GB637999A - Process for the production of oxygen-containing organic compounds - Google Patents

Abstract

In a process for the production of oxygen-containing organic compounds by reacting an olefinic compound with carbon monoxide and hydrogen in the presence of a previously prepared catalyst comprising a metal carbonyl (see Group IV (b)), examples are given in which the catalyst is a solution of cobalt carbonyl in cyclohexane and is prepared by heating a mixture of reduced, sintered, cobalt oxide with carbon monoxide under high pressure.ALSO:Oxygen containing organic compounds such as aldehydes, acetals and alcohols are obtained by reacting at a temperature of 75 DEG to 250 DEG C. and at raised pressure an olefinic compound with carbon monoxide and hydrogen in the presence of a previously prepared catalyst comprising a metal carbonyl, especially cobalt, nickel and iron carbonyl. The temperature is preferably 100 DEG to 200 DEG C. and the pressure 50 to 1500 atmospheres, and the amount of catalyst is preferably from 0.1 to 10 per cent of the total weight of the reaction mixture. The molar ratio of CO : H2 : olefine is preferably within the range of 1 : 2 : 1 to 2 : 4 : 1. One way of carrying out the process is to inject a mixture of carbon monoxide and hydrogen under high pressure into a mixture of the olefinic compound and a solution of the metal carbonyl in a pressure-resistant vessel. To avoid decomposing the carbonyl catalyst during distillation of the crude reaction products carbon monoxide is conducted through the liquid at 100-200 DEG C. under 100-150 atmospheres pressure and the pressure on the resultant effluent gas is then decreased to about atmospheric pressure, whereby a portion of the aldehyde in the gas separates and the metal carbonyl is recovered from the liquid which condenses. The effluent gas is then scrubbed with an inert liquid organic solvent, preferably at below 0 DEG C., to recover the rest of the aldehyde. The recovered catalyst may be recycled to the reaction vessel. Specified olefinic compounds are monoolefines, p diolefines, aryl substituted olefines and substituted olefines such as the ethers, esters, carboxylic acids halides, ketones, aldehydes and anhydrides containing olefinic unsaturation. Sterically-hindered olefinic compounds such as tetramethyl ethylene may also be used. A polymerization inhibitor may be added and an inert organic liquid may be employed as reaction medium. This liquid may suitably be xylene or diethyl benzene in any of their isomeric forms or cyclohexane, ethyl benzene, saturated esters and saturated ethers. When the reaction is conducted in the presence of alcohols, acetals are formed. The process may be batchwise or continuous and the reactor may be lined with inert materials such as glass, porcelain or inert metals, but preferably with silver or copper. In examples: (1) a mixture of reduced, sintered cobalt oxide and cyclohexane is heated with carbon monoxide to form a solution of cobalt carbonyl, the solution is filtered and the filtrate diluted with cyclohexane; a mixture of cyclohexane and ethylene is then introduced and the mixture heated under pressure with a gas comprising 2 volumes of hydrogen per volume of carbon monoxide (CO : 2H2). Distillation of the product yields propionaldehyde and n-propanol; (2) iron carbonyl is used as catalyst and the reaction is effected as in (1) and yields the same products; (3) and (4) a -acetoxy propionaldehyde and acrolein are obtained by heating a mixture of vinyl acetate, cobalt carbonyl and hydroquinone with a mixture of carbon monoxide and hydrogen in the presence of cyclohexane and methyl acetate respectively; (5) b ,g -dimethyl valeraldehyde and a trimeric aldehyde (C6H13CHO)3 are obtained from tetramethyl ethylene using cyclohexane as reaction medium; (6) methyl 4-oxobutyrate is obtained from methyl acrylate using cobalt carbonyl as catalyst and benzene as diluent; (7) propionaldehyde is obtained from ethylene using nickel carbonyl as catalyst and cyclohexane as inert diluent; (8) a mixture of butadiene, hydroquinone and a solution of cobalt carbonyl in cyclohexane obtained as in (1) are reacted with a mixture of carbon monoxide and hydrogen yielding a series of aldehyde-containing fractions; (9) n-butyraldehyde is obtained from propylene using a cyclohexane solution of cobalt carbonyl as catalyst and diethyl ether as diluent; (10) a mixture of D 3-tetrahydrobenzaldehyde diisobutylacetal, cobalt carbonyl and cyclohexane is reacted with CO : H2 yielding a mixture of aldehydes and acetals; (11) a mixture of a cyclohexane solution of cobalt carbonyl obtained as in (1) and methyl vinyl ether is reacted with CO : 2H2 yielding on distillation methanol, acetaldehyde, 3-methoxy-propionaldehyde and its dimethyl acetal; (12) a mixture of carbon monoxide, hydrogen and ethylene (molar ratio 2 : 1 : 1) is passed through a copper tube concurrently with a solution of cobalt carbonyl in xylene at elevated temperature and pressure, propionaldehyde being obtained from the product by bubbling carbon monoxide through it at elevated temperature and pressure. After cooling and letting down to atmospheric pressure a cobalt carbonyl solution containing a small amount of propionaldehyde is obtained and may be recycled. The bulk of the propionaldehyde freed from cobalt carbonyl is recovered from the exit gases; (13) a solution of n-butyraldehyde in diethyl ether obtained as in (9) is treated for recovery of the aldehyde as in (12); (14) propylene is reacted with carbon monoxide and hydrogen in a manner similar to that of (12) but using cobalt carbonyl in diethyl benzene solution; normal and isobutyraldehydes are obtained. Specifications 614,010 and 631,316 are referred to.