Patent GB-751841-A (GB)
Title: Derivative products of the urethanes of glycols and processes for the manufacture thereof
IPC: C07C271/06
Filed: 1951-07-20
Abstract: The invention comprises (1) reacting carbamate esters of glycols with organic isocyanates; (2) the products of (1) of the following-types: <FORM:0751841/IV(a)/1> <FORM:0751841/IV(a)/2> <FORM:0751841/IV(a)/3> <FORM:0751841/IV(a)/4> <FORM:0751841/IV(a)/5> <FORM:0751841/IV(a)/6> <FORM:0751841/IV(a)/7> <FORM:0751841/IV(a)/8> where R and R1 are aliphatic hydrocarbon radicals (same or different), R1 and R11 are hydrogen, alkyl, aryl, aralkyl or cycloalkyl, R2 is alkyl, aryl, aralkyl or cycloalkyl, and R3 is alkylene, arylene, aralkylene or cycloalkylene; and (3) products of (1) of the formula <FORM:0751841/IV(a)/9> where the radicals are in (2) with the proviso that if one of R1 and R11 is hydrogen the other of these is different from R2.  The nature of the products depends on the proportions of the reactants, temperature, duration of heating and presence or absence of solvents.  Reaction may occur at the nitrogen atom as well as the oxygen atom to give allophanates, the production of the latter being favoured by temperatures above 100 DEG  C., while simple glycol esters are usually formed at lower temperatures.  The mixed urethane-allophanates IV are obtained by carrying out the reaction first at a low then a high temperature. The cyclic compounds VII result from further heating of the products V and VI (e.g. to 100-120 DEG  C.).  In the examples: (1) ethylene glycol mono-N-ethylcarbamic ester and phenyl isocyanate give a product of type IX; (2) type IX from ethylene glycol mono-N:N-dibutylcarbamic ester; (3) type IX from ethylene glycol monocarbamic ester and phenyl isocyanate; (4) type IX from ethylene glycol mono - (piperidine - N - carboxylic) ester and phenyl isocyanate; (5) type IX from b -hydroxyisopropyl carbamate and phenyl isocyanate; (6) type IX from b -hydroxyisopropyl N-ethylcarbamate and phenyl isocyanate; (7) type I from ethylene glycol monocarbamic ester and hexamethylene di-isocyanate; (8) type I from ethylene glycol mono-N:N-diethylcarbamic ester and hexa-methylene di-isocyanate; (9) type I from ethylene glycol mono-N:N-dibutylcarbamic ester and hexamethylene di-isocyanate; (10) type I from ethylene glycol monocarbamic ester and toluylene di-isocyanate; (11) type I from b -hydroxyisopropyl carbamate and hexamethylene di-isocyanate; (12) type I from b  - hydroxyisopropyl N - ethylcarbamate and hexamethylene di-isocyanate; (13) type I from b -hydroxyisopropyl carbamate and toluylene di-isocyanate; (14) type I from ethylene diamine N:N1-dicarboxylic di-(b -hydroxyethyl) ester and phenyl isocyanate; (15) type VIII from hydrazine N:N1 - dicarboxylic di - (b  - hydroxyethyl) ester and phenyl isocyanate; (16) type I from hexa-methylenediamine N:N1-dicarboxylic di - (b  - hydroxyethyl) ester and phenyl isocyanate; (17) type II from ethylene glycol di-(N-b -hydroxyethylcarbamic) ester and phenyl isocyanate; (18) type III from ethylene glycol mono-N-ethylcarbamic ester and toluylene di-isocyanate; (19) type IV (with some type I) from ethylene glycol monocarbamic ester and toluylene di-isocyanate; (20) type IV from ethylene glycol mono-N-methylcarbamic ester and toluylene di-isocyanate; (21) type III from ethylene glycol monocarbamic ester and hexamethylene di-isocyanate; (22) type III from ethylene glycol mono N-ethylcarbamic ester and hexamethylene di-isocyanate; (23) type V from ethylene glycol monocarbamic ester and toluylene di-isocyanate; further heating converts it to type VII; (24) type V from ethylene glycol mono-N-ethylcarbamic ester and toluylene diisocyanate; (25) type VII from ethylene glycol N-ethylcarbamic ester and hexamethylene diisocyanate; (26) type VI from ethylene glycol mono-N-ethylcarbamic ester and hexamethylene-di-isocyanate; further heating converts it to type VII; (27) type V from ethylene glycol mono-N:N-diethylcarbamic ester and hexamethylene di-isocyanate; (28) type V from b -hydroxyisopropyl carbamate and hexamethylene di-isocyanate; further heating converts it to type VII.  Reference has been directed by the Comptroller to Specification 689,705.