JPH107637A - Substituted alkylbenzylidene hydrazine compounds, their preparation and agricultural and horticultural pesticides - Google Patents

Abstract

(57) [Problem] To provide a substituted alkylbenzylidenehydrazine compound useful as a pesticide for agricultural and horticultural use. SOLUTION: The substituted alkylbenzylidenehydrazine compound of the present invention has the following formula: [Wherein, R ¹ represents a phenyl group or the like; R ² and R ³ represent a hydrogen atom or the like; R ⁴ represents an alkyl group or the like;
Represents NR ⁵ R ⁶ , N = CR ⁷ NR ⁸ R ^{9 and the} like (R ⁵
Represents an alkoxycarbonyl group or the like; R ⁶ represents a hydrogen atom or the like; R ⁷ , R ⁸ and R ⁹ represent an alkyl group or the like. X represents S, SO, SO ₂ , O or the like. ] Is shown.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel substituted alkylbenzylidenehydrazine compound which is a pest control agent for agricultural and horticultural use useful as an insecticide and the like.

[0002]

The compound similar to the substituted alkylbenzylidene hydrazine compound of the present invention includes Current Science (India) 3
2 (9) 404-5 (1963) describes 4-hydroxymethylbenzophenone 2,4-dinitrophenylhydrazone, which compound is shown to be an intermediate of (4-hydroxymethyl) diphenylmethane. . However, the structures of these compounds are considerably different from those of the compounds of the present invention as described above, and furthermore, no investigation has been made as to whether or not they show usefulness as insecticides or the like. On the other hand, as a compound similar to an important intermediate in the synthesis of the substituted alkylbenzylidenehydrazine compound of the present invention, JP-A-62-294652 discloses the following formula:

[0003]

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(Wherein, R represents a hydrogen atom or a lower alkyl group; Y represents a halogen atom, a lower alkyl group or a lower haloalkyl group; m represents 0, 1, 2 or 3; The definitions of R, Y and m are limited to this compound only.). Also, J.I. Appl. Polym. Sci. , 26
(4), 1148 (1981) has the following equation:

[0005]

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The compound represented by the formula (1) is described as a raw material for a polymer. However, the structures of these compounds are different from the compounds of the present invention as described above. Accordingly, an object of the present invention is to provide a novel substituted alkylbenzylidenehydrazine compound, a method for producing the same, and a pesticidal composition for agricultural and horticultural use which is useful as an insecticide containing the compound as an active ingredient.

[0007]

Means for Solving the Problems As a result of investigations to solve the above problems, the present inventors have found that a novel substituted alkylbenzylidenehydrazine compound is useful as a pesticide for agricultural and horticultural use useful as an insecticide and the like. The present inventors have found that they have remarkable controlling activity, and have completed the present invention. That is,
The present invention is as follows. According to a first aspect, the following formula (1):

[0008]

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[In the formula, each substituent is as follows. R
¹ is an unsubstituted or substituted halogen atom, a haloalkyl group having 1 to 4 carbon atoms, a nitro group, a cyano group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, An alkylthio group having 1 to 4 carbon atoms, a haloalkoxy group having 1 to 4 carbon atoms,
A phenyl group having 4 haloalkylsulfonyloxy groups or an alkylsulfonyloxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 8 carbon atoms, or a haloalkyl group having 1 to 4 carbon atoms. R ² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group, or a halogen atom. R ³ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom. R
⁴ is an alkyl group having 1 to 8 carbon atoms, 2 to 2 carbon atoms
5 alkenyl groups, cycloalkyl groups having 3 to 8 carbon atoms, alkynyl groups having 2 to 5 carbon atoms, unsubstituted or substituted as halogen atoms or 1 to 4 carbon atoms
Phenyl group, benzyl group, phenethyl group, haloalkyl group having 1 to 4 carbon atoms, haloalkenyl group having 2 to 6 carbon atoms,
Alkylsulfonyl groups, haloalkylsulfonyl groups having 1 to 4 carbon atoms, cyano group, A ¹ COOR ¹⁰ ,
Hydrogen atom, A ¹ OR ¹⁰ , COA ¹ OR ¹⁰ , COR
¹⁰ represents a cyanoalkyl group.

Y is NR ⁵ R ⁶ , N = CR ⁷ NR ⁸ R ⁹ ,
Alternatively, R ⁷ and R ⁸ are linked to form a 4- to 8-membered N
= Represents CR ⁷ NR ⁸ R ⁹ . R ⁵ is COOR ¹¹ , a hydrogen atom, COR ¹² , SO ² R ¹³ , SO ₂ NHR ¹⁰ ,
SO ₂ NHCH ₂ Ph, SO ₂ NR ¹⁰ R ¹⁰ ′, C
ONHR ¹⁴ , CSNHR ¹⁵ , A ¹ COOR ¹⁰ , C
OA ² R ¹⁶ , CONR ¹⁰ R ¹⁰ ′, CSSR ¹⁰ ,
An alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms,
Represents a cycloalkyl group having 3 to 8 carbon atoms, a formyl group, or A ¹ OR ¹⁰ ; R ⁶ is a hydrogen atom, COOR
¹⁷ , COR ¹⁸ , SO ₂ R ¹³ , COA ¹ R ¹⁹ , an alkyl group having 1 to 8 carbon atoms, COCOOR ¹⁰ , S
CR ²⁰ R ²⁰ R ²⁰ , SNR ²¹ R ²¹ ′, A ¹ OR
²¹ , CH ₂ OA ¹ OR ¹⁰ , formyl group, SNR ¹⁰
COOR ²¹ , SNR ¹⁰ A ¹ COOR ¹⁰ ′, a haloalkyl group having 1 to 4 carbon atoms, A ¹ SR ¹⁵ , or a benzyl group. R ⁵ and R ⁶ may be linked together with N to form a 4- to 8-membered ring. R ⁷ represents an alkyl group having 1 to 4 carbon atoms, a hydrogen atom, or a phenyl group. R ⁸ represents an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. R ⁹ is an alkyl group having 1 to 4 carbon atoms, a phenyl group, an alkynyl group having 2 to 5 carbon atoms,
Represents a formyl group, COR ¹⁰ , or a hydrogen atom. X represents S, SO, SO ₂ , O, or NR ²² .

The above-mentioned A ¹ , A ² and R ¹⁰ -R
²² is as follows. A ¹ represents an alkylene group having 1 to 4 carbon atoms, and A ² represents an alkylene group having 1 to 10 carbon atoms. R ¹⁰ and R ¹⁰ ′ have 1 carbon atom
Represents up to 4 alkyl groups. R ¹¹ has 1 to 8 carbon atoms
Represents an alkyl group, a phenyl group, a benzyl group, or an alkenyl group having 3 to 5 carbon atoms. R ¹² is an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms,
Unsubstituted or a phenyl group having a halogen atom, a haloalkyl group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, or Represents a pyridyl group having a substituent or a halogen atom as a substituent. R ¹³ is a haloalkyl group having 1 to 4 carbon atoms or 1 carbon atom.
Represents up to 4 alkyl groups. R ¹⁴ is an unsubstituted or phenyl group having 1 to 4 carbon atoms haloalkyl groups as substituents, 1-8 alkyl group carbon atoms, or a phenylsulfonyl group. R ¹⁵ is a phenyl group,
Alternatively, it represents an alkyl group having 1 to 4 carbon atoms. R ¹⁶
Is an alkoxy group having 1 to 4 carbon atoms,
4 alkylthio groups, alkylcarbonyloxy groups having 2 to 4 carbon atoms, halogen atoms, imidazole groups,
Represents an alkylcarbonylamino group having 2 to 5 carbon atoms or a pyridyl group.

R ¹⁷ is an alkyl group having 1 to 8 carbon atoms, a phenyl group, a benzyl group, or a group having 2 to 5 carbon atoms.
Alkenyl groups. R ¹⁸ is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group, an alkenyl group having 2 to 5 carbon atoms,
Alternatively, it represents an unsubstituted or pyridyl group having a halogen atom as a substituent. R ¹⁹ is an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, COO
Representing the R ^10. R ²⁰ represents a halogen atom. R ²¹ and R ²¹ ′ represent an alkyl group having 1 to 8 carbon atoms.
R ^{22 represents a} hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkylcarbonyl group having 2 to 5 carbon atoms, or a formyl group. And a substituted alkylbenzylidenehydrazine compound [compound (1)]. A second invention provides the following formula (2 ′):

[0013]

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(Wherein R ⁴ ′ is an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, 5 alkynyl groups, phenyl group, benzyl group, phenethyl group, unsubstituted or substituted alkyl group having a halogen atom or an alkyl group having 1 to 4 carbon atoms,
Haloalkyl groups, haloalkenyl groups having 2 to 6 carbon atoms, alkylsulfonyl groups having 1 to 4 carbon atoms,
Haloalkylsulfonyl group having 1 to 4 carbon atoms, cyano group, A ¹ COOR ¹⁰ , A ¹ OR ¹⁰ , COA ¹ OR
Represents ¹⁰ , COR ¹⁰ , or a cyanoalkyl group.
R ^{1 to} R ³ , R ¹⁰ , A ¹ and X have the same meanings as described above. ) [Compound (2 ′)]. The third invention provides the following formula (2):

[0015]

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(Wherein, R ^{1 to} R ⁴ and X are as defined above) and the following formula (3):

[0017]

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Wherein R ⁵ and R ⁶ have the same meanings as defined above, and are reacted with a compound (3) represented by the following formula (1a):

[0019]

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(Wherein, R ^{1 to} R ⁶ and X have the same meanings as described above). A fourth invention provides the following equation (4):

[0021]

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(Wherein R ^{1 to} R ⁴ and X have the same meanings as described above) and the following formula (5):

[0023]

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(Where R ²³ is R ¹⁰ , OR ¹¹ , N
It represents the HR ¹⁴ or ^{NR 10 R} 10 '. Z represents a halogen atom, OCOR ¹³ , OR ¹⁰ , OH. Note that R
¹⁰ , R ¹¹ , R ¹³ and R ¹⁴ are as defined above. The compound (5) represented by the following formula (1a-i):

[0025]

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(Wherein R ^{1 to} R ⁴ , X and R ²³ have the same meanings as described above), and the following formula (1a-vi):

[0027]

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(Wherein, R ^{1 to} R ⁴ , X and R ²³ have the same meanings as described above). The fifth invention is based on the following formula (4-
i):

[0029]

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(Wherein R ^{1 to} R ⁵ and X are as defined above) and the following formula (6):

[0031]

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(Wherein, R ⁶ is as defined above. G
Represents a halogen atom, an OCOR ^13. A) reacting the compound (6) with the compound (1). A sixth invention provides the following formula (1a-iv):

[0033]

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Wherein R ^{1 to} R ⁶ have the same meanings as defined above, and the compound (1a-iv) is reacted with an oxidizing agent. The following formula (1a-v):

[0035]

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(Wherein R ^{1 to} R ⁶ have the same meanings as described above; m is 1 or 2). The seventh invention relates to an agricultural and horticultural pesticide containing the compound (1) as an active ingredient.

[0037]

BEST MODE FOR CARRYING OUT THE INVENTION A novel substituted alkylbenzylidene hydrazine compound [Compound (1)] [Compound (1a), compound (1b), compound (1c) described later), which is a target compound and a starting compound, and The production raw material [compound (2) and the novel compound (2 ′),
Various substituents represented by compound (3) and the like] are as follows. [Compound (1)] As compound (1), Y is NR ⁵ R
⁶ , N = CR ⁷ NR ⁸ R ⁹ . And R ⁷ and R ⁷ in CR ⁷ NR ⁸ R ^9
8 is the following equation (1c):

[0038]

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(Wherein, R ^{1 to} R ⁴ , R ⁹ and X have the same meanings as described above; and n represents an integer of 1 to 5). A pyrrolidine which preferably forms a 5-membered ring at n = 2. Hereinafter, Y
Is a compound represented by NR ⁵ R ⁶ as a compound (1a),
A compound represented by CR ⁷ NR ⁸ R ⁹ is a compound (1b),
The compound in which R ⁷ and R ⁸ in N = CR ⁷ NR ⁸ R ⁹ are linked to form a 4- to 8-membered ring is referred to as compound (1c).

[R ¹ ] Examples of R ¹ include a phenyl group, an alkyl group having 1 to 8 carbon atoms, and a haloalkyl group having 1 to 4 carbon atoms. Compound (1)
R ¹ in is preferably a phenyl group or an alkyl group having 1 to 8 carbon atoms; more preferably a phenyl group or an alkyl group having 1 to 8 carbon atoms in the compound (1a); In 1b) and compound (1c), it is a phenyl group. R ¹ in compound (2) is preferably a phenyl group or an alkyl group having 1 to 8 carbon atoms. Examples of the phenyl group include unsubstituted or substituted halogen atoms, haloalkyl groups having 1 to 4 carbon atoms, nitro groups, cyano groups, alkyl groups having 1 to 4 carbon atoms, and 1 to 4 carbon atoms. Alkoxy group, alkylthio group having 1 to 4 carbon atoms, haloalkoxy group having 1 to 4 carbon atoms, haloalkylsulfonyloxy group having 1 to 4 carbon atoms or alkylsulfonyloxy having 1 to 4 carbon atoms Those having a group can be mentioned.

As the phenyl group in the compound (1a), a halogen atom, a haloalkyl group having 1 to 4 carbon atoms, a nitro group, a cyano group, an alkyl group having 1 to 4 carbon atoms, C1 -C4 alkoxy group, C1 -C4 alkylthio group, C1 -C4 haloalkoxy group, C1 -C1
A 4-haloalkylsulfonyloxy group or an alkylsulfonyloxy group having 1 to 4 carbon atoms; the phenyl group in the compound (1b) and the compound (1c) preferably has a halogen atom as a substituent. The phenyl group in the compound (2) is preferably an unsubstituted or substituted halogen atom, a haloalkyl group having 1 to 4 carbon atoms, a nitro group, a cyano group, an alkyl group having 1 to 4 carbon atoms, An alkoxy group having 1 to 4 atoms or an alkylthio group having 1 to 4 carbon atoms, a haloalkoxy group having 1 to 4 carbon atoms, a haloalkylsulfonyloxy group having 1 to 4 carbon atoms or 1 carbon atom It has 4 to 4 alkylsulfonyloxy groups. Examples of the halogen atom for the substituent include a chlorine atom, an iodine atom, a bromine atom, and a fluorine atom. The number and position of the substituents are not particularly limited; preferably, the number of the substituents is 1 or 2
And the positions of the substituents are the 2-, 3- and 4-positions.

As the haloalkyl group for the substituent, alkyl is linear or branched, and chlorine, iodine,
Examples thereof include those having a halogen atom such as a bromine atom and a fluorine atom;
4 and having a fluorine atom; more preferably CF ₃ . The number and position of the substituents are not particularly limited; preferably, the number of the substituents is one, and the position of the substituent is preferably the 4-position. The number and position of the nitro group of the substituent are not particularly limited; preferably, the number of the substituent is 1 and the position of the substituent is preferably the 4-position. Although the number and position of the cyano group of the substituent are not particularly limited; preferably, the number of the substituent is one,
The position of the substituent is preferably at the 4-position. Examples of the alkyl group for the substituent include straight-chain or branched ones; preferably CH ₃ . The number and position of the substituents are not particularly limited; preferably, the number of the substituents is one, and the position of the substituent is preferably the 4-position.

The alkoxy group for the substituent may be a straight-chain or branched one;
CH _3. The number and position of the substituents are not particularly limited, but the number of the substituents is preferably one, and the position of the substituent is preferably the 4-position. Examples of the alkylthio group for the substituent include a straight-chain or branched one; preferably SCH ₃ . The number and position of the substituents are not particularly limited, but the number of the substituents is preferably one, and the position of the substituent is preferably the 4-position. Examples of the haloalkoxy group for the substituent include straight-chain or branched ones having a halogen atom such as a chlorine atom, an iodine atom, a bromine atom, and a fluorine atom; preferably those having a fluorine atom. More preferably OCH ₂ CF ₃ , OCF ₃ , OCH
F ₂ and OCBrF ₂ . The number and position of the substituents are not particularly limited, but the number of the substituents is preferably one, and the position of the substituent is preferably the 4-position.

Examples of the haloalkylsulfonyloxy group for the substituent include straight-chain or branched ones having a halogen atom such as a chlorine atom, an iodine atom, a bromine atom and a fluorine atom; ₂ C
F is _3. The number and position of the substituents are not particularly limited, but the number of the substituents is preferably one, and the position of the substituent is preferably the 4-position. The alkylsulfonyloxy group for the substituent may be straight-chain or branched; preferably, it is OSO ₂ CH ₃ . The number and position of the substituents are not particularly limited, but the number of the substituents is preferably one, and the position of the substituent is preferably the 4-position. Examples of the alkyl group having 1 to 8 carbon atoms include linear or branched ones; preferably, the alkyl group has 1 to 6 carbon atoms;
More preferably, CH ₃ , C ₂ H ₅ , nC ₃ H ₇ , i
_{-C 3 H 7, n-C} 4 H 9, i-C 4 H 9, t-C 4 H
₉ and the like. Examples of the haloalkyl group having 1 to 4 carbon atoms include straight-chain or branched haloalkyl groups having a halogen atom such as a chlorine atom, an iodine atom, a bromine atom, and a fluorine atom; ₃ .

[R ² ] Examples of R ² include a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group, and a halogen atom. In the compound (1a), a hydrogen atom, An alkyl group, a cyano group and a halogen atom; in the compound (1b), preferably a hydrogen atom and an alkyl group; in the compound (1c), preferably a hydrogen atom; and in a compound (2), preferably a hydrogen atom ,
It is an alkyl group. Examples of the alkyl group and the halogen atom include the same as those described for R ¹ ; preferably, the alkyl group is CH ₃ .

[R ³ ] Examples of R ³ include a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom and the like; in the case of compound (1a), preferably a hydrogen atom, an alkyl group, A halogen atom; a compound (1
In b), a hydrogen atom or an alkyl group is preferable; in compound (1c), a hydrogen atom is preferable; in compound (2), a hydrogen atom or an alkyl group is preferable.
Examples of the alkyl group and the halogen atom include the same as those described for R ¹ ;
The alkyl group is CH ₃ and the halogen atom is a fluorine atom.

[R ⁴ ] R ⁴ is a group having 1 to 8 carbon atoms.
Alkyl groups, alkenyl groups having 2 to 5 carbon atoms,
A cycloalkyl group having 3 to 8 carbon atoms, 2 carbon atoms
-5 alkynyl groups, phenyl groups, benzyl groups, phenethyl groups, haloalkyl groups having 1-4 carbon atoms, haloalkenyl groups having 2-6 carbon atoms, 1-4 carbon atoms
Alkylsulfonyl groups, haloalkylsulfonyl groups having 1 to 4 carbon atoms, cyano group, A ¹ COOR ¹⁰ ,
Hydrogen atom, A ¹ OR ¹⁰ , COA ¹ OR ¹⁰ , COR
¹⁰ , a cyanoalkyl group and the like (A
¹ represents 1-4 alkylene group having carbon ^{atoms; R 10}
Represents an alkyl group having 1 to 4 carbon atoms. )

R ⁴ in the compound (1) is preferably an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, and 3 to 8 carbon atoms in the compound (1a). Cycloalkyl group, alkynyl group having 2 to 5 carbon atoms, phenyl group, benzyl group, phenethyl group, haloalkyl group having 1 to 4 carbon atoms, haloalkenyl group having 2 to 6 carbon atoms, carbon atom An alkylsulfonyl group having 1 to 4 carbon atoms, a haloalkylsulfonyl group having 1 to 4 carbon atoms, a cyano group, A ¹ COOR ¹⁰ , a hydrogen atom, A ¹ OR ¹⁰ , COA ¹ OR ¹⁰ , a cyanoalkyl group; In the compound (1b), an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group, Compound (1c), an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, phenyl And haloalkyl groups having 1 to 4 carbon atoms.

R ⁴ in the compound (2) is preferably an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, Alkynyl group having 2 to 5 carbon atoms, phenyl group, benzyl group, phenethyl group, 1 to 4 carbon atoms
Haloalkyl groups, haloalkenyl groups having 2 to 6 carbon atoms, alkylsulfonyl groups having 1 to 4 carbon atoms,
A cyano group, a hydrogen atom, CSOR ^10, or the like cyanoalkyl group. Examples of the alkyl group include a linear or branched alkyl group; preferably an alkyl group having 1 to 4 carbon atoms; and more preferably CH ₃ or C _{2.
H 5, n-C 3 H} 7, i-C 3 H 7, n-C 4 H 9, s
-C is a _{4 H 9, t-C 4} H 9. Examples of the alkenyl group include a linear or branched one;
Preferably it has 3 carbon atoms; more preferably CH ₂ CH ＝ CH ₂ . Cycloalkyl groups preferably have 3 to 6 carbon atoms; more preferably have 5 or 6 carbon atoms.

Examples of the alkynyl group include linear or branched ones; preferably those having three carbon atoms; more preferably CH ₂ C≡CH
It is. Examples of the phenyl group include those that are unsubstituted or have a halogen atom or an alkyl group having 1 to 4 carbon atoms as a substituent. The phenyl group in compound (1b) and compound (1c) is preferably unsubstituted. Examples of the alkyl group and the halogen atom for the substituent of the phenyl group include the same as those described for R ¹ ; preferably, the alkyl group is CH ₃ and the halogen atom is a chlorine atom.
The position of the substituent is not particularly limited, but is preferably 4-position.

Examples of the haloalkyl group include those in which the alkyl is linear or branched and has a halogen atom such as a chlorine atom, an iodine atom, a bromine atom, and a fluorine atom; It has 1 to 4 chlorine atoms, bromine atoms and fluorine atoms. And as a preferable haloalkyl group, CH
F ₂ , CF ₃ , CH ₂ CF ₃ , CH ₂ CCl ₃ , CH ₂
C ₂ F ₅ , CH (CF ₃ ) ₂ , CBrF ₂ , CHFCH
F ₂ , CF ₂ CFClH, CF ₂ CHFCF ₃ , CH _{2
CH 2 CF 3, CH 2 Cl} , and the like can be illustrated CF 2 CHClF; more preferably, _{CHF 2,} CH 2
CF ₃ , CF ₃ , CH ₂ Cl, CF ₂ CHClF and the like. As the haloalkenyl group, alkenyl is linear or branched, and includes a chlorine atom, an iodine atom, a bromine atom,
Examples thereof include those having a halogen atom such as a fluorine atom; preferably those having 2 to 5 carbon atoms and having a fluorine atom; more preferably CH = CH-CF = CF ₂ , CF = CFCF ₃ , CF =
CHF.

Examples of the alkylsulfonyl group include those in which alkyl is linear or branched; preferably, it is SO ₂ CH ₃ . Examples of the haloalkylsulfonyl group include those in which alkyl is linear or branched and having a halogen atom such as a chlorine atom, an iodine atom, a bromine atom, and a fluorine atom; preferably, SO ₂ CF ₃ . . As A ¹ COOR ¹⁰ , A
¹ is an alkylene group having 1 to 4 carbon atoms, and R ¹⁰
Is a linear or branched alkyl group having 1 to 4 carbon atoms, preferably CH ₂
COOC ₂ H ₅ . A ¹ OR ¹⁰ is most preferably CH ₂ OCH ₃ . COA ¹ OR ¹⁰ is most preferably COCH ₂ OCH ₃ . COR ¹⁰ is
Most preferably, it is CSOC ₂ H ₅ . A cyanoalkyl group is most preferably CH ₂ CN.

[R ⁵ ] As R ⁵ , COOR ¹¹ , a hydrogen atom, COR ¹² , SO ₂ R ¹³ , SO ₂ NH
R ¹⁰ , SO ₂ NHCH ₂ Ph (Ph represents a phenyl group), SO ₂ NR ¹⁰ R ¹⁰ ′, CONHR
¹⁴ , CSNHR ¹⁵ , A ¹ COOR ¹⁰ , COA ² R
^{16, CONR 10 R 10 ',} CSSR 10, carbon atoms 1-8C alkyl group number 2 to 5 alkenyl group having a carbon atom, 2-5 alkynyl group carbon atoms, carbon atoms 3 to 8 Cycloalkyl groups, formyl groups, A ¹ OR
^{10 and the} like. Examples of COOR ¹¹ include those in which R ¹¹ is an alkyl group having 1 to 8 carbon atoms, a phenyl group, a benzyl group, or an alkenyl group having 3 to 5 carbon atoms; Preferably, the linear or branched carbon atom number is 1-6.
Number of things, more preferably of 1 to 4; Alkenyl groups, there may be mentioned a straight or branched, preferably -CH ₂ CH ₌ CH 2. As COR ¹² , R ¹² is an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms,
A cycloalkyl group having 3 to 8 carbon atoms, a phenyl group,
Alternatively, a pyridyl group can be used. R
The alkyl group in ¹² is preferably a linear or branched one having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.

The haloalkyl group for R ¹² includes
Alkyl is linear or branched, and includes those having a halogen atom such as a chlorine atom, an iodine atom, a bromine atom and a fluorine atom, and preferably have 1 to 4 carbon atoms and a fluorine atom. And more preferably CF ₃ . The cycloalkyl group for R ¹² preferably has 3 to 6 carbon atoms, and more preferably has 3 carbon atoms.
Examples of the phenyl group for R ¹² include unsubstituted or those having a halogen atom, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, or an alkoxy group having 1 to 4 carbon atoms as a substituent; The halogen atom of the group is preferably a fluorine atom or a chlorine atom; the alkyl group of the substituent is preferably CH ₃ ;
The alkoxy group for the substituent is preferably OCH ₃ .

The pyridyl group for R ¹² is unsubstituted or has a halogen atom as a substituent (2
-Pyridyl group, 3-pyridyl group or 4-pyridyl group)
And the halogen atom is preferably a chlorine atom. Examples of SO ₂ R ¹³ include those in which R ¹³ is an alkyl group having 1 to 4 carbon atoms or a haloalkyl group having 1 to 4 carbon atoms; The alkyl group is preferably linear. Or a haloalkyl group, more preferably CH ₃ ; as the haloalkyl group, an alkyl group having a straight or branched alkyl group and having a halogen atom such as a chlorine atom, an iodine atom, a bromine atom, and a fluorine atom. Examples thereof include those having 1 to 4 carbon atoms and a fluorine atom, and more preferably CF ₃ . SO ₂ NHR ¹⁰
Is most preferably SO ₂ NHCH ₃ , SO ₂ N
HC ₂ H _5, is _SO 2 _NHC 3 _{H 7.} SO ₂ NR
^{As 10} R ¹⁰ ′, most preferably, SO ₂ N (CH
₃ ) ₂ , SO ₂ N (CH ₃ ) C ₂ H ₅ .

[0056] As CONHR ^{14 may} include those ^{R 14} carbon atoms 1-8C alkyl, phenyl or having 1-4 haloalkyl group carbon atoms as an unsubstituted or substituted group is a phenylsulfonyl group The alkyl group is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. Examples of CSNHR ¹⁵ include those in which R ¹⁵ is an alkyl group having 1 to 4 carbon atoms or a phenyl group; the alkyl group is preferably a linear or branched one, and more preferably CH. ₃ . A ¹ COOR ¹⁰ is most preferably CH ₂ COOCH ₃ . COA ² R ¹⁶
A ² is an alkylene group having 1 to 10 carbon atoms, R ¹⁶ is an alkoxy group having 1 to 4 carbon atoms,
Alkylthio group having 1 to 4 carbon atoms, 2 to 2 carbon atoms
Examples thereof include those having 5 alkylcarbonyloxy groups, halogen atoms, imidazole groups, or alkylcarbonylamino groups having 2 to 5 carbon atoms, and pyridyl groups. The alkoxy group for R ¹⁶ is preferably a linear or branched one, and more preferably OCH ₃ .

As the alkylthio group for R ¹⁶ ,
Preferably of the linear or branched, more preferably from SCH _3. The alkylcarbonyloxy group for R ¹⁶ is preferably linear or branched, and more preferably OCOCH ₃ . R
Examples of the halogen atom in ¹⁶ include a chlorine atom, an iodine atom, a bromine atom, and a fluorine atom, and a chlorine atom is preferred. The alkylcarbonylamino group for R ¹⁶ is preferably a linear or branched one, and more preferably NHCOCH ₃
It is. CONR ¹⁰ R ¹⁰ ′ is most preferably CON (CH ₃ ) ₂ . The CSSR ^10, most preferably CSSCH _3. 1 carbon atom
Examples of the alkyl group having up to 8 alkyl groups are preferably linear or branched ones having 1 to 6 carbon atoms; more preferably those having 1 to 4 carbon atoms. . Alkenyl groups having 2 to 5 carbon atoms include straight-chain or branched ones; preferably an allyl group. As the alkynyl group having 2 to 5 carbon atoms, a linear or branched alkynyl group can be exemplified. Examples of the cycloalkyl group having 3 to 8 carbon atoms include a linear or branched cycloalkyl group. A
Most preferably, ¹ OR ¹⁰ is CH ₂ OC ₂ H ₅
It is.

[R ⁶ ] R ⁶ is a hydrogen atom, COO
R ¹⁷ , COR ¹⁸ , SO ² R ¹³ , COA ¹ R ¹⁹ ,
An alkyl group having 1 to 8 carbon atoms, COCOOR ¹⁰ ,
SCR ²⁰ R ²⁰ R ²⁰ , SNR ²¹ R ²¹ ′, A ¹ O
R ²¹ , CH ₂ OA ¹ OR ¹⁰ , formyl group, SNR
¹⁰ COOR ²¹ , SNR ¹⁰ A ¹ COOR ¹⁰ , haloalkyl group having 1 to 4 carbon atoms, benzyl group, A ¹ S
And the like can be mentioned R ^15. Examples of COOR ¹⁷ include those in which R ¹⁷ is an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, a phenyl group or a benzyl group. The alkyl group for R ¹⁷ is preferably a linear or branched one having 1 to 6 carbon atoms, more preferably 1 to 6 carbon atoms.
To four it is intended; the alkenyl group, preferably a _{CH 2 CH} = _CH 2. As COR ¹⁸ , R
¹⁸ is an alkyl group having 1 to 8 carbon atoms, 3 carbon atoms
~ 8 cycloalkyl groups, phenyl groups, 2 carbon atoms
And those having from 5 to 5 alkenyl groups or pyridyl groups.

The alkyl group for R ¹⁸ is preferably a linear or branched one having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms; Is a group having 3 to 6 carbon atoms, more preferably a group having 3 carbon atoms; the phenyl group is preferably unsubstituted or has a halogen atom at the 2- or 4-position as a substituent Things. SO ₂ R ¹³ is most preferably SO ₂ CF
₃ , SO ₂ CH ₃ . As COA ¹ R ¹⁹ , R
Those in which ¹⁹ is an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms or COOR ¹⁰ can be exemplified. The alkoxy group for R ¹⁹ is preferably a linear or branched one, more preferably OCH ₃ ; the alkylthio group is preferably a linear or branched one, and more preferably it is SCH _3; in COOR ^10, preferably COOC ₂ H _5. The alkyl group having 1 to 8 carbon atoms is preferably a linear or branched one having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.

COCOOR ¹⁰ is most preferably COCOOCH ₃ . SCR ²⁰ R ^{20 As} R ²⁰ , R ²⁰ is a chlorine atom, an iodine atom, a bromine atom or a fluorine atom, which may be different from each other; preferably SCCl ₃ . As SNR ²¹ R ²¹ ′,
R ²¹ and R ²¹ ′ may be different from each other and have 1 to 1 carbon atoms.
8 alkyl groups; the alkyl group is preferably a linear or branched one having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, most preferably _{SN (n-C 4 H 9} ) _2. As A ¹ OR ²¹ , A ¹ is preferably CH ₂ , (CH ₂ ) ₂ ;
²¹ is preferably a linear or branched carbon atom having 1 to 1
Six, more preferably one to four;
Most preferably _{CH 2 OCH 3, CH 2 O} (C 3 H 7 -
_{i), CH 2 O (C} 4 H 9 -n), a CH 2 _OC 2 _{H 5.} Most preferably, CH ₂ OA ¹ OR ¹⁰ is CH ₂ OC ₂ H ₄ OCH ₃ .

SNR ¹⁰ COOR ²¹ is most preferably SN (CH ₃ ) COOC ₄ H ₉ , SN (i-C
_{3 H 7) COOC 2 H 5} , SN (CH 3) COOC 2 H
₅ As SNR ¹⁰ A ¹ COOR ¹⁰ ′,
Most preferably _{SN (i-C 3 H 7} ) C 2 H 4 COOC
It is a ₂ H _5. The haloalkyl group having 1 to 4 carbon atoms can be a straight-chain or branched one; most preferably, CH ₂ CH ₂ F, CH ₂ CH ₂ B
r, CH ₂ CH ₂ Cl. As A ¹ SR ¹⁵ ,
A ¹ is alkylene having 1 to 4 carbon atoms;
¹⁵ but it can be mentioned a phenyl group or an alkyl group having 1 to 4 carbon atoms; the A ^1, C
H ₂ and (CH ₂ ) ₂ are preferred. As the alkyl group for R ¹⁵ , CH ₃ is preferable. Most preferred as A ¹ SR ₁₅ are CH ₂ CH ₂ SPh, CH ₂ SP
h, CH ₂ SCH ₃ . [R ⁵ and R ⁶ ] R ⁵ and R ⁶ are linked together with N to form 4
A 5-membered ring; preferably a 5-membered ring; more preferably a succinimide formed.

[R ⁷ ] R ⁷ is a group having 1 to 4 carbon atoms.
Alkyl groups, hydrogen atoms, phenyl groups and the like. Alkyl groups can include straight or branched ones; preferably CH ₃ , C ₂
It is H _5. [R ⁸ ] Examples of R ⁸ include an alkyl group having 1 to 4 carbon atoms and a hydrogen atom. Alkyl groups can be straight or branched; preferably CH ₃ , C ₂ H ₅ .

[R ⁹ ] R ⁹ is a group having 1 to 4 carbon atoms.
Alkyl group, phenyl group, alkynyl group having 2 to 5 carbon atoms, CHO, COR ¹⁰ , hydrogen atom and the like; in compound (1b), preferably alkyl group, phenyl group, alkynyl group In compound (1c), preferably an alkyl group, CHO, COR
^{10 is} a hydrogen atom. Examples of the alkyl group include a linear or branched one;
H ₃ and C ₂ H ₅ . Alkynyl groups can include straight or branched ones; preferably CH ₂ C≡CH. COR ¹⁰ is most preferably COCH ₃ .

[X] X is S, SO, SO ₂ ,
O, NR ^{22 and the} like; compound (1
In b) and compound (1c), S is preferred. N
The R ^22, can be exemplified by R ²² is a 2-5 alkylcarbonyl group having a carbon atom, a formyl group, a hydrogen atom or alkyl of 1 to 4 carbon atoms group;
The alkylcarbonyl group is preferably a linear or branched one, more preferably COCH ₃ ; the alkyl group is preferably a linear or branched one, and more preferably CH _3. It is.

Compound (1) also includes geometric isomers and mixtures thereof. As the compound (1), compounds obtained by combining the above-mentioned various substituents can be mentioned, and preferable compounds from the viewpoint of drug efficacy are as follows. (1) R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms, and R ⁵ and R ⁶ are linked together with N to form 4 A compound (1a) which forms an 8-membered ring and X is S; (2) R ¹ is a phenyl group, R ² , R ³ and R ⁶ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is COOR ¹¹ , X Is a compound (1a). (3) R ¹ is a phenyl group, R ² and R ⁶ are hydrogen atoms, R ³ is an alkyl group having 1 to 4 carbon atoms, and R ⁴ is an alkyl group having 1 to 8 carbon atoms. And R is
Compound (1) wherein ⁵ is COOR ¹¹ and X is S
a). (4) R ¹ is a phenyl group, and R ² has 1 to 1 carbon atoms.
4 alkyl groups, R ³ and R ⁶ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms,
Compound (1) wherein ⁵ is COOR ¹¹ and X is S
a).

(5) R ¹ is a phenyl group, and R ² and R
³ and R ⁶ are hydrogen atoms, and R ⁴ has 2 to 5 carbon atoms.
Alkenyl groups, R5 is COOR ¹¹ ;
Compound (1a) wherein X is S. (6) R ¹ is a phenyl group, R ² , R ³ and R ⁶ are hydrogen atoms, R ⁴ is a cycloalkyl group having 3 to 8 carbon atoms, R ⁵ is COOR ¹¹ ; Compound (1a) wherein X is S. (7) R ¹ is a phenyl group, R ² , R ³ and R ⁶ are hydrogen atoms, R ⁴ is an alkynyl group having 2 to 5 carbon atoms, R ⁵ is COOR ¹¹ , X Is a compound (1a). (8) R ¹ and R ⁴ are phenyl groups, R ² , R ³ and R ⁶ are hydrogen atoms, R ⁵ is COOR ¹¹ ,
Compound (1a) wherein X is S.

(9) R ¹ is a phenyl group, and R ² and R
Compound (1a) in which ³ and R ⁶ are hydrogen atoms, R ^{4 is a} benzyl group, R ⁵ is COOR ¹¹ , and X is S. (10) R ¹ is a phenyl group, and R ² , R ³ and R ⁶
Is a hydrogen atom, R ⁴ is a haloalkyl group having 1 to 4 carbon atoms, R ⁵ is COOR ¹¹ and X is S (1a). (11) R ¹ is a phenyl group, and R ^{2 to} R ⁴ and R ⁶
Is a hydrogen atom, R ⁵ is COOR ¹¹ , X is S
Compound (1a) which is (12) R ¹ is a phenyl group, and R ² , R ³ and R ⁶
Is a hydrogen atom, R ⁴ is A ¹ OR ¹⁰ ; R ⁵ is COOR ¹¹ ; and X is S (1a). (13) R ¹ is a phenyl group, and R ² , R ³ and R ⁶
Is a hydrogen atom; R ⁴ is COA ¹ OR ¹⁰ ;
Compound (1) wherein ⁵ is COOR ¹¹ and X is S
a). (14) Compounds wherein R ¹ is a phenyl group, R ² , R ³ , R ⁵ and R ⁶ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms, and X is S (1a).

(15) R ¹ is a phenyl group, and R ² ,
A compound (1a) in which R ³ , R ⁵ and R ⁶ are hydrogen atoms, R ⁴ is a haloalkyl group having 1 to 4 carbon atoms, and X is S. (16) R ¹ is a phenyl group, and R ² , R ³ and R ⁶
Is a hydrogen atom, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is COR ¹² and X is S (1a). (17) R ¹ is a phenyl group, and R ² , R ³ and R ⁶
Is a hydrogen atom, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is CONHR ¹⁴ , and X is S (1a). (18) R ¹ is a phenyl group, and R ² , R ³ and R ⁶
There is a hydrogen atom, ^{R 4} is alkyl group having 1 to 8 carbon atoms atoms, ^{R 5} is ^COA 2 ^{R 16,} compounds wherein X is S (1a). (19) R ¹ is a phenyl group, and R ² , R ³ and R ⁶
Is a hydrogen atom, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is CSSR ¹⁰ and X is S (1a).

(20) R ¹ is a phenyl group, and R ² ,
R ³ and R ⁶ are hydrogen atoms, and R ⁴ has 1 to 1 carbon atoms.
8 alkyl groups, R ⁵ is a formyl group, X
Is a compound (1a). (21) R ¹ is a phenyl group, and R ² , R ³ and R ⁶
Is a hydrogen atom, R ⁴ is a haloalkenyl group having 2 to 6 carbon atoms, R ⁵ is COOR ¹¹ , X is S
Compound (1a) which is (22) R ¹ is a phenyl group, and R ² , R ³ and R ⁶
Is a hydrogen atom, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is SO ₂ NHR ¹⁰ and X is S (1a). (23) R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is COOR ¹¹ , R ⁶ is COOR ¹⁷
And X is S (1a). (24) R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is a haloalkyl group having 1 to 4 carbon atoms, R ⁵ is COOR ¹¹ and R ⁶ is COOR
^17. Compound (1a), wherein X is S.

(25) R ¹ is a phenyl group, and R ² ,
R ³ and R ⁵ are hydrogen atoms, and R ⁴ has 1 to 1 carbon atoms.
8 alkyl groups, R ⁶ is COOR ¹⁷ ,
Compound (1a) wherein X is S. (26) ^{R 1} is a phenyl group, ^{R 2} and ^{R 3} are hydrogen atoms, ^{R 4} is alkyl group having 1 to 8 carbon atoms atoms, ^{R 5} is ^A 1 ^{OR 10, R 6} Is COOR ¹⁷
And X is S (1a).

(27) R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is COOR ¹¹ , R Compound (1a) wherein ⁶ is COR ¹⁸ and X is S. (28) R ¹ is a phenyl group, and R ² , R ³ and R ⁵
Is a hydrogen atom, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁶ is COR ¹⁸ , and X is S (1a). (29) R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is COR ¹² and R ⁶ is COR ^18. Compound (1a), wherein X is S. (30) R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ and R ⁶ are SO ₂ R ¹³ , A compound (1a) wherein X is S.

(31) R ¹ is a phenyl group, and R ² ,
R ³ and R ⁵ are hydrogen atoms, and R ⁴ has 1 to 1 carbon atoms.
8 alkyl groups, R ⁶ is SO ₂ R ¹³ ,
Compound (1a) wherein X is S. (32) R ¹ is a phenyl group, and R ² , R ³ and R ⁵
Is a hydrogen atom, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁶ is COA ¹ R ¹⁹ , and X is S (1a). (33) R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is COOR ¹¹ and R ⁶ is carbon 1 atom
A compound having 1 to 4 alkyl groups and X is S (1
a). (34) R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is COR ¹² and R ⁶ is carbon atom 1 atom
A compound (1) in which four alkyl groups and X is S
a).

(35) R ¹ is a phenyl group, and R ² ,
R ³ and R ⁵ are hydrogen atoms, and R ⁴ has 1 to 1 carbon atoms.
A compound (1a) having 8 alkyl groups, wherein R ⁶ is COCOOR ¹⁰ and X is S. (36) R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is COOR ¹¹ , R ⁶ is SCR ²⁰ R
^{20 A} compound (1a) wherein R is ²⁰ and X is S. (37) R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is COOR ¹¹ , R ⁶ is SNR ²¹ R
^A compound (1a) wherein X is S; (38) R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is COOR ¹¹ and R ⁶ is CH ₂ OR
^{10. A} compound (1a) wherein X is S.

(39) R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is COOR ¹¹ , R ⁶ is CH ₂ OA ¹ OR ¹⁰ and a compound (1) wherein X is S
a). (40) R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is COOR ¹¹ and R ⁶ is formyl A compound of the formula (1a), wherein X is S; (41) R ¹ is a phenyl group, and R ² , R ³ and R ⁶
Is a hydrogen atom, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is COOR ¹¹ , and X is SO (1a). (42) R ¹ is a phenyl group, and R ² , R ³ and R ⁶
Is a hydrogen atom, R ⁴ is a cycloalkyl group having 3 to 8 carbon atoms, R ⁵ is COOR ¹¹ , X is S
Compound (1a) which is O.

(43) R ¹ is a phenyl group, and R ² ,
R ³ and R ⁶ are hydrogen atoms, and R ⁴ has 1 to 1 carbon atoms.
A compound (1a) having 4 haloalkyl groups, R ⁵ is COOR ¹¹ , and X is SO. (44) R ¹ is a phenyl group, and R ² is a group having 1 carbon atom
R ³ and R ⁶ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms,
Compounds (1) wherein R ⁵ is COOR ¹¹ and X is SO
a). (45) R ¹ is a phenyl group, and R ² , R ³ and R ⁶
Is a hydrogen atom, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is COR ¹² and X is SO. (46) R ¹ is a phenyl group, and R ² , R ³ and R ⁶
Is a hydrogen atom, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is a formyl group, and X is SO (1a).

(47) R ¹ is a phenyl group, and R ² ,
Compound (1a) in which R ³ , R ⁵ and R ⁶ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms, and X is SO. (48) R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is COOR ¹¹ , R ⁶ is COOR ¹⁷
And X is SO (1a). (49) R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is COR ¹² , R ⁶ is COR ^18. Compound (1a), wherein X is SO. (50) R ¹ is a phenyl group, and R ² , R ³ and R ⁶
Is a hydrogen atom, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is COOR ¹¹ , and X is SO ₂ (1a).

(51) R ¹ is a phenyl group, R ² is an alkyl group having 1 to 4 carbon atoms, and R ³ and R ⁶
Is a hydrogen atom, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is COOR ¹¹ , and X is SO ₂ (1a). (52) R ¹ is a phenyl group, and R ² , R ³ and R ⁶
Is a hydrogen atom, R ⁴ is a haloalkyl group having 1 to 4 carbon atoms, R ⁵ is COOR ¹¹ , X is SO
Compound (1a), which is ₂ . (53) R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is COOR ¹¹ and R ⁶ is COOR ¹⁷
And X is SO ₂ (1a). (54) R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is COOR ¹¹ and R ⁶ is COR ^18. Compound (1a), wherein X is SO ₂ . (55) R ¹ is a phenyl group, and R ² , R ³ and R ⁶
Is a hydrogen atom, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is COR ¹² and X is SO ₂ (1a).

(56) R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is COR ¹² , R ⁶ is C
A compound (1a) which is OR ¹⁸ and X is SO ₂ . (57) R ¹ is a phenyl group, and R ² , R ³ and R ⁶
Is a hydrogen atom, R ⁴ is a haloalkyl group having 1 to 4 carbon atoms, R ⁵ is COOR ¹¹ and X is O. (1a). (58) R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is COOR ¹¹ and R ⁶ is SNR ¹⁰ C
A compound (1a) which is OOR ²¹ and X is S. (59) R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is COOR ¹¹ , R ⁶ is SNR ¹⁰ A
¹ COOR ¹⁰ ′, wherein X is S (1
a).

(60) R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is COOR ¹¹ , R ^A compound (1a) in which ⁶ is a haloalkyl group having 1 to 4 carbon atoms and X is S. (61) R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is COOR ¹¹ , R ⁶ is A ¹ SR ¹⁵
And X is S (1a). (62) R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is COR ¹² , R ⁶ is A Compound (1a) wherein ^{1 is} OR ²¹ and X is S. (63) R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is COR ¹² , R ⁶ is benzyl A compound of the formula (1a), wherein X is S; (64) R ¹ is a phenyl group, and R ² , R ³ and R ⁶
Is a hydrogen atom, R ⁴ is an alkyl group having 1 to 8 carbon atoms, R ⁵ is COR ¹² , R ⁶ is SO ₂ N
Compound (1a) which is HCH ₂ Ph and X is S.

(65) R ¹ is a phenyl group, and R ² ,
Compound (1a) in which R ³ and R ⁶ are a hydrogen atom, R ⁴ is a cyanohaloalkyl group, R ⁵ is COOR ¹¹ and X is S. (66) R ¹ is a phenyl group, R ² , R ³ , R ⁵ and R ⁶ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms, and X is SO ₂ Compound (1a). (67) R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 6 carbon atoms, and R ^{7 to} R ⁹ are 1 to 4 carbon atoms. (1b) wherein X is S. (68) R ¹ is a phenyl group, and R ² , R ³ and R ⁷
Is a hydrogen atom, R ⁴ is an alkyl group having 1 to 6 carbon atoms, R ⁸ and R ⁹ are an alkyl group having 1 to 4 carbon atoms, and X is S (1b). . (69) R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is a haloalkyl group having 1 to 4 carbon atoms, and R ^{7 to} R ⁹ are 1 to 4 carbon atoms. (1b) wherein X is S.

More preferable examples of the compound (1) include those having the preferable substituents described above. Specific compounds (1) include compounds [(1a-1) to (1a-1) described in Tables 6 to 39 described below.
(1a-17), (1a-28), (1a-29),
(1a-32), (1a-35), (1a-38)-
(1a-43), (1a-45) to (1a-48),
(1a-50), (1a-52), (1a-53),
(1a-55), (1a-58), (1a-63),
(1a-64), (1a-68), (1a-73),
(1a-75), (1a-78), (1a-80)-
(1a-83), (1a-83), (1a-89),
(1a-95), (1a-98), (1a-100),
(1a-107), (1a-123), (1a-13)
4) to (1a-141), (1a-147), (1a-
164), (1a-168), (1a-169), (1
a-171), (1a-172), (1a-174)-
(1a-176), (1a-178) to (1a-18)
0), (1a-185) to (1a-188), (1a-
190), (1a-192), (1a-195), (1
a-196), (1a-199) to (1a-233),
(1a-235) to (1a-255), (1a-26)
6), (1a-273), (1a-275), (1a-
281), (1a-283) to (1a-286), (1
a-293), (1a-303) to (1a-306),
(1a-319), (1a-321), (1a-32)
2), (1a-334) to (1a-348), (1a-
350)-(1a-362), (1a-365)-(1
a-387), (1a-389), (1a-390)
(1a-427), (1b-1), (1b-2), (1
b-13), (1b-20), (1b-37), (1b
-38)].

[Compound (2 ')] As the compound (2'), those obtained by combining the substituents described above can be mentioned, and the following are preferable. (A) The compound wherein R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 8 carbon atoms, and X is S. (B) The compound wherein R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 4 carbon atoms, and X is SO. (C) The compound wherein R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 4 carbon atoms, and X is SO ₂ . (D) The compound wherein R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is an alkenyl group having 2 to 5 carbon atoms, and X is S. (E) The compound wherein R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is a cycloalkyl group having 3 to 8 carbon atoms, and X is S. (F) The compound wherein R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is a benzyl group, and X is S. (G) The compound wherein R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is a haloalkyl group having 1 to 4 carbon atoms, and X is S.

(H) Compounds wherein R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is a haloalkyl group having 1 to 4 carbon atoms, and X is O. (I) A compound wherein R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is an alkyl group having 1 to 4 carbon atoms, and X is NH. (J) The compound wherein R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is CSO- (alkyl group having 1 to 4 carbon atoms), and X is S. (K) The compound wherein R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is an alkynyl group having 2 to 5 carbon atoms, and X is S. Specific examples of the compound (2 ′) include the compounds (2-1) to (2-79) described in Tables 1 to 5 described below. [Synthesis of Compound (1)] As a preferred embodiment for producing Compound (1), in addition to Production Methods 1 to 4 described as the third to sixth inventions, the following four (Production Methods 5 to 8) Can be mentioned. Production method 5 is based on the following formula (4):

[0074]

Embedded image

(Wherein R ^{1 to} R ⁴ and X are as defined above) and the following formula (7):

[0076]

Embedded image

(Wherein, R ^{7 to} R ⁹ have the same meanings as described above), and the compound (1b) is produced by reacting the compound (7). Manufacturing method 6
Is a compound (4) and the following formula (8):

[0078]

Embedded image

(Wherein, R ^{7 to} R ⁹ have the same meanings as described above), by reacting with the compound (8) represented by the following formula (1b):

[0080]

Embedded image

(Wherein R ^{1 to} R ⁴ , R ^{7 to} R ⁹ and X
Is as defined above. )) To produce the compound (1b). Production method 7 comprises compound (4) and the following formula (9):

[0082]

Embedded image

(Wherein, R ¹⁰ is as defined above. W
Represents an oxygen atom or a sulfur atom. Is reacted with a compound (9) represented by the following formula (1a-i).
i):

[0084]

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Wherein R ^{1 to} R ⁴ , R ¹⁰ , W and X
Is as defined above. (1a-i)
This is a method for producing i). Production method 8 is a method for preparing compound (4)
And the following equation (10):

[0086]

Embedded image

(Wherein R ¹³ has the same meaning as described above; Q represents a halogen atom, OSO ₂ R ¹² or OH). iii):

[0088]

Embedded image

(Wherein R ^{1 to} R ⁴ , R ¹³ and X are as defined above) (1a-iii)
It is a method of manufacturing. [Synthesis of Compound (2)] The following five types (Synthesis Methods 1 to 5) can be mentioned as preferred embodiments for synthesizing the intermediate represented by the above formula (2). The synthesis method 1 is based on the following formula (11):

[0090]

Embedded image

(Wherein R ^{1 to} R ³ have the same meanings as described above), and an alkyl halide is reacted to give the following formula (2a):

[0092]

Embedded image

(Wherein R ^{1 to} R ⁴ have the same meanings as described above). This is a method for synthesizing the compound (2) of the compound (2a) shown below. The synthesis method 2 is based on the following formula (12):

[0094]

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(Wherein, R ^{1 to} R ³ have the same meanings as described above; Ha ¹ represents a halogen atom). This is a method for synthesizing the compound (2) shown below. In the synthesis method 3, the compound (12) is reacted with an alcohol to obtain the following formula (2b):

[0096]

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(Wherein, R ^{1 to} R ⁴ have the same meanings as described above). In the synthesis method 4, the compound (12) is reacted with an amine to obtain a compound represented by the following formula (2c):

[0098]

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(Wherein X ² represents NH or NR ^10. R ^{1 to} R ⁴ and R ¹⁰ have the same meanings as described above). Is the way. Synthetic method 5 comprises reacting compound (2a) with an oxidizing agent to obtain the following formula (2d):

[0100]

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(Wherein R ^{1 to} R ⁴ have the same meaning as described above; m is 1 or 2).
This is a method for synthesizing the compound (2). Production methods 1 to 8 of compound (1) and synthesis methods 1 to 5 of compound (2) are described below.
Will be described in more detail. [Production Method 1] As shown below, compound (1a) [in the case where Y is NR ⁵ R ⁶ in compound (1), by dehydrating and condensing compound (2) and compound (3) in a solvent. ] Is manufactured. Further, the reaction can be promoted by using an acidic catalyst.

[0102]

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(In the formula, R ^{1 to} R ⁶ and X have the same meanings as described above.) The type of the solvent is not particularly limited as long as it does not directly participate in the reaction. For example, benzene, toluene, Xylene, methylnaphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, dichloroethane, trichlorethylene, cyclohexane and other chlorinated aromatic, aliphatic and cycloaliphatic Hydrocarbons: ethers such as diethyl ether, tetrahydrofuran, dioxane; alcohols such as methanol, ethanol, ethylene glycol, etc .; amides such as N, N-dimethylformamide, N, N-dimethylacetamide Acetonitrile, propionitrile, etc. Such nitriles; 1,3-dimethyl-2-imidazolidinone; dimethyl sulfoxide; and mixtures of the above-mentioned solvents.

The amount of the solvent used is such that the compound (2) is 1-80.
% By weight; preferably from 1 to 50% by weight. Examples of the type of the acidic catalyst include mineral acids such as hydrochloric acid, sulfuric acid and nitric acid; organic acids such as formic acid, acetic acid, propionic acid, methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid; pyridine hydrochloride, triethylamine hydrochloride Acid addition salts of amines such as salts; and Lewis acids such as boron trifluoride ether complex. The amount of the acidic catalyst to be used is 0.001 to 1-fold the molar amount of the compound (2). The reaction temperature is not particularly limited, but is within a temperature range from room temperature to the boiling point of the solvent to be used; a temperature of the boiling point or lower is preferable. The reaction time varies depending on the above concentration and temperature; it is usually 0.3 to 24 hours.

The amount of the starting compound used is 0.5 to 2 moles of the compound (3) with respect to the compound (2); preferably 0.8 to 1.5 moles. As the compound (2), the compounds [(1a-1) to
(1a-427)], compounds [(1b-1) to (1b-
38)] and compound (2) comprising substituents R ^{1 to} R ⁴ corresponding to compounds [(1c-1) to (1c-27)] {compound [(2) _(1a-1) ~ (2)
_(1a-427) ], compound [(2) _(1b-1) to
(2) _(1b-38) ], compound [(2) _(1c-1)
To (2) _(1c-27) ]. For example, in the compound (2) _(1a-1) , R ^{1 in the} formula represented by the compound (2) is a 4-chlorophenyl group, R ² and R ³ are hydrogen atoms, R ⁴ is CH ₃ , and X is S. is there. ｝.

As the compound (3), for example, if a commercially available product cannot be used, Chemiche Belic
Hte, 47 , 2183 (1914), a method of reacting hydrazine with diethyl carbonate, J. Am. Or
g. Chem. , 34 , 1713 (1969), a method of reacting hydrazine with isocyanate,
Or J. Am. Chem. Soc. , 72 , 2762
It can be produced and used by a method of reacting hydrazine with dialkyl sulfate described in (1950). As the compound (3), the compounds [(1a-1) to (1a-427)], the compounds [(1b-1) to (1b-48)], and the compound [(1
c-1) to (1c-27)], and a compound (3) consisting of substituents R ⁵ and R ⁶ corresponding to the compounds [(3) _(1a-1 ) to (3) _{(1a- 427)} ],
Compound [(3) _(1b-1) to
(3) ( _1b-48) ], compound [(3) _(1c-1)
To (3) _(1c-27) ]. For example, in the compound (3) _(1a-1) , R ^{5 in the} formula represented by the compound (3) is COOC ₂ H ₅ and R ⁶ is a hydrogen atom. ]. [Production Method 2] Compound (1a-i) and compound (1a-i) are reacted by reacting compound (4) with compound (5) in a solvent in the presence of a base and / or a condensing agent as shown below. 1a-vi).

[0107]

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(Wherein R ^{1 to} R ⁴ , R ²³ , X and Z
Is as defined above. Examples of the condensing agent include dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, carbonyldiimidazole, diethyl cyanophosphate and the like. The type of the solvent is not particularly limited as long as it is a non-aqueous solvent, but preferably, methylene chloride, chloroform, toluene, benzene, THF, ethyl ether and the like are used. The amount of the solvent to be used may be such that the amount of the compound (4) is 1 to 80% by weight; however, it is preferably 1 to 50% by weight. The ratio of the compound (4) and the condensing agent to be used is preferably 1 to 2 mol, preferably 1 to 1.1 mol, per 1 mol of the compound (5). The reaction temperature is not particularly limited, but is preferably 0 to room temperature. Examples of the type of base include triethylamine, sodium hydride, 1,8-diazabicyclo [5.
4.0] undec-7-ene, sodium methoxide,
Sodium ethoxide, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate and the like can be used.
The amount of use is 1 to 1 mol of compound (5).
Although it can be added at a ratio of 2 mol, preferably 1 to
1.2 mol is good. The reaction time varies depending on the above concentration and temperature, but can be carried out by stirring for 0.5 to 6 hours.

The amount of the base to be used is 0.001 to 5 times the molar amount of the compound (4). The amount of raw material compound used is
Compound (5) is 0.5 to 50 moles per mole of Compound (4); preferably 0.8 to 10 moles. Compound (5) is, for example, commercially available acetyl chloride,
Acetic anhydride, benzoyl chloride, ethyl chloroformate and the like can be used. [Production Method 3] As shown below, compound (1a) is produced by reacting compound (4-i) with compound (6) in a solvent in the presence of a base.

[0110]

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(In the formula, R ^{1 to} R ⁶ , X and G have the same meanings as described above.) As the type of the solvent, in addition to those described in Production Method 1,
Ketones such as acetone and methyl ethyl ketone can be used. The amount of the solvent to be used may be such that the compound (4-i) is used in an amount of 1 to 80% by weight; preferably, 1 to 50% by weight. As the type of base,
There is no particular limitation, and for example, triethylamine, pyridine, 4-N, N-dimethylaminopyridine, N, N-dimethylaniline, 1,8-diazabicyclo [5.4.
0] organic bases such as undec-7-ene; alkali metal alkoxides such as sodium methoxide and sodium ethoxide; sodium amide, sodium hydroxide,
Inorganic bases such as potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate and the like: butyllithium, lithium diisopropylamide, bistrimethylsilyllithium amide and the like.

The amount of the base to be used is 0.001 to 5 moles compared to Compound (4-i). The reaction temperature is not particularly limited, but is in a temperature range of -30 ° C to 200 ° C;
Preferably it is 0-80 degreeC. The reaction time varies depending on the concentration and temperature described above; it is usually 0.1 to 100 hours; preferably 0.3 to 24 hours. The amount of the starting compound used is 0.5 to 50 times the molar amount of the compound (6) with respect to the compound (4-i);
It is 8 to 10 times mol. Compound (6) is, for example, commercially available acetyl chloride, methyl iodide, methoxymethyl chloride, acetic anhydride, benzoyl chloride, methoxyacetyl chloride, chloroacetyl chloride,
Methanesulfonyl chloride, trifluoroacetic anhydride,
Methyl chloroformate, ethyl chloroformate, phenyl chloroformate, trichloromethylsulfenyl chloride and the like can be used. Also, J.I. Chem. So
c. , 1932 , 1040, etc. can be used, which can be obtained by reacting disulfide with chlorine or sulfuryl chloride by the method described in the literature.

[Production Method 4] As shown below, compound (1)
a-iv) is reacted in a solvent in the presence of an oxidizing agent to give compound (1a-v) [in compound (1), when Y is NR ⁵ R ⁶ and X is SO or SO ₂ ]. To manufacture.

[0114]

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(Wherein R ^{1 to} R ⁶ and m have the same meanings as described above).
Ketones such as acetone and methyl ethyl ketone can be used. The amount of the solvent used is determined based on the compound (1a-i
v) can be used to be from 1 to 80% by weight; however, 1 to 50% by weight is preferred. Examples of the oxidizing agent include peracids such as hydrogen peroxide, peracetic acid, perbenzoic acid, and m-chloroperbenzoic acid; sodium metaperiodate; hydroperoxide; ozone; selenium dioxide; chromic acid; Acyl; iodine; N-bromosuccinimide; iodosylbenzene; sulfuryl chloride; hydrous silica gel; t-butyl hypochlorite; oxone (Aldrich potassium peroxymonosulfate) and the like. The amount of the oxidizing agent used is the same as that of the compound (1a-i
It is 0.01 to 5 moles with respect to v). The reaction temperature is
Although not particularly limited, it is in a temperature range of -80 to 100C; preferably -60 to 100C. The reaction time varies depending on the above concentration and temperature;
-100 hours; preferably 0.1-24 hours.

The compounds (1a-v) are described in Table 6 below.
[34] [(1a-4), (1a-5),
(1a-7), (1a-8), (1a-10), (1a
-11), (1a-13), (1a-14), (1a-
17), (1a-18), (1a-20), (1a-2)
1), (1a-23), (1a-24), (1a-2)
6), (1a-27), (1a-29), (1a-3)
0), (1a-33), (1a-34), (1a-3)
6), (1a-37), (1a-39) to (1a-4)
1), (1a-43), (1a-44), (1a-4)
6) to (1a-51), (1a-53), (1a-5)
4), (1a-56), (1a-57), (1a-5)
9) to (1a-61), (1a-63), (1a-6)
5) to (1a-67), (1a-69), (1a-7)
0), (1a-76), (1a-77), (1a-7)
9), (1a-80), (1a-82), (1a-8)
3), (1a-96), (1a-97), (1a-9)
9), (1a-105), (1a-106), (1a-
108), (1a-109), (1a-114), (1
a-115), (1a-117), (1a-118),
(1a-137) to (1a-139), (1a-18)
1) to (1a-184), (1a-186), (1a-
187), (1a-206), (1a-207), (1
a-209), (1a-214), (1a-215),
(1a-221), (1a-243), (1a-24)
4), (1a-251) to (1a-253), (1a-
255), (1a-261), (1a-262), (1
a-267) to (1a-270), (1a-272),
(1a-273), (1a-279), (1a-28)
7), (1a-288), (1a-291), (1a-
292), (1a-295), (1a-296), (1
a-304), (1a-305), (1a-307),
(1a-308), (1a-310), (1a-31)
1), (1a-316), (1a-317), (1a-
339), (1a-351), (1a-363), (1
a-364), (1a-367), (1a-368),
(1a-383), (1a-384), (1a-39)
3), (1a-398), (1a-399), (1a-
404), (1a-405), (1a-412) to (1)
a-415), (1a-421)] and the like.

[Production Method 5] As shown below, compound (1) is reacted with compound (7) in the presence of a condensing agent in the absence or presence of a solvent to give compound (1).
b) is manufactured.

[0118]

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(Wherein R ^{1 to} R ⁴ , R ^{7 to} R ⁹ and X
Is as defined above. As the type of the solvent, the same one as described in Production method 1 can be used. The amount of the solvent to be used may be such that the amount of the compound (4) is 1 to 80% by weight; however, it is preferably 1 to 50% by weight. Examples of the type of the condensing agent include organic chlorides such as tosyl chloride and pivaloyl chloride; Lewis acids such as triethyloxonium tetrafluoroborate and titanium tetrachloride; cyclohexylcarbodiimide, phosphorus pentachloride, polyphosphoric acid, and phosphorus oxychloride. Dehydrating agents and the like can be mentioned. The amount of the condensing agent to be used is 0.001 to 5 moles compared to Compound (4). The reaction temperature is not particularly limited.
Within the temperature range of 0 ° C; preferably between 50 and 150 ° C. The reaction time varies depending on the above concentration and temperature; it is usually 0.1 to 100 hours;
3 to 24 hours. The amount of the starting compound to be used is 0.5 to 50 times mol of compound (7) relative to compound (4); preferably 0.8 to 10 times mol.

Compound (7) is commercially available, for example, N, N-
Dimethylformamide and the like can be used. Examples of the compound (7) include a compound (7) consisting of substituents R ⁷ , R ⁸ and R ⁹ corresponding to the compounds (1b-1) to (1b-48) shown in Tables 35 to 37 described below. [Compound (7) _(1b-1) to (7)
_(1b-48) . For example, compound (7)
_(1b-1) is a compound represented by the formula (7):
⁷ , R ⁸ and R ⁹ are CH ₃ . ]. [Production Method 6] As shown below, compound (4) is reacted with compound (8) without or in a solvent to give compound (1b) [in compound (1), wherein Y is N
= CR ⁷ NR ⁸ R ⁹ ].

[0121]

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Wherein R ^{1 to} R ⁴ , R ^{7 to} R ⁹ and X
Is as defined above. As the type of the solvent, the same one as described in Production method 1 can be used. The amount of the solvent used is 1 to 80% by weight of the compound (4): preferably 1 to 50%.
% By weight. The reaction temperature is not particularly limited, but is in a temperature range from room temperature to 200 ° C .;
0 ° C. The reaction time varies depending on the concentration and temperature described above; it is usually 0.1 to 100 hours; preferably 0.3 to 24 hours. The amount of the starting compound to be used is 0.5 to 50 times mol of compound (8) relative to compound (4); preferably 0.8 to 10 times mol. Compound (4) can be produced by reacting compound (2) with hydrazine as shown below, in the same manner as in the normal synthesis of hydrazone.

[0123]

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(Wherein R ^{1 to} R ⁴ and X have the same meanings as described above.) [Production methods 7 and 8] As shown below, compound (4) and compound [(9) or (10) ] In a solvent in the presence of a base to give a compound [(1a-i
i) or (1a-iii)].

[0125]

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(Wherein, R ^{1 to} R ⁴ , R ¹⁰ , R ¹³ ,
Q, W and X are as defined above. As the type of the solvent, the same one as described in Production method 1 can be used. The amount of the solvent to be used may be such that the amount of the compound (4) is 1 to 80% by weight; however, it is preferably 1 to 50% by weight. As the type of the base, the same one as described in Production method 2 can be used. The amount of the base to be used is 0.001 to 5 times the molar amount of the compound (4). The reaction temperature is not particularly limited, but is in a temperature range from room temperature to 200 ° C; preferably 50 to 150 ° C. The reaction time depends on the concentration,
It varies depending on the temperature; usually from 0.1 to 100 hours; preferably from 0.3 to 24 hours.

The amount of the starting compound used is 0.5 to 50 times mol of the compound ((9) or (10)) with respect to the compound (4); preferably 0.8 to 10 times mol. . As the compound (9), for example, commercially available products such as methyl isocyanate, phenyl isocyanate, phenyl isothiocyanate, and methyl isothiocyanate can be used. As the compound (10), for example, commercially available methanesulfonyl chloride, trifluoromethanesulfonyl chloride, methanesulfonic anhydride, trifluoromethanesulfonic anhydride, benzenesulfonic acid chloride and the like can be used.

After completion of the reaction, the target compound (1) produced as described above is subjected to ordinary post-treatments such as extraction, concentration, filtration and the like, and if necessary, recrystallization, various chromatographic techniques and the like. Can be appropriately purified by the above-mentioned means.
Compound (2) can be synthesized by the following five synthesis methods. (Synthesis Method 1) Compound (2) is reacted with compound (11) in the presence of a base to give compound (2).
a) [Compound (2) wherein X is S] is synthesized. As the type of the solvent, the same one as described in Production method 1 can be used. Examples of the alkyl halide include methyl iodide, ethyl iodide, propargyl bromide, and dichloromethane.
Compound (11) is, for example,

・ J. Org. Chem. , 27 , 93
(1962) Method of reacting benzyl halide with thiourea to give an isothiuronium salt, followed by treatment with a base. Org. Chem. , 34 , 4170 (196
9) A method in which benzyl halide is reacted with o-ethyl potassium dithiocarbonate to form a dithiocarbonate and then subjected to acidic hydrolysis. JP-A No. 62-294652. Reaction of benzyl halide with potassium hydrosulfide in the presence of a phase transfer catalyst. It can be manufactured by a method for causing the above.

As the compound (11), the following Tables 6 to 3
Those having R ^{1 to} R ³ shown in 9 can be mentioned. The combination of the compound (11) and the alkyl halide used may be any of the substituents R ^{1 to} R ⁴ shown in the compound (2).
Is made to correspond. The type of the base is not particularly limited. For example, triethylamine, pyridine, 4
Organic bases such as -N, N-dimethylaminopyridine, N, N-dimethylaniline, 1,8-diazabicyclo [5.4.0] undec-7-ene; alkali metal alkoxides such as sodium methoxide and sodium ethoxide Inorganic bases such as sodium amide, sodium hydride, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate; butyllithium, lithium diisopropylamide, bistrimethylsilyllithium amide, etc. Can be.

The amount of the base to be used is 0.001 to 5 moles compared to Compound (11). The amount of the solvent used is 1 to 80% by weight of compound (11); preferably 1 to 5%.
0% by weight. The reaction temperature is not particularly limited.
In the temperature range of ２００200 ° C .; preferably 5-50 ° C.
It is. The reaction time varies depending on the concentration and temperature described above; it is usually 0.1 to 100 hours; preferably 0.3 to 24 hours. The amount of the raw material compound used is such that the alkyl halide is 0.5 to 50 based on the compound (11).
It is a molar amount; preferably 0.8 to 10 times. Examples of the compound (2a) include compounds having substituents R ^{1 to} R ⁴ shown in Tables 6 to 39 described below.

(Synthesis Method 2) Compound (2a) is synthesized by reacting compound (12) with a thiol in the presence of a base. As the type of the solvent, the same one as described in Production method 1 can be used. As the kind of the base, the same one as described in the synthesis method 1 can be used. The amount of the base used is the same as that of compound (12)
0.001 to 5 times mol. Examples of the thiols include methyl mercaptan sodium solution, ethyl mercaptan, aryl mercaptan, 6-butyl mercaptan, propyl mercaptan, isopropyl mercaptan, cyclopentyl mercaptan, benzenethiol,
Benzyl mercaptan, phenethyl mercaptan and the like can be mentioned. Compound (12) is, for example, An
gew. Chem. , 71 , 349 (1959);
Org. Chem. , 30 , 38 (1965), Or
g. Synth. V, 328 (1973) and the like, for example, by a method of halogenating alkylbenzene.

As the compound (12), the following Tables 6 to 3
Those having the substituents R ^{1 to} R ³ shown in 9 can be mentioned. The combination of the compound (12) and the thiol used corresponds to that having the substituents R ^{1 to} R ³ shown in the compound (2). The amount of the solvent used depends on the amount of the compound (1
2) is from 1 to 80% by weight; preferably from 1 to 50% by weight. The reaction temperature is not particularly limited.
Within the temperature range of 00C; preferably between 5 and 50C. The reaction time varies depending on the above concentration and temperature; it is usually 0.1 to 100 hours;
3 to 24 hours. The amount of the starting compound to be used is 0.5 to 50 moles of alkyl halide relative to compound (13); preferably 0.8 to 10 moles.

(Synthesis Method 3) Compound (2b) [compound (2) in which X is O] is synthesized by reacting compound (12) with an alcohol in the presence of a base. As the kind of the base, the same one as described in the synthesis method 1 can be used. The amount of the base to be used is 0.001 to 5 moles compared to Compound (12). Examples of alcohols include ethyl alcohol, methyl alcohol, isopropyl alcohol, propyl alcohol, t-butyl alcohol, cyclopropyl alcohol, allyl alcohol, propargyl alcohol, benzyl alcohol, trifluoroethanol, hexafluoroisopropanol, trichloroethanol, and pentafluoropropanol. And the like. Combinations of the compound (12) and alcohols used correspond to those having substituents R ^{1 to} R ³ shown in Tables 6 to 39 described below. The reaction temperature is not particularly limited, but is in the temperature range of 0 to 200 ° C; preferably room temperature to 100 ° C.

The reaction time varies depending on the concentration and temperature described above; it is usually 0.1 to 100 hours; preferably 0.3 to 24 hours. The amount of the starting compound used is such that the alcohol is 0.5 to 50 moles per mole of the compound (12); preferably 0.8 to 10 moles. The (Synthesis 4) The compound (12) with an amine compound by reacting in the presence of a base (2c) [compound in (2), X is compounds wherein NR ^22] to synthesize. As the kind of the base, the same one as described in the synthesis method 1 can be used. The amount of the base to be used is 0.001 to 5 moles compared to Compound (12). Examples of the amines include methylamine, dimethylamine, ethylamine, diethylamine, benzylamine, allylamine, propargylamine, cyclopentylamine, aniline, phenethylamine, isopropylamine, and t-butylamine. The reaction temperature is not particularly limited, but is in the temperature range of 0 to 200 ° C; preferably room temperature to 100 ° C.

The reaction time varies depending on the concentration and temperature described above; it is usually 0.1 to 100 hours; preferably 0.3 to 24 hours. The amount of the starting compound to be used is 0.5 to 50 times mol of compound (12); preferably 0.8 to 10 times mol of compound (12). (Synthesis method 5) Compound (2d) [in compound (2), X is reacted by reacting compound (2a) with an oxidizing agent.
Is SO or SO ₂ ]. As the type of the solvent, the same one as described in Production method 1 can be used. As the oxidizing agent, peracids such as hydrogen peroxide, peracetic acid, perbenzoic acid, and m-chloroperbenzoic acid;
Sodium metaperiodate; Hydroperoxide; Ozone; Selenium dioxide; Chromic acid; Dinitrogen tetroxide; Acyl nitrate; Iodine; N-bromosuccinimide; Iodosylbenzene; Sulfuryl chloride; Water-containing silica gel; Oxone (potassium peroxymonosulfate, manufactured by Aldrich) and the like.

The amount of the oxidizing agent to be used is 0.01 to 5 times the molar amount of the compound (2a). The amount of the solvent used is 1 to 80% by weight of the compound (2a); preferably 1 to 5%.
0% by weight. The reaction temperature is not particularly limited,
In the temperature range of 80-100 ° C; preferably -60
５０50 ° C. The reaction time varies depending on the concentration and temperature described above; it is usually 0.1 to 100 hours; preferably 0.3 to 24 hours. The amount of the starting compound used is such that the alkyl halide is 0.1 to the compound (2a).
It is 5 to 50 moles; preferably 0.8 to 10 moles. As the compound (2d), X ² is SO or S
O ₂ , a substituent R ¹ corresponding to Tables 6 to 39 described below;
Mention may be made ~R ^4.

[0138] As the pests in agricultural and horticultural the controlling effect is observed in pesticides for agricultural horticultural [controlling effect] The compound of the present invention (1), agricultural and horticultural pests [eg Hemiptera (planthoppers, leafhoppers , Aphids,
Whiteflies, etc.), lepidopterans (armyworms, such as Spodoptera litura), moths, locust beetles, scabbards, sink beetles, cabbage beetles, etc., Coleoptera (e.g., beetles, weevil, chrysomelids, beetles, etc.),
Acari (Acari: Tetranychidae, Tetranychidae, etc.), Sanitary pests (for example, flies, mosquitoes, cockroaches, etc.), and grain storage pests (Konustomodoki, Mame weevil, etc.), Examples include corn rootworm, root-knot nematode, pine wood nematode, and mite in soil.

[Pest control agent] The pest control agent for agricultural and horticultural use of the present invention has a remarkable insecticidal effect, and contains at least one compound (1) as an active ingredient. Compound (1) can be used alone,
Usually, a carrier, surfactant, dispersant, adjuvant, etc. are blended by a usual method (for example, prepared as a composition such as powder, emulsion, fine granule, granule, wettable powder, oily suspension, aerosol, etc.) Is preferably used. As a carrier,
For example, solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, urea; hydrocarbons (kerosene, mineral oil, etc.), aromatic hydrocarbons (benzene, toluene, xylene) Chlorinated hydrocarbons (chloroform, carbon tetrachloride, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, cyclohexanone, isophorone, etc.), esters (ethyl acetate, ethylene glycol acetate, dibutyl maleate, etc.) ), Alcohols (methanol, n-hexanol, ethylene glycol, etc.), polar solvents (dimethylformamide, dimethylsulfoxide, etc.), liquid carriers such as water; gas carriers such as air, nitrogen, carbon dioxide, freon (in this case, , Mixed Can be injected together).

Examples of surfactants and dispersants which can be used to improve the performance of the agent, such as adhesion to animals and plants, improvement in absorption, and dispersion, emulsification, spreading of drugs, include alcohol sulfates and alkyls. Sulfonate, lignin sulfonate, polyoxyethylene glycol ether and the like can be mentioned. In order to improve the properties of the preparation, for example, carboxymethylcellulose, polyethylene glycol, gum arabic and the like can be used as an auxiliary agent. In the production of the present agent, the above-mentioned carrier, surfactant, dispersant, and auxiliary can be used alone or in appropriate combination according to the respective purposes. When the compound (I) of the present invention is formulated, the concentration of the active ingredient is usually 1 to 50% by weight for emulsions, usually 0.3 to 25% by weight for powders, and usually 1 to 90% for wettable powders.
% By weight, usually 0.5 to 5% by weight for granules, 0.5 to 5% by weight for oils and 0.1 to 5% by weight for aerosols. These preparations can be diluted to an appropriate concentration and applied to various uses by spraying them on plant foliage, soil, or the water surface of paddy fields, or directly applying them, depending on the purpose.

[0141]

EXAMPLES The present invention will be specifically described below with reference examples and examples. Note that these examples do not limit the scope of the present invention. Example 1 Synthesis of Compound (2) (1) Synthesis of 4-chloro-4 ′-(methylthiomethyl) benzophenone [Compound (2-1)] 4-Chloro-4′-bromomethylbenzophenone (31
g) was dissolved in acetonitrile (100 ml), and methyl mercaptan sodium solution (15% solution) (50 g)
Was slowly added, and the mixture was stirred at room temperature for 3 hours. After completion of the reaction, the reaction solution was poured into water, toluene (150 ml) was added, the organic layer was washed twice with water, dried over anhydrous sodium sulfate, and then toluene was distilled off under reduced pressure. The obtained solid was reconstituted with isopropyl ether (200 ml) to obtain 20 g of the target compound as white crystals.

¹ H-NMR (CDCl ₃ -TMS),
(Δ ppm) 2.00 (s, 3H), 3.72 (s, 2H), 7.3
0 to 7.80 (m, 8H)

(2) 4-chloro-4 '-(methylsulfonylmethyl) benzophenone [compound (2-
3)] Synthesis of OXONE (manufactured by Aldrich) (6 g) prepared by dissolving 4-chloro-4 ′-(methylthiomethyl) benzophenone (2.6 g) in methanol (80 ml) and dissolving in water (30 ml) under ice cooling. .1 g) was added dropwise, followed by stirring for 30 minutes. After completion of the reaction, the reaction solution was poured into water, and the precipitated pale yellow solid was separated by filtration, dissolved in ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure. The obtained solid was purified by silica gel column chromatography (Wakogel C-200, hexane: ethyl acetate = 2: 1 elution) to obtain 2.6 g of the target compound as white crystals. -CI-MS m / z 309 (m + 1)

(3) 4-fluoro-4 '-(methylsulfinylmethyl) benzophenone [compound (2-8)]
Synthesis of 4-Fluoro-4 ′-(methylthiomethyl) benzophenone (2.6 g) in methanol (60 ml)
OXONE dissolved in water (20ml) at -30 ° C or lower
(Aldrich) (3.8 g) was added dropwise and then 10
Stirred for minutes. After completion of the reaction, the reaction solution was poured into water, and the precipitated pale yellow solid was separated by filtration, dissolved in ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure. The obtained solid was purified by silica gel column chromatography (Wakogel C-200, elution with hexane: ethyl acetate: methanol = 10: 5: 1) to give the target compound as white crystals.
4 g were obtained. -CI-MS m / z 277 (m + 1)

(4) Synthesis of 4-methoxy-4 '-(methylthiomethyl) benzophenone [compound (2-16)] 4-Fluoro-4'-methylthiomethylbenzophenone (4.4 g) was suspended in methanol (50 ml). The mixture became cloudy, a 28% methanol solution of sodium methylate (6.0 g) was added, and the mixture was heated under reflux for 12 hours. After completion of the reaction, methanol was distilled off under reduced pressure, ethyl acetate (50 ml) was added, the organic layer was washed with water, dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure. The obtained oil was subjected to silica gel column chromatography (Wakogel C-200,
Purification with hexane: ethyl acetate = 6: 1) yielded 2.6 g of the target compound as a colorless viscous liquid.

¹ H-NMR (CDCl ₃ -TMS),
(Δ ppm) 2.02 (s, 3H), 3.74 (s, 2H), 3.8
7 (s, 3H), 6.95 to 7.85 (m, 8H)

(5) 4-chloro-4 '-(difluoromethylthiomethyl) benzophenone [compound (2-3)
3)] Synthesis of 4-chloro-4 ′-(mercaptomethyl) benzophenone (0.5 g) and potassium carbonate (0.3 g) in DMF
(30 ml), and chlorodifluoromethane was blown in at 45 ° C. with stirring for 0.5 hour. The reaction solution was poured into water, toluene (50 ml) was added, the organic layer was washed twice with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was purified by silica gel column chromatography (Wakogel C-200, hexane: ethyl acetate = 8: 1 elution) to obtain 0.5 g of the target compound as a white solid.

¹ H-NMR (CDCl ₃ -TMS),
(Δ ppm) 4.06 (s, 2H), 6.58 to 7.02 (t, 1
H), 7.40 to 7.85 (m, 8H)

(6) 4-chloro-4 '-(trifluoromethylthiomethyl) benzophenone [compound (2-3)
4)] Synthesis of 4-chloro-4′-bromomethylbenzophenone (1.
8 g) is dissolved in 100 ml of acetonitrile, and copper trifluoromethanethiol (manufactured by Tokyo Chemical Industry) (1 g) is suspended. After heating under reflux for 70 hours, the reaction solution is poured into water, 50 ml of toluene is added, and the organic layer is washed twice with water. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The resulting solid is subjected to column chromatography (Wakogel C
-200, hexane: ethyl acetate = 6: 1 elution) to obtain 0.7 g of the target compound as a white solid.・ Melting point 75-76 ° C

(7) 4-chloro-4 '-(2,2,2-
Synthesis of trifluoroethylthiomethyl) benzophenone [compound (2-35)] In 30 ml of toluene, 4-chloro-4 ′-(mercaptomethyl) benzophenone (1.0 g), 1-iodo-2,
Dissolve 2,2-trifluoroethane (0.8 g)
1,8-diazabicyclo [5.4.0] undec-7-
Ene (0.7 g) was added dropwise at room temperature. After stirring at room temperature for 1 hour, the reaction solution was poured into water, and 50 ml of toluene was added.
The organic layer is washed twice with water. After drying over anhydrous sodium sulfate,
The solvent was distilled off under reduced pressure. The obtained oil was purified by column chromatography (Wakogel C-200, elution with hexane: ethyl acetate = 8: 1) to give 0.7 g of the target compound as a white solid. -Melting point 60
~ 62 ° C

(8) 4-chloro-4 '-(2,2,2-
Synthesis of trifluoroethoxymethyl) benzophenone [compound (2-51)] 4-chloro-4′-bromomethylbenzophenone (5.
0g), 2,2,2-trifluoroethanol (5.0
g) and potassium carbonate (3.5 g) in DMF (60 m
After stirring at 100 ° C. for 5 hours, the reaction solution was poured into water, toluene (150 ml) was added, the organic layer was washed twice with water, dried over anhydrous sodium sulfate, and then the solvent was removed under reduced pressure. Distilled off. The obtained solid was purified by silica gel column chromatography (Wakogel C-200, hexane: ethyl acetate = 6: 1 elution) to obtain 4.4 g of the target compound as white crystals.

(9) Synthesis of 4-chloro-4 '-(methylaminomethyl) benzophenone [compound (2-59)] 4-chloro-4'-bromomethylbenzophenone (5.
0 g) and a 40% methylamine methanol solution (6.0%).
g) and potassium carbonate (3.5 g) in DMF (60 m
After stirring at 60 ° C. for 10 hours, the reaction mixture was poured into water, ethyl acetate (150 ml) was added, and the organic layer was separated into 2 parts.
After washing with water and drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The obtained solid is subjected to silica gel column chromatography (Wakogel C-200, hexane:
Purification with ethyl acetate (4: 1 elution) yielded 3.6 g of the target compound as white crystals.

(10) 4-chloro-4 '-(propargylthiomethyl) benzophenone [Compound (2-68)]
Synthesis of 4-chloro-4 ′-(mercaptomethyl) benzophenone (0.5 g) and potassium carbonate (0.3 g) in DMF
(30 ml) and propargyl bromide (0.3
g) was added dropwise at room temperature. After stirring at 40-50 ° C. for 1 hour, the reaction solution was poured into water, and toluene (50 ml) was added.
The organic layer was washed twice with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was subjected to silica gel column chromatography (Wakogel C-200,
Purification with hexane: ethyl acetate = 8: 1) yielded 0.5 g of the target compound as a colorless viscous liquid.

CI-MS m / z 301 (m + 1) ¹ H-NMR (CDCl ₃ , δ ppm) 2.3 (s, 1H), 3.1 (s, 2H), 3.95
((S, 2H), 7.35-7.85 (m, 8H)

(11) R ^{1 to} R ⁴ and X in Tables 6 to 37
Synthesis of compound (2) having the following Tables 6 to 3 according to the method described in the above (1) to (10).
Compound (2) having R ^{1 to} R ⁴ and X in 9 was synthesized. Among the compounds (2) synthesized as described above, the novel compound (2 ′) and its physical properties are shown in Tables 1 to 5 and Table 40 described later.

[0156]

[Table 1]

[0157]

[Table 2]

[0158]

[Table 3]

[0159]

[Table 4]

[0160]

[Table 5]

Example 2 Synthesis of Compound (1) (1) Synthesis of 4-chloro-4 '-(methylthiomethyl) benzophenone N'-ethoxycarbonylhydrazone [compound (1a-1)] 4-chloro-4 '-(Methylthiomethyl) benzophenone (2.7 g) and ethyl carbazate (1.2 g) were dissolved in toluene (50 ml), and boron trifluoride ethyl ether complex (0.2 m) was added thereto.
l) was added and the mixture was heated under reflux for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, water was added to wash the toluene layer, and the mixture was dried over anhydrous sodium sulfate, and then toluene was distilled off under reduced pressure.
The obtained oil was subjected to silica gel column chromatography (Wakogel C-200, hexane: ethyl acetate = 5:
Purification by 1 elution) yielded 2.4 g of the target compound as white crystals.

(2) Synthesis of 4-chloro-4 '-(methylsulfinylmethyl) benzophenone N'-ethoxycarbonylhydrazone [compound (1a-4)] 4-chloro-4'-(methylthiomethyl) benzophenone N'- Ethoxycarbonylhydrazone (1.0 g) was dissolved in methanol (30 ml), and OXONE (manufactured by Aldrich) (1.9 g) dissolved in water (10 ml) was added dropwise at −30 ° C. or lower, followed by stirring for 10 minutes. After completion of the reaction, the reaction solution was poured into water, and the precipitated pale yellow solid was separated by filtration, dissolved in ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure. did. The obtained solid was purified by silica gel column chromatography (Wakogel C-200, elution with hexane: ethyl acetate: methanol = 10: 5: 1) to obtain 0.8 g of the target compound as white crystals.

¹ H-NMR (CDCl ₃ -TMS),
(Δ ppm) 1.20 to 1.40 (m, 3H), 2.46 to 2.63
(3H), 3.90-4.06 (m, 2H), 4.12
４4.40 (m, 2H), 7.15 to 7.60 (m, 8
H), 7.70 to 7.90 (m, 1H)

(3) Synthesis of 4-chloro-4 '-(methylsulfonylmethyl) benzophenone N'-ethoxycarbonylhydrazone [compound (1a-5)] 4-chloro-4'-(methylthiomethyl) benzophenone N'- Ethoxycarbonylhydrazone (1.0 g) was dissolved in methanol (30 ml), and water (10 m
OXONE (Aldrich) dissolved in l) (3.
After 8 g) was added dropwise, the mixture was stirred for 30 minutes. After the reaction,
The reaction solution was poured into water, and the precipitated pale yellow solid was separated by filtration, dissolved in ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure. The obtained solid was purified by silica gel column chromatography (Wakogel C-200, elution with hexane: ethyl acetate = 2: 1) to obtain 0.9 g of the target compound as white crystals.

¹ H-NMR (CDCl ₃ -TMS),
(Δ ppm) 1.25 to 1.40 (m, 3H), 2.45 to 2.95
(M, 3H), 4.20-4.40 (m, 4H), 7.
15-7.60 (m, 8H), 7.74-7.88
(M, 1H)

(4) Synthesis of 4-fluoro-4 '-(methylsulfinylmethyl) benzophenone N'-ethoxycarbonylhydrazone [compound (1a-10)] 4-Fluoro-4'-(methylsulfinylmethyl) benzophenone (1 2.0 g) and ethyl carbazate (0.5 g) were suspended in toluene (50 ml), and boron trifluoride ethyl ether complex (0.1 ml) was added thereto, followed by heating under reflux for 3 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, water was added to wash the toluene layer, and dried over anhydrous sodium sulfate, and then toluene was distilled off under reduced pressure. The obtained oil was subjected to silica gel column chromatography (Wakogel C-200, hexane:
Purification with ethyl acetate: methanol = 10: 5: 1) yielded 0.9 g of the target compound as white crystals.
Obtained.

¹ H-NMR (CDCl ₃ -TMS),
(Δ ppm) 1.20-1.40 (m, 3H), 2.45-2.65
(M, 3H), 3.90-4.12 (m, 2H), 4.
15 to 4.35 (m, 2H), 6.96 to 7.65
(M, 8H), 7.85 to 7.90 (m, 1H)

(5) Synthesis of 4-fluoro-4 '-(methylsulfonylmethyl) benzophenone N'-ethoxycarbonylhydrazone [compound (1a-11)] 4-Fluoro-4'-(methylsulfonylmethyl) benzophenone (1 2.0 g) and ethyl carbazate (0.5 g) were suspended in toluene (50 ml), and boron trifluoride ethyl ether complex (0.1 ml) was added thereto, followed by heating under reflux for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, water was added to wash the toluene layer, and the mixture was dried over anhydrous sodium sulfate, and then toluene was distilled off under reduced pressure. The obtained oil was subjected to silica gel column chromatography (Wakogel C-200, hexane:
Purification with ethyl acetate (2: 1 elution) yielded 0.8 g of the target compound as white crystals.

¹ H-NMR (CDCl ₃ -TMS),
(Δ ppm) 1.20 to 1.42 (m, 3H), 2.75 to 3.00
(M, 3H), 4.10 to 4.40 (m, 4H), 6.
95-7.70 (m, 8H), 7.70-7.90
(M, 1H)

(6) 4-chloro-4 '-(ethylsulfonylmethyl) benzophenone N'-ethoxycarbonylhydrazone [compound (1a-40) and compound (1a)
-41)] 4-Chloro-4 '-(ethylthiomethyl) benzophenone N'-ethoxycarbonylhydrazone (1.0 g)
Was dissolved in methanol (120 ml), and water (2
OXONE (Aldrich) dissolved in 5 ml)
(1.79 g) was added dropwise, and the mixture was stirred for 10 minutes, then the temperature was raised to room temperature, the reaction solution was poured into water, the precipitated pale yellow solid was collected by filtration, dissolved in ethyl acetate, washed with water, and sulfuric anhydride was added. After drying over sodium, ethyl acetate was distilled off under reduced pressure. The obtained oily product was purified by silica gel column chromatography (Wakogel C-200, toluene: ethyl acetate = 3: 1 elution) to obtain 0.22 g of a white crystalline compound (1a-40) and a white crystalline compound. 0.44 g of (1a-41) was obtained.

¹ H-NMR (CDCl ₃ -TMS),
(Δ ppm) [Compound (1a-40)] 1.36 (t, 3H), 1.39 (t, 3H), 2.8
5 (q, 2H), 4.15 to 4.35 (m, 4H),
7.15 to 7.80 (m, 9H)

[Compound (1a-41)] 1.32 (t, 3H), 1.47 (t, 3H), 3.0
3 (q, 2H), 4.10 to 4.40 (m, 4H),
7.10 to 7.85 (m, 9H)

(7) Synthesis of 4-chloro-4 '-(phenylthiomethyl) benzophenone N'-ethoxycarbonylhydrazone [compound (1a-68)] 4-chloro-4'-(phenylthiomethyl) benzophenone (2 0.7g) and

(8) 4-chloro-4 '-(2,2,2-
Trifluoroethoxymethyl) benzophenone N'-
Ethoxycarbonylhydrazone [compound (1a-12
3) Synthesis of 4-chloro-4 '-(2,2,2-trifluoroethoxymethyl) benzophenone (0.5 g) and ethyl carbazate (0.3 g) were dissolved in toluene (30 ml), Boron trifluoride ethyl ether complex (0.1 ml) was added, and the mixture was heated under reflux for 3 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, water was added to wash the toluene layer, and dried over anhydrous sodium sulfate, and then toluene was distilled off under reduced pressure. The obtained oil was subjected to silica gel column chromatography (Wakogel C-200,
Purification with toluene: ethyl acetate = 9: 1) gave 0.4 g of the target compound as a colorless viscous liquid.

¹ H-NMR (CDCl ₃ -TMS),
(Δ ppm) 1.20 to 1.40 (br, 3H), 3.70 to 4.1
0 (m, 2H), 4.20 to 4.40 (br, 2H),
4.65 to 4.75 (d, 2H), 7.10 to 7.60
(M, 8H), 7.70 to 7.90 (m, 1H)

(9) Synthesis of 4-chloro-4 '-(methylaminomethyl) benzophenone N'-ethoxycarbonylhydrazone [compound (1a-127)] 4-chloro-4'-(methylaminomethyl) benzophenone (0 0.5 g) and ethyl carbazate (0.3 g)
Was dissolved in toluene (30 ml), and boron trifluoride ethyl ether complex (0.
1 ml) and heated under reflux for 5 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, water was added to wash the toluene layer, and the mixture was dried over anhydrous sodium sulfate, and then toluene was distilled off under reduced pressure. The obtained oil was subjected to silica gel column chromatography (Wakogel C-200, toluene: ethyl acetate =
(4: 1 elution) to obtain 0.3 g of the target compound as a white solid.

¹ H-NMR (CDCl ₃ -TMS),
(Δ ppm) 1.20 to 1.40 (br, 3H), 1.40 to 1.8
0 (br, 1H), 2.30 to 2.60 (d, 3H),
3.60-3.90 (d, 2H), 4.10-4.40
(Br, 2H), 7.10 to 7.60 (m, 8H),
7.70 to 7.90 (m, 1H)

(10) 4-chloro-4 '-(methylthiomethyl) benzophenone hydrazone [compound (1a-
134)] 4-Chloro-4 '-(methylthiomethyl) benzophenone (2.7 g) and hydrazone monohydrate (1.5 g) were dissolved in ethanol (30 ml), and concentrated sulfuric acid (0.1 m
l) was added and the mixture was heated under reflux for 6 hours. After completion of the reaction, ethanol was distilled off from the reaction mixture under reduced pressure, ethyl acetate (50 ml) was added, the mixture was washed twice with water, dried over anhydrous sodium sulfate, and toluene was distilled off under reduced pressure. The obtained oil was purified by silica gel column chromatography (Wakogel C-200, elution with hexane: ethyl acetate = 5: 1) to obtain 2.3 g of the target compound as pale yellow crystals.

¹ H-NMR (CDCl ₃ -TMS),
(Δ ppm) 1.98 to 2.10 (3H), 3.62 to 3.75 (2
H) 5.36-5.50 (m, 2H), 7.15-
7.55 (m, 8H)

(11) 4-chloro-4 '-(methylthiomethyl) benzophenone N'-acetylhydrazone [compounds (1a-135) and (1a-13)
6)] Compound (1a-134) (2.2 g) and triethylamine (1.2 g) were dissolved in chloroform (50 ml), and acetic anhydride (1.0 g) was added dropwise under ice-cooling. Stirred overnight. After completion of the reaction, the reaction solution was washed with water, dried over anhydrous sodium sulfate, and then chloroform was distilled off under reduced pressure. The obtained oil was purified by silica gel column chromatography (Wakogel C-200, elution with hexane: ethyl acetate = 3: 1) to obtain 1.3 g of a white crystalline compound (1a-135) and a white crystalline compound. 0.7 g of (1a-136) was obtained.

¹ H-NMR (CDCl ₃ -TMS),
(Δ ppm) [Compound (1a-135)] 2.10 (s, 3H), 2.45 (s, 3H), 3.7
6 (s, 2H), 7.15 to 7.60 (m, 8H),
8.46 (s, 1H)

[Compound (1a-136)] 2.00 (s, 3H), 2.40 (s, 3H), 3.6
8 (s, 2H), 7.15 to 7.60 (m, 8H),
8.12 (s, 1H)

(12) Synthesis of 4-chloro-4 '-(methylthiomethyl) benzophenone N', N'-diacetylhydrazone [compound (1a-140)] 4-chloro-4 '-(methylthiomethyl) benzophenone hydrazone ( 1.2 g) was dissolved in DMF (30 ml), sodium hydride (60%) (0.32 g) was added, acetyl chloride (0.8 g) was added dropwise at room temperature, and the mixture was stirred at room temperature for 2 hours. The reaction solution was poured into water, and extracted by adding ethyl acetate (80 ml). The organic layer was washed with brine, dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure. The obtained oil was purified by silica gel column chromatography (Wakogel C-200, eluted with toluene: ethyl acetate = 5: 1) to obtain 0.6 g of the target compound as a pale yellow oil.

¹ H-NMR (CDCl ₃ -TMS),
(Δ ppm) 2.03 (s, 3H), 2.11 (s, 3H), 2.2
4 (s, 3H), 3.67 (s, 2H), 7.10
7.60 (m, 8H)

(13) Synthesis of 4-chloro-4 '-(methylthiomethyl) benzophenone N'-(N-4-trifluoromethylphenylcarbamoyl) hydrazone [compounds (1a-146) and (1a-147)] -Chloro-4 '-(methylthiomethyl) benzophenone hydrazone (0.8 g) is dissolved in toluene (40 ml), and the mixture is stirred at room temperature with 4-trifluoromethylphenyl isocyanate (0.52 g) and triethylamine (0.05 ml). Was added and stirred for 4.5 hours. After completion of the reaction, toluene was added to the reaction mixture for extraction. The organic layer was washed with brine, dried over anhydrous sodium sulfate, and then toluene was distilled off under reduced pressure. The obtained residue is subjected to silica gel column chromatography (Wakogel C-20).
By purifying with 0, toluene: ethyl acetate = 25: 1), 0.28 g of a compound (1a-146) as a white powder and 0.24 g of a compound (1a-147) as a white powder were obtained.

¹ H-NMR (CDCl ₃ -TMS),
(Δ ppm) [Compound (1a-146)] 2.03 (s, 3H), 3.60 (s, 2H), 7.1
5-7.70 (m, 13H), 8.48 (s, 1H)

[Compound (1a-147)] 2.10 (s, 3H), 3.75 (s, 2H), 7.2
0 to 7.75 (m, 13H), 8.43 (s, 1H)

(14) Synthesis of 4-chloro-4 '-(methylthiomethyl) benzophenone N'-methylhydrazone [compound (1a-173)] 4-chloro-4'-(methylthiomethyl) benzophenone (2.9 g) , Methylhydrazone (5 ml) and acetic acid (0.5 ml) were dissolved in ethanol (100 ml) and stirred for 6 hours. After completion of the reaction, ethanol was distilled off from the reaction mixture under reduced pressure, and ethyl acetate was added for extraction. Then, the organic layer was washed with brine, dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure.
Drying yielded 3.0 g of the target compound as a brown oil.

¹ H-NMR (CDCl ₃ -TMS),
(Δ ppm) 1.96 to 2.08 (3H), 3.00 (3H),
62 to 3.72 (2H), 5.03 to 5.26 (1
H), 7.10 to 7.50 (8H)

(15) Synthesis of 4-chloro-4 '-(mercaptomethyl) benzophenone N'-ethoxycarbonylhydrazone [compound (1a-178)] 4-chloro-4'-(chloromethylthiomethyl) benzophenone (0. 3 g) and ethyl carbazate (0.2 g).
g) was dissolved in toluene (20 ml), and boron trifluoride ethyl ether complex (0.1 m
l) was added and the mixture was heated under reflux for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, the toluene layer was washed with water, dried over anhydrous sodium sulfate, and then toluene was distilled off under reduced pressure. The obtained oil was purified by silica gel column chromatography (Wakogel C-200, toluene: ethyl acetate = 9: 1 elution) to give 0.2 g of the target compound as a colorless candy.

¹ H-NMR (CDCl ₃ -TMS),
(Δ ppm) 1.20 to 1.40 (m, 3H), 1.70 to 1.95
(M, 1H), 3.70-3.90 (m, 2H), 4.
20-4.40 (m, 2H), 7.10-7.60
(M, 8H), 7.70 to 7.90 (m, 1H)

(16) Synthesis of 4-bromo-4 '-(ethylthiomethyl) benzophenone N'-ethoxycarbonylhydrazone [compound (1a-190)] 4-bromo-4'-(ethylthiomethyl) benzophenone (1 .72 g) and ethyl carbazate (1.6 g)
Was dissolved in toluene (50 ml), and boron trifluoride ethyl ether complex (0.2 m
l) was added and the mixture was heated under reflux for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, the toluene layer was washed with water, dried over anhydrous sodium sulfate, and then toluene was distilled off under reduced pressure. The obtained oil was purified by silica gel column chromatography (Wakogel C-200, eluted with toluene: ethyl acetate = 9: 1) to obtain 0.55 g of the target compound as a yellow oil.

¹ H-NMR (CDCl ₃ -TMS),
(Δ ppm) 1.21 (t, 3H), 1.30 (t, 3H), 2.3
5 to 2.58 (m, 2H), 3.70 to 3.80 (s,
2H), 4.15 to 4.35 (m, 2H), 7.13 to
7.60 (m, 8H) 7.68 to 7.85 (br, 1H)

(17) Synthesis of 4-chloro-4 '-(methylthiomethyl) benzophenone N'-methyl-N'-acetylhydrazone [compound (1a-199)] 4-chloro-4'-(methylthiomethyl) benzophenone N′-methylhydrazone (1.0 g) was dissolved in chloroform (30 ml), and triethylamine (0.4 g) was dissolved.
g) was added, acetic anhydride (0.4 g) was added dropwise at room temperature, and the mixture was stirred at room temperature for 6 hours. Toluene was added to the reaction solution for extraction, and the organic layer was washed with brine, dried over anhydrous sodium sulfate, and then toluene was distilled off under reduced pressure. The obtained oil was purified by silica gel column chromatography (Wakogel C-200, eluted with toluene: ethyl acetate = 10: 1) to obtain 0.8 g of the target compound as a yellow oil.

¹ H-NMR (CDCl ₃ -TMS),
(Δ ppm) 2.00 to 2.05 (m, 3H), 2.35 (s, 3
H) 2.71 to 2.76 (m, 3H), 3.70 to
3.75 (m, 2H) 7.10 to 7.60 (m, 8H)

(18) Synthesis of 4-chloro-4'-ethylthiomethylbenzophenone N'-formylhydrazone [compound (1a-208)] 4-chloro-4'-ethylthiomethylbenzophenone hydrazone (3.0 g), A mixture of 88% formic acid (30 ml) was heated at reflux for 5 hours. After completion of the reaction, the reaction solution was cooled to room temperature, poured into water, and added with 50 ml of ethyl acetate.
The organic layer is washed twice with water. After drying over anhydrous sodium sulfate,
The solvent was distilled off under reduced pressure. The obtained oil was purified by column chromatography (Wakogel C-200, elution with toluene: ethyl acetate = 15: 1) to obtain 0.5 g of a yellow oil.

¹ H-NMR (CDCl ₃ -TMS),
(Δ ppm) 1.20 to 1.34 (m, 3H), 2.37 to 2.59
(M, 2H), 3.70-3.80 (m, 2H), 7.
10 to 7.60 (m, 8H), 8.35 to 8.52
(M, 1H), 8.81 to 8.88 (m, 1H)

(19) Synthesis of 4-chloro-4'-ethylthiomethylbenzophenone N'-chloroacetylhydrazone [compound (1a-212)] 4-chloro-4'-ethylthiomethylbenzophenone
Hydrazone (6.0 g), triethylamine (4 ml)
Was dissolved in toluene (60 ml), a solution of chloroacetyl chloride (3 g) in toluene (10 ml) was slowly added dropwise with stirring at room temperature, and the mixture was stirred for 8 hours. After completion of the reaction, the mixture was poured into water, ethyl acetate (100 ml) was added, and the organic layer was washed twice with water. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The obtained oil was purified by column chromatography (Wakogel C-200, toluene: ethyl acetate = 10: 1 elution) to obtain 3.6 g of a white powder.

Melting point 80 to 85 ° C. ¹ H-NMR (CDCl ₃ -TMS), (δ ppm) 1.20 to 1.38 (m, 3H), 2.40 to 2.60
(M, 2H), 3.70 to 4.70 (m, 4H), 7.
20-7.62 (m, 8H), 8.40-9.42
(M, 1H)

(20) Synthesis of N-[(4-chloro-4'-ethylthiomethyldiphenylmethylidene) amino] succinimide [compound (1a-213)] 4-chloro-4'-ethylthiomethylbenzophenone
Hydrazone (1.0 g), triethylamine (1.5 m
l) A catalytic amount of N, N-dimethylaminopyridine was dissolved in toluene (20 ml), a solution of succinyl chloride (0.6 g) in toluene (3 ml) was gradually added with stirring at room temperature, and the mixture was stirred for 8 hours. After the completion of the reaction, the mixture was poured into water, 50 ml of ethyl acetate was added, and the organic layer was washed twice with water. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The obtained oil was subjected to column chromatography (Wakogel C-200, toluene: ethyl acetate = 1).
(0: 1 elution) to give the white powder as 0.1.
4 g were obtained.

Melting point 110-117 ° C. ¹ H-NMR (CDCl ₃ -TMS), (δ ppm) 1.20-1.30 (m, 3H), 2.37-2.65
(M, 6H), 3.73 (m, 2H), 7.18-7.
70 (m, 8H)

(21) Synthesis of 4-chloro-4 '-(ethylthiomethyl) benzophenone N', N'-diethoxycarbonylhydrazone [compound (1a-225)] 4-chloro-4 '-(ethylthiomethyl ) Benzophenone N'-ethoxycarbonylhydrazone (1.0 g)
Was dissolved in N, N-dimethylformamide, sodium hydride (0.22 g) was added, and the mixture was stirred at room temperature for 30 minutes. Ethyl chlorocarbonate (0.6 g) was added and the mixture was further stirred. After completion of the reaction, water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and brine, dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure. The resulting oil was purified by silica gel column chromatography (Wakogel C-200, elution with toluene: ethyl acetate = 9: 1) to obtain 0.93 g of the target compound as a colorless transparent oil.

(22) Synthesis of 4-chloro-4 '-(ethylthiomethyl) benzophenone N'-trichloromethylsulfenyl-N'-methoxycarbonylhydrazone [compound (1a-226)] (Methylthiomethyl) benzophenone N'-methoxycarbonylhydrazone (1.0 g)
Was dissolved in tetrahydrofuran (25 ml), sodium hydride (0.14 g) was added, and the mixture was stirred at room temperature for 30 minutes. Trichloromethylsulfenyl chloride (0.65
g) was added and the mixture was stirred at room temperature. After completion of the reaction, water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and brine, dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure. The resulting oil is subjected to silica gel column chromatography (Wakogel C-
200, toluene: ethyl acetate = 9: 1 elution) to obtain 0.36 g of the target compound in the form of a pale yellow transparent candy.
Obtained.

(23) 4-chloro-4 '-(ethylthiomethyl) benzophenone N'-(di-n-butylaminosulfenyl) -N'-methoxycarbonylhydrazone [compounds (1a-229) and (1a- 230)] 4-Chloro-4 '-(ethylthiomethyl) benzophenone N'-methoxycarbonylhydrazone (1.0 g)
Was dissolved in 30 ml of dichloromethane, and triethylamine (0.42 g) and di-n-butylaminosulfenyl chloride (0.57 g) were added thereto under ice cooling, and the mixture was refluxed for 6 hours. After completion of the reaction, water was added, and the mixture was extracted with ethyl acetate.
The organic layer was washed with brine, dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure. The obtained residue is subjected to silica gel column chromatography (Wakogel C-2).
00, toluene: ethyl acetate = 19: 1) to give the target compound (1a-229) as a light brown transparent solid.
And 0.24 g of the target compound (1
a-230) (isomer) was obtained in an amount of 0.11 g.

(24) 4-chloro-4 '-(ethylthiomethyl) benzophenone N'-methoxycarbonyl-
N'-methoxymethylhydrazone [compound (1a-23
5)] Synthesis of 4-chloro-4 ′-(ethylthiomethyl) benzophenone N′-methoxycarbonylhydrazone (1.0 g)
Was dissolved in tetrahydrofuran (25 ml), sodium hydride (0.17 g) was added, and the mixture was stirred at room temperature for 30 minutes. Chloromethyl methyl ether was added and the mixture was further stirred. After completion of the reaction, water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous sodium sulfate,
Ethyl acetate was distilled off under reduced pressure. The obtained oil is subjected to silica gel column chromatography (Wakogel C-20).
(0, toluene: ethyl acetate = 9: 1 elution) to obtain 0.35 g of the target compound in the form of pale yellow transparent candy.

(25) 4-chloro-4 '-(ethylthiomethyl) benzophenone N'-formyl-N'-methoxycarbonylhydrazone [compound (1a-250)]
Synthesis of 4-chloro-4 ′-(ethylthiomethyl) benzophenone N′-methoxycarbonylhydrazone (4.1 g)
Was dissolved in tetrahydrofuran (100 ml), sodium hydride (0.17 g) was added, and the mixture was stirred at room temperature for 30 minutes. 20 ml of an ether solution of acetyl formate (11 g)
Was added and stirred at room temperature. Water was added to the reaction solution, which was extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous sodium sulfate, and then ethyl acetate was distilled off under reduced pressure. The obtained oil is subjected to silica gel column chromatography (Wako gel C-200, toluene: ethyl acetate = 9: 1 elution).
To give 0.32 g of the target compound as a viscous oil.

(26) 4-chlorophenyl-4'-ethylthiomethylbenzophenone N '-(6-chloro-3
-Pyridylcarbonyl) hydrazone [compound (1a-3)
87)] Synthesis of 4-chlorophenyl-4′-ethylthiomethylbenzophenone hydrazone (5 g) and 6-chloro-3-pyridinecarboxylic acid (4 g) in dichloromethane (40 ml)
Under stirring at room temperature, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (5 g) was added, and the mixture was stirred at room temperature for 4 hours. After completion of the reaction, water was added to the reaction mixture, the target compound was extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was purified by column chromatography (Wakogel C-200), eluting with toluene: ethyl acetate = 10: 1) and crystallized from hexane to give
6.5 g of the target product was obtained as colorless crystals.

(27) 4-chloro-4 '-(methylthiomethyl) benzophenone N'-dimethylamino-1-
Ethylidenehydrazone [compounds (1b-1) and (1b
-2)] Synthesis A mixture of the compound (1a-134) (1.0 g) and N, N-dimethylacetamide dimethyl acetal (1.5 g) was heated to reflux for 6 hours. After completion of the reaction, toluene (50 ml) was added to the reaction mixture, washed twice with water, dried over anhydrous sodium sulfate, and then toluene was distilled off under reduced pressure. The obtained oily matter was purified by silica gel column chromatography (Wakogel C-200, elution with hexane: ethyl acetate = 5: 1) to obtain 0.9 g of a compound (1b-1) as a yellow crystal. 0.3 g of a thick liquid compound (1b-2) was obtained.

¹ H-NMR (CDCl ₃ -TMS),
(Δ ppm) [Compound (1b-1)] 2.00 (s, 3H), 2.36 (s, 3H), 2.9
0 (s, 6H), 3.66 (s, 2H), 7.20-
7.60 (m, 8H),

[Compound (1b-2)] 2.05 (s, 3H), 2.36 (s, 3H), 2.9
0 (s, 6H), 3.70 (s, 2H), 7.23-
7.60 (m, 8H),

(28) 4-chloro-4 '-(methylthiomethyl) benzophenone N'-(N, N-dimethylaminomethylidene) hydrazone [compound (1b-20)]
N, N-dimethylformamide (0.44 g) was added to toluene (30 ml), and phosphorus oxychloride (0.38 g) dissolved in toluene (5 ml) was added dropwise at 25 ° C., followed by stirring at room temperature for 6 hours. After that, it was confirmed that a yellow oily layer was formed below, and dissolved in toluene (5 ml).
-Chloro-4 '-(methylthiomethyl) benzophenone hydrazone (0.6 g) was added dropwise at 30 to 35 ° C.
Next, after stirring at 40 ° C. for 3 hours and cooling, the reaction solution was poured into water, a 10% aqueous sodium hydroxide solution was added, and toluene (30 ml) was added for extraction. The toluene layer was washed twice with water and dried over anhydrous sodium sulfate, and then toluene was distilled off under reduced pressure. The obtained oil was purified by silica gel column chromatography (Wakogel C-200, elution with hexane: ethyl acetate = 5: 1) to obtain 0.3 g of the target compound as a pale yellow viscous liquid.

¹ H-NMR (CDCl ₃ -TMS),
(Δ ppm) 1.95 to 2.10 (m, 3H), 2.90 (s, 6)
H) 3.68-3.72 (m, 2H), 7.10
7.60 (m, 8H), 8.15 (s, 1H)

(29) Synthesis of 4-chloro-4 '-(methylthiomethyl) benzophenone N'-(1-methyl-2-pyrrolididen) hydrazone [compound (1c-2)] Toluene (30 ml) was mixed with 1-methyl- 2-Pyrrolidone (0.6 g) was added, and phosphorus oxychloride (0.38 g) dissolved in toluene (5 ml) was added dropwise at 25 ° C., and the mixture was stirred at room temperature for 6 hours. It was confirmed that it was formed below, and the solution was dissolved in toluene (5 ml).
Chloro-4 '-(methylthiomethyl) benzophenone
Hydrazine (0.6 g) was added dropwise at 30-35 ° C.
Next, after stirring at 40 ° C. for 3 hours and cooling, the reaction solution was poured into water, a 10% aqueous sodium hydroxide solution was added, and toluene (30 ml) was added for extraction. The toluene layer was washed twice with water and dried over anhydrous sodium sulfate, and then toluene was distilled off under reduced pressure. The obtained oil was purified by silica gel column chromatography (Wakogel C-200, eluted with hexane: ethyl acetate = 5: 1) to give 0.3 g of the target compound as a white solid.

¹ H-NMR (CDCl ₃ -TMS),
(Δ ppm) 1.90 to 2.10 (m, 5H), 2.80 (s, 3
H) 2.95-3.03 (t, 2H), 3.30-
3.38 (t, 2H), 3.65 (s, 2H), 7.1
0 to 7.60 (m, 8H)

(30) Synthesis of Compound (1) in Tables 6 to 39 According to the methods described in the above (1) to (29), Tables 6 to 3
Compound (1) in No. 9 was synthesized. The compounds (1) synthesized as described above and their physical properties are shown in Tables 6 to 47.

[0219]

[Table 6]

[0218]

[Table 7]

[0219]

[Table 8]

[0220]

[Table 9]

[0221]

[Table 10]

[0222]

[Table 11]

[0223]

[Table 12]

[0234]

[Table 13]

[0235]

[Table 14]

[0236]

[Table 15]

[0237]

[Table 16]

[0238]

[Table 17]

[0239]

[Table 18]

[0240]

[Table 19]

[0241]

[Table 20]

[0242]

[Table 21]

[0243]

[Table 22]

[0244]

[Table 23]

[0245]

[Table 24]

[0246]

[Table 25]

[0247]

[Table 26]

[0248]

[Table 27]

[0249]

[Table 28]

[0250]

[Table 29]

[0251]

[Table 30]

[0252]

[Table 31]

[0253]

[Table 32]

[0254]

[Table 33]

[0255]

[Table 34]

[0256]

[Table 35]

[0257]

[Table 36]

[0258]

[Table 37]

[0259]

[Table 38]

[0260]

[Table 39]

[0261]

[Table 40]

[0262]

[Table 41]

[0263]

[Table 42]

[0264]

[Table 43]

[0265]

[Table 44]

[0266]

[Table 45]

[0267]

[Table 46]

[0268]

[Table 47]

Example 3 [Preparation of preparation] (1) Preparation of granule 5 parts by weight of compound (1a-1), 35 parts by weight of bentonite, 57 parts by weight of talc, neoperex powder (trade name, manufactured by Kao Corporation) 1) 1 part by weight and 2 parts by weight of sodium ligninsulfonate were uniformly mixed, and then a small amount of water was added and kneaded, followed by granulation and drying to obtain granules.

(2) Preparation of wettable powder 10 parts by weight of compound (1a-1), 70 parts by weight of kaolin, 18 parts by weight of white carbon, 1.5 parts by weight of Neoperex powder (trade name; manufactured by Kao Corporation) And 0.5 parts by weight of Demol (trade name; manufactured by Kao Corporation) were uniformly mixed and then pulverized to obtain a wettable powder.

(3) Preparation of Emulsion To 20 parts by weight of the compound (1a-1) and 70 parts by weight of xylene, 10 parts by weight of toxanone (trade name; manufactured by Sanyo Chemical Industries, Ltd.) was added, mixed uniformly, and dissolved. An emulsion was obtained.

(4) Preparation of Dust A powder was obtained by uniformly mixing 5 parts by weight of the compound (1a-1), 50 parts by weight of talc and 45 parts by weight of kaolin.

Example 4 [Efficacy test] (1) Efficacy test for Spodoptera litura [0273] Each of the wettable powders of compounds (1) shown in Tables 6 to 39 prepared according to Example 3 was added to a surfactant (0.01%) , And soybean leaves were immersed in each of these chemical solutions for 30 seconds, placed one by one in each plastic cup, and air-dried. In each of these cups, ten cutworm armyworms (2nd instar larvae) were released, covered, left in a constant temperature room at 25 ° C., and two days later, the number of live and dead insects in each cup was counted to determine the insecticidal rate. The insecticidal effect was evaluated in four stages (A: 100%, B: less than 100 to 80) depending on the range of the mortality.
%, C: less than 80 to 60%, D: less than 60%). Table 48 shows the results.

[0274]

[Table 48]

(2) Efficacy test for Japanese moths Each wettable powder of compound (1) shown in Tables 6 to 39 prepared according to Example 3 was diluted to 300 ppm with water containing a surfactant (0.01%). Then, cabbage leaf pieces (5 × 5 cm) were immersed in each of these chemical solutions for 30 seconds, placed one by one in each plastic cup, and air-dried. Next, 10 moths (3rd instar larvae) were released into each of these cups, covered, and allowed to stand in a constant temperature room at 25 ° C. After 2 days, the number of live and dead insects in each cup was counted to determine the mortality. I asked. The results of the evaluation of the insecticidal effect were evaluated according to the four-step evaluation method described in the above (1) in Table 49.
Shown in

[0276]

[Table 49]

(3) Efficacy test on brown planthopper Each wettable powder of compound (1) shown in Tables 6 to 39 prepared according to Example 3 was diluted to 300 ppm with water containing a surfactant (0.01%). Then, rice seedlings were immersed in each of these chemical solutions for 30 seconds, air-dried, and then inserted into respective glass cylinders. Next, 10 brown planthoppers (4th instar larvae) were released into each of these glass cylinders, covered with a porous lid,
After 4 days, the number of live and dead insects on each glass cylinder was counted to determine the mortality. The results of the evaluation of the insecticidal effect are shown in Table 50 by the four-step evaluation method described in the above (1).

[0278]

[Table 50]

[0279]

The novel substituted alkylbenzylidenehydrazine compound of the present invention has an excellent agricultural and horticultural pest control effect.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location A01N 43/36 A01N 43/36 CB 43/40 101 43/40 101B 43/44 43/44 43 / 50 43/50 C 47/34 47/34 G C07C 249/00 9451-4H C07C 249/00 249/16 9451-4H 249/16 251/88 9451-4H 251/88 C07D 205/04 C07D 205/04 207/14 207/14 207/50 207/50 213/82 213/82 223/12 223/12 A 225/02 225/02 233/61 103 233/61 103 (72) Inventor Koichi Goka Ube, Yamaguchi Prefecture 1978, Kobe, Ube-shi, Ube-shi, Ube Research Institute (72) Inventor Takaaki Kuwata 5, 1978, Kozagushi, Obe-shi, Ube, Yamaguchi, Japan

Claims (10)

[Claims] 1. The following formula (1): [Each substituent in the formula is as follows. R ¹ is unsubstituted or substituted as a halogen atom, a haloalkyl group having 1 to 4 carbon atoms, a nitro group, a cyano group, a carbon atom having 1 to 4 carbon atoms.
Alkyl groups, alkoxy groups having 1 to 4 carbon atoms,
Alkylthio group having 1 to 4 carbon atoms, 1 to 4 carbon atoms
A phenyl group having 4 haloalkoxy groups, a haloalkylsulfonyloxy group having 1 to 4 carbon atoms or an alkylsulfonyloxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 8 carbon atoms, or carbon 1 atom
Represents four haloalkyl groups. R ² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group, or a halogen atom. R ³ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom. R ⁴ is an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkynyl group having 2 to 5 carbon atoms, unsubstituted Or a phenyl group having a halogen atom or an alkyl group having 1 to 4 carbon atoms as a substituent, a benzyl group, a phenethyl group, a haloalkyl group having 1 to 4 carbon atoms, and 2 to 6 carbon atoms.
Haloalkenyl groups, alkylsulfonyl groups having 1 to 4 carbon atoms, haloalkylsulfonyl groups having 1 to 4 carbon atoms, cyano group, A ¹ COOR ¹⁰ , hydrogen atom, A
¹ OR ¹⁰ , COA ¹ OR ¹⁰ , COR ¹⁰ , or a cyanoalkyl group. Y is NR ⁵ R ⁶ , N = CR ⁷
NR ⁸ R ⁹ , or N = CR ⁷ NR ⁸ R ^{9 in} which R ⁷ and R ⁸ are linked to form a 4- to 8-membered ring. R ⁵ is COO
R ¹¹ , hydrogen atom, COR ¹² , SO ² R ¹³ , SO ₂
NHR ¹⁰ , SO ₂ NHCH ₂ Ph, SO ₂ NR ¹⁰ R
¹⁰ ′, CONHR ¹⁴ , CSNHR ¹⁵ , A ¹ COO
R ¹⁰ , COA ² R ¹⁶ , CONR ¹⁰ R ¹⁰ ′, CS
SR ¹⁰ , an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a formyl group Alternatively, it represents A ¹ OR ¹⁰ . R ⁶ is a hydrogen atom, COOR ¹⁷ , COR ¹⁸ , SO ₂ R ¹³ , COA
¹ R ¹⁹ , an alkyl group having 1 to 8 carbon atoms, COCO
OR ¹⁰ , SCR ²⁰ R ²⁰ R ²⁰ , SNR
²¹ R ²¹ ′, A ¹ OR ²¹ , CH ₂ OA ¹ OR ¹⁰ ,
Formyl group, SNR ¹⁰ COOR ²¹ , SNR ¹⁰ A ¹
COOR ¹⁰ ′ represents a haloalkyl group having 1 to 4 carbon atoms, A ¹ SR ¹⁵ , or a benzyl group. R ⁵ and R
⁶ may be linked with N to form a 4- to 8-membered ring. R ⁷ represents an alkyl group having 1 to 4 carbon atoms, a hydrogen atom, or a phenyl group. R ⁸ has 1 to 1 carbon atoms
Represents four alkyl groups or hydrogen atoms. R ⁹ represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, an alkynyl group having 2 to 5 carbon atoms, a formyl group, COR ¹⁰ , or a hydrogen atom. X represents S, SO, SO ₂ , O, or NR ²² . Incidentally, the above-mentioned ^A 1, ^{A 2} and ^{R 10} ~
R ²² is as follows. A ¹ represents an alkylene group having 1 to 4 carbon atoms, and A ² represents an alkylene group having 1 to 10 carbon atoms. R ¹⁰ and R ¹⁰ ′ represent an alkyl group having 1 to 4 carbon atoms. R ¹¹ has 1 to 1 carbon atoms
It represents eight alkyl groups, phenyl groups, benzyl groups, or alkenyl groups having 3 to 5 carbon atoms. R ¹² is an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, unsubstituted or halogen atom, and 1 to 4 carbon atoms. A haloalkyl group, an alkyl group having 1 to 4 carbon atoms,
It represents a hydroxyl group, a phenyl group having an alkoxy group having 1 to 4 carbon atoms as a substituent, or an unsubstituted or pyridyl group having a halogen atom as a substituent. R ¹³ represents a haloalkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms. R ¹⁴ is unsubstituted or a phenyl group having a haloalkyl group having 1 to 4 carbon atoms as a substituent, an alkyl group having 1 to 8 carbon atoms,
Alternatively, it represents a phenylsulfonyl group. R ¹⁵ represents a phenyl group or an alkyl group having 1 to 4 carbon atoms. R
¹⁶ is an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, an alkylcarbonyloxy group having 2 to 4 carbon atoms, a halogen atom, an imidazole group, and 2 to 5 carbon atoms. Represents an alkylcarbonylamino group or a pyridyl group. R ¹⁷ has 1 to 1 carbon atoms.
It represents eight alkyl groups, phenyl groups, benzyl groups, or alkenyl groups having 2 to 5 carbon atoms. R ¹⁸ is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a phenyl group, an alkenyl group having 2 to 5 carbon atoms, or an unsubstituted or substituted halogen atom. Represents a pyridyl group. R ¹⁹ has 1 to 1 carbon atoms
4 alkoxy groups, 1-4 alkylthio group carbon atoms, represents a COOR ^10. R ²⁰ represents a halogen atom. R ²¹ and R ²¹ ′ represent an alkyl group having 1 to 8 carbon atoms. R ²² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkylcarbonyl group having 2 to 5 carbon atoms, or a formyl group. A substituted alkylbenzylidenehydrazine compound [compound (1)]. 2. The formula (1) according to claim 1, wherein Y
Is a substituted alkylbenzylidenehydrazine compound represented by NR ⁵ R ⁶ . 3. The formula (1) according to claim 1, wherein Y
Is a substituted alkylbenzylidenehydrazine compound represented by N = CR ⁷ NR ^{8R 9} . 4. In the formula (1) according to claim 1, N = CR wherein Y is a bond of R ⁷ and R ⁸ to form a 4- to 8-membered ring.
Substituted alkyl benzylidene hydrazine compound showing a ⁷ NR ⁸ R ^9. 5. The following formula (2 ′): (Wherein R ⁴ ′ is an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and a cycloalkyl group having 2 to 5 carbon atoms. Alkynyl group, unsubstituted or substituted phenyl group having a halogen atom or an alkyl group having 1 to 4 carbon atoms, benzyl group, phenethyl group, haloalkyl group having 1 to 4 carbon atoms, 2 to 6 carbon atoms Haloalkenyl groups, alkylsulfonyl groups having 1 to 4 carbon atoms, 1 carbon atoms
~ 4 haloalkylsulfonyl groups, cyano groups, A ¹ C
OOR ¹⁰ , A ¹ OR ¹⁰ , COA ¹ OR ¹⁰ , CSO
R ¹⁰ represents a cyanoalkyl group. R ^{1 to} R ³ ,
R ¹⁰ , A ¹ and X have the same meanings as in claim 1. (2 '). 6. The following formula (2): (Wherein R ^{1 to} R ⁴ and X have the same meanings as described in claim 1), and a compound (2) represented by the following formula (3): (Wherein R ⁵ and R ⁶ have the same meanings as described in claim 1), characterized by reacting with a compound (3) represented by the following formula (1a): (Wherein, R ^{1 to} R ⁶ and X have the same meanings as described in claim 1). 7. The following formula (4): (Wherein, R ^{1 to} R ⁴ and X have the same meanings as in claim 1), and a compound represented by the following formula (5): (Wherein, R ²³ represents R ¹⁰ , OR ¹¹ , NHR ¹⁴ or NR ¹⁰ R ¹⁰ ′. Z is a halogen atom, OC
OR ¹³ , OR ¹⁰ , and OH. Note that R ¹⁰ , R
¹⁰ ′, R ¹¹ , R ¹³ and R ¹⁴ have the same meaning as in claim 1. Wherein the compound is reacted with a compound (5) represented by the following formula (1a-i): (Wherein, R ^{1 to} R ⁴ , X and R ²³ have the same meanings as described above), and a compound (1a-i) represented by the following formula (1a-i):
vi): embedded image (In the formula, R ^{1 to} R ⁴ , X and R ²³ have the same meanings as described above.) A method for producing a compound (1a-Vi) represented by the formula: 8. The following formula (4-i): (Wherein R ^{1 to} R ⁵ and X have the same meanings as described in claim 1) and a compound (4-i) represented by the following formula (6): (Wherein, R ⁶ is as defined in claim 1. G is
A halogen atom, a OCOR ^13. 7. The process for producing a compound (1a) according to claim 6, wherein the compound (1) is reacted with the compound (6). 9. The following formula (1a-iv): (Wherein, R ^{1 to} R ⁶ have the same meanings as in claim 1). A compound (1a-iv) represented by the following formula (1a-iv) is reacted with an oxidizing agent. : (Wherein, R ^{1 to} R ⁶ are as defined in claim 1).
m represents 1 or 2. ) (1a-
v) Preparation method. 10. A pest control agent for agricultural and horticultural use comprising a substituted alkylbenzylidenehydrazine compound represented by the formula (1) according to claim 1 as an active ingredient.