Carbonylation higher aliphatic alcohols

Transition metal carbonyls and their derivatives are remarkably effective and varied in their ability to catalyze reactions between unsaturated molecules (e.g., CO and olefinic compounds) or between certain saturated and unsaturated molecules (e.g., olefins and H2 or H20). The carbonyl derivatives of cobalt are particularly active catalysts for such reactions and have been put to use in the industrial synthesis of higher aliphatic alcohols. In fact, much of the growth in knowledge concerning catalysis by metal carbonyls has been stimulated by the industrial importance of the Fischer-Tropsch synthesis, and by the economically less important, but chemically more tractable, hydroformylation reaction. 

Oxysulfides and mercaptans of carbonyl compounds with the above mentioned mercaptans Methyl alcohol Higher aliphatic alcohols Acetol... 

Muzart s group has recently described the use of molybdenum catalysts with the hydrogen peroxide adduct, sodium percarbonate and a phase-transfer agent.198 The molybdenum catalyst used in the study was Mo02(acac)2, and the solvents screened were dichloroethane and acetonitrile. The active species is a Mo peroxo complex and in common with other methods based on Mo and W catalysts, secondary, allylic and benzylic alcohols react quickly, and give higher yields of carbonyl product than primary aliphatic alcohols. 

The aerobic oxidation of benzylic and allylic alcohols to their corresponding carbonyl compounds in [C4Ciim][PF6] with TEMPO-CuCl (TEMPO = 2,2,6,6-tetramethylpiperidinyl-l-oxy) as catalyst was found to proceed at higher rates than that of aliphatic alcohols, which is in agreement with results in classical solvents.[75] After product extraction with diethyl ether, the ionic liquid was washed with water and dried at 70°C, prior to the next run. In that manner catalyst activity remained relatively stable for 8 cycles. 

The carbonyl reductase from Candida magnoliae catalyzed the enantioselective reduction of a diversity of ketones, including aliphatic and aromatic ketones and a- and /3-ketoesters (Figure 7.17), to anti-Prelog configurated alcohols in excellent optical purity (99% ee or higher) [56]. 

Acids, carbonyl compounds, ethers, amines, and alcohols have transfer constants higher than those of aliphatic hydrocarbons, corresponding to C—H breakage and stabilization of the radical by an adjacent O, N, or carbonyl group. 

The reaction of 1,3-dibromopropene with carbonyl compounds mediated by indium in water gives 3,3-disubsti-tuted propene 63 (Scheme 55). In the formation of 63, 1,3-dibromopropene acts as a w-allyl dianion synthon. Aromatic aldehydes generally have a higher selectivity than aliphatic ones in the product formation. Unsubstituted and electron-withdrawing group-substituted benzaldehydes give mainly 3,3-disubstituted propene 63. For electron-rich benzaldehydes, the formation of both 3,3- 63 and 1,3-disubstituted propene 64 is dramatically decreased and the selectivity is reversed completely to give diene 65 and homoallylic alcohol 66.219... 

Volk and Schnitzer (1973) concluded that variations in the functional group components and spectral properties of humic acids from a group of Florida mucks indicated that higher rates of humification were related to (1) greater amounts of carboxyl, phenolic hydroxyl, quinone, and ketonic carbonyl groups (2) fewer alcoholic hydroxyl groups and aliphatic structures, as per IR evidence and (3) increments in EJEf, ratios and free-radical contents as revealed by ESR spectroscopy (Table 12). 

Deoxygenation of carbonyl compounds. This system, which has been shown to reduce alcohols to hydrocarbons, also reduces aliphatic and aromatic ketones and aromatic aldehydes to hydrocarbons. Yields are higher when the BF3 is scrubbed by HF before use. The reaction proceeds stepwise, since intermediate alcohols can be isolated. A large excess of the silane is required. 

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