1127-42-0Relevant articles and documents
Reductive activation of arenes: XIV.Effect of medium on the products ratio in the alkylation of nitrobenzene radical anion sodium salt
Selivanov,Shteingarts
, p. 1719 - 1722 (2001)
The product of nitrobenzene reduction by 1 equiv of sodium reacted with tert-butyl iodide in liquid ammonia and its mixtures with tetrahydrofuran and hexamethylphosphoramide to afford a mixture of compounds alkylated either by the functional group (N-alkylation) or at the benzene ring (C-alkylation). The ratio of N-and C-alkylation products decreases in the solvents series NH3-THF (5.7) > NH3 (1.0) > NH3-HMPA (0.6).
REDUCTIVE ACTIVATION OF ARENES. VI. REACTION OF THE PRODUCT OF THE ONE-ELECTRON REDUCTION OF NITROBENZENE BY SODIUM IN LIQUID AMMONIA WITH ISOMERIC BUTYL IODIDES
Selivanov, V. A.,Shteingarts, V. D.
, p. 1654 - 1662 (2007/10/02)
The reaction of the product of the reduction of nitrobenzene by one equivalent of sodium in liquid ammonia with n-butyl, sec-butyl, and isobutyl iodides leads to the corresponding N,O-dialkylphenylhydroxylamines as the major products through an SN2 mechanism.The analogous reaction with tert-butyl iodide gives approximately equal amounts of products of butylation in the benzene ring, namely, 4-tert-butylnitrobenzene and 4-tert-butylaniline, and at the nitro-group, namely, N-tert-butylaniline and N-tert-butylphenylhydroxylamine.The formation of these N-tert-butyl produ cts is probably the result of the transfer of an electron from the nitrobenzene radical-anion to the alkyl iodide and subsequent recombination of the tert-butyl radical with the nitrobenzene radical-anion.The increase in the fraction of tert-butylation at the nitro group in going from hexamethylphosphorotriamide or its mixture with tetrahydrofuran as the solvent to liquid nitrogen is probably a consequence of a greater role for interaction with the medium, which affects the distribution of the spin density in the nitrobenzene radical-anion or on the relative stability of the transition states responsible for the competing recombination pathways.