Patent GB-1112784-A (GB)
Title: Substituted diphenylamines
IPC: C10M169/00
Filed: 1967-03-13
Abstract: Polymeric compounds are stabilized against oxidative deterioration by compounds of the formulae <FORM:1112784/C3/1> where R1 is phenyl or p-tolyl, R2 and R3 are methyl, phenyl or p-tolyl, R4 is methyl, phenyl, p-tolyl or neopentyl, R5 is methyl, phenyl, p-tolyl or 2-phenylisobutyl, R6 is methyl,  <FORM:1112784/C3/2> where R7 is methyl, phenyl or p-tolyl, X is methyl, ethyl, sec-alkyl of 3-10 carbon atoms, a ,a -dimethyl-benzyl, a -methyl benzyl, Cl, Br, carboxyl or a Zn, Cd, Ni, Pb, Sn, Mg or Cu carboxylate, Y is H, methyl, ethyl, sec-alkyl of 3-10 carbon atoms, Cl or Br. <FORM:1112784/C3/3> where R8 is H, primary, secondary or tertiary alkyl (excepting compounds falling within formula II) of 1-10 carbon atoms or alkoxyl of 1-10 carbon atoms which may be straight chain or branched, X1 and Y1 are H (excepting compounds falling within formula I), methyl, ethyl, sec-alkyl of 3-10 carbon atoms, Cl or Br, <FORM:1112784/C3/4> where R9 is phenyl or p-tolyl, R10 is methyl, phenyl, p-tolyl or 2-phenylisobutyl, R11 is methyl, phenyl or p-tolyl,  <FORM:1112784/C3/5> where R12 is phenyl or p-tolyl, R13 is methyl, phenyl or p-tolyl, R14 is methyl, phenyl, p-tolyl or 2-phenylisobutyl and R15 is H, a ,a -dimethylbenzyl, a  - methylbenzyl, triphenylmethyl or a ,a ,p-trimethylbenzyl.  A dialkyl 3,31-thiodipropionate may be present as a further stabilizer.  The polymeric compound may be a natural or synthetic rubber such as an alpha-olefin polymer, polyacetal or acrylonitrile -butadiene-styrene thermoplastic.ALSO:Natural and synthetic lubricants are stabilized against oxidative deterioration by compounds of the formulae <FORM:1112784/C4-C5/1> where R1 is phenyl or p-tolyl, R2 and R3 are methyl, phenyl or p-tolyl, R4 is methyl, phenyl, p-tolyl or neopentyl, R5 is methyl, phenyl, p-tolyl or 2-phenylisobutyl, R6 is methyl, <FORM:1112784/C4-C5/2> where R7 is methyl, phenyl or p-tolyl, X is methyl, ethyl, sec-alkyl of 3-10 carbon atoms, a ,a -dimethyl-benzyl, a -methyl benzyl, Cl, Br, carboxyl or a Zn, Cd, Ni, Pb, Sn, Mg or Cu carboxylate, Y is H, methyl, ethyl, sec-alkyl of 3-10 carbon atoms, Cl or Br <FORM:1112784/C4-C5/3> where R8 is H, primary, secondary or tertiary alkyl (excepting compounds falling within Formula II) of 1-10 carbon atoms or alkoxyl of 1-10 carbon atoms which may be straight chain or branched, X1 and Y1 are H (excepting compounds falling within Formula I), methyl, ethyl, sec-alkyl of 3-10 carbon atoms, Cl or <FORM:1112784/C4-C5/4> where R9 is phenyl or p-tolyl, R10 is methyl, phenyl, p-tolyl or 2-phenylisobutyl, R11 is methyl, phenyl or p-tolyl, <FORM:1112784/C4-C5/5> where R12 is phenyl or p-tolyl, R13 is methyl, phenyl or p-tolyl, R14 is methyl, phenyl, p-tolyl or 2-phenylisobutyl and R15 is H, a ,a -dimethylbenzyl, a  - methylbenzyl, triphenylmethyl or a ,a ,-trimethylbenzyl.  A dialkyl 3,31-thiodipropionate may be present as a further stabilizer.  The lubricant may be a natural lubricating oil obtained from petroleum or a synthetic lubricant such as alkyl esters of dicarboxylic acids or fatty acid esters of polyols.ALSO:The invention comprises compounds of the formulae <FORM:1112784/C2/1> where R1 is phenyl or p-tolyl, R2 and R3 are methyl, phenyl or p-tolyl, R4 is methyl, phenyl, p-tolyl or neopentyl and R5 is methyl, phenyl, p-tolyl or 2-phenylisobutyl, R6 is methyl, <FORM:1112784/C2/2> where R7 is methyl, phenyl or p-tolyl, X is methyl, ethyl, sec-alkyl of 3-10 carbon atoms, a ,a -dimethylbenzyl, a -methylbenzyl, Cl, Br, carboxyl or a Zn, Cd, Ni, Pb, Sn, Mg or Cu carboxylate, Y is H, methyl, ethyl, secalkyl of 3-10 carbon atoms, Cl or Br, <FORM:1112784/C2/3> where R8 is H, primary, secondary or tertiary alkyl (excepting compounds falling within Formula (II) of 1-10 carbon atoms or alkoxyl of 1-10 carbon atoms which may be straight chain or branched, X1 and Y1 are H (excepting compounds falling within Formula (I)), methyl, ethyl, sec-alkyl of 3-10 carbon atoms, Cl or Br, <FORM:1112784/C2/4> where R9 is phenyl or p-tolyl, R10 is methyl, phenyl, p-tolyl or 2-phenylisobutyl, R11 is methyl, phenyl or p-tolyl, <FORM:1112784/C2/5> where R12 is phenyl or p-tolyl, R13 is methyl, phenyl or p-tolyl, R14 is methyl, phenyl, p-tolyl or 2-phenylisobutyl and R15 is H, a ,a -dimethylbenzyl, a  - methylbenzyl, triphenylmethyl or a ,a ,p-trimethylbenzyl.  The compounds may be prepared by alkylating the appropriate diphenylamine or phenylnaphthylamine with the appropriate olefin using an acid catalyst and, if desired, subsequently brominating, chlorinating or neutralizing the product. The unsymmetric diphenylamines may be prepared by condensing an appropriately substituted aniline with o-chlorobenzoic acid, decarboxylating if desired, and alkylating in the presence of an acid catalyst, or by alkylating diphenylamine with a vinyl type olefin and further alkylating the product with an appropriate alkylating agent in the presence of an acid catalyst.