Oxygenates by Homologation or CO Hydrogenation with Metal Complexes

Born and initially developed in various industrial laboratories, mainly in U.S.A. and Gennany, homogeneous phase catalytic carbon monoxide hydrogenation and alcohols and their derivatives carbonylation and homologation, have generally been considered and reviewed separately in the course of their 40 years history without concern for common aspects in the chemical transfonnations and in catalysis. Thanks to researchers of Japanese companies participating in the National C 1 Chemistry Project (1980-1987) the scientific and technical approaches in this field have been unified and applied in parallel, in the light of some common aspects of the chemical reactions and mechanisms. Now, at a moment when research seems becahned, a general presentation and discussion of the most recent topics might be an useful basis for further development of this chemistry. To delimit and simplify the discussion of the chemical aspects and the nature of the catalysts involved, the present review is limited to reactions employing homogeneous metal complexes for the direct conversion of syngas to oxygenates and to the hydrocarbonylation of these last to homologous derivatives. Since the previous practically contemporary reviews by Dombek [in Adv. Organomet. Chern. (1983)] on CO hydrogenation and by the present authors [in Asp.Homog.Catal.(Reidel Pu.l984)] on alcohol homologation fully cover the literature up to 1982, here we mainly refer to work done after 1982, and consider the cited reviews as covering the historical development of research in the 1940- 1980 period.

Inhalt

Glossary of Abbreviations. Preface. Monoalcohols, Glycols, and their Ethers and Esters by CO Hydrogenation; G. Braca, A.M. Raspolli Galletti, G. Sbrana. 1. Introduction. 2. Cobalt Catalysts. 3. Ruthenium Catalysts. 4. Rhodium Catalysts. 5. Other Catalysts. 6. Reaction Mechanism. 7. Industrial Process Development. 8. References. Alcohols and Derivatives by Homologation with Syn Gas; G. Braca, A.M. Raspolli Galletti, G. Sbrana. 1. Introduction. 2. Hydrocarbonylation of Alcohols. 3. Hydrocarbonylation of Aliphatic Ethers. 4. Hydrocarbonylation of Carboxylic Acid Esters. 5. Homologation of Acetic Acid in the Presence of Ruthenium/Iodide or Rhodium/Iodide Catalysts. 6. Homologation of Methyl Halides. 7. Reaction Mechanism. 8. Industrial Process Development. 9. References. Hydrocarbonylation of Aldehydes and their Derivatives; M. Marchionna. 1. Introduction. 2. Hydroformylation of Formaldehyde to Glycol Aldehyde. 3. Hydrocarbonylation of Formaldehyde to Ehtylene Glycol. 4. Hydrocarbonylation of Formaldehyde to Acetaldehyde and/or Ethanol. 5. Hydrocarbonylation of Formaldehyde to Higher Oxygenated Products. 6. Hydrocarbonylation of Higher Aldehydes. 7. Conclusions. 8. References.