5336-53-8

Usage

Uses

Used in Research and Development:
N-Nitrosodibenzylamine is used as a research chemical for studying its mutagenic effects on Salmonella typhimurium and its ability to induce DNA strand breaks in isolated rat hepatocytes. This helps scientists understand the potential carcinogenic and toxic effects of nitrosamines and their impact on cellular processes.

Production Methods

Human exposure to NDBzA was not suspected, but then there were reports of the compound in hams wrapped in rubber netting. Concentrations of NDBzA from 10 to 100 ppb were common, and some were as high as 512 ppb. Like other nitrosamines in rubber, NDBzA arose by nitrosation of dialkylamino compounds (in this case dibenzyl-) during manufacture.

Synthesis Reference(s)

Tetrahedron Letters, 25, p. 2619, 1984 DOI: 10.1016/S0040-4039(01)81245-4

Safety Profile

Moderately toxic by ingestion.Mutation data reported. When heated to decomposition itemits toxic vapors of NOx

Carcinogenicity

There is a single report of a test of nitrosodibenzylamine for carcinogenicity in rats using high doses and that is completely negative; in contrast, nitrosobenzylphenylamine is a weak, but definite, esophageal carcinogen in rats. NDBzA is not mutagenic to bacteria in the presence or absence of rat liver microsomes. Although there is no information about metabolism and activation of NDBzA, the alpha-acetoxy derivative (which presumably is the ester of the alpha-hydroxy derivative that would be formed in vivo) is both carcinogenic to rats and mutagenic to bacteria.

InChI:InChI=1/C14H14N2O/c17-15-16(11-13-7-3-1-4-8-13)12-14-9-5-2-6-10-14/h1-10H,11-12H2

Upstream product

• 64-17-5 ethanol 
• 20735-22-2 dibenzyl-amine; nitrite 
• 509-14-8 tetranitromethane 
• 10479-25-1 N,N-dibenzylethanamine 
• 102-05-6 N-methyldibenzylamine 
• 620-40-6 tribenzylamine 
• 103-49-1 dibenzylamine 
• 110-46-3 isopentyl nitrite 
• 10575-94-7 N-benzyl-N-nitrosobenzamide 
• 17761-41-0 N-chloro-N-(phenylmethyl)-benzenemethanamine 
• 25370-09-6 dibenzylcarbamyl chloride 
• 89970-60-5 C₇H₆ClN₂O₂^(1-)*Na⁽¹⁺⁾ 
• 85166-50-3 N-Nitroso-N-benzylhydroxylamine Sodium Salt 
• 35517-91-0 N,N-Dibenzylthiocarbamoylchlorid 

Downstream Products

• 5802-60-8 N,N-dibenzylhydrazine 
• 21136-32-3 1,1-dibenzyl-2-benzylidenehydrazine 
• 103-49-1 dibenzylamine 
• 39886-68-5 C₂₄H₂₅N₃O₄ 
• 100-52-7 benzaldehyde 
• 100-44-7 benzyl chloride 
• 100-51-6 benzyl alcohol 
• 20002-23-7 N-nitroso<α,α,α'α'-2H4>dibenzylamine 
• 3488-55-9 N-hydroxy-N'-(phenylmethyl)-benzenecarboximidamide 

Relevant academic research and scientific papers

KINETIC STUDY ON THE NITROSATION OF DIBENZYLAMINE IN A MODEL SYSTEM

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).

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.

Oxone-sodium nitrite mediated N-nitrosamines formation under mild conditions from secondary amines

Herein, we report an efficient synthesis of N-nitrosamines from cyclic, aliphatic, benzylic, and aromatic secondary amines via a novel straightforward, efficient, and mild chemical process using sodium nitrite and Oxone in methanol as a solvent at 0–5 °C. The demonstrated methodology accounts well for the parameters like cost-effective, short reaction time, clean and safe handling along with good to excellent yields.

Substrate promiscuity of ortho-naphthoquinone catalyst: Catalytic aerobic amine oxidation protocols to deaminative cross-coupling and n-nitrosation

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.

Direct Transformation of Arylamines to Aryl Halides via Sodium Nitrite and N-Halosuccinimide

A one-pot universal approach for transforming arylamines to aryl halides via reaction with sodium nitrite (NaNO2) and N-halosuccinimide (NXS) in DMF at room temperature under metal- and acid-free condition is described. This new protocol that is complementary to the Sandmeyer reaction, is suggested to involve the in situ generation of nitryl halide induce nitrosylation of aryl amine to form the diazo intermediate which is halogenated to furnish the aryl halide.

N-Isocyanodialkylamines generated in situ for the Joullié–Ugi reaction with indolenines

N-Isocyanodialkylamines are rare isocyanide surrogates for the Ugi-type reactions. To avoid problems with instability and the obnoxious smell of these reagents, we optimized and employed a convenient protocol for in situ dehydration of N,N-dialkyl-N′-formyl hydrazines to give the respective N-isocyanodialkylamines which were utilized in the reaction with indolenines and acetic acid. The reaction was demonstrated to give modest to excellent yields of products incorporating the N-isocyanodialkylamine but not the carboxylic acid component.

An efficient synthesis of: N -nitrosamines under solvent, metal and acid free conditions using tert -butyl nitrite

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.

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.

Facile N-nitrosation of secondary amines using poly(N,N'-dibromo-Nethylene- benzene-1,3-disulfonamide) and N,N,N′,N′-tetrabromobenzene-1,3- disulfonamide/NaNO2 under mild conditions

In this research project, a combination of poly(N,N′-dibromo-N- ethylene-benzene-1,3-disulfonamide) [PBBS] and/or (N,N,N′,N′- tetrabromobenzene-1,3-disulfonamide) [TBBDA] with sodium nitrite in the presence of wet SiO2 (50% w/w) was used as an efficient nitrosating agent for the conversion of secondary amines to their corresponding nitroso compounds. N-Nitrosation reaction has been performed in dichloromethane at room temperature under mild and heterogeneous conditions. The reaction is operationally simple and corresponding products were achieved in good to excellent yields.

Ionic liquid 1-(4-nitritobutyl)-3-methylimidazolium chloride as a new reagent for the efficient N-nitrosation of secondary amines under mild conditions

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.