Patent GB-798438-A (GB)
Title: Improvements in or relating to the preparation of ortho-substituted phenolic compounds
IPC: C08G8/30
Filed: 1955-04-22
Abstract: The invention comprises compounds of the general formula: <FORM:0798438/IV (b)/1> where R1 and R2 are (1) halogenated ethyl or secondary or tertiary alkyl groups; or (2) secondary or tertiary alkyl or cycloalkyl groups having not less than 8 carbon atoms which can have aryl substituents or cyclo- or substituted cycloaliphatic substituents; or (3) R1 is halogen and R2 is an ethyl group or a secondary or tertiary alkyl group having from 3 to 20 carbon atoms, which can have a halogen substituent or aryl or haloaryl substituents; and where X1 and X2 are hydrogen, halogen, -OR, -NH2, or -COOR1, where R is a hydrocarbon radical and R1 is a hydrocarbon group of 1-20 carbon atoms.  The invention further comprises a process for making o-substituted hydroxy aromatic compounds by reacting a hydroxy aromatic compound having hydrogen on at least one of the nuclear carbon atoms ortho to a hydroxy group, with an organic compound containing ethylenic or acetylenic linkages in the presence of one or more aluminium or magnesium phenoxide catalysts.  The aromatic hydroxy compounds used are mono- or polyhydroxy and mono- or poly-nuclear and may contain as further substituents alkyl, aryl, cycloalkyl, alkoxy, alkenyl, halogen, amino, alkylamino, nitro, aceto or carboxylic ester groups. Examples of those specified are p-chloro-phenol, o-cyclohexyl-phenol, catechol, pyrogallol, eugenol, saligenin, hydroxyacetophenone, hydroxydiphenyls, ethyl hydroxybenzoate, 3 - methyl - naphthol - 1, 9 - aminoanthrol-1, phenanthrol and ar-2-tetralol.  The organic compounds containing ethylenic or acetylenic linkages are mono-, poly-, or cycloolefines, which may be substituted by aryl, aryloxy, alkoxy, hydroxy, carboxylic ester, halogen or amino, and acetylenes.  Among those specified are 2-methyl-amylene, heptadienes, styrene, propargyl ethyl ether, divinyl ether, propenyl acetate, hexene-5-ol-1, methyl oleate, vinyl chloride, 5-amino-pentene-1, and ethyl acetylene. The use of olefines or substituted olefines in the reaction gives an o-alkyl-or o-substituted alkyl-hydroxy aromatic compound; the use of acetylenes results in an o-vinyl- or o-substituted-vinyl-hydroxy aromatic compound, which may react with more phenol to give a di-(hydroxy-aromatic) ethane.  Many compounds prepared by the process are specified.  The reaction may be conducted at temperatures of 0-500 DEG  C. and pressures of 1-3000 atmospheres or higher using a continuous or batch technique, the reaction mixture is then hydrolysed and the products isolated by fractional distillation. Inert solvents such as n-octane, isooctane, cyclohexane, benzene and alkyl benzenes may be used for the reactants, and for gaseous reactants inert gases such as hydrogen, nitrogen, propane, ethane, methane, helium, argon and neon may act as diluents.  The catalyst, of which the phenoxide portion may be the same as or different from the phenol being alkylated, may be preformed or prepared in situ by reaction of the phenol with aluminium or magnesium metal or with a salt of aluminium or magnesium and an acid weaker than the phenol, or by reaction of the sodium phenolate with an aluminium or magnesium halide such as AlCl3 or AlBr3.  In examples, phenol is reacted in the presence of aluminium phenoxide with (1) ethylene, (2) propylene, (4) cyclohexene, (6) to (8) isobutylene, (9) diisobutylene, (10) decene-1, (11) methallyl methyl ether, (12) styrene, (13) isoprene, and in the presence of magnesium phenoxide, with (3) propylene and (5) isobutylene; in Example (14) 1-naphthol is reacted with propylene in the presence of aluminium naphthoxide.  Reference has been directed by the Comptroller to Specification 776,204.ALSO:Anol, eugenol and isoeugenol are polymerized in the presence of an aluminium or magnesium phenoxide catalyst such as aluminium anolate. Polymers are also prepared by reacting phenols with acetylene or acetylenic compounds in the presence of aluminium or magnesium phenoxide catalysts, o-hydroxy styrene and 1 : 1-di-(2-hydroxy-phenyl) ethane being intermediates in the polymer formation between phenol and acetylene.  Reference has been directed by the Comptroller to Specification 776,204, [Group IV (b)].