Patent GB-437072-A (GB)
Title: A process for the manufacture of cyclic compounds
IPC: C07C2/66
Filed: 1934-11-30
Abstract: Side chains are introduced into unsaturated non-hydroxylated cyclic compounds (including aromatic compounds) by reacting the compounds with olefinic hydrocarbons in the presence of substantially anhydrous phosphorus pentoxide.  Specified cyclic compounds are benzene, naphthalene, anthracene and their homologues and substitution products, and heterocyclic compounds such as pyridine, quinoline and thiophene.  The olefines may be single olefines such as ethylene, propylene, butylene or amylene, or mixtures thereof, or more complex mixtures such as cracked distillates or cracked vapours or gases or hydrocarbon fractions consisting mainly of olefines containing the same number of carbon atoms in the molecule.  The process may be applied to the manufacture of chemical compounds or to the production of mixtures suitable for use as motor fuels or lubricating oils.  The reaction is preferably effected at 150--300 DEG  C. under a pressure not exceeding 50 atm.  The following methods of procedure are referred to: (a) the vapours of the reagents are passed through phosphorus pentoxide supported on a carrier; (b) phosphorus pentoxide is suspended in a liquid mixture of the reagents; (c) the oxide is suspended in one of the reagents, and the vapour of the other reagent is passed in; (d) the oxide is suspended in an inert liquid, which may or may not be readily separable from the reaction product, and the reagents are then added; thus, gasoline, kerosene or stove oil may be used as inert liquid in the production of motor fuel or lubricating oil by treating aromatic hydrocarbons with light olefines or their mixtures, or cracked gases or vapours.  The process may be continuous or intermittent. When the reaction is effected in the liquid phase, a supplementary agent having a peptizing effect on the phosphorus pentoxide is preferably added to the mixture; suitable peptizing agents are oxidized mineral oils, bitumens containing oxy compounds, such as asphalt, coal-tar pitch, wood-tar pitch, or hard-wood pitch, cresols, aldehydes, ketones, and salts of organic acids such as copper oleate, copper acetate, and copper naphthenate; metallic halides such as cupric chloride, ferric chloride or antimony trichloride may be added instead of or in addition to the peptizing agents.  A stabilizing agent having the effect of a protective colloid, e.g. lamp black, fuller's earth or subdivided silica, may also be added instead of or in addition to the peptizing agent.  In the examples, (1) ethylene is passed at 250 DEG  C. and 27 atm. pressure into a mixture of benzene with subordinate proportions of phosphorus pentoxide, cresol (as peptizing agent), and lamp black; mono- and poly-ethylbenzenes are obtained; (2) as in example 1, except that liquid isobutylene is used instead of ethylene; mono- and poly-butylbenzenes are obtained; (3) ethylene is passed at 225 DEG C. and 40 atm. pressure into a mixture of Borneo light distillate (rich in aromatic hydrocarbons), with phosphorus pentoxide, cresol and lamp black, and the product is distilled to yield a motor fuel and a lubricating oil; (4) a cracked distillate of boiling point 40--87 DEG  C. containing about 80 per cent of olefines, is mixed with benzene and subordinate proportions of phosphorus pentoxide, cresol and lamp black, and the mixture is heated to 225 DEG  C.; a motor fuel and a lubricating oil are obtained by distilling the product; (5) a lubricating oil containing undesired olefines is treated with benzene and phosphorus pentoxide as described in example 4; an oil of high resistance to sludging and oxidation is obtained; (6) a lubricating oil of high aromatic content is treated with ethylene and phosphorus pentoxide as described in example 3, whereby the viscosity index of the oil is raised.  The Specification as open to inspection under Sect. 91 states that the olefinic hydrocarbons in the process described above may be replaced by (1) acetylene or other organic compounds capable of direct addition of halogen, e.g. unsaturated ethers, ketones, aldehydes or organic acid anhydrides, or (2) alkyl or aralkyl halides, or (3) mercaptans of any kind.  It includes an example in which ethylbenzene is obtained by heating benzene with ethyl mercaptan to 300 DEG  C. under pressure in the presence of phosphorus pentoxide, cresol and lamp black. Benzophenone and aromatic nitro compounds are additional peptizing agents mentioned.  This subject - matter does not appear in the Specification as accepted.ALSO:For the production of mixtures suitable for use as motor fuels or lubricating oils, unsaturated non-hydroxylated cyclic compounds (including aromatic compounds) are treated with olefinic hydrocarbons in the presence of substantially anhydrous phosphorus pentoxide.  Specified cyclic compounds are benzene, naphthalene, anthracene and their homologues and substitution products, and heterocyclic compounds such as pyridine, quinoline and thiophene.  The olefines may be single olefines such as ethylene, propylene, butylene or amylene, or mixtures thereof, or more complex mixtures such as cracked distillates or cracked vapours or gases or hydrocarbon fractions consisting mainly of olefines containing the same number of carbon atoms in the molecule.  The reaction is preferably effected at 150--300 DEG  C. under a pressure not exceeding 50 atm.  The following methods of procedure are referred to: (a) the vapours of the reagents are passed through phosphorus pentoxide supported on a carrier; (b) phosphorus pentoxide is suspended in a liquid mixture of the reagents; (c) the oxide is suspended in one of the reagents, and the vapour of the other reagent is passed in; (d) the oxide is suspended in an inert liquid, which may or may not be readily separable from the reaction product, and the reagents are then added; thus, gasoline, kerosene or stove oil may be used as inert liquid in the production of motor fuel or lubricating oil by treating aromatic hydrocarbons with light olefines or their mixtures, or cracked gases or vapours.  The process may be continuous or intermittent.  When the reaction is effected in the liquid phase, a supplementary agent having a peptizing effect on the phosphorus pentoxide is preferably added to the mixture; suitable peptizing agents are oxidized mineral oils, bitumens containing oxy compounds, such as asphalt, coal-tar pitch, wood-tar pitch, or hard-wood pitch, cresols, aldehydes, ketones, and salts of organic acids such as copper oleate, copper acetate, and copper naphthenate; metallic halides such as cupric chloride, ferric chloride or antimony trichloride may be added instead of or in addition to the peptizing agents.  A stabilizing agent having the effect of a protective colloid, e.g. lamp black, fuller's earth or sub-divided silica, may also be added instead of or in addition to the peptizing agent.  In the examples: (1) ethylene is passed at 225 DEG  C. and 40 atm. pressure into a mixture of Borneo light distillate (rich in aromatic hydrocarbons), with phosphorus pentoxide, cresol and lamp black, and the product is distilled to yield a motor fuel and a lubricating oil; (2) a cracked distillate of boiling point 40--87 DEG  C., containing about 80 per cent of olefines, is mixed with benzene and subordinate proportions of phosphorus pentoxide, cresol and lamp black, and the mixture is heated to 225 DEG  C.; a motor fuel and a lubricating oil are obtained by distilling the product; (3) a lubricating oil containing undesired olefines is treated with benzene and phosphorus pentoxide as described in example 2; an oil of high resistance to sludging and oxidation is obtained; (4) a lubricating oil of high aromatic content is treated with ethylene and phosphorus pentoxide as described in example 1, whereby the viscosity index of the oil is raised.  The Specification as open to inspection under Sect. 91 states that the olefinic hydrocarbons in the process described above may be replaced by (1) acetylene or other organic compounds capable of direct addition of halogen, e.g. unsaturated ethers, ketones, aldehydes or organic acid anhydrides or (2) alkyl or aralkyl halides or (3) mercaptans of any kind.  Benzophenone and aromatic nitro compounds are additional peptizing agents mentioned.  This subject-matter does not appear in the Specification as accepted.