Patent GB-481909-A (GB)
Title: Manufacture of aromatic compounds alkylated in the nucleus
IPC: C07C39/06
Filed: 1936-09-22
Abstract: Aromatic compounds are alkylated in the nucleus by reaction with olefine mixtures (or fractions thereof) obtained by polymerizing the olefines resulting from the dehydration of the higher alcohols, containing about 5-12 carbon atoms, obtained in the synthesis of methanol.  The dehydration of these alcohols is effected in known manner, e.g. with phosphoric or sulphuric acid, phosphorus pentoxide, or phosphoric acid on a carrier; the polymerization of the olefines so obtained is also effected in known manner, e.g. by means of boron fluoride or its molecular compounds, phosphoric acid or an active earth.  The condensation of the polymerized olefines or their fractions with the aromatic compounds is effected in the presence of a condensation catalyst, e.g. boron fluoride and its molecular compounds, aluminium chloride, sulphuric acid, phosphoric acid, perchloric acid, sulphoacetic acid, p-toluenesulphonic acid or an active earth. The aromatic compounds which may be treated include aromatic hydrocarbons, nuclearly hydroxylated aromatic compounds, and acids of the type AXRCOOH, where A is a mono- or poly-nuclear aromatic radicle, X is oxygen or sulphur, and R is an aliphatic hydrocarbon radicle, which may be interrupted by oxygen; specified acids of this type are phenoxyacetic, cresoxyacetic, xylenoxyacetic, naphthoxyacetic, phenylmercaptoacetic, and phenoxyethoxyacetic acids. In the examples: (1) phenol and a tetradecylene are condensed in the presence of boron fluoride to yield a tetradecylphenol; (2) phenol and an olefine polymer of average molecular weight 180 or (example 3) 185 or (example 4) 257 or (example 5) 245 are condensed in the presence of boron fluoride; (6) phenol and a tetradecylene are condensed in the presence of aluminium chloride; (7) o-cresol and a tetradecylene are condensed in the presence of boron fluoride; (8) b -naphthol and a tetradecylene are condensed in acetic acid solution in the presence of boron fluoride; the tetradecyl-b -naphthyl acetate obtained as a by-product is saponified with alcoholic caustic potash; (9) benzene is condensed with a tetradecylene in the presence of boron fluoride and phosphoric acid; (10) naphthalene is condensed with a crude dodecylene in the presence of boron fluoride and phosphoric acid; (11) salicylic acid and an olefine mixture of average molecular weight 185 are condensed in the presence of boron fluoride; (12) phenoxyacetic acid and a dodecylene are condensed in the presence of boron fluoride to yield a dodecylphenoxyacetic acid; (13) phenoxyacetic acid and a tetradecylene or (example 14) an olefine polymer of average molecular weight 185 are condensed in the presence of boron fluoride; (15) phenanthrene and a tetradecylene are condensed in the presence of boron fluoride and phosphoric acid; (16) a mixture of isomeric cresotinic acids and a dodecylene-tetradecylene mixture are condensed in the presence of boron fluoride; in each example, the olefine used is a polymer (generally a dimer or a trimer) of an olefine or olefine mixture obtained by dehydrating a higher alcohol or alcohol mixture (generally an isohexyl or isoheptyl alcohol or a mixture thereof) obtained in the synthesis of methanol.