The Mild N-Nitrosation of Secondary Amines with Trichloro Nitromethane

Pathways for N-Nitroso Compound Formation: Secondary Amines and Beyond

“…The employment of organic nitro compounds as nitrosating agent precursors is much less widespread compared to sodium nitrite, nitrogen oxides, and nitrosyl halides and derivatives. In general, N-nitrosation by the means of organic nitro compounds requires harsher conditions (i.e., high temperatures 84 and/or long reaction times 80 ) and to the best of our knowledge has only been applied to secondary and tertiary amines.…”

“…Some organic nitro compounds can generate effective nitrosating agents. These nitrosating agent precursors include bromonitromethane, 79 trichloronitromethane, 80 and tetranitromethane. 81 In the case of tetranitromethane, it may be that homolysis occurs generating NO 2 /N 2 O 4 .…”

“…81 In the case of tetranitromethane, it may be that homolysis occurs generating NO 2 /N 2 O 4 . Trichloronitromethane is believed to decompose into nitrosyl chloride, 80 the active nitrosating agent. N-Nitrosation by bromonitromethane is a result of substitution of the bromine by a secondary amine followed by nitrite formation via an iminium intermediate which reacts with nitrite (Scheme 36).…”

Tin(IV) Chloride-Sodium Nitrite as a New Nitrosating Agent for N-Nitrosa­tion of Amines, Amides and Ureas under Mild and Heterogeneous Conditions

“…20 and more recently charcoal impregnated with N 2 O 4 , 21 bis(triphenylphosphine)nitrogen(1+) nitrite, 22 trichloronitromethane, 23 and some supramolecular complexes of NO x /NO + , 24 have also been reported.…”

Selective N-Nitrosation of Amines,N-Alkylamides andN-Alkylureasby N2O4Supported on Cross-Linked Polyvinylpyrrolidone(PVP-N2O4)

“…7a,9 N-Nitrosamines and N-nitrosoamides are regarded as carcinogenic compounds and special care should be taken during their synthesis and handling. 5a Nitrosamines are usually synthesized by the reaction of secondary amines with nitrosating agents 4a,9a such as, nitrous acid (generated in situ from sodium nitrite and acids in aqueous or chloroform/HCl media), 10 alkyl nitrites, 11 nitrosyl chloride (NOCl), 12 nitosonium tetrafluoroborate, 12 [NO + •crown•H(NO 3 ) 2 -], 13 trichloronitromethane, 14 nitrogen oxides (N 2 O 3 15 or N 2 O 4 16 ), NO in the presence of O 2 , 17 Fremy's salt, 18 N-haloamides and sodium nitrite under phase-transfer conditions, 19 and recently by lithium amides with NO. 20 N-Nitrosoamides has been found to be very useful precursors for the preparation of esters, 21a,b hyroxy compounds, 21a,b carboxamides 21c and thioesters.…”