Aluminum ethylate

Several species of bacteria under suitable conditions cause / -butyraldehyde to undergo the Canni22aro reaction (simultaneous oxidation and reduction to butyric acid and butanol, respectively) this reaction can also be cataly2ed by Raney nickel (7). The direct formation of butyl butyrate [109-21 -7] or isobutyl isobutyrate [97-85-8](Vish.ch.erik.o reaction) from the corresponding aldehyde takes place rapidly with aluminum ethylate or aluminum butyrate as catalyst (8). An essentially quantitative yield of butyl butyrate, CgH2 02, from butyraldehyde has been reported usiag a mthenium catalyst, RuH,[P(C,H,)3], (9). 

Chemical Designations - Synonyms Aluminum ethyl dichloride EADC Chemical Formula CjHjAICIj. 

C4HgN20 557-11-9) see Chlormerodrin Al-allyl-Wieland-Gumlich aldehyde iodide see under N -allylheminottoxiferine iodide aluminum ethylate... 

ETHYLAMINUM DICHLORIDE EADC, Aluminum Ethyl Dichloride Flammable Liquid 3 3 3 W... 

Most of these compds are liquids or low melting solids which easily catch fire in air and react violently with water. As examples of these compds may be cited aluminum ethyl diiodide, Al(CaHs)Ia solid, mp 35-7°, hp 158-60°at 4 mm and aluminum diethyl iodide,... 

Aldehydes and Ketones. Esters are obtained readily by condensation of aldehydes in the presence of alcoholate catalysis such as aluminum ethylate, AI(OC H5) , by the Tishchenko reaction. 

The action of a small proportion of aluminum ethylate on pure chloral or chloral diluted with benzene leads to the formation of trichloroethyl trichloroacetate in the same manner that ethyl acetate is formed from acetaldehyde by aluminum ethylate, but the yields are small. A slightly better yield is obtained when molecular proportions are employed, but it is only in the presence of a large amount of an alcohol that good yields are obtained. 

Aluminum ethylate is now obtainable commercially. The author recommends the following method of preparation 1 which has been checked ... 

Unchanged alcohol is removed by distillation from an oil bath until the residual material melts to a dark-colored liquid. It is then poured into a Claisen flask and distilled under reduced pressure, using a short air condenser and a Pyrex suction-flask as a receiver. Since aluminum ethylate tends to sublime, a glass-wool filter is inserted between the receiving flask and the vacuum line to prevent clogging. A free flame is necessary and distillation should be rapid. While the distillate is still liquid it is poured into a Pyrex flask and allowed to cool. It forms a tough, white mass which must be preserved in a well-stoppered flask to prevent adsorption of water vapor. A yield of 90 per cent of the theoretical amount may be obtained. 

Even by simple refluxing of the mixture without separation of the aldehyde, a yield of 65 per cent may be obtained.3 The reaction between the aluminum ethylate and the chloral is in... 

With the purpose of employing a more soluble form of complexed lithium hydride in such a process, Ziegler and Gellert heated ethylene in ether under pressure at 120-140 °C with LAH, which had been prepared for the first time by Schlesinger and coworkers. To Ziegler s gratification LAH was smoothly converted into lithium tetraethylaluminate (10), which could be isolated in high yield as a crystalline adduct. As proof of structure, the same adduct was also synthesized by the admixture of the lithium and aluminum ethyl derivatives in a 1 1 ratio (Scheme 2). This study represents the first authenticated instance of hydroalumination. 

A series of Al, In, and Ti complexes coordinated by a similar tridentate sulfonamide ligand system has been reported (Figure 7). The aluminum ethyl complex in the series is the least active and controlled, polymerizing 100 equiv. of rac-LA... 

The use of aluminum ethylate in the presence of alcohol offers a means of reducing many compounds which could not be reduced in the desired manner by the more customary methods. Meerwein and his students have used the method to convert bromal into tribromoethyl alcohol and have also prepared cin-namyl alcohol and various halogenated cinnamyl and crotyl alcohols from the corresponding aldehydes.4,5 In all cases excellent yields are obtained. 

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