Nitrobenzene and Aniline

Equip a 500 ml. three-necked flask with an efficient stirrer (e.g., a Hershberg stirrer. Fig. II, 7, 8) and a reflux condenser stopper the third neck. Place a solution of 30 g. of sodium hydroxide in 100 ml. of water, and also 20-5 g. (17-1 ml.) of pure nitrobenzene in the flask, immerse it in a water bath maintained at 55-60°, and add 21 g. of anhydrous dextrose in small portions, with continuous stirring, during 1 hour. Then heat on a boiUng water bath for 2 hours. Pour the hot mixture into a 1 litre round-bottomed flask and steam distil (Fig. II, 40, 1) to remove aniline and nitrobenzene. When the distillate is clear (i.e., after about 1 htre has been collected), pour the residue into a beaker cooled in an ice bath. The azoxybenzene soon sohdifies. Filter with suction, grind the lumps of azoxybenzene in a mortar, wash with water, and dry upon filter paper or upon a porous plate. The yield of material, m.p. 35-35-5°, is 13 g. Recrystallise from 7 ml. of rectified spirit or of methyl alcohol the m.p. is raised to 36°. ... 

Determination of boiling points. Distillation method (Fig. II, 12, 1) for carbon tetrachloride (25 nil. distillation flask and small water condenser), and SiwoloboflF s method (Fig. II, 12, 2) for carbon tetrachloride, aniline and nitrobenzene. Calibration curve for thermometer. Determination of b.p. of unknown liquid. 

W 0 H L - A U E Phenazine synthesis Synthesis of phenazine N-oxide from anilines and nitrobenzene... 

Predict the products of electrophilic nitration of toluene, aniline and nitrobenzene. 

Compare the geometry of para-nitroaniline to those of both aniline and nitrobenzene. Is there any evidence for push-pull resonance contributors Is there shortening of bonds to the amino and nitro groups Are the bonds in the ring localized Is the dipole moment for para-nitroaniline smaller, larger or about the same as the sum of the dipole moments for aniline and nitrobenzene What does your result say about the importance of push-pull resonance contributors ... 

Piotrowski, J.K. 1984. Phenol, aniline, and nitrobenzene. Pp. 165-175 in Biological monitoring and surveillance of workers exposed to chemicals, A.Aitio, V. Riihimaki, and H.Vanio, eds. New York Hemisphere. 

Aniline and nitrobenzene electrophilic substitution reactivity We briefly consider the effect of pi-donor or pi-acceptor substituents on aromatic conjugation patterns for two representative examples aniline (23) and nitrobenzene (24). The leading NBO interactions between ring and substituent in these species are depicted in Fig. 3.47. 

Variations in retention and selectivity have been studied in cyano, phenyl, and octyl reversed bonded phase HPLC columns. The retention of toluene, phenol, aniline, and nitrobenzene in these columns has been measured using binary mixtures of water and methanol, acetonitrile, or tetrahydrofuran mobile phases in order to determine the relative contributions of proton donor-proton acceptor and dipole-dipole interactions in the retention process. Retention and selectivity in these columns were correlated with polar group selectivities of mobile-phase organic modifiers and the polarity of the bonded stationary phases. In spite of the prominent role of bonded phase volume and residual silanols in the retention process, each column exhibited some unique selectivities when used with different organic modifiers [84],... 

Aliphatic analogues of aniline and nitrobenzene were discovered somewhat later. Methy-lamine and ethylamine were first prepared by Wurtz in 184914, and thereafter many aliphatic amines were made and their properties studied13, particularly by Hofmann15. 

Pendergrass SM An approach for estimating workplace exposure to o-toluidine, aniline, and nitrobenzene. Am Ind Hyg Assoc J 55 733-737, 1994... 

Phenol > Toluene > p-Bromotoluene > Bromobenzene Aniline and nitrobenzene don t undergo Friedel-Crafts alkylations. 

Methaemoglobinaemia may be induced by oxidising drugs sulphonamides, nitrites, nitrates (may also occur in drinking water), primaquine, -caine local anaesthetics, dapsone, nitrofurantoin, nitroprusside, vitamin K analogues, chlorates, aniline and nitrobenzene. In the rare instance of there being urgency, methylene blue 1 mg/kg slowly i.v. benefits within 30 min. (Ascorbic acid competes directly with the chemical cause but is inadequate in severe cases, which are the only ones that need treatment.)... 

Fig. 6.6. Molecular graphs showing the bond critical points, calculated from theoretically determined charge densities for aniline and nitrobenzene. The numbers to the right of each structure give the changes in the f contribution to the charge on carbon relative to their values in benzene, while those to the left of each structure give the changes in the a contribution to...

A less restrictive implementation of the procedure, find-all-pathways, on the initial chemical species set, would employ the. operators K or K and would generate several additional reactions of interest. Among these additional reactions of particular interest are, the decomposition reaction of nitrobenzene and the disproportionation of nitrobenzene with N-phenyl hydroxylamine forming aniline and nitrobenzene ... 

Use Spartan View to obtain the dipole moments of aniline, nitrobenzene, and 4-nitro-aniline. Is the dipole moment of 4-nitroani ine the sum of the dipole moments of aniline and nitrobenzene Compare electrostatic potential maps and geometries for all three structures, and draw resonance structures for 4-nitroaniline that account for your observations. 

SCHEME 4. Carbonylation of aniline and nitrobenzene to methyl N -phenyl carbamate (Catalytica Associates, Nippon Kokan and Haldor Topsoe), and conversion to isocyanates... 

Derivation By treatment of aniline and nitrobenzene with glycerol and sulfuric acid and heat. 

BJ Blaauboer, CWM Van Flolsteijn. Formation and disposition of N-hydroxy-lated metabolites of aniline and nitrobenzene by isolated rat hepatocytes. Xenobiotica 13(5) 295-302, 1983. 

Radovic and coworkers [38] recently investigated the effects on the adsorption process of the pH and the nature of the functional groups on the aromatic adsorptive and the adsorbent. For this purpose, they used an as-received activated carbon oxidized with nitric acid and nitrided with ammonia to study the adsorption of aniline and nitrobenzene, which are, respectively, electron-donating and electron-withdrawing groups. Results found by these authors, together vidth... 

Albrecht W, Neumann Fl-G. 1985. Biomonitoring of aniline and nitrobenzene Flemoglobin binding in rats and analysis of adducts. Arch Toxicol 57 1-5. 

Patil S, Shinde VM. 1988. Biodegradation studies of aniline and nitrobenzene in aniline plant waste waters by gas chromatography. Environ Sci Technol 22 1160-1165. 

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