924-16-3Relevant articles and documents
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.
The Use of Potassium/Sodium Nitrite as a Nitrosating Agent in the Electrooxidative N-Nitrosation of Secondary Amines
Chen, Zuxing,Gao, Meng,Lu, Cuifen,Ma, Chao,Ruan, Mengyao,Wang, Feiyi,Wang, Ying,Yang, Guichun,You, Shiqi
supporting information, p. 3289 - 3293 (2021/07/02)
We report herein on the electrochemical N-nitrosation of secondary amines using widely available sodium/potassium nitrite as a nitrosating agent. This approach not only eliminates the need for using a combination of sodium/potassium and a strong acid but also has good functional group tolerance. The reaction is compatible with the late-stage modification of pharmaceutical compounds and could be conducted in gram scale with a high reaction efficiency. Preliminary mechanistic studies indicate that the N-nitrosation occurs via the anodic oxidation of KNO2 into an NO2 radical which is then transformed into an NO+ cation.
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.
In situ generated amine as a Lewis base catalyst in the reaction of 3,7-dinitro-1,3,5,7-tetraazabicyclo[3.3.1]nonane in nitric acid: Experimental and DFT study
Zhang, Yu,Chi, Guoli,He, Ying,Xu, Zishuai,Zhang, Luyao,Luo, Jun,Zhou, Baojing
supporting information, (2019/04/08)
The problem how ammonium nitrate affects the nitrolysis of 3,7-dinitro-1,3,5,7-tetraazabicyclo[3.3.1]nonane (DPT) in nitric acid to prepare 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) has puzzled chemists for decades. In this paper, experimental work and theoretical calculation are described to investigate the long-standing challenge. The experiment results showed that ammonium nitrate or alkylammonium chlorides were in favor of the formation of 1-nitroso-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane (MNX) but hindered the conversion of MNX to HMX. A plausible catalytic mechanism was proposed. In which ammonia or amines, in situ generated from the unfavorable balance with their salts, act as Lewis base catalysts. At the same time, the DFT computation results reveal that rigid bicyclic transition states established with 1-hydroxymethyl-3,5,7-trinitro-1,3,5,7-tetraazacyclooctane, ammonia (or amines) and three water molecules lead to very low activation energies. Then, a novel process for the preparation of MNX with excellent yield up to 78.5% was developed, which is free of the use of NaNO2 or N2O4 as nitroso resources.
A combined experimental and DFT mechanistic study for the unexpected nitrosolysis of: N -hydroxymethyldialkylamines in fuming nitric acid
Zhang, Yu,Zou, Po,Han, Yingbin,Geng, Yongliang,Luo, Jun,Zhou, Baojing
, p. 19310 - 19316 (2018/05/31)
The reaction of dimorpholinomethane in fuming HNO3 was investigated. Interestingly, the major product was identified as N-nitrosomorpholine and a key intermediate N-hydroxymethylmorpholine was detected during the reaction by 1H-NMR tracking which indicates that the reaction proceeds via an unexpected nitrosolysis process. A plausible nitrosolysis mechanism for N-hydroxymethyldialkylamine in fuming nitric acid involving a HNO3 redox reaction is proposed, which is supported by both experimental results and density functional theory (DFT) calculations. The effects of ammonium nitrate and water on the nitrosolysis were studied using different ammonium salts as additives and varying water content, respectively. Observations show the key role of ammonium ions and a small amount of water in promoting the nitrosolysis reaction. Furthermore, DFT calculations reveal an essential point that ammonia, merged from the decomposition of the ammonium salts, acts as a Lewis base catalyst, and the hydroxymethyl group of the substrate participates in a hydrogen-bonding interaction with the NH3 and H2O molecules.
An efficient synthesis of: N -nitrosamines under solvent, metal and acid free conditions using tert -butyl nitrite
Chaudhary, Priyanka,Gupta, Surabhi,Muniyappan, Nalluchamy,Sabiah, Shahulhameed,Kandasamy, Jeyakumar
supporting information, p. 2323 - 2330 (2016/05/19)
Synthesis of various N-nitroso compounds from secondary amines is reported using tert-butyl nitrite (TBN) under solvent free conditions. Broad substrate scope, metal and acid free conditions, easy isolation procedure and excellent yields are few important features of this methodology. The acid labile protecting groups such as tert-butyldimethylsilyl (TBDMS) and tert-butyloxycarbonyl (Boc) as well as sensitive functional groups such as phenols, olefins and alkynes are found to be stable under the standard reaction conditions. Besides N-nitrosation, TBN is also found to be an efficient reagent in few other transformations including aryl hydrazines to aryl azides and primary amides to carboxylic acids under mild conditions.
Synthesis and characterization of secondary nitrosamines from secondary amines using sodium nitrite and p-toluenesulfonic acid
Sabat, Carles Mir,Delalu, Henri
, p. 674 - 678 (2015/07/01)
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.
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.
Ionic liquid 1-(4-nitritobutyl)-3-methylimidazolium chloride as a new reagent for the efficient N-nitrosation of secondary amines under mild conditions
Valizadeh, Hassan,Gholipour, Hamid,Shomali, Ashkan
experimental part, p. 467 - 470 (2012/06/15)
1-(4-Nitritobutyl)-3-methylimidazolium chloride has been developed as a new reagent for efficient nitrosation of secondary amines at 0 °C to room temperature. A variety of N-nitrosamines were prepared in excellent yields by use of this task-specific ionic liquid under mild and heterogeneous conditions.
1-butyl-3-methylimidazolium nitrite as a reagent for the efficient n-nitrosation of secondary amines
Valizadeh,Gholipour
experimental part, p. 857 - 861 (2012/06/18)
1-Butyl-3-methylimidazolium nitrite, [bmim]NO2 was used as a new effective reagent for the preparation of N-nitrosamines from the corresponding secondary amines at 0 °C to room temperature, under mild conditions in good to excellent yields.
