Patent GB-651203-A (GB)
Title: New or improved method for the reduction of esters, glycerides and nitriles
IPC: C07C29/147
Filed: 1947-06-26
Abstract: Esters, glycerides and nitriles are reduced by means of sodium and an alcohol at elevated temperature and under normal pressure conditions to obtain aliphatic alcohols and amines respectively, there being added to the reaction mixture a substance such as ammonium chloride, or substances such as carbon dioxide and water, which will liberate an acid progressively under the conditions of the reaction, the said acid decomposing the sodium alcoholate as fast as it is formed in the course of the reaction whereby the alcoholate is converted to the sodium salt of the acid which is precipitated.  In a modification the substances added to the reaction mixture consist of ammonia and hydrochloric acid, added separately.  Other specified substances which may be added to the reaction mixture are acid salts having a slight solubility in alcohol.  The process may be carried out in a continuous manner, thus when ammonium chloride is used it is introduced into the first of a series of n tubes (n being at least 3), each containing a tubular agitator and 1/nth of the required amount of sodium is added in small pieces at the front end of each tube.  This process may be applied to example (1) below all the esterbutanol mixture containing all the ammonium chloride being added at the front end of the first tube.  Between the outlet end of a tube and inlet end of the following tube a portion of the butanol is distilled so that at the end of the procedure most of the butanol has been removed.  The temperature of the first tube is 80 DEG  C., the other tubes having gradually rising temperatures with the last at 110 DEG  C.  Beyond the last tube the normal procedure of distilling, washing and decanting is carried out.  In further examples: (1) sodium is added gradually to a mixture of whale oil and anhydrous butanol and during the addition of the sodium, ammonium chloride is also added in six equal portions.  The temperature is maintained at 100-115 DEG  C. and the emission of ammonia gradually entrains the greater portion of the butyl alcohol.  Heavy alcohols and glycerine are recovered; (2) carbon dioxide is atomised into a solution of butyl oleate in butanol by means of a perforated hollow agitator, sodium is added gradually in small pieces and hydrated sodium carbonate is also added gradually to provide the necessary water content.  The temperature is initially 80 DEG  C. and rises to the boiling point of the mixture at the end of the reaction.  The butanol is entrained by the carbon dioxide and remaining butanol is distilled.  Oleic alcohol is recovered after cooling enough hot water to dissolve the sodium carbonate.  Rape seed oil may be reduced similarly, but a 40 per cent excess of the theoretical amount of sodium is necessary in this case; (3) ammonium chloride is added to stearic nitrile in butyl alcohol, the temperature kept at about 80 DEG C. and sodium added gradually. Secondary octadecylamine and primary octadecylamine are obtained; (4) sodium is added gradually to a mixture of butanol and a portion of the butyl oleate to be reduced in a flask fitted with a reflux condenser and carbon dioxide passed through the mixture. After a small amount of sodium has been introduced a flow of water is directed into the mixture through the top of the condenser and the remainder of the butyl oleate is added gradually, the temperature being maintained at 92 DEG  C.  After adding all the oleate the temperature is raised to 115 DEG  C. and after adding hot water to dissolve the sodium carbonate formed the organic layer is distilled to remove butanol and oleic alcohol recovered.  The same procedure may be applied to glycerides, e.g. palm kernel oil which yields a crude product having a high hydroxyl value. Specifications 346,237, 351,359, 358,721 and U.S.A. Specification 2,019,022 are referred to.  The Specification as open to inspection under Sect. 91 refers to the use of any substance which will decompose the alcoholate as it is formed and for this purpose mentions mineral or organic acids, acid anhydrides and chlorinated compounds which condense with the alcoholates.  This subject-matter does not appear in the Specification as accepted.