Patent GB-539281-A (GB)
Title: Improvements in or relating to the preparation of aliphatic substituted aromatic sulphonic acids and salts thereof
IPC: C07C309/28
Filed: 1940-03-02
Abstract: 539,281. Alkylated and acylated aromatic sulphonic acids; wetting &c. agents. COLGATE-PALMOLIVE-PEET CO. March 2, 1940, No. 3964. Convention date, March 4, 1939. [Classes 2 (iii) and 15 (ii)] [Also in Group III] Aliphatic substituted aromatic compounds in which the aliphatic radicle contains at least 6 carbon atoms are sulphonated in a solvent comprising liquid sulphur dioxide as the major constituent. The formation of the aliphatic substituted aromatic compound may be effected before the sulphonation as a separate step or simultaneously therewith. Aliphatic compounds for the nuclear substitution are olefines, carboxylic acid halides, aliphatic halogenated compounds and aliphatic alcohols. The following aliphatic compounds are specified: hexene to undecene, tetradecene, hexadecene, octadecene, cerotene, cyclohexene, cracked and dehydrogenated petroleums, polymerised isobutylene, polymerised isoamylene, benzoylchloride, stearoylchloride, lauroylchloride, myristoyl chloride, hexyl to dodecylalcohol, myristyl, cetyl, octadecyl, oleyl, montanyl and carnaubyl alcohol, octa-decandiol, ceryl, cyclohexyl, methylcyclohexyl, and melissyl alcohols, alcohols derived from cocobutter, soya bean, tallow, cottonseed, talloil, Japan wax, China wax, montan wax, ceresine, ozocerite, stearone and laurone and olefines derived from these alcohols by dehydration. By processes of catalytic dehydrogenation, halogenation, cracking and dehydrohalogenation aliphatic compounds suitable for the nuclear substitution may be prepared from any liquid or solid paraffin such as mineral oils, petroleum jelly, liquid petrolatum, hydrocarbons obtained by distilling, cracking, reducing or hydrogenating mineral oils, tars, oxides of carbon and schist oils, lignite wax, brown coal and ceresin. The halogenation of the hydrocarbons may be effected in the presence of the aromatic component. The aromatic compounds may contain more,than one aliphatic substituent and the aliphatic compounds may be linked with more than one aromatic radicle. Suitable aliphatic compounds for the latter process are octadecenylchloride, octadecadiene, octadecenyl alcohol, octadecandiol, dichloroctadecane, dichlordodecane. Halogenated fatty acids, hydroxy fatty acids, mono and poly olefinic fatty acids, monochlorpalmitic acid, linoleic acid, dichlorstearic acid, ricinoleic acid, lauroyl glycerolmonochlorhydrin, tetraethylene glycol, ethyloleate, octadecenylethylether, dodecylchloracetate and dichlorlaurone are also mentioned. Specified aromatic compounds which may be used are, toluene, xylene, cumene, cymeme, ethylbenzene, acenaphthene, phenanthrene, anthracene, methylnaphthalene, ethylnaphthalene, tetrahydronaphthalene, triphenylmethane, diphenylmethane, fluorene, styrene, indene; coumarone, coal tar fractions or extracts, benzylchloride, phenanthrone, acetophenone, diphenylketone, diphenyloxide, veratrol, benzylalcohol, phenols, alkylolphenols, hydroquinone, resorcinol and halogen derivatives. Furfural, kojic acid and cyclopentadienes are mentioned. The alkylation or acylation may be assisted by solvents such as benzene, methane, butane, ethylene, petroleum ether, dioxane, ether, carbonbisulphide, carbontetrachloride, chloroform, dichlorethane, trichlorethylene and dichlordifluormethane as well as liquid sulphur dioxide, and refrigeration may be effected by partial evaporation. For the sulphonation, sulphuric acid, oleum, sulphonylchloride, a mixture of sulphurdioxide and chlorine, sulphur trioxide, acetylsulphuric acid, bromsulphonic acid and chlorsulphonic acid may be used and assistants such as acetic anhydride and chloride, glacial acetic acid, propionic, boric and butyric anhydride and phosphorus pentoxide. The product which may contain more than one sulphonic group may be worked up by adding water to cause the formation of layers or by extracting the solid salts formed by neutralization by means of solvents such as alcohol, dioxane, acetone or butyl alcohol. In the neutralization, alkalies, ammonia, mono-, di-, or tri-, ethanolamine, mono-, di- or triglycerolamine, pyridine or piperidine may be used. Calcium, lithium, magnesium and mercury salts are'also mentioned. Aluminium-chloride, boronfluoride, bromides and chlorides of iron, zinc, antimony, boron, tin, titanium and indium, floridin, tonsil, fullers earth and sulphuric acid and its acid derivatives may be used as catalysts for the alkylation process. The products, which are stated to have wetting, solubilizing, detergent, water softening, dispersing, penetrating and equalizing properties may be used in association with soap, rosinates, long chain alcohol sulphates, monoglyceridesulphates, sulphonated mineral oil extracts, turkey red oil, lecithin, glycerolamines, di- and triethanolamines, sodium carbonate, silicate and phosphate, borax, dyes, lakes, pigments, abrasives, silica, pumice, feldspar, chalk, infusorial earth, bentonite, talc, starch, carbontetrachloride, perchlorethylene, glycerol, alcohol, glycoltetrahydrofurfuryl alcohol, phenol, cyclohexa n o 1, tetrahydronaphthalene, pin e oil, mineral oils, deodorants, fats, oils, fatty acids, monoglycerides, vitamins, waxes, gums, glue, resins, phenylmercurychloride, hydroxybenzoicmethylester, mercurychloride, aluminium chloride, sodium sulphate, chloride, acetate, bicarbonate, hypochlorite, thiosulphate, hydrosulphite and hyposulphate and similar potassium and ammonium salts, tetraphosphoric acid, hexametaphosphoric acid, pyrophosphoric acid and their alkali metal, ammonia and amine salts or alkyl esters. The compositions may be used as or in insecticides, cements, antiseptics, water softeners, disinfectants, water paints, polishes, sizes, glues, shellac and casein compositions, tooth and mouth detergents, laundry blueing, bleaching, dyeing, softening, lubricating and discharging compositions, depilatories, dust preventing compositions, antifreezing, anti-fogging and anti-corrosion compositions, wood impregnants, electrolytic baths, etching compositions, cosmetics, shaving preparations, shampoos, hair lotions, tanning agents, fat liquors, photographic solutions, paint, varnish and grease removers, dry cleaners, petroleum de-emulsifying compositions, lypolitics preparations of resins and plasticizers such as aliphatic substituted phenolaldehyde, aliphatic substituted arylsulphonamide and aliphatic substituted arylsulphonamidealdehyde resins. In examples: (1) dodecylchloride is condensed with benzene in the presence of liquid sulphur dioxide and aluminiumchloride in an autoclave and the product sulphonated by means of a mixture of oleum and liquid sulphur dioxide, it is finally added to ice water, neutralized, extracted with gasoline and dried: (2) naphthalene is condensed with diisoamylene and sulphonated and the product washed with ether, neutralized and extracted with isopropyl alcohol: (3) diphenyl dissolved in dichorethane is treated with a liquid sulphur dioxide extract of cracked mineral oil, 96 per cent sulphuric acid being used for the condensation; the product is sulphonated in liquid sulphur dioxide, ice water added and the resulting three layers separated; the middle layer, after washing with liquid sulphur dioxide is freed from dissolved sulphur dioxide, washed with an aqueous solution of sodium chloride and sulphate, neutralised with soda and sprayed into hot gases. The process may be conducted in a continuous manner.