Patent GB-823259-A (GB)
Title: New esters and process for their manufacture
Filed: 1956-08-30
Abstract: The invention comprises esters of formula <FORM:0823259/IV (a)/1> where R and R1 are alkyl, cycloalkyl, alkoxyalkyl, or a saturated oxacycloalkyl-alkyl radical containing 1-7 carbon atoms and R may also represent hydrogen, R11 is hydrogen, alkyl, or alkoxy-alkyl residue containing 1-4 carbon atoms, R111 is hydrogen or a methyl or ethyl residue, n is 7-15, the groups within the bracket being similar or dissimilar residues, at least half of them being <FORM:0823259/IV (a)/2> The esters may be prepared by converting <FORM:0823259/IV (a)/3> if desired in the form of a reactive derivative thereof, e.g. an anhydride, halide, ester or metal salt into an ester, with a polyglycol of the formula <FORM:0823259/IV (a)/4> in the presence of a basic condensing agent, e.g. pyridine or a metal alcoholate.  If a metal salt is used, a reactive ester of the polyglycol is used as the other reactant.  Alternatively, a corresponding compound containing a substituent convertable into the group R.NH, e.g. a free amino, or nitro group may be converted into the compounds of the invention. The reactions may be carried out in the presence or absence of a diluent and/or a condensing agent or catalyst and at ordinary or elevated temperature and at atmospheric or superatmospheric pressure. Examples are given of the preparation of <FORM:0823259/IV (a)/5> from 2-n-butoxy-4-amino benzoic acid methyl ester and nona-ethylene glycol monomethyl ether, <FORM:0823259/IV (a)/6> from 2-n-butoxy-4-n-butylamino benzoic acid methyl ester and nona ethylene glycol monomethyl ether, <FORM:0823259/IV (a)/7> from ortho-(n)-hexoxy-para-dibenzylamino benzoic acid and nona-ethylene glycol-monomethyl ether.  The two benzyl groups of the intermediate product are removed by hydrogenation. <FORM:0823259/IV (a)/8> from meta - (n) - butoxy - para - dibenzylamino benzoic acid and nono-ethylene glycol-monoethyl ether; the two benzyl groups of the intermediate product are removed by hydrogenation <FORM:0823259/IV (a)/9> from ortho - (n) - butoxy - ethoxy - para cyclopentylamino benzoic acid methyl ester and nona-ethylene glycol monomethyl ether, <FORM:0823259/IV (a)/100> from ortho - (n) - butoxy - ethoxy - para - cyclopentylamino benzoic acid methyl ester and undeca-ethylene glycol monomethyl ether, <FORM:0823259/IV (a)/111> from ortho-methoxy-para-tetrahydro pyranyl (2) methylamino benzoic acid methyl ester and nono-ethyleneglycol monomethyl ether, <FORM:0823259/IV (a)/122> from meta - (n) - butoxy - para - dibenzyl - amino benzoic acid and heptaethylene glycol, <FORM:0823259/IV (a)/133> from ortho - (n) - butoxy - para - butylamino benzoic acid methyl ester and polyethylene glycol mono-methyl ether of average molecular weight of 750, <FORM:0823259/IV (a)/144> from ortho - (n) - hexoxy - para - dibenzyl - amino benzoic acid and hepta-ethylene glycol-o ,o 1-di-[2-hydroxy-n-propyl-ether (1)]. <FORM:0823259/IV (a)/155> where n has an average value of about 12 and n+y of about 15, from meta-(n)-butoxy-para-dibenzyl-amino-benzoic acid and a polyether alcohol obtained from polyethylene glycol monomethyl ether and 1,2-propylene oxide. <FORM:0823259/IV (a)/166> from 3-(n)-heptoxy-5-dibenzylamino benzoic acid methyl este and octo-ethylene glycol-o -methyl ether o 1-(2-hydroxy-3-ethoxy propyl ether). <FORM:0823259/IV (a)/177> from 3-(n) - heptoxy-5-dibenzylamino-benzoic acid methyl ester and deca-ethylene glycol monomethyl ether.  The starting materials and intermediates may be made by known methods.  Specification 728,583 is referred to.