Patent GB-506301-A (GB)
Title: Process for the manufacture of acylated ethers
IPC: C07C317/22
Filed: 1938-03-31
Abstract: 506,301. Acylated halogenated ethers and their conversion products wetting- agents. ROHM & HAAS CO. March 31, 1938, No. 9845. Convention date, April 8, 1937. Sample furnished. [Classes 2 (iii) and 15 (ii)] Ethers of the formula R(OCnH2n)xY, where R is an aromatic radicle, n is 2-4, x is an integer less than four, and Y is a halogen atom, are treated with an acylating agent in the presence of a Friedel-Crafts catalyst. An acyl radicle is thus introduced into the radicle R, and the halogen atom Y is unaffected. Specified acylating agents are phosgene, thionyl chloride, carbon tetrachloride, fatty acids or their anhydrides or halides, polycarboxylic acids or their' anhydrides such as succinic; maleic, glutaric or phthalic anhydride, polycarboxylic acid halides such as succinyl, phthalyl or sebacyl chloride, and aromatic or heterocyclic acids or their anhydrides or chlorides, such as benzoyl, naphthoyl or furoyl chloride. In the examples : (1) phthalic anhydride and #- phenoxy - #<1> - chlorodiethyl ether yield XC6H4OC2H4OC2H4Cl, where X is o-carboxybenzoyl; (2) succinic anhydride and #-phenoxy- #<1>-chlorodiethyl ether yield ClC2H4OC2H4OC6 H4COC2H4COOH; (3) maleic anhydride and # - phenoxy - #<1> - chlorodiethyl ether yield ClC2H4OC2H4OC6H4COCH: CHCOOH ; (4) phthalic anhydride and #-phenoxyethyl chloride yield XC6H4OC2H4Cl, where X is o-carboxybenzoyl; (5) phthalic anhydride and #-ochlorophenoxy - #<1>- chtorodiethyl ether or (example, 6) # - o - methoxyphenoxy - #<1>- chlorodiethyl ether or (example 7) #-2-naphthoxy-#<1>- chlorodiethyl ether or (example 9) #-o-tolyl- - oxy - #<1> chlorodiethyl ether yield products analogous to that of example 1; (8) hexahydrophthalic anhydride and #-phenoxy-#<1>-chlorodiethyl ether yield a hexahydro derivative of the product of example 1 ; (10) thionyl chloride and #-phenoxy-#<1>-chlorodiethyl ether yield SO(C6H4OC2H4OC2H4OC2Cl)2; (11) acetyl chloride (or acetic anhydride) and #-phenoxy-#<1>-chlorodiethyl ether yield #-acetylphenoxy-#<1>-chlorodiethylether; homologous products are obtainable from homologues of acetyl chloride and acetic anhydride, such as lauroyl, stearoyl or caproyl chloride or butyric or propionic anhydride ; in each example the reaction is effected in the presence of aluminium chloride, but other Friedel-Crafts catalysts, such as aluminium bromide, boron fluoride, ferric chloride, antimony chloride, stannic chloride or titanium chloride may also be used. Reference is made also to the treatment of ethers of the formula above, in which Y is bromine or iodine. The products may be subjected to various reactions whereby the halogen atom Y is eliminated ; thus, they may be treated with metal sulphites to yield sulphonates, with sodium sulphide to yield thioethers, with sodium hydrosulphide to yield mercaptans, with alkali salts of fatty acids to yield esters, with primary, secondary or tertiary amines to yield amines or quaternary ammonium compounds, and with inorganic thiocyanates or dithiocarbamates to yield organic thiocyanates or dithiocarbamates. According to the groups present, the products so obtained may be used as capillary-active compounds, textile assistants, plasticizers, resins, insecticides and drugs. A sample has been furnished under Sect. 2 (5) of 4 : 4<1>-di(chlorethoxyethoxy)-benzophenone, prepared. by condensing #-phenoxy-#<1>-chlorodiethyl ether.with carbon tetrachloride in the presence of aluminium chloride, and decomposing the product with water.