Patent GB-469548-A (GB)
Title: Improvements in or relating to condensation reactions
IPC: C07C2/70
Filed: 1935-12-23
Abstract: Condensation products are manufactured by condensing one or more organic compounds having one or more olefinic double linkages with one or more aromatic or mixed aromatic alicyclic hydrocarbons, their homologues or substitution products, in the presence of aqueous perchloric acid, with or without other acids, e.g. sulphuric, acetic or phosphoric acid.  Suitable aromatic components are benzene hydrocarbons, naphthalene, anthracene, phenanthrene, tetrahydronaphthalene, octahydroanthracene, chlorobenzene, 1-chloronaphthalene, phenol and its homologues and substitution products, e.g. chloro- and nitrophenols and cresols, 1- and 2 - naphthol, o- and p - oxydiphenyl, p-p<1>-dioxydiphenylmethane, phenol and naphthol ethers, dioxy- and trioxybenzenes and their ethers, and diphenylene oxide. As olefinic compounds may be employed true olefines from ethylene to its high homologues, e.g. cetene, octadecene, eicosene, and docosene, cyclo-olefines, e.g. cyclopentene, cyclohexene and its homologues, pinene, camphene and octahydronaphthalenes, aromatic olefines, e.g. styrene and stilbene, cyclo-olefinic aromatic hydrocarbons, e.g. dihydronaphthalene, substituted olefinic hydrocarbons, e.g. unsaturated halogen hydrocarbons, alcohols, aldehydes, ketones and carboxylic acids, and derivatives and substitution products thereof, e.g. allyl bromide, allyl and oleic alcohols and their ethers and esters, acrolein, crotonaldehyde, cinnamic aldehyde, mesityl oxide, benzalacetone, acrylic, crotonic, undecylenic, oleic, elaidic, maleic, fumaric, cinnamic and tetrahydrobenzoic acids and their anhydrides and esters. In examples, the following substances are condensed together, in the presence of 70 per cent perchloric acid unless otherwise stated: (1) toluene and isobutylene (or the gas mixture obtained by treating isobutyl alcohol with dehydrating agents), producing mono-and di-tert.-butyltoluene; (2) tetrahydronaphthalene and octahydronaphthalene (obtained by treating 2-decalol with dehydrating agents), yielding decalyltetrahydronaphthalene; (3) naphthalene and trimethylethylene to produce tert.-amylnaphthalene and some diamylnaphthalene; (4) phenol and cyclohexene to yield mono-, di- and tri-cyclohexylphenols; (5) o-cresol and octene (obtained by distilling n-octyl alcohol with phosphoric acid), producing sec.-octyl-o-cresols; (6) m-cresol and propylene to produce mono- and di-isopropyl-m-cresols; the propylene may be replaced by ethylene, yielding the corresponding ethylated m-cresols; (7) p-chlorophenol and dodecene (obtained by distilling n-dodecyl alcohol with anhydrous zinc chloride), producing sec.-dodecyl - p - chlorophenol; (8) o-nitrotoluene and propylene to yield isopropyl-o-nitrotoluene; (9) ar.-6-tetralol and dihydronaphthalene (in the presence of 60 per cent perchloric acid); (10) 1-naphthol and methylcyclohexene (obtained by dehydration of a technical mixture of isomeric methylcyclohexanols) (in the presence of 50 per cent perchloric acid); (11) 2-naphthol and 5-(methylcyclohexyl) - 1 - methylcyclohexene - 1 : 2 (obtained by dehydration of 4-(methylcyclohexyl)-2-methylcyclohexanol which is obtainable by condensing technical methylcyclohexene with o-cresol and hydrogenating the product) (in the presence of 60 per cent perchloric acid); (12) anisol and butylene gas (obtained by dehydration of n-butyl alcohol) (in the presence of 60 per cent perchloric acid), yielding o- and p-sec.-butylanisol; (13) p-p<1>-dioxydiphenylmethane and octahydronaphthalene; (14) resorcinol and styrene (in the presence of acetic acid and 25 per cent perchloric acid), producing phenylethylresorcinol and some di-(phenylethyl)-resorcinol; (15) phenol and oleic acid, the product being esterified with butanol to produce oxyphenylstearic acid butyl ester (which may be hydrogenated to oxycyclohexylstearic acid butyl ester) and some oxyphenylenedistearic acid dibutyl ester; (16) o-cresol and undecylenic acid to yield a cresylundecanic acid and the monolactone of the corresponding diundecanic acid; (17) p-cresol and cyclohexylidenecyclohexanone; (18) a technical mixture of cresols, and sperm oil or glycerides of unsaturated or hydroxy fatty acids; (19) 2-naphthol and oleic acid; (20) 2-naphthol and crotonic acid to yield a product of the probable formula <FORM:0469548/IV/1> (21) 1-naphthol and maleic anhydride to produce a 1-hydroxynaphthylsuccinic acid in which the succinic radicle is probably in the 2-position; (22) hydroquinone and cinnamic acid (in the presence of acetic acid and 70 per cent perchloric acid), producing 4-phenyl-6-hydroxyhydrocoumarine.  Azo dyes.--The product of example (21) above yields with diazotized p-nitraniline a blue dyestuff which changes to red with acids.  The Specification as open to inspection under Sect. 91 contains also examples of the condensation of o-cresoxyacetic acid and a cracked benzine fraction in the presence of 70 per cent perchloric acid, o-cresol and octene in the presence of hydrochloric acid and 40 per cent perchloric acid (or perchloric acid liberated in situ from sodium perchlorate), chloronaphthalene and cinnamic acid in the presence of 70 per cent perchloric acid, a -methylnaphthalene and oleic alcohol in the presence of 60 per cent perchloric acid, and o-cresol and octadecadiene (obtained by splitting off water from oleic alcohol) in the presence of 60 per cent perchloric acid.  This subject-matter does not appear in the Specification as accepted.