Patent GB-709478-A (GB)
Title: Polyethylene glycol derivatives and a process of making the same
IPC: C07C309/73
Filed: 1951-02-13
Abstract: The invention comprises compounds of the formula RO(CH2CH2O)nCH2CH2O . SO2R1 wherein R and R1 are hydrocarbon radicals and n is an integer from 4 to 20.  Such compounds are obtained by reacting a compound of the formula RO(CH2CH2O)nCH2CH2OH with an agent capable of replacing the -OH group by the group -O.SO2R1, e.g with a sulphonyl chloride or bromide R1SO,Cl or R1SO2Br.R1 may represent a methyl, ethyl, phenyl or tolyl radical and R may represent a methyl, ethyl, propyl, 2-ethylbutyl, 2-heptyl, diisobutylmethyl, phenyl, tolyl, a - or b - naphthyl, cyclohexyl, cyclopentyl, benzyl, benzhydryl, o - phenylnamyl, fluorenyl, lauryl or cetyl radical.  Reaction may be effected in the presence of pyridine or inorganic acid-binding agents.  In examples (1) polyethylene glycol methyl ether (M.Wt. 350, and the average value of n being about 6) is reacted with benzene sulphonyl chloride whilst keeping the mixture alkaline, to give the corresponding benzene sulphonic acid ester. The product is purified by partition between chloroform and water and then between a mixture of benzene and ether and water.  In the process of this example polyethylene glycol methyl ethers of molecular weight 550 and 750 respectively or polyethylene glycol monoethyl, butyl, propyl, phenyl, or cresyl derivatives may also be used; the benzene sulphonic acid ester of polyethylene glycol b -naphthyl ether is prepared similarly to (1).  Unused benzene sulphonyl chloride is removed by adding ammonia to a two-phase mixture of the product in chloroform, and water and separating the benzene sulphonamide produced.  In the same manner polyethylene glycol moncyclohexyl, cyclopentyl or benzyl ethyl ether may be reacted.  Similarly the polyethylene glycol derivative of formula C6H5(CH2)4 CH2O(CH2CH2O)4CH2CH2OH(from o - phenyl-namyl alcohol reacted with 5 moles of ethylene oxide) may be converted to the benzene sulphonic acid ester.  In an analagous manner polyethylene glycol monolauryl or cetyl ether may be reacted with benzene sulphonyl chloride or other sulphonic acid halides, e.g. methane sulphonic acid bromide, ethane sulphonic acid chloride or p-toluene sulphonyl chloride.ALSO:The invention comprises compounds of the formula <FORM:0709478/IV (b)/1> , wherein R and R1 are hydrocarbon radicals and n is an integer from 4 to 20.  Such compounds are obtained by reacting a compound of the formula RO(CH2CH2O)nCH2CH2OH with an agent capable of replacing the OH group by the group O.SO2R1, e.g. with a sulphonyl chloride or bromide R1SO2Cl or R1SO2Br.R1 may represent a methyl, ethyl, phenyl or tolyl radical and R may represent a methyl, ethyl, propyl, 2-ethyl-butyl, 2-heptyl, diisobutyl-methyl, phenyl, tolyl, a - or b -naphthyl, cyclohexyl, cyclopentyl, benzyl, benzhydryl, o -phenyl-n-amyl, fluorenyl, lauryl or cetyl radical.  Reaction may be effected in the presence of pyridine or inorganic acid-binding agents.  In examples: (1) polyethylene glycol methyl ether (M.wt. 350, and the average value of n being about 6) is reacted with benzene sulphonyl chloride while keeping the mixture alkaline, to give the corresponding benzene sulphonic acid ester.  The product is purified by partition between chloroform and water and then between a mixture of benzene and ether and water.  In the process of this example, polyethylene glycol monomethyl ethers of molecular weight 550 and 750, respectively, may also be used, or polyethylene glycol mono-ethyl, butyl, propyl, phenyl or cresyl derivatives; (2) the benzene sulphonic acid ester of polyethylene glycol b -naphthyl ether is prepared similarly to (1). Unused benzene sulphonyl chloride is removed by adding ammonia to a two-phase mixture of the product in water and separating the benzene sulphonamide produced.  In the same manner polyethylene glycol monocyclohexyl, cyclopentyl or benzyl ether may be reacted. Similarly the polyethylene glycol derivative of formula C6H5(CH2)4CH2O . (CH2CH2O)4 . CH2CH2OH (from o -phenyl-n-amyl alcohol reacted with 5 mols. of ethylene oxide) may be converted to the benzene sulphonic ester.  In an analogous manner polyethylene glycol mono-lauryl or cetyl ether may be reacted with benzene sulphochloride, or other sulphonic acid halides, e.g. methane sulphonyl bromide, ethane sulphonyl chloride or p-toluene sulphonyl chloride.