Patent GB-360493-A (GB)
Title: Improvements in the manufacture and production of derivatives of ethers
IPC: C07C209/08
Filed: 1930-07-07
Abstract: The ethers obtainable by condensing saturated organic compounds, containing halogenated aliphatic chains of at least ten carbon atoms, with polyhydric aliphatic or mon- or poly-hydric cycloaliphatic alcohols, phenols, or naphthols, or with the alkali-metal compounds of any of these, are treated with phosphoric acid, phosphorus pentoxide, phosphorus halides, or sulphonating agents, whereby products having emulsifying and dispersing properties are obtained. The halogenated compounds from which the ethers are derived may also contain hydroxyl, carboxyl, or carbonyl groups, and may be obtained by halogenating suitable petroleum fractions or their oxidation products, products from the liquefaction of coal, brown coal tar oils, montan wax, acids of animal or vegetable oils or fats, higher alcohols such as decyl or dodecyl alcohol, or higher ketones such as diamyl ketone. The hydroxyl compounds with which the halogenated compounds may be reacted include ethers or esters of glycols still containing a free hydroxyl group, such as glycol monoalkyl ethers and halogenhydrins, cyclohexanol and its homologues, and halogenated phenols or naphthols.  The products obtained by treating the ethers with phosphoric acid, &c., or with sulphonating agents may be acid esters or sulphonic acids, and may be used, as such or as salts, in the production of oil emulsions for spinning, or for the preparation of finely divided pigments.  According to the examples, (1) petroleum boiling at 150-300 DEG  C. is chlorinated and then reacted with a solution of sodium in ethylene glycol; the product is converted into the acid sulphuric ester by treatment with chlorsulphonic acid, or into an acid phosphoric ester by treatment with phosphorus pentoxide; (2) a middle oil boiling at 200-310 DEG  C. is chlorinated and then reacted with sodium phenolate, b -naphtholate, resorcinolate, or an alkyl naphtholate such as dibutyl naphtholate; the product is sulphonated by treatment at 100-120 DEG  C. with fuming sulphuric acid; (3) the chlorinated petroleum used in example 1 is treated with resorcinol or pyrogallol and soda, and the product is treated with fuming sulphuric acid at 40 DEG  C.ALSO:The ethers obtainable by condensing saturated organic compounds, containing halogenated aliphatic chains of at least ten carbon atoms, with polyhydric aliphatic or mono- or polyhydric cycloaliphatic alcohols, phenols, or naphthols, or with the alkali-metal compounds of any of these, are treated with phosphoric acid, phosphorus pentoxide, phosphorus halides, or sulphonating agents, whereby products having wetting, cleansing, tanning, emulsifying and like properties are obtained. The halogenated compounds from which the ethers are derived may also contain hydroxyl, carboxyl, or carbonyl groups, and may be obtained by halogenating suitable petroleum fractions or their oxidation products, products from the liquefaction of coal, brown coal tar oils, montan wax, acids of animal or vegetable oils or fats, higher alcohols such as decyl or dodecyl alcohol, or higher ketones such as diamyl ketone.  The hydroxyl compounds with which the halogenated compounds may be reacted include ethers or esters of glycols still containing a free hydroxyl group, such as glycol monoalkyl ethers and halogenhydrins, cyclohexanol and its homologues, and halogenated phenols or naphthols.  The preparation of the ethers may be effected at atmospheric or raised pressure in the presence or absence of diluents, e.g. benzene, chlorbenzene, nitrobenzene, ligroin, tetrachlorethane, or cyclohexanone, and with or without a catalyst or an acid-binding agent, e.g. copper or its salts, aluminium chloride, zinc chloride, soda, caustic soda, sodium acetate, pyridine, or dimethylaniline.  The products obtained by treating the ethers with phosphoric acid, &c., or with sulphonating agents may be acid esters or sulphonic acids, and may be used, as such or as salts, in the production of preparations for treating textiles, e.g. oil emulsions for spinning, or as assistants in the production of drilling greases or in greasing leather or in softening or waterproofing textiles, or as levelling agents in dyeing, or for the preparation of finely divided pigments.  According to the examples, (1) petroleum boiling at 150-300 DEG  C. is chlorinated and then reacted with a solution of sodium in ethylene glycol; the product is converted into the acid sulphuric ester by treatment with chlorsulphonic acid, or into an acid phosphoric ester by treatment with phosphorus pentoxide; (2) a middle oil boiling at 200-310 DEG  C. is chlorinated and then reacted with sodium phenolate, b -naphtholate, resorcinolate, or an alkyl naphtholate such as dibutyl naphtholate; the product is sulphonated by treatment at 100-120 DEG  C. with fuming sulphuric acid; (3) the chlorinated petroleum used in example 1 is treated with resorcinol or pyrogallol and soda, and the product is treated with fuming sulphuric acid at 40 DEG  C.  Dibutyl naphthol is prepared by heating a naphthalene sulphonic acid with 2 mols. of n-butyl alcohol in the presence of sulphuric acid, and subjecting the product to alkali fusion.