Nitro derivatives of benzene

By substitution of the univalent radical (NOa) for the hydrogen of benzene a series of substitution products are obtainable, corresponding to the series of haloid derivatives, phenols, etc. (see pp. 397-403). 

Mono-nitro-benzene—Nitro-benzol—Nitro-benzene—Essence of Mirbane—CeH((NOa)—133—is obtained by the moderated action f fuming HNOa, or of a mixture of HNOa and HaSOa on benzene. 

It is a yellow, sweet liquid, with an odor of bitter almonds sp. gr. 1.309 at 15° (59° F.) boils at 213° (415°.4 P.) almost insoluble in water very soluble in alcohol and ether. Concentrated HaSOi dissolves, and, when boiling, decomposes it. Boiled with fuming HNOa, it is converted into binitro-benzene. It is converted into anilin by reducing agents. 

It has been used in perfumery as artijieial essence of bitter almonds but as inhalation of its vapor, even largely diluted with air, causes headache, drowsiness, difficulty of respiration, cardiac irregularity, loss of muscular power, convulsions, and coma, its use for that purpose is to be condemned. Taken internally it is an active poison. 

Nitro-benzol may be distinguished from oil of bitter almonds (benzoic aldehyde) by HaSO , which does not color the former and by the action of acetic acid and iron filings, which convert nitro-benzene into anilin, wliose presence is detected by the reactions for that substance (q.v.). 

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Toxicity. Picric Acid is more toxic than the nitro derivatives of toluene, xylene or naphthalene. It is, however, much less toxic than nitro derivatives of benzene... 

Addition of nitro compounds (such as nitro derivatives of benzene and toluene) neither changes the pH nor the shape of the curve. 

This methodology was applied to annulation of the pyridine ring (see structure 260). Nitro derivatives of benzene, naphthalene, thiophene, pyridine and quinoline... 

Nitro derivatives of benzene, when boiled with sodium hydroxide in methyl alcohol solution are reduced to azoxy compounds (pp. 31, 237, 251). Nitro derivatives of toluene under these conditions are oxidized to nitro derivatives of stilbene (pp. 70, 283, 302). 

In the case of nitro derivatives of benzene at least two nitro groups should be present on the ring. Here are the most typical reactions, as suggested by Meisen-heimer ... 

The investigation of sulphurless vulcanizing agents, including the use of poly-nitro derivatives of benzene, has been completed by Mark and his co-workers [94]). 

Nitro derivative of benzene Heat of combustion (at constant volume), kcal/mole Heat of formation (for amorphous carbon), kcal/mole... 

Fig 50. Heats of formation of nitro derivatives of benzene and toluene (a) and heats of nitration of benzene and toluene (b) in kcal/mole. (Garner and Abernethy [50]). 

Of all nitro derivatives of toluene, trinitrotoluene is the most important as an explosive. It is by the most often used high explosive among those derived from aromatic compounds. It is popular because it is simple and relatively safe to manufacture, Mid has high explosive power, and above all because its high chemical stability and low sensitiveness to impact and friction make it safe to handle. In addition, its toxicity is low and thus it compares favourably in this respect with the nitro derivatives of benzene. 

Explosive mixtures of alkali metal chlorates with carbon-rich organic compounds such as wood dust, petroleum, oils, fats and nitro derivatives of benzene and toluene they may also contain nitrate esters. Their strength is lower than that of ammonium nitrate explosives in powder form. Chlorate explosives must not be stored together with ammonium nitrate explosives, since ammonium chlorate, which is formed when these two substances are brought into contact, decomposes and explodes. 

Many nitro derivatives of benzene and naphthalene were of importance in the past, since toluene - the starting compound in the manufacture of TNT - could only be prepared by distillation of coal. Owing to the advances in petrochemistry, toluene is now available in practically unlimited amounts the bulk of the toluene now produced is employed as the starting material for the preparation of toluene diisocyanate (TDI) used in the production of plastics. 

Steinmetz, H. (1915). Crystallographic study of some nitro derivatives of benzene. Zeitschrift, 54,467-97. [212]... 

A study was made of the ultraviolet spectra of benzene, alkyl-, amino-, and nitro-derivatives of benzene, diphenyl-amine, triphenylmethane, triphenylcarbinol, and anthra-quinone adsorbed on zeolites with alkali exchange cations, on Ca- and Cu-zeolites, and on decationized zeolites. The spectra of molecules adsorbed on zeolites totally cationized with alkali cations show only absorption bands caused by molecular adsorption. The spectra of aniline, pyridine, triphenylcarbinol, and anthraquinone adsorbed on decationized zeolite and Ca-zeolite are characterized by absorption of the corresponding compounds in the ionized state. The absorption bands of ionized benzene and cumene molecules appear only after uv-excitation of the adsorbed molecules. The concentration of carbonium ions produced during adsorption of triphenylcarbinol on Ca-zeolite and on the decationized zeolite depends on the degree of dehydroxyla-tion of the zeolite. 

Nitro derivatives of benzene Nitro derivatives of diphenyl... 

Thermochemica) properties of nitro derivatives of benzene Literature... 

Chapter 6. Nitro derivatives of benzene, toluene and other aromatics 13K... 

NITRO DERIVATIVES OF BENZENE, TOLUENE AND AROMATICS Nitrobenzene (Vol. I, p. 231)... 

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