Patent GB-1083006-A (GB)
Title: Substituted trisulfonylmethanes and methods for their use
Inventor: SCANLEY CLYDE STEPHEN
IPC: C07C317/00
Filed: 1964-11-18
Abstract: Useful oil additives are substituted trisulphonyl methanes of the formula <FORM:1083006/C4-C5/1> wherein R1 represents the functional group -CnH2n-Z-CnH2n + 1, where Z is methylene, phenylene, naphthylene, cyclohexylene, or oxy, with the provision that n + m must be an integer from 4 to 21, R2 and R3 each represent an alkyl, phenyl, tolyl, cyclohexyl or the group R1 above or an ammonium or metal salt thereof, the metal cations having a valency of 1 to 4 (see Division C2). Examples describe the use of the trisulphonyl methanes as (a) thickening agents wherein a solution of sodium tris-[dodecylsulphonyl] methane is made by dissolving tris-[dodecylsulphonyl] methane in an S.A.E. 20 lubricating oil base and then neutralizing by adding aqueous sodium hydroxide at 150 DEG C. The cooled product is a thick grease; (b) demulsifiers, wherein a sample of "West Texas" crude oil containing water emulsified in the oil is treated with a 5% solution of sodium tris-[n-heptylsulphonyl] methane thereby causing a separation of most of the water; and (c) additives in lubricating films, wherein incorporation of 1% tris-[n-dodecylsulphonyl] methane in an S.A.E. 20 grade mineral oil reduces the steel or steel coefficient of friction (lubricated with that oil).ALSO:One or more ethylenically unsaturated monomers that are substantially insoluble in water are polymerized in aqueous emulsion in the presence, as emulsifier, of a trisulphonyl methane derivative of the formula <FORM:1083006/C3/1> wherein R1 represents the functional group -CnH2n-Z-CmH2m+1, where Z is methylene, phenylene, naphthylene, cyclohexylene or oxy, with the provision that n+m must be an integer from 4 to 21, R2 and R3 each represent alkyl, phenyl, tolyl, cyclohexyl or the group R1 above or an ammonium or metal salt thereof, the metal cations having a valency of 1 to 4. Suitable monomers include maleic esters, dienes, styrenes, acrylic and methacrylic esters, vinyl and vinylidene halides, acrylic and methacrylic acids and nitriles, vinyl or allyl esters of saturated or unsaturated mono- and poly-carboxylic acids, vinyl ethers and vinyl ketones. Suitable polymerization catalysts include peracetic acid, sodium or potassium persulphate, benzoyl peroxide and lauryl peroxide, possibly in conjunction with sodium bisulphite.  The polymer can be recovered from the emulsion by coagulation, e.g. by freezing or adding coagulating agents.  Examples illustrate the preparation of methyl methacrylate/ethyl acrylate copolymer, styrene/ethyl acrylate copolymer and polyvinyl acetate, employing sodium tris-(n - heptylsulphonyl) - methane as emulsifier; monomer and catalyst are introduced during the course of polymerization.ALSO:The invention comprises substituted trisulphonylmethanes of the formula <FORM:1083006/C2/1> wherein R1 represents the functional group -CnH2n-Z-CmH2m+1, where Z is methylene 1,4-phenylene, naphthylene, 1,4-cyclohexylene or oxy with the provision that n + m must be a whole number from 4 to 21, R2 and R3 each represent an alkyl, phenyl, tolyl, cyclohexyl or the group defined as R1 above or an ammonium or metal salt thereof, the metal cations having a valency of 1 to 4, provided that R1\s4R2\s4R3\s4 alkyl.  They are prepared by reacting a mercaptan of the formula RSH wherein R has any of the values specified for R1, R2 or R3 above with formic acid or its lower alkyl esters in the presence of anhydrous HCl to form a substituted trithioorthoformate of the formula (R)S3CH which is then reacted with an excess of peracetic acid in the presence of an inert solvent such as chloroform at a temperature of - 20 DEG  to - 30 DEG  C. and thereafter the reaction mixture is allowed to warm to room temperature and the product is recovered or treated with a base to obtain the salt.  A preferred class of the compounds is one wherein at least one of the alkyl groups of R1-R3 is an alkyl group of more than 7 carbon atoms.  Although chloroform is the preferred solvent for the reaction inert halohydrocarbon solvents such as dichloroethane and methylene chloride may also be used.  The compounds may be used as emulsifiers (see Division C3), water repellant agents (see Division D1), oil additives (see Division C5), anti-adhesion agents (see Division B5), paper-sizing agents (see Division B2) and as promoters of dropwise condensation (see Division C4).ALSO:Materials are made water repellant by treating them with a solution of a substituted trisulphonyl-methane of the formula: <FORM:1083006/D1-D2/1> wherein R1 represents the functional group -CnH2n-ZCmH2m+1 where Z is methylene, phenylene, naphthylene, cyclohexylene or oxy, with the provision that n+m must be an integer from 4 to 21, R2 and R3 each represent an alkyl, phenyl, tolyl, cyclohexyl group or the group R1 above or an ammonium or metal salt thereof, the metal cations having a valency of 1 to 4 (see Division C2).  In an Example, cotton cloth is dipped in an aqueous 1 % solution of AlCl3-6H2O, wrung out, dipped in a 0.1 % solution of sodium tris-[n-heptylsulfonyl] methane, wrung out and dried to provide a cloth which was not wetted by water droplets.  Paper may be sized using a compound of the above formula.  In an Example sodium tris-[n-dodecylsulfonyl] methane is used to replace rosin soap in a standard paper sizing procedure using alum as the size-anchoring agent.ALSO:Laxative compositions are prepared by admixing a minor amount of a substituted trisulphonyl methane of the formula: <FORM:1083006/A5-A6/1> wherein R1 represents the functional group -CnH2n-Z-CnH2m+1 where Z is methylene, 1,4-phenylene, naphthylene, 1,4-cyclohexylene, or oxy, with the proviso that n+m must be a whole number from 4 to 21; R2 and R3 each represent an alkyl, phenyl, tolyl, cyclohexyl, or the group R1, or an ammonium or, metal salt thereof, the metal cations having a valency of 1 to 4, with a major amount of a pharmaceutical carrier.  They can be administered in the form of a syrup, tablets or capsuled powders.