Patent GB-545521-A (GB)
Title: Improvements in or relating to the manufacture of sulphonyl chlorides
IPC: C07C309/78
Filed: 1940-08-23
Abstract: 545,521. Sulphonyl chlorides. DU PONT DE NEMOURS & CO., E. I. Aug. 23, 1940, No. 13383. Convention date, Aug. 23, 1939 [Class 2 (iii)]  Sulphonyl chlorides are prepared by reacting a hydrocarbon or a hydrocarbon oil containing a trimethylene radical with sulphuryl chloride in the presence of actinic light and as a catalyst an organic base. Compounds which are preferred as catalysts comprise heterocyclic bases and their derivatives. Usually nitrogenous bases are preferred but substituted phosphines such as triphenylphosphine may also be used. The reaction is particularly applicable to saturated aliphatic and alicyclic hydrocarbons, and the sulphonyl chlorides thus formed may be hydrolized either by boiling with water or by treatment with an alkali to yield water-soluble sulphonic acids. The reaction proceeds best in the liquid state and temperatures within the range 40‹-75‹C. are preferred. It may be carried out in the presence of sulphur dioxide and oxygen and is preferably carried out in the presence of an organic solvent. Starting materials mentioned include saturated aliphatic straight and branched chain hydrocarbons such as octane, isooctane, nonane, decane, dodecane, cetane, octadecane, white oils, saturated kerosenes and saturated petrols, alicyclic compounds such as menthane, naphthenes, camphane and cyclopentane, alkylated aromatic compounds such as propyl-, octyl-, decyl-, dodecyl-, and hexadecyl-benzenes, octyl-, decyl-, and dodecylnaphthalene, and mixtures of alkylated compounds obtained by condensing chlorinated kerosenes.or white oils with aromatic hydrocarbons. There may also be used polyalkylated aromatic compounds such as dibutyl-, triamyl-, tetra-amyl-, and dioctyl benzenes, and dioctyl-, and didodecyl naphthalene. Catalysts mentioned include pyridine, quinoline, quinaldine, dimethylethylene diamine, N : N : N<SP>1</SP> : N<SP>1</SP>- tetramethyl-hexamethylenediamine, nicotine, N-dimethyl-O-dimethyl-glycinenitrile, hexamethylenediamine, α-aminopyridine, 2 : 6- diamino -pyridine, phenanthroline, piperidine, isoquinoline, octadecylamine, ethylenediamine, N-dimethyl-cyclohexylamine, dimethylaniline, tributylamine, isoamylamine, m-nitrodimethylaniline, N-(p-methoxylbenzyl) lauramide, tetramethylammonium formate, N : N'-disalicylaldiaminoethane, N-(2-ethylhexanylidine)-2- ethylhexylamine, 2-amido-2-methylpropanol-1, N-dimethylmethoxyacetamide, N-isobutylundecylenamide, nicotinic amide, morpholine, stearyldimethylamineoxide, pyridinium acethydrazide, triphenylphosphine, (trimethylaminoethylstearate) methyl' sulphate, 2-mercaptothiazoline, allylthiourea, tetramethylthiuramdisulphide, and tetramethylthiuram-monosulphide. Examples are given of the preparation of compounds of the invention. Specifications 511,614 and 516,214 are referred to. The Specification as open to inspection under Sect. 91 included the application of the process of the invention to organic compounds other than hydrocarbons and hydrocarbon oils. Additional starting materials specified include carboxylic acids such as stearic and palmitic acids, sulphonic acids, halogenated hydrocarbons such as dodecyl bromide, alcohols such as lauryl alcohol, aldehydes such as heptaldehyde, ketones such as pentadecanone-8, esters such as methyl stearate, glycerides such as lard and palm oil, acylated amines such as N-lauryl a; etamide and saturated heterocyclic compounds such as piperidine, acetyl piperidine and decahydrocarbazole. In the case of oxygen containing compounds such as aliphatic acids the catalyst may be omitted. Catalysts other than organic bases are also included, compounds mentioned being lauramide, butyrolactam, dodecyl carbamate, xylylheptadecylketoxime, hexamethylene diisocyanate, acetamide, methallylisothiocyanate, phenylethyleneoxide, and thiophenol. This subject-matter does not appear in the Specification as accepted.