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%).

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• 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)

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• 1983
  • 1983-11-15 EP EP19840900175 patent/EP0134216A4/de active Pending
  • 1983-11-15 WO PCT/US1983/001814 patent/WO1984002699A1/en not_active Application Discontinuation

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