Patent GB-371144-A (GB)
Title: Manufacture of esters of sulphonated aromatic carboxylic acids
IPC: C07C309/58
Filed: 1931-03-30
Abstract: As emulsifying agents may be employed the esters of aromatic sulpho-dicarboxylic acids or their salts which are manufactured by esterification or reaction of a sulphonic acid or a sulphonate of an aromatic o- or peri-dicarboxylic acid or a substitution product thereof, or an anhydride halide or ester thereof, such as a sulphonic acid of phthalic or naphthalic acid or anhydride, a sulpho-4-chlorophthalic acid or a 4-sulphophthalic acid trichloride with a compound containing alcoholic hydroxyl groups and more than two carbon atoms, or a derivative of such compound. Suitable alcoholic compounds are mono- and polyhydric, saturated or unsaturated aliphatic alcohols with normal or branched carbon chains and containing hydroxyl groups linked to primary, secondary or tertiary carbon atoms, or derivatives of these still containing a free hydroxyl group, e.g. isopropyl, butyl, amyl, and octyl alcohols, diethylene glycol and its monoethyl ether, and glycerin, also natural or synthetic higher fatty alcohols or alcohols derived from waxes, e.g. cetyl, stearyl, and oleyl alcohols or mixtures thereof, oxidation products of aliphatic hydrocarbons or alcohol-like compounds or mixtures thereof obtainable by catalytic hydrogenation, also diacetone alcohol, hydrogenized final distillates of acetone or alcohols obtained by hydration of the unsaturated hydrocarbons formed by cracking of acid resin or residual pitch from the distillation of aliphatic raw materials, also naturally occurring or artificially produced mixtures such as fusel oil, sulphite spirit fusel oil or the commercial mixture of higher alcohols, also aliphatic-aromatic alcohols such as benzyl alcohol, hydrogenated or partially hydrogenated phenols, cresols or naphthols, e.g. cyclohexanol or methylcyclohexanols, also ammonia derivatives containing hydroxyl groups, e.g. triethanolamine, also derivatives of these hydroxyl compounds, such as their oxides or halides.  Examples describe the products of reaction of: (1) sulphophthalic anhydride with amyl, butyl or secondary octyl alcohol; (2) b -sulphophthalic acid trichloride with amyl alcohol (the product being neutralized with caustic soda); (3) mono-sodium phthalic anhydride b -sulphonate with sulphite spirit fusel oil or (4) with fusel oil or methyl cyclohexanol; (5) sulphophthalic anhydride with the commercial mixture of palmityl and stearyl alcohols (the product being neutralized); (6) 4-chlorophthalic anhydride sulphonation product with amyl alcohol (which product may be neutralized); (7) naphthalic anhydride 3-sulphonic acid with amyl alcohol (used directly or after neutralization).  In the examples in which neutralization is effected, organic bases may be used for this purpose.  Specifications 306,116, [Class 2 (iii), Dyes &c.], 350,425, 350,595, 351,456, 363,770, and 371,088 are referred to.  The Specification as open to inspection under Sect. 91 (3) (a) comprises also the use of esters from sulphonic acids or sulphonates of aromatic dicarboxylic acids other than o- and peridicarboxylic acids, or derivatives thereof, such as a sulphonic acid of isophthalic acid or anhydride or of terephthalic acid, and of esters with compounds containing phenolic hydroxyl groups, such as phenols and cresols, and describes in examples the products of esterification of sulphophthalic anhydride with p-cresol and of sulphoterephthalic acid with amyl alcohol.  This subject-matter does not appear in the Specification as accepted.ALSO:Esters of aromatic sulpho-dicarboxylic acids or their salts are manufactured by esterification or reaction of a sulphonic acid or a sulphonate of an aromatic o- or peri-dicarboxylic acid or a substitution product thereof, or an anhydride, halide or ester thereof, such as a sulphonic acid of phthalic or naphthalic acid or anhydride, a sulpho-4-chlorophthalic acid or a 4-sulphophthalic acid trichloride, with a compound containing alcoholic hydroxyl groups and more than two carbon atoms or a derivative of such compound. Suitable alcoholic compounds are mono- and polyhydric saturated or unsaturated aliphatic alcohols with normal or branched carbon chains and containing hydroxyl groups linked to primary, secondary or tertiary carbon atoms, or derivatives of these still containing a free hydroxyl group, e.g. isopropyl, butyl, amyl and octyl alcohols, diethyleneglycol and its monoethyl ether, and glycerin, also natural or synthetic higher fatty alcohols or alcohols derived from waxes, e.g. cetyl, stearyl and oleyl alcohols or mixtures thereof, oxidation products of aliphatic hydrocarbons or alcohol-like compounds or mixtures thereof obtainable by catalytic hydrogenation, also diacetone alcohol, hydrogenized final distillates of acetone or alcohols obtained by hydration of the unsaturated hydrocarbons formed by cracking of acid resin or residual pitch from the distillation of aliphatic raw materials, also naturally occurring or artificially produced mixtures such as fusel oil, fusel oil from sulphite spirit or the commercial mixture of higher alcohols, also aliphatic-aromatic alcohols such as benzyl alcohol, hydrogenated or partially hydrogenated phenols, cresols or naphthols, e.g. cyclohexanol or methylcyclohexanols, also ammonia derivatives containing hydroxyl groups, e.g. triethanolamine, also derivatives of these hydroxyl compounds such as their oxides or halides.  The esterification may be effected in the presence of agents tending to accelerate esterification such as hydrogen chloride gas or concentrated sulphuric acid, and the water produced may be removed by means of a material which forms an azeotropic mixture with water.  Instead of starting with a sulphonic acid chloride, this may be produced during the esterification, for example by the use of phosphorus oxychloride. The esters may also be made by double decomposition, for instance by causing an ester of a lower alcohol to react with a higher alcohol. The sulphonic acid may be in the form of the sulphonation mass obtained by heating the parent material with sulphuric anhydride under pressure and removing the greater part of the excess of sulphonating agent.  The products are soluble in water and have a pronounced tendency to assist wetting, cleansing and emulsification. In examples: (1) sulphophthalic anhydride (obtained by heating phthalic anhydride with excess of sulphuric anhydride and reducing the excess of sulphonating agent to about 12 per cent) is esterified with amyl, butyl or secondary octyl alcohol; (2) b -sulphophthalic acid trichloride is esterified with amyl alcohol and the product neutralized with caustic soda; the product induces wetting, for instance in carbonizing acid; (3) mono-sodium phthalic anhydride b -sulphonate (obtained by prolonged heating under diminished pressure of the acid sodium salt of phthalic acid b -sulphonic acid) is heated with sulphite spirit fusel oil, benzene and concentrated hydrochloric acid in a vessel having a stirrer, a reflux condenser and a water trap; the product is applicable as an auxiliary in the textile industry, e.g. as an aid in carbonizing; (4) the mono-sodium salt of sulphophthalic acid anhydride is heated with fusel oil and toluene in the apparatus of (3); the fusel oil may be replaced by methylcyclohexanol; (5) sulphophthalic anhydride (obtained by prolonged heating under diminished pressure of phthalic acid b -sulphonic acid) is esterified with the commercial mixture of palmityl and stearyl alcohols; after neutralization the product is suitable as a washing agent, e.g. for raw wool; (6) 4-chlorophthalic anhydride is sulphonated by heating in a closed vessel with excess of sulphuric anhydride, most of the excess of sulphonating agent is removed and the sulphonation product is heated with amyl alcohol; the product may be neutralized yielding a substance which assists wetting in water or carbonizing acid; (7) naphthalic anhydride 3-sulphonic acid (obtained by prolonged heating in a vacuum of the free acid) is esterified with amyl alcohol; the product may be used as a wetting agent either directly or after neutralization. In the examples in which neutralization is effected, organic bases may be used for this purpose.  Specifications 306,116, [Class 2 (iii), Dyes &c.], 350,425, 350,595, 351,456, 363,770, and 371,088 are referred to.  The Specification as open to inspection under Sect. 91 (3) (a) comprises also the use of sulphonic acids or sulphonates of aromatic dicarboxylic acids other than o- and peridicarboxylic acids, or derivatives thereof, such as a sulphonic acid of isophthalic acid or anhydride or of terephthalic acid, and of compounds containing phenolic hydroxyl groups such as phenols or cresols, and contains examples of the esterification of sulphophthalic anhydride with p-cresol and of sulphoterephthalic acid (obtained by heating terephthalic acid with excess of sulphuric anhydride) with amyl alcohol.  This subject-matter does not appear in the Specification as accepted.