Patent GB-762761-A (GB)
Title: Manufacture of new amides
IPC: C07D215/50
Filed: 1953-06-26
Abstract: The invention comprises amides of the formula <FORM:0762761/IV(b)/1> where R is a C2-C7 aliphatic or alicyclic hydrocarbon residue, R1 and R4 are hydrogen or C1-C7 alkyl, n is greater than 1, and R2 and R3 are hydrogen or one of them may be methyl or methoxymethyl provided that more than n/2 residues of the type (CH2.CH2.O) are present.  In preferred compounds the number n ranges from 5 to 25, e.g. 5 to 9. The compounds are made by condensing quinoline derivatives of the formula <FORM:0762761/IV(b)/2> where X is the same as -OR above or is a substituent convertible thereto (e.g. halogen), with the appropriate polyglycol amine in the presence of an inorganic or organic acid-binding agent, e.g. an excess of the amine.  In the examples the following are prepared by direct condensation of the acid halide (X = OR) with the amine: R = n-butyl, R1 = R4 = methyl, R2 = R3 = H, n = 5, 7, 9 and 12; R = R1 = n - butyl, R2 = R3 = 4, R4 = methyl, n = 17; R = cyclopentyl, R1 = R4 = methyl, R2 = R3 = H, n = 7; R = n - butyl, R1 = R2 = R3 = R4 = H, n = 5; also R = n-butyl, R1 = H, R4 = methyl, n = one propylene oxide residue and 7 ethylene oxide residues.  In further examples an amide is prepared from 2-chlorocinchoninic acid chloride and b -methoxy-b 1-methylamino - diethylether and the chlorine atom then replaced by n-butoxy and by ethoxy. The compounds mentioned above where n is 12 or 17 are mixtures of various polyglycol derivatives in which the figure stated represents the average chain length.  Acid chlorides.-2 - n - Butoxycinchoninic acid chloride and 2-cyclopentoxycinchoninic acid chloride are prepared from the corresponding acids and thionyl chloride.  2 - Cyclopentoxycinchoninic acid is made by reacting 2-chlorocinchoninic acid chloride with sodium cyclopentanolate and hydrolysing the resulting cyclopentyl ester.  Polyglycol amines of the formula R1NH-(CHR2-CHR3-O)n-R4 are obtained by the action of ammonia or a primary amine on the corresponding halides or the sulphonic esters of the corresponding polyglycols.  Amines thus prepared are di-, penta-, hepta-, nona-, dodeca-and heptadeca-ethylene glycol monomethyl ether monomethylamines (the last two being mixtures where the numbers 12 and 17 represent the average chain length), penta-ethylene glycol monoamine and hepta-ethylene glycol monomethyl ether mono-(2-aminopropyl)-ether.  Polyglycol sulphonic esters are made as in Specification 709,478, detailed preparations being given as follows: (1) diethylene glycol monomethyl ether mono benzenesulphonic ester is reacted with triethylene glycol to give pentaethylene glycol monomethyl ether and the latter esterified with benzene sulphochloride; (2) the product of (1) is condensed with diethylene glycol and the resulting hepta-ethylene glycol monomethyl ether esterified with benzene sulphochloride; (3) the ester obtained from (2) is reacted with diethylene glycol to give nonaethylene glycol monomethyl ether and the latter esterified with benzene sulphochloride; (4) the ester of (2) is condensed with propylene glycol to yield hepta-ethylene glycol monomethyl ether mono-(2-oxypropyl)-ether which is then esterified with benzene sulphochloride; (5) triethylene glycol is converted into its mono- and di-benzene sulphonic esters and the former condensed with diethylene glycol to give penta-ethylene glycol; this is then esterified with benzene sulphochloride and the product separated into mono- and di-esters.  There are also mentioned the benzenesulphonic esters of polyethylene glycol monomethyl esters of average molecular weight 550 and 787, corresponding to an average of 12 and 17 oxyethylene residues respectively.