Patent GB-473438-A (GB)
Title: A process for the production of substituted phenols and fuels
IPC: C07C37/14
Filed: 1936-05-04
Abstract: Alkylated phenols and fuel oils of reduced olefine content are obtained from cracking benzines containing a substantial proportion of olefinic hydrocarbons, or from fractions thereof consisting of mixtures of substances, by treating the benzines or their fractions with phenol or a homologue thereof in the presence of a metal halide such as aluminium chloride, zinc chloride or ferric chloride, with or without a hydrogen halide; the products are then separated.  The hydrogen halide, when used, may be taken as such or formed in situ from an organic halide such as benzyl chloride or a tertiary aliphatic or alicyclic halide.  The volatile portions of the benzine may be vaporized during the reaction and may then be (1) passed with hydrogen halide over a known catalyst, e.g. asbestos and bismuth chloride, the resulting alkyl halides being collected separately and reacted with the phenol in the presence of a metal halide, as described above, or (2) passed in admixture with hydrogen halide into a high-boiling solvent also capable of reacting with hydrogen halide, e.g. dipentene or a tertiary alcohol, or a mixture containing such a solvent, e.g. pine oil, the mixture of halides so obtained being then brought to reaction with the phenol under the conditions described above, or (3) passed, with or without hydrogen halide, into a mixture of a phenol and a metal halide, or (4) passed, as such or as a solution in a solvent of the type defined above, into a reacting mixture of phenol, organic halide, and metal halide. When the unsaturated constituents of the benzine consist entirely or mainly of mono-olefines, the alkylphenols obtained may be refined by distillation and used for the manufacture of synthetic resins by reaction with aldehydes.  When the benzine contains a substantial proportion of hydrocarbons with more than one double bond, distillation of the alkylphenols yields a resinous residue useful in the manufacture of varnishes.  The unreacted portion of the benzine is preferably freed from halogen compounds, e.g. by saponification with alkalies, before it is used as a fuel.  In the examples: (1) a mixture of a cracking benzine, phenol and aluminium chloride is treated with gaseous hydrogen chloride, and the product is steam-distilled to remove the unreacted fraction of the benzine and unchanged phenol; the residual alkylphenols may be distilled in vacuo and condensed with formaldehyde; (2) volatile fractions and hydrogen chloride evolved from the reaction mixture of example 1 are passed over an asbestos and bismuth chloride catalyst at 80 DEG  C. and the products are condensed and reacted with phenol in the presence of aluminium chloride and zinc chloride; the condensation step may be omitted, and in this case two reaction vessels in series may be used; the unreacted benzine fractions are separated from the alkylphenols produced, the latter including p-tertiary-amylphenol; (3) a cresol mixture containing aluminium chloride and zinc chloride is saturated with hydrogen chloride, and then treated with a cracking benzine, the products being separated as before; (4) a cracking benzine is heated with phenol and aluminium chloride, and the vapours from the reaction vessel are mixed with hydrogen chloride and passed into a mixture of phenol and aluminium chloride, either directly or after passage over an asbestos catalyst; the products of each reaction are separated, as before; (5) a fraction, boiling up to 85 DEG  C., of the benzine used in example 4 is mixed with phenol and zinc chloride, and tert.-butyl chloride is added, the products being then separated; in place of the butyl chloride, another tertiary alkyl chloride or a tertiary dichloride, e.g. dipentene dihydrochloride, or benzyl chloride may be used; if aluminium chloride is used instead of zinc chloride, addition of tert.butyl chloride or like reagent is unnecessary; (6) a fraction, boiling above 85 DEG  C., of the benzine used in example 4 is treated with aluminium chloride and commercial xylenol; the unreacted benzine is then removed, and the residual mixture of unreacted xylenols with substituted phenols produced in the reaction is used for the manufacture of synthetic resins.  The Specification as open to inspection under Sect. 91 states that sulphuric and acetic acids, or hydrochloric and acetic acids, may be used as condensing agents in the process, and includes an example in which a cracking benzine is treated with phenol in the presence of sulphuric and acetic acids, the products being then separated.  It states also that the whole of the benzine may be vaporized and passed with hydrogen chloride over a catalyst, the products being then brought to reaction with a phenol.  This subject-matter does not appear in the Specification as accepted.ALSO:Fuel oils of reduced olefine content are obtained from cracking benzines containing a substantial proportion of olefinic hydrocarbons, or from fractions thereof consisting of mixtures of substances, by treating the benzines or their fractions with phenol or a homologue thereof in the presence of a metal halide such as aluminium chloride, zinc chloride or ferric chloride, with or without a hydrogen halide; the products are then separated. The hydrogen halide, when used may be taken as such or formed in situ from an organic halide such as benzyl chloride or a tertiary aliphatic or alicyclic halide.  The unreacted portion of the benzine is preferably freed from halogen compounds, e.g. by saponification with alkalies, before it is used as a fuel.  In examples, (1) a mixture of a cracking benzine, phenol and aluminium chloride is treated with gaseous hydrogen chloride, and the product is steam-distilled to remove the unreacted fraction of the benzine and unchanged phenol; (2) a cresol mixture containing aluminium chloride and zinc chloride is saturated with hydrogen chloride, and then treated with a cracking benzine, the products being separated as before; (3) a fraction, boiling up to 85 DEG  C., of a cracking benzine is mixed with phenol and zinc chloride, and tert.-butyl chloride is added, the products being then separated; in place of the butyl chloride, another tertiary alkyl chloride or a tertiary dichloride, e.g. dipentene dihydrochloride or benzyl chloride, may be used; if aluminium chloride is used instead of zinc chloride, addition of tert.-butyl chloride or like reagent is unnecessary; (4) a fraction, boiling above 85 DEG  C., of a cracking benzine is treated with aluminium chloride and commercial zylenol, and the unreacted benzine is removed.  The Specification as open to inspection under Sect. 91 states that sulphuric and acetic acids, or hydrochloric and acetic acids, may be used as condensing agents in the process, and includes an example in which a cracking benzine is treated with phenol in the presence of sulphuric and acetic acids, the products being then separated.  This subject-matter does not appear in the Specification as accepted.