyl group, C _2-6 alkynyl group,
C _2-6 haloalkynyl group, C _1-6 alkanoyl group, C _2-6
Haloalkanoyl group, C _7-11 arylcarbonyl group, C
_8-12 aralkylcarbonyl group, C _2-8 alkoxycarbonyl group, C _7-11 aryloxycarbonyl group, C _8-12 aralkyloxycarbonyl group, C _1-6 alkylsulfonyl group, C _7-11 aralkylsulfonyl group, C _{A 1-6} haloalkylsulfonyl group, a C _6-10 arylsulfonyl group or a group represented by -SY, wherein Y is Embedded image [Chemical 4] Embedded image [Chemical 6] [Chemical 7] Embedded image Or a group represented by S—R ^4c , wherein R ^4a and R ^4e are C _1-6 alkyl group, C _1-6 haloalkyl group, C _3-7
Cycloalkyl group, C _4-8 cycloalkylalkyl group,
Phenyl group, benzyl group or phenethyl group, C _2-6 cyanoalkyl group, C _2-6 alkoxyalkyl group, C _3-8 alkoxycarbonylalkyl group or C _4-8 dialkylaminocarbonylalkyl group which may be substituted, respectively. And R ^4a and R ^4e may form a saturated 3 to 7 membered ring which may contain an oxygen atom, a sulfur atom or another nitrogen atom together with the adjacent nitrogen atom, and R ^4b is a fluorine atom. Atom, C _1-6 alkyl group, C _3-7 cycloalkyl group, C
_3-7 cycloalkyloxy group, C _2-8 dialkylamino group, C _1-6 haloalkyl group, optionally substituted phenyl group or phenoxy group, C _1-6 alkoxy group, cyano group, nitro group, C _2-6 alkenyloxy group,
C _4-8 alkoxyalkoxy group, C _1-4 alkylthio group,
A C _2-6 alkoxycarbonyl group, a C _3-9 dialkylaminocarbonyl group, phenyl or a C _1-4 alkoxy group substituted with 1 to 6 halogens, a morpholino group, a piperidino group, a pyrrolidino group, a 1-naphthoxy group, It is 2,2-dimethyl-2,3-dihydro-7-benzofuranoyl alkoxy group, or _{ON = C (CH 3) SCH} 3 group, R ^4c and R ^4d
Is a C _1-4 alkyl group, a C _1-4 haloalkyl group or an optionally substituted phenyl group, and R ^4c and R ^{4d each represent} (CH
₂ ) ₂ , (CH ₂ ) ₃ or CH ₂ C (CH ₃ ) ₂ CH ₂ , wherein Y ¹ , Y ² and Y ³ are oxygen atoms or sulfur atoms. 5. The compound according to claim 1, wherein R ² is an optionally substituted C _1-6 alkyl group. 6. optionally R ³ is substituted C _7-11 arylcarbonyl group, an optionally substituted C _8-12 aralkyl group, C _2-8 alkoxycarbonyl group, may be substituted A C _7-11 aryloxycarbonyl group,
Optionally substituted C _8-12 aralkyloxycarbonyl group, cyano group, nitro group, C _1-6 alkylthio group, C
_1-6 alkylsulfinyl group, C _1-6 alkylsulfonyl group, C _1-6 haloalkylthio group, C _1-6 haloalkylsulfinyl group, C _1-6 haloalkylsulfonyl group, optionally C _6-10 arylthio which may be substituted Group, optionally substituted C _6-10 arylsulfinyl group, optionally substituted C _6-10 arylsulfonyl group, N-C _1-6 alkylcarbamoyl group, N, N-di (C _1-6 alkyl) carbamoyl group, optionally substituted N-(C _6-10 aryl) carbamoyl group, an optionally substituted N, N-di (according to claim 1 wherein the C _6-10 arylcarbamoyl) group Compound. 7. An insecticidal composition or a bactericidal composition comprising the compound according to claim 1 or a salt thereof.