Amination of Toluene with Trichloramine-Lewis Acid Catalyst¹

Chemistry of n-haloamines. XVIII. Rearrangement of 1-N,N-dichloroaminoapocamphane by aluminum chloride

“…Yields of 93-99% of the iV,iV-dichloroamine generally were obtained, as indicated by titration for positive chlorine. 33 Reaction of l-AvV-Dichloroaminoapocamphane (2) with Aluminum Chloride. A 50-ml solution of 2 (ca.…”

Nitrenium Ions and Problem of Direct Electrophilic Amination of Aromatic Compounds

“…An unusual orientation was observed in the amination of benzene derivatives with NHCl 2 or NCl 3 in the presence of AlCl 3 : m-toluidine was obtained from toluene (yield 25 and 42%, respectively), m-chloroaniline from chlorobenzene, and 3,5-xylidine from m-xylene [107,108]. This reaction direction was rationalized in terms of the addition-elimination mechanism involving initial attack by Cl + ion on the substrate and subsequent addition of NCl 2 -anion [109] (Scheme 5).…”

“…N-Halo amines have long been used as reagents for amination of aromatic compounds (see [105][106][107][108][109] and references therein). The amination of benzene, toluene, tert-butylbenzene, N,N-dimethylaniline, and naphthalene with chloro(dimethyl)amine in nitromethane or nitropropane in the presence of AlCl 3 gave the corresponding dimethylamino-substituted arenes in 90, 54, 47, 21, and 32% yield, respectively [105].…”

Benzylic bromination in the reactions of benzyl methyl ether and related compounds with N-bromosuccinimide

“…The identification of nmr absorptions for C8H8CH(Br)-OCH2C8H8 and for the N-succinimidyl derivatives of the various ethers (except for --methoxybenzylsuccinimide) was made by inference as based on the absorptions of structurally related 4.93 C8H6CH(Br)OC8H4Cl-p € C8H6CH(NC4H402)0C8H4Cl-p/ e " Tetramethylsilane was used as an internal reference. 6 The succinimidyl group proton signal is at 7.47. 6 The succinimidyl group proton signal is at r 7.75. d The succinimidyl group proton signal is at r 7.50.…”

“…6 The succinimidyl group proton signal is at 7.47. 6 The succinimidyl group proton signal is at r 7.75. d The succinimidyl group proton signal is at r 7.50.…”