| 摘要 |
A process for the manufacture of butanedicarboxylic acid esters, wherein (A) AN AQUEOUS COBALT SALT SOLUTION IS TREATED, AT FROM 50 DEG TO 200 DEG C. and under a pressure of from 50 to 500 bars, with excess carbon monoxide and hydrogen in the presence of active charcoal laden with cobalt carbonyl, (B) THE RESULTING AQUEOUS SOLUTION OF COBALT CARBONYL HYDRIDE IS EXTRACTED WITH BUTADIENE OR WITH A HYDROCARBON MIXTURE CONTAINING BUTADIENE AND THE AQUEOUS PHASE IS SEPARATED OFF, (C) THE BUTADIENE, OR BUTADIENE-HYDROCARBON MIXTURE, CONTAINING COBALT CARBONYL HYDRIDE, COBALT CARBONYL AND BUTENYL-COBALT TRICARBONYL IS REACTED WITH CARBON MONOXIDE AND AN EXCESS OF AN ALKANOL OF 1 TO 4 CARBON ATOMS IN THE PRESENCE OF FROM 0.5 TO 2 MOLES, PER MOLE OF BUTADIENE, OF A TERTIARY NITROGEN BASE HAVING A PKa of from 3 to 11, at from 80 DEG to 150 DEG C. under a pressure of from 300 to 2,000 bars, and (D) THE RESULTING REACTION MIXTURE IS FREED FROM THE TERTIARY NITROGEN BASE CONTAINED THEREIN, EXCEPT FOR FROM 0.1 TO 0.3 MOLE PER MOLE OF PENTENOIC ACID ESTER, AND FROM EXCESS HYDROCARBONS, THE PENTENOIC ACID ESTER REMAINING IN THE REACTION MIXTURE IS REACTED WITH CARBON MONOXIDE AND AN EXCESS OF AN ALKANOL OF 1 TO 4 CARBON ATOMS AT FROM 140 DEG TO 200 DEG C. and under pressures of from 100 to 400 bars in the presence of the amounts of cobalt carbonyl and tertiary nitrogen base contained in the reaction mixture, and excess alkanol and free nitrogen base are then distilled off, and (E) THE REACTION MIXTURE WHICH REMAINS, AND WHICH CONTAINS COBALT CATALYST, THE BUTANEDICARBOXYLIC ACID ESTER AND BY-PRODUCTS IS TREATED WITH AN OXIDIZING AGENT IN AN AQUEOUS ACID MEDIUM AND THE MIXTURE IS SEPARATED INTO AN ORGANIC PHASE, FROM WHICH THE BUTANEDICARBOXYLIC ACID ESTER IS ISOLATED BY DISTILLATION, AND INTO AN AQUEOUS PHASE CONTAINING COBALT SALTS.
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