Nitrobiphenyl

Pacseri I, Magos L, Batskor lA Threshold and toxic limits of some amino and nitro compounds. AMA Arch Ind Health 18 1-8, 1958 

Hamblin DO Aromatic nitro and amino compounds. In Patty FA (ed) Industrial Hygiene and Toxicology, 2nd ed, Vol 2, Toxicology, pp 2105-2147. New York, Interscience, 1963 

Beauchamp RO Jr, Irons RD, Rickert DE, et al A critical review of the literature on nitrobenzene toxicity. CRC Crit Rev Toxicol 11 33-84, 1982 

Hamm TE Jr Ninety-Day Inhalation Toxicity Study of Nitrobenzene in F344 Rats, CD Rats, and B6C3F1 Mice Final Study Report. Research Triangle Park, NC, CRT, 1984 

Medinsky MA, Irons RD Sex, strain and species differences in the response of rodents to nitrobenzene vapors. In Rickert DE (ed) The Toxicity of Nitroaromatic Compounds, pp 35-51. New York, Hemisphere Publishing, 1985 

Insoluble in water slightly soluble in cold alcohol but more readily soluble in hot alcohol soluble in chloroform and ether.1 

Highly toxic.2 An experimental carcinogen via oral route.3 Induces bladder cancer in dogs. TLV, no exposure permitted.5 

Wear butyl rubber gloves, protective laboratory coat, and eye protection. 

On skin. Wash with strong soap solution immediately. Rinse well. 

Spills. Scoop up solid into appropriately labeled container. Dispose of by burning see waste disposal procedure.2 

Submitted by C. E. Kaslow and R. M. Summers.1 Checked by James Cason and B. H. Walker. 

l-(m-Nitrophenyl)-3,3-dimethyltriazene. To a 3-1. threenecked flask containing 276 g. (2 moles) of technical grade m-nitroaniline (Note 1) are added 250 ml. of concentrated hydrochloric acid and 500 ml. of hot water. The contents of the flask are heated to about 85° to dissolve the w-nitroaniline then 550 ml. of concentrated hydrochloric acid is added, and the solution is cooled rapidly. A stirrer, a thermometer, and a longstemmed dropping funnel are attached to the flask, and its contents are then cooled to —3 to —5° by means of a salt-ice bath. A solution of 144 g. (2.09 moles) of sodium nitrite in 350 ml. of water is added dropwise under the surface of the acid solution 

m-Nitrobiphenyl. To a 5-1. three-necked flask equipped with a sealed mechanical stirrer, a dropping funnel, and a reflux condenser are added 116.4 g. (0.6 mole) of 1 - (m-nitrophenyl)-3,3-dimethyltriazene and 2.5 1. of benzene. The benzene solution is heated to maintain refluxing and stirred vigorously while a solution of 148 g. (0.8 mole) of 94% toluenesulfonic acid (Note 7) in 750 ml. of benzene is added dropwise (Note 8) over a period of 4 4.5 hours. The refluxing is continued for 1-1.5 hours (Note 9) 

du Pont de Nemours and Company technical product, m.p. 111-112°, was used. 

The time required for the addition varies from 1.5 to 2 hours. 

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Fig. 4.58. Raman spectra of nitrophenyl modi- 1336 and 1586 cm" might be affected by sub-fied (A) and untreated (B) glassy carbon, the dif- traction of closely neighboring, much stronger ference between spectra A and B (C), and the re- bands of the carbon bulk. Five further marked ference spectrum of solid 4-nitrobiphenyl (D). surface bands are clearly visible in the difference The strongest surface bands at approximately spectrum C [4.292],...

Methoxy-4 -nitrobiphenyl 1,1 -Biphenyl, 4-methoxy-4 -nitro- (9) (2143-90-0) 4-Nitrophenyl trifluoromethanesulfonate Methanesulfonic acid, trifluoro-, p-nitrophenyl ester (8) Methanesulfonic add, trifluoro-, 4-nitrophenyl ester (9) (17763-80-3)... 

J. K. Stille, Antonio M. Echavarren, Robert M. Williams, and James A. Hendrix 97 4-METHOXY-4-NITROBIPHENYL... 

Nitro polycyclic aromatic hydrocarbons are environmental contaminants which have been detected in airborne particulates, coal fly ash, diesel emission and carbon black photocopier toners. These compounds are metabolized Tn vitro to genotoxic agents through ring oxidation and/or nitroreduction. The details of these metabolic pathways are considered using 4-nitrobiphenyl, 1- and 2-nitronaphthalene, 5-nitro-acenaphthene, 7-nitrobenz[a]anthracene, 6-nitro-chrysene, 1-nitropyrene, 1,3-, 1,6- and 1,8-dinitro-pyrene, and 1-, 3- and 6-nitrobenzo[a] pyrene as examples ... 

Some subsequent discussion on compound 3 followed our original paper on this subject (N. Masciocchi, M. Bergamo, A. Sironi, Comments on the elusive crystal structure of 4-iodo-4 -nitrobiphenyl Chem. Comm, 1998,1347-1348 J. Hulliger, P. J. Langley, On intrinsic and extrinsic defect-forming mechanisms determining the disordered structure of 4-iodo-4 -nitrobi-phenyl Chem Comm, 1998, 2557-2558), but these papers, which describe the effects of small amounts of 4,4 -dinitrobiphenyl impurity in 3, only reinforce the idea of structures based on N02—I synthons. 

Other high-boiling solvents such as nitrobenzene and 2-nitrotoluene can also be used in the solvent process, but 4-nitrobiphenyl, a listed carcinogen, is produced when nitrobenzene is employed. One way to avoid the formation of substituted biphenyls is to employ a polysubstituted toluene as solvent, the substituents being chlorine or alkyl groups, mainly propyl. These are difficult to prepare but they have been patented by Toyo Inks. 

Naphthylamine Benzidine 4-Aminobiphenyl 4-Nitrobiphenyl 1 -Naphthylamine Importation and use in manufacture of these are prohibited by legislation, e.g. in the U.K., except if present at less than 1% in another material Use of this is controlled by legislation, e.g. in the U.K. 

The reaction depicted above proceeds also in other aprotic but not in protic solvents, and (7r,7c )-nitroaromatics (1-nitro-, 2-nitro- and 2-chloro-4-nitro-naphthalene, 4-nitrobiphenyl) seem to be more reactive than several nitrobenzenes. However, the lifetime of the excited state of the respective nitroaromatic may play a dominating role in these cases. 

The triplet state of 4-nitrobiphenyl has been observed in laser flashed benzene solution (. max 540 nm, t 10 ns at room temperature) 32). 4-Nitrobiphenyl and 4,4 -dinitrobiphenyl have been photoreduced by sodium formate in buffered aqueous methanolic solution 43i>) 15% 4-aminobiphenyl and 11% 4,4 -azobi-phenyl as well as 49% 4-amino-4 -nitrobiphenyl and 20% 4,4 -(p-nitrophenyl)-azoxybenzene, respectively, could be isolated and identified by comparison with authentic samples. 

Quenching by TMDD has also been observed for the photomethoxylation of 1-nitroazulene (see Section B.I) and the photocyanation of 4-nitrobiphenyl 126). Thus these substitutions also probably proceed via excited triplet states. 

Soil Benzidine was added to different soils and incubated in the dark at 23 °C under a carbon dioxide-free atmosphere. After 1 yr, 8.3 to 11.6% of the added benzidine degraded to carbon dioxide primarily by microbial metabolism and partially by hydrolysis (Graveel et al, 1986). Tentatively identified biooxidation compounds using GC/MS include hydroxybenzidine, 3-hydroxybenzidine, 4-amino-4 -nitrobiphenyl, A(A -dihydroxybenzidine, 3,3 -dihydroxybenzidine and 4,4 -dinitrobiphenyl (Baird et al, 1977). Under aerobic conditions, the half-life was estimated to be 2 to 8 d (Lu et ah, 1977). 

In the presence of hydrogen peroxide and acetylcholine at pH 11 and 20 °C, benzidine oxidized to 4-amino-4 -nitrobiphenyl (Aksnes and Sandberg, 1957). 

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