Patent GB-980233-A (GB)
Title: Substituted anilines and compositions containing the same
IPC: C08K5/18
Filed: 1961-06-13
Abstract: An invention comprises isobornyloxyanilines of the general formula <FORM:0980233/C2/1> in which R represents a 2-isobornyl group and R1 is a hydrogen atom, an aliphatic group having 1 to 20 carbon atoms or an alicyclic group having 5 or 6 carbon atoms in the alicyclic ring. Specified compounds claimed are para-(isobornyl-2-oxy) aniline, N-isopropyl para-(isobornyl-2-oxy) aniline, N-cyclohexyl para-(isobornyl-2-oxy) aniline.  The isobornyloxyanilines may be prepared by reducing 2-isobornyl para-nitrophenyl ether to para-(isobornyl-2-oxy) aniline and, when an N-substituted aniline is required, monoalkylating or alkenylating the aniline with an alkylating or alkenylating agent having 1 to 20 carbon atoms, e.g. a dialkyl ketone, and reducing with hydrogen in the presence of an hydrogenating catalyst or with a cycloalkylating agent having 5 to 6 carbon atoms in the alicyclic ring, e.g. a cycloalkanone and reducing with hydrogen the resulting Schiff's base in the presence of the hydrogenating catalyst.  The 2-isobornyl para-nitrophenyl ether employed may conveniently be prepared by the condensation of para-nitrophenol and camphene in the presence of a boron trifluoride catalyst.  Specified groups for R1 are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary-butyl, tertiary-butyl, amyl, hexyl, octyl, secondary-octyl, nonyl, decyl, dodecyl, octadecyl, cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, ethylcyclohexyl, propyl-cyclohexyl, isopropylcyclohexyl, butylcyclohexyl, amylcyclohexyl, cyclopentyl, methylcyclopentyl, ethylcyclopentyl, propylcyclopentyl, isopropylcyclopentyl, butylcyclopentyl and amylcyclopentyl.  In an example to a mixture of paranitrophenol, chloroform and boron trifluoride etherate was added a solution of camphene in chloroform at a temperature below 25 DEG  C.  The reaction mixture was stirred at room temperature for 14 hours, then diluted with ether and washed well with 10% sodium hydroxide solution and water to remove unreacted paranitrophenol.  The ethereal solution was dried and evaporated to give isobornyl para-nitrophenyl ether which was reduced using palladium on charcoal as a catalyst.  The catalyst was removed by filtration and the ethanol by distillation.  The residual oil was distilled to give para-(isobornyl-2-oxy) aniline which crystallized on standing. Other examples are given.  The compounds are used as antidegradants for different kinds of rubber.ALSO:Compounds having the general formula <FORM:0980233/C3/1> in which R represents 2-isobornyl groups and R1 is a hydrogen atom, an aliphatic group having 1-20 carbon atoms or an alicyclic group having 5-6 carbon atoms in the alicylic ring, are used as anti-degradants for natural rubber in its various forms, for example latex, crepe, smoked sheets, gutta-percha, balata and cyclo rubbers and synthetic elastomers such as polybutadiene, polyisoprene and isobutylene copolymerized with a small proportion of a diolefin.  They may be used for unvulcanized as well as vulcanized rubber and may be added to styrene-butadiene rubber at the time of manufacture.