Patent GB-654654-A (GB)
Title: Sulpho-tricarboxylic acid compounds and process of preparing same
IPC: C07C309/17
Filed: 1947-07-08
Abstract: Aliphatic sulphotricarboxylic acids are produced by a process characterized in that a saturated aliphatic tricarboxylic acid is heated with a sulphonating agent stronger than sulphuric acid; alkali metal sulphonates are produced by a process characterized in that a halogen substituted saturated or unsaturated aliphatic tricarboxylic acid is heated with an alkali metal sulphite; alkali metal or ammonium sulphonates of aliphatic tricarboxylic acids or esters thereof are produced by a process characterized in that unsaturated aliphatic tricarboxylic acids or esters thereof are heated with an alkali metal or ammonium bisulphite and suphonated aliphatic tricarboxylic acids produced by any of the above methods may be esterified with an alcohol.  Aliphatic tricarboxylic acids mentioned as starting materials include ethane tricarboxylic, propane a ,a ,g -tricarboxylic, tricarballylic, propane a ,a ,g -tricarboxylic, tricarballylic, propane a ,b ,b -tricarboxylic, propane a ,a ,b -tricarboxylic, a -carboxy adipic, isobutane tricarboxylic, ethylene tricarboxylic, aconitic, isoaconitic, g -butylene a ,b ,g -tricarboxylic and methyl aconitic acids.  Representative of alcohols mentioned which may be used in the formation of esters are methyl, octyl, hexadecyl, stearyl alcohols, higher alcohol mixtures obtained as by-products in the manufacture of methanol from carbon monoxide and hydrogen, polyhydric and ether alcohols such as ethylene glycol, diethylene glycol, diethylene glycol propyl ether, and cyclic alcohols such as cyclohexanol, benzyl alcohol, furfuryl alcohol, a -terpineol and borneol.  Mixed esters may also be prepared with any one combination of alcohols including monohydric saturated or unsaturated aliphatic alcohols, aliphatic polyhydric alcohols, their esters having at least one remaining free hydroxyl group and other polyhydric alcohols with at least one free hydroxyl group and in which one or more hydroxy groups have been previously reacted with an acid such as monoricinolein, diricinolein, monostearin and mono olein, acid alcohols such as ricinoleic acid, triricinolein and such polyhydroxy bodies containing one or more free hydroxy groups in the remainders of which carboxylic acid residues have been introduced. In several examples aconitates are sulphonated with sodium, potassium or ammonium bisulphite, ammonium bisulphite and sulphite or acidified ammonium sulphite, the aconitate employed as starting material being, in examples: (1) triisoamyl, (2) triethyl butyl, (3) tri-n-hexyl, (4) trioctyl, (5) tri-2 (ethyl butyl), (6) di-(2-ethyl hexyl) ethyl, (7) distearyl ethyl, (8) a mixture obtained on esterifying commercial secondary heptyl alcohol, (9) a mixture obtained on esterifying crude primary and secondary alcohols obtained as a by-product in methanol synthesis, (12) tricyclohexyl, (13) tributoxy diethylene glycyl, (14) a mixture of mono-, di- and tri-cetyl aconitates obtained by esterifying commercial cetyl alcohol.  In examples (10) aconitic acid is heated with sodium bisulphite to yield the monosodium salt of sulphotricarballylic acid and (11) ethane tricarboxylic acid is heated with oleum to yield a mixture of mono- and disulphoethane tricarboxylic acids, excess sulphuric acid being removed with barium hydroxide; (15) 2-ethyl butanol is esterified with the sulphoethane tricarboxylic acid mixture prepared according to example (11), and in (16) with the monosodium salt of sulphotricarballylic acid prepared according to example (10) in the presence of toluene sulphonic acid; (17) an insecticidal spreader is obtained by treating an aqueous solution of the product of example (2) with copper sulphate; (18) aconitic acid is treated with gaseous hydrogen bromide in acetic acid solution, the product is warmed with sodium sulphite and the mixture evaporated to dryness with water and hydrochloric acid.  The residue may be dissolved in sodium hydroxide and again evaporated to dryness. The following starting materials are obtained in examples: (1) triisoamyl aconitate by esterifying citric acid isoamyl alcohol in the presence of hydrochloric acid and dehydrating the citric ester with acetyl chloride; (2) tri-(2-ethyl butyl)-aconitate is obtained by heating citric acid and 2-ethyl butyl alcohol in the presence of sulphuric acid and dehydrating the product with thionyl chloride; (3) tri-n-hexyl, and (4) tri-octyl aconitate are obtained by the method of example (2); (6) di-(ethyl hexyl)-ethyl aconitate by alcoholysis of triethyl aconitate; (7) diethyl stearyl aconitate by alcoholysis of triethyl aconitate. Applications of the surface activity of the compounds are mentioned (see Groups I, III, IV (c), VI and VIII).ALSO:Aliphatic sulphotricarboxylic acids and esters and salts thereof are stated to have surfaceactive properties and may be employed for degreasing, cleansing and scouring fibre, woodwork, floor coverings, tiles, hides, leather and metalware.  They may also be used in the wetting, sizing, desizing, bleaching, mercerizing, lustring, delustring, weighting, lubricating, finishing, degumming, printing, softening and dyeing of various textile and fibrous materials.  They may be used to prepare soluble, difficulty soluble or pigment dyestuffs in finely-divided, easily soluble or dispersible form, as dyeing assistants and in printing textile fabrics, either by incorporation or in the printing or discharge pastes, coating and sizing compositions from casein, starch, higher fatty alcohols, natural and synthetic resins, rubber and in writing and printing inks, emulsified paints and varnishes, pigment emulsions, froths or foams (e.g. over electrolytic cells), porous fibrous batts, porous concrete, cellular or porous synthetic resin compositions or fire extinguishing foams.  They may be used alone or with other surface active materials.  Representative of many aliphatic sulphotricarboxylic acids or derivatives prepared in examples, (see Group IV (b)), are triamyl, diethylstearyl and tricyclohexyl sulphotricarballylates, mono- and di-sulpho ethane tricarboxylic acids, the monosodium salt of sulphotricarballylic acid and the copper salt of tri-(ethyl butyl)-ester of sulphotricarballylic acid. Representative of many aliphatic tricarboxylic acid starting materials mentioned are ethane tricarboxylic acid, propane a ,a ,g -tricarboxylic acid, ethylene tricarboxylic acid, the aconitic acids and g -butylene a ,b ,g -tricarboxylic acids. Among alcohols mentioned from which esters may be derived are ethyl or stearyl alcohols, polyhydric and ether alcohols such as ethylene glycol and diethylene glycol propyl ether, cyclic alcohols such as cyclohexanol, furfuryl alcohol, esters of polyhydric alcohols having at least one free hydroxy group and in which one or more hydroxy groups have been reacted with an acid, e.g. diricinolein, acid alcohols such as ricinoleic acid and triricinolein.  The products may be employed as emulsifying and dispersing agents (see Groups III, VI and VIII).ALSO:Aliphatic sulphotricarboxylic acids and esters and salts thereof are stated to be emulsifying and de-emulsifying agents. They may be employed in the emulsification or dispersion of animal, vegetable or mineral oils, esters, fats and waxes to be used as cutting, lubricating, impregnating, coating, dressing, finishing waterproofing, waxing, sizing and preserving agents and in the preparation of coating and sizing compositions from casein, starch, rosin, gums, asphaltic and bituminous materials. De-emulsifying processes in which the products may be employed include the breaking of mineral oil and water emulsions and in the treatment of oil carrying strata for the improvement of the yield of oil wells. Representative of many sulphotricarboxylic acids or derivatives prepared in examples (see Group IV (b)) are triamyl, diethylstearyl and tricyclohexyl sulphotricarballylates, mono and disulpho ethane tricarboxylic acids, the monosodium salt of sulphotricarballylic acid and the copper salt of the tri-(ethyl butyl) ester of sulphotricarballylic acid.  Representative of many aliphatic tricarboxylic acid starting materials mentioned are ethane tricarboxylic acid, propane a ,a ,g -tricarboxylic acid, ethylene tricarboxylic acid, the aconitic acids and g -butylene a ,b ,g -tricarboxylic acids.  Among alcohols mentioned from which the esters may be derived are ethyl and stearyl alcohols, polyhydric and ether alcohols such as ethylene glycol and diethylene glycol propyl ether, cyclic alcohols such as cyclohexanol, furfuryl alcohol, esters of polyhydric alcohols having at least one free hydroxy group and in which one or more hydroxy groups have been reacted with an acid, e.g. diricinolein, acid alcohols such as ricinoleic acid and tricinolein. Other applications of the surface active properties of the compounds are given (see Groups IV (c), VI, VIII).ALSO:Aliphatic sulphotricarboxylic acids and esters and salts thereof may be used to prepare emulsions or dispersions of germicidal, insecticidal or fungicidal materals.  In example (17) the copper salt of tri(ethyl butyl) sulphotricarballylic acid is stated to be a spreader in insecticidal compositions. Representative of many other sulphotricarboxylic acids or derivatives prepared in examples (see Group IV(b)), are triamyl, diethyl stearyl and tricyclohexyl sulphotricaballylates, mono- and disulphoethane tricarboxylic acids and the mono sodium salt of sulphotricarballylic acid. Representative of many aliphatic tricarboxylic acid starting materials mentioned are ethane tricarboxylic acid, propane a a  g tricarboxylic acid, ethylene tricarboxylic acid, the aconitic acids and g -butylene a  b  g  tricarboxylic acids.  Among alcohols mentioned from which the esters may be derived are ethyl and stearyl alcohols, polyhydric and ether alcohols such as ethylene glycol and diethylene glycol propyl ether, cyclic alcohols such as cyclohexanal, f