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EP0134216A4 - PROCEDE DE PREPARATION D'ACIDES -g(a)-CETO-CARBOXYLIQUES. - Google Patents

PROCEDE DE PREPARATION D'ACIDES -g(a)-CETO-CARBOXYLIQUES.

Info

Publication number
EP0134216A4
EP0134216A4 EP19840900175 EP84900175A EP0134216A4 EP 0134216 A4 EP0134216 A4 EP 0134216A4 EP 19840900175 EP19840900175 EP 19840900175 EP 84900175 A EP84900175 A EP 84900175A EP 0134216 A4 EP0134216 A4 EP 0134216A4
Authority
EP
European Patent Office
Prior art keywords
organohalide
keto
carbon atoms
alkyl
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP19840900175
Other languages
German (de)
English (en)
Other versions
EP0134216A1 (fr
Inventor
John Yuchu Lee
Joachim Wilhelm Wolfram
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ethyl Corp
Original Assignee
Ethyl Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US06/457,520 external-priority patent/US4492798A/en
Priority claimed from US06/529,570 external-priority patent/US4532345A/en
Application filed by Ethyl Corp filed Critical Ethyl Corp
Publication of EP0134216A1 publication Critical patent/EP0134216A1/fr
Publication of EP0134216A4 publication Critical patent/EP0134216A4/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide

Definitions

  • ⁇ -keto-carboxylic acids can be prepared by reacting an organohalide in a liquid solvent medium with carbon monoxide at elevated temperature and elevated pressure in the presence of a catalytic amount of a metal carbonyl compound and an alkali metal inorganic base or an alkaline earth metal inorganic base characterized by utilizing as the organohalide a compound of the formula:
  • R, R' and R which may be the same or different, represent hydrogen or linear or branched alkyl radicals having up to about 6 carbon atoms, and n is 0 or an integer from 1-5 when A contains one benzene ring, and n is 0 or an integer from 1-7 when A contains two condensed benzene rings and m is 0-20.
  • the reaction is carried out in the presence of a mixture of water and alcohol as a reaction medium in which the carbonylation of the organohalide takes place.
  • the alcohols employed for the reaction may be straight-chain, branched or cyclic, and preferably contain from 1 to 6 carbon atoms.
  • Methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, tert- butanol, and tert-amyl alcohol may be mentioned as examples.
  • Cyclic ethers such as tetrahydrofuran, also may be used.
  • a particularly preferred solvent alcohol is tert-butanol.
  • the amount of basic agent used can vary within wide limits.
  • the molar ratio of the alkali metal or alkaline earth metal base to organohalide reactant is from 10:1 to 1:1, preferably from 6:1 to 2:1.
  • lower alkyl esters of the ⁇ -keto-carboxylic acid products of the present invention can be prepared by esterifying the ⁇ -keto-carboxylic acid product according to conventional esterification techniques employing lower aliphatic alkanol and acid catalysts such as, for example, BF 3 , BF 3 HCl, BF 3 MeOH, BF 3 Et 2 O or diazomethane at suitable reaction conditions.
  • lower aliphatic alkanol and acid catalysts such as, for example, BF 3 , BF 3 HCl, BF 3 MeOH, BF 3 Et 2 O or diazomethane at suitable reaction conditions.
  • Example No. 24 A comparison between Example No. 24 and Example No. 22 in the table indicates that at approximately the same reaction conditions a reduction in the amount of LiOH used in the reaction has an adverse effect on the yield of benzylpyruvic acid by reducing the yield from about 66% in Example No. 22 to about 20% in Example No. 24.
  • Reference to Example No. 23 indicates that NaOH is a less reactive base than either LiOH or Ca(OH) 2 affording only a 16% yield of benzylpyruvic acid.
  • a comparison between Example No. 27 and Example No. 32 demonstrates the effect a reduction in pressure has on the yield of benzylpyruvic acid when Ca(OH) 2 is used as the basic agent. At similar reaction conditions, the yield of acid dropped from approximately 77% in Example No.
  • 6-phenoxy-2-oxo-hexanoic acid of 78% purity. Major impurities in the crude product were identified as 5-phenoxy pentanoic acid (10%) and 6-phenoxy-2-hydroxy hexanoic acid (12%).

Landscapes

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

Abstract

Procédé de préparation d'acides alpha-céto-carboxyliques par la réaction d'un organo-halogénure dans un milieu solvant liquide avec de l'oxyde de carbone à température et pression élevées en présence d'une quantité catalytique d'un composé de carbonyle métallique et d'une base inorganique de métal alcalin ou d'une base inorganique de métal alcalino-terreux, caractérisé par l'utilisation en tant qu'organo-halogénure d'un composé de formule RX, dans laquelle X représente un atome d'halogène et R est un groupe alkyle primaire ou secondaire, un groupe arylalkyle primaire possèdant deux ou plusieurs atomes de carbone dans sa partie alkyle liée à l'atome d'halogène, ou bien un groupe d'aryloxy-alkyle primaire ou secondaire.
EP19840900175 1983-01-13 1983-11-15 PROCEDE DE PREPARATION D'ACIDES -g(a)-CETO-CARBOXYLIQUES. Pending EP0134216A4 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US06/457,520 US4492798A (en) 1982-03-01 1983-01-13 Process for preparing arylalkylpyruvic acids
US457520 1983-01-13
US529570 1983-09-06
US06/529,570 US4532345A (en) 1983-09-06 1983-09-06 Process for preparing aryloxyalkylpyruvic acids

Publications (2)

Publication Number Publication Date
EP0134216A1 EP0134216A1 (fr) 1985-03-20
EP0134216A4 true EP0134216A4 (fr) 1985-07-01

Family

ID=27038635

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19840900175 Pending EP0134216A4 (fr) 1983-01-13 1983-11-15 PROCEDE DE PREPARATION D'ACIDES -g(a)-CETO-CARBOXYLIQUES.

Country Status (2)

Country Link
EP (1) EP0134216A4 (fr)
WO (1) WO1984002699A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4820823A (en) * 1985-02-27 1989-04-11 Director-General Of Agency Of Industrial Science And Technology Process of producing α-keto acids
FR2590565B1 (fr) * 1985-11-27 1988-01-08 Rhone Poulenc Spec Chim Procede de preparation d'alpha-hydroxyacides

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2026478A (en) * 1978-06-26 1980-02-06 Dynamit Nobel Ag Process for producing alkali metal salts of aryl pyruvic acids

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2600541C3 (de) * 1975-01-09 1978-06-08 Rhone-Poulenc Industries, S.A., Paris Verfahren zur Herstellung von Phenylbrenztraubensäure oder Arylbrenztraubensäuren
ES496382A0 (es) * 1979-10-31 1982-03-01 Byk Gulden Lomberg Chem Fab Procedimiento para la preparacion de acidos oxocarboxilicos sustituidos
US4351952A (en) * 1980-07-01 1982-09-28 Montedison S.P.A. Process for preparing phenyl pyruvic acids

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2026478A (en) * 1978-06-26 1980-02-06 Dynamit Nobel Ag Process for producing alkali metal salts of aryl pyruvic acids

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO8402699A1 *

Also Published As

Publication number Publication date
WO1984002699A1 (fr) 1984-07-19
EP0134216A1 (fr) 1985-03-20

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Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB LI LU NL SE

17P Request for examination filed

Effective date: 19850118

17Q First examination report despatched

Effective date: 19870715

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

RIN1 Information on inventor provided before grant (corrected)

Inventor name: LEE, JOHN, YUCHU

Inventor name: WOLFRAM, JOACHIM, WILHELM