WO2012091158A1 - A process for 2-oxo-4-methylthiobutanoic acid or salts thereof - Google Patents

A process for 2-oxo-4-methylthiobutanoic acid or salts thereof Download PDF

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WO2012091158A1
WO2012091158A1 PCT/JP2011/080574 JP2011080574W WO2012091158A1 WO 2012091158 A1 WO2012091158 A1 WO 2012091158A1 JP 2011080574 W JP2011080574 W JP 2011080574W WO 2012091158 A1 WO2012091158 A1 WO 2012091158A1
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methanethiol
oxo
metal salts
salts
acid
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PCT/JP2011/080574
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French (fr)
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Taro Hirose
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Sumitomo Chemical Company, Limited
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Publication of WO2012091158A1 publication Critical patent/WO2012091158A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/18—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of thiols to unsaturated compounds

Definitions

  • the present invention relates to a process for producing 2-oxo-4-methylthiobutanoic acid or salts thereof.
  • 2-oxo-4-methylthiobutanoic acid or salts thereof is useful as starting material for methionine which is an essential amino acid (see for example, WO 2006/113085 pamphlet) . It is also known that 2-oxo-4- methylthiobutanoic acid or salts thereof is useful as a feed additive (see for example, US Patent Publicaiton No. 2008/0069920) .
  • An object of the present invention is to provide a novel process for producing 2 -oxo-4 -methylthiobutanoic acid or salts thereof.
  • the present inventor has intensively studied to find out the process for producing 2 -oxo-4 -methylthiobutanoic acid or salts thereof, and as a result, has completed the present invention.
  • the present invention provides:
  • a process for producing 2 -oxo-4 -methylthiobutanoic acid or salts thereof comprises a step of reacting methanethiol metal salts and 2-oxo-3-butenoic acid.
  • step is a step of reacting methanethiol metal salts and 2- oxo-3-butenoic acid in the presence of water.
  • the present invention enables to provide a novel process for producing 2 -oxo- -methylthiobutanoic acid or salts thereof.
  • the present invention comprises a step of reacting methanethiol metal salts and 2-oxo-3-butenoic acid.
  • the step of reacting of methanethiol metal salts and 2-oxo-3-butenoic acid is sometimes referred to the present reaction.
  • the present reaction enables to produce 2-oxo-4-methylthiobutanoic acid or salts thereof.
  • the 2-oxo-3-butenoic acid used in the present reaction can be prepared for example, by a method of oxidizing 1,2- dihydroxy-3-butene .
  • Example of the method of oxidizing 1, 2-dihydroxy-3 -butene includes a method described in JP-A- 2008-526720, specifically, a method of oxidizing 1,2- dihydroxy- 3 -butene in the presence of a catalyst.
  • Example of the catalyst used in the method of oxidizing 1, 2-dihydroxy-3-butene includes a catalyst comprising a noble metal, preferably a catalyst comprising at least one kind of noble metal selected from the group consisting of palladium, platinum, ruthenium, iridium and rhodium, and more preferably a catalyst comprising at least one kind of noble metal selected from the group consisting of palladium and platinum.
  • the catalyst may be a catalyst supported in a carrier (hearinafter, sometimes referred to a supported catalyst) .
  • Example of the carrier includes almina, silica, activated charcoal, graphite and the others.
  • the content of noble metal as opposed to the supported catalyst is for example, 0.1 to 20 % by weight and preferably 0.5 to 10 % by weight.
  • the oxidation catalyst may further comprise at least one kind of a cocatalyst selected from the group consisting of bismuth, lead, antimony, tin, niobium, tellurium, indium, gallium, zinc, copper, nickel, cobalt, tungsten, molybdenum, rhenium, vanadium, chromium, manganese and iron, or at least one kind of a cocatalyst selected from the group consisiting of bismuth and lead.
  • An amount of the cocatalyst is for example, 0.00005 to 5 parts by weight and preferably 0.00005 to 1 part(s) by weight, as opposed to 1 part by weight of the noble metal .
  • the oxidation catalyst is a supported catalyst comprsing at least one kind of noble metal selected from the group consisting of palladium and platinum and at least one kind of cocatalyst selected from the group consisting of bismuth and lead.
  • the oxidation catalyst can be prepared, for example by a method of reducing a catalyst precursor that is prepared by an impregnation method.
  • a reagent for reduction includes formaldehyde, sodium formate, sodium borohydride, hydrogen, hypophosphorous acid, hydrazine and reducing sugar.
  • a reduction temperature is selected from for example, a range of 20°C to 400°C.
  • Oxidation of 1, 2 -dihydroxy-3 -butene is preferably carried out in the presence of solvent.
  • the solvent is not particulalrly limited unless it can be one that solubilizes 1, 2 -dihydroxy-3 -butene, and includes for example, water; a chain hydrocarbons such as pentane, hexane, heptane, octane, nonane and the others; an alicyclic hydrocarbons such as cyclohexane and the others; an aromatic hydrocarbons such as benzene, styrene, ethylbenzene, toluene, xylene, isopropylbenzene and the others; esters such as ethyl formate, butyl formate, isobutyl formate, ethyl acetate, allyl acetate, propyl acetate, butyl acetate, hexyl acetate, ethyl propionate, vinyl propionate, ethyl acrylate, butyl acrylate, methyl isobut
  • Oxygen is used in oxidation of l,2-dihydroxy-3-butene.
  • Example of oxygen includes molecular oxygen, air, mixed gas of oxygen and inert gas .
  • Oxidation of 1 , 2 -dihydroxy-3 -butene is carried out for example, by mixing 1, 2 -dihydroxy-3 -butene, oxidation catalyst and solvent, and then by stirring the resulting mixture in the presence of oxygen under a pressured condition or atmospheric pressure condition.
  • Oxidation of 1 , 2 -dihydroxy-3 -butene is preferably carried out under pH 4 to 11 condition and more preferably under pH 5.5 to 7.5 condition. Adjustment of pH can be carried out for example, by adding alkali metal hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide and the others; alkaline-earth metal hydroxide such as calcium hydroxide, magnesium hydroxide and the others; alkali metal or alkaline-earth metal carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate and the others to the above mixture.
  • alkali metal hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide and the others
  • alkaline-earth metal hydroxide such as calcium hydroxide, magnesium hydroxide and the others
  • alkali metal or alkaline-earth metal carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate and the others to the above mixture.
  • the reaction temperature is selected from for example, a range of 10°C to 95°C and preferably a range of 25°C to 70°C.
  • the reaction period is for example, 20 min. to 15 hours .
  • the methanethiol metal salts used in the present reaction are commercially available, or may be prepared by reacting methanethiol and metal-containing base.
  • Example of the metal-containing base includes alkali metal hydroxide, alkaline-earth metal hydroxide, alkali metal alkoxide and alkaline-earth metal alkoxide .
  • Example of alkali metal hydroxide includes lithium hydroxide, sodium hydroxide and potassium hydroxide, and example of alkaline- earth metal hydroxide includes calcium hydroxide and barium hydroxide.
  • Example of alkali metal alkoxide includes sodium methoxide, sodium ethoxide, lithium methoxide, lithium ethoxide, potassium methoxide and potassium ethoxide
  • example of alkaline-earth metal alkoxide includes calcium methoxide and calcium ethoxide.
  • the amount used of the metal-containing base is for example, 0.8 to 2 moles, preferably 0.9 to 1.5 moles and more preferably 0.95 to 1.1 moles, as opposed to 1 mole of methanethiol .
  • the methanethiol metal salts can be prepared in the presence of solvent.
  • the solvent can be selected depending on a kind of the metal-containg base as needed, and includes for example, water; a chain hydrocarbons such as pentane, hexane, heptane, octane, nonane and the others; an alicyclic hydrocarbons such as cyclohexane and the others; an aromatic hydrocarbons such as benzene, styrene, ethylbenzene, toluene, xylene, isopropylbenzene and the others; ethers such as dibutyl ether, 1-isopropoxybutane, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, 1-ethoxybutane, diisopropylether, tetrahydrofuran and the others; nitriles such as butyronitrile, acetonitrile, propionitrile and
  • the mixed solvent may be one that is mixed homogeneously or one that is separated into two or more layers.
  • the amount used of the solvent is preferably 0.1 to 20 part by weight and more preferably 1 to 10 part by weight, as opposed to 1 part by weight of methanethiol.
  • Example of a method for preparing the methanethiol metal salts includes a method of adding the metal- containing base to a methanethiol-containing solution or a liquified methanethiol, or a method of adding a methanethiol-containing solution or a liquified methanethiol to a metal-containing base.
  • the preparation temperature is varied depending on the metal-containing base or the solvent, but can be selected from for example, the range of -25°C to 25°C and preferably the range of -10°C to 10°C.
  • the methanethiol metal salts prepared may be used directly or may be used after being subjected to a concentration treatment or a purification treatment and the others .
  • methanethiol metal salts includes methanethiol alkali metal salts such as litium methane thiolate, sodium methane thiolate, potassium methane thiolate and the others and methanethiol alkaline-earth metal salts such as calcium methane thiolate, barium methane thiolate and the others .
  • methanethiol used in the present reaction are for example, 0.5 to 2.0 moles and preferably 0.9 to 1.1 moles, as opposed to 1 mole of 2-oxo-3-butenoic acid.
  • the present invention can be carried out in the presence of solvent .
  • Example of the solvent used in the present reaction includes water; a chain hydrocarbons such as pentane, hexane, heptane, octane, nonane and the others; an alicyclic hydrocarbons such as cyclohexane and the others; an aromatic hydrocarbons such as benzene, styrene, ethylbenzene, toluene, xylene, isopropylbenzene and the others; ethers such as dibutyl ether, 1-isopropoxybutane , 1, 2-dimethoxyethane, 1, 2-diethoxyethane, 1-ethoxybutane, diisopropylether, tetrahydrofuran and the others; nitriles such as butyronitrile , acetonitrile, propionitrile and the others; ketones such as cyclopentanone, dipropyl ket
  • the mixed solvent may be one that is mixed homogeneously or one that is separated into two or more layers.
  • the solvent is preferably water.
  • the amount used of the solvent is for example, 0.1 to 100 part by weight and preferably 1 to 50 part by weight, as opposed to 1 part by weight of 2-oxo-3- butenoic acid.
  • the rection temperature in the present reaction is selected from for example, a range of -30°C to 30°C and preferably a range of -20°C to 20°C.
  • the reaction temperature is below -30°C, the present reaction tends to slow, while when the reaction temperature is over 30°C, the 2-oxo-3-butenoic acid used in the present reaction tends to decompose .
  • the reaction period of the present reaction is for example, 10 min. to 24 hours, and preferably 1 to 10 hour (s) .
  • the present reaction can be carried out in the absence of catalyst, and preferably can be carried out by the following methods:
  • (D) a method of adding the 2-oxo-3-butenoic acid or a solution containing the same to the methanethiol metal salts and adjusting the resulting mixture to the above- mentioned reaction temperature of the present reaction, and more preferably can be carried out by the above method of (A) .
  • the present reaction is more preferably carried out by adding the methanethiol metal salts to the 2-oxo-3-butenoic acid or the solution containing the same that is adjusted to the temperature selected from a range of -30°C to 30°C, and is further preferably carried out by adding methanethiol metal salts to the 2-oxo-3-butenoic acid or the solution containing the same that is adjusted to the temperature selected from the range of -20°C to 20°C
  • the process degree of the present reaction can be confirmed by analytical means such as gas chromatography, high-performance liquid chromatography, thin-layer chromatography, nuclear magnetic resonance spectrum analysis, infrared absorption spectrum analysis and the others .
  • a mineral acid such as sulfuric acid, hydrochloric acid and the others, is added to a reaction mixture, and the resulting acidic mixture is mixed with water-immiscible organic solvent, and then an extraction treatment can be carried out to take out 2-oxo-4-methylthiobutanoic acid.
  • Example of the water-immiscible organic solvent includes esters such as methyl acetate, ethyl acetate, butyl acetate and the others, aromatic hydrocarbons such as toluene, xylene and the others, ethers such as tert-butyl methyl ether, di-n-butyl ether and the others, halogenated solvents such as chlorobenzene, dichlorobenzene and the others, ketones such as methyl isobutyl ketone and the others .
  • esters such as methyl acetate, ethyl acetate, butyl acetate and the others
  • aromatic hydrocarbons such as toluene, xylene and the others
  • ethers such as tert-butyl methyl ether, di-n-butyl ether and the others
  • halogenated solvents such as chlorobenzene, dichlorobenzene and the others
  • ketones such as methyl isobuty
  • 2-0xo-4-methylthiobutanoic acid taken out can be subjected to washing treatment such as water washing and the others, or purification treatment such as distillation, column chromatography, crystallizaiton and the others.
  • 2-Oxo-4-methylthiobutanoic acid obtained in such manner may be salts thereof wherein H + that can be dissociated from its carboxy group is replaced with an optional cation.
  • the cation includes alkali metal ion such as sodium, potassium and the others, alkaline-earth metal ion such as calcium, barium and the others, and ammonium ion such as triethylammonium ion and the others.
  • Aqueous 2-oxo-3-butenoic acid solution was prepared by oxidizing 1 , 2 -dihydroxy-3 -butene according to the method described in Example 7 of JP-A 2008-526720.
  • Example 1 The aqueous solution obtained was used in the below- mentioned Example 1 directly without concentration treatment .
  • Example 1> The aqueous 2-oxobut-3-enoic acid solution lmL was cooled to -10°C, and thereto was added aqueous sodium methane thiolate solution (content of sodium methane thiolate: 15%) 20mg, and the resulting mixture was stirred at 0°C for 3.5 hours.
  • the resulting reaction mixture was analyzed by liquid chromatography/mass spectrometry and confirmed a formation of objective 2-oxo-4-methylthiobutanoic acid.

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  • Organic Chemistry (AREA)
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Abstract

The present invention provides a novel process for producing 2-oxo-4-methylthiobutanoic acid or salts thereof. A process for producing 2-oxo-4-methylthiobutanoic acid or salts thereof comprises a step of reacting methanethiol metal salts and 2-oxo-3-butenoic acid. Specific example of the methanethiol metal salts includes methanethiol alkali metal salts such as litium methane thiolate, sodium methane thiolate, potassium methane thiolate and the others and methanethiol alkaline-earth metal salts such as calcium methane thiolate, barium methane thiolate and the others.

Description

DESCRIPTION
A PROCESS FOR 2 -OXO-4 -METHYLTHIOBUTANOIC ACID OR SALTS THEREOF
TECHNICAL FIELD
The present invention relates to a process for producing 2-oxo-4-methylthiobutanoic acid or salts thereof. BACKGROUND ART
It is known that 2-oxo-4-methylthiobutanoic acid or salts thereof is useful as starting material for methionine which is an essential amino acid (see for example, WO 2006/113085 pamphlet) . It is also known that 2-oxo-4- methylthiobutanoic acid or salts thereof is useful as a feed additive (see for example, US Patent Publicaiton No. 2008/0069920) .
As a process for producing 2 -oxo-4 -methylthiobutanoic acid or salts thereof, for example, the above US Patent Publicaiton No. 2008/0069920 suggests a process by mixing an aqueous 2-oxo-3-butenoic acid solution and gaseous or liquid methyl mercaptan (methanethiol) in the presence of a catalyst . DISCLOSURE of INVENTION (PROBLEMS TO BE SOLVED BY INVENTION)
An object of the present invention is to provide a novel process for producing 2 -oxo-4 -methylthiobutanoic acid or salts thereof.
(MEANS TO SOLVE PROBLEMS)
The present inventor has intensively studied to find out the process for producing 2 -oxo-4 -methylthiobutanoic acid or salts thereof, and as a result, has completed the present invention.
That is, the present invention provides:
[1] A process for producing 2 -oxo-4 -methylthiobutanoic acid or salts thereof comprises a step of reacting methanethiol metal salts and 2-oxo-3-butenoic acid.
[2] The process according to the above [1] , wherein the step is a step of reacting methanethiol metal salts and 2- oxo-3-butenoic acid in the presence of water.
[3] The process according to the above [1] or [2] , wherein the methanethiol metal salts is methanethiol alkali metal salts or methanethiol alkaline-earth metal salts.
[4] The process according to the above [1] or [2] , wherein the methanethiol metal salts is methanethiol alkali metal salts .
[5] The process according to the above [1] or [2] , wherein the methanethiol metal salts is sodium methane thiolate. (EFFECT OF INVENTION)
The present invention enables to provide a novel process for producing 2 -oxo- -methylthiobutanoic acid or salts thereof.
MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention is explained in detail .
The present invention comprises a step of reacting methanethiol metal salts and 2-oxo-3-butenoic acid. Hereinafter the step of reacting of methanethiol metal salts and 2-oxo-3-butenoic acid is sometimes referred to the present reaction. The present reaction enables to produce 2-oxo-4-methylthiobutanoic acid or salts thereof.
The 2-oxo-3-butenoic acid used in the present reaction can be prepared for example, by a method of oxidizing 1,2- dihydroxy-3-butene . Example of the method of oxidizing 1, 2-dihydroxy-3 -butene includes a method described in JP-A- 2008-526720, specifically, a method of oxidizing 1,2- dihydroxy- 3 -butene in the presence of a catalyst.
Example of the catalyst used in the method of oxidizing 1, 2-dihydroxy-3-butene (heareinafter , sometimes referred to oxidation catalyst) includes a catalyst comprising a noble metal, preferably a catalyst comprising at least one kind of noble metal selected from the group consisting of palladium, platinum, ruthenium, iridium and rhodium, and more preferably a catalyst comprising at least one kind of noble metal selected from the group consisting of palladium and platinum. The catalyst may be a catalyst supported in a carrier (hearinafter, sometimes referred to a supported catalyst) . Example of the carrier includes almina, silica, activated charcoal, graphite and the others. When the supported catalyst is used, the content of noble metal as opposed to the supported catalyst is for example, 0.1 to 20 % by weight and preferably 0.5 to 10 % by weight.
The oxidation catalyst may further comprise at least one kind of a cocatalyst selected from the group consisting of bismuth, lead, antimony, tin, niobium, tellurium, indium, gallium, zinc, copper, nickel, cobalt, tungsten, molybdenum, rhenium, vanadium, chromium, manganese and iron, or at least one kind of a cocatalyst selected from the group consisiting of bismuth and lead. An amount of the cocatalyst is for example, 0.00005 to 5 parts by weight and preferably 0.00005 to 1 part(s) by weight, as opposed to 1 part by weight of the noble metal .
More preferably, the oxidation catalyst is a supported catalyst comprsing at least one kind of noble metal selected from the group consisting of palladium and platinum and at least one kind of cocatalyst selected from the group consisting of bismuth and lead.
The oxidation catalyst can be prepared, for example by a method of reducing a catalyst precursor that is prepared by an impregnation method. Example of a reagent for reduction includes formaldehyde, sodium formate, sodium borohydride, hydrogen, hypophosphorous acid, hydrazine and reducing sugar. A reduction temperature is selected from for example, a range of 20°C to 400°C.
Oxidation of 1, 2 -dihydroxy-3 -butene is preferably carried out in the presence of solvent.
The solvent is not particulalrly limited unless it can be one that solubilizes 1, 2 -dihydroxy-3 -butene, and includes for example, water; a chain hydrocarbons such as pentane, hexane, heptane, octane, nonane and the others; an alicyclic hydrocarbons such as cyclohexane and the others; an aromatic hydrocarbons such as benzene, styrene, ethylbenzene, toluene, xylene, isopropylbenzene and the others; esters such as ethyl formate, butyl formate, isobutyl formate, ethyl acetate, allyl acetate, propyl acetate, butyl acetate, hexyl acetate, ethyl propionate, vinyl propionate, ethyl acrylate, butyl acrylate, methyl isobutanoate, methyl butanoate, and the others; ethers such as dibutyl ether, 1-isopropoxybutane, 1, 2 -dimethoxyethane, 1, 2-diethoxyethane, 1-ethoxybutane, diisopropylether, tetrahydrofuran and the others; nitriles such as butyronitrile, acetonitrile, acrylonitrile, propionitrile and the others; ketones such as cyclopentanone, dipropyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, 5- methylhexane-2-one, 2-pentanone, methyl ethyl ketone and and the others; and mixed solvent thereof, and is preferably water.
Oxygen is used in oxidation of l,2-dihydroxy-3-butene. Example of oxygen includes molecular oxygen, air, mixed gas of oxygen and inert gas .
Oxidation of 1 , 2 -dihydroxy-3 -butene is carried out for example, by mixing 1, 2 -dihydroxy-3 -butene, oxidation catalyst and solvent, and then by stirring the resulting mixture in the presence of oxygen under a pressured condition or atmospheric pressure condition.
Oxidation of 1 , 2 -dihydroxy-3 -butene is preferably carried out under pH 4 to 11 condition and more preferably under pH 5.5 to 7.5 condition. Adjustment of pH can be carried out for example, by adding alkali metal hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide and the others; alkaline-earth metal hydroxide such as calcium hydroxide, magnesium hydroxide and the others; alkali metal or alkaline-earth metal carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate and the others to the above mixture.
The reaction temperature is selected from for example, a range of 10°C to 95°C and preferably a range of 25°C to 70°C. The reaction period is for example, 20 min. to 15 hours .
The methanethiol metal salts used in the present reaction are commercially available, or may be prepared by reacting methanethiol and metal-containing base. Example of the metal-containing base includes alkali metal hydroxide, alkaline-earth metal hydroxide, alkali metal alkoxide and alkaline-earth metal alkoxide . Example of alkali metal hydroxide includes lithium hydroxide, sodium hydroxide and potassium hydroxide, and example of alkaline- earth metal hydroxide includes calcium hydroxide and barium hydroxide. Example of alkali metal alkoxide includes sodium methoxide, sodium ethoxide, lithium methoxide, lithium ethoxide, potassium methoxide and potassium ethoxide, and example of alkaline-earth metal alkoxide includes calcium methoxide and calcium ethoxide.
The amount used of the metal-containing base is for example, 0.8 to 2 moles, preferably 0.9 to 1.5 moles and more preferably 0.95 to 1.1 moles, as opposed to 1 mole of methanethiol .
The methanethiol metal salts can be prepared in the presence of solvent. The solvent can be selected depending on a kind of the metal-containg base as needed, and includes for example, water; a chain hydrocarbons such as pentane, hexane, heptane, octane, nonane and the others; an alicyclic hydrocarbons such as cyclohexane and the others; an aromatic hydrocarbons such as benzene, styrene, ethylbenzene, toluene, xylene, isopropylbenzene and the others; ethers such as dibutyl ether, 1-isopropoxybutane, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, 1-ethoxybutane, diisopropylether, tetrahydrofuran and the others; nitriles such as butyronitrile, acetonitrile, propionitrile and the others; ketones such as cyclopentanone, dipropyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, 5- methylhexane-2-one, 2-pentanone, methyl ethyl ketone and and the others; polar solvent such as N, N-dimethylformamide and dimethylsulfoxide ; and mixed solvent thereof. The mixed solvent may be one that is mixed homogeneously or one that is separated into two or more layers. The amount used of the solvent is preferably 0.1 to 20 part by weight and more preferably 1 to 10 part by weight, as opposed to 1 part by weight of methanethiol.
Example of a method for preparing the methanethiol metal salts includes a method of adding the metal- containing base to a methanethiol-containing solution or a liquified methanethiol, or a method of adding a methanethiol-containing solution or a liquified methanethiol to a metal-containing base.
The preparation temperature is varied depending on the metal-containing base or the solvent, but can be selected from for example, the range of -25°C to 25°C and preferably the range of -10°C to 10°C.
The methanethiol metal salts prepared may be used directly or may be used after being subjected to a concentration treatment or a purification treatment and the others .
Specific example of methanethiol metal salts includes methanethiol alkali metal salts such as litium methane thiolate, sodium methane thiolate, potassium methane thiolate and the others and methanethiol alkaline-earth metal salts such as calcium methane thiolate, barium methane thiolate and the others .
The amounts used of methanethiol used in the present reaction are for example, 0.5 to 2.0 moles and preferably 0.9 to 1.1 moles, as opposed to 1 mole of 2-oxo-3-butenoic acid.
The present invention can be carried out in the presence of solvent . Example of the solvent used in the present reaction includes water; a chain hydrocarbons such as pentane, hexane, heptane, octane, nonane and the others; an alicyclic hydrocarbons such as cyclohexane and the others; an aromatic hydrocarbons such as benzene, styrene, ethylbenzene, toluene, xylene, isopropylbenzene and the others; ethers such as dibutyl ether, 1-isopropoxybutane , 1, 2-dimethoxyethane, 1, 2-diethoxyethane, 1-ethoxybutane, diisopropylether, tetrahydrofuran and the others; nitriles such as butyronitrile , acetonitrile, propionitrile and the others; ketones such as cyclopentanone, dipropyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, 5- methylhexane-2-one, 2-pentanone, methyl ethyl ketone and and the others; polar solvent such as Ν,Ν-dimethylformamide and dimethylsulfoxide; and mixed solvent thereof. The mixed solvent may be one that is mixed homogeneously or one that is separated into two or more layers. The solvent is preferably water. The amount used of the solvent is for example, 0.1 to 100 part by weight and preferably 1 to 50 part by weight, as opposed to 1 part by weight of 2-oxo-3- butenoic acid.
The rection temperature in the present reaction is selected from for example, a range of -30°C to 30°C and preferably a range of -20°C to 20°C. When the reaction temperature is below -30°C, the present reaction tends to slow, while when the reaction temperature is over 30°C, the 2-oxo-3-butenoic acid used in the present reaction tends to decompose .
The reaction period of the present reaction is for example, 10 min. to 24 hours, and preferably 1 to 10 hour (s) . The present reaction can be carried out in the absence of catalyst, and preferably can be carried out by the following methods:
(A) a method of adjusting 2-oxo-3-butenoic acid or a solution containing the same to the above-mentioned reaction temperature of the present reaction and thereto adding methanethiol metal salts;
(B) a method of adjusting the methanethiol metal salts to the above-mentioned reaction temperature of the present reaction and thereto adding the 2-oxo-3-butenoic acid or a solution containing the same;
(C) a method of adding the methanethiol metal salts to the 2-oxo-3-butenoic acid or a solution containing the same and adjusting the resulting mixture to the above-mentioned reaction temperature of the present reaction; or
(D) a method of adding the 2-oxo-3-butenoic acid or a solution containing the same to the methanethiol metal salts and adjusting the resulting mixture to the above- mentioned reaction temperature of the present reaction, and more preferably can be carried out by the above method of (A) . That is, the present reaction is more preferably carried out by adding the methanethiol metal salts to the 2-oxo-3-butenoic acid or the solution containing the same that is adjusted to the temperature selected from a range of -30°C to 30°C, and is further preferably carried out by adding methanethiol metal salts to the 2-oxo-3-butenoic acid or the solution containing the same that is adjusted to the temperature selected from the range of -20°C to 20°C The process degree of the present reaction can be confirmed by analytical means such as gas chromatography, high-performance liquid chromatography, thin-layer chromatography, nuclear magnetic resonance spectrum analysis, infrared absorption spectrum analysis and the others .
After a completion of the present reaction, for example, a mineral acid such as sulfuric acid, hydrochloric acid and the others, is added to a reaction mixture, and the resulting acidic mixture is mixed with water-immiscible organic solvent, and then an extraction treatment can be carried out to take out 2-oxo-4-methylthiobutanoic acid. Example of the water-immiscible organic solvent includes esters such as methyl acetate, ethyl acetate, butyl acetate and the others, aromatic hydrocarbons such as toluene, xylene and the others, ethers such as tert-butyl methyl ether, di-n-butyl ether and the others, halogenated solvents such as chlorobenzene, dichlorobenzene and the others, ketones such as methyl isobutyl ketone and the others .
2-0xo-4-methylthiobutanoic acid taken out can be subjected to washing treatment such as water washing and the others, or purification treatment such as distillation, column chromatography, crystallizaiton and the others.
2-Oxo-4-methylthiobutanoic acid obtained in such manner may be salts thereof wherein H+ that can be dissociated from its carboxy group is replaced with an optional cation. Example of the cation includes alkali metal ion such as sodium, potassium and the others, alkaline-earth metal ion such as calcium, barium and the others, and ammonium ion such as triethylammonium ion and the others.
EXAMPLES
Next, the present invention is described in more detail below with some examples, but the present invention should not be construed to be limited thereto.
<Preparation Example 1> (2-oxo-3-butenoic acid)
Aqueous 2-oxo-3-butenoic acid solution was prepared by oxidizing 1 , 2 -dihydroxy-3 -butene according to the method described in Example 7 of JP-A 2008-526720.
The aqueous solution obtained was used in the below- mentioned Example 1 directly without concentration treatment . <Example 1> The aqueous 2-oxobut-3-enoic acid solution lmL was cooled to -10°C, and thereto was added aqueous sodium methane thiolate solution (content of sodium methane thiolate: 15%) 20mg, and the resulting mixture was stirred at 0°C for 3.5 hours.
The resulting reaction mixture was analyzed by liquid chromatography/mass spectrometry and confirmed a formation of objective 2-oxo-4-methylthiobutanoic acid.
Also the resulting reaction mixture was analyzed by high-performance liquid chromatography (manufactured by Shimadzu Corp.) under the following analytical condition, to confirm a formation of 2-oxo-4-methylthiobutanoic acid in 19.5% (liquid chromatgraphy area normalization method) . (Anaytical condition)
LC column : Sumipax Lichrosob RP-18
(30cmx4.0mm, ΙΟμπι)
Column temperature : 40 °C
Mobile phase : isocratic
Mobile phase A: 1-pentane sulfonic acid 2.64g/2850mL water Mobile phase B: acetonitrile
0 min B 5%
60 min B 5% STOP
Flow rate : 1 mL/min
Detection wavelength: 210nm
Measurement time : 60min INDUSTRIAL APPLICABILITY
It is known that 2 -oxo-4 -methylthiobutanoic acid or salts thereof is useful as starting material for methionine which is an essential amino acid. It is also known that 2- oxo-4 -methylthiobutanoic acid or salts thereof is useful as a feed additive. Accordingly, a novel process for preparing 2 -oxo-4 -methylthiobutanoic acid or salts thereof of the present invention is industrially applicable.

Claims

1. A process for producing 2-oxo-4-methylthiobutanoic acid or salts thereof comprises a step of reacting methanethiol metal salts and 2-oxo-3-butenoic acid.
2. The process according to claim 1, wherein the step is a step of reacting methanethiol metal salts and 2-oxo-3- butenoic acid in the presence of water.
3. The process according to claim 1 or claim 2, wherein the methanethiol metal salts is methanethiol alkali metal salts or methanethiol alkaline-earth metal salts.
4. The process according to claim 1 or claim 2, wherein the methanethiol metal salts is methanethiol alkali metal salts .
5. The process according to claim 1 or claim 2, wherein the methanethiol metal salts is sodium methane thiolate.
PCT/JP2011/080574 2010-12-27 2011-12-26 A process for 2-oxo-4-methylthiobutanoic acid or salts thereof WO2012091158A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004509102A (en) * 2000-09-14 2004-03-25 グリュネンタール・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング Method for producing chiral compound
JP2008526720A (en) * 2004-12-30 2008-07-24 アディセオ・アイルランド・リミテッド Methods for synthesizing and utilizing 2-oxo-4-methylthiobutanoic acid, its salts and derivatives
WO2010021855A1 (en) * 2008-08-19 2010-02-25 Dow Agrosciences Llc Improved process for the addition of thiolates to alfa, beta-unsaturated carbonyl or sulfonyl compounds

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004509102A (en) * 2000-09-14 2004-03-25 グリュネンタール・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング Method for producing chiral compound
JP2008526720A (en) * 2004-12-30 2008-07-24 アディセオ・アイルランド・リミテッド Methods for synthesizing and utilizing 2-oxo-4-methylthiobutanoic acid, its salts and derivatives
WO2010021855A1 (en) * 2008-08-19 2010-02-25 Dow Agrosciences Llc Improved process for the addition of thiolates to alfa, beta-unsaturated carbonyl or sulfonyl compounds

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