Aluminum acetate ethoxide

Ethyl acetate [141-78-6] is produced commercially by the Tischenko condensation of acetaldehyde using an aluminum ethoxide catalyst (60). The Tischenko reaction of acetaldehyde with isobutyraldehyde [78-84-2] yields a mixture of ethyl acetate, isobutyl acetate [110-19-0] and isobutyl isobutyrate [97-85-8] (61). 

Acetylacetone has been prepared by the reaction of acetyl chloride with aluminum chloride followed by hydrolysis,3 and by the condensation of acetone with ethyl acetate under the influence of sodium,4 sodamide,5 and sodium ethoxide,5-6-7 and by the reaction of acetone and acetic anhydride in the presence of boron trifluoride.8... 

The neutralization values were influenced by reduction with strong reducing agents, lithium aluminum hydride, sodium borohydride, and amalgamated zinc plus hydrochloric acid (35, 46). For the most part, the consumption of NajCOj and of NaOEt decreased in equivalent amounts. This is further confirmation of the assumption that lactones of the fluorescein type or of the lactol type are present. The reaction with sodium ethoxide was shown to be no true neutralization, that is, exchange of H+for Na+, at all, but an addition reaction w ith the formation of the sodium salt of a semi-acetal or ketal ... 

Further Reduction to a Hydrocarbon. In the reduction of benzo-phenone with aluminum ethoxide the formation of 7% of diphenyl-methane was observed. When benzohydrol was treated with aluminum ethoxide under the same conditions, 28% reduction to diphenylmethane occurred.12 In these reactions acetic acid, rather than acetaldehyde,-was formed from the ethoxide. Aluminum isopropoxide does not give this type of undesirable reaction with this reagent, pure benzohydrol is easily obtained in 100% yield from benzophenone.6 37 However, one case of reduction of a ketone to the hydrocarbon has been observed with aluminum isopropoxide.17 When 9, 9-dimethylanthrone-10 (XU) was reduced in xylene solution, rather than in isopropyl alcohol, to avoid formation of the ether (see p. 190), the hydrocarbon XUII was formed in 65% yield. The reduction in either xylene or isopropyl alcohol was very slow, requiring two days for completion. 

The Henry reaction is routinely performed in the presence of only catalytic quantities of a base. Several base catalysts including alkali metal hydroxides, carbonates, bicarbonates, alkoxides, calcium and barium hydroxides and magnesium and aluminum ethoxides have been used. Anion-exchange resins and, among organic bases, primary and tertiary amines and ammonium acetate and fluoride have proven to be... 

Ethyl acetate, prepared industrially from acetaldehyde and catalytic amounts of aluminum ethoxide, contains acetic acid, ethanol, and water as impurities. 100 g of ethyl acetate dissolves 3.3 g of water at 25° the azeotrope contains 8.5% of water. 

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