932-83-2

Basic information

• Product Name: N-NITROSOHEXAMETHYLENEIMINE
• Synonyms: hexahydro-1-nitroso-1h-azepin;hexahydro-1-nitroso-1h-azepine;n-6-mi;n-nitrosoazacycloheptane;n-nitrosohexahydroazepine;n-nitrosoperhydroazepine;N-NITROSOHEXAMETHYLENEIMINE;HEXAHYDRO-1-NITROSOAZEPINE
• CAS NO: 932-83-2
• Molecular Formula: C₆H₁₂N₂O
• Molecular Weight: 128.17
• EINECS: 213-258-6
• Mol File: 932-83-2.mol

Chemical Properties

• Boiling Point: 233 °C(lit.)
• Flash Point: 99 °C
• Appearance: /
• Density: 1.06 g/mL at 25 °C(lit.)
• Vapor Pressure: 0.0414mmHg at 25°C
• Refractive Index: n20/D 1.497(lit.)
• Storage Temp.: 2-8°C
• Solubility: Chloroform (Slightly), Methanol (Slightly)
• PKA: -3.18±0.20(Predicted)
• Water Solubility: 12.82g/L(24 oC)
• CAS DataBase Reference: N-NITROSOHEXAMETHYLENEIMINE(CAS DataBase Reference)
• NIST Chemistry Reference: N-NITROSOHEXAMETHYLENEIMINE(932-83-2)
• EPA Substance Registry System: N-NITROSOHEXAMETHYLENEIMINE(932-83-2)

Safety Data

• Hazard Codes: T
• Statements: 45-22-36/37/38
• Safety Statements: 53-36/37/39-45
• WGK Germany: 3
• RTECS: CM3325000
• Hazardous Substances Data: 932-83-2(Hazardous Substances Data)

Usage

Uses

N-Nitrosohexamethylenimine is a carcinogen.

Safety Profile

Poison by ingestion. Experimental teratogenic and reproductive effects. Questionable carcinogen with experimental neoplastigenic data. Mutation data reported. Many N-nitroso compounds are carcinogens. When heated to decomposition it emits very toxic fumes of NO, and SOx. See also N-NITROSO COMPOUNDS.

InChI:InChI=1/C6H12N2O/c9-7-8-5-3-1-2-4-6-8/h1-6H2

Upstream product

• 111-49-9 hexamethylene imine 
• 544-16-1 n-Butyl nitrite 
• 543-67-9 n-propyl nitrite 

Relevant articles and documents

The Use of Potassium/Sodium Nitrite as a Nitrosating Agent in the Electrooxidative N-Nitrosation of Secondary Amines

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.

N-nitrosation of secondary amines using supported perchloric acid on silica gel and stereoselectivity study of nitrosated products

N-Nitrosation of different types of secondary amines has been proceeded using supported perchloric acid on silica gel and sodiume nitrite under heterogeneous conditions. The operational system is simple and high pure products can be easily isolated with good to high yields.

Efficient procedure for chemoselective N-nitrosation of secondary amines with trichloromelamine-NaNO2

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.

Molybdate sulfuric acid/NaNO2: A novel heterogeneous system for the N-nitrosation of secondary amines under mild conditions

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.

Alumina-methanesulfonic acid (AMA)/NaNO2 as an efficient procedure for the chemoselectivite N-nitrosation of secondary amines

A combination of alumina/methanesulfonic acid (AMA) and sodium nitrite was used as an effective nitrosating agent for the nitrosation of secondary amines under mild and heterogeneous conditions in good to excellent yields. Copyright Taylor & Francis Group, LLC.

The use of Nafion-H/NaNO2 as an efficient procedure for the chemoselective N-nitrosation of secondary amines under mild and heterogeneous conditions

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.

Structural features of aliphatic N-nitrosamines of 7-azabicyclo[2.2.1]heptanes that facilitate N-NO bond cleavage

N-Nitrosamines can be considered as potential nitric oxide (NO)/nitrosonium ion (NO+) donors. However, the relation of the structures of N-nitrosamines, in particular of aliphatic N-nitrosamines, to the characteristics of release of NO or NO+ remains unclear. Here we show that aliphatic N-nitrosoamines of 7-azabicyclo[2.2.1]heptanes can undergo heterolytic N-NO bond cleavage. On the basis of the observation of reduced rotational barriers of the N-NO bonds in solution and nitrogen-pyramidal structures of the N-nitroso group in the solid state, we postulate that N-NO bond cleavage of N-nitrosamines is enhanced by a reduction of the resonance in the N-NO group. Computational studies suggest that these structural features of the N-nitrosamines of 7-azabicyclo[2.2.1]heptane are derived from angle strain imposed on the CNC angles.

Formation of Nitrosamines in Alkaline Conditions: a Kinetic Study of the Nitrosation of Linear and Cyclic Secondary Amines by Nitroalkanes

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.