86-30-6

Usage

Uses

Used in Historical Rubber Industry:
N-Nitrosodiphenylamine was historically used as a rubber additive for its properties, but its use has been discontinued due to its carcinogenic effects.
Used in Environmental and Food Contaminant Monitoring:
N-Nitrosodiphenylamine is listed as a drinking water contaminant candidate list 3 (CCL 3) compound by the EPA, indicating its importance in monitoring environmental and food contaminants for public health and safety.

Air & Water Reactions

Insoluble in water.

Reactivity Profile

N-Nitrosodiphenylamine may be sensitive to moisture at elevated temperatures in strongly acidic solutions. May react vigorously with oxidizing agents. May undergo trans-nitrosation reactions with secondary amines .

Health Hazard

ACUTE/CHRONIC HAZARDS: When heated to decomposition N-Nitrosodiphenylamine emits toxic fumes of nitrogen oxides.

Fire Hazard

Flash point data for N-Nitrosodiphenylamine are not available; however, N-Nitrosodiphenylamine is probably combustible.

Flammability and Explosibility

Nonflammable

Safety Profile

Moderately toxic by ingestion. An eye irritant. Questionable carcinogen with experimental carcinogenic and tumorigenic data. Human mutation data reported. Dangerous fire hazard when exposed to heat, flame, or oxidzing materials. Can react vigorously with oxidizing materials. When heated to decomposition it emits highly toxic fumes of NOx,. See also NITROSAMINES.

Potential Exposure

N-Nitrosodiphenylamine is not a naturally occurring substance; it is a man-made chemical that is no longer produced in the United States. It was used in the manufacture of plastics, resins, rubber and synthetic textiles; to help control processes involved in making rubber products, such as tires and mechanical goods; however, in the early 1980s, the United States manufacturers stopped producing N-nitrosodiphenylamine because new and more efficient chemicals were found to replace its uses. In addition, the use of N-nitrosodiphenylamine had several undesirable side effects which do not occur with the replacement chemicals.

Carcinogenicity

Two feeding experiments with NDPhA in rats were totally negative (no tumors). One used daily doses of 120 mg/kg body weight to a total dose of 65 g/kg, and another used a lower dose for only 53 weeks. Another experiment involved larger groups of rats and mice and higher doses. In mice, after 2 years, there was occasional hyperplasia of the bladder mucosa, but no tumors; in rats given 4000 mg NDPhA/kg diet for 2 years, 16/45 males and 40/49 females had transitional cell carcinomas of the bladder. IARC classified NDPhA as not classifiable as to carcinogenicity in humans (Group 3).

Environmental fate

Chemical/Physical. At temperatures greater than 85 °C, technical grades may decompose to nitrogen oxides (IARC, 1978). N-Nitrosodiphenylamine will not hydrolyze because it does not contain a hydrolyzable functional group (Kollig, 1993). At influent concentrations of 10, 1.0, 0.1, and 0.01 mg/L, the GAC adsorption capacities were 510, 120, 91, and 38 mg/g, respectively (Dobbs and Cohen, 1980).

Shipping

UN2811 Toxic solids, organic, n.o.s., Hazard Class: 6.1; Labels: 6.1-Poisonous materials, Technical Name Required.

Incompatibilities

Incompatible with oxidizers (chlorates, nitrates, peroxides, permanganates, perchlorates, chlorine, bromine, fluorine, etc.); contact may cause fires or explosions. Keep away from alkaline materials, strong bases, strong acids, oxoacids, epoxides. Contact with reducing agents may form hydrazine; hydrogen bromide. Light sensitive; rapidly decomposes.

Waste Disposal

Burn in admixture with flammable solvent in furnace equipped with afterburner and scrubber.

InChI:InChI=1/C12H10.H2N2O/c1-3-7-11(8-4-1)12-9-5-2-6-10-12;1-2-3/h1-10H;(H2,1,3)

Upstream product

• 110-86-1 pyridine 
• 64-17-5 ethanol 
• 509-14-8 tetranitromethane 
• 552-82-9 benzhydrylidene(methyl)amine 
• 712-51-6 Diphenylaminoxid-Radikal 
• 632-52-0 tetraphenylhydrazine 
• 29111-46-4 N-phenylaminoacetyl hydrazide 
• 537-67-7 diphenylamine hydrochloride 
• 109-95-5 ethyl nitrite 
• 122-39-4 diphenylamine 
• 71-43-2 benzene 
• 530-50-7 1,1-Diphenylhydrazine 
• 70570-03-5 dinitroformaldehyde diphenylhydrazone 
• 674-81-7 nitrosoguanidine 

Downstream Products

• 39606-58-1 1,1'-diethyl-2,2'-diphenyl-[3,3']azoindole 
• 39606-59-2 1,2,1',2'-tetraphenyl-[3,3']azoindole 
• 86844-02-2 9-phenyl-6,7,8,9-tetrahydro-5H-carbazole 
• 4435-12-5 azophenin 
• 297766-64-4 1,3-Diphenyltriazen 
• 606-88-2 N,N,N'-triphenylhydrazine 
• 92-52-4 biphenyl 
• 108-95-2 phenol 
• 38573-62-5 bis(2,4-dibromophenyl)amine 
• 21565-18-4 (2-nitro-phenyl)-(4-nitro-phenyl)-nitroso-amine 
• 3665-70-1 p-nitrodiphenylnitrosamine 
• 21565-15-1 N-nitroso(2-nitrophenyl)phenylamine 
• 40317-17-7 N,N'-dinitroso-N,N'-diphenyl-benzidine 
• 24495-33-8 4-azidodiphenylamine 

Relevant academic research and scientific papers

One-Pot Tandem ortho-Naphthoquinone-Catalyzed Aerobic Nitrosation of N-Alkylanilines and Rh(III)-Catalyzed C-H Functionalization Sequence to Indole and Aniline Derivatives

The nitroso group served as a traceless directing group for the C-H functionalization of N-alkylanilines, ultimately removed after functioning either as an internal oxidant or under subsequent reducing conditions. The unique ability of o-NQ catalysts to aerobically oxidize the N-alkylanilines without using solvents and stoichiometric amounts of oxidants has rendered the new opportunity to develop the telescoped catalyst systems without a need for directly handling the hazardous N-nitroso compounds.

Access to Branched Allylarenes via Rhodium(III)-Catalyzed C-H Allylation of (Hetero)arenes with 2-Methylidenetrimethylene Carbonate

A rhodium(III)-catalyzed C-H allylation of (hetero)arenes by using 2-methylidenetrimethylene carbonate as an efficient allylic source has been developed for the first time. Five different directing groups including oxime, N-nitroso, purine, pyridine, and pyrimidine were compatible, delivering various branched allylarenes bearing an allylic hydroxyl group in moderate to excellent yields.

Rh(iii)-catalyzed, hydrazine-directed C-H functionalization with 1-alkynylcyclobutanols: A new strategy for 1: H -indazoles

Rh(iii)-catalyzed coupling of phenylhydrazines with 1-alkynylcyclobutanols was realized through a hydrazine-directed C-H functionalization pathway. This [4+1] annulation, based on the cleavage of a Csp-Csp triple bond in alkynylcyclobutanol, provides a new pathway to prepare diverse 1H-indazoles under mild reaction conditions. This journal is

Rhodium(iii)-catalyzed indole synthesis at room temperature using the transient oxidizing directing group strategy

Rh-catalyzed reactions of N-alkyl anilines with internal alkynes at room temperature have been developed using an in situ generated N-nitroso group as a transient oxidizing directing group. Due to mild reaction conditions, this method enabled synthesis of a broad range of N-alkyl indoles, including even two indole-based medicinal compounds. Our work disclosed the feasibility of the transient oxidizing directing group strategy in C-H functionalization reactions, which possesses the potential to enhance overall step-economy and impart new reactivity patterns to substrates.

4-amino diphenylamine preparation method

The invention discloses a 4-amino diphenylamine preparation method which includes the steps: slowly dropping concentrated hydrochloric acid into concentrated sulfuric acid, drying generated HCl gas bythe concentrated sulfuric acid and then leading the HCl gas into n-butyl alcohol for absorbing the gas; adding diphenylamine, sodium nitrite, water and methylbenzene, dissolving the diphenylamine bystirring, and then dropping hydrogen chloride for reaction with n-butyl alcohol solution; performing standing and liquid separation, removing water phase and organic phase vacuum desolvation agents, adding water, stirring the solution and performing suction filtration, washing and drying to obtain 4-nitroso diphenylamine; adding the 4-nitroso diphenylamine into an autoclave, adding solvents and catalysts, replacing air in the autoclave by hydrogen and performing hydrogenation reaction; filtering catalyzed hydrogenation liquid, decompressing the desolvation agents and finally performing rectification to obtain 4-amino diphenylamine. According to the preparation method, under the condition of low and medium pressure, composite skeleton nickel catalysts replace traditional noble metal catalysts for hydrogenation reduction of 4-amino diphenylamine, waste gas, waste water and industrial residues are fewer, environmental protection is benefited, and production cost is reduced.

Four-Coordinate Copper Halonitrosyl {CuNO}10 Complexes

While copper nitrosyl complexes are implicated in numerous biological systems, isolable examples remain limited. In this report, we show that [Cl3CuNO]?, with a {CuNO}10 electron configuration, can be generated by nitrite reduction at a copper(I) dichloride anion or by nitric oxide addition to a copper(II) trichloride precursor. The bromide analogue, [Br3CuNO]? was synthesized analogously, and both copper halonitrosyl complexes were characterized by X-ray diffraction and a variety of spectroscopic methods. Experimental data and multireference (CASSCF/NEVPT2) calculations provide strong evidence for a CuII–NO. ground state. Both [Cl3CuNO]? and [Br3CuNO]? release and recapture NO. reversibly, and exhibit nitrosative reactivities toward a wide range of biological nucleophiles, such as amines, alcohols, and thiols.

Copper(II) activation of nitrite: Nitrosation of nucleophiles and generation of NO by thiols

Nitrite (NO2-) and nitroso compounds (E-NO, E = RS, RO, and R2N) in mammalian plasma and cells serve important roles in nitric oxide (NO) dependent as well as NO independent signaling. Employing an electron deficient β-diketiminato copper(II) nitrito complex [C12NNf6]Cu(κ2-O2N)-THF, thiols mediate reduction of nitrite to NO. In contrast to NO generation upon reaction of thiols at iron nitrite species, at copper this conversion proceeds through nucleophilic attack of thiol RSH on the bound nitrite in [CuII](κ2-O2N) that leads to S-nitrosation to give the S-nitrosothiol RSNO and copper(Il) hydroxide [CuII]-OH. This nitrosation pathway is general and results in the nitrosation of the amine Ph2NH and alcohol tBuOH to give Ph2NNO and tBuONO, respectively. NO formation from thiols occurs from the reaction of RSNO and a copper(II) thiolate [CuII]-SR intermediate formed upon reaction of an additional equiv thiol with [CuII]-OH.

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.

Palladium-catalyzed oxidative C-H bond acylation of N-nitrosoanilines with toluene derivatives: A traceless approach to synthesize N-alkyl-2-aminobenzophenones

A palladium-catalyzed cascade cross-coupling of N-nitroso-anilines and toluene derivatives for the direct synthesis of N-alkyl-2-aminobenzophenones is described. N-nitroso groups in anilines can act as the traceless directing groups while toluene derivatives can serve as effective acyl precursors under mild reaction conditions.

Rhodium(III)-catalyzed N-nitroso-directed C-H addition to ethyl 2-oxoacetate for cycloaddition/fragmentation synthesis of indazoles

RhIII-catalyzed N-nitroso-directed C-H addition to ethyl 2-oxoacetate allows subsequent construction of indazoles, a privileged heterocycle scaffold in synthetic chemistry, through the exploitation of reactivity between the directing group and installed group. The formal [2+2] cycloaddition/fragmentation reaction pathway identified herein, a unique reactivity pattern hitherto elusive for the N-nitroso group, emphasizes the importance of forward reactivity analysis in the development of useful C-H functionalization-based synthetic tools. The synthetic utility of the protocol is demonstrated with the synthesis of a tri-cyclic-fused ring system. The diversity of covalent linkages available for the nitroso group should enable the extension of the genre of reactivity reported herein to the synthesis of other types of heterocycles.