Patent GB-1077669-A (GB)
Title: Sulphoxide syntheses
IPC: C11D1/755
Filed: 1963-12-23
Abstract: Detergent compositions comprise a 2-ketoalkyl alkyl sulphoxide surfactant of the general formula <FORM:1077669/C4-C5/1> wherein R is a C1 to C28 hydrocarbon group attached to the sulphur by a single covalent bond, R1 and R2 are each hydrogen or a C1 to C30 alkyl group, R4 is a C1 to C29 hydrocarbon group, and each of R, R1 and R2 may contain 0 to 5 ether, thioether and/or imino linkages, and/or have appended thereto from 0 to 5 amino groups, and which has detergent properties, together with a water-soluble alkaline detergency builder salt.  Such compounds having detergent properties are those wherein at least one of the R groups is a long-chain hydrophobic group; suitable groups may be those derived from tallow or coconut oils.  The compositions may be in liquid, bar, flake, granular or tabletted forms, the preferred builder being sodium tripolyphosphate.  Compositions illustrated contain the said builder salt and, as the detergent, 2-ketoundecyl methyl sulphoxide, 2-ketotridecyl methyl sulphoxide or 2-ketopentadecyl methyl sulphoxide.  Their detergent efficacy is compared with similar compositions containing either sodium tallow alkyl sulphate or sodium tetrapropylene benzene sulphonate. The active compounds are prepared by reacting alkali metal salts of sulphinyl carbanions with natural fatty or oily triglyceride ester mixtures (see Division C2).ALSO:Novel 2-keto-alkyl alkyl sulphoxides of the general formula <FORM:1077669/C2/1> wherein R is a C1 to C28 hydrocarbon group attached to the sulphur atom by a single covalent bond, R1 and R2 are each hydrogen or a C1 to C30 alkyl group, R4 is a C1 to C29 hydrocarbon group, and each of R, R1 and R2 may contain from 0 to 5 ether, thioether, and/or imino linkages, and/or have from 0 to 5 amine groups appended thereto, are prepared by reacting a salt of a sulphinyl carbanion of the formula <FORM:1077669/C2/2> wherein R, R1 and R2 are as above and M is an alkali metal, with an acylating agent which may be:  -(1) a carboxylic acid ester of the formula <FORM:1077669/C2/3> wherein R4 is as above, R5 is a C1 to C20 alkyl residue of the esterifying alcohol, n is 1 to 3, being the number of -OH groups in the said alcohol, and there are not more than 60 carbon atoms in the ester molecule, (2) an acyl chloride of the formula <FORM:1077669/C2/4> wherein R4 is as above and m is 1 or 2, (3) an acid anhydride of the formula <FORM:1077669/C2/5> wherein R4 is as above, (4) a carbonic acid diester of the formula <FORM:1077669/C2/6> wherein R5 is as above, (5) succinic anhydride, or (6) phthalic anhydride.  The sulphinyl carbanion starting materials may be prepared by reacting a base (i.e. sodium, potassium or lithium hydroxides, amides, hydrides or alkyls) with a sulphoxide of formula corresponding to that shown above for the carbanion salt, wherein M is replaced by H.  Suitable esters for use in (1) above are those derived from ethyl or methyl alcohols, triglycerides or propylene glycol, and acetic, benzoic, naphthoic, phenylacetic, toluic, para-ethyl benzoic, cinnamic, propionic, butyric, or stearic and similar higher fatty carboxylic acids, or dibasic acids such as succinic and phthalic acids.  The reaction first forms a keto-sulphinyl carbanion, which is then decomposed by adding a compound having available active hydrogen, such as water, or an alcohol, or an alkyl halide.  The products of preparation (1) when a dicarboxylic acid ester is used, and of preparation (4), have two sulphinyl groups in the molecule.  The products of preparations (5) and (6), wherein the said dicarboxylic anhydrides are employed, have carboxylate groups, and are, respectively, 5-alkylsulphinyl-laevulinic acid derivatives (e.g. the Na salt of 5-methylsulphinyl laevulinic acid) and ortho carboxybenzoylmethyl alkyl sulphoxides.  An example is given for the preparation of 2-keto-tridecylmethyl sulphoxide from ethyl laurate and the sodium salt of methyl sulphinyl carbanion, the product of this reaction being decomposed with water to give the said sulphoxide. Also referred to are the reaction of the said carbanion with glyceryl trilaurate, to give the same product, and with ethyl acetate to give 2-ketopropyl methyl sulphoxide; the said carbanion is also reacted with diethyl carbonate and with dimethyl succinate, giving bis(methyl sulphinyl) ketone and 1,6-bis(methylsulphinyl)-hexane-2,5-dione respectively.  Specifically mentioned are 2 ketoundecyl methyl sulphoxide and 2-ketopentadecyl methyl sulphoxide, as being detergent materials (see Divisions C4-C5) and also benzoylmethyl methyl sulphoxide.