Patent GB-807229-A (GB)
Title: Improvements in or relating to amine alkylation
IPC: C07C209/68
Filed: 1955-04-21
Abstract: Ortho-substituted primary or secondary aromatic amines are made by reacting (1) an aromatic amine having at least one hydrogen on the amino nitrogen and a hydrogen on at least one nuclear carbon atom ortho to the amino group with (2) an olefin, acetylene, olefinically unsaturated amine or ether, or acetylenically unsaturated amine or ether, the process being conducted in the presence of one or more aluminium anilide-type catalysts at temperatures in the range of 50 DEG  to 500 DEG  C. and at pressures of less than 100 atmospheres and substantially in the absence of hydrogen.  The invention also comprises amines of the general formula <FORM:0807229/IV (b)/1> where R1 is a methyl or ethyl radical, R2 is an ethyl or isopropyl radical, and X1 and X2 are the same or different and are hydrogen or halogen atoms or alkoxy groups.  In the above process "aluminium amide-type" means an aluminium amide obtainable by reacting aluminium with the amino hydrogen from a primary or secondary aromatic amine in which the aromatic portion can be mono- or polynuclear and which may or may not have other substituents thereon.  The substituent introduced into the ortho-position of the amine in the above process comprises an alkyl group when an olefine is used or an amino- or ether-substituted alkyl group when an olefinic amine or ether is used.  When heptyne-1 is reacted with aniline however the product is of the formula <FORM:0807229/IV (b)/2> Aromatic amines which may be used in the process may be mono- or poly-nuclear and mono-or poly-amino such as amino benzenes, naphthalenes, anthracenes and phenanthrenes and may carry alkyl, aryl, alkaryl, cycloalkyl, substituted cycloalkyl, halogen, alkoxy and aryloxy substituents on the aromatic ring.  A large number are mentioned including aniline, the toluidines, anisidines, chloroanilines, N-methylaniline and anisidine, phenylene diamine, diphenylamine, benzidine, naphthylamine and N-isopropylanthrylamine.  Olefines mentioned include ethylene, propylene, butylene, cyclohexene, dodecene, styrene, vinyl ethyl ether, divinyl ether, ethylamine, crotonyl amine and 5-amino-pentene-1.  Acetylene, propyne, butyne, heptyne and decyne may also be used.  In the aluminium anilide-type catalyst the aromatic portion may be the same as or different from that of the aromatic amine being alkylated.  The catalyst may be made by reacting an aromatic amine with aluminium metal, an aluminium alkyl, lithium aluminium hydride or an aromatic sodium compound such as phenyl sodium and aluminium chloride, or by reacting an alkali or alkaline-earth metal anilide-type compound with an aluminium halide. The process may be effected without a diluent or in the presence of paraffins, cycloparaffins or aromatic hydrocarbons such as n-octane, iso-octane, cyclohexane, benzene and alkyl benzenes, or an excess of the amine may be used. Gaseous diluents such as propane, methane, ethane, nitrogen, helium and argon may also be used.  The process may be conducted in a batch manner or continuously by passing the reactants together with the catalyst through a reaction zone, the product being separated by hydrolysis and continuous fractional distillation.  In examples ethylene is reacted with (1) aniline, (2) o-toluidine, (5) 1-naphthylamine, (6) N-methyl aniline, (10) N-ethyl aniline, and (11) N-ethyl-3-chloroaniline; propylene is reactedl with (3) aniline and (7) N-methyl aniline; isobutylene is reacted with (4) aniline; and decene-1 (8) and cyclohexene (9) one each reacted with N-methyl aniline.  Reference has been directed by the Comptroller to Specification 756,538.