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WO2005066109A1 - Procede pour obtenir d'acides 2-hydroxy-carboxyliques - Google Patents

Procede pour obtenir d'acides 2-hydroxy-carboxyliques Download PDF

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Publication number
WO2005066109A1
WO2005066109A1 PCT/IB2003/006202 IB0306202W WO2005066109A1 WO 2005066109 A1 WO2005066109 A1 WO 2005066109A1 IB 0306202 W IB0306202 W IB 0306202W WO 2005066109 A1 WO2005066109 A1 WO 2005066109A1
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WO
WIPO (PCT)
Prior art keywords
bis
palladium
catalyst
acid
compound
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Application number
PCT/IB2003/006202
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English (en)
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WO2005066109B1 (fr
Inventor
Raghunath Vitthal Chaudhari
Sunil Sopana Tonde
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Council Of Scientific & Industrial Research
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Priority to PCT/IB2003/006202 priority Critical patent/WO2005066109A1/fr
Priority to AU2003298472A priority patent/AU2003298472A1/en
Priority to US10/808,965 priority patent/US20050143600A1/en
Publication of WO2005066109A1 publication Critical patent/WO2005066109A1/fr
Publication of WO2005066109B1 publication Critical patent/WO2005066109B1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to a process for the preparation of 2-hydroxy carboxylic acids.
  • the present invention relates to a process wherein an enol ester and a hydroxyl compound react with carbon monoxide in presence of a palladium catalyst, containing one or more ligands having one or more coordinating N, O and/ or P atoms and a solvent at a temperature and a pressure, to produce 2-acetoxy ester and/ or 2- hydroxy ester of corresponding carboxylic acid, of the corresponding carboxylic acid which on further catalytic hydrolysis produce 2-hydroxy carboxylic acid.
  • the process has potential importance when applied to vinyl acetate.
  • vinyl acetate reacts with a hydroxyl compound and carbon monoxide to give 2-acetoxy propionic acid or 2-acetoxy propionate ester and/ or lactate ester, which can be converted to lactic acid on hydrolysis.
  • Lactic acid is important commercially in baking industry, cheese industry, in dying wool, to make plasticisers for resin, etc. Background and prior art references of the present Application Lactic acid has been produced industrially by fermentation of molasses, but the process is costly and inefficient, and produces large amount of byproducts, making product separation and purification expensive.
  • Another commercial rout for lactic acid is hydrocyanation of acetaldehyde followed by hydrolysis of cyanohydrin with H 2 SO .
  • US patent 4,072,709 provides a process for the production of lactic acid in which, alpha- aceloxy-propanaldehyde formed by hydroformylation of vinyl acetate is oxidized to alpha-aceloxy-propionic acid, which is further hydrolysed to lactic acid.
  • the process involves three steps for the formation of lactic acid.
  • US patent 4,377,708 provides a process for hydrocarbonylation of vinyl acetate using CO and water as reactants with vinyl acetate.
  • special precautions are taken for the stability of the catalyst, reactants and products. The process needs to maintain the concentration of water not more than 3 weight percent of the medium, so as to avoid hydrolysis of reactant vinyl acetate to acetic acid and acetaldehyde.
  • European patent 0144188 provides a process for alkoxycarbonylation of enol esters with hydroxyl compounds using Pd, Rh and Ni catalysts and further hydrolysis of the products to hydroxy acids.
  • the process operates at low concentration of hydroxyl compound ( ⁇ 10 times of enol ester), further the process doesn't provide catalyst separation method and reuse, showing inefficiency of the catalyst.
  • Palladium catalysed hydrocarbonylation of enol esters have been reported in Bull Chem. Soc. Jpn. 69, 1337-1345 (1996).
  • the process needs high pressure of CO (150-250 atm.) and a base such as pyridine or its derivatives.
  • loading of the catalyst is high (5 mol% of enol ester) which gives less activity in terms of turn over number. Also the process is applicable only for acetoxy esters and hydroxy esters, and not for the important product like hydroxy acids such as lactic acid.
  • the main object of the present invention is to provide a process for the preparation of 2- hydroxy carboxylic acids, which overcomes the drawbacks of low activity, catalyst stability, use of toxic chemicals, and the severe operating conditions.
  • the present invention provides a process for the preparation of 2-hydroxy carboxylic acids, which comprises; a) Carbonylation of an enol ester with carbon monoxide and a hydroxyl compound in presence of a palladium catalyst, an oxygen and/ or nitrogen and/ or phosphorus containing ligand(s) with molar ratio of 25:1,000 and a solvent at a temperature in the range of 50-250°C, at a pressure in the range of 50- 2000 psig, to obtain carbonylated ester; b) hydrolyzing the carbonylated ester with an acid catalyst at a temperature of 10- 125°C, to obtain 2-hydroxy carboxylic acid.
  • the molar concentration ratio of enol ester/catalyst used is in the range of 25 to 1,000.
  • the molar concentration ratio of hydroxyl compound/enol ester is not less than one.
  • the carbonylation catalyst is recycled and used for the carbonylation step.
  • hydroxyl compound used is a compound having formula R-OH, where R is H or primary, secondary or tertiary alkyl group containing 1-7 carbon atoms selected from the group of compounds such as water, methanol, ethanol, propanol, iso- propanol, butanol, isobutanol, t-butanol, pentanol.
  • the catalyst used comprises palladium (II) or palladium (0) compound having formula ABxCy, where A stands for palladium, B is an organic ligand containing one or more coordinating nitrogen and/ or oxygen and/ or phosphorus atom/s and C is any halogen atom such as F, CI, Br or I and (x+y) is an integer ranging from 1 to 4, individually x and y can vary in the range of 0 to 4.
  • Such palladium compounds can be selected from the group consisting of palladium chloride, palladium bromide, palladium iodide, and palladium acetate; or a metal complex of palladium such as bis(acetylacetonato)palladium(II), bis(triphenylphosphine)dichloropalladium(II), bis(triphenylphosphine)dibromopalladium (II), bis(triphenylphosphine)diiodopalladium (II), bis(pyridine)dichlor ⁇ palladium(II), bis(pyridine)didromopalladium(II) , bis(pyridine)diiodopalladium(II) , bis(acetonotrile)dichloropalladium( ⁇ ), bis(benzonitrile)dichloropalladi m(II), and tetrabis(triphenylphosphine)palladium(0).
  • the ligand is a compound containing one or more coordinating O atom/s selected from the group such as acetyl acetonate, salicylaldehyde, p- toluenesulphonic acid, compounds containing one or more coordinating N atom/s such as pyridine, pipyridine, triethyl amine, tributyl amine, quinoli ⁇ e, isoquinoline, o- phenylenediamine, p-phenylenediamine, ethylenediamine, or coordinating N and O atoms such as 8-hydroxy quinoline, bis(saliylidene)ethylenediamine, salicylaldoxime, picolinic acid, nicotinic acid, anthranilic acid, one or more P containing compound such as trimethyl phosphine, triethyl phosphine, tri-n-butyl phosphine, tri-t-butyl phosphine, tricyclo
  • the solvent used is an organic solvent selected from toluene, benzene, chloroform, dichloromethane, dichloroethane, chlorobenzene, o-dichlorobenzene, p-dichlorobenzene or ketone selected from a group consisting of acetone, ethyl methyl ketone, diethyl ketone, acetophenone or a cyclic ether such as tetrahydrofuran, dioxan, or nitrile selected from acetonitrile, benzonitrile.
  • the carbonylation product is separated by vacuum distillation or solvent extraction using appropriate solvent, and the carbonylation catalyst is recycled and reused for the carbonylation step.
  • hydrolysis of carbonylation products is carried out with the catalyst selected from the group consisting acidic catalysts as p-toluene sulphonic acid, aq. Hydrochloric acid, or a resin like amberlite at a temperature in the range of 10-125°C; the catalyst can be separated by distillation or filtration and reused for hydrolysis.
  • the catalyst selected from the group consisting acidic catalysts as p-toluene sulphonic acid, aq. Hydrochloric acid, or a resin like amberlite at a temperature in the range of 10-125°C; the catalyst can be separated by distillation or filtration and reused for hydrolysis.
  • the contents of the autoclave were flushed thrice with carbon monoxide at room temperature. Thereafter, the contents were heated at 100°C.
  • the autoclave was pressurized with carbon monoxide to 800 psig after the temperature was attained.
  • the contents were stirred for 4 hours continuously.
  • the reactor was then cooled to room temperature and the gas was vented off.
  • the contents of the autoclave were flushed thrice with carbon monoxide at room temperature. Thereafter, the contents were heated at 100°C.
  • the autoclave was pressurized with carbon monoxide to 800 psig after the temperature was attained.
  • the contents were stirred for 10 hours continuously.
  • the reactor was then cooled to room temperature and the gas was vented off.
  • the liquid contents were analysed by gas chromatography. The results of the gas chromatography showed 97.66% conversion of vinyl acetate with 61.42% selectivity to methyl-2-acetoxy propionate and 18.98%o selectivity to methyl lactate with turn over number of 399.4.
  • the autoclave was pressurized with carbon monoxide to 800 psig after the temperature was attained. The contents were stirred for 4 hours continuously. The reactor was then cooled to room temperature and the gas was vented off. The liquid contents were analysed by gas chromatography.
  • the contents of the autoclave were flushed thrice with carbon monoxide at room temperature. Thereafter, the contents were heated at 100°C.
  • the autoclave was pressurized with carbon monoxide to 800 psig after the temperature was attained.
  • the contents were stirred for 4 hours continuously.
  • the reactor was then cooled to room temperature and the gas was vented off.
  • the liquid contents were analysed by gas chromatography. The results of the gas chromatography showed 99% conversion of vinyl acetate with 76.45% selectivity to methyl-2-acetoxy propionate with turn over number of 411.
  • the contents of the autoclave were flushed thrice with carbon monoxide at room temperature. Thereafter, the contents were heated at 100°C.
  • the autoclave was pressurized with carbon monoxide to 800 psig after the temperature was attained.
  • the contents were stirred for 8 hours continuously.
  • the reactor was then cooled to room temperature and the gas was vented off.
  • the liquid contents were analysed by gas chromatography. The results of the gas chromatography showed 99% conversion of vinyl acetate with 2% selectivity to methyl-2-acetoxy propionate with turn over number of 10.
  • the contents of the autoclave were flushed thrice with carbon monoxide at room temperature. Thereafter, the contents were heated at 100°C.
  • the autoclave was pressurized with carbon monoxide to 800 psig after the temperature was attained.
  • the contents were stirred for 4 hours continuously.
  • the reactor was then cooled to room temperature and the gas was vented off.
  • the liquid contents were analysed by gas chromatography. The results of the gas chromatography showed 91.43% conversion of vinyl acetate with 35.67% selectivity to methyl-2-acetoxy propionate and 25.65% selectivity to methyl lactate with turn over number of 295.
  • the contents of the autoclave were flushed thrice with carbon monoxide at room temperature. Thereafter, the contents were heated at 100°C.
  • the autoclave was pressurized with carbon monoxide to 800 psig after the temperature was attained.
  • the contents were stirred for 4 hours continuously.
  • the reactor was then cooled to room temperature and the gas was vented off.
  • the liquid contents were analysed by gas chromatography. The results of the gas chromatography showed 82.65%) conversion of vinyl acetate with 4%> selectivity to methyl-2-acetoxy propionate and 42.56% selectivity to methyl lactate with turn over number of 202.
  • EXAMPLE 10 A 50 ml autoclave was charged with the following: Vinyl acetate: 0.025 mol Methanol: 23 ml PdCl 2 (PPh 3 ) 2 : 0.00005 mol Acetyl acetone: 0.001 mol The contents of the autoclave were flushed thrice with carbon monoxide at room temperature. Thereafter, the contents were heated at 100°C. The autoclave was pressurized with carbon monoxide to 800 psig after the temperature was attained. The contents were stirred for 3 hours continuously. The reactor was then cooled to room temperature and the gas was vented off. The liquid contents were analysed by gas chromatography.
  • the catalyst from example 13 was separated by filtration and added to 1.44 g of methyl- 2-acetoxy propionate and 15 ml water. Thereafter the contents were heated to 80°C for 3 hours. The analysis was done by gas chromatography. The results showed 41.77% conversion of methyl-2-acetoxy propionate with 100 % selectivity to lactic acid.
  • the process of the invention provides an alternative catalytic system for the production of lactic acid, which is economic and efficient.
  • the process provides the method for catalyst separation and its reuse.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé à deux étapes pour obtenir de l'acide hydroxy-carboxylique (par exemple, acide lactique), consistant 1) à effectuer la carbonylation d'un ester enolique (par exemple, acétate de vinyle) en présence d'un composé hydroxyle (par exemple, méthanol) en utilisant un catalyseur de palladium (par exemple, PdCl2(PPh3)2), un ligand comportant O-, N- et/ou P- et un solvant, à 50-150 °C/50-2000 psi pour obtenir un hydroxyester (par exemple méthyle ester de l'acide lactique) et un acétoxyester (par exemple, méthyle ester de l'acide 2-acetoxypropionique), à séparer et à recycler le catalyseur de carbonylation et 2) à hydrolyser les produits issus de l'étape 1) pour obtenir des acides 2-hydroxycarboxyliques (par exemple, acide lactique) en utilisant des catalyseurs acides (par exemple, TsOH, aq HCl, résines) à 10-125 °C, à séparer et à recycler le catalyseur de l'hydrolyse.
PCT/IB2003/006202 2003-12-26 2003-12-26 Procede pour obtenir d'acides 2-hydroxy-carboxyliques WO2005066109A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
PCT/IB2003/006202 WO2005066109A1 (fr) 2003-12-26 2003-12-26 Procede pour obtenir d'acides 2-hydroxy-carboxyliques
AU2003298472A AU2003298472A1 (en) 2003-12-26 2003-12-26 A process for the preparation of 2-hydroxy carboxylic acids
US10/808,965 US20050143600A1 (en) 2003-12-26 2004-03-25 Process for the preparation of 2-hydroxy carboxylic acids

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IB2003/006202 WO2005066109A1 (fr) 2003-12-26 2003-12-26 Procede pour obtenir d'acides 2-hydroxy-carboxyliques

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WO2005066109B1 WO2005066109B1 (fr) 2005-09-29

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112321431A (zh) * 2019-06-12 2021-02-05 赢创运营有限公司 由烃制备羧酸或其盐的方法
CN114539058A (zh) * 2020-11-24 2022-05-27 中国科学院大连化学物理研究所 一种甲醇和低碳烯烃多相催化制甲酯类化合物的方法
CN115605456A (zh) * 2020-05-21 2023-01-13 国立大学法人九州大学（Jp） 酯化合物的制造方法
CN116947637A (zh) * 2023-06-15 2023-10-27 广东仁康达材料科技有限公司 一种长碳链烯烃氢甲酯化的方法及用于氢甲酯化反应的设备

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH589571A5 (en) * 1973-07-25 1977-07-15 Pino Piero Hydrocarboxylation of olefinically unsaturated cpds. - giving linear acids and/or esters, using palladium-diphosphino complex catalysts
EP0144118A1 (fr) * 1983-08-29 1985-06-12 The Standard Oil Company Alcoxycarbonylation ou carbonylation avec du CO et avec un composé organique hydroxylé
EP0495548A2 (fr) * 1991-01-15 1992-07-22 Shell Internationale Researchmaatschappij B.V. Procédé de carbonylation d'oléfine
WO2004050599A1 (fr) * 2002-11-30 2004-06-17 Lucite International Uk Limited Carbonylation d'acetate de vinyle

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH589571A5 (en) * 1973-07-25 1977-07-15 Pino Piero Hydrocarboxylation of olefinically unsaturated cpds. - giving linear acids and/or esters, using palladium-diphosphino complex catalysts
EP0144118A1 (fr) * 1983-08-29 1985-06-12 The Standard Oil Company Alcoxycarbonylation ou carbonylation avec du CO et avec un composé organique hydroxylé
EP0495548A2 (fr) * 1991-01-15 1992-07-22 Shell Internationale Researchmaatschappij B.V. Procédé de carbonylation d'oléfine
WO2004050599A1 (fr) * 2002-11-30 2004-06-17 Lucite International Uk Limited Carbonylation d'acetate de vinyle

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
KUDO, K. ET AL: "Palladium(II)-catalyzed hydroesterification of enol esters: remarkable .alpha.-substituent effect upon regioselectivity", REACTION KINETICS AND CATALYSIS LETTERS , 59(1), 29-33 CODEN: RKCLAU; ISSN: 0304-4122, 1996, XP008034211 *
KUDO, KIYOSHI ET AL: "Hydrocarbonylation of enol esters catalyzed by a palladium(II) complex", BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN , 69(5), 1337-1345 CODEN: BCSJA8; ISSN: 0009-2673, 1996, XP002293064 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112321431A (zh) * 2019-06-12 2021-02-05 赢创运营有限公司 由烃制备羧酸或其盐的方法
CN112321431B (zh) * 2019-06-12 2024-07-02 赢创奥克森诺有限责任两合公司 由烃制备羧酸或其盐的方法
CN115605456A (zh) * 2020-05-21 2023-01-13 国立大学法人九州大学（Jp） 酯化合物的制造方法
EP4155290A4 (fr) * 2020-05-21 2024-06-19 Kyushu University, National University Corporation Procédé de production d'un composé ester
CN114539058A (zh) * 2020-11-24 2022-05-27 中国科学院大连化学物理研究所 一种甲醇和低碳烯烃多相催化制甲酯类化合物的方法
CN116947637A (zh) * 2023-06-15 2023-10-27 广东仁康达材料科技有限公司 一种长碳链烯烃氢甲酯化的方法及用于氢甲酯化反应的设备

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Publication number Publication date
AU2003298472A1 (en) 2005-08-12
WO2005066109B1 (fr) 2005-09-29

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