Heterogeneous alcohol synthesis

He was a Professor of Industrial Chemistry, School of Engineering, Polytechnic Institute of Milan, Milan, Italy since 1937. He became involved with applied research, which led to the production of synthetic rubber in Italy, at the Institute in 1938. He was also interested in the synthesis of petrochemicals such as butadiene and, later, oxo alcohols. At the same time he made important contributions to the understanding of the kinetics of some catalytic processes in both the heterogeneous (methanol synthesis) and homogeneous (oxosynthesis) phase. In 1950, as a result of his interest in petrochemistry, he initiated the research on the use of simple olefins for the synthesis of high polymers. This work led to the discovery, in 1954, of stereospecific polymerization. In this type of polymerization nonsymmetric monomers (e.g., propylene, 1-butene, etc.) produce linear high polymers with a stereoregular structure. 

Hu, X.D. Scientific Basis for Design of Heterogeneous Catalysts—A Study of Higher Alcohol Synthesis Catalysts, Ph.D dissertation. University of Delaware, 1989. 

Yamaguchi K, Kobayashi H, Oishi T, Mizuno N (2012) Heterogeneously catalyzed synthesis of primary amides directly from primary alcohols and aqueous ammonia. Angew Chem Int Ed 51(2) 544-547... 

Clay-supported heteropoly acids such as H3PW12O40 are more active and selective heterogeneous catalysts for the synthesis of MTBE from methanol and tert-butanol, etherification of phenethyl alcohols with alkanols, and alkylation of hydroquinone with MTBE and tert-butanoi (Yadav and Kirthivasan, 1995 Yadav and Bokade, 1996 Yadav and Doshi, 2000), and synthesis of bisphenol-A (Yadav and Kirthivasan, 1997). 

The synthesis and olefin metathesis activity in protic solvents of a phosphine-free ruthenium alkylidene bound to a hydrophilic solid support have been reported. This heterogeneous catalyst promotes relatively efficient ring-closing and cross-metathesis reactions in both methanol and water.200 The catalyst-catalyzed cross-metathesis of allyl alcohol in D20 gave 80% HOCH2CH=CHCH2OH. 

The Fischer-Tropsch synthesis, which may be broadly defined as the reductive polymerization of carbon monoxide, can be schematically represented as shown in Eq. (1). The CHO products in Eq. (1) are any organic molecules containing carbon, hydrogen, and oxygen which are stable under the reaction conditions employed in the synthesis. With most heterogeneous catalysts the primary products of the reaction are straight-chain alkanes, while the secondary products include branched-chain hydrocarbons, alkenes, alcohols, aldehydes, and carboxylic acids. The distribution of the various products depends on both the type of catalyst and the reaction conditions employed (4). 

The Koenigs-Knorr method in the presence of an insoluble silver salt proceeds mainly with inversion of configuration. Silver silicate and silver-silicate-aluminate have often been used as the heterogeneous catalyst. This procedure has been traditionally used for the synthesis of p-mannosidcs and has been recently reviewed.35 However, it only works well with very reactive halides and sufficiently reactive alcohol components. 

An important issue concerning the use of heterogeneous catalysts for biodiesel synthesis is the lack of systematic research exploring the principles of solid catalyst activity for transesterification of TGs and esterification of FFAs with alcohols. For instance, the question about the true catalytic nature of some solid bases, called heterogeneous, remains unanswered. For example, the most active heterogeneous catalysts reported to date is Ba(OH)2. However, due to its... 

The procedure for getting the polymer-bound ligands is very easy to reproduce. Three jS-functionalized aromatic ketones were successfully reduced to the corresponding alcohols by heterogeneous asymmetric hydrogen transfer reaction with formic acid-triethylamine azeotrope as the hydrogen donor. One of the product alcohols (19c) is an intermediate for the synthesis of optically active fluoxetine. 

---