Trichloramine, amination

Subsequently it was found that trimethylsilyl azide in triflic acid is a more efficient and improved reagent for aminations (169). Amination of toluene in the presence of trichloramine—A1 CL proceeds predominantly at the / -position. 

Die Reaktion von Trichloramin mit tert.-Alkyl-chloriden in Dichlormethan in Gegenwart von Aluminiumchlorid fuhrt in einigen Fallen zur Bildung der entsprechenden tert.-Alkyl-amine in hohen Ausbeuten1. 

Figure 11.13. General scheme of breakpoint chlorination difference between total residual Cl and chlorine dose reflects chlorine demand, primarily from ammonium and amines. Before breakpoint, most Cl is in combined forms, primarily mono- and dichloramine after the breakpoint, the combined residual consists of slow-reacting organic chloramines. Added Cl remains in free form after the breakpoint. Sharpness of breakpoint and minimum observed Cl concentration depend on pH, temperature, and time of reaction. Loss of residual Cl at breakpoint is caused by oxidation of di- and trichloramines to Nj according to reactions 33a and 33b and other reactions. (Adapted from Brezonik, 1994.)...

Amination of diphenyl with trichloramine in odichlorobenzene in the presence of aluminum chloride gives 3-aminodiphenyl in up to 27% yield.4... 

The amination reaction is not limited to aromatic hydrocarbons it is also applicable to r-alkanes. r-Butyl chloride reacts with trichloramine in the presence of aluminum chloride to give f-butylamine in 88% yield.5 Methylcyclohexane is converted into 1-amino-1-methylcyclohexane in yields as high as 67% (based on trichloramine). The most satisfactory conditions use C7H14-A1C13-NC13 in a 2 2 1 ratio with methylene chloride as solvent and a temperature of 0 5°.6 Under the same conditions adamantane gives 1 -aminoadamantane in nearly quantitative yield.7... 

Amination. Dimethylformamide. Tetrakis(dimethylamino) titanium. Trichloramine. 

The chemistry of chloramines has been reviewed by Kovacic et al. (1970). In water, depending on pH and concentration, monochloramine (NH2CI), dichloramine (NHCI2), or trichloramine (NCI3), may be present, in addition to organic chloramines derived from amines. 

---