Patent GB-1080199-A (GB)
Title: Process of preparing hydroxy-alkyl alkyl sulphoxides
IPC: C11D1/755
Filed: 1963-12-23
Abstract: Detergent compositions comprise, as an active detergent ingredient, a hydroxy-alkyl alkyl sulphoxide of the general formula <FORM:1080199/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; and each of R, R1 and R2 may contain 0 to 5 ether, thioether and/or imino linkages and/or have from 0-5 amino groups appended thereto; and R3 and R4 are each hydrogen or a C1 to C30 alkyl, aryl, alkylaryl, or cycloalkyl radical which may contain 0 to 5 ether and/or thioether linkages; and Q is an integer of from 1 to 50; together with a diluent and/or one or more other detergent surfactants.  The preferred inventive compounds have the above formula, but wherein R3 has from 8 to 18 carbon atoms, R is a methyl group, and R1, R2 and R4 are all hydrogen, with Q being 1. Alternatively, R3 may have the structure R5-O-CH2- wherein R5 is a C8 to C18 alkyl group.  The compositions may be in the form of built detergents, such as liquid, bar, flake, granular, or tabletted granular compositions, including such forms for toilet application and dish-washing.  Other ingredients may be water-soluble inorganic alkaline builder salts such as alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates, and such salts of ammonium or substituted ammonium (e.g. triethanolamine); water-soluble organic alkaline sequestering builder salts such as alkali metal, ammonium or substituted ammonium aminopolycarboxylates, e.g. ethylene-diamine acetates and nitrolo-acetates; alkali metal salts of phytic acid, and water-soluble salts of ethane-1-hydroxy-1,1-diphosphonate. Other detergents in the compositions may be anionic, e.g. sodium coconut soap, sodium dodecyl benzene sulphonate, and potassium tallow alkyl sulphate; non-ionic, e.g. dodecyldimethyl amine oxide and a condensate of coconut fatty alcohol with 5.5 moles of ethylene oxide; zwitterionic, e.g. 3-(N,N-dimethyl-N-hexadecyl - ammonio) - 2 - hydroxy - propane-1-sulphonate; ampholytic, e.g. sodium 3-dodecylamino-propionate; or cationic, e.g. cetyl-trimethyl ammonium bromide.  Other diluents or additives include perfumes, anti-tarnishing agents, anti-redeposition agents, bacteriostats, fluorescers, suds builders and suds depressors.  An example is given wherein compositions comprising sodium tripolyphosphate as a builder and the following inventive compounds: 3 - hydroxy - tridecymethyl -, 3 - hydroxy - pentadecylmethyl -, 3-hydroxy - 4 - dodecoxybutylmethyl -, and 3-hydroxy - 4 - decoxybutylmethyl - sulphoxides, are compared in detergent effectiveness with a conventional detergent composition. A composition of 3-hydroxy-tridecylmethyl sulphoxide and soluble soap is also mentioned. The inventive compounds are prepared by hydrolysing the product of a reaction of sulphinyl carbanion salts and epoxide containing compounds (see Division C2).ALSO:The invention comprises hydroxy-alkyl sulphoxides having the general formula <FORM:1080199/C3/1> wherein Q is an integer of from 1 to 50, R is a C1 to C28 hydrocarbon group attached to the sulphur by a single co-valent bond, R1 and R2 are each hydrogen or a C1 to C30 alkyl group, R3 and R4 are each hydrogen or a C1 to C30 alkyl, alkyl-aryl, aryl, or cycloalkyl group, and any of R, R1,R2,R3 and R4 may contain 0 to 5 ether and/or thioether linkages, and R, R1 and R2 may further contain 0-5 imino linkages and/or have 0 to 5 amino groups appended to the hydrocarbon chain.  The sulphoxides are prepared by reacting an alkali metal salt of a sulphinyl carbanion with a monoepoxide compound to give an intermediate ion according to the reaction <FORM:1080199/C3/2> wherein M is the alkali metal, and R, R1, R2, R3 and R4 are as defined above, the said ion then being caused to react with further amounts of monoepoxide (which may be the same or different from that used to form the ion), to give a reaction product which reacts with compounds containing an active hydrogen (i.e. water), and is hydrolyzed to the required sulphoxide. The reaction of dodecyl sulphinyl carbanion salt with Q moles of ethylene oxide followed by hydrolysis to give a compound of formula C12H25SOCH2(CH2CH2O)QH is mentioned.  Suitable starting materials are the sodium or potassium salt of methyl sulphinyl carbanion, or of a sulphinyl carbanion wherein R1 and R2 are hydrogen and R is C2 to C22 straight or branched chain alkyl, and one or more of the following epoxides: dodecylene-, ethylene-, propylene-, hexadecylene-, octadecylene-, butylene-, cyclohexene-, styrene-, and p-methylstyrene-oxides; and octyl-, decyl-, dodecyl-, tetradecyl-, hexadecyl-, and octadecyl-glycidyl ethers.  Use of the di-epoxide, butadienediepoxide, is also mentioned.  Other epoxides are those derived from mixtures of fatty alcohols, such as that wherein R3 is a C6 to C18 straight chain alkyl group and R4 is hydrogen; and epoxides wherein R3 has the formula R5-O-CH2- when R5 is C8 to C18 alkyl. The reaction is suitably carried out in anhydrous solvent, such as aliphatic or aromatic ethers or hydrocarbons, cyclic ethers, amines which include anhydrous liquid ammonia and dimethyl formamide, or preferably in dimethyl sulphoxide, at a temperature between 0 DEG and 100 DEG  C.  The inventive compounds are useful in detergent compositions (see Divisions C4-C5) or as intermediates in the preparation of surface-active agents.ALSO:Hydroxy-alkyl alkyl sulphoxides are prepared by reacting a salt of a sulphinyl carbanion having the formula <FORM:1080199/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, 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 amino groups appended thereto, with at least one epoxide compound of formula <FORM:1080199/C2/2> or <FORM:1080199/C2/3> wherein each of R3 and R4 is hydrogen or a C1 to C30 hydrocarbon radical which may contain from 0 to 5 ether and/or thioether linkages, which radical is selected from alkyl, aryl, alkyl-aryl, and cycloalkyl groups, and R6 is a C2 to C30 hydrocarbon radical containing one epoxide group and 0 to 5 ether and/or thioether linkages, which radical is selected from alkyl, aryl, alkyl-aryl, and cyclo-alkyl groups, and then treating the reaction product with a compound containing a reactive hydrogen atom.  When the epoxide compound is a monoepoxide (i.e. having the first of the above alternative formulae) the said reaction product is reacted with water as an active hydrogen compound to provide novel hydroxy-alkyl alkyl sulphoxides having the general formula <FORM:1080199/C2/4> wherein R, R1, R2, R3 and R4 are as defined above.  Alternatively, the said reaction product may react with further amounts of monoepoxide, to give products which, after hydrolysis with water, yield hydroxy sulphoxides containing ether linkages, of the formula <FORM:1080199/C2/5> wherein R to R4 are as before and Q is an integer of 1 to 50 (see Division C3).  When these sulphoxides contain sufficiently long chain hydrophobic groups, they are useful in surface-active compositions (see Divisions C4-C5).  When using a di-epoxide reactant (i.e. of the second of the alternative formulae given above), both epoxy groups take part in the reactions corresponding to those of the mono-epoxy compounds.  The preferred reactants are alkali metal salts of methyl sulphinyl carbanion, and the following monoepoxides:  dodecylene-, ethylene-, propylene-, hexadecylene-, octadecylene-, butylene-, styrene-, cyclohexene-, or p-methyl styrene-oxides, or octyl-, decyl-, dodecyl-, tetradecyl-, hexadecyl-, and octadecyl-glycidyl ethers.  As a diepoxide, butadiene-diepoxide is mentioned.  Also, mixtures of epoxides derived from mixtures of fatty alcohols may be used.  Examples are given for the preparation of:  (1) 3-hydroxy-tridecyl methyl sulphoxide, by reaction of dodecene-1-oxide with methyl sulphinyl carbanion (sodium salt) followed by hydrolysis with water of the unisolated product (dodecyl sulphinyl carbanion). The said product is also reacted first with 4 moles of ethylene oxide, followed by aqueous hydrolysis, to give a material of formula C12H25-SO-CH2-(CH2CH2O)4-H (2) 3-Hydroxy-propyl methyl sulphoxide, by reaction of ethylene oxide with methyl sulphinyl carbanion (sodium salt) and subsequent aqueous hydrolysis; (3) 3-Hydroxy-4-dodecyl-oxybutyl methyl sulphoxide, by reaction of dodecyl glycidyl ether and methyl sulphinyl carbanion, with subsequent aqueous hydrolysis.