Amination of m-dialkylbenzenes with trichloramine-aluminum chloride

Chemistry of N-bromamines and N-chloramines

“…RíNHCl + Fe2+ -> R2NH Factors affecting the orientation, as well as the extent of sidechain attack, in amination of alkylbenzenes include the size of the side-chain, solvent, and inductive effects. 166 In addition, positional selectivity was influenced by reaction temperature and the nature of the catalyst.156 Relative rates were determined for the three aminating species153•154 (Table VII). A scrutiny of the entire data indicates varying degrees of electrophilic character associated with the attacking radicals.…”

Chemistry of N-haloamines. 25. Amination of acyclic and cyclic alkanes with trichloramine-aluminum chloride

“…Dicyclohexyl gave only small amounts of basic material, in contrast to less hindered cycloalkanes (methylcyclohexane, decalin, and hydrindan).12•15 Also, the Ce amine from 3-methylpentane is derived from the least hindered cation (2-methyl-2-pentyl) from rearrangement. Similarly, both 2-(p-tolyl)pentane (11) and 3-(/z-tolyl)pentane ( 12) produced the same product, 2-(ptolyl)-2-pentylamine. 19 The size of the nucleophile may favor interaction with the least hindered carbocation.…”

Organocatalysis with a Fluorous Tag: Asymmetric Reduction of Imines with Trichlorosilane Catalyzed by Amino Acid-Derived Formamides

“…The same strategy has now been employed in the synthesis of 3c , d and 5a − d . However, while 3,5-( t -Bu) 2 C 6 H 3 NH 2 , required for the synthesis of 3d , is commercially available, its lower homologue 3,5-( i -Pr) 2 C 6 H 3 NH 2 ( 8 ) was essentially unknown . We have now synthesized 8 (Scheme ) via reduction of the corresponding nitro derivative 7 (SnCl 2 , 99%), which in turn was prepared from 2,6-diisopropyl-4-nitroaniline ( 6 ) in two steps, using diazotation (NaNO 2 , AcOH), followed by reduction (FeSO 4 , DMF; 63%) …”