PREPARATION OF HALOGENATED CARBOXYLIC ACID ESTERS

• Main Author: WILLIAM C. BAIRD JR
• Format: Patent
• Language: English
• Published: 30.11.1971
• Subjects: ACYCLIC OR CARBOCYCLIC COMPOUNDS; CHEMISTRY; METALLURGY; ORGANIC CHEMISTRY

Substituted carboxylic acid esters are prepared by reacting a non-tertiary olefine with a source of carboxylate ions and an inorganic metal salt in the presence of a Group VIII metal salt and an anhydrous solvent at between 50 DEG and 250 DEG C. to produce a saturated carboxylic acid solvent substituted by the anionic component of the inorganic metal salt. Ethylene, propylene, butene-1, cis-butene-2, transbutene-2, pentene-1, pentene-2, hexene-1, hexene-2, hexene-3, t-butylethylene, 3-methylbutene-1, norbornylene, norbornadiene, cyclopentene, cyclooctene, and cyclododecene are mentioned, and the inorganic metal salt may be a halide, cyanide, nitrate, nitrite, sulphate, sulphite, bisulphate, bisulphite, phosphate or phosphite, and the cupric and ferric salts are preferred. Suitable solvents are carboxylic acids, nitriles and esters, and mixtures of carboxylic acids with up to 50 vol. per cent of pentane, hexane, isooctane, benzene, carbon tetrachloride, chloroform and dichloroethane. Examples describe the preparation of 1-chloro-2-acetoxy ethane from ethylene, 2-bromo-7-acetoxynorbornane from norbornylene, 1-bromo-2 -acetoxypropane and 2 - bromo - 1 - acetoxypropane from propylene, 1-chloro-2-acetoxybutane and 1 - acetoxy - 2 - chlorobutane from t-butyl ethylene, 1-chloro-2-acetoxycyclopentane from cyclopentene, 1-chloro-2-acetoxybutane and 1 - acetoxy - 2 - chlorobutane from butene - 1, B - nitrato - isopropyl propanoate from propylene, 1 - bisulphato - 2 - butyoxy-4-methylpentane from 4 - methyl - pentene - 1 and 1-nitrato-2-acetoxypropane from propylene.