Patent GB-662656-A (GB)
Title: Esters of sulphonyl alcohols and compositions containing such esters
IPC: C07C315/02
Filed: 1949-02-15
Abstract: Esters of sulphonyl alcohols having the general formula RSO2(CH2)nOOCR1, in which R and R1 are the same or different alkyl, cyclo-alkyl or aryl groups and n is greater than one, are plasticizers, either by themselves or in conjunction with known plasticizers, for organic thermoplastic materials, particularly for the polymers and copolymers of vinyl compounds such as polyvinyl chloride and for cellulose acetate and cellulose nitrate.  In the examples, flexible compositions are obtained by milling together (a) polyvinyl chloride and 2-n-butyl-sulphonyl-ethyl-1-naphthenate; (b) polyvinyl chloride, di - (2 - n - butylsulphonyl - ethyl - 1) adipate and di-(2-ethylhexyl) phthalate and white lead; (c) polyvinyl chloride, 2-(41-chloro-phenyl-sulphonyl)-ethyl-1-acetate and white lead.ALSO:Compounds, which are esters of sulphonyl alcohols and have the general formula RSO2 (CH2)nOOCR1, in which R and R1 represent identical or different alkyl, cycloalkyl or aryl groups, are prepared by oxidizing a thioether alcohol of general formula RS(CH2)nOH to the corresponding sulphonyl alcohol and then esterifying the sulphonyl alcohol by reacting it with a carboxylic acid or an anhydride or acid halide thereof; or alternatively the thioether alcohol may be first esterified and then oxidized to the corresponding sulphonyl ester. Thioether alcohols used as starting materials may be prepared by known methods, e.g. by reacting an aliphatic, cycloaliphatic or aromatic mercaptan with an alkylene oxide or an alkylene halohydrin. Suitable mercaptans are those derived from petroleum, methyl, ethyl, n-propyl, isopropyl and allyl mercaptans, cyclohexane thiol, thiophenol, thionaphthol and thiocresol.  The hydrocarbon portion of the mercaptan may be substituted by groups which do not interfere with the subsequent reactions.  Suitable alkylene oxides or halohydrins are ethylene oxide, propylene oxide, butylene oxide, amylene oxide, ethylene chlorhydrin and propylene bromohydrin. Suitable oxidizing agents for the thioether alcohol or ester are for example, hydrogen peroxide, fuming nitric acid, potassium permanganate, chromic acid and perbenzoic acid.  The oxidation may be carried out in the presence of solvents or diluents, e.g. glacial acetic acid, acetone, benzene, toluene and xylene.  Preferably the temperature is in the range 50 DEG -150 DEG  C.  The esterification may be carried out upon the sulphonyl alcohol or the thioether alcohol by means of a carboxylic acid, anhydride or acid halide in the presence, if desired of a catalyst, e.g. sulphuric acid, gaseous hydrogen chloride or paratoluene sulphonic acid.  Suitable esterifying agents are acetic, propionic, butyric, valeric, acrylic, methacrylic, naphthenic and stearic acids, acetyl chloride, propionyl bromide and acetic anhydride.  The carboxylic acids or derivatives thereof used in the esterification stage may be di- or poly-carboxylic acids, e.g. oxalic, maleic, succinic, adipic, tartaric and phthalic acids and in these cases either acid or neutral esters may be obtained.  The sulphonyl esters formed are softening agents or plasticizers, either by themselves or in conjunction with known plasticizers, for organic thermoplastic materials, e.g. polymers and copolymers of vinyl compounds such as polyvinyl chloride and for cellulose acetate and cellulose nitrate.  In the examples: (a) 2-n-butylthioethan-1-ol, prepared from n-butyl mercaptan and ethylene chlorhydrin, is esterified with naphthenic acids to give 2-n-butylthioethyl-1-naphthenate which is then oxidized with hydrogen peroxide to 2-n-butylsulphonylethyl-1-naphthenate; (b) 2-propylthioethan-1-ol, prepared by reacting a propyl mercaptan fraction obtained by the distillation of crude petroleum mercaptans and ethylene chlorhydrin, is oxidized with hydrogen peroxide and then esterified with acetic anhydride to give 2-propylsulphonylethyl-1-acetate; (c) 2-propylsulphonylethan-1-ol is reacted with benzoyl chloride to give 2-propylsulphonylethyl benzoate; (d) 2-n-butylthioethan-1-ol is oxidized by hydrogen peroxide to give 2-n-butylsulphonylethan-1-ol which is esterified with naphthenic acids to give 2-n-butyl-sulphonylethyl-1-naphthenate; (e) 2-n-butylsulphonylethan-1-ol is esterified with adipyl chloride to give di-(2-n-butylsulphonylethyl-1)-adipate; (f) 4-chlorothiophenol is reacted with ethylene chlorohydrin to give 2-(41-chlorophenylthio)-ethan-1-ol which is oxidized with hydrogen peroxide to give 2 - (41 - chlorophenylsulphonyl) - ethan - 1-ol; this product is esterified with acetyl chloride to give 2-(41-chlorophenylsulphonyl)-ethyl-1-acetate; examples are also given of flexible compositions obtained from various esters of sulphonyl alcohols with polyvinyl chloride.  The products, subject to the condition that if either of the groups R or R1 is aryl, then the other is not alkyl, are claimed as new compounds.