摘要 |
Carboxylic acids or their salts, esters, thioesters or amides are prepared by reacting together (1) an organic halide, a sulphonic acid ester or sulphuric acid ester of the formula RX, RX2, ROSO2R1 and R2SO4 in which represents a saturated or ethylenically unsaturated aliphatic or cycloaliphatic hydrocarbon radical or such a compound substituted by an alkoxy, acyl, acyloxy, aryl, nitro, nitrato or cyano substituent, X is halogen, and R1 represents an alkyl, alkenyl cyclo-alkyl, aryl, or aralkyl radical, said X, X2, OSO2R1 and SO4 radicals being attached only to primary or secondary aliphatic or cyclo-aliphatic carbon atoms of the R radicals, (2) carbon monoxide, (3) a salt of cobalt or iron hydrocarbonyl and (4) water, alcohols, phenols, mercaptans, ammonia or primary or secondary amines in the presence of sufficient base to keep the reaction mixture basic. The acid is formed from the product by hydrolysis with acidification. Many starting materials are listed and the reaction may be in a two stage process. Examples describe the preparation of methyl phenylacetate from benzyl bromide, methyl nonanoate from 1-iodooctane or 1-chlorooctane, methyl 2-methyl octanoate from 2-iodooctane, methyl acetate from methyl p-toluenesulphonate, methyl 3-butenoate from allyl bromide, dimethyl malonate from methyl chloroacetate, p-phenylenediacetic acid from a ,a 1-dichloro-p-xylene, a -naphthylacetic acid from 1-chloromethylnaphthalene, phenylacetanilide from benzyl chloride, phenyl thioacetate from methyl iodide, dimethyl malonate from methyl chloroacetate, dimethyl methyl malonate from methyl a -bromopropionate, ethyl hexanoate from 1-iodopentane, cyclohexyl hexanoate from iodopentane, methyl methoxyacetate from chloromethyl methyl ether, and methyl propionate from diethyl sulphate. |