Patent GB-800875-A (GB)
Title: Production of esters
Inventor: GASSON EDWARD JAMES
IPC: C07D213/803
Filed: 1955-11-25
Abstract: Carboxylic acid esters are prepared by reacting the corresponding nitrile with a polyhydric alcohol in non-acidic, liquid phase, and preferably in the presence of added water, at a temperature at which ammonia is evolved from the liquid reaction medium, and removing the formed ammonia from the reaction zone. Specified nitriles are benzonitrile, terephthalonitrile, isophthalonitrile, m- and p-tolunitriles, b -naphthonitrile, m- and p-nitrobenzonitriles, m-and p-chlorobenzonitriles, a -, b - and g -cyanopyridines, a - and b -furonitriles, fumaronitrile, and adiponitrile.  Suitable alcohols include ethylene glycol, propylene glycols, butylene glycols and glycerol. The process may be carried out in a continuous or batchwise manner.  In general it is desirable to use excess alcohol, for instance about 5-10 mols. of alcohol per mol. of cyanide radical present.  Water is required for the reaction.  In the absence of added water, the water is derived by dehydration of a portion of the alcohol in the reaction, but it is preferred to add at least the theoretical quantity of water to promote the formation of normal esters rather than ether esters, but the concentration of water in the total reaction mixture should preferably not exceed 20 per cent by volume.  If superatmospheric pressures are used more water may be tolerated than otherwise.  The water may be added continuously or intermittently to maintain the level of free water between about 10 and 50 per cent of that required for complete reaction of the nitrile originally present.  The water may be added in the liquid or the gaseous state.  It is preferred to evaporate part or all of the formed free ammonia as the reaction proceeds, although more preferably the ammonia is allowed to build up temporarily in the initial stages and is only removed in the later stages of the reaction.  The ammonia removal may be done periodically or continuously by keeping the reaction mixture boiling and/or by passing on inert gas, e.g. N2 stream through the mixture, preferably saturated with water.  In general the lower limit of the reaction temperature is about 100 DEG  C., but preferred temperatures are from about 150-280 DEG  C.  If desired a basic catalyst may be added, preferably in molar proportions up to about 1/50 based on the cyanide groups present, such as alkali or alkaline earth metal hydroxides and salts with weak inorganic or organic acids, e.g. carbonates, bicarbonates and acetates; organic bases such as pyridine, and ammonia.  It is preferred to carry out the reaction only to a limited conversion, remove the formed ester either continuously or batchwise and recycle the other components.  The products are useful as intermediates in the preparation of polymers, in the case of esters prepared from dinitriles, and as solvents and plasticizers. In examples: (1) hydroxyethyl benzoate admixed with di-(1,2-benzoyloxy)-ethane and esters of higher glycols is prepared by heating benzonitrile and ethylene glycol with a magnesia catalyst, a stream of dry nitrogen being passed through the mixture; (2) hydroxyethyl benzoate with some di-(1,2-benzoyloxy)-ethane is prepared as in (1) except that water is added initially and a stream of wet nitrogen is used; (3) bis-(2-hydroxyethyl) terephthalate is prepared from terephthalonitrile and ethylene glycol with and without sodium methoxide as catalyst, water being added initially and a stream of wet nitrogen passed through the mixture; (4) bis-(2-hydroxyethyl) terephthalate; and (5) bis-(2-hydroxyethyl) isophthalate are prepared from terephthalonitrile and isophthalonitrile respectively and ethylene glycol in the presence of sodium methoxide, a stream of wet nitrogen being passed through the mixture and the required water being either all added initially or in portions as the reaction proceeds; (6) di-(2,3-dihydroxy-n-propyl) terephthalate from terephthalonitrile and glycerol; (7) di-(2-hydroxyethyl) fumarate from fumaronitrile and ethylene glycol; and (8) di-(2-hydroxyethyl) adipate from adiponitrile and ethylene glycol are prepared as in (5).