Amines nitro compds

TNT forms charge-transfer, or 7r, complexes with polycyclic aromatic hydrocarbons, aromatic amines, and aromatic nitro compds a number of these are listed below in Table 2. The complexes with three amines (diphenylamine, diethyl-aniline, p-anisidine) have characteristic colors this forms the basis for a rapid and convenient thin-layer chromatographic analytical procedure (Ref 34) for the identification of very small amounts of TNT. (For a discussion of the many color reactions of TNT, and of composite expls containing it, see Vol 3, C405-L ff)... 

Amines and hydroxylamines from nitro compds. nhOH... 

Copper(I,II) sulfite Nitro compds. from amines... 

Palladium-carbon Amines from nitro compds. 

Nickel boride hydrogen chloride Ar. amines from nitro compds. Selective reduction... 

Palladium II)-Schiff base complex Amines from nitro compds. s. 44, 54... 

Alcohols from oxo compds. 20 eqs. NaBH4 added to a soln. of 5 eqs. ZrC in THF at room temp, under N2, a soln. of 4 eqs. acetophenone in the same solvent added, and the mixture stirred at room temp, for 5 h - 1-phenylethanol. Y 96%. ZrCl4 is inexpensive, easy to use, and does not affect ar. nitro compds. and bromides. F.e., also reduction of carboxylic acids, esters and halides to prim, alcohols, and amides, oximes, alkoximes, nitriles, and imines to amines, s. S. Itsuno et al.. Synthesis 1988, 995-6. 

A novel insoluble green complex of palladium(II) and N,N -salicylideneethylenedi-amine (salen) functions as a selective heterogeneous catalyst, notably for the reduction of alkynes in the presence of alkenes, and of the latter in the presence of certain functional groups. E ciVEthylene from acetylene derivs. A soln. of startg. acetylene deriv. in EtOH hydrogenated for 17 min in the presence of the palladium(ll) complex (prepared from potassium tetrachloropalladate, salen, and triethylamine) cis-product. Y 100%. Reduction of alkenes is considerably slower however, terminal olefins may be reduced in the presence of internal olefins esters, oxo compds., dibenzyl ether, and iodobenzene were unaffected. F.e., also ar. amines from nitro compds. s. J.M. Kerr et al.. Tetrahedron Letters 29, 5545-48 (1988). 

Triflic acid added to benzene under N, after warming to 55 added dropwise, the soln. stirred until evolution of N2 ceased (50 min total reaction time), cooled to room temp., and poured onto ice aniline. Y 95%. The method is fast, convenient, and quantitative for amination of alkyl- and monohalogeno-arenes substrates that are protonated by triflic acid (e.g. ar. nitro compds.), or strongly deactivated arenes, are not suitable. F.e.s. G.A. Olah, T.D. Ernst, J. Org. Chem. 54, 1203 (1989). 

Potassium per oxymonosulfate j tetra-n-butylammonium hydrogen sulfate Ar. nitro compds. from amines NH2... 

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