Patent GB-452866-A (GB)
Title: Manufacture of organic compounds containing acid salt-forming groups
IPC: C07C59/13
Filed: 1935-02-23
Abstract: Organic compounds having an acid character and suitable for use as wetting, emulsifying, or dispersing agents are prepared by causing an aromatic or hydroaromatic hydroxyl compound which is substituted in the nucleus at least once by an aliphatic radical having more than three carbon atoms, or an aromatic-aliphatic radical, to react with an aliphatic etherifying agent which contains an acid salt forming group whose carbon chain is interrupted at least once by oxygen nitrogen or sulphur.  The compounds so produced have the general formula R--O--R1--X, where R is an aromatic or hydroaromatic radical which contains as a substituent at least one aliphatic or aromatic-aliphatic radical with more than three carbon atoms and may contain another substituent.  R1 is an aliphatic radical, the carbon chain of which is interrupted at least once by oxygen, nitrogen or sulphur, and X is an acid salt forming group.  Alkylated aromatic or hydroaromatic bodies mentioned are para-n-butylphenol, amylcresol, di-isobutylphenol, isohexylnaphthol, oleylphenol, isododecylphenol, isooctyl-resorcinol, di-isobutylcyclohexanol, isohexylcyclohexanol, and iso-octyl-methylcyclohexanol, as an example of the second component there may be mentioned b -chlorodiethylether-b <1>-sulphonic acid (Cl--CH2.CH2.O.CH2.CH2.SO3H).  The compounds of the present invention may also be made in stages. For example, one of the above aromatic or hydro-aromatic hydroxy compounds may be caused to react with an aliphatic etherifying agent having an uninterrupted carbon chain but capable of undergoing further reactions, and the intermediate product thus formed, caused to react with a halogen substituted aliphatic carboxylic or sulphonic acid, or a polybasic aliphatic carboxylic acid.  Examples of materials which are condensed to form the intermediate products are aliphatic radicals substituted by hydroxyl, sulph-hydryl, or a primary or secondary amino group, or an aliphatic radical capable of forming such a group (ethylene oxide, ethyleneimine, ethylene sulphide).  The acid salt forming group is introduced at a later stage.  Where a halogen hydrin or an alkylene oxide is used, the intermediate product has the probable constitution <FORM:0452866/IV/1> where R is an aliphatic hydrocarbon radical. Before introducing the acid group it may be an advantage, or in the case of the introduction of a radical of a polybasic oxygen containing mineral acid it is necessary, to repeat once or several times the reaction with a halogen hydrin or an alkylene oxide whereby an intermediate product is formed of the probable constitution <FORM:0452866/IV/2> where R is an aliphatic hydrocarbon radical, and X is 1 or a higher whole number.  The acid salt forming group is introduced in known manner, for example, by reaction with a halogen fatty acid, by esterification with one carboxyl group of a dibasic aliphatic carboxylic acid, by introduction of a radical of a polybasic oxygen containing mineral acid, or by introducing a sulphonic acid group.  In an analogous manner there may be obtained bodies in which the aliphatic radical is interrupted by nitrogen or sulphur.  Thus the above aromatic or hydro-aromatic hydroxy compounds may be caused to react with an alkylene sulphide or an alkylene imine to yield intermediate products of the type <FORM:0452866/IV/3> and <FORM:0452866/IV/4> respectively.  These products are then caused to react with a halogen fatty acid as before.  Alternatively an alkylphenol or an alkylphenol hydroxyalkylated in the hydroxyl group may be esterified with thiodiglycollic acid, or an alkylated phenol reacted with a halogen-alkyl sulphonic acid, the corresponding sulphochloride made therefrom reduced to the sulphinic acid and thus reacted with a halogen fatty acid to yield <FORM:0452866/IV/5> In examples: (1) para-isohexylphenol is reacted in alcoholic solution with glycol chlorhydrin.  The product is treated with sodium ethylate and then reacted with sodium chloro-acetate in xylene solution; (2) para-isobutylphenol is reacted with ethylene oxide at 140 DEG  C. in the presence of alkali, and the dioxyethyl ether of para-isobutylphenol treated with sodium and then reacted with sodium chloracetate.  Instead of para - isobutylphenol, para - isobutylcyclohexanol may be used; (3) para-isododecylphenol are etherified as in example (1) and the ether so obtained treated in methyl alcoholic solution with the sodium salt of b -chloropropionic acid; (4) para-oleyl-ortho-cresol is reacted with ethylene oxide as in example (2) to yield trioxethyl-oleyl-cresol which is then treated first with sodium and then with sodium chloracetate in decahydronaphthalene solution; (5) para-isohexyl-ortho-chlorophenol is treated with ethylene oxide, sodium ethylate, and sodium chloracetate as described above; (6) 1-iso-octyl-4-cyclohexyl-glycol ether is treated with sodium ethylate and the sodium salt of chlorethane-sulphonic acid according to the method described in p example (2).  Instead of the sodium salt of chlorethane-sulphonic acid there may be used the sodium salt of chloracetic acid; (7) ortho-benzylphenol is reacted with ethylene chlorhydrin to give the corresponding ortho-benzylphenylglycol ether which is then treated in xylene solution with sodium amide.  When the evolution of ammonia ceases, sodium chloracetate is added to give the sodium salt of ortho-benzylphenyl-glycol ether-acetic acid.  By starting with parabenzylphenol, the corresponding para-benzylphenylglycol ether-acetic acid is obtained.  If ortho- or para-benzylphenol is reacted with ethylene sulphide, there is obtained the ortho- or para-benzylphenoxyethylhydrosulphide, which may be reacted with chloracetic acid in a manner similar to that described above to yield ortho- or para-benzylphenoxyethylthioacetic acid; (8) para-isononylphenol is reacted with ethylene chlorhydrin to form para-isononylphenylglycol ether which is then treated first with sodamide in xylene and then with sodium chloracetate to give the sodium salt of para-isononylphenylglycol ether-acetic acid. Nonylphenol when reacted with ethylene sulphide gives nonylphenoxyethylhydrosulphide which may be converted as described above to nonylphenoxyethyl-thioacetic acid; (9) the phenyl ester of lauric acid is transformed into para-laurophenone, the ketone is reduced to para-n-dodecylphenol which is then heated in a closed vessel with ethyleneimine to give paradodecyl - phenoxethylamine. This amine is heated with sodium chloracetate in the presence of an acid binding agent to give para-n-dodecylphenoxethyliminodiacetic acid.  Instead of the sodium salt of chloracetic acid, there may be used an equivalent amount of the sodium salt of chlorethane sulphonic acid to give para-n-dodecylphenoxethyliminodiethanesulphonic acid; (10) the mixture of alkylphenols prepared by causing hardened fish oil fatty acid to react with phenol in the presence of borontrifluoride, and reducing the mixture of ketones is boiled in alkaline alcoholic solution with b -chlordiethylether-b <1>-sulphonate to yield the mixture of sodium salts of alkylphenoxyglycolether-ethanesulphonic acids; (11) into a hot alkaline alcoholic solution of octylphenol there is added sodium b -chlordiethylether-b <1>-sulphonate, and the mixture boiled for 5 hours under reflux to yield sodium octylphenoxy-ethoxy-ethane sulphonate.  In the form of their water soluble salts, the compounds of the present invention strongly reduce surface tension, and are therefore used as wetting, emulsifying, dispersing, and cleansing agents in the textile industry and leather industry.  They may be used alone or in admixture with soaps or soap-like agents such as the sulphonic acid esters of alcohols of high molecular weight, or the condensation products of natural fatty acids with hydroxyethane- or aminoethane-sulphonic acids, or sarcosine.  They may also be used with hardness reducing agents such as sodium pyrophosphate and sodium metaphosphate.