- Facile Formation of N-Nitrosamines from Bromonitromethane and Secondary Amines
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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.
- Challis, Brian C.,Yousaf, Taher I.
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- Sulfur-to-nitrogen transnitrosation: Transfer of nitric oxide from S-nitroso compounds to diethanolamine and the role of intermediate sulfur-to-sulfur transnitrosation
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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.
- Al-Mustafa, Ahmed H,Sies, Helmut,Stahl, Wilhelm
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- Synthesis and characterization of secondary nitrosamines from secondary amines using sodium nitrite and p-toluenesulfonic acid
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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.
- Sabat, Carles Mir,Delalu, Henri
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- NITROSATION REAGENTS AND METHODS
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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.
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Paragraph 00158-00160; 00164; 00182; 00183; 00186-00189; ...
(2022/02/06)
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- Versatile new reagent for nitrosation under mild conditions
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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.
- Galloway, Jordan D.,Sarabia, Cristian,Fettinger, James C.,Hratchian, Hrant P.,Baxter, Ryan D.
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supporting information
p. 3253 - 3258
(2021/05/06)
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- Substrate promiscuity of ortho-naphthoquinone catalyst: Catalytic aerobic amine oxidation protocols to deaminative cross-coupling and n-nitrosation
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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.
- Kim, Hun Young,Oh, Kyungsoo,Si, Tengda
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p. 9216 - 9221
(2019/10/08)
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- Copper(II)-catalyzed oxidative N-nitrosation of secondary and tertiary amines with nitromethane under an oxygen atmosphere
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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.
- Sakai, Norio,Sasaki, Minoru,Ogiwara, Yohei
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supporting information
p. 11638 - 11641
(2015/07/15)
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- Iodide-catalyzed synthesis of N-nitrosamines via C-N cleavage of nitromethane
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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.
- Zhang, Jie,Jiang, Jiewen,Li, Yuling,Wan, Xiaobing
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p. 11366 - 11372
(2013/12/04)
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- Bismuth chloride-sodium nitrite: A novel reagent for chemoselective N-nitrosation
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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.
- Chaskar, Atul C.,Langi, Bhushan P.,Deorukhkar, Amol,Deokar, Hrushikesh
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experimental part
p. 604 - 612
(2009/07/04)
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- Efficient procedure for chemoselective N-nitrosation of secondary amines with trichloromelamine-NaNO2
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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.
- Bamoniri,Zolfigol,Mirjalili,Fallah
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p. 1393 - 1396
(2008/03/27)
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- Molybdate sulfuric acid/NaNO2: A novel heterogeneous system for the N-nitrosation of secondary amines under mild conditions
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Wet molybdate sulfuric acid (=dioxo[bis(sulfato-κO)]molybdenum; MSA), a new solid acid, can be used in combination with sodium nitrite (NaNO 2) to transform a variety of secondary amines to the corresponding N-nitroso compounds under mild, heterogeneous conditions (Table). The process has several advantages: the reagents are inexpensive and non-hazardous, the reaction is clean, fast, and high-yielding, and MSA can be readily removed by filtration and re-used (after treatment with HCl) without loss of activity. Further, only N-nitrosation was observed, but no C- or O-nitrosation.
- Montazerozohori, Morteza,Karami, Bahador
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p. 2922 - 2926
(2007/10/03)
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- The reaction of peroxynitrite with morpholine (secondary amines) revisited: The overlooked hydroxylamine formation
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The reaction of peroxynitrite/peroxynitrous acid with morpholine as a model compound for secondary amines is reinvestigated in the absence and presence of carbon dioxide. The concentration- and pH-dependent formation of N-nitrosomorpholine and N-nitromorpholine as reported in three previous papers ([25] [26] [14]) is basically confirmed. However, 13C-NMR spectroscopic product analysis shows that, in the absence of CO2, N-hydroxymorpholine is, at pH≥7, the major product of this reaction, even under anaerobic conditions. The formation of N-hydroxymorpholine has been overlooked in the three cited papers. Additional (ring-opened) oxidation products of morpholine are also detected. The data account for radical pathways for the formation of these products via intermediate morpholine-derived aminyl and α-aminoalkyl radicals. This is further supported by EPR-spectrometric detection of morpholine-derived nitroxide radicals, i.e., morpholin-4-yloxy radicals. N-Nitrosomorpholine, however, is very likely formed by electrophilic attack of peroxynitrite-derived N2O4. 15N-CIDNP Experiments establish that, in the presence of CO2, N-nitro- and C-nitromorpholine are generated by radical recombination. The present results are in full accord with a fractional (28±2% ) homolytic decay of peroxynitrite/peroxynitrous acid with release of free hydroxyl and nitrogen dioxide radicals.
- Kirsch, Michael,Korth, Hans-Gert,Wensing, Angela,Lehnig, Manfred,Sustmann, Reiner,De Groot, Herbert
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p. 2399 - 2424
(2007/10/03)
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- Dinitrogen tetroxide-impregnated charcoal (N2O 4/charcoal): Selective nitrosation of amines, amides, ureas, and thiols
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Efficient N-nitrosation of amines, amides, and ureas, and also S-nitrosation of thiols were performed with dinitrogen tetroxide impregnated on activated charcoal (N2O4/charcoal) in CH 2Cl2 at room temperature. High selectivity was observed for N-nitrosation of dialkyl amines, N-alkylamides and N-alkylureas. Dealkylation and N-nitrosation of trialkylamines were also performed by this reagent. Copyright Taylor & Francis, Inc.
- Iranpoor, Nasser,Firouzabadi, Habib,Pourali, Ali Reza
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p. 1517 - 1526
(2007/10/03)
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- Selective N-nitrosation of amines, N-alkylamides and N-alkylureas by N2O4 supported on cross-linked polyvinylpyrrolidone (PVP-N2O4)
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N2O4 was supported on the cross-linked polyvinylpyrrolidone (PVP) to afford a solid, stable and recyclable nitrosating agent. This reagent shows excellent selectivity for N-nitrosation of dialkyl amines in the presence of diaryl-, arylalkyl-, trialkylamines and also for secondary amides in dichloromethane at room temperature under mild and heterogeneous conditions. Also N-nitroso-N-alkyl amides can be selectively prepared in the presence of primary amides and N-phenylamides under similar reaction conditions. Selective N-nitrosation or dealkylation and N-nitrosation of tertiary amines can also be performed by this reagent.
- Iranpoor, Nasser,Firouzabadi, Habib,Pourali, Ali-Reza
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p. 1591 - 1597
(2007/10/03)
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- The use of Nafion-H/NaNO2 as an efficient procedure for the chemoselective N-nitrosation of secondary amines under mild and heterogeneous conditions
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A combination of Nafion-H and sodium nitrite in the presence of wet SiO2 was used as an effective agent for the N-nitrosation of secondary amines under mild and heterogeneous conditions in good to excellent yields.
- Zolfigol, Mohammad Ali,Habibi, Davood,Mirjalili, BiBi Fatemeh,Bamoniri, Abdolhamid
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p. 3345 - 3349
(2007/10/03)
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- Silica sulfuric acid/NaNO2 as a novel heterogeneous system for the chemoselective N-nitrosation of secondary amines under mild conditions
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Neat chlorosulfonic acid reacts with silica gel to give silica sulfuric acid in which sulfuric acid is immobilized on the surface of silica gel via a covalent bond. A combination of silica sulfuric acid and sodium nitrite in the presence of wet SiO2 was used as an effective nitrosating agent for the nitrosation of secondary amines to their corresponding nitroso derivatives under mild and heterogeneous conditions in excellent yields.
- Zolfigol, Mohammad Ali,Bamoniri, Abdolhamid
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p. 1621 - 1624
(2007/10/03)
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- Hydrogen bonding of 2-tetrazenes, 2. Synthesis and structural studies of hydroxyalkyl-substituted 2-tetrazenes
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Five hydroxyethyl-2-tetrazenes (1 - 5) and their methyl ethers (6 - 10) have been synthesized and hydrogen bonding in these compounds has been investigated by theoretical and spectroscopic (IR, 1H NMR, 15N NMR) methods. The structure of 1,1,4,4-tetrakis(2-hydroxyethyl)-2-tetrazene (4) was determined by X-ray diffraction analysis. Several conformations with intramolecular hydrogen bonds were investigated by ab initio B3LYP as well as semiempirical SCF calculations. In all cases, conformers with OH---N hydrogen bonds with azo nitrogen atoms as acceptors (conformers A, B, C) are found as most stable. In compounds with small or flexible N1- and N4- substituents R besides the hydroxyethyl group (3, 4), hydrogen bonds forming six-membered rings, with the R groups taking syn positions at the N1-N2 and N3-N4 bonds (conformer A), are preferred over those with seven-membered rings and R taking anti positions (conformer B). Steric interaction in the other compounds (1, 2, 5) leads to destabilization of conformers A and conformers B become more stable. A special case is presented by compound 4 which has only hydroxyethyl substituents on the 2-tetrazene unit. In the most stable conformer (4C) there are two OH---O and one OH---N hydrogen bonds. By IR solution measurements intra- and intermolecular hydrogen bonds could be distinguished. Association shifts Δδ measured by 1H NMR spectroscopy, indicate that the investigated compounds exhibit comparable association properties with intermolecular association clearly prevailing. 15N NMR spectra of compounds 1 - 10 in two solvents have been measured if solubility was sufficient. The data indicate that all nitrogen atoms of 1 - 5 participate in H bonding. In the crystalline state, molecules 4 adopt a conformation without intramolecular H bonds (4D) and are associated by intermolecular OH---O hydrogen bonds that form a three-dimensional network. An untypical decomposition pattern was discovered for benzyl derivatives 5 and 10.
- Porath, Bernd,Rademacher, Paul,Boese, Roland,Bl?ser, Dieter
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p. 365 - 376
(2007/10/03)
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- In vitro DNA deamination by α-nitrosaminoaldehydes determined by GC/MS- SIM quantitation
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The deamination of DNA bases by three α-nitrosaminoaldehydes, butylethanalnitrosamine, methylethanalnitrosamine, and N-nitroso-2- hydroxymorpholine (NHMOR), the direct metabolite of potent animal carcinogen N-nitrosodiethanolamine, was demonstrated by a set of in vitro experiments. The deamination of guanine, adenine, and cytosine bases in nucleotides, oligonucleotides, and calf thymus DNA gave xanthine, hypoxanthine, and uracil, respectively. The order of relative reactivities of the bases was as listed above. Deamination of cytosine to uracil was detected by the reaction of 32P-labeled oligonucleotide ([5'-32P]CGAT) followed by enzymatic hydrolysis. Quantitative analysis of deamination of guanine and adenine in calf thymus DNA was performed by a gas chromatography/mass spectrometry- selected ion monitoring method. Both the extent and the rate of the deamination reactions which occur by transnitrosation from the α- nitrosaminoaldehyde to the base were determined for formation of xanthine and hypoxanthine. The deamination of guanine by NHMOR remained significant at low substrate levels.
- Park, Misun,Loeppky, Richard N.
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- Direct Conversion of Terpenylalkanolamines to Ethylidyne N-Nitroso Compounds
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A series of mono- and diterpenylalkanolamines bearing isopropylidene functionality on the terpene group was reacted with sodium nitrite in aqueous acetic acid to yield ethylidyne N-nitroso analogues.The key feature of this direct conversion involved initial N-nitrosation followed by apparent elimination of a "CH4" unit (not necessarily methane) from the isopropylidene double bond.The product distribution data for ethylidyne nitrosamines derived from tertiary terpenyl alkanolamines reflect the conformational outcome of the nitrosative dealkylation process.For β,γ-unsaturated allylic diterpenylethanolamines, electronic effects appeared to be important for controlling the product distribution of ethylidyne nitrosamines in light of the highly selective α-cleavage observed in the nitrosation reactions.
- Abidi, S. L.
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p. 2687 - 2694
(2007/10/02)
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