Patent GB-807099-A (GB)
Title: Process for the preparation of c-alkyl isocyclic amines containing polyglycol residues
Filed: 1956-02-24
Abstract: Amines containing polyglycol residues are obtained by first reacting in the absence of a catalyst an isocyclic amine substituted on a cyclic carbon atom by an alkyl residue containing at least 6 carbon atoms with one molecular equivalent of an alkylene oxide per active hydrogen atom carried by the amine and subsequently reacting the amine containing at least one monoglycol residue so obtained with a further amount of alkylene oxide in the presence of a known oxyalkylation catalyst.  The free terminal groups of the oxyalkylated products may be subsequently esterified with sulphuric, phosphoric, chlorosulphonic, phthalic or fatty acids.  The intermediate amine containing at least one monoglycol residue may be subjected to a purification treatment such as recrystallisation before being reacted with further alkylene oxide.  Specified amine reactants are hexylaniline, octylaniline, dodecylaniline, hexadecylaniline, octadecylaniline, octadecyl-N-methylaniline, dodecyl - N - ethylaniline, dodecyl - N - methylaniline, decylnaphthylamine, hexylnaphthylamine, decylcyclohexylamine and dodecylcyclohexylamine. Specified alkylene oxides are ethylene oxide and propylene oxide. Specified oxyalkylation catalysts are alkali metals such as Na and K, and alcoholates such as sodium methylate or ethylate.  In examples: (1) 1 mol. of ethylene oxide is reacted with 0.5 mol. of para-octylaniline and the product is reacted with a further 1.5 mol. of ethylene oxide in presence of sodium methylate (the process is compared with those using a catalyst for both steps and for neither step); (2) ethylene oxide is reacted with 0.5 mol. of para-dodecylaniline to give N : N - diethanol - para - dodecylaniline, which is further reacted with ethylene oxide in presence of sodium methylate until a total of 3.5 mol. of ethylene oxide per active hydrogen atom have been added to the original amine; (3) ethylene oxide is reacted with 0.5 mol. of para-hexadecylaniline and the product further reacted with ethylene oxide in presence of sodium ethylate until a total of 8.5 mol. of ethylene oxide has been added to the original amine; (4) 2 mol. of ethylene oxide are added to 1 mol. of commercial C-dodecylaniline and the product is reacted with a further 8 mol. of ethylene oxide in presence of sodium methylate; (5) 0.8 mol. of a mixture of C-dodecylaniline, N-methyl - C - dodecylaniline and N : N - dimethyl-C-dodecylaniline (prepared by methylating 1 mol. of C-dodecylamine with 1 mol. of dimethyl sulphate) is reacted with 0.8 mol. of ethylene oxide to give a mixture of N : N-diethanol - C - dodecylaniline, N - methyl - N - ethanol - C - dodecylaniline and N : N - dimethyl - C - dodecylaniline, the latter compound is isolated by fractionation and a 0.2 mol. portion thereof is reacted with 2 mol. of ethylene oxide in presence of sodium methylate to give a product containing an average of 11 polyglycol residues per molecule; (6) 1 mol. of ethylene oxide is reacted with 0.5 mol. of 4-dodecylcyclohexylamine and the product further reacted with ethylene oxide in presence of sodium ethylate or metallic sodium until to the original amine; and (7) 0.75 mol. 4 mol. of ethylene oxide have been added of hexylnaphthylamine is reacted with 1.5 mol. of ethylene oxide to give N : N-diethanol-with ethylene oxide in presence of sodium methylate until 9 mol. of ethylene oxide have been added to the original amine.