Addition of carbon monoxide

Often the aldehyde is hydrogenated to the corresponding alcohol. In general, addition of carbon monoxide to a substrate is referred to as carbonylation, but when the substrate is an olefin it is also known as hydroformylation. The eady work on the 0x0 synthesis was done with cobalt hydrocarbonyl complexes, but in 1976 a low pressure rhodium-cataly2ed process was commerciali2ed that gave greater selectivity to linear aldehydes and fewer coproducts. 

Without other alternatives, the carboxyalkyl radicals couple to form dibasic acids HOOC(CH)2 COOH. In addition, the carboxyalkyl radical can be used for other desired radical reactions, eg, hydrogen abstraction, vinyl monomer polymerization, addition of carbon monoxide, etc. The reactions of this radical with chloride and cyanide ions are used to produce amino acids and lactams employed in the manufacture of polyamides, eg, nylon. 

Use of alcohol as a solvent for carbonylation with reduced Pd catalysts gives vinyl esters. A variety of acrylamides can be made through oxidative addition of carbon monoxide [630-08-0] CO, and various amines to vinyl chloride in the presence of phosphine complexes of Pd or other precious metals as catalyst (14). 

Although the addition of carbon monoxide to a carbonium ion R+ leads to a product R—C =0, with a new carbon-carbon bond, one may raise the question whether this oecurs by direct alkylation at carbon ... 

Stille JK (1991) Hydroformylation and related additions of carbon monoxide to alkenes and alkynes. In Trost BM, Fleming I, Paquette LA (eds) Comprehensive organic synthesis. Pergamon, Oxford, p 913... 

Metal Complexes as Catalysts for Addition of Carbon Monoxide... 

Since 1985, several thousands of publications have appeared on complexes that are active as catalysts in the addition of carbon monoxide in reactions such as carbonylation of alcohols, hydroformylation, isocyanate formation, polyketone formation, etc. It will therefore be impossible within the scope of this chapter to review all these reports. In many instances we will refer to recent review articles and discuss only the results of the last few years. Second, we will focus on those reports that have made use explicitly of coordination complexes, rather than in situ prepared catalysts. Work not containing identified complexes but related to publications discussing well-defined complexes is often mentioned by their reference only. Metal salts used as precursors on inorganic supports are often less well defined and most reports on these will not be mentioned. 

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