- 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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- The Use of Potassium/Sodium Nitrite as a Nitrosating Agent in the Electrooxidative N-Nitrosation of Secondary Amines
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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.
- Chen, Zuxing,Gao, Meng,Lu, Cuifen,Ma, Chao,Ruan, Mengyao,Wang, Feiyi,Wang, Ying,Yang, Guichun,You, Shiqi
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supporting information
p. 3289 - 3293
(2021/07/02)
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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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- 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
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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.
- Zhang, Yu,Chi, Guoli,He, Ying,Xu, Zishuai,Zhang, Luyao,Luo, Jun,Zhou, Baojing
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supporting information
(2019/04/08)
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- A combined experimental and DFT mechanistic study for the unexpected nitrosolysis of: N -hydroxymethyldialkylamines in fuming nitric acid
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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.
- Zhang, Yu,Zou, Po,Han, Yingbin,Geng, Yongliang,Luo, Jun,Zhou, Baojing
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p. 19310 - 19316
(2018/05/31)
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- An efficient synthesis of: N -nitrosamines under solvent, metal and acid free conditions using tert -butyl nitrite
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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.
- Chaudhary, Priyanka,Gupta, Surabhi,Muniyappan, Nalluchamy,Sabiah, Shahulhameed,Kandasamy, Jeyakumar
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supporting information
p. 2323 - 2330
(2016/05/19)
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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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p. 674 - 678
(2015/07/01)
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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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- Ionic liquid 1-(4-nitritobutyl)-3-methylimidazolium chloride as a new reagent for the efficient N-nitrosation of secondary amines under mild conditions
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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.
- Valizadeh, Hassan,Gholipour, Hamid,Shomali, Ashkan
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experimental part
p. 467 - 470
(2012/06/15)
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- 1-butyl-3-methylimidazolium nitrite as a reagent for the efficient n-nitrosation of secondary amines
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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.
- Valizadeh,Gholipour
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experimental part
p. 857 - 861
(2012/06/18)
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- N-nitrosation of secondary amines using p-TSA-NaNO2 as a novel nitrosating agent under mild conditions
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A combination of p-toluenesulfonic acid (p-TSA) and sodium nitrite was used as a novel effective nitrosating agent for the N-nitrosation of secondary amines to their corresponding nitroso derivatives under mild and heterogeneous conditions in moderate to excellent yields.
- Borikar, Sanjay P.,Paul, Vincent
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experimental part
p. 654 - 660
(2011/02/27)
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- Synthesis of N,N-dialkylnitramines from secondary ammonium nitrates in liquid or supercritical carbon dioxide
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An efficient explosion-proof method was developed for the preparation of N,N-dialkylnitramines by treatment of dialkylammonium nitrates with a mixture of nitric acid and acetic anhydride in the presence of ZnCl2 in liduid or supercritical carbon dioxide.
- Kuchurov,Fomenkov,Zlotin
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experimental part
p. 2058 - 2062
(2011/01/08)
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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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- A simple and efficient method for the N-nitrosation of secondary amines with NaNO2-Ac2O under mild conditions
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Secondary amines can be easily converted into their corresponding nitroso derivations using NaNO2-Ac2O as a nitrosating agent in dichloromethane at room temperature with high yields.
- Hou, Jian-Ye,Wang, Yu-Lu,Wang, Jin-Ye
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p. 626 - 627
(2007/10/03)
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- A highly convenient new methodology for the synthesis of N-nitrosamines from lithium amides
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N-nitrosoalkylamines were efficiently synthesized from the reaction of lithium amides with NO at atmospheric pressure using dialkylamines as starting materials. With asymmetric amines stereoselectivity is observed giving rise to different amounts of E and Z isomers.
- Nudelman,Bonatti
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p. 1825 - 1827
(2007/10/03)
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- KINETIC STUDY ON THE NITROSATION OF DIBENZYLAMINE IN A MODEL SYSTEM
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A kinetic study of the formation of N-nitrosodibenzylamine (NDBzA), from the nitrosation of dibenzylamine (DBzA) by sodium nitrite, was performed in a model system under conditions (temperature, pH) that are similar to those encountered in the industrial production of hams processed in elastic rubber nettings. The nitrosation reaction was carried out in a KH2PO4 buffer (0.5 M) at pH 5.8 and at a temperature of 69 deg C. Since DBzA is insoluble in an aqueous buffer system, a non-ionic surfactant, Tween 20, was used as a solubilizing agent. The nitrosation reaction exhibited first-order kinetics with respect to DBzA and second-order kinetics with respect to nitrite. The calculated rate constant was 4.7 +/- 0.5 M-2/min. The pH profile of NDBzA formation eas also determined. The optimal pH of NDBzA formation, 3.12, was close to the pKa of nitrous acid (HNO2, pKa = 3.1).
- Ayala, N. L.,Fiddler, W.,Gates, R. A.,Pensabene, J. W.
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p. 1015 - 1020
(2007/10/03)
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- Reaction of methylmagnesium iodide with dibutylcyanamide and dibutylnitrosamine
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The reaction of methylmagnesium iodide with di(n-butyl)cyanamide results in dibutylamine, dibutylisopropylamine, and acetonitrile, while the reaction with di(n-butyl)nitrosamine affords acetaldehyde dibutylhydrazone.Formaldehyde, acetone, and 2-butanone dibutylhydrazones, as well as acetaldehyde butyl(1-methylbutyl)hydrazone, 2-butanone butyl(1-methylbutyl)hydrazone, 1,1-dibutyl-2,2-dimethylhydrazone, and 1,1-dibutyl-2-ethyl-2-methylhydrazine were also identified in minor amounts.Di(n-butyl)nitramine reacts with methylmagnesium iodide to give di(n-butyl)nitrosamine. - Key words: di(n-butyl)cyanamide; di(n-butyl)nitrosamine; methylmagnesium iodide; formaldehyde dibutylhydrazone; 2-butanone dibutylhydrazone; acetaldehyde butyl(1-methylbutyl)hydrazone; 2-butanone butyl(1-methylbutyl)hydrazone; 1,1-dibutyl-2,2-dimethylhydrazine; 1,1-dibutyl-2-ethyl-2-methylhydrazine; di(n-butyl)nitramine.
- Polivin, Yu. N.,Karakhanov, R. A.,Kelarev, V. I.,Sheveleva, T. S.,Ugrak, B. I.
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p. 1991 - 1994
(2007/10/02)
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- Formation of Nitrosamines in Alkaline Conditions: a Kinetic Study of the Nitrosation of Linear and Cyclic Secondary Amines by Nitroalkanes
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A study has been made of the nitrosation of sixteen secondary amines, six alkylamines (dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine) and ten cyclic secondary amines (2-methylaziridine, azetidine, pyrrolidine, piperidine, 2-methylpiperidine, homopiperidine, heptamethyleneimine, piperazine, 1-methylpiperazine and morpholine) by nitropropane and nitrobutane in a strongly basic medium (-> = 0.1 mol dm-3).The nitrites were not formed in situ (i.e. in the actual bulk of the reaction medium) but rather were isolated,purified and used in pure form.The rate equation (i) was found v = k2obs (i).The fitting of the experimental results to the Taft correlation points to a nucleophilic attack on nitrite esters by the amines.Analysis of the log k2/pKa and log k2/Ei(v) correlations indicates orbital control of the reactions studied.These results, together with the fact that the reactivity of the different amines diminishes ostensibly when the values of the 13C-H nuclear spin coupling constant in the series of corresponding cycloalkanes increase, show that the overall hybridization of the nitrogen atom in the cycle changes from sp2 in the triangular nucleophile methylaziridine to sp3 in larger cycles.The results obtained at different temperatures and with water-tetrahydrofuran media, together with a study of isotope effects suggest that these reactions occur through a highly ordered transition state and that the role of solvation should not be overlooked.
- Calle, Emilio,Casado, Julio,Cinos, Jose L.,Mateos, Francisco J. Garcia,Tostado, Manuel
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p. 987 - 991
(2007/10/02)
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- Reactions of trifluoroamine oxide: A route to acyclic and cyclic fluoroamines and N-nitrosoamines
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Acyclic secondary fluoroamines and N-nitrosoamines R2NF and R2NNO (R = CH3, C2H5, n-C3H7, i-C3H7, n-C4H9, i-C4H9, c-C6H11) and saturated nonaromatic heterocyclic fluoroamines and N-nitrosoamines R NF and R NNO [R = c-C4H8, c-C5H10, 2,6-(CH3)2-c-C5H8, 2,2,6,6-(CH3)4-c-C5H6] were prepared by reacting trifluoroamine oxide (NF3O) with the respective amine at ≤0 °C in a 1:2 molar ratio. The amine hydrofluoride salts are also formed. Trifluoroamine oxide is a very effective fluorinating and nitrosating reagent and provides an excellent route to >NF- and >NNO-containing compounds. With PF5, 2,2,6,6-(CH3)4-c-C5H6NFgave [CH2CH2CH2C(CH3)2N +=C(CH3)2]PF6-.
- Gupta, Om Dutt,Kirchmeier, Robert L.,Shreeve, Jean'ne M.
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p. 2383 - 2386
(2007/10/02)
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- 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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p. 1598 - 1599
(2007/10/02)
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- N-NITROSATION OF SECONDARY AMINES EFFECTED BY ELECTROCHEMICAL OXIDATION OF NITRITE ION IN WEAKLY BASIC MEDIA
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Constant current electrolysis of sodium nitrite in aqueous acetonitrile containing secondary amines at ambient temperature resulted in the formation of the corresponding N-nitrosamines in good yields.KEYWORDS - N-nirosation; secondary amine; sodium nitrite; electrochemical oxidation; constant current electrolysis
- Masui, Masaichiro,Yamawaki, Norihiko,Ohmori, Hidenobu
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p. 459 - 461
(2007/10/02)
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- Nitrosamines from Tertiary Amines and Dinitrogen Tetraoxide
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A preparative nitrosolysis of aliphatic acyclic and cyclic tertiary monoamines to nitrosoamines was brought about by treatment with dinitrogen tetraoxide in carbon tetrachloride at 0-40 deg C.Dealkylation was restricted, where applicable, to demethylation.Competitive oxidation to an amide was observed in the formation of dibutylformamide from tributylamine.Diamine dinitrate salts, without nitrosamine formation, were obtained from 1,4-dimethylpiperazine and 1,4-diazabicyclo-octane; however, each dinitrate salt thermolysed at 180-200 deg C to give a small amount of 1,4-dinitrosopiperazine.In acetic anhydride dinitrogen tetraoxide converted amines less efficiently, gave lower yield of nitrosoamines, was less selective in dealkylation, and introduced the formation of by-products.
- Boyer, Joseph H.,Pillai, T. Perumal
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p. 1661 - 1664
(2007/10/02)
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- Fremy's Salt (Potassium Nitrosodisulphonate): A Nitrosating Reagent for Amines
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Treatment of secondary and tertiary amines with Fremy's salt in aqueous sodium carbonate or pyridine solution gives moderate yields of the corresponding N-nitrosoamines.
- Castedo, Luis,Riguera, Ricardo,Vazquez, M. Pilar
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p. 301 - 302
(2007/10/02)
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