100-75-4Relevant articles and documents
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
, p. 3289 - 3293 (2021)
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.
Synthesis and properties of 2-hydroxyethyl derivatives of methylene-bis(1-oxy-3, 3-dialkyl-1-triazene 2-oxides)
Smirnov,Nikitin,Gordeev,Pokhvisneva,Ternikova,Luk’yanov
, p. 2706 - 2711 (2015)
Synthetic approach to 2-hydroxyethyl derivatives of methylene-bis(1-oxy-3, 3-dialkyl-1triazene 2-oxides), promising NO donors, which can release NO in living organisms was developed. Some transformations of the hydroxyethyl moiety of the synthesized compounds were studied.
THE OXIDATION OF HYDROXYLAMINE BY FREMY'S SALT. PREPARATION OF N-NITROSAMINES AND TETRAZENES
Tato, M. P. Vazquez,Castedo, Luis,Riguera, Ricardo
, p. 623 - 626 (1985)
Treatment of secondary amines with Fremy's salt in aqueous sodium carbonate solution and in the presence of hydroxylamine gives a high yield of either N-nitrosamines or sym-tetrazenes.A mechanism for these conversions is proposed.
Synthesis of N,N-dialkylnitramines from secondary ammonium nitrates in liquid or supercritical carbon dioxide
Kuchurov,Fomenkov,Zlotin
, p. 2058 - 2062 (2009)
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.
N-nitrosation of secondary amines using p-TSA-NaNO2 as a novel nitrosating agent under mild conditions
Borikar, Sanjay P.,Paul, Vincent
, p. 654 - 660 (2010)
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.
The reaction of peroxynitrite with morpholine (secondary amines) revisited: The overlooked hydroxylamine formation
Kirsch, Michael,Korth, Hans-Gert,Wensing, Angela,Lehnig, Manfred,Sustmann, Reiner,De Groot, Herbert
, p. 2399 - 2424 (2006)
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.
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Lovejoy,Vosper
, p. 2325 (1968)
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Ph3P/Br2/n-Bu4NNO2 as an efficient system for the preparation of N-nitrosamines and azides
Iranpoor, Nasser,Firouzabadi, Habib,Nowrouzi, Najmeh
, p. 4242 - 4244 (2008)
The combination PPh3/Br2/n-Bu4NNO2 was developed as a new reagent system for the efficient preparation of N-nitrosamines and azides from the corresponding amines and hydrazine derivatives, respectively, at 0 °C to room temperature, in excellent yields.
N-nitrosation of secondary amines with [NO+·Crown·H (NO3)2-]
Zolfigol,Zebarjadian,Chehardoli,Keypour,Salehzadeh,Shamsipur
, p. 3619 - 3620 (2001)
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Molybdate sulfuric acid/NaNO2: A novel heterogeneous system for the N-nitrosation of secondary amines under mild conditions
Montazerozohori, Morteza,Karami, Bahador
, p. 2922 - 2926 (2006)
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.
N-nitrosation of secondary amines under mild and heterogeneous conditions
Zolfigol,Bagherzadeh,Choghamarani,Keypour,Salehzadeh
, p. 1161 - 1166 (2001)
A combination of potassium monopersulfate 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.
Comparative study of nitroso group transfer in colloidal aggregates: Micelles, vesicles and microemulsions
Garcia-Rio,Herves,Mejuto,Perez-Juste,Rodriguez-Dafonte
, p. 372 - 380 (2003)
A kinetic study was carried out on nitroso group transfer from N-methyl-N-nitroso-p-toluenesulfonamide (MNTS) to different secondary amines: morpholine (MOR), piperazine (PIP), dimethylamine (DMA) and piperidine (PIPER) in micelles of dodecyltrimethylammonium bromide (LTABr) and in vesicles of dioxadecyltrimethylammonium chloride (DODAC). Amine nucleophiles were chosen on the basis of their hydrophobicity and basicity. The observed rate constant, kobs, shows opposite behavior in micelles and vesicular systems. kobs for micelle systems decreases as the surfactant concentration increases. This behavior can be interpreted according to the distribution of the reagents among the different pseudophases of the system and the physicochemical properties of the latter. It has been observed that the product of the rate constant in the micellar pseudophase and the distribution constant of the amine, k2mKmR2NH, retains a sequence similar to the reactivity observed in water. The differences observed can be explained on the basis of the different hydrophobicity of the amines and consequently different values of KmR2NH. In all cases a catalytic effect on the addition of vesicles was observed reaching a limiting value of kobs. The kinetic behavior can be explained quantitatively on the basis of a single pseudophase model, k2vKvR2NH in the vesicular systems of DODAC displays a variation which is analogous with the micellar systems but approximately 35 times greater, which in turn indicates the greater hydrophobic character of the vesicles of DODAC by comparison with the micelles of LTABr. In AOT/isooctane/water microemulsions we have found similar behavior where the product is approximately 22 times lower than in vesicles, indicating that the polarity of the interface of the microemulsions is greater than that of the micelles of LTABr and smaller than that of DODAC vesicles. The comparative analysis of the reactivities in the interface of the microemulsion and in an aqueous medium shows that the reactive position in the interface changes as the hydrophobic character of the amine varies.
Thermal Decomposition of Nitramines: Dimethylnitramine, Diisopropylnitramine, and N-Nitropiperidine
Oxley, J. C.,Hiskey, M.,Naud, D.,Szekeres, R.
, p. 2505 - 2509 (1992)
Kinetics and activation parameters of the solution thermolysis of nitramines dimethylnitramine, diisopropylnitramine, and N-nitropiperidine were determined over the temperature range 200-300 deg C.Each formed the corresponding nitrosamine as the only, or major, condensed-phase product.For dimethylnitramine the products were completely characterized.The observations of a large positive activation volume in the thermolysis of dimethylnitramine and of the slowing of the decomposition reaction with increased solvent viscosity both suggest that the rate-determining step is homolysis, the N-NO2 bond being the most obvious point for this.Nitrosamines could be produced by this route; however, when doubly 15N-labeled dimethylnitramine was heated with unlabeled dimethylnitramine, little scrambling of the label in the reactant was observed.Label scrambling was observed in the nitrosamine but could have resulted from subsequent N-NO homolysis.Scrambling of the label in the product gases and the observation of a kinetic isotope effect when perdeuterated dimethylnitramine was decomposed were explained in terms of a second decomposition route involving transfer of hydrogen from the α carbon to one of the NO2 oxygens.
Efficient and chemoselective N-nitrosation of secondary amines under mild and heterogeneous conditions with sodium nitrite and oxalic acid two hydrate
Zolfigol, Mohammad Ali
, p. 905 - 910 (1999)
Secondary amines can be quantitatively converted to their corresponding nitroso derivatives with a combination of oxalic acid and sodium nitrite in dichloromethane at room temperature.
Selective N-nitrosation of amines, N-alkylamides and N-alkylureas by N2O4 supported on cross-linked polyvinylpyrrolidone (PVP-N2O4)
Iranpoor, Nasser,Firouzabadi, Habib,Pourali, Ali-Reza
, p. 1591 - 1597 (2003)
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.
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Oae,S. et al.
, p. 913 - 917 (1978)
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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
Zhang, Yu,Chi, Guoli,He, Ying,Xu, Zishuai,Zhang, Luyao,Luo, Jun,Zhou, Baojing
, (2019)
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.
Differences in the activity of neutral and ionized β-cyclodextrin on the nitrosation of amines by phenylpropyl nitrites
Iglesias
, p. 1025 - 1035 (2000)
The influence of β-cyclodextrin (β-CD) on the base-catalyzed hydrolysis reaction of 1-phenyl-1-propyl, 2-phenyl-1propyl and 3-phenyl-1-propyl nitrites and on the nitrosation of pyrrolidine, piperidine and N-methylcyclohexylamine by the aforementioned alkyl nitrites (RONO) is studied in aqueous buffers of the amines and in an alkaline medium with [OH-] = 0.20 M. The hydrolysis reaction is catalyzed by the presence of β-CD owing to the formation of reactive 1:1 inclusion complexes between the alkyl nitrite and the ionized β-CD; the addition of potential inhibitors, such as dodecyltrimethylammonium bromide monomers, accelerates the reaction even more. The effect is quite significant in the case of 1-phenyl-1-propyl nitrite and is viewed as a case of allostery. In the presence of neutral β-CD, the nitrosation by 1-phenyl-1-propyl nitrite, either of pyrrolidine or piperidine, is inhibited by β-CD addition; however, the nitrosation reaction of piperidine by 2-phenyl-1-propyl nitrite is catalyzed (passing through a maximum) by β-CD, whereas the nitrosation of pyrrolidine promoted by 3-phenyl-1-propyl nitrite exhibits practically no change upon β-CD addition. In alkaline media (containing ionized β-CD) the nitrosation of pyrrolidine by 1-phenyl-1-propyl nitrite is inhibited by the presence of β-CD; in contrast, the nitrosation of both piperidine and N-methylcyclohexylamine is catalyzed in all cases, but the degree of catalysis depends not only on the alkyl nitrite structure, but also on the type and concentration of the amine. Kinetic results are quantitatively interpreted on the basis of the proposed reaction mechanism in each case, and the kinetic rate constants of the different steps are determined. Comparison of the results obtained in aqueous alkaline media and in aqueous buffers of the amines themselves allows us to establish important characteristics of the transition state of the reaction.
Fremy's Salt (Potassium Nitrosodisulphonate): A Nitrosating Reagent for Amines
Castedo, Luis,Riguera, Ricardo,Vazquez, M. Pilar
, p. 301 - 302 (1983)
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.
Trichloroisocyanuric acid/NaNo2 as a novel heterogeneous system for the N-nitrosation of N,N-dialkylamines under mild conditions
Zolfigol, Mohammad Ali,Choghamarani, Arash Ghorbani,Hazarkhani, Hassan
, p. 1002 - 1004 (2002)
A combination of trichloroisocyanuric acid and sodium nitrite in the presence of wet SiO2 was used as an effective nitrosating agent for the nitrosation of N,N-dialkyl amines to their corresponding nitroso derivatives under mild and heterogeneous conditions in moderate to excellent yields.
Visible-Light-Induced Photoaddition of N-Nitrosoalkylamines to Alkenes: One-Pot Tandem Approach to 1,2-Diamination of Alkenes from Secondary Amines
Patil, Dilip V.,Si, Tengda,Kim, Hun Young,Oh, Kyungsoo
supporting information, p. 3105 - 3109 (2021/05/05)
The generation of aminium radical cation species from N-nitrosoamines is disclosed for the first time through visible-light excitation at 453 nm. The developed visible-light-promoted photoaddition reaction of N-nitrosoamines to alkenes was combined with the o-NQ-catalyzed aerobic oxidation protocol of amines to telescope the direct handling of harmful N-nitroso compounds, where the desired α-amino oxime derivatives were obtained in a one-pot tandem N-nitrosation and photoaddition sequence.
Optimization of biaryloxazolidinone as promising antibacterial agents against antibiotic-susceptible and antibiotic-resistant gram-positive bacteria
Wu, Yachuang,Ding, Xiudong,Yang, Yifeng,Li, Yingxiu,Qi, Yinliang,Hu, Feng,Qin, Mingze,Liu, Yajing,Sun, Lu,Zhao, Yanfang
, (2019/10/23)
We previously discovered a series of novel biaryloxazolidinone analogues bearing a hydrazone moiety with potent antibacterial activity. However, the most potent compound OB-104 exhibited undesirable chemical and metabolic instability. Herein, novel biaryloxazolidinone analogues were designed and synthesized to improve the chemical and metabolic stability. Compounds 6a-1, 6a-3, 14a-1, 14a-3 and 14a-7 showed significant antibacterial activity against the tested Gram-positive bacteria as compared to radezolid and linezolid. Further studies indicated that most of them exhibited improved water solubility and chemical stability. Compound 14a-7 had MIC values of 0.125–0.25 μg/mL against all tested Gram-positive bacteria, and showed excellent antibacterial activity against clinical isolates of antibiotic-susceptible and antibiotic-resistant bacteria. Moreover, it was stable in human liver microsome. From a safety viewpoint, it showed non-cytotoxic activity against hepatic cell and exhibited lower inhibitory activity against human MAO-A compared to linezolid. The potent antibacterial activity and all these improved drug-likeness properties and safety profile suggested that compound 14a-7 might be a promising drug candidate for further investigation.
