P Nitrochlorobenzene

Prepared by heating p-nitrochlorobenzene with concentrated aqueous ammonia in an autoclave at 170°C. It is also prepared by alkaline hydrolysis of p-nitroacetanilide or by nitrating and hydrolysing benzylideneaniline. 

Kinetics of the reaction of p-nitrochlorobenzene with the sodium enolate of ethyl cyanoacetate are consistent with this mechanism. Also, radical scavengers have no effect on the reaction, contrary to what would be expected for a chain mechanism in which aryl radicals would need to encounter the enolate in a propagation step. The reactant, /i-nitrophenyl chloride, however, is one which might also react by the addition-elimination mechanism, and the postulated mechanism is essentially the stepwise electron-transfer version of this mechanism. The issue then becomes the question of whether the postulated radical pair is a distinct intermediate. 

Nitric acid, 98 Nitric oxide, 98 Nitrilotriacetic acid, 98 p-Nitroaiiiline, 99 Nitrobenzene, 99 Nitrocarbono SA, 146 Nitrocellulose, 99 p-Nitrochlorobenzene, 99 Nitroethane, 99 Nitrofen, 99 Nitrogen, 99 Nitrogen dioxide, 99 Nitrogen oxides, 99 Nitrogen trifluoride, 99 Nitroglycerin, 100 Nitrokemia 200 Rt., 167 Nitromethane, 100 5-Nitro-o-anisidine, 99 5-Nitro-o-toluidine, 100 Nitrophenols, 100... 

The enamine (28) did not undergo C arylation with p-nitrochlorobenzene under these conditions, and at higher temperatures N arylation and subsequent eleavage with formation of N-(4-nitrophenyl) pyrrolidine takes place (68). 

In the arylations of enamines with very reactive aryl halides (352,370) such as 2,4-dinitrochlorobenzene, the closely related mechanistic pathway of addition of the enamine to the aromatic system, followed by elimination of halide ion, can be assumed. The use of n-nitroarylhalides furnishes compounds which can be converted to indolic products by reductive cycliza-tion. Less reactive aryl halides, such as p-nitrochlorobenzene, lead only to N-arylation or oxidation products of the enamines under more vigorous conditions. 

The use of a PTC, tetramethylammonium hydroxide, to carry out the coupling under aeration of nitrobenzene and aniline to give nitroso diphenylamine (which on catalytic reduction with H2 gives 4-aminodiphenylamine, required in the rubber industry) may be cited as a green chemistry route compared to the established process based on p-nitrochlorobenzene and aniline where Cl is wasted (Bashkin et al. 1999). 

Synonyms AI3-15387 BRN 508691 CCRIS 142 l-Chloro-4-nitrobenzene 4-Chloronitro-benzene 4-Chloro-l-nitrobenzene p-Chloro-l-nitrobenzene EINECS 202-809-6 4-Nitrochlor-obenzene p-Nitrochlorobenzene 4-Nitrophenyl chloride p-Nitrophenyl chloride NSC 9792 PCNB PNCB UN 1578. 

Nitro-l,l -biphenyl, see 4-Nitrobiphenyl p-Nitrobiphenyl, see 4-Nitrobiphenyl Nitrocarbol, see Nitromethane 4-Nitrochlorobenzene, see p Chloronitrobenzene p-Nitrochlorobenzene, see p Chloronitrobenzene Nitrochloroform, see Chloropicrin Nitrochloropropane, see 1-Chloro-l-nitropropane... 

Nair RS, Johannsen FR, Levinskas GJ, et al Subchronic inhalation toxicity of p-nitroani-line and p-nitrochlorobenzene in rats. Fundam Appl Toxicol 6 618-627, 1986... 

ACGIH p-Nitrochlorobenzene. Documentation of the Threshold Limit Values and Biological Exposure Indices, 7th ed, pp 3, Cincinnati, OH, American Conference of Governmental Industrial Hygienists, 2001... 

Problem 11.62 Explain these observations (a) p-Nitrobenzenesulfonic acid is formed from the reaction of p-nitrochlorobenzene with NaHSO, but benzenesulfonic acid cannot be formed from chlorobenzene by this reaction. (f>) 2,4,6-Trinitroanisole with NaOC H, gives the same product as 2,4,6-trinitrophenetole with NaOCHj. <... 

Methylamine Methyl alcohol Morpholine Nitrobenzene p-Nitrochlorobenzene Nitrotoluene Phenyl ester-biphenyl vapor mix... 

The potential energy surfaces for the fragmentation of the radical anions of p-nitrochlorobenzene and p- and m-chloroacetophenones have been explored using first principle methods215. The presence of n and a radical anions and the intramolecular ET from the ji to the o surface are reported therein. 

Tetranuclear aromatic diamines were prepared on the basis of bis-phenols derived from 1,1,1-trichloro-2,2-di-(p-methoxyphenyl)-ethane under the action of pyridine hydrochloride [26, 27]. Interaction of the bis-phenols with two-fold molar amounts of p-nitrochlorobenzene led to the formation of 4,4 -bis(/ -nitrophenoxy [-arylenes, which were reduced to the corresponding 4,4 -bis(/ -aminophenoxy[-arylenes [28] (Scheme 2.11). Similar compounds containing two additional amino groups were prepared by the interaction of 3,3 -dinitro-4,4 -dichlorobenzophenone with two-fold molar amounts of potassium p-nitrophenolate [29] followed by reduction of the tetranitro compounds thus formed [29] (Scheme 2.12). 

---