C. Siswanto et Jf. Rathman, SELECTIVE N-ALKYLATION OF ANILINE BY MICELLAR CATALYSIS, Journal of colloid and interface science, 196(1), 1997, pp. 99-102
Reactions of aniline with 1-bromobutane to form N-butylaniline and N,N
-dibutylaniline were performed in single-phase aqueous surfactant syst
ems. Reaction rate, yield, and selectivity of the N-alkyl product were
monitored for different initial compositions, and much higher reactio
n rate, yield, and selectivity were observed in comparison to reaction
s of neat components. Excess aniline increased yield and selectivity,
while excess 1-bromobutane had the opposite effect. The lipophilic rea
ctant (1-bromobutane) and both products are solubilized almost entirel
y in the surfactant micelles. The formation of relatively small amount
s of N,N-dibutylaniline effectively inhibited further alkylation of N-
butylaniline, so that high selectivities (>20) of the N-alkyl were obt
ained. Added sodium hydroxide caused small decreases in yield and sele
ctivity and showed that pi-I-dependent dissociation equilibria of the
various amine species do not have a major influence on reaction charac
teristics. (C) 1997 Academic Press.