WO2012081712A1 - Procédé de préparation d'un composé acide hydroxycarboxylique ou d'un sel de celui-ci - Google Patents

Procédé de préparation d'un composé acide hydroxycarboxylique ou d'un sel de celui-ci Download PDF

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Publication number
WO2012081712A1
WO2012081712A1 PCT/JP2011/079264 JP2011079264W WO2012081712A1 WO 2012081712 A1 WO2012081712 A1 WO 2012081712A1 JP 2011079264 W JP2011079264 W JP 2011079264W WO 2012081712 A1 WO2012081712 A1 WO 2012081712A1
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Prior art keywords
group
salt
acid
compound
methylthio
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PCT/JP2011/079264
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English (en)
Inventor
Kazuyasu Tani
Taro Hirose
Koji Hagiya
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Sumitomo Chemical Company, Limited
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Application filed by Sumitomo Chemical Company, Limited filed Critical Sumitomo Chemical Company, Limited
Publication of WO2012081712A1 publication Critical patent/WO2012081712A1/fr

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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
    • C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups

Definitions

  • the present invention relates to a process of a hydroxycarboxylic acid compound or a salt thereof.
  • Hydroxycarboxylic acid compounds such as 4-methylthio- 2-hydroxybutyric acid are important compounds for biological reactions.
  • 4 -methylthio-2 - hydroxybutyric acid is a compound used as an additive agent for forage.
  • Hydrogen cyanide is a toxic material, and needs to be handled with, for example, adequate care and suitable equipments thereof.
  • the present inventions are as follows.
  • R 1 is an optionally substituted C1-C12 alkyl group or an optionally substituted C3-C12 cycloalkyl group, and n is an integer of 1 to 4
  • R 1 and n are both as defined above
  • transition metal catalyst is a catalyst comprising at least one element compound selected from the group consisting of ruthenium, rhodium, palladium, platinum and iridium in which the element compound is supported on a carrier.
  • ketocarboxylic acid compound of Formula (2) is the ketocarboxylic acid compound of Formula (2) :
  • the salt of the ketocarboxylic acid compound of Formula (2) means a salt wherein H + dissociable from -COOH in Formula (2) is replaced with a cation.
  • the cation includes, for example, alkali metal ions such as lithium ion, sodium ion and potassium ion; and alkaline earth metal ions such as calcium ion and magnesium ion.
  • ketocarboxylic acid compound of Formula (2) and a salt thereof are optionally referred to as Compound (2) .
  • Formula (1) means that H + dissociable from -COOH in Formula (1) is replaced with a cation.
  • the cation used herein includes, for example, alkali metal ions such as lithium ion, sodium ion and potassium ion; and alkaline earth metal ions such as calcium ion and magnesium ion.
  • the moiety of the carboxylic acid in Compound (1) corresponds to that of Compound (2) used in the present process (i.e., carboxylic acid or a salt thereof, and the type of the salt in case of a salt) .
  • R 1 is an optionally substituted C1-C12 alkyl group or an optionally substituted C3-C12 cycloalkyl group, and n is an integer of 1 to 4.
  • the C1-C12 alkyl group defined as an optionally substituted C1-C12 alkyl group in R 1 includes, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec- butyl group, tert-butyl group, pentyl group, octyl group and decyl group; and the C3-C12 cycloalkyl group defined as an optionally substituted C3-C12 cycloalkyl group in R 1 includes, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group.
  • the C1-C12 alkyl group and the C3-C12 cycloalkyl group may be optionally substituted with at least one group selected from the group consisting of, for example, C6-C20 aryl groups such as phenyl group, 1-naphthyl group, 2- naphthyl group, and 4-methylphenyl group; C1-C12 alkoxy groups such as methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, isobutyloxy group, sec- butyloxy group, and tert-butyloxy group; C1-C6 perfluoroalkyloxy groups such as trifluoromethoxy group and pentafluoroethoxy group; and halogen atoms such as fluorine atom and chlorine atom.
  • C6-C20 aryl groups such as phenyl group, 1-naphthyl group, 2- naphthyl group, and 4-methylpheny
  • C6-C20 aryl groups, C1-C12 alkoxy groups and C1-C6 perfluoroalkyloxy groups may be further substituted with at least one group selected from the group consisting of C6-C20 aryl groups, C1-C12 alkoxy groups and C6-C20 aryloxy groups.
  • substituted C1-C12 alkyl group and the substituted C3-C12 cycloalkyl group in R 1 includes naphthalen-l-ylmethyl group, naphthalen-2-ylmethyl group, methoxymethyl group, ethoxymethyl group, isopropyloxymethyl group, butyloxymethyl group, isobutyloxymethyl group, sec-butyloxymethyl group, tert- butyloxymethyl group, phenoxymethyl group, 2- methylphenoxymethyl group, 4 -methylphenoxymethyl group, 1- phenylethyl group, 2 -phenylethyl group, 1- (naphthalen-1- yl)ethyl group, 1- (naphthalen-2-yl) ethyl group, l-(4- methylphenyl) ethyl group, 1- (3 , 4-dimethylphenyl) ethyl group, 1- (4-methoxyphenyl) ethyl group, l
  • R 1 is preferably an optionally substituted C1-C12 alkyl group; more preferably C1-C4 alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, and tert-butyl group; and even more preferably methyl group .
  • Compound (2) examples include 3- methylthio-2-oxopropionic acid, 3-tert-butylthio-2- oxopropionic acid, 3-ethylthio-2-oxopropionic acid, 4- methylthio-2-oxobutyric acid, 4-ethylthio-2-oxobutyric acid 2-oxo-4-propylthiobutyric acid, 5-methylthio-2-oxopentanoic acid, 5-ethylthio-2-oxopentanoic acid, 2-oxo-5-
  • Compound (2) may be commercially available or prepared by well-known processes such as those described in "Bull. Agr. Chem. Soc. Japan, Vol. 21, No. 6, pp. 333-336 (1957)" and "Journal of Labelled Compounds and Radiopharmaceuticals Vol. XXXVI, No. 5, pp. 431-437 (1995)".
  • Compound (1) includes 2 -hydroxy- 3- (methylthio) propionic acid, 3-tert-buthylthio-2- hydroxypropionic acid, 3-ethylthio-2-hydroxypropionic acid, 2 -hydroxy-4 - (methylthio) butyric acid, 4-ethylthio-2- hydroxybutyric acid, 2 -hydroxy-4 - (propylthio) butyric acid, 2 -hydroxy-5- (methylthio) pentanoic acid, 5-ethylthio-2- hydroxypentanoic acid, 2 -hydroxy-5- (propylthio) pentanoic acid, 2 -hydroxy-6- (methylthio) hexanoic acid, 6-ethylthio-2- hydroxyhexanoic acid, 2 -hydroxy-6- (propylthio) hexanoic acid and salts thereof.
  • the present invention comprises a step of reacting Compound (2) and hydrogen in the presence of a transition metal catalyst (hereinafter, optionally referred to as the present reaction) .
  • the transition metal catalyst used herein includes, for example, iron group element compounds such as nickel and cobalt; and noble metal element compounds such as ruthenium, rhodium, palladium, platinum and iridium.
  • the transition metal catalyst used herein may be, for example, a catalyst comprising at least one element compound selected from transition metal elements (e.g. iron group elements and noble metal elements) which is supported on a carrier (hereinafter, optionally referred to as a carrier-supported catalyst) .
  • the carrier used herein includes, for example, active carbon, alumina, silica and zeolite .
  • the carrier-supported catalyst used herein includes, for example, ruthenium/carbon (Ru/C) , rhodium/carbon (Rh/C) , palladium/carbon (Pd/C) , platinum/carbon (Pt/C) , iridium/carbon (Ir/C) , and platinum/alumina (Pt/alumina) .
  • Ru/C ruthenium/carbon
  • Rh/C rhodium/carbon
  • Pd/C palladium/carbon
  • platinum/carbon Pt/C
  • Ir/C iridium/carbon
  • platinum/alumina platinum/alumina
  • the amount of the transition metal element compound contained in the carrier-supported catalyst is, for example, 0.1 wt3 ⁇ 4 to 30 wt% and preferably 0.5 wt% to 20 wt% based on the total weight of the carrier and the transition metal element compound.
  • the transition metal catalyst used herein may be, for example, a non-carrier-supported catalyst comprising at least one element compound selected from transition metal elements such as iron group elements and noble metal elements.
  • the non-carrier-supported catalyst used herein includes, for example, reduced nickel, sponge nickel (Raney® nickel) , reduced cobalt, sponge cobalt (Raney® cobalt) , ruthenium black, rhodium black, palladium black, platinum black, iridium black, ruthenium oxide, rhodium oxide, palladium oxide, platinum oxide, and iridium oxide .
  • the transition metal catalyst used herein is preferably a catalyst of the noble metal element compound supported on a carrier, or sponge nickel or sponge cobalt; more preferably a catalyst of at least one element compound selected from the group consisting of ruthenium, rhodium, palladium, platinum and iridium which is supported on a carrier; and even more preferably, a catalyst of at least one element compound selected from the group consisting of platinum and rhodium which is supported on a carrier.
  • the transition metal catalyst used herein may be commercially available or prepared by well-known processes.
  • the amount of the transition metal catalyst used herein may vary depending on, for example, the below- described factors (e.g. the reaction temperature, the amount of the reaction reagent or solvent, and the hydrogen partial pressure) , ⁇ and it is typically in the range of 0.0001 part to 10 parts, and preferably 0.001 part to 5 parts by weight of the transition metal element per 1 part by weight of Compound (2) .
  • a carrier-supported catalyst comprising at least one element compound selected from the group consisting of ruthenium, rhodium, palladium, platinum and iridium is used as a transition metal catalyst
  • the amount of the transition metal catalyst is preferably in the range of 0.01 part to 0.1 part by weight of the transition metal element per 1 part by weight of Compound (2) .
  • the partial pressure thereof is typically 10 MPa or less, preferably 0.01 MPa to 5 MPa, more preferably 0.02 MPa to 2 MPa, and even more preferably 0.05 MPa to 1.5 MPa.
  • the hydrogen used herein may be generated from formic acid or a salt thereof by a well-known method.
  • the present reaction is preferably carried out in the presence of a solvent.
  • the solvent used herein includes, for example, aliphatic hydrocarbon solvents such as pentane, hexane, isohexane, heptane, isoheptane, octane, isooctane, nonane, isononane, decane, isodecane, undecane, dodecane, cyclopentane, cyclohexane, methylcyclohexane, tert- butylcyclohexane, and petroleum ether; ether solvents such as tetrahydrofuran, methyltetrahydrofuran, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, tert- butyl methyl ether
  • the amount of the solvent used herein is preferably 1 mL to 200 mL, and more preferably 10 mL to 150 mL per 1 g of Compound (2) .
  • Methods for carrying out the present reaction include, for example, the followings.
  • a method which comprises mixing Compound (2) and a transition metal catalyst, and then stirring the resultant mixture under hydrogen gas atmosphere .
  • a method which comprises mixing Compound (2) and formic acid, optionally adding a base such as sodium hydroxide and potassium hydroxide to the mixture to adjust the pH thereof, and then adding a transition metal catalyst to the resultant mixture .
  • a base such as sodium hydroxide and potassium hydroxide
  • the reaction temperature of the present reaction is in the range of typically 0°C to 100°C, preferably 20°C to 90 °C, and more preferably 30 °C to 70 °C.
  • the reaction time of the present reaction may vary depending on, for example, the reaction temperature, the amount of the reaction reagent or solvent, and the hydrogen partial pressure, but it is typically 1 hour to 24 hours.
  • the progression of the reaction can be monitored by analytical methods such as thin- layer chromatography, gas chromatography, and high performance liquid chromatography.
  • Compound (1) can be obtained by treating the resultant mixture with post- treatments such as filtration, neutralization, extraction, and water-washing, and then isolating it by treatments such as distillation.
  • post- treatments such as filtration, neutralization, extraction, and water-washing
  • the hydrogen can be removed from the reaction mixture, for example, by injecting nitrogen gas into the reaction mixture.
  • the obtained Compound (1) may be purified by treatments such as extractive purification; distillation; and adsorption on, for example, active carbon, silica, and alumina . Examples
  • reaction mixtures were analyzed with high performance liquid chromatograph (manufactured by Shimadzu Corporation) under the analysis conditions shown below, and the conversion rates and selectivity rates were calculated based on the formulae shown below.
  • Additive agent sodium 1-pentanesulfonate Concentration of additive agent: 2.5 mmol/L pH of mobile phase: pH 3 (adjusted by
  • Example 2 To a 50 mL autoclave were added 50 mg of sodium 4- methylthio-2-oxobutyrate, 5 g of distilled water and 61 mg of Raney® cobalt (wet weight) , and the mixture was stirred. After the autoclave was pressurized to 1 MPaG (gauge pressure) with hydrogen, the mixture was heated to 50 °C and stirred for 6 hours. A portion of the reaction mixture was analyzed by high performance liquid chromatography to find that the conversion rate of sodium 4 -methylthio-2- oxobutyrate was 14.6 % and the selectivity rate of 2- hydroxy-4- (methylthio) butyric acid was 21.2 %.
  • the present invention is useful as a process of hydroxycarboxylic acid compound or salt thereof such as 4- methylthio-2-hydroxybutyric acid.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Le présent procédé permet de préparer un composé acide hydroxycarboxylique de Formule (1) ou un sel de celui-ci par réaction d'un composé acide cétocarboxylique de Formule (2) ou d'un sel de celui-ci et d'hydrogène en présence d'un catalyseur métal de transition, sans utiliser de cyanure d'hydrogène.
PCT/JP2011/079264 2010-12-13 2011-12-12 Procédé de préparation d'un composé acide hydroxycarboxylique ou d'un sel de celui-ci WO2012081712A1 (fr)

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JP2010-276653 2010-12-13
JP2010276653A JP2012126651A (ja) 2010-12-13 2010-12-13 ヒドロキシカルボン酸化合物またはその塩の製造方法

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WO2012081712A1 true WO2012081712A1 (fr) 2012-06-21

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114727988A (zh) * 2019-11-22 2022-07-08 建明实业股份有限公司 通过格氏偶联和硫醇化反应制备α-羟基酯的工艺

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2745745A (en) * 1952-10-30 1956-05-15 Monsanto Chemicals Poultry feed
US20080069920A1 (en) * 2004-12-30 2008-03-20 Adisseo Ireland Limited Synthesis and Applications of 2-Oxo-4-Methylthiobutyric Acid, Its Salts and Its Derivatives
US20090053781A1 (en) * 2004-10-14 2009-02-26 Sumitomo Chemical Company, Limited Method for Producing 2-hydroxy-4-(methylthio)butyric Acid

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2745745A (en) * 1952-10-30 1956-05-15 Monsanto Chemicals Poultry feed
US20090053781A1 (en) * 2004-10-14 2009-02-26 Sumitomo Chemical Company, Limited Method for Producing 2-hydroxy-4-(methylthio)butyric Acid
US20080069920A1 (en) * 2004-12-30 2008-03-20 Adisseo Ireland Limited Synthesis and Applications of 2-Oxo-4-Methylthiobutyric Acid, Its Salts and Its Derivatives

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Industrial Organic Chemistry", 1978, TOKYO KAGAKU-DOJIN, pages: 273 - 275
BULL. AGR. CHEM. SOC. JAPAN, vol. 21, no. 6, 1957, pages 333 - 336
JOURNAL OF LABELLED COMPOUNDS AND RADIOPHARMACEUTICALS, vol. XXXVI, no. 5, 1995, pages 431 - 437

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114727988A (zh) * 2019-11-22 2022-07-08 建明实业股份有限公司 通过格氏偶联和硫醇化反应制备α-羟基酯的工艺

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