JP2001163853A - Sulfide compound and method for producing 6- acetylthiochroman derivative or 5- acetyldihydrobenzo[b]thiophene derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sulfide compound highly useful as an intermediate for producing pyrazole derivatives and cyclohexanedione derivatives which are the active ingredients of herbicides, and to provide a method for simply and inexpensively producing a 6-acetylthiochromane derivative or a 5- acetyldihydrobenzo[b]thiophene derivative from the sulfide compound. SOLUTION: This sulfide derivative represented by the formula [1] (R1 and R2 are each a halogen atom or an alkyl; R3 to R7 are each hydrogen atom and an alkyl), and the method for producing the 6-acetylthiochromane derivative or a 5-acetyldihydrobenzo[b]thiophene derivative, comprising cyclizing the sulfide compound with a protonic acid or with a Lewis acid and the protonic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a sulfide compound having high utility as an intermediate for producing a pyrazole derivative and a cyclohexanedione derivative, which are active ingredients of a herbicide, and a 6-acetylthiochroman derivative or 5-sulfide compound using the sulfide compound. The present invention relates to a method for producing an acetyldihydrobenzo [b] thiophene derivative.

[0002]

2. Description of the Related Art Herbicides are extremely important agents for saving labor for weed control and improving productivity of agricultural and horticultural crops.
For this reason, research and development of herbicides have been actively carried out for many years, and a wide variety of drugs are currently in practical use. However, even today, there is a demand for the development of a new drug having more excellent herbicidal properties, particularly a drug capable of controlling only the target weed selectively and at a low dose without causing phytotoxicity to cultivated crops. I have.

Hitherto, at the time of cultivation of corn and the like, atrazine which is a triazine herbicide and arachlor and metolachlor which are acid anilide herbicides have been used. By the way, atrazine has low activity on grasses, and arachlor and metolachlor have low activities on broadleaf weeds. Therefore, at the moment,
It is difficult to control gramineous and broadleaf weeds at once with a single agent. Furthermore, these herbicides require a high dose and are not preferred because they have a large impact on the environment.

[0004] In order to solve such a problem, international application WO 96/25412 and international application WO 97/254 have been proposed.
No. 03064 proposes a novel pyrazole derivative and a novel cyclohexanedione derivative having a thiochroman ring and a dihydrobenzo [b] thiophene ring.

[0005] The novel pyrazole derivatives and novel cyclohexanedione derivatives described in these international application specifications are:
General formula (A),

[0006]

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The thiochroman-6-carboxylic acid derivative and dihydrobenzo [b] thiophen-5-carboxylic acid derivative represented by the general formula (B) or the general formula (C) are prepared in the presence of a dehydrating agent and a base.

[0008]

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It is produced by reacting with a pyrazole derivative or a cyclohexanedione derivative represented by In addition, the international application WO96 / 25412 discloses a method for producing a compound (a) in which X ⁶ is hydrogen and p is 1 in the aromatic carboxylic acid derivative (A), for example, the following reaction step It is shown.

[0010]

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Furthermore, the specification of the international application discloses, for example, the following reaction steps as a method for producing the 6-acetylthiochroman derivative (J) as a production intermediate.

[0012]

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By the way, in the method for producing the 6-acetylthiochroman derivative (J) described in the specification of this international application, a thiophenol derivative represented by the general formula (F) is used as a starting material. This thiophenol derivative can be produced by a known production method, for example, New Experimental Chemistry Course 14 Synthesis and Reaction of Organic Compounds III (Maruzen Co., Ltd., 1986
It is produced by the production method described in the section of “Synthesis Method via Dithiocarbonate” on page 1704. However, the production process is complicated and the production cost is high.

[0014]

DISCLOSURE OF THE INVENTION The present invention relates to a sulfide compound having high utility as an intermediate for producing a pyrazole derivative and a cyclohexanedione derivative which are active ingredients of a herbicide, and a 6-acetylthiochroman derivative or a sulfide compound using the sulfide compound. An object of the present invention is to provide a method for producing a 5-acetyldihydrobenzo [b] thiophene derivative simply and inexpensively.

[0015]

The present inventors have conducted various studies to solve the above-mentioned problems, and as a result, have found that a novel sulfide compound having a specific chemical structure and a 6-
The present inventors have found a method for producing an acetylthiochroman derivative or a 5-acetyldihydrobenzo [b] thiophene derivative by simple steps, and have completed the present invention based on these findings.

That is, the gist of the present invention is as follows. (1) General formula [1],

[0017]

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[0018] [wherein, R ^1, R ² are, each independently represents a halogen atom or an alkyl group having 1 to 4 carbon atoms, R ^3,
R ⁴ , R ⁵ , R ⁶ , and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁵ and R ⁶ and R ⁶ and R ⁷ may be arbitrarily bonded to each other on a carbon atom to form a saturated hydrocarbon ring having a 3- to 7-membered ring structure. ] The sulfide compound represented by these. (2) General formula [1],

[0019]

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[0020] [wherein, R ^1, R ² are, each independently represents a halogen atom or an alkyl group having 1 to 4 carbon atoms, R ^3,
R ⁴ , R ⁵ , R ⁶ , and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁵ and R ⁶ and R ⁶ and R ⁷ may be arbitrarily bonded to each other on a carbon atom to form a saturated hydrocarbon ring having a 3- to 7-membered ring structure. A sulfide compound represented by the general formula [2], which is subjected to a cyclization reaction in the presence of a protonic acid;

[0021]

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[0022] [wherein, R ^1, R ² are, each independently represents a halogen atom or an alkyl group having 1 to 4 carbon atoms, R ^8,
R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ¹¹ and R ¹² and R ¹² and R ¹³ may be arbitrarily bonded to each other on a carbon atom to form a 3- to 7-membered saturated hydrocarbon ring. n represents 1 or 0. And a 5-acetyldihydrobenzo [b] thiophene derivative represented by the following formula: (3) General formula [1],

[0023]

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[0024] [wherein, R ^1, R ² are, each independently represents a halogen atom or an alkyl group having 1 to 4 carbon atoms, R ^3,
R ⁴ , R ⁵ , R ⁶ , and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁵ and R ⁶ and R ⁶ and R ⁷ may be arbitrarily bonded to each other on a carbon atom to form a saturated hydrocarbon ring having a 3- to 7-membered ring structure. A sulfide compound represented by the general formula [2], wherein the cyclization reaction is carried out in the presence of a Lewis acid and a protonic acid.

[0025]

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[0026] [wherein, R ^1, R ² are, each independently represents a halogen atom or an alkyl group having 1 to 4 carbon atoms, R ^8,
R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ¹¹ and R ¹² and R ¹² and R ¹³ may be arbitrarily bonded to each other on a carbon atom to form a 3- to 7-membered saturated hydrocarbon ring. n represents 1 or 0. And a 5-acetyldihydrobenzo [b] thiophene derivative represented by the following formula: (4) General formula [3],

[0027]

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[Wherein R ¹ and R ² each independently represent a halogen atom or an alkyl group having 1 to 4 carbon atoms, and X ¹ represents a halogen atom. The acetophenone compound represented by the general formula [4]

[0029]

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[Wherein R ¹ and R ² each independently represent a halogen atom or an alkyl group having 1 to 4 carbon atoms, and M represents a hydrogen atom or an alkali metal. To produce a thiophenol compound represented by the general formula [5],

[0031]

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[Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R
⁷ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁵ and R ⁶ and R ⁶ and R ⁷ are arbitrarily bonded to each other on a carbon atom to form a 3- to 7-membered ring. It may form a saturated hydrocarbon ring having a structure. X ² represents a halogen atom. General formula [1] characterized by reacting an allyl halide compound represented by

[0033]

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[0034] [wherein, R ^1, R ² are, each independently represents a halogen atom or an alkyl group having 1 to 4 carbon atoms, R ^3,
R ⁴ , R ⁵ , R ⁶ , and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁵ and R ⁶ and R ⁶ and R ⁷ may be arbitrarily bonded to each other on a carbon atom to form a saturated hydrocarbon ring having a 3- to 7-membered ring structure. ] The method for producing a sulfide compound represented by the formula: (5) General formula [3],

[0035]

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[In the formula, R ¹ and R ² each independently represent a halogen atom or an alkyl group having 1 to 4 carbon atoms, and X ¹ represents a halogen atom. The acetophenone compound represented by the general formula [6],

[0037]

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[Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R
⁷ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁵ and R ⁶ and R ⁶ and R ⁷ are arbitrarily bonded to each other on a carbon atom to form a 3- to 7-membered ring. It may form a saturated hydrocarbon ring having a structure. X ² represents a halogen atom. A general formula [1] characterized by reacting an S-allylisothiuronium salt represented by

[0039]

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[0040] [wherein, R ^1, R ² are, each independently represents a halogen atom or an alkyl group having 1 to 4 carbon atoms, R ^3,
R ⁴ , R ⁵ , R ⁶ , and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁵ and R ⁶ and R ⁶ and R ⁷ may be arbitrarily bonded to each other on a carbon atom to form a saturated hydrocarbon ring having a 3- to 7-membered ring structure. ] The method for producing a sulfide compound represented by the formula: (6) General formula [3],

[0041]

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[Wherein, R ¹ and R ² each independently represent a halogen atom or an alkyl group having 1 to 4 carbon atoms, and X ¹ represents a halogen atom. The acetophenone compound represented by the general formula [5],

[0043]

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[Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R
⁷ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁵ and R ⁶ and R ⁶ and R ⁷ are arbitrarily bonded to each other on a carbon atom to form a 3- to 7-membered ring. It may form a saturated hydrocarbon ring having a structure. X ² represents a halogen atom. General formula [6] obtained by the reaction of an allyl halide compound represented by the formula

[0045]

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Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R
⁷ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁵ and R ⁶ and R ⁶ and R ⁷ are arbitrarily bonded to each other on a carbon atom to form a 3- to 7-membered ring. It may form a saturated hydrocarbon ring having a structure. X ² represents a halogen atom. A general formula [1] characterized by reacting an S-allylisothiuronium salt represented by

[0047]

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[0048] [wherein, R ^1, R ² are, each independently represents a halogen atom or an alkyl group having 1 to 4 carbon atoms, R ^3,
R ⁴ , R ⁵ , R ⁶ , and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁵ and R ⁶ and R ⁶ and R ⁷ may be arbitrarily bonded to each other on a carbon atom to form a saturated hydrocarbon ring having a 3- to 7-membered ring structure. ] The method for producing a sulfide compound represented by the formula:

[0049]

BEST MODE FOR CARRYING OUT THE INVENTION In the sulfide compound represented by the general formula [1] of the present invention, the halogen atoms represented by R ¹ and R ² in the general formula [1] include a fluorine atom, a chlorine atom and a bromine. Any of an atom and an iodine atom may be used. Examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹ , R ² and R ^{3 to} R ⁷ include a methyl group, an ethyl group,
propyl group such as n-propyl group, i-propyl group, n
And butyl groups such as -butyl group, i-butyl group, sec-butyl group and t-butyl group.

The sulfide compound has the general formula
R in [1]^FiveAnd R⁶And R⁶And R ⁷And each is optional
Are bonded to each other on a carbon atom of
It may have a structure in which a hydrocarbon ring is formed. Soshi
This R^FiveAnd R⁶And cycloalkene when formed with
Examples of the nil group include a cyclobutenyl group and a cyclopentenyl group.
Group, cyclohexenyl group, cycloheptenyl group and the like.
It is. In addition, the cycloalkenyl group formed here
Is substituted by an alkyl group having 1 to 3 carbon atoms, and
When the total number of carbon atoms of the alkyl-substituted cycloalkenyl group is 10
May be within.

The cycloalkyl group when formed from R ⁶ and R ⁷ includes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group,
A cycloheptyl group. The cycloalkyl group formed here may be substituted by an alkyl group having 1 to 3 carbon atoms, and the total number of carbon atoms of the alkyl-substituted cycloalkyl group may be 9 or less.

The sulfide compound represented by the general formula [1] is subjected to a cyclization reaction in the presence of a protonic acid, so that the sulfide compound is more useful as an intermediate for producing an active ingredient of a herbicide. -Acetylthiochroman derivatives or 5-acetyldihydrobenzo [b] thiophene derivatives can be produced.

Examples of the protonic acid that can be used in this cyclization reaction include mineral acids such as sulfuric acid and phosphoric acid, sulfonic acids such as methanesulfonic acid and p-toluenesulfonic acid, and acidic ion exchange resins. Particularly preferred is sulfuric acid. The amount of the protonic acid used here is 0.1 to 3 equivalents, preferably 0.2 to 1.2 equivalents, based on the sulfide compound. If the amount of the protonic acid is less than 0.1 equivalent relative to the sulfide compound, the reaction may take a long time, and the amount of the protonic acid may be If the amount exceeds 3 equivalents to the compound, the amount of by-products may increase.

The solvent used here is not particularly limited as long as it does not hinder the reaction. Halogenated aliphatic hydrocarbon solvents such as methylene chloride and 1,2-dichloroethane, chlorobenzene, toluene, xylene And aromatic hydrocarbon solvents such as nitrobenzene. Preferred are methylene chloride and 1,2-dichloroethane.

The reaction temperature for carrying out this cyclization reaction is from 0 ° C. to the reflux temperature of the solvent, preferably from 40 ° C. to 6 ° C.
0 ° C. And reaction time is 1 to 96 hours normally, Preferably it is 36 to 48 hours.

In the cyclization reaction of the sulfide compound represented by the above general formula [1] with a protonic acid, the desired 6-acetylthiochroman derivative and 5-acetyldihydrobenzo [b] thiophene derivative are obtained. In addition, a by-product may be generated, and a dimer or trimer of a sulfide compound as a raw material may be obtained depending on reaction conditions. In addition, the following general formula,

[0057]

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[0058] wherein, R ¹ and R ² have the same meaning as R ^1, R ² in the general formula (1). A diaryl disulfide compound represented by, for example, di (4
-Acetyl-2,5-dimethylphenyl) disulfide, di (4-acetyl-2-chloro-5-methylphenyl) disulfide, di (4-acetyl-5-chloro-2)
-Methylphenyl) disulfide and the like may be formed. These diaryl disulfide compounds can be returned to the raw material thiophenol compound by reduction.

The sulfide compound represented by the above general formula [1] is subjected to a cyclization reaction in the presence of a Lewis acid and a protic acid to give a 6-acetylthiochroman derivative or 5-acetyldihydrobenzo [ b)
Thiophene derivatives can be produced.

As the Lewis acid used here, aluminum chloride, iron chloride, zinc chloride and the like can be mentioned, but aluminum chloride is preferable. The amount of the Lewis acid to be used is 1 to 7 equivalents, preferably 3 to 4.5 equivalents, based on the sulfide compound. If the amount of the Lewis acid used is less than 1 equivalent to the sulfide compound, the reaction yield may be reduced, and the amount of the Lewis acid used may be 7 equivalents to the sulfide compound. This is because, when it exceeds, the amount of by-product generated may increase.

In this production method, the protonic acid used in combination with the Lewis acid functions as a co-catalyst.
Protic acids suitable for use herein include sulfuric acid,
Examples include mineral acids such as hydrochloric acid, carboxylic acids such as acetic acid and formic acid, and sulfonic acids such as methanesulfonic acid and p-toluenesulfonic acid. In addition, alcohols such as hydrogen chloride gas, water, and methanol also function as co-catalysts. Among these protic acids, hydrochloric acid and acetic acid are particularly preferably used. The amount of the protonic acid to be used is 0.1 to 3 equivalents, preferably 0.2 to 1.2 equivalents, based on the sulfide compound.

The reaction is also preferably carried out using a solvent, for example, a halogenated hydrocarbon solvent such as methylene chloride or 1,2-dichloroethane, or an aromatic solvent such as chlorobenzene, dichlorobenzene, dichlorotoluene or nitrobenzene. Hydrocarbon solvents are exemplified. Of these, methylene chloride and 1,2-dichloroethane are particularly preferred.

The reaction temperature for carrying out the cyclization reaction is from -10 ° C to the reflux temperature of the solvent, preferably from 0 ° C to 20 ° C. The reaction time is usually 1 to
24 hours, preferably 2 to 8 hours.

Incidentally, in the method of subjecting the sulfide compound represented by the general formula [1] to a cyclization reaction in the presence of a Lewis acid and a protonic acid, the desired 6
In addition to the -acetylthiochroman derivative and the 5-acetyldihydrobenzo [b] thiophene derivative, as a by-product, a dimer of a raw material sulfide compound or the above diaryl disulfide compound may be produced depending on reaction conditions. In addition,

[0065]

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[Wherein, R ^{1 to} R ⁷ are the same as those of the above-mentioned general formula [2]
Has the same meaning as R ^{1 to} R ^{7 in} A hydrochloride addition compound represented by the formula: (4-acetyl-2,5-
Dimethylphenyl) (3-chloro-3-methylbutane)
Sulfide, (4-acetyl-2-chloro-5-methylphenyl) (3-chloro-3-methylbutane) sulfide, (4-acetyl-2,5-dimethylphenyl) (2
-Chloro-2-methylpropane) sulfide, (4-acetyl-2-chloro-5-methylphenyl) (2-chloro-2-methylpropane) sulfide, and the like may be formed. These hydrochloric acid adducts are converted to the desired 6-acetylthiochroman derivative and 5-acetyldihydro compound by a cyclization reaction in the presence of the above-mentioned Lewis acid and protonic acid or a cyclization reaction in the presence of only the Lewis acid. It can be converted to a benzo [b] thiophene derivative.

Further, the following equation:

[0068]

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[Wherein R ¹ and R ² are the same as defined in the above general formula [1]
Has the same meaning as R ¹ and R ^{2 in} A thioester compound represented by, for example, S- (4-acetyl-
2,5-dimethylphenyl) thioacetate, S-
(4-acetyl-2-chloro-5-methylphenyl) thioacetate, S- (4-acetyl-5-chloro-2-
Methylphenyl) thioacetate or a thiophenol compound such as 4-acetyl-2,5-dimethylthiophenol, 4-acetyl-2-chloro-5-methylthiophenol, 4-acetyl-5-chloro-2-methylthiophenol, etc. May be generated. These thioester compounds can be converted to the thiophenol compound by hydrolysis, and this thiophenol compound can be used as a raw material for producing a sulfide compound represented by the general formula [1].

In addition, the following equation:

[0071]

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[Wherein, R ^{1 to} R ¹³ and n have the same meanings as R ^{1 to} R ¹³ and n in the general formula [2]. Deacetylated thiochroman derivatives such as 4,4,5,8-tetramethylthiochroman, 8-chloro-4,4,5-trimethylthiochroman or benzothiophene derivatives such as 2,3 −
Dihydro-3,3,4,7-tetramethylbenzo [b]
Thiophene, 7-chloro-2,3-dihydro-3,
3,4-Trimethylbenzo [b] thiophene may be formed. These deacetylated compounds can be converted to the desired 6-acetylthiochroman derivative and 5-acetyldihydrobenzo [b] thiophene derivative by acetylating them.

Further, in order to reduce the formation of the diaryl disulfide compound, which is a by-product in the cyclization reaction of the sulfide compound represented by the general formula [1], the reaction system represented by the general formula [5] The represented allyl halide compounds may be added. The amount of the halogenated allyl compound to be added is 0.1 to 2 equivalents, preferably 0.2 to 1 equivalent, based on the sulfide compound as the raw material.

Next, a method for producing the sulfide compound represented by the general formula [1] of the present invention will be described. The first production method of this sulfide compound is represented by the following reaction formula,

[0075]

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Wherein R ^{1 to} R ⁷ , X ¹ , X ² and M
Are R ^{1 to} R ⁷ in the general formulas [1] to [5], X
^It has the same meaning as ¹ , X ² and M. ]. That is, the starting material represented by the general formula [3]
Is reacted with an alkali metal sulfide to obtain a thiophenol compound represented by the general formula [4] or an alkali metal salt thereof. Then
The obtained thiophenol compound or an alkali metal salt thereof is reacted with an allyl halide compound represented by the general formula [5] to obtain a target sulfide compound represented by the general formula [1]. is there.

In this production process, the thiophenol compound or its alkali metal salt obtained by the reaction of the acetophenone compound with the alkali metal sulfide can be continuously reacted with the allyl halide compound without isolation. Or a thiophenol compound obtained by acidification (where M in the general formula [4] is a hydrogen atom)
May be reacted with a thiophenol compound and an allyl halide compound in the presence of a base.

The base used herein is not particularly limited, but includes alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and the like. Suitable examples include inorganic bases such as alkali metal bicarbonate and organic bases such as pyridine and triethylamine.

Examples of the alkali metal sulfide include sodium bisulfide, potassium bisulfide, sodium sulfide, potassium sulfide, and the like, and preferably sodium bisulfide. The amount of the alkali metal sulfide used is 1 to 4 equivalents, preferably 2 to 4 equivalents to the acetophenone compound.
2.5 equivalents.

The solvent used here is not particularly limited as long as it does not hinder the reaction. Lower alcohols such as methanol, ethanol and propanol, ketones such as acetone and methyl isobutyl ketone, tetrahydrofuran, dioxane and dimethoxy Ethers such as ethane and diethylene glycol dimethyl ether;
Examples include aprotic polar solvents such as N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone, and preferred are aprotic polar solvents such as N, N-dimethylformamide.

The reaction temperature for carrying out this reaction is as follows:
Room temperature to 130 ° C, preferably 80 ° C to 100 ° C
It is. The reaction time is usually 1 to 8 hours, preferably 2 to 3 hours.

In this reaction, in addition to the objective thiophenol compound, by-products represented by the following general formula:

[0083]

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[0084] wherein, R ¹ and R ² have the same meaning as R ¹ and R ² in the general formula (1). And di (4-acetyl-2,5-dimethylphenyl) sulfide, di (4-acetyl-2-chloro-5-methylphenyl) sulfide, di (4-acetyl-5- Chloro-2
-Methylphenyl) sulfide and the like may be formed. In addition, the above-mentioned diaryl disulfide compound may be formed, but this diaryl disulfide compound can be converted to a thiophenol compound when reduced.

Next, in the reaction of the thiophenol compound thus obtained with the allyl halide compound, the amount of the allyl halide compound to be used is 1 to 4 equivalents, preferably 1.0 equivalent to the acetophenone compound. 2-2
Equivalent.

In the case of performing the reaction continuously without isolating the thiophenol compound, the solvent used in this reaction may be the same as the solvent used in the previous reaction. When the thiophenol compound is isolated and the next reaction is performed, N, N-dimethylformamide, N, N
Aprotic polar solvents such as N-dimethylacetamide and N-methylpyrrolidone, ketones such as acetone and methyl isobutyl ketone, and halogenated hydrocarbon solvents such as methylene chloride and 1,2-dichloroethane can be used. Among these solvents, N, N-dimethylformamide and acetone are preferably used.

The reaction temperature of the reaction between the thiophenol compound and the allyl halide compound is 0 ° C. to 80 ° C.
° C, preferably 0 ° C to 50 ° C. The reaction time is usually 0.5 to 4 hours, preferably 1 to 2 hours.

In this reaction, various by-products are produced depending on the reaction conditions, in addition to the target sulfide compound. For example,

[0089]

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[Wherein R ^{3 to} R ⁷ are the same as those of the above-mentioned general formula [1]
Has the same meanings as R ^{3 to} R ⁷ . A diallyl sulfide compound represented by, for example, di (3-methyl-
2-Butene) sulfide and di (2-methyl-2-propene) sulfide may be formed. Also, the following equation:

[0091]

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[Wherein R ^{3 to} R ⁷ are the same as those of the above-mentioned general formula [1]
Has the same meanings as R ^{3 to} R ⁷ . ], For example, di (3-methyl-2-butene) disulfide and di (2-methyl-2-propene) disulfide. Further, in a reaction using a thiophenol compound in which R ¹ in the general formula [3] is a halogen atom, the following formula:

[0093]

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[0094] wherein, R ² to R ⁷ and X ¹ is the general formula (1) R ² in and [3] to R ⁷ and X ¹
Has the same meaning as And the positional isomers of the sulfide compound represented by the general formula [2], for example, (2-acetyl-5-chloro-4-methylphenyl) (3-methyl-2-butene) sulfide and , (2-
Acetyl-4,5-dichlorophenyl) (3-methyl-
2-butene) sulfide, (2-acetyl-5-chloro-4-methylphenyl) (2-methyl-2-propene)
Sulfide, (2-acetyl-4,5-dichlorophenyl) (2-methyl-2-propene) sulfide and the like may be formed.

Next, the second method for producing the sulfide compound represented by the general formula [1] of the present invention is represented by the following reaction formula:

[0096]

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Wherein R ^{1 to} R ⁷ , X ¹ and X ² are
R ¹ to R ¹ in the general formulas [1], [3] and [5]
It has the same meaning as R ⁷ , X ¹ and X ² . ]. That is, an acetophenone compound represented by the general formula [3] as a starting material is reacted with an S-allylisothiuronium salt represented by the general formula [6] and an alkali metal hydroxide to form the compound represented by the general formula [ This is a method for obtaining the sulfide compound represented by 1).

The S-allylisothiuronium salt represented by the general formula [6] is preferably produced by a method of producing by reacting an allyl halide compound represented by the general formula [5] with thiourea. is there.

In producing the sulfide compound represented by the general formula [1], an allyl halide compound represented by the general formula [5] is reacted with thiourea to form an S-allylisothiuronium salt. , After isolation, the S-
A method in which an acetophenone compound and an alkali metal hydroxide are reacted with the allylisothiuronium salt may be employed, or the S-allylisothiuronium salt obtained by the reaction of the allyl halide compound with thiourea may be used alone. A method of continuously reacting the product with an acetophenone compound and an alkali metal hydroxide without separation may be employed. Further, a method of reacting an allyl halide compound with thiourea in the coexistence of an acetophenone compound, and then adding an alkali metal hydroxide thereto to cause a reaction may be employed.

The ratio of thiourea used in this reaction is as follows:
0.5 to 1.5 equivalents based on the allyl halide compound,
Preferably it is 0.8 to 1.2 equivalents. The solvent used here is not particularly limited as long as it does not hinder the reaction, and is a two-layer solvent of water with an alcohol such as methanol or ethanol, water or an aromatic hydrocarbon solvent such as toluene or xylene. And a two-layer solvent of ethanol, an aromatic hydrocarbon solvent and water.

The reaction temperature of the reaction between the halogenated allyl compound and thiourea is from room temperature to the reflux temperature of the solvent, preferably from 50 ° C to 110 ° C. The reaction time is usually 1 to 16 hours, preferably 1 to 3 hours.

Next, regarding the reaction of the acetophenone compound with the S-allylisothiuronium salt and the alkali metal hydroxide, the ratio of the S-allylisothiuronium salt used here is 1 to 4 with respect to the acetophenone compound.
Equivalent, preferably 1.1 to 1.5 equivalents. The use ratio of the alkali metal hydroxide used here is 2 to 8 equivalents, preferably 2.2 to 2 with respect to the acetophenone compound.
3 equivalents.

The alkali metal hydroxide used in this reaction includes sodium hydroxide, potassium hydroxide and the like, and is usually used as an aqueous solution. Also,
The solvent used in this reaction is not particularly limited, but alcohols such as methanol and ethanol; aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; A two-layer system of an aromatic hydrocarbon solvent such as xylene and water is exemplified. Among these solvents, a two-layer system of ethanol, an aromatic hydrocarbon solvent and water is preferable.
In a two-layer system of an aromatic hydrocarbon solvent and water, a phase transfer catalyst is preferably added to the two-layer system. Examples of the phase transfer catalyst suitable for use herein include tetra-n-butylammonium chloride and tetra-bromide bromide. Examples include quaternary ammonium salts such as n-butylammonium, and quaternary phosphonium salts such as tetra-n-butylphosphonium chloride and tetra-n-butylphosphonium bromide.

The reaction temperature of the reaction of the acetophenone compound with the S-allylisothiuronium salt and the alkali metal hydroxide is from room temperature to the reflux temperature of the solvent, preferably from 50 ° C to 110 ° C. The reaction time is usually 1 to 12 hours, preferably 1 to 8 hours.

In this reaction, in addition to the target sulfide compound represented by the general formula [1], as a by-product, the same diallyl sulfide as the by-product at the time of the reaction in the first production method is used. Compounds, diallyl disulfide compounds and regioisomers of sulfide compounds may form.

In this reaction, when a compound in which R ³ is a hydrogen atom in the S-allylisothiuronium salt represented by the general formula [6] is used, the following formula:

[0107]

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[Wherein, R ^{1 to} R ⁷ are the same as those of the above general formula [1]
Has the same meanings as R ^{1 to} R ⁷ . A double bond regioisomer, for example, (4-acetyl-2,
5-dimethylphenyl) (3-methyl-1-butene) sulfide, (4-acetyl-2-chloro-5-methylphenyl) (3-methyl-1-butene) sulfide,
(4-acetyl-2,5-dimethylphenyl) (2-methyl-1-propene) sulfide, (4-acetyl-2
-Chloro-5-methylphenyl) (2-methyl-1-propene) sulfide and the like may be formed.

[0109]

EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 (4-acetyl-2,5-
Production of dimethylphenyl) (3-methyl-2-butene) sulfide (1) Production of thiophenol compound As an alkali metal sulfide, 70% sodium hydrosulfide 63
g (787 mmol, 3.0 equiv.)
It was suspended in 200 ml of N-dimethylformamide and heated to 100 ° C. Next, 47.9 g (262 mmol) of 4-chloro-2,5-dimethylacetophenone was used as an acetophenone compound.
A solution dissolved in 150 ml of N-dimethylformamide was added dropwise to the previously prepared suspension of sodium hydrosulfide over 1 hour. After the dropwise addition, the reaction solution was heated to 150 ° C., and reacted while stirring for 4 hours.

(2) Production of sulfide compound The reaction mixture containing the thiophenol compound obtained in the above (1) was cooled to 10 to 15 ° C, and 1-chloro-3-methyl as an allyl halide compound was added thereto. 44.3 ml (393 mmol, 1.5 equivalents) of 2-butene was added dropwise over 43 minutes while maintaining the temperature at 10 to 15 ° C. After the dropwise addition, the temperature of the reaction solution was returned to room temperature, and the reaction was performed with stirring for 2 hours.

Subsequently, water was added to the obtained reaction mixture,
Extracted with toluene. The extract was washed sequentially with water three times and saturated saline once, and then dried over anhydrous sodium sulfate. Further, the solvent is distilled off under reduced pressure, and the crude product is purified by silica gel column chromatography to obtain the desired (4-acetyl-2,5-dimethylphenyl).
37.5 g (yield 58%) of (3-methyl-2-butene) sulfide was obtained. Structural formula and ¹ H of the obtained compound
Table 1 shows the NMR data.

Example 2 (4-acetyl-2-chloro-5-methylphenyl) (3-methyl-2-butene)
Production of sulfide (1) Production of thiophenol compound Instead of 4-chloro-2,5-dimethylacetophenone as an acetophenone compound, 4,5-dichloro-2-
Use methyl acetophenone and set the reaction temperature to 80 ° C
A thiophenol compound was produced in the same manner as in Example 1, (1) except that the reaction time was changed to 2 hours.

(2) Production of sulfide compound The desired (4-acetyl-2-chloro-5-methylphenyl) (3-methyl-2-butene) sulfide was prepared in the same manner as in Example 1, (2). , With a yield of 84%.

Structural formula and ¹ H-NM of the obtained compound
Table 1 shows the R data. When the crude product obtained by this reaction was purified by silica gel column chromatography, a by-product was obtained in a yield of 7%. About this by-product, ¹ H-NMR (deuterated chloroform solvent; TMS
(Standard), the result was 2.44 (s, 6H) pp
m, 2.59 (s, 6H) ppm, 7.01 (s, 2
H) ppm, an absorption peak was observed at 7.79 (s, 2H) ppm.

[0116]

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The compound was identified as di (4-acetyl-2-chloro-5-methylphenyl) sulfide.

Example 3 (4-acetyl-5-chloro-2-methylphenyl) (3-methyl-2-butene)
Production of sulfide (1) Production of S-allylisothiuronium salt 7.6 g (100 mmol) of thiourea was added to ethanol 1
The suspension was suspended in 0 ml and heated to the reflux temperature. Then, 12 g (110 mmol, 1.1 equivalents) of 1-chloro-3-methyl-2-butene as an allyl halide compound was added dropwise to the previously prepared suspension over 30 minutes, and 2 g
Heated to reflux for an hour. Next, the obtained reaction product was cooled to room temperature, 60 ml of n-hexane was added to precipitate a solid, and the solid was separated by filtration and dried to obtain 15.5 g of 3-methyl-2-butenylisothiuronium chloride ( Yield 8
6%).

(2) Production of sulfide compound As an acetophenone compound, 2,4-dichloro-5-
Using 8.3 g (41 mmol) of methyl acetophenone, 8.2 g (45 mmol, 1.1 mmol) of 3-methyl-2-butenylisothiuronium chloride obtained in the above (1) was used.
Eq.) And 1.4 g (4.3 mmol, 0.1 eq.) Of tetra-n-butylammonium bromide as a phase transfer catalyst.
After suspending in 25 ml of toluene and raising the temperature to 70 ° C., a 20% by weight aqueous sodium hydroxide solution 21 was added.
Milliliter (128 mmol, 3.1 eq) was added dropwise over 30 minutes and then stirred at 90 ° C. for 2 hours.

Next, ice water was added to the obtained reaction mixture, and the mixture was extracted with toluene. Further, the extract was washed successively with 5% hydrochloric acid, water and saturated saline, and then dried over anhydrous sodium sulfate. Then, the solvent is distilled off under reduced pressure, and the obtained crude product is purified by silica gel column chromatography to obtain the desired (4-acetyl-5-chloro-2-methylphenyl) (3-methyl-2-methylphenyl). 7.6 g (69% yield) of butene) sulfide were obtained.

The structural formula of the obtained compound and ¹ H-NM
Table 1 shows the R data. When the crude product obtained by this reaction was purified by silica gel column chromatography, a by-product was obtained in a yield of 12%. About this by-product, ¹ H-NMR (deuterated chloroform solvent; TM
1.72 (s, 3H) p
pm, 1.74 (s, 3H) ppm, 2.38 (s, 3H)
H) ppm, 2.58 (s, 3H) ppm, 3.51
(D, 2H) ppm, 5.28 (d, 1H) ppm,
7.30 (s, 1H) ppm, 7.62 (s, 1H) p
pm, an absorption peak was observed.

[0122]

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(2-acetyl-5-chloro-4-methylphenyl) (3-methyl-2-butene) sulfide represented by the following formula:

Example 4 Production of (4-acetyl-5-chloro-2-methylphenyl) (2-methyl-2-propene) sulfide (1) Production of S-allylisothiuronium salt Instead of 1-chloro-3-methyl-2-butene used in (1), 1-chloro-2-methyl-2
-Same as (1) of Example 3 except that propene was used. (2) Production of sulfide compound 3-methyl-2-chloride used in (2) of Example 3
2-Methyl chloride instead of butenylisothiuronium
Except that 2-propenylisothiuronium was used, the target (4-acetyl-acetyl) was prepared in the same manner as in Example 3, (2).
5-chloro-2-methylphenyl) (2-methyl-2-
Propene) sulfide was obtained in 70% yield.

Structural formula and ¹ H-NM of the obtained compound
Table 1 shows the R data. When the crude product obtained by this reaction was purified by silica gel column chromatography, a by-product was obtained in a yield of 18%. About this by-product, ¹ H-NMR (deuterated chloroform solvent; TM
1.89 (s, 3H) p
pm, 2.37 (s, 3H) ppm, 2.59 (s, 3
H) ppm, 3.52 (s, 2H) ppm, 4.95
(S, 1H) ppm, 5.02 (s, 1H) ppm,
7.33 (s, 1H) ppm, 7.61 (s, 1H) p
pm, an absorption peak was observed.

[0126]

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(2-acetyl-5-chloro-4-methylphenyl) (2-methyl-2-propene)
It was found to be a sulfide.

Example 5 Production of (4-acetyl-2-chloro-5-methylphenyl) (2-methyl-2-propene) sulfide (1) Production of S-allylisothiuronium salt Thiourea 1 g (14 mmol) of ethanol 10
It was suspended in milliliters and heated to the reflux temperature. Then, 1.3 g (14 mmol, 1.4 equivalents) of 1-chloro-3-methyl-2-propene as an allyl halide compound was added dropwise to the suspension prepared above over 18 minutes, and 5 g
Heated to reflux for an hour. (2) Production of sulfide compound The reaction solution obtained in the above (1) is cooled, and
2.0 g of dichloro-2-methylacetophenone (9.
8 mmol), and the temperature was raised to 70 ° C. again.
6.8 ml (41 mmol, 4.2 equivalents) of an aqueous solution of sodium hydroxide at a concentration of% by weight was added dropwise over 8 minutes, and then the mixture was refluxed for 7 hours.

Next, ice water was added to the obtained reaction mixture, and the mixture was extracted with toluene. In addition, 5% hydrochloric acid,
After washing with water and saturated saline solution in that order, it was dried over anhydrous sodium sulfate. Then, the solvent is distilled off under reduced pressure, and the obtained crude product is purified by silica gel column chromatography to obtain the desired (4-acetyl-2-chloro-
1.6 g (yield 64%) of 5-methylphenyl) (2-methyl-2-propene) sulfide was obtained. Table 1 shows the structural formula and ¹ H-NMR data of the obtained compound.

Example 6 6-acetyl-4,4,4
Production of 5,8-tetramethylthiochroman As a sulfide compound as a raw material, (4-acetyl-2,
1.0 g (4.0 mmol) of 5-dimethylphenyl) (3-methyl-2-butene) sulfide was added to 1,2 of the solvent.
-Dissolved in 5 ml of dichloroethane and added thereto 0.1 g of concentrated sulfuric acid as protonic acid (1.0 mmol, 0.1 mmol).
(25 equivalents) and a cyclization reaction was carried out at 40 ° C. with stirring for 48 hours.

Ice water was added to the resulting reaction mixture to give 1,
The mixture was extracted with 2-dichloroethane, washed sequentially with an aqueous sodium hydrogen carbonate solution and saturated saline, and then dried over anhydrous sodium sulfate. Next, the solvent was distilled off under reduced pressure, and the crude product was purified by silica gel column chromatography to obtain 0.55 g of the desired 6-acetyl-4,4,5,8-tetramethylthiochroman (55% yield). I got Table 1 shows the structural formula and ¹ H-NMR data of the obtained compound.

Example 7 Production of 6-acetyl-8-chloro-4,4,5-trimethylthiochroman In Example 6, (4-acetyl-2,
Instead of (5-dimethylphenyl) (3-methyl-2-butene) sulfide, (4-acetyl-2-chloro-5-
Example 6 was repeated except that methylphenyl) (3-methyl-2-butene) sulfide was used.

As a result, the desired 6-acetyl-8-
Chloro-4,4,5-trimethylthiochroman yield 4
Obtained at 3%. The structural formula and ¹ H-
The NMR data is shown in Table 1.

Example 8 Production of 6-acetyl-5-chloro-4,4,8-trimethylthiochroman As a Lewis acid, 2.96 g of aluminum chloride (22.
2 mmol, 3.0 equivalents), suspended in 10 ml of 1,2-dichloroethane, cooled to 0 ° C. in an ice-water bath, and then added with concentrated hydrochloric acid 0.1% as a protonic acid.
6 ml (1.9 mmol, 0.26 equivalent) was added dropwise, and the mixture was stirred for 3 minutes until the reaction temperature returned to 0 ° C.

Next, as a sulfide compound, 2.0 g (7.4 mmol) of (4-acetyl-5-chloro-2-methylphenyl) (3-methyl-2-butene) sulfide was used. 1-chloro-3-methyl-2- as an allyl halide compound for suppressing the formation of
Butene 0.17 ml (1.5 mmol, 0.2
(Equivalent) in 10 ml of 1,2-dichloroethane was added dropwise over 30 minutes while maintaining the temperature at 0 to 2 ° C., and the mixture was stirred for 5 hours.

Then, the obtained reaction product solution was added to ice,
Extracted twice with 1,2-dichloroethane. The obtained extract was washed twice with an aqueous sodium hydroxide solution and then dried over anhydrous sodium sulfate. Then, the solvent is distilled off under reduced pressure,
By purifying the obtained crude product by silica gel column chromatography, the desired 6-acetyl-5
-Chloro-4,4,8-trimethylthiochroman 0.6
0 g (30% yield) was obtained.

Structural formula of the obtained compound and ¹ H-NM
Table 1 shows the R data. Further, the above sodium hydroxide washing solution was acidified with concentrated hydrochloric acid and extracted with ethyl acetate.
After drying with anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain 0.52 g of a by-product (yield: 35%).
The obtained by-product was analyzed by ¹ H-NMR (deuterated chloroform solvent; TMS standard), and as a result, 2.30
(S, 3H) ppm, 2.63 (s, 3H) ppm,
3.50 (s, 1H) ppm, 7.30 (s, 1H) p
pm, an absorption peak was observed at 7.52 (s, 1H) ppm.

[0138]

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4-acetyl-5-chloro-2 represented by
-Methylthiophenol was confirmed.

Example 9 Production of 5-acetyl-2,3-dihydro-3,3,4,7-tetramethylbenzo [b] thiophene The starting material used in Example 8 (4-acetyl-5- Chloro-2-methylphenyl) (3-methyl-2-butene)
Instead of sulfide, (4-acetyl-2,5-dimethylphenyl) (2-methyl-2-propene) sulfide is used, and 1-chloro- as an allyl halide compound added for suppressing generation of by-products is used. Except that 2-methyl-2-propene was used, the same procedure was followed as in Example 8 to obtain the desired 5-acetyl-2,3-dihydro-3,3,4,7-.
Tetramethylbenzo [b] thiophene was obtained with a yield of 83%. Table 1 shows the structural formula and ¹ H-NMR data of the obtained compound.

Example 10 Production of 5-acetyl-7-chloro-2,3-dihydro-3,3,4-trimethylbenzo [b] thiophene As a Lewis acid, 3.12 g of aluminum chloride (23.4)
Mmol, 3.0 equiv.), Which was suspended in 5 ml of 1,2-dichloroethane, and (4)
-Acetyl-2-chloro-5-methylphenyl) (2-
A solution prepared by dissolving 2.0 g (7.8 mmol) of methyl-2-propene) sulfide and 0.45 ml of acetic acid (7.9 mmol, 1.0 equivalent) in 5 ml of 1,2-dichloroethane was added to The solution was added dropwise over 28 minutes while maintaining the temperature at １２12 ° C., followed by stirring for 2 hours. Next, the obtained reaction mixture was added to ice, extracted twice with 1,2-dichloroethane, and dried over anhydrous sodium sulfate.
Further, the solvent was distilled off under reduced pressure, and the crude product was purified by silica gel column chromatography to obtain the desired 5-acetyl-7-chloro-2,3-dihydro-3,
1.36 g of 3,4-trimethylbenzo [b] thiophene
(68% yield).

Structural formula and ¹ H-NM of the obtained compound
Table 1 shows the R data. Further, upon purification of the above crude product by silica gel column chromatography,
0.28 g (18% yield) of the first by-product was obtained.
About the ^{first by} -product obtained here, ¹ H-NMR
(Deuterated chloroform solvent; TMS standard), the result was 2.48 (s, 6H) ppm, 2.55 (s, 6
H) ppm, 7.37 (s, 2H) ppm, 7.69
An absorption peak was observed at (s, 2H) ppm, and the following formula:

[0143]

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The compound was identified to be di (4-acetyl-2-chloro-5-methylphenyl) disulfide. In addition, at the time of the above purification, the second by-product 0.1.
11 g (5% yield) were obtained. The second by-product obtained here was analyzed by ¹ H-NMR (deuterated chloroform solvent; TMS standard). As a result, 1.72 (s,
6H) ppm, 2.51 (s, 3H) ppm, 2.56
(S, 3H) ppm, 3.42 (s, 2H) ppm,
7.17 (s, 1H) ppm, 7.70 (s, 1H) p
pm, an absorption peak was observed.

[0145]

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(4-Acetyl-2-chloro-5-methylphenyl) (2-chloro-2-methylpropane) sulfide represented by the following formula:

Reference Example Production of 2,4-dichloro-5-methylacetophenone 2,4-Dichloro-5-methylacetophenone used in this example was produced by the following method. 15 g (112 mmol, 1.1 equivalents) of aluminum chloride were added to 2,4
After suspending in 16.1 g (100 mmol) of dichlorotoluene and raising the temperature to 50 ° C., 7.8 ml (110 mmol, 1.1 equivalents) of acetyl chloride was added dropwise over 15 minutes, and then 1.70 g at 70 ° C. The reaction was performed with stirring for 5 hours.

Next, after cooling the reaction mixture, ice water was added and the mixture was extracted with toluene. The extract was washed sequentially with 5% hydrochloric acid, water and saturated saline, and then dried over anhydrous sodium sulfate. Further, the solvent is distilled off under reduced pressure, and the crude product is purified by distillation under reduced pressure to obtain the desired compound 1
6.7 g (82% yield) were obtained. ¹ H-NMR (deuterated chloroform solvent; TMS standard) for the obtained compound
2.36 (s, 3H) ppm,
2.63 (s, 3H) ppm, 7.42 (s, 1H) p
An absorption peak was observed at pm, 7.45 (s, 1H) ppm, and it was confirmed that this compound was 2,4-dichloro-5-methylacetophenone.

[0149]

[Table 1]

[0150]

According to the present invention, a novel sulfide compound having high utility as an intermediate for producing a pyrazole derivative and a cyclohexanedione derivative, which are active ingredients of a herbicide, and a 6-acetylthiochroman derivative or It is possible to provide a method for producing a 5-acetyldihydrobenzo [b] thiophene derivative in a simple process at low cost.

Claims (6)

[Claims] 1. A compound represented by the general formula [1]: [Wherein, R ¹ and R ² each independently represent a halogen atom or an alkyl group having 1 to 4 carbon atoms, and R ³ , R ⁴ , R ⁵ ,
R ⁶ and R ⁷ each independently represent a hydrogen atom or a carbon number of 1 to 4;
Represents an alkyl group. Also, R ⁵ and R ⁶ and R ⁶ and R
⁷ may be arbitrarily bonded to each other on a carbon atom to form a 3- to 7-membered saturated hydrocarbon ring. ] The sulfide compound represented by these. 2. A compound of the general formula [1] [Wherein, R ¹ and R ² each independently represent a halogen atom or an alkyl group having 1 to 4 carbon atoms, and R ³ , R ⁴ , R ⁵ ,
R ⁶ and R ⁷ each independently represent a hydrogen atom or a carbon number of 1 to 4;
Represents an alkyl group. Also, R ⁵ and R ⁶ and R ⁶ and R
⁷ may be arbitrarily bonded to each other on a carbon atom to form a 3- to 7-membered saturated hydrocarbon ring. A cyclization reaction of the sulfide compound represented by the general formula [2], [Wherein, R ¹ and R ² each independently represent a halogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁸ , R ⁹ , R ¹⁰ ,
R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ¹¹ and R ¹² and R
¹² and R ¹³ are each optionally bonded to each other on a carbon atom,
It may form a 3- to 7-membered saturated hydrocarbon ring. n represents 1 or 0. And a 5-acetyldihydrobenzo [b] thiophene derivative represented by the following formula: 3. A compound of the general formula [1] [Wherein, R ¹ and R ² each independently represent a halogen atom or an alkyl group having 1 to 4 carbon atoms, and R ³ , R ⁴ , R ⁵ ,
R ⁶ and R ⁷ each independently represent a hydrogen atom or a carbon number of 1 to 4;
Represents an alkyl group. Also, R ⁵ and R ⁶ and R ⁶ and R
⁷ may be arbitrarily bonded to each other on a carbon atom to form a 3- to 7-membered saturated hydrocarbon ring. Wherein the sulfide compound represented by the general formula [2] is subjected to a cyclization reaction in the presence of a Lewis acid and a protonic acid. [Wherein, R ¹ and R ² each independently represent a halogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁸ , R ⁹ , R ¹⁰ ,
R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ¹¹ and R ¹² and R
¹² and R ¹³ are each optionally bonded to each other on a carbon atom,
It may form a 3- to 7-membered saturated hydrocarbon ring. n represents 1 or 0. And a 5-acetyldihydrobenzo [b] thiophene derivative represented by the following formula: 4. A compound of the general formula [3] [Wherein, R ¹ and R ² each independently represent a halogen atom or an alkyl group having 1 to 4 carbon atoms, and X ¹ represents a halogen atom. The acetophenone compound represented by the general formula [4] is reacted with an alkali metal sulfide. [Wherein, R ¹ and R ² each independently represent a halogen atom or an alkyl group having 1 to 4 carbon atoms, and M represents a hydrogen atom or an alkali metal. To produce a thiophenol compound represented by the general formula [5]: ^{Wherein, R 3, R 4, R} 5, R 6, R 7 are, each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁵
And R ⁶ and R ⁶ and R ⁷ may be arbitrarily bonded to each other on a carbon atom to form a 3- to 7-membered saturated hydrocarbon ring. X ² represents a halogen atom. ]
Reacting an allyl halide compound represented by the general formula [1]: [Wherein, R ¹ and R ² each independently represent a halogen atom or an alkyl group having 1 to 4 carbon atoms, and R ³ , R ⁴ , R ⁵ ,
R ⁶ and R ⁷ each independently represent a hydrogen atom or a carbon number of 1 to 4;
Represents an alkyl group. Also, R ⁵ and R ⁶ and R ⁶ and R
⁷ may be arbitrarily bonded to each other on a carbon atom to form a 3- to 7-membered saturated hydrocarbon ring. ] The method for producing a sulfide compound represented by the formula: 5. A compound represented by the general formula [3]: [Wherein, R ¹ and R ² each independently represent a halogen atom or an alkyl group having 1 to 4 carbon atoms, and X ¹ represents a halogen atom. The acetophenone compound represented by the general formula [6]: ^{Wherein, R 3, R 4, R} 5, R 6, R 7 are, each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁵
And R ⁶ and R ⁶ and R ⁷ may be arbitrarily bonded to each other on a carbon atom to form a 3- to 7-membered saturated hydrocarbon ring. X ² represents a halogen atom. ]
Wherein an S-allylisothiuronium salt represented by the following formula and an alkali metal hydroxide are reacted: [Wherein, R ¹ and R ² each independently represent a halogen atom or an alkyl group having 1 to 4 carbon atoms, and R ³ , R ⁴ , R ⁵ ,
R ⁶ and R ⁷ each independently represent a hydrogen atom or a carbon number of 1 to 4;
Represents an alkyl group. Also, R ⁵ and R ⁶ and R ⁶ and R
⁷ may be arbitrarily bonded to each other on a carbon atom to form a 3- to 7-membered saturated hydrocarbon ring. ] The method for producing a sulfide compound represented by the formula: 6. A compound of the general formula [3] [Wherein, R ¹ and R ² each independently represent a halogen atom or an alkyl group having 1 to 4 carbon atoms, and X ¹ represents a halogen atom. The acetophenone compound represented by the general formula [5], ^{Wherein, R 3, R 4, R} 5, R 6, R 7 are, each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁵
And R ⁶ and R ⁶ and R ⁷ may be arbitrarily bonded to each other on a carbon atom to form a 3- to 7-membered saturated hydrocarbon ring. X ² represents a halogen atom. ]
A general formula [6] obtained by reacting an allyl halide compound represented by the following formula with thiourea: ^{Wherein, R 3, R 4, R} 5, R 6, R 7 are, each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁵
And R ⁶ and R ⁶ and R ⁷ may be arbitrarily bonded to each other on a carbon atom to form a 3- to 7-membered saturated hydrocarbon ring. X ² represents a halogen atom. ]
Wherein an S-allylisothiuronium salt represented by the following formula and an alkali metal hydroxide are reacted: [Wherein, R ¹ and R ² each independently represent a halogen atom or an alkyl group having 1 to 4 carbon atoms, and R ³ , R ⁴ , R ⁵ ,
R ⁶ and R ⁷ each independently represent a hydrogen atom or a carbon number of 1 to 4;
Represents an alkyl group. Also, R ⁵ and R ⁶ and R ⁶ and R
⁷ may be arbitrarily bonded to each other on a carbon atom to form a 3- to 7-membered saturated hydrocarbon ring. ] The method for producing a sulfide compound represented by the formula: