JP2010132583A - Insecticidal 3-iminopropanoic acid derivative - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new 3-imino-propanoic acid derivative exhibiting an insecticidal effect. <P>SOLUTION: The 3-imino-propanoic acid derivative is represented by formula (I) (wherein X<SP>1</SP>, X<SP>2</SP>and X<SP>3</SP>are each O or S; R<SP>1</SP>and R<SP>2</SP>are each alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, an aromatic hydrocarbon group, heterocyclic, or R<SP>1</SP>and R<SP>2</SP>may be bonded to form a ring; R<SP>3</SP>is alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, an aromatic hydrocarbon group or heterocyclic; R<SP>4</SP>is alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, an aromatic hydrocarbon group or heterocyclic; and R<SP>1</SP>to R<SP>4</SP>each may be substituted). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a novel 3-iminopropanoic acid derivative and its use as an insecticide.

Patent Documents 1 and 2 describe that iminopropene compounds have insecticidal activity.
JP 2008-1681A US 2008-4323-A1

  As a result of searching for a novel compound having insecticidal activity, the present inventors have found a 3-iminopropanoic acid derivative represented by the following formula (I).

式中、
Ｘ^１、Ｘ^２及びＸ^３は、それぞれ独立して、Ｏ又はＳを示し、
Ｒ^１及びＲ^２は、それぞれ独立して、置換されていてもよいアルキル、置換されていてもよいシクロアルキル、置換されていてもよいアルケニル、置換されていてもよいシクロアルケニル、置換されていてもよいアルキニル、置換されていてもよい芳香族炭化水素基、又は置換されていてもよい複素環式基を示し、
また、Ｒ^１とＲ^２は、−Ｘ^１−Ｃ−Ｘ^２−と一緒になって環を形成してもよく、
Ｒ^３は、置換されていてもよいアルキル、置換されていてもよいシクロアルキル、置換されていてもよいアルケニル、置換されていてもよいシクロアルケニル、置換されていてもよいアルキニル、置換されていてもよい芳香族炭化水素基、又は置換されていてもよい複素環式基を示し、そして
Ｒ^４は、置換されていてもよいアルキル、置換されていてもよいシクロアルキル基、置換されていてもよいアルケニル、置換されていてもよいシクロアルケニル、置換されていてもよいアルキニル、置換されていてもよい芳香族炭化水素基、又は置換されていてもよい複素環式基を示す。

Where
X ¹ , X ² and X ³ each independently represent O or S;
R ¹ and R ² are each independently an optionally substituted alkyl, an optionally substituted cycloalkyl, an optionally substituted alkenyl, an optionally substituted cycloalkenyl, a substituted An alkynyl which may be substituted, an aromatic hydrocarbon group which may be substituted, or a heterocyclic group which may be substituted;
R ¹ and R ² may form a ring together with —X ¹ —C—X ² —,
R ³ is an optionally substituted alkyl, an optionally substituted cycloalkyl, an optionally substituted alkenyl, an optionally substituted cycloalkenyl, an optionally substituted alkynyl, an optionally substituted Represents an aromatic hydrocarbon group which may be substituted, or an optionally substituted heterocyclic group, and R ⁴ represents an optionally substituted alkyl, an optionally substituted cycloalkyl group, an optionally substituted A good alkenyl, an optionally substituted cycloalkenyl, an optionally substituted alkynyl, an optionally substituted aromatic hydrocarbon group, or an optionally substituted heterocyclic group.

  The compound of the formula (I) of the present invention can be obtained by the following production method.

Production method (a): {In the formula (I), when X ² and X ³ represent S and R ² and R ³ have the same definition at the same time, R ² is defined as R ³ . }
Formula (II):

式中、Ｘ^１、Ｒ^１及びＲ^４は前記と同義を示す、
で表わされる化合物を、ハロゲン化剤と反応させ、次いで、
式（ＩＩＩ）：
Ｒ^３−ＳＨ （ＩＩＩ）
式中、Ｒ^３は前記と同義を示す、
で表わされる化合物と反応させる方法。

In the formula, X ¹ , R ¹ and R ⁴ are as defined above,
Is reacted with a halogenating agent;
Formula (III):
R ³ —SH (III)
In the formula, R ³ is as defined above,
The method of making it react with the compound represented by these.

Production method (b): {When X ³ represents S in formula (I)}
Formula (IV):

式中、Ｘ^１、Ｘ^２、Ｒ^１、Ｒ^２及びＲ^４は前記と同義を示す、
で表わされる化合物を、
式（Ｖ）：
Ｒ^３−Ｙ （Ｖ）
式中、Ｒ^３は前記と同義を示し、そしてＹはハロゲンを示す、
で表わされる化合物と反応させる方法。

In the formula, X ¹ , X ² , R ¹ , R ² and R ⁴ have the same meanings as described above,
A compound represented by
Formula (V):
R ³ -Y (V)
In which R ³ is as defined above and Y represents halogen,
The method of making it react with the compound represented by these.

Production method (c): {when X ¹ , X ² and X ³ represent S in formula (I)}
Formula (VI):

式中、Ｒ^３及びＲ^４は前記と同義を示す、
で表わされる化合物を、塩基又はフッ化物と反応させ、次いで
式（ＶＩＩ）：
Ｒ^１−ＳＨ （ＶＩＩ）
式中、Ｒ^１は前記と同義を示す、
で表わされる化合物と反応させる方法。

In the formula, R ³ and R ⁴ are as defined above.
And a compound of formula (VII):
R ¹ -SH (VII)
In the formula, R ¹ is as defined above,
The method of making it react with the compound represented by these.

Production method (d): {When X ³ represents O in the formula (I)}
Formula (VIII):

式中、Ｘ^１、Ｘ^２、Ｒ^１、Ｒ^２及びＲ^４は前記と同義を示す、
で表わされる化合物を、メーヤワイン試薬と反応させる方法。

In the formula, X ¹ , X ² , R ¹ , R ² and R ⁴ have the same meanings as described above,
The compound represented by this is made to react with the Mayer wine reagent.

Production method (e): {when X ¹ , X ² and X ³ represent O in formula (I)}
Formula (IX):

式中、Ｒ^１、Ｒ^２及びＲ^４は前記と同義を示し、そしてＭはメチル、エチル又はｐ−トリルを示す、
で表わされる化合物を、
式（Ｘ）：
Ｒ^３−ＯＨ （Ｘ）
式中、Ｒ^３は前記と同義を示す、
で表わされる化合物と反応させる方法。

In which R ¹ , R ² and R ⁴ are as defined above, and M represents methyl, ethyl or p-tolyl,
A compound represented by
Formula (X):
R ³ —OH (X)
In the formula, R ³ is as defined above,
The method of making it react with the compound represented by these.

  The compounds of formula (I) according to the invention show a strong insecticidal action.

In this specification,
“Alkyl” is, for example, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl. , N-decyl, n-undecyl, n-dodecyl and the like linear or branched C _1-12 alkyl, preferably C _1-6 alkyl.

“Cycloalkyl” refers to, for example, C _3-8 cycloalkyl of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, preferably C _3-6 cycloalkyl.

“Alkenyl” refers to C, such as vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl and the like. _2-6 alkenyl is shown, preferably C _2-4 alkenyl.

“Cycloalkenyl” is, for example, 1-cyclopropenyl, 2-cyclopropenyl, 1-cyclobutenyl, 2-cyclobutenyl, 1-cyclopentenyl, 2-cyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl, C _3-8 cycloalkenyl such as 1-cycloheptenyl, 2-cycloheptenyl, 3-cyclopentenyl, 4-cyclopentenyl, 1-cyclooctenyl and the like, preferably C _5-6 cycloalkenyl is shown.

“Alkynyl” refers to C _2-6 alkynyl such as, for example, ethynyl, propargyl, 1-propynyl, 3-butane-1-ynyl, 4-pentane-1-ynyl, 5-hexane-1-ynyl, C represents _2-4 alkynyl.

  The “aromatic hydrocarbon group” represents a group represented by phenyl, α-naphthyl, and β-naphthyl, and preferably represents phenyl.

  “Heterocyclic group” refers to a 5- or 6-membered heterocyclic group optionally containing O, S or N as a heteroatom, preferably containing 1 to 3 heteroatoms, provided that O Represents a 5-membered or 6-membered heterocyclic group which does not contain 3 groups. Specific examples of the heterocyclic group include furyl, thienyl, pyrrolyl, isoxazolyl, pyrazolyl, oxazolyl, oxathiazolyl, imidazolyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, benzoxazolyl And quinolyl.

  In each “optionally substituted” group, the substituent generally includes substituents possible in the field of organic chemistry, such as alkyl, alkoxy, alkylthio, acyl, halogen, nitro, cyano, amino, Alkylamino, dialkylamino, haloalkyl, haloalkoxy, haloalkylthio, alkoxyalkyl, alkylthioalkyl, alkoxycarbonyl, alkylsulfonyl, alkylsulfinyl, haloalkylsulfinyl, haloalkylsulfonyl, alkenyl, alkynyl, haloalkenyl, haloalkynyl, alkylcarbamoyl, acylamino, Aminocarbonyl, aralkyl, heterocyclic group-substituted alkyl and the like are shown.

In the compound of formula (I):
X ¹ , X ² and X ³ each independently represent O or S;
R ¹ and R ² are each independently an _optionally substituted C _1-12 alkyl, an _optionally substituted C _3-8 cycloalkyl, an _optionally substituted C _2-6 alkenyl, a substituted 5-membered optionally containing optionally substituted C _3-8 cycloalkenyl, optionally substituted C _2-6 alkynyl, optionally substituted phenyl, or optionally substituted O, S, N Or a 6-membered heterocyclic group,
R ¹ and R ² may be combined to form a ring,
R ³ is an _optionally substituted C _1-12 alkyl, an _optionally substituted C _3-8 cycloalkyl, an _optionally substituted C _2-6 alkenyl, an optionally substituted C _3- 5- or 6-membered heterocyclic group optionally containing ₈ cycloalkenyl, optionally substituted C _2-6 alkynyl, optionally substituted phenyl, or optionally substituted O, S, N R ⁴ represents an _optionally substituted C _1-12 alkyl group, an _optionally substituted C _3-8 cycloalkyl group, an _optionally substituted C _2-6 alkenyl group, a substituted An optionally substituted C _3-8 cycloalkenyl group, an optionally substituted C _2-6 alkynyl group, an optionally substituted phenyl, or an optionally substituted heteroatom selected from O, S and N Optionally including Represents a 5- or 6-membered heterocyclic group,
The compound of the case is preferred.

Among them, in the compound of formula (I)
X ¹ , X ² and X ³ each independently represent O or S;
R ¹ and R ² are each independently an _optionally substituted C _1-6 alkyl, an optionally substituted C _3-6 cycloalkyl, an optionally substituted C _2-4 alkenyl, a substituted Optionally substituted C _5-6 cycloalkenyl, optionally substituted C _2-4 alkynyl, optionally substituted phenyl, or optionally substituted heteroatom 1 selected from O, S and N Represents a 5- or 6-membered heterocyclic group containing ~ 3, but not 3 O
R ¹ and R ² may form a ring together with —X ¹ —C—X ² —,
R ³ is an optionally substituted C _1-6 alkyl group, an optionally substituted C _3-6 cycloalkyl, an optionally substituted C _2-4 alkenyl, an optionally substituted C _{5 -6} cycloalkenyl, optionally substituted C _2-4 alkynyl, optionally substituted phenyl, or optionally substituted O, S and N containing 1 to 3 heteroatoms, Represents a 5- or 6-membered heterocyclic group not containing 3 O, and R ⁴ is an optionally substituted C _1-6 alkyl, an optionally substituted C _3-6 cyclo Alkyl, optionally substituted C _2-4 alkenyl, optionally substituted C _5-6 cycloalkenyl, optionally substituted C _2-4 alkynyl, optionally substituted phenyl, or substituted May A 5- or 6-membered heterocyclic group containing 1 to 3 heteroatoms selected from O, S and N, but not 3 O;
Especially preferred are compounds of the case.

  The compounds of formula (I) of the present invention may have asymmetric carbons, and thus the compounds include optical isomers.

The production method (a) can be represented by the following reaction formula when, for example, N- (4-methylphenyl) -3- (phenylsulfanyl) prop-2-enamide and benzenethiol are used as raw materials.

  When the production method (b) uses, for example, 3-[(4-fluorophenyl) sulfanyl] -N- (3-methylphenyl) -3- (phenylsulfanyl) propanethioamide and isobutyl iodide as raw materials, It is represented by the reaction formula of

  The production method (c) is represented by the following reaction formula when, for example, cyclopentyl N-phenyl-3- (trimethylsilyl) prop-2-inimidothioate and cyclopentanethiol are used as raw materials.

  In the production method (d), for example, 3-[(4-fluorophenyl) sulfanyl] -N- (3-methylphenyl) -3- (phenylsulfanyl) propanamide and trimethyloxonium tetrafluoroborate are used as raw materials. When used, it is represented by the following reaction formula.

  The production method (e) is represented by the following reaction formula when, for example, methyl-N- (3-methylphenyl) -3,3-bis (phenoxy) propanimide sulfonate and methanol are used as raw materials.

  In the production method (a), the compound of the formula (II) is exemplified by Chemical and Pharmaceutical Bulletin Vol. 12, pp. 1854 to 1861, 2000, and can be easily synthesized. A typical example thereof is N-phenyl-3-phenylsulfanyl-acrylamide.

Similarly, the compound of the formula (III) is a well-known compound, and typical examples thereof include the following compounds.
Benzenethiol,
2-methylbenzenethiol,
3-methylbenzenethiol,
4-methylbenzenethiol,
2-fluorobenzenethiol,
3-fluorobenzenethiol,
4-fluorobenzenethiol,
2-chlorobenzenethiol,
3-chlorobenzenethiol,
4-chlorobenzenethiol.

  Examples of the halogenating agent include oxalyl chloride, thionyl chloride, phosphorus pentachloride, phosphorus oxychloride and the like.

The reaction of the production method (a) can be carried out in a suitable diluent, and examples of the diluent used in that case include
Aliphatic, cycloaliphatic and aromatic hydrocarbons (which may optionally be chlorinated), such as pentane, hexane, cyclohexane, petroleum ether, benzene, toluene, xylene, dichloromethane, dichloroethane and the like;
Ethers such as ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM) and the like;
Nitriles such as acetonitrile, propionitrile, acrylonitrile and the like;
Examples of the esters include ethyl acetate and amyl acetate.

The reaction of the production method (a) is preferably carried out in the presence of a base. Examples of the base include alkali metal hydroxides, carbonates and bicarbonates such as sodium hydrogen carbonate, hydrogen carbonate, etc. as inorganic bases. Potassium, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.
As organic bases, tertiary amines, dialkylaminoanilines and pyridines such as triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA), N, N-dimethylaniline, N, N-diethylaniline , Pyridine, 4-dimethylaminopyridine (DMAP), 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo "5.4.0" undec-7-ene (DBU), etc. Can be mentioned.

  The reaction of the production method (a) can be carried out within a substantially wide temperature range. In general, it can be carried out between about -40 and about 200 ° C, preferably between about -20 and about 110 ° C. The reaction is preferably carried out under normal pressure, but can be operated under pressure or reduced pressure.

  In carrying out the reaction of the production method (a), for example, after reacting 1 mol of the compound of the formula (II) with 1 mol amount to a slight excess amount of a base and a halogenating agent in a diluent such as dichloromethane. The desired compound of formula (I) can be obtained by reacting 1 mol amount to a slight excess of compound of formula (III).

  In the production method (b), the compound of the formula (IV) is represented by the following formula (XI):

式中、Ｘ^１、Ｘ^２、Ｒ^１、Ｒ^２及びＹは前記と同義を示す、
で表わされる化合物より調製したグリニャール試薬を、下記式（ＸＩＩ）：
Ｒ^４−Ｎ＝Ｃ＝Ｓ （ＸＩＩ）
式中、Ｒ^４は前記と同義を示す、
で表わされるイソチオシアネートと反応させることにより得ることができる。

In the formula, X ¹ , X ² , R ¹ , R ² and Y are as defined above,
A Grignard reagent prepared from the compound represented by formula (XII):
R ⁴ —N═C═S (XII)
In the formula, R ⁴ is as defined above.
It can obtain by making it react with the isothiocyanate represented by these.

The above reaction can be carried out in a suitable diluent. Examples of the diluent used in this case are as follows:
Aliphatic, cycloaliphatic and aromatic hydrocarbons (which may optionally be chlorinated), such as pentane, hexane, cyclohexane, petroleum ether, benzene, toluene, xylene, dichloromethane, dichloroethane and the like;
Ethers such as ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM) and the like;
Can be mentioned.

  The above reaction can be carried out within a substantially wide temperature range. In general, it can be carried out between about -40 and about 200 ° C, preferably between about -20 and about 110 ° C. The reaction is preferably carried out under normal pressure, but can be operated under pressure or reduced pressure.

  In carrying out the above reaction, for example, 1 mol of a compound of formula (XI) is reacted with 1 mol to a slight excess of magnesium in a diluent such as tetrahydrofuran, and then 1 mol to a slight excess. A compound of formula (IV) can be obtained by reacting an amount of a compound of formula (XII).

  The compounds of formula (XI) are known compounds and many are commercially available.

Specific examples thereof include 2-chloromethyl-1,3-dioxolane,
Examples thereof include 2-bromomethyl-1,3-dioxolane.

  The compounds of formula (XII) are known compounds and many are commercially available.

Specific examples thereof include phenyl isothiocyanate,
2-methylphenyl isothiocyanate,
3-methylphenyl isothiocyanate,
4-methylphenyl isothiocyanate and the like can be mentioned.

In the production method (b), when X ¹ represents S, the compound of the formula (IV) is represented by the following formula (XIII):

式中、Ｒ^１、Ｒ^２、Ｒ^４及びＸ^２は前記と同義を示す、
で表わされる化合物を例えば、硫化剤と反応させることにより得られる。

In the formula, R ¹ , R ² , R ⁴ and X ² are as defined above,
For example, it can be obtained by reacting a compound represented by

  The above reaction can be carried out by reacting with phosphorus pentasulfide in a suitable diluent such as pyridine at about 20 ° C. to about 115 ° C. for 10 minutes to 24 hours.

  Further, instead of the sulfurizing agent in the above reaction, Lawesson's reagent (Lawesson reagent: 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetane-2,4-disulfide) is used. The reaction can be carried out at about 20 ° C. to about 111 ° C. for 10 minutes to 24 hours.

The compound of the formula (XIII) is
Formula (XIV):

式中、Ｒ^１、Ｒ^２及びＸ^２は前記と同義を示す、
で表わされる化合物を縮合剤の存在下、
式（ＸＶ）：
Ｒ^４−ＮＨ_２ （ＸＶ）
式中、Ｒ^４は前記と同義を示す、
で表わされる化合物と反応させることにより得られる。

In the formula, R ¹ , R ² and X ² are as defined above.
In the presence of a condensing agent,
Formula (XV):
R ⁴ —NH ₂ (XV)
In the formula, R ⁴ is as defined above.
It can be obtained by reacting with a compound represented by the formula:

In the above reaction, examples of the condensing agent include Mukaiyama reagent (2-chloro-N-methylpyridinium iodide), DCC (1,3-dicyclohexylcarbodiimide hydrochloride), EDC (1-ethyl-3- (3-dimethylaminopropyl). ) Carbodiimide hydrochloride), CDI (carbonyldiimidazole), dimethylpropynylsulfonium bromide, propargyltriphenylphosphonium bromide, DEPC (diethyl cyanophosphate) and the like.

The above reaction can be carried out in a suitable diluent, and examples of the diluent used here include aliphatic, cycloaliphatic and aromatic hydrocarbons (which may be chlorinated in some cases). ), For example, hexane, cyclohexane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, dichloromethane, dichloroethane, carbon tetrachloride, etc .;
Ethers such as ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF) and the like;
Nitriles such as acetonitrile, propionitrile, acrylonitrile and the like;
Esters such as ethyl acetate, amyl acetate and the like;
Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like can be mentioned.

  The above reaction can be carried out within a substantially wide temperature range. In general, it can be carried out between about -40 and about 200 ° C, preferably between about -20 and about 110 ° C. The reaction is preferably carried out under normal pressure, but can be operated under pressure or reduced pressure.

  In carrying out the above reaction, for example, 1 mol amount to a slight excess amount of the compound of the formula (XV) and 1 mol amount to a slight excess amount of the condensing agent per 1 mol of the compound of the formula (XIV). The compound of formula (XIII) can be obtained by reacting in a diluent such as dichloromethane.

The compound of formula (XIII) may alternatively be
Formula (XVI):

式中、Ｒ^１、Ｒ^２及びＸ^２は前記と同義を示し、Ｈａｌは、ハロゲンを示す、
で表わされる化合物を塩基の存在下で、
前記式（ＸＶ）の化合物と反応させることにより得ることもできる。

In the formula, R ¹ , R ² and X ² have the same meaning as described above, Hal represents halogen,
In the presence of a base,
It can also be obtained by reacting with the compound of the formula (XV).

  The compound of the above formula (XVI) can be obtained by reacting the compound of the above formula (XIV) with a halogenating agent.

  Examples of the halogenating agent include oxalyl chloride, thionyl chloride, thionyl bromide and the like.

An alternative method for obtaining the compound of formula (XIII) described above can be carried out in a suitable diluent, and examples of diluents used in this case are as follows:
Aliphatic, cycloaliphatic and aromatic hydrocarbons (which may optionally be chlorinated), such as pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, dichloromethane, dichloroethane and the like;
Ethers such as ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM) and the like;
Ketones such as acetone, methyl ethyl ketone (MEK), methyl-isopropyl ketone, methyl isobutyl ketone (MIBK) and the like;
Nitriles such as acetonitrile, propionitrile, acrylonitrile and the like;
Examples of the esters include ethyl acetate and amyl acetate.

Examples of the base include alkali metal hydroxides, carbonates and bicarbonates as inorganic bases, such as sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide. etc:
As organic bases, tertiary amines, dialkylaminoanilines and pyridines such as triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA), N, N-dimethylaniline, N, N-diethylaniline , Pyridine, 4-dimethylaminopyridine (DMAP), 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), etc. Can be mentioned.

The above alternative method can also be carried out by a method using a phase transfer catalyst. As an example of the diluent used in this case,
water;
Aliphatic, cycloaliphatic and aromatic hydrocarbons (which may optionally be chlorinated) such as pentane, hexane, cyclohexane, benzene, toluene, xylene, etc .;
Ethers such as ethyl ether, methyl ethyl ether, methyl butyl ether, isopropyl ether, butyl ether and the like;
Examples of phase transfer catalysts that may be mentioned include quaternary ions such as tetramethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium bissulfate, tetrabutylammonium iodide, trioctylmethylammonium. Chloride, benzyltriethylammonium bromide, butylpyridinium bromide, heptylpyridinium bromide, benzyltriethylammonium chloride, etc .;
Crown ethers such as dibenzo-18-crown-6, dicyclohexyl-18-crown-6, 18-crown-6 and the like;
Cryptands such as [2.2.2] -cryptate, [2.1.1] -cryptate, [2.2.1] -cryptate, [2.2. B] -cryptate, [2O2O2S] -cryptate, [3.2.2] -cryptate and the like.

  The above alternative can be carried out within a substantially wide temperature range. Generally, it can be carried out between about -40 to about 200 ° C, preferably between about -20 to about 200 ° C. The reaction is preferably carried out under normal pressure, but can be operated under pressure or reduced pressure.

  In carrying out the above alternative method, for example, 1 mol of the compound of the formula (XIV) is chlorinated with oxalyl chloride according to a conventional method to obtain the compound of the formula (XVI). A compound of formula (XIII) can be obtained by reacting 1 mol to a slight excess of the compound in pyridine.

  The compound of the formula (XIV) is represented by the following formula (XVII):

式中、Ｒ^１は前記と同義を示す、
で表わされる化合物をハロゲン化剤と反応させ、次いで、ルイス酸の存在下に下記式（ＸＶＩＩＩ）：
Ｒ^２−Ｘ^２−Ｈ （ＸＶＩＩＩ）
式中、Ｒ^２およびＸ^２は前記と同義を示す、
で表わされる化合物と反応させることにより得ることができる。

In the formula, R ¹ is as defined above,
And a compound represented by the following formula (XVIII) in the presence of a Lewis acid:
R ² -X ² -H (XVIII)
In the formula, R ² and X ² are as defined above.
It can obtain by making it react with the compound represented by these.

  In the above reaction, N-chlorosuccinimide, N-bromosuccinimide, sulfuryl chloride, or the like can be used as the halogenating agent.

  Examples of the Lewis acid include zinc chloride and titanium chloride.

The above reaction can be carried out in a suitable diluent, and examples of the diluent used here include aliphatic, cycloaliphatic and aromatic hydrocarbons (which may be chlorinated in some cases). ), For example, hexane, cyclohexane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, dichloromethane, dichloroethane, carbon tetrachloride, etc .;
Ethers such as ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF) and the like;
Nitriles such as acetonitrile, propionitrile, acrylonitrile and the like;
Examples of the esters include ethyl acetate and amyl acetate.

Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like can be mentioned.

  The above reaction can be carried out within a substantially wide temperature range. In general, it can be carried out between about -40 and about 200 ° C, preferably between about -20 and about 110 ° C. The reaction is preferably carried out under normal pressure, but can be operated under pressure or reduced pressure.

  In carrying out the above reaction, for example, after reacting 1 mol of the compound of the formula (XVII) with a 1 mol amount to a slight excess of a halogenating agent in a diluent such as dichloroethane, 1 mol amount of Lewis acid The target compound can be obtained by reacting a compound of formula (XVIII) in an amount of 5 mol and 1 mol and an excess of 1 mol.

The compound of formula (XVII) which is a raw material is a known compound, and many are commercially available.
Specific examples thereof include 3-phenylsulfanyl-propionic acid.

The compound of the formula (XVIII) as a raw material is a known compound, and many are commercially available.
Specific examples include phenol,
2-methylphenol,
3-methylphenol,
4-methylphenol,
2-fluorophenol,
3-fluorophenol,
4-fluorophenol,
2-chlorophenol,
3-chlorophenol,
4-chlorophenol,
Benzenethiol,
2-methylbenzenethiol,
3-methylbenzenethiol,
4-methylbenzenethiol,
2-fluorobenzenethiol,
3-fluorobenzenethiol,
4-fluorobenzenethiol,
2-chlorobenzenethiol,
3-chlorobenzenethiol,
4-chlorobenzenethiol and the like can be mentioned.

  In the production method (b), the compound of the formula (V) is a known compound, and typical examples include methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide and the like.

The reaction of the production method (b) can be carried out in a suitable diluent, and examples of the diluent used in this case include
Aliphatic, cycloaliphatic and aromatic hydrocarbons (which may optionally be chlorinated), such as pentane, hexane, cyclohexane, petroleum ether, benzene, toluene, xylene, dichloromethane, dichloroethane and the like;
Ethers such as ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM) and the like;
Nitriles such as acetonitrile, propionitrile, acrylonitrile and the like;
Esters such as ethyl acetate, amyl acetate and the like;
Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like can be mentioned.

The reaction of the production method (b) is desirably carried out in the presence of a base.
As a base, an alkali metal hydroxide, carbonate, bicarbonate, etc. as an inorganic base, such as sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, etc. :
As organic bases, tertiary amines, dialkylaminoanilines and pyridines such as triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA), N, N-dimethylaniline, N, N-diethylaniline , Pyridine, 4-dimethylaminopyridine (DMAP), 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), etc. Can be mentioned.

  The production method (b) can be carried out within a substantially wide temperature range. In general, it can be carried out between about -40 and about 200 ° C, preferably between about -20 and about 110 ° C. The reaction is preferably carried out under normal pressure, but can be operated under pressure or reduced pressure.

  In carrying out the production method (b), for example, with respect to 1 mol of the compound of the formula (IV), in a diluent such as N, N-dimethylformamide, 1 mol amount to a slight excess amount of the base and the compound of the formula (V) The desired compound of formula (I) can be obtained by reacting with the compound.

  In the production method (c), the compound of the formula (VI) can be synthesized according to a known method described in WO2007 / 063702, for example, cyclopentyl N-phenyl-3- (trimethylsilyl) prop-2-inimidothio. Ate.

  The compound of the formula (VII) is a compound well known as thiols, and examples thereof include methanethiol, ethanethiol, and benzenethiol.

  In the above production method (c), hydroxides, carbonates and bicarbonates of alkali metals as inorganic bases, such as sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, lithium hydroxide, water, etc. Examples thereof include sodium oxide and potassium hydroxide.

  Examples of the fluoride include an alkali metal fluoride or a quaternary ammonium fluoride salt such as potassium fluoride and tetrabutylammonium fluoride.

The reaction of the production method (c) can be carried out in a suitable diluent. Examples of the diluent used in this case are as follows:
Aliphatic, cycloaliphatic and aromatic hydrocarbons (which may optionally be chlorinated), such as pentane, hexane, cyclohexane, petroleum ether, benzene, toluene, xylene, dichloromethane, dichloroethane and the like;
Alcohols such as methanol, ethanol, propanol, isopropanol, butanol and the like;
Ethers such as ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM) and the like;
Nitriles such as acetonitrile, propionitrile, acrylonitrile and the like;
Esters such as ethyl acetate, amyl acetate and the like;
Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like can be mentioned.

The production method (c) can be carried out within a substantially wide temperature range. In general, it can be carried out between about -40 and about 200 ° C, preferably between about -20 and about 110 ° C. The reaction is preferably carried out under normal pressure, but it can also be operated under pressure or reduced pressure. In carrying out the production method (c), for example, with respect to 1 mol of the compound of the formula (VI) The desired compound of formula (I) can be obtained by reacting with 0.05 mole to 1 mole of base in a diluent such as methanol and then reacting with 1 mole of compound of formula (VII). .

  In the production method (d), the compound of the formula (VIII) can be synthesized according to the method described in Synthesis (1982), pages 137 to 138, for example, 3,3-dimethoxy-N-phenylpropanamide. Can be mentioned.

  Moreover, as a Mayer wine reagent, the well-known trimethyloxonium tetrafluoroborate can be mentioned.

The reaction of the production method (d) can be carried out in a suitable diluent. Examples of the diluent used in this case are as follows:
Aliphatic, cycloaliphatic and aromatic hydrocarbons (which may optionally be chlorinated), such as pentane, hexane, cyclohexane, petroleum ether, benzene, toluene, xylene, dichloromethane, chloroform, dichloroethane and the like;
Can be mentioned.

The production method (d) can be carried out within a substantially wide temperature range. In general, it can be carried out between about -40 and about 200 ° C, preferably between about -20 and about 110 ° C. The reaction is preferably carried out under normal pressure, but it can also be operated under pressure or reduced pressure. When carrying out the production method (d), for example, with respect to 1 mol of the compound of the formula (VIII) The desired compound of formula (I) can be obtained by reacting 1 molar amount to a slight excess of Mayer wine reagent in a diluent such as dichloromethane.

The compound of formula (IX) in the production method (e) is
Formula (XIX):

式中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は前記と同義を示す、
で表わされる化合物を、酸化剤と反応させることにより、得ることができる。

In the formula, R ¹ , R ² , R ³ and R ⁴ are as defined above,
Can be obtained by reacting with a oxidant.

  The compound of the above formula (XIX) is a compound included in the formula (I) of the present invention.

Examples of the oxidizing agent include metachloroperbenzoic acid, peracetic acid, potassium metaperiodate, potassium hydrogen persulfate, hydrogen peroxide, and the like;
Can be mentioned.

The above reaction can be carried out in a suitable diluent. Examples of the diluent used in this case are as follows:
Aliphatic, cycloaliphatic and aromatic hydrocarbons (which may optionally be chlorinated), such as pentane, hexane, cyclohexane, petroleum ether, benzene, toluene, xylene, dichloromethane, dichloroethane and the like;
Alcohols such as methanol, ethanol, propanol, butanol, etc .;
Acids, such as formic acid, acetic acid, etc .;
Can be mentioned.

  The above reaction can be carried out within a substantially wide temperature range. In general, it can be carried out between about -40 and about 200 ° C, preferably between about -20 and about 110 ° C. The reaction is preferably carried out under normal pressure, but can be operated under pressure or reduced pressure.

  In carrying out the above reaction, for example, 1 mol to 5 mol of an oxidizing agent in a diluent such as tetrahydrofuran is reacted with 1 mol of the compound of formula (XIX) to give the desired compound of formula (IX). Obtainable.

  The above reaction can be performed, for example, according to the method described in Experimental Science, Chemical Society of Japan, 4th edition, volume 24, page 365, 1992 published by Maruzen.

The reaction of the production method (e) can be carried out in a suitable diluent. Examples of the diluent used in this case are as follows:
Aliphatic, cycloaliphatic and aromatic hydrocarbons (which may optionally be chlorinated), such as pentane, hexane, cyclohexane, petroleum ether, benzene, toluene, xylene, dichloromethane, dichloroethane and the like;
Ethers such as ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM) and the like;
Nitriles such as acetonitrile, propionitrile, acrylonitrile and the like;
Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and the like;
Alcohols such as methanol, ethanol, propanol, butanol and the like can be mentioned.

The reaction of the production method (e) is preferably carried out in the presence of a base. As such a base, an alkali metal hydride, alkoxide, hydroxide, carbonate, bicarbonate, etc. as an inorganic base, for example, Sodium hydride, sodium methoxide, sodium ethoxide, sodium bicarbonate, potassium bicarbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.
As organic bases, tertiary amines, dialkylaminoanilines and pyridines such as triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA), N, N-dimethylaniline, N, N-diethylaniline , Pyridine, 4-dimethylaminopyridine (DMAP), 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), etc. Can be mentioned.

  The production method (e) can be carried out within a substantially wide temperature range. In general, it can be carried out between about -40 and about 200 ° C, preferably between about -20 and about 110 ° C. The reaction is preferably carried out under normal pressure, but can be operated under pressure or reduced pressure.

In carrying out the production method (e), for example, 1 mol of an excess amount of a base and 1 mol of an amount of slightly to a slight excess in a diluent such as N, N-dimethylformamide with respect to 1 mol of the compound of the formula (IX) The desired compound of formula (I) can be obtained by reacting an excess of the compound of formula (X).
In the above-described method for producing the compound of formula (I) of the present invention, the compound as a raw material (starting material, intermediate) includes a novel compound, and these compounds are represented by the following formula (XX) or formula ( XIV).

  Formula (XX):

式中、Ｘ^１、Ｘ^２、Ｘ^３、Ｒ^１、Ｒ^２及びＲ^４は前記と同義を示す、
で表わされる化合物。

In the formula, X ¹ , X ² , X ³ , R ¹ , R ² and R ⁴ are as defined above,
A compound represented by

  Formula (XIV):

式中、Ｘ^２、Ｒ^１及びＲ^２は前記と同義を示す、
で表わされる化合物。

In the formula, X ² , R ¹ and R ² are as defined above,
A compound represented by

  The compounds of formula (I) according to the invention exhibit a strong insecticidal action. Accordingly, the compounds of formula (I) of the present invention can be used as insecticides. And the active compound of Formula (I) of this invention exhibits the exact control effect with respect to a harmful insect, without giving a phytotoxicity with respect to a cultivated plant. The compounds of the present invention can also be used for the control of a wide variety of pests such as harmful sucking insects, chewable insects and other plant parasitic pests, storage pests, sanitary pests, etc. It can be applied for their eradication.

  Examples of such pests include the following pests.

As insects,
Coleoptera, for example,
Adzuki bean weevil (Callosobruchus Chinensis), maize weevil (Sitophilus zeamais), red flour beetle (Tribolium castaneum), the giant beetle, Epilachna vigintioctopunctata (Epilachna vigintioctomaculata), Tobii Lom Na tailed click beetle (Agriotes ogurae fuscicollis), rufocuprea (Anomala rufocuprea), Colorado potato beetle (Leptinotarsa decemlineata), corn root worms (Diabrotica spp.), Pinewood red beetle (Monochumus alternatus endai), rice weevil (Lissohoptrus oryzoph) lus), Hirata beetle (Lyctus brunneus), cucurbit leaf beetle (Aulacophora femoralis);
Lepidoptera, for example
Gypsy moth (Lymantria dispar), lackey moth (Malacosoma neustria), cabbage butterfly (Pieris rapae crucivora), common cutworm (Spodoptera litura), cabbage armyworm (Mamestra brassicae), rice stem borer (Chilo suppressalis), the European corn borer (Ostrinia nubilalis), streaks moth (Cadra cautella ), Chamodium spider oyster (Adoxophys honmai), Codlinga (Cydia pomonella), Kaburayaga (Agrotis segetum), Hachinotsutsu Riga (Galleria melonella), Konaga (Plutella x tella), fake American tobacco budworm (Heliothis virescens), mandarin orange leafminer (Phyllocnistis citrella);
Stink bugs, for example,
Leafhopper (Nepotettix cinticices), Green planthopper (Nilaparvata lugens), Pseudococcus comstocci, Mushroom aphid (Unaspis yanonus) , Lip phis erysimi, Stephanitis nashi, Neara spp., Trialeurodes vaporiarum, sp. Larva;
Thrips pests, for example
Southern palm thrips (Trips palmi), Citrus thrips (Franklinella occidentalis);
Grasshopper pests, for example,
African Kela (Gryllotalpa africana), Grasshopper (Locusta migratoria);
Cockroach pests, for example
German cockroaches (Blatella germanica), American cockroaches (Periplaneta americana), white-tailed termites (Reticulitermes supertus), termites (Coptothermes formosanus);
Fly pests, for example
House fly (Musca domestica), Aedes aegypti, Panax fly (Delia platula), Culex pipiens pallens (Cinex pipens pellens), Cyprus pistol
Etc. Also,
As mites, for example,
Tetanychus cinnabarinus, Tetanychus urticae, Pannychus citri, Acrops pelekassi, Tarsonemus spp.
Etc. further,
As nematodes, for example,
Meloidogyne incognita, pinewood nematode (Bursaphelenchus xylophylus), rice scented nematode (Aphelenchoes bessey), Heterodera lesnegu
Etc.

  Furthermore, in the field of veterinary medicine, the novel compounds of the present invention can be used effectively against a variety of harmful animal parasites (internal and ectoparasites) such as insects and helminths. Examples of such animal parasites include the following pests.

Examples of insects include
Horseflies (Gasterophilus spp.), Flies (Stomoxys spp.), White lice (Trichodictes spp.), Red turtles (Rhodnius spp.), Black fleas (Ctenocephalides canis) ul, C
Etc.

As mites, for example,
Mite (Ornithodoros spp.), Tick (Ixodes spp.), Mite (Boophilus spp.)
Etc.

  In the present invention, a substance having an insecticidal action against pests including all of them is sometimes called an insecticide.

  When used as an insecticide, the active compounds of the present invention can be in the form of conventional preparations. Formulation forms include, for example, liquids, emulsions, wettable powders, granular wettable powders, suspensions, powders, foams, pastes, tablets, granules, aerosols, active compound infiltration-natural and synthetic, microcapsules, Seed coatings, preparations with combustion devices (eg, combustion devices include fumigation and fumigation cartridges, cans, coils, etc.), ULV [cold mist, warm mist], etc. Can do.

  These preparations can be produced in a manner known per se. For example, the active compound may be a developing agent, ie a liquid diluent or carrier; a liquid gas diluent or carrier; a solid diluent or carrier, and optionally a surfactant, ie an emulsifier and / or a dispersant and It can be produced by mixing with a foam-forming agent or the like.

  When water is used as a developing agent, for example, an organic solvent can also be used as an auxiliary solvent.

  Examples of the liquid diluent or carrier include aromatic hydrocarbons (for example, xylene, toluene, alkylnaphthalene, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (for example, chlorobenzenes, ethylene chloride, chloride) Methylenes), aliphatic hydrocarbons (eg, cyclohexane, paraffins (eg, mineral oil classification)), alcohols (eg, butanol, glycol and their ethers, esters, etc.), ketones (eg, acetone, methyl ethyl ketone) , Methyl isobutyl ketone, cyclohexanone, etc.), strong polar solvents (eg, dimethylformamide, dimethyl sulfoxide, etc.), water and the like.

  Examples of the liquefied gas diluent or carrier include those which are gases at room temperature and normal pressure, for example, aerosol propellants such as bran, propane, nitrogen gas, carbon dioxide, and halogenated hydrocarbons.

  Examples of the solid diluent include ground natural minerals (for example, kaolin, clay, talc, chalk, quartz, attapul guide, montmorillonite, diatomaceous earth, etc.), ground synthetic minerals (for example, highly dispersed silicic acid, alumina, silicates, etc.) And so on.

  Solid carriers for granules include, for example, crushed and fractionated rocks (eg calcite, marble, pumice, gabbro, dolomite, etc.), synthetic particles of inorganic or organic powders, organic substances (eg sawdust) , Coconuts, corn cobs, tobacco stems, etc.).

  Examples of emulsifiers and / or foaming agents include nonionic and anionic emulsifiers [eg, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (eg, alkylaryl polyglycol ethers), alkyl sulfonates, and alkyl sulfates. , Aryl sulfonates, etc.], albumin hydrolysis products, and the like.

  Examples of the dispersant include lignin sulfite waste liquid and methylcellulose.

  Fixing agents can also be used in preparations (powder, granules, emulsions), and examples of the fixing agent include carboxymethyl cellulose, natural or synthetic polymers (for example, gum arabic, polyvinyl alcohol, and polyvinyl acetate). Can be mentioned.

  Colorants can also be used, for example, inorganic pigments (eg iron oxide, titanium oxide, Prussian blue, etc.), alizarin dyes, organic dyes such as azo dyes or metal phthalocyanine dyes, and further And trace elements such as iron, manganese, boron, copper, cobalt, molybdenum, and zinc salts.

  The formulation generally can contain the active ingredient in an amount in the range of 0.1 to 95% by weight, preferably 0.5 to 90% by weight.

  The active compounds of the formula (I) according to the invention are in the form of their commercially useful preparations and in the use forms prepared from these preparations, other active compounds such as insecticides, baits, fungicides, acaricides. It can also be present as a mixture with nematocides, fungicides, growth regulators, herbicides and the like. Here, examples of the insecticide include organic phosphorus agents, carbamate agents, carboxylate agents, chlorinated hydrocarbon agents, arylpyrazole agents, neonicotinoid agents, insecticides produced from microorganisms, and the like. Can be mentioned.

  Furthermore, the active compounds of the formula (I) according to the invention can also be present as admixtures with synergists, such formulations and use forms being those that are commercially useful. The synergist is not necessarily active per se, but is a compound that enhances the action of the active compound.

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

  The practical use concentration of the active compounds of the formula (I) according to the invention can be, for example, in the range of 0.0000001 to 100% by weight, preferably 0.00001 to 1% by weight.

  The compound of the formula (I) of the present invention can be used in a usual manner adapted to the use form.

  The active compound of the present invention has effective stability against alkalis on lime substances when used for sanitary pests and pests against stored products, and also exhibits excellent residual effects in wood and soil.

  In addition, the active compound of the present invention has low toxicity to warm-blooded animals and can be used safely.

  Next, the present invention will be described in more detail by way of actual examples, but the present invention should not be limited to this.

Synthesis example 1
Synthesis of phenyl-N- (4-methylphenyl) -3,3-bis (phenylsulfanyl) propanimidothioate

  To a dichloromethane solution of N- (4-methylphenyl) -3- (phenylsulfanyl) prop-2-enamide (1.0 g) was added pyridine (0.32 g) at 0 ° C., followed by oxalyl chloride (0.52 g). Of dichloromethane was added dropwise. After stirring for 30 minutes, benzenethiol (0.41 g) was added, and the mixture was stirred at room temperature for 13 hours. A saturated aqueous sodium hydrogen carbonate solution was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine and dried over magnesium sulfate. The residue was purified by silica gel column chromatography to obtain phenyl-N- (4-methylphenyl) -3,3-bis (phenylsulfanyl) propanimidothioate (0.2 g).

Synthesis example 2
Synthesis of 2-methylpropyl (1) -3-[(4-fluorophenyl) sulfanyl] -N- (3-methylphenyl) -3- (phenylsulfanyl) propanimidothioate

Synthesis Example 2-1
Synthesis of 3-[(4-fluorophenyl) sulfanyl] -3- (phenylsulfanyl) propanoic acid

  To a solution of 3- (phenylsulfanyl) propanoic acid (2.0 g) in 1,2-dichloroethane (30 ml) was added N-chlorosuccinimide (1.5 g) little by little under ice cooling, and the mixture was stirred at room temperature for 3 hours. After completion of stirring, tetrahydrofuran (30 ml) and zinc chloride (2.0 g) were added, and 4-fluorothiophenol (1.2 g) was added dropwise under ice cooling. After stirring at room temperature for 10 hours, the reaction solution was washed with saturated brine and dried over magnesium sulfate. The solvent was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 3-[(4-fluorophenyl) sulfanyl] -3- (phenylsulfanyl) propanoic acid (2.2 g).

Synthesis Example 2-2
Synthesis of 3-[(4-fluorophenyl) sulfanyl] -N- (3-methylphenyl) -3- (phenylsulfanyl) propanamide

  To a solution of 3-[(4-fluorophenyl) sulfanyl] -3- (phenylsulfanyl) propanoic acid (2.2 g) in dichloromethane (50 ml) was added 3-methylaniline (1.0 g), 1-ethyl-3- (3 -Dimethylaminopropyl) carbodiimide hydrochloride (2.0 g) and 4-dimethylaminopyridine (0.1 g) were added. After stirring at room temperature for 1 hour, the reaction solution was washed with saturated brine and dried over magnesium sulfate. The solvent was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography to give 3-[(4-fluorophenyl) sulfanyl] -N- (3-methylphenyl) -3- (phenylsulfanyl) propanamide (1. 7 g) was obtained.

Synthesis Example 2-3
Synthesis of 3-[(4-fluorophenyl) sulfanyl] -N- (3-methylphenyl) -3- (phenylsulfanyl) propanethioamide

  To a solution of 3-[(4-fluorophenyl) sulfanyl] -N- (3-methylphenyl) -3- (phenylsulfanyl) propanamide (1.0 g) in tetrahydrofuran (30 ml) was added Lawesson's reagent (1.2 g). It was. After stirring at 60 ° C. for 10 hours, the solvent was concentrated under reduced pressure, the residue was purified by silica gel column chromatography, and 3-[(4-fluorophenyl) sulfanyl] -N- (3-methylphenyl) -3- (Phenylsulfanyl) propanethioamide (1.0 g) was obtained.

Synthesis Example 2-4
Synthesis of 2-methylpropyl (1) -3-[(4-fluorophenyl) sulfanyl] -N- (3-methylphenyl) -3- (phenylsulfanyl) propanimidothioate

  3-[(4-Fluorophenyl) sulfanyl] -N- (3-methylphenyl) -3- (phenylsulfanyl) propanethioamide (0.4 g) in N, N-dimethylformamide (50 ml) in isobutyl iodide (50 ml) 0.3 g) was added. Potassium carbonate (0.2 g) was added under ice cooling, and the mixture was stirred at 10 ° C. to 15 ° C. for 2 hours. The reaction solution was poured into ice and extracted with hexane, and the organic layer was dried over magnesium sulfate. The solvent was concentrated under reduced pressure, the residue was purified by silica gel column chromatography, and 2-methylpropyl (1) -3-[(4-fluorophenyl) sulfanyl] -N- (3-methylphenyl) -3- ( Phenylsulfanyl) propanimidothioate (0.2 g) was obtained.

Synthesis example 3
Synthesis of cyclopentyl 3,3-bis (cyclopentylsulfanyl) -N-phenyl propanimidothioate

  To a methanol solution of cyclopentyl N-phenyl-3- (trimethylsilyl) prop-2-inimidothioate (0.91 g) was added potassium carbonate (0.02 g) at 0 ° C., and the mixture was stirred for 1 hour. Thereafter, a methanol solution of cyclopentanethiol (0.37 g) was added at 0 ° C. and stirred for 15 hours. The solvent was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography to obtain cyclopentyl 3,3-bis (cyclopentylsulfanyl) -N-phenylpropanimidothioate (0.15 g).

Synthesis example 4
Synthesis of 2-methylpropyl-2- (1,3-dioxolan-2-yl) -N- (4-methylphenyl) ethaneimidothioate

Synthesis Example 4-1
Synthesis of 2- (1,3-dioxolan-2-yl) -N- (4-methylphenyl) ethanethioamide

  Iodine (0.06 g) was added to a suspension of magnesium (0.15 g) in tetrahydrofuran (THF), and a THF solution of 2-bromomethyl-1,3-dioxolane (1.0 g) was slowly added dropwise with heating. After heating to reflux for 2 hours, the mixture was cooled to 0 ° C., a THF solution of 4-methylphenyl isothiocyanate (0.89 g) was added dropwise, and the mixture was heated to reflux for 5 hours. The reaction solution was cooled to room temperature, diluted hydrochloric acid was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine and dried over magnesium sulfate. After concentrating the solvent under reduced pressure, the residue was purified by silica gel column chromatography to obtain 2- (1,3-dioxolan-2-yl) -N- (4-methylphenyl) ethanethioamide (0.25 g). .

Synthesis Example 4-2
Synthesis of 2-methylpropyl-2- (1,3-dioxolan-2-yl) -N- (4-methylphenyl) ethaneimidothioate

  A solution of 2- (1,3-dioxolan-2-yl) -N- (4-methylphenyl) ethanethioamide (0.25 g), isobutyl iodide (0.29 g) and potassium carbonate (0.22 g) in acetonitrile. Heated to reflux for 3 hours. After cooling to room temperature, water was added and extracted with ethyl acetate. The organic layer was dried with magnesium sulfate. After concentrating the solvent under reduced pressure, the residue was purified by silica gel column chromatography and 2-methylpropyl-2- (1,3-dioxolan-2-yl) -N- (4-methylphenyl) ethaneimidothioate. (0.25 g) was obtained.

  The compounds of formula (I) of the present invention obtained by the same method as in the above synthesis examples are shown in Tables 1 to 4. Table 5 shows the physical property values of the representative compounds. The compounds of the above synthesis examples are also shown in the table.

The indications in the table indicate the following.
Ph: phenyl, i-Bu: isobutyl,
c-Pen: cyclopentyl, Et: ethyl, n-Pr: n-propyl,
i-Pr: isopropyl, n-Bu: n-butyl,
i-Bu: isobutyl, s-Bu: sec-butyl,
c-Hex: cyclohexyl

Biological Test Example 1: Tests against Spodoptera litura larvae Preparation of reagent solution Solvent: 3 parts by weight of dimethylformamide Emulsifier: 1 part by weight of polyoxyethylene alkylphenyl ether In order to prepare a formulation of a suitable active compound, the active compound 1 part by weight was mixed with the above amount of solvent containing the above amount of emulsifier and the mixture was diluted with water to a predetermined concentration.

Test method Immerse the sweet potato leaves in a reagent solution diluted with water at a predetermined concentration, air dry the chemical solution, place it in a petri dish with a diameter of 9 cm, release 10 third-instar larvae and place them in a constant temperature room at 25 ° C for 2 days. And after 4 days, sweet potato leaves were added, and after 6 days, the number of dead insects was examined to calculate the insecticidal rate.

  In this test, the results of 2 dishes in 1 ward were averaged.

  As a result of the above test, the active ingredient concentration was 500 ppm. Of the compound showed an insecticidal rate of 100%.

  1-4, 1-358, 1-397, 1-435, 1-448, 1-572, 1-578, 1-659, 1-672, 1-745

Biological Test Example 2: Test against Taninychus urticae (dispersion test)
Test method 50 to 100 adults of the spider mite were inoculated on the leaves of two real leaves grown in a 6 cm diameter pot, and one day later, a diluted water solution of a predetermined concentration of the active compound prepared above was A sufficient amount was sprayed using a spray gun. After spraying, the miticide rate was calculated after 6 days in the greenhouse.

  As a result of the above test, the active ingredient concentration was 500 ppm. This compound showed an insecticidal rate of 90% or more.

  1-358, 1-397, 1-572, 1-578, 1-639, 1-745

Biological test example 3: Test against cucumber leaf beetle (Alacophora femorialis) (dispersion test)
Test method The cucumber leaves were immersed in a diluted solution of the active compound prepared in the above concentration, air-dried, then placed in a plastic cup containing sterilized black soil, and 5 larvae of the leaf beetle were released. . Six days later, the number of dead insects was examined, and the insecticidal rate was calculated.

  As a result of the above test, the active ingredient concentration was 500 ppm. Of the compound showed an insecticidal rate of 100%.

  1-4, 1-358, 1-397, 1-435, 1-448, 1-572, 1-578, 1-659, 1-672, 1-792

Biological Test Example 4: Organic Phosphorus and Carbamate Resistant Resistance to Peach Aphid (Myzus persicae) Test Method Organic Phosphorus and Carbamates Grown on Two Leaves of Eggplant Grown in a 6 cm Diameter Pot About 30 to 50 aphid-resistant peach aphids were inoculated per seedling, and one day after the inoculation, a sufficient amount of an aqueous diluted solution of the active compound prepared above was sprayed using a spray gun. After spraying, it was left in the greenhouse and the insecticidal rate was calculated 7 days after spraying. The test was repeated twice.

  As a result of the above test, the active ingredient concentration was 500 ppm. This compound showed an insecticidal rate of 90% or more.

  1-4, 1-358, 1-397, 1-435, 1-572, 1-578, 1-659, 1-672

Biological test example 5: Injection test on Boophilus microplus Preparation of reagent solution Solvent: Dimethyl sulfoxide To make a formulation of the appropriate active compound, 10 mg of the active compound is dissolved in 0.5 ml of the above solvent and the mixture is dissolved. Diluted with water to a predetermined concentration.

Test Method The compound solution prepared above was injected into the abdomen of five adult males with stagnation. The tick was transferred to a petri dish and reared in a cage for a certain period.

  After a certain period of time, the fatality rate of the tick tick was determined. 100% means that all eggs laid were not hatched, and 0% means that all eggs were hatched.

  As a result of the above test, at an active ingredient concentration of 20 μg / head, for example, the following compound No. Of the compound showed an insecticidal rate of 100%.

  1-4, 1-358, 1-397, 1-448, 1-572, 1-578, 1-659, 1-672

Biological Test Example 6: Tests on sheep flies (Lucilia cuprina) Test Method About 20 to 30 test tubes containing 1 cubic centimeter of ground beef and 0.5 ml of an aqueous compound solution prepared as in Test Example 5 above. We put sheep fly larvae.

  After a certain period of time, the percentage of mortality of sheep fly was measured. In that case, 100% means that all sheep flies have died and 0% means that they are all alive.

  As a result of the above test, the active ingredient concentration was 100 ppm. Of the compound showed an insecticidal rate of 100%.

  1-4, 1-358, 1-397, 1-435, 1-448, 1-572, 1-578, 1-659, 1-672

Biological Test Example 7: Test on Housefly (Musca domestica) Test Method As a test preparation stage, a sponge of a certain size is impregnated with a mixture of sugar and an aqueous compound solution prepared in the same manner as in Test Example 5 above. Placed inside. Ten adult houseflies were placed in a container and covered with a hole for ventilation.

  After a certain period of time, the percentage of housefly mortality was measured. In that case, 100% means that all house flies have died and 0% means that they are all alive.

  As a result of the above test, the active ingredient concentration was 100 ppm. Of the compound showed an insecticidal rate of 100%.

  1-4, 1-435, 1-448

Formulation Example 1 (Granule)
To a mixture of 10 parts of the present compound (No. 1-4), 30 parts of bentonite (montmorillonite), 58 parts of talc (talc), and 2 parts of lignin sulfonate, 25 parts of water is added, and the mixture is well hatched and extruded. It is made into 10-40 mesh granules with a granulator and dried at 40-50 ° C. to give granules.

Formulation Example 2 (Granule)
95 parts of clay mineral particles having a particle size distribution in the range of 0.2 to 2 mm are placed in a rotary mixer, and under rotation, 5 parts of the compound of the present invention (No. 1-358) is sprayed together with the liquid diluent. After squeezing, it is dried at 40-50 ° C. to give granules.

Formulation Example 3 (Emulsion)
30 parts of the compound of the present invention (No. 1-397), 55 parts of xylene, 8 parts of polyoxyethylene alkylphenyl ether and 7 parts of calcium alkylbenzenesulfonate are mixed and stirred to obtain an emulsion.

Formulation Example 4 (wettable powder)
15 parts of the present compound (No. 1-435), 80 parts of a mixture of white carbon (hydrous amorphous silicon oxide fine powder) and powdered clay (1: 5), 2 parts of sodium alkylbenzenesulfonate and sodium alkylnaphthalenesulfonate 3 parts of formalin condensate is pulverized and mixed to obtain a wettable powder.

Formulation Example 5 (hydrated granules)
20 parts of the present compound (No. 1-572), 30 parts of sodium lignin sulfonate and 15 parts of bentonite and 35 parts of calcined diatomaceous earth powder are thoroughly mixed, added with water, extruded on a 0.3 mm screen and dried. To obtain hydrated granules.

  The novel 3-iminopropanoic acid derivative of the present invention has an excellent insecticidal action as an insecticide, as shown in the above examples.

Claims (6)

Formula (I):

Where
X ¹ , X ² and X ³ each independently represent O or S;
R ¹ and R ² are each independently an optionally substituted alkyl, an optionally substituted cycloalkyl, an optionally substituted alkenyl, an optionally substituted cycloalkenyl, a substituted An alkynyl which may be substituted, an aromatic hydrocarbon group which may be substituted, or a heterocyclic group which may be substituted;
R ¹ and R ² may form a ring together with —X ¹ —C—X ² —,
R ³ is an optionally substituted alkyl, an optionally substituted cycloalkyl, an optionally substituted alkenyl, an optionally substituted cycloalkenyl, an optionally substituted alkynyl, an optionally substituted Represents an aromatic hydrocarbon group which may be substituted, or an optionally substituted heterocyclic group, and R ⁴ represents an optionally substituted alkyl, an optionally substituted cycloalkyl group, an optionally substituted A good alkenyl, an optionally substituted cycloalkenyl, an optionally substituted alkynyl, an optionally substituted aromatic hydrocarbon group, or an optionally substituted heterocyclic group;
The 3-iminopropanoic acid derivative represented by these. X ¹ , X ² and X ³ each independently represent O or S;
R ¹ and R ² are each independently an _optionally substituted C _1-12 alkyl, an _optionally substituted C _3-8 cycloalkyl, an _optionally substituted C _2-6 alkenyl, a substituted 5-membered optionally containing optionally substituted C _3-8 cycloalkenyl, optionally substituted C _2-6 alkynyl, optionally substituted phenyl, or optionally substituted O, S, N Or a 6-membered heterocyclic group,
R ¹ and R ² may be combined to form a ring,
R ³ is an _optionally substituted C _1-12 alkyl, an _optionally substituted C _3-8 cycloalkyl, an _optionally substituted C _2-6 alkenyl, an optionally substituted C _3- 5- or 6-membered heterocyclic group optionally containing ₈ cycloalkenyl, optionally substituted C _2-6 alkynyl, optionally substituted phenyl, or optionally substituted O, S, N R ⁴ represents an _optionally substituted C _1-12 alkyl group, an _optionally substituted C _3-8 cycloalkyl group, an _optionally substituted C _2-6 alkenyl group, a substituted An optionally substituted C _3-8 cycloalkenyl group, an optionally substituted C _2-6 alkynyl group, an optionally substituted phenyl, or an optionally substituted heteroatom selected from O, S and N Optionally including Represents a 5- or 6-membered heterocyclic group,
The compound of claim 1. X ¹ , X ² and X ³ each independently represent O or S;
R ¹ and R ² are each independently an _optionally substituted C _1-6 alkyl, an optionally substituted C _3-6 cycloalkyl, an optionally substituted C _2-4 alkenyl, a substituted Optionally substituted C _5-6 cycloalkenyl, optionally substituted C _2-4 alkynyl, optionally substituted phenyl, or optionally substituted heteroatom 1 selected from O, S and N Represents a 5- or 6-membered heterocyclic group containing ~ 3, but not 3 O
R ¹ and R ² may form a ring together with —X ¹ —C—X ² —,
R ³ is an optionally substituted C _1-6 alkyl group, an optionally substituted C _3-6 cycloalkyl, an optionally substituted C _2-4 alkenyl, an optionally substituted C _{5 -6} cycloalkenyl, optionally substituted C _2-4 alkynyl, optionally substituted phenyl, or optionally substituted O, S and N containing 1 to 3 heteroatoms, Represents a 5- or 6-membered heterocyclic group not containing 3 O, and R ⁴ is an optionally substituted C _1-6 alkyl, an optionally substituted C _3-6 cyclo Alkyl, optionally substituted C _2-4 alkenyl, optionally substituted C _5-6 cycloalkenyl, optionally substituted C _2-4 alkynyl, optionally substituted phenyl, or substituted May A 5- or 6-membered heterocyclic group containing 1 to 3 heteroatoms selected from O, S and N, but not 3 O;
The compound of claim 1.   An insecticide containing the compound according to any one of claims 1 to 3 as an active ingredient. Formula (XX):

Wherein X ¹ , X ² , X ³ , R ¹ , R ² and R ⁴ have the same meaning as described in claim 1,
A compound represented by Formula (XIV):

In the formula, X ² , R ¹ and R ² have the same meaning as described in claim 1,
A compound represented by