1116-54-7Relevant academic research and scientific papers
Facile Formation of N-Nitrosamines from Bromonitromethane and Secondary Amines
Challis, Brian C.,Yousaf, Taher I.
, p. 1598 - 1599 (1990)
Bromonitromethane readily converts secondary amines to N-nitrosamines in aqueous and organic solvents at room temperature via reaction of an iminium ion intermediate with nitrite ion.
Sulfur-to-nitrogen transnitrosation: Transfer of nitric oxide from S-nitroso compounds to diethanolamine and the role of intermediate sulfur-to-sulfur transnitrosation
Al-Mustafa, Ahmed H,Sies, Helmut,Stahl, Wilhelm
, p. 127 - 136 (2001)
S-Nitrosothiols are formed in vivo and are involved in NO signaling. We investigated the sulfur-to-nitrogen transnitrosation activity of S-nitrosocysteine, S-nitrosoglutathione, S-nitrosohomocysteine, S-nitrosocysteinylglycine and S-nitroso-N-acetylcysteine in their reaction with the secondary amine diethanolamine in vitro. The resulting N-nitrosodiethanolamine, a strong carcinogen, was formed in yields of up to 11% from S-nitrosocysteine and S-nitrosocysteinylglycine, whereas the transnitrosation activity of the other S-nitroso compounds was weak. However, the addition of L-cysteine to a solution of S-nitrosohomocysteine and diethanolamine accelerated the decomposition of S-nitrosohomocysteine and resulted in a significant formation of N-nitrosodiethanolamine accompanied by the intermediate generation of S-nitrosocysteine. Thus, reactive nitrosothiols can be formed from less reactive analogs via sulfur-to-sulfur transnitrosation. We suggest that this affects regulation of NO trafficking in vivo. The reaction provides an alternative mechanism for the generation of carcinogenic N-nitroso derivatives.
Synthesis and characterization of secondary nitrosamines from secondary amines using sodium nitrite and p-toluenesulfonic acid
Sabat, Carles Mir,Delalu, Henri
, p. 674 - 678 (2015)
We synthesized nitrosamines (R2N-NO) with R = iPr (1), nPr (2), nBu (3), and hydroxyethyl (4) from the amine using sodium nitrite/p-toluenesulfonic acid in CH2Cl2. The rate of formation of 1-4 increases in the direction iPr2CH2OH. Compounds 1-3 were obtained as colorless solids, whereas 4 is a bright yellow liquid. Compounds 1-4 were characterized by elemental analysis, MS, IR, and multinuclear NMR (1H, 13C, and 15N) spectroscopies. Additionally, we measured the UV/Vis spectra of all compounds, which show maxima of absorption at approximately 221 nm and molar extinction coefficients between 3043 and 4859 Lmol-1cmr-1. We calculated the optimized structures of 1-4 (B3LYP/6-311+G(d,p)) and computed the NMR spectroscopic chemical shifts and infrared frequencies. Furthermore, we carried out a natural bond orbital (NBO) analysis of the nitrosamine moiety. Lastly, the compounds described in this work are valuable starting materials for the synthesis of 2-tetrazenes with potential interest to replace highly toxic hydrazines in rocket propulsion.
Versatile new reagent for nitrosation under mild conditions
Galloway, Jordan D.,Sarabia, Cristian,Fettinger, James C.,Hratchian, Hrant P.,Baxter, Ryan D.
supporting information, p. 3253 - 3258 (2021/05/06)
Here we report a new chemical reagent for transnitrosation under mild experimental conditions. This new reagent is stable to air and moisture across a broad range of temperatures and is effective for transnitrosation in multiple solvents. Compared with traditional nitrosation methods, our reagent shows high functional group tolerance for substrates that are susceptible to oxidation or reversible transnitrosation. Several challenging nitroso compounds are accessed here for the first time, including 15N isotopologues. X-ray data confirm that two rotational isomers of the reagent are configurationally stable at room temperature, although only one isomer is effective for transnitrosation. Computational analysis describes the energetics of rotamer interconversion, including interesting geometry-dependent hybridization effects.
NITROSATION REAGENTS AND METHODS
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Paragraph 00158-00160; 00164; 00182; 00183; 00186-00189; ..., (2022/02/06)
Provided are compounds that can find use as nitrosation reagents. Provided are nitrosation methods that include reacting a substrate with one of the provided nitrosation reagents and thereby generating a nitrosation product. Provided are kits including a nitrosation reagent. Provided are compositions wherein the nitrosation reagent is enriched in the 15N isotope.
Substrate promiscuity of ortho-naphthoquinone catalyst: Catalytic aerobic amine oxidation protocols to deaminative cross-coupling and n-nitrosation
Kim, Hun Young,Oh, Kyungsoo,Si, Tengda
, p. 9216 - 9221 (2019/10/08)
ortho-Naphthoquinone-based organocatalysts have been identified as versatile aerobic oxidation catalysts. Primary amines were readily cross-coupled with primary nitroalkanes via deaminative pathway to give nitroalkene derivatives in good to excellent yields. Secondary and tertiary amines were inert to ortho-naphthoquinone catalysts; however, secondary nitroalkanes were readily converted by ortho-naphthoquinone catalysts to the corresponding nitrite species that in situ oxidized the amines to the corresponding N-nitroso compounds. Without using harsh oxidants in a stoichiometric amount, the present catalytic aerobic oxidation protocol utilizes the substrate promiscuity feature to provide a facile access to amine oxidation products under mild reaction conditions.
Copper(II)-catalyzed oxidative N-nitrosation of secondary and tertiary amines with nitromethane under an oxygen atmosphere
Sakai, Norio,Sasaki, Minoru,Ogiwara, Yohei
supporting information, p. 11638 - 11641 (2015/07/15)
The combination of a catalytic amount of Cu(OTf)2 and less than a stoichiometric amount of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) under an O2 atmosphere effectively promoted the N-nitrosation of both secondary aromatic/aliphatic amines and tertiary aromatic amines with nitromethane (CH3NO2) leading to the preparation of N-nitrosamine derivatives.
Iodide-catalyzed synthesis of N-nitrosamines via C-N cleavage of nitromethane
Zhang, Jie,Jiang, Jiewen,Li, Yuling,Wan, Xiaobing
, p. 11366 - 11372 (2013/12/04)
An iodide-catalyzed process to synthesize N-nitrosamines has been developed using TBHP as the oxidant. The mild catalytic system succeeded in cleaving the carbon-nitrogen bond in nitromethane. This methodology uses commercially available, inexpensive catalysts and oxidants and has a wide substrate scope and operational simplicity.
Bismuth chloride-sodium nitrite: A novel reagent for chemoselective N-nitrosation
Chaskar, Atul C.,Langi, Bhushan P.,Deorukhkar, Amol,Deokar, Hrushikesh
experimental part, p. 604 - 612 (2009/07/04)
Bismuth(III) chloride-sodium nitrite was used as a mild and efficient reagent for N-nitrosation of various tetrazoles, secondary amines, and amides under ambient conditions. Nitrosation took place chemoselectively at the nitrogen atom, giving corresponding N-nitroso derivatives in good to excellent yield. Copyright Taylor & Francis Group, LLC.
Efficient procedure for chemoselective N-nitrosation of secondary amines with trichloromelamine-NaNO2
Bamoniri,Zolfigol,Mirjalili,Fallah
, p. 1393 - 1396 (2008/03/27)
A combination of trichloromelamine and sodium nitrite in the presence of wet silica gel was used as an effective nitrosating agent for the transformation of secondary amines into the corresponding N-nitroso derivatives under mild and heterogeneous conditions in good to excellent yields.
