Patent GB-387621-A (GB)
Title: Manufacture of esters from aldehydes and of catalysts suitable for use therein
IPC: B01J23/06
Filed: 1932-09-19
Abstract: The conversion of aldehydes into esters is effected with a catalyst containing aluminium, zinc, alkoxyl, and chlorine in chemical combination, advantageously in an indifferent organic diluent.  The catalyst may be made by reacting a solution or suspension of aluminium alcoholate with zinc chloride, or by adding zinc oxide, carbonate, or alcoholate to a mixture of aluminium alcoholate and chloride, or by oxidizing a mixture of aluminium alcoholate and chloride and metallic zinc such as is produced according to French Patent 705,843 or by combining aluminium, zinc, alkoxyl, and chlorine in any other manner.  In examples: (1) a mixture of aluminium filings, aluminium chloride, anhydrous ethyl alcohol, and ethyl acetate, is boiled under reflux until aluminium ethylate is formed, and after cooling anhydrous zinc chloride is added; unattacked aluminium is removed, and pure acetaldehyde is run in while cooling to 25 DEG  C., ethyl acetate being produced; (2) chlorine is passed into a mixture of aluminium filings, ethyl alcohol, and ethyl acetate, unconsumed aluminium is removed, and zinc oxide is added, which passes gradually into solution; (3) ethyl alcohol is added to a mixture of aluminium filings, aluminium chloride, and ethyl acetate at a raised temperature, aluminium ethylate being produced; after cooling and removing excess aluminium dry precipitated zinc carbonate is added and dissolves; butyraldehyde may be converted into butyl butyrate with this catalyst at 35 DEG  C.; (4) filings of aluminium containing small proportions of copper, zinc, silicon and iron, together with ethyl alcohol and ethyl acetate, are treated with chlorine to produce a mixture containing a dispersion of zinc, as in French Patent 705,843; air is then passed in until the zinc disappears.  Instead of ethyl acetate, another diluent such as a hydrocarbon, for instance xylene may be used, and the aluminium alcoholate may correspond with another alcohol such as butyl alcohol. The catalysts are suitable for the production of esters from aliphatic aldehydes of higher molecular weight, aromatic aldehydes such as benzaldehyde, and hydroaromatic aldehydes.ALSO:The conversion of aldehydes into esters is effected with a catalyst containing aluminium, zinc, alkoxyl, and chlorine in chemical combination; advantageously in an indifferent organic diluent.  The catalyst may be made by reacting a solution or suspension of aluminium alcoholate with zinc chloride, or by adding zinc oxide, carbonate, or alcoholate to a mixture of aluminium alcoholate and chloride, or by oxidizing a mixture of aluminium alcoholate and chloride and metallic zinc such as is produced according to French Specification 705,843 or by combining aluminium, zinc, alkoxyl, and chlorine in any other manner. In examples, (1) a mixture of aluminium filings, aluminium chloride, anhydrous ethyl alcohol, and ethyl acetate, is boiled under reflux, until aluminium ethylate is formed, and after cooling anhydrous zinc chloride is added; unattacked aluminium is removed, and pure acetaldehyde is run in while cooling to 25 DEG  C., ethyl acetate being produced; (2) chlorine is passed into a mixture of aluminium filings, ethyl alcohol and ethyl acetate, unconsumed aluminium is removed, and zinc oxide is added, which passes gradually into solution; (3) ethyl alcohol is added to a mixture of aluminium filings, aluminium chloride and ethyl acetate at a raised temperature, aluminium ethylate being produced; after cooling and removing excess aluminium, dry precipitated zinc carbonate is added and dissolves; butyraldehyde may be converted into butyl butyrate with this catalyst at 35 DEG  C.; (4) Filings of aluminium containing small proportions of copper, zinc, silicon, and iron, together with ethyl alcohol and ethyl acetate, are treated with chlorine to produce a mixture containing a dispersion of zinc, as in French Specification 705,843; air is then passed in until the zinc disappears.  Instead of ethyl acetate, another diluent such as a hydrocarbon, for instance xylene may be used, and the aluminium alcoholate may correspond with another alcohol such as butyl alcohol.  The catalysts are suitable for the production of esters from aliphatic aldehydes of higher molecular weight, aromatic aldehydes such as benzaldehyde, and hydroaromatic aldehydes.