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.

Klappentext

The homogeneous catalytic hydrogenation of CO and the carbonylation and homologation of alcohols and their derivatives emerged nearly 40 years ago, in the U.S.A. and Germany. Since that time, the two topics have generally been reviewed separately, with no concern for their common aspects, in terms of both the chemical transformations involved, nor for the catalytic aspects, until Japanese workers, during the National Csub1/sub Chemistry Project, which ran from 1980 to 1987, unified both the scientific and technological approaches in the field. The literature from 1940--1980 has been well reviewed, and so the time is now ripe for a thorough, careful review of work accomplished since then. br/ Under the editorial inspiration of Professor Braca, emOxygenates by/em emHomologation or CO Hydrogenation with Metal Complexes/em presents an authoritative reconsideration and review of research on oxygenate production by CO hydrogenation, and the homologation of alcohols, aldehydes, ethers and esters in the presence of transition metal complexes. The three chapters of the book, each presenting a masterly overview of its topic, are entitled: Monoalcohols, Glycols and their Ethers and Esters by CO Hydrogenation; Alcohols and Derivatives by Homologation with SynGas; and Hydrocarbonylation of Aldehydes and their Derivatives. br/ The chapters are presented in a common format, presenting the performances of the catalytic systems of different metals, followed by a general discussion of the reaction mechanism along the successive reaction steps, from the activation of the substrates up to their chemical modification and the restoration of the catalysts. Attention is also paid to the problems of stability and deactivation of the catalytic systems and to the difficulties of the industrial development of the reactions. br/br/ (2nd text) br/ This volume presents an overview of the current status of research into homogeneous phase catalytic carbon monoxide hydrogenation and the carbonylation and homologation of alcohols and their derivatives, with emphasis on the progress which has been made since 1982.br/ The concents are divided into three major chapters. Chapter 1 deals with monoalcohols, glycols and their ethers and esters by carbon monoxide hydrogenation. Chapter 2 discusses alcohols and their derivatives by homologation with syngas. Chapter 3 considers the hydrocarbonylation of aldehydes and their derivatives. br/ The organization of the material in each of these chapters follows a common scheme. The performance of catalytic systems of different metals is presented and then reaction mechanisms are discussed for successive reaction steps, from the activation of substrates to their chemical modifications and the restoration of catalysts. Attention is also paid to problems of stability and deactivation of catalytic systems. The difficulties associated with the industrial development of the various reactions is also considered. br/ For research organic chemists in academia and industry whose work involves catalysis. br/

Inhalt
Monoalcohols, Glycols, and their Ethers and Esters by CO Hydrogenation.- Department of Chemistry and Industrial Chemistry, University of Pisa, ITALY.- 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.- Department of Chemistry and Industrial Chemistry, University of Pisa (ITALY).- 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 Reactiom mechanism.- 8 Industrial processes development.- 9 References.- Hydrocarbonylation of aldehydes and their derivatives.- SNAM PROGETTI S.p.A. S.Donato Milanese (ITALY).- 1 Introduction.- 2 Hydroformylation of formaldehyde to glycol aldehyde.- 3 Hydrocarbonylation of formaldehyde to ethylene 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.