JP2005139098A - Method for producing 1-thio-2-propanone derivative and 5-methyl-5-thiomethylhydantoin derivative - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide methods for simply and industrially producing a 1-thio-2-propanone derivative and a 5-methyl-5-thiomethylhydantoin derivative which are useful as intermediates for medicines and the like, respectively, while suitably controlling unpleasant odors. <P>SOLUTION: The method for producing an odor-controlled 1-thio-2-propanone derivative is characterized by reacting a haloacetone with mercaptan to produce the 1-thio-2-propanone derivative and then washing the 1-thio-2-propanone derivative or its solution with a basic solution. The method for producing 5-methyl-5-thiomethylhydantoin derivative from the 1-thio-2-propanone derivative obtained by the method is also disclosed. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for producing a 1-thio-2-propanone derivative and a 5-methyl-5-thiomethylhydantoin derivative useful as an intermediate of a pharmaceutical product. More specifically, the present invention relates to a method for producing a 1-thio-2-propanone derivative and a 5-methyl-5-thiomethylhydantoin derivative with suppressed odor.

  The 5-methyl-5-thiomethylhydantoin derivative and the 1-thio-2-propanone derivative that is a raw material thereof are described in WO01 / 72702 (Patent Document 1) and WO01 / 72703 (Patent Document 2). It is useful as an intermediate for pharmaceuticals such as anti-inflammatory drugs. As an example of synthesizing the above compound, for example, the following method is known.

  1) Sodium and mercaptan are added to ethanol, chloroacetone is added to synthesize a 1-thio-2-propanone derivative, water is added to perform ether extraction, and then drying and concentration are performed to obtain 1-thio-2- Isolate the propanone derivative. A 1-thio-2-propanone derivative is dissolved in 70-80% ethanol, and potassium cyanide and ammonium carbonate are reacted to synthesize a 5-methyl-5-thiomethylhydantoin derivative. Ethanol is removed by concentration, and the crude product is cooled and crude. A 5-methyl-5-thiomethylhydantoin derivative is obtained (Agr. Biol. Chem., 1971, 35, 53-57: Non-patent document 1).

  2) Sodium hydroxide and mercaptan are added to water / ethanol, and chloroacetone is added to synthesize a 1-thio-2-propanone derivative. After adding water and extracting with ether, 1-thio- is obtained after drying and concentration. 2-Propanone derivative is isolated. After dissolving 1-thio-2-propanone derivative in 60% ethanol and reacting with potassium cyanide and ammonium carbonate, the solution is concentrated and cooled to obtain a crude 5-methyl-5-thiomethylhydantoin derivative (Bull. Korean Chem. Soc., 1988, 9, 231-235: Non-Patent Document 2).

  As a result of preliminary examination of the above method by the present inventors, the 1-thio-2-propanone derivative and 5-methyl-5-thiomethylhydantoin derivative obtained by the above method have a strong odor (mercapto odor). It became clear that Due to this odor, when handling 1-thio-2-propanone derivatives on an industrial scale or producing 5-methyl-5-thiohydantoin derivatives from 1-thio-2-propanone derivatives, the odor does not leak to the surrounding environment. Such a treatment and equipment are required, which is a problem in efficiently producing a 5-methyl-5-thiohydantoin derivative.

However, in the above-mentioned prior art documents, not only a method for suppressing odor, but also whether the odor is caused by a 1-thio-2-propanone derivative or 5-methyl-5-thiomethylhydantoin derivative itself, or by impurities mixed therein. Even not described or suggested.
WO01 / 72702 WO01 / 72703 Agr. Biol. Chem. , 1971, 35, 53-57 Bull. Korean Chem. Soc. , 1988, 9, 231-235

  In the production of 1-thio-2-propanone derivatives and 5-methyl-5-thiomethylhydantoin derivatives useful as intermediates for pharmaceuticals, the present invention solves the above problems and suitably suppresses odor. The object is to provide a practical method for producing thio-2-propanone derivatives and 5-methyl-5-thiomethylhydantoin derivatives on a large scale (industrial scale).

  As a result of investigations by the present inventors to solve the above problems, surprisingly, the odor of the 1-thio-2-propanone derivative and the 5-methyl-5-thiomethylhydantoin derivative is mainly an impurity rather than the compound itself. Surprisingly, after synthesizing the intermediate 1-thio-2-propanone derivative, the solution of 1-thio-2-propanone derivative or 1-thio-2-propanone derivative was replaced with a basic solution. It was found that by adding a simple operation such as washing, the above-mentioned problem can be solved by suitably suppressing odor.

That is, the present invention relates to the general formula (1):
CH ₃ COCH ₂ X (1)
(Wherein X represents a halogen atom), the general formula (2):
R ₁ SH (2)
(In the formula, R ₁ has an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted aralkyl group having 7 to 20 carbon atoms, or a substituent. And a mercaptan represented by the general formula (3):

(Wherein R ₁ is as defined above), and the 1-thio-2-propanone derivative or a solution thereof is washed with a basic solution. The present invention relates to a method for producing a 1-thio-2-propanone derivative with suppressed odor.

Furthermore, the present invention relates to a general formula (1):
CH ₃ COCH ₂ X (1)
(Wherein X represents a halogen atom), the general formula (2):
R ₁ SH (2)
(Wherein R ₁ is the same as above) is reacted with a general formula (3):

(Wherein R ₁ is the same as above), the 1-thio-2-propanone derivative or the solution thereof is washed with a basic solution, (4):

(Wherein R ₁ is the same as above), a odor-suppressed 5-methyl-5-thiomethylhydantoin derivative characterized in that It also relates to the manufacturing method.

  According to the present invention, 1-thio-2-propanone derivatives and 5-methyl-5-thiomethylhydantoin derivatives useful as intermediates for pharmaceuticals and the like are suitably produced even on a large scale (industrial scale). be able to.

The present invention will be further described below.
The haloacetone used in the present invention is represented by the formula (1). In the formula (1), X represents a halogen atom, and examples of the haloacetone represented by the formula (1) include fluoroacetone, chloroacetone, bromoacetone, and iodoacetone. Preferred is chloroacetone or bromoacetone, and more preferred is chloroacetone.

The mercaptan used in the present invention is represented by the formula (2). In the formula (2), R ₁ has an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, and a substituent. Represents an aryl group having 6 to 20 carbon atoms which may be present.

  The alkyl group having 1 to 20 carbon atoms is not particularly limited, and may be a linear alkyl group such as a methyl group, an ethyl group, or a propyl group, or an isopropyl group, an isobutyl group, a t-butyl group, or a neopentyl group. And a branched alkyl group such as a t-pentyl group. The alkyl group may be unsubstituted or may have a substituent. Examples of the substituent include an amino group, a hydroxyl group, a phenyl group, an aryl group, an alkanoyl group, an alkenyl group, an alkynyl group, an alkoxyl group, a nitro group, and a halogen atom.

  Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, p-methoxybenzyl group, phenethyl group, naphthylmethyl group and the like. The aralkyl group may be unsubstituted or may have a substituent. Examples of the substituent include amino group, hydroxyl group, phenyl group, aryl group, alkanoyl group, alkenyl group, alkynyl group, alkoxyl group, nitro group, halogen atom and the like.

  Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group and a naphthyl group. The aryl group may be unsubstituted or may have a substituent. Examples of the substituent include amino group, hydroxyl group, phenyl group, aryl group, alkanoyl group, alkenyl group, alkynyl group, alkoxyl group, nitro group, halogen atom and the like.

Among them, R ₁ is preferably the alkyl group or the aralkyl group, more preferably a t-butyl group or a benzyl group, and further preferably a t-butyl group.

  Next, a method for producing the 1-thio-2-propanone derivative represented by the formula (3) will be described. The 1-thio-2-propanone derivative (3) can be produced by reacting the haloacetone (1) and mercaptan (2) in the presence of a base in a solvent or without a solvent.

  The base to be used is not particularly limited, and for example, an inorganic base such as an alkali metal or alkaline earth metal hydroxide may be used, or a liquid or solid organic base may be used. Further, these bases may be used as an aqueous solution or a solution. Preferred are aqueous solutions of alkali metal hydroxides such as sodium hydroxide, lithium hydroxide and potassium hydroxide, and aqueous solutions of alkaline earth metal hydroxides such as barium hydroxide, magnesium hydroxide and calcium hydroxide, particularly preferred. Is an aqueous solution of the above alkali metal hydroxide, in particular an aqueous sodium hydroxide solution.

  The amount of the base used is not particularly limited as long as it is equivalent to the mercaptan or more, but the equivalent of the base is 1 to 10 times mol, preferably 1 to 3 times mol to the mercaptan used in the reaction. From the viewpoint of stability under basic conditions, the amount is more preferably 1 to 1.5 times mol.

  The solvent to be used is not particularly limited. The reaction may be performed in a highly polar solvent such as water or alcohol, or may be performed in a mixed solution of a highly polar solvent and a less polar solvent. When the reaction is carried out with an aqueous solvent, the 1-thio-2-propanone derivative is particularly preferable since it can be separated and taken out without being dissolved in water after the reaction.

  The feed concentration is not particularly limited, but it is usually carried out at a mercaptan concentration of 0.5 to 50% by weight. It is preferably 1 to 40% by weight, more preferably 5 to 30% by weight, especially 10 to 20% by weight. If the concentration is too low, the volumetric efficiency is poor and not efficient.

  The amount of haloacetone used is not particularly limited as long as it is equivalent to or higher than the mercaptan, but the equivalent of haloacetone is 1 to 10 times mol, preferably 1 to 3 times mol to the mercaptan used in the reaction. From a viewpoint, it is 1.0-1.5 times mole more preferably.

    The temperature during the reaction is not particularly limited, but is usually 100 ° C. or lower, preferably 80 ° C. or lower, more preferably 60 ° C. or lower, still more preferably 40 ° C. or lower, especially 30 ° C. or lower. The lower limit may be a temperature at which the reaction system does not freeze, and is usually 0 ° C. or higher, preferably 5 ° C. or higher. Usually, it can be suitably performed at room temperature.

Next, cleaning with a basic solution performed in the present invention will be described.
The 1-thio-2-propanone derivative obtained by the above reaction may be washed as it is in the reaction solution, or a conventional separation method such as separation, extraction, concentration, crystallization, or column chromatography. Alternatively, they may be washed after being separated and isolated by a combination thereof. When an aqueous solvent is used for the synthesis of the 1-thio-2-propanone derivative, the reaction solution is usually separated into a 1-thio-2-propanone derivative layer and an aqueous solution layer. It is preferable to wash the thio-2-propanone derivative layer with a basic solution.

  In the case of washing the isolated 1-thio-2-propanone derivative, washing may be performed without diluting with a solvent, or washing with diluting with a solvent.

  The solvent used for dilution is not particularly limited as long as it dissolves the 1-thio-2-propanone derivative and does not inhibit the washing of the basic solution. It may be diluted with a mixed solvent of water and an organic solvent, or may be diluted with an organic solvent. Examples of the organic solvent include hydrocarbon solvents and ester solvents.

  Although it does not specifically limit as a hydrocarbon type organic solvent, For example, toluene, benzene, xylene, hexane, a cyclohexane, a heptane etc. are mentioned, Preferably it is toluene from the point of economical efficiency.

  The ester solvent is not particularly limited, and examples thereof include methyl acetate, ethyl acetate, propyl acetate, methyl propionate, and ethyl propionate, and ethyl acetate is preferable.

  The above organic solvents may be used alone or in combination.

  From the viewpoint of volumetric efficiency and low waste, it is preferable to wash with a basic solution without diluting the 1-thio-2-propanone derivative with a solvent.

  The basic solution used in the present invention is preferably a basic aqueous solution, but is not particularly limited, and an alkali metal or alkaline earth metal hydroxide may be used as the aqueous solution, or a liquid or solid organic base. May be used as a solution or dissolved in a solvent such as water. Preferably, an aqueous solution of an alkali metal hydroxide such as sodium hydroxide, lithium hydroxide, potassium hydroxide or the like, or barium hydroxide, magnesium hydroxide, water, which is unlikely to remain in the 1-thio-2-propanone derivative. An aqueous solution of an alkaline earth metal hydroxide such as calcium oxide is preferable, and an aqueous solution of the above alkali metal hydroxide, particularly an aqueous sodium hydroxide solution is particularly preferable.

  Although the usage-amount of a basic solution is not specifically limited, It is 0.01-10 times mole with respect to the mercaptan used for reaction as an equivalent of a base, Preferably it is 0.05-1 times mole, More preferably, it is 0.8. 1 to 0.5 times mole.

  The concentration of the basic solution is not particularly limited, but is usually 0.5 to 50%, preferably 1 to 10%, and more preferably 2 to 5%. If the concentration is too low, the volumetric efficiency is poor and not efficient.

  Although it does not specifically limit about the frequency | count of washing | cleaning with a basic solution, Usually, 1-5 times, Preferably it is 2-4 times, More preferably, it is 3 times. When the number of washings exceeds 5, the effect is not commensurate with the number of washings and it is not efficient.

  The temperature at the time of washing is not particularly limited, but is usually 100 ° C. or lower, preferably 80 ° C. or lower, more preferably 60 ° C. or lower, still more preferably 40 ° C. or lower, especially 30 ° C. or lower. The lower limit may be a temperature at which the washing system does not freeze, and is usually 0 ° C. or higher, preferably 10 ° C. or higher. Usually, it can be suitably performed at room temperature.

  Finally, the conversion of a 1-thio-2-propanone derivative whose odor is suppressed by washing into a 5-methyl-5-thiomethylhydantoin derivative will be described.

  Hydantoin derivative synthesis from 1-thio-2-propanone derivative is, for example, a general method of hydantoin synthesis (Bucherer's hydantoin synthesis), that is, the 1-thio-2-propanone derivative is converted to metal cyanide and ammonium in a solvent. It can be carried out by a method of reacting with a compound. The solvent to be used is not particularly limited, and the reaction may be performed with a mixed solvent of water and an organic solvent, or the reaction may be performed using only water as a solvent.

  Examples of the organic solvent include alcohol solvents, ether solvents, nitrile solvents, hydrocarbon solvents, ester solvents, and the like.

  Although it does not specifically limit as said alcohol solvent, For example, ethyl alcohol, methyl alcohol, n-propyl alcohol, isopropyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol etc. are mentioned, Preferably methyl alcohol or ethyl alcohol It is.

  Although it does not specifically limit as said ether solvent, For example, diethyl ether, diisopropyl ether, tetrahydrofuran, 1, 4- dioxane, 1, 2- dimethoxyethane etc. are mentioned, Preferably it is tetrahydrofuran.

  Although it does not specifically limit as said nitrile type solvent, For example, acetonitrile, propionitrile, etc. are mentioned, Preferably it is acetonitrile.

  Although it does not specifically limit as said hydrocarbon type organic solvent, For example, toluene, benzene, xylene, hexane, a cyclohexane, a heptane etc. are mentioned, Preferably it is toluene from the point of economical efficiency.

  Although it does not specifically limit as said ester solvent, For example, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate etc. are mentioned, Preferably ethyl acetate is mentioned.

  The above organic solvents may be used alone or in combination.

  It is most preferable to carry out the reaction only with water from the viewpoint of waste suppression and from the viewpoint that separation or concentration is not required after the reaction.

  The metal cyanide used in the reaction of hydantoin synthesis is not particularly limited, and potassium cyanide, sodium cyanide, silver cyanide, cuprous cyanide, sodium cyanide cuprate, potassium cyanide cuprate, cobalt potassium cyanide, etc. The use of potassium cyanide or sodium cyanide is preferred.

  The amount of metal cyanide used is not particularly limited as long as it is equivalent to or greater than that of 1-thio-2-propanone derivative. From the viewpoint of the above, it is preferably 1 to 2 moles, more preferably 1.1 to 1.3 moles from the economical viewpoint.

  The ammonium compound used for the reaction of hydantoin synthesis is not particularly limited, and ammonia water, ammonium carbonate, or ammonium bicarbonate can be used alone or in combination, but ammonia can be used in the reaction because there is little sublimation of the reagent during the reaction. It is preferable to use water and ammonium bicarbonate in combination, and it is more preferable to use ammonium bicarbonate.

  The amount of the ammonium compound used is not particularly limited as long as it is equivalent to or more than that of the 1-thio-2-propanone derivative. And preferably 2 to 5 times mol, and more preferably 3 to 4 times mol from an economical viewpoint.

  Although the temperature at the time of reaction is not specifically limited, Usually, it is performed between 0-100 degreeC, Preferably it is between 30-80 degreeC, More preferably, it is between 40-70 degreeC, More preferably, it is between 50-60 degreeC.

  After completion of the reaction, in the same manner as in Non-Patent Document 1 and Non-Patent Document 2 described above, the reaction solution is concentrated and then cooled to precipitate a 5-methyl-5-thiomethylhydantoin derivative. Without cooling, the 5-methyl-5-thiomethylhydantoin derivative may be deposited and then filtered to obtain. More preferably, after cooling, neutralization is performed to further precipitate a 5-methyl-5-thiomethylhydantoin derivative, followed by filtration.

  “Neutralization” as used herein means adjusting the pH of the reaction solution to a region where crystals are precipitated, and in order to obtain good results in both yield and purity, the pH is adjusted to 1.0 to 9.5. It is preferable to adjust to a region, more preferably a region of 1.0 to 7.0.

  The 5-methyl-5-thiomethylhydantoin derivative collected by filtration may be taken out as it is or may be washed with a solvent.

  As a solvent used for washing, an aqueous solvent or an organic solvent can be used. As the aqueous solvent, water, acidic aqueous solution or alkaline aqueous solution can be used.

  Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid, and aqueous solutions thereof. Examples of the alkali include aqueous solutions or hydroxides of alkali metal hydroxides such as sodium hydroxide, lithium hydroxide, and potassium hydroxide. Examples include aqueous solutions of alkaline earth metal hydroxides such as barium, magnesium hydroxide, and calcium hydroxide.

  Examples of the organic solvent to be used include alcohol solvents, ether solvents, nitrile solvents, hydrocarbon solvents, ester solvents, and ketone solvents. Although it does not specifically limit as alcohol solvent, For example, ethyl alcohol, methyl alcohol, n-propyl alcohol, isopropyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol etc. are mentioned, Preferably it is methyl alcohol or ethyl alcohol. is there.

  Although it does not specifically limit as said ether solvent, For example, diethyl ether, diisopropyl ether, tetrahydrofuran, 1, 4- dioxane, 1, 2- dimethoxyethane etc. are mentioned, Preferably it is tetrahydrofuran.

  Although it does not specifically limit as said nitrile type solvent, For example, acetonitrile, propionitrile, etc. are mentioned, Preferably it is acetonitrile.

  Although it does not specifically limit as a hydrocarbon type organic solvent, For example, toluene, benzene, xylene, hexane, a cyclohexane, heptane etc. are mentioned, Preferably it is toluene.

  Although it does not specifically limit as said ester solvent, For example, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate etc. are mentioned, Preferably ethyl acetate is mentioned.

  Although it does not specifically limit as said ketone solvent, For example, acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone etc. are mentioned, Preferably it is acetone.

  The above organic solvents may be used alone or in combination.

  Among the above, water or an acidic or alkaline aqueous solution is preferable, and water is more preferable.

  The 5-methyl-5-thiomethylhydantoin derivative after washing is taken out and dried. The drying method is not particularly limited, and drying such as reduced pressure drying (vacuum drying) or warm air drying can be performed.

  As described above, according to the present invention, the 1-thio-2-propanone derivative or the 1-thio-2-propanone derivative solution is washed with a basic solution, thereby reducing the odor. A 2-propanone derivative can be obtained and subsequently converted to hydantoin, whereby the above problem can be solved brilliantly.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Production Example 1 Production Method of 1-t-Butylthio-2-propanone In a 500 ml three-necked flask purged with nitrogen, t-butyl mercaptan (45.1 g, 0.5 mmol), chloroacetone (50.9 g, 0.55 mmol), 166 g of water was added and stirred. After cooling to a liquid temperature of 10 ° C. or lower, 120 g of a 20 wt% sodium hydroxide aqueous solution was added dropwise at a rate to maintain the internal temperature, and the mixture was stirred at 25 ° C. for 2 hours for reaction. After completion of the reaction, the reaction solution was separated to obtain 63.8 g of crude 1-t-butylthio-2-propanone.

Example 1 Method for Washing Crude 1-t-Butylthio-2-propanone To the crude 1-t-butylthio-2-propanone obtained in Production Example 1, 69.5 g of a 3 wt% aqueous sodium hydroxide solution was added. The mixture was stirred for 30 minutes and allowed to stand for 30 minutes for liquid separation. This operation was further repeated twice to obtain 1-t-butylthio-2-propanone. The odor of the obtained 1-t-butylthio-2-propanone was greatly improved as compared with that before washing.
In addition, in this compound, the measurement result of t-butyl mercaptan considered to cause odor is shown in Reference Example 1.

(Example 2) Method for producing 5-t-butylthiomethyl-5-methylhydantoin 265.9 g of 1.5 wt% aqueous sodium hydroxide solution was added to 1-t-butylthio-2-propanone obtained in Example 1. Sodium cyanide (29.4 g, 0.6 mmol) and ammonium bicarbonate (138.4 g, 1.75 mmol) were sequentially added, heated to 55 ° C., and stirred for 13 hours. After cooling the reaction solution to 10 ° C., 35% hydrochloric acid was added at a rate to maintain the internal temperature, and the pH was adjusted to 7. After aging for 30 minutes, the precipitated crystals were collected by filtration and washed sequentially with 120 g of water and 120 g of toluene. This was dried under reduced pressure at 35 ° C. overnight to obtain 88.5 g of 5-t-butylthiomethyl-5-methylhydantoin (yield based on t-butyl mercaptan: 80.1%). The odor of the obtained 5-t-butylthiomethyl-5-methylhydantoin was significantly suppressed as compared with Comparative Example 1.

(Comparative Example 1) Method for Producing 5-t-Butylthiomethyl-5-methylhydantoin A 500-ml three-necked flask purged with nitrogen was charged with t-butyl mercaptan (45.1 g, 0.5 mmol) and chloroacetone (50.9 g,. 55 mmol) and 166 g of water were added and stirred. After cooling to a liquid temperature of 10 ° C. or lower, 120 g of a 20 wt% sodium hydroxide aqueous solution was added dropwise at a rate to maintain the internal temperature, and the mixture was stirred at 25 ° C. for 2 hours for reaction. After completion of the reaction, sodium cyanide (29.4 g, 0.6 mmol) and ammonium bicarbonate (138.4 g, 1.75 mmol) were sequentially added to the solution containing crude 1-t-butylthio-2-propanone. The mixture was heated to 0 ° C. and stirred for 13 hours. After cooling the reaction solution to 10 ° C., 35% hydrochloric acid was added at a rate to maintain the internal temperature, and the pH was adjusted to 7. After aging for 30 minutes, the precipitated crystals were collected by filtration and washed sequentially with 120 g of water and 120 g of toluene. The mixture was dried under reduced pressure at 35 ° C. overnight to obtain 99.4 g of 5-t-butylthiomethyl-5-methylhydantoin (yield from t-butyl mercaptan: 90%). The obtained solid had a strong odor.

(Reference Example 1) t-butyl mercaptan measurement result To a 1000 ml Meyer flask, 20 μl of crude 1-t-butylthio-2-propanone before washing and 1-t-butylthio-2-propanone after washing were added. , Sealed. After standing for 10 minutes, as a result of measuring t-butyl mercaptan with a gas detector tube (reference: manufactured by GASTEC, detector tube No. 75 for t-butyl mercaptan), crude 1-t-butylthio-2 before washing -Propanone was 33.4 ppm or more, whereas 1-t-butylthio-2-propanone after one washing was 24 ppm, and 1-t-butylthio-2-propanone after two washings was 6. It was 7 ppm, and it was 3.4 ppm for 1-t-butylthio-2-propanone after washing three times.

Claims (8)

General formula (1):
CH ₃ COCH ₂ X (1)
(Wherein X represents a halogen atom), the general formula (2):
R ₁ SH (2)
(In the formula, R ₁ has an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted aralkyl group having 7 to 20 carbon atoms, or a substituent. And a mercaptan represented by the general formula (3):

(Wherein R ₁ is as defined above), and the 1-thio-2-propanone derivative or a solution thereof is washed with a basic solution. A method for producing a 1-thio-2-propanone derivative with suppressed odor. General formula (1):
CH ₃ COCH ₂ X (1)
(Wherein X represents a halogen atom), the general formula (2):
R ₁ SH (2)
(In the formula, R ₁ has an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted aralkyl group having 7 to 20 carbon atoms, or a substituent. And a mercaptan represented by the general formula (3):

(Wherein R ₁ is the same as above), the 1-thio-2-propanone derivative or the solution thereof is washed with a basic solution, (4):

(Wherein R ₁ is the same as above), a odor-suppressed 5-methyl-5-thiomethylhydantoin derivative characterized in that Production method. The production method according to claim 1 or 2, wherein the synthesis of the 1-thio-2-propanone derivative represented by the formula (3) is performed in an aqueous solution of a metal hydroxide. The production method according to any one of claims 1 to 3, wherein the basic solution used for washing is an aqueous solution of a metal hydroxide. 5. The method according to claim 4, wherein the metal hydroxide is an alkali metal hydroxide or an alkaline earth metal hydroxide. 6. The process according to claim 5, wherein the alkali metal hydroxide is sodium hydroxide, potassium hydroxide or lithium hydroxide. The production method according to any one of claims 1 to 6, wherein R ₁ is a tertiary alkyl group having 4 to 15 carbon atoms which may have a substituent. The production method according to claim 1, wherein R ₁ is a t-butyl group.