Nitrobenzene with carbon tetrachloride

In the preparation of hydrocarbons an alkyl, aryl, or aralkyl halide is mixed with an excess of an aromatic hydrocarbon, and anhydrous aluminum chloride is added in small portions. The reagents must be free from moisture. If the reactants are not liquid or the reaction is very vigorous, a solvent is used. Benzene, nitrobenzene, carbon disulfide, or o-dichlorobenzene may be employed as solvents. When polyhalides are used, more than one molecule of the hydrocarbon may react. For example, benzene with chloroform yields triphenylmethane, and benzene with carbon tetrachloride gives triphenylmethyl chloride ... 

Solvent Stability. It is not always essential that a prospective solvent, well suited for a particular sulfonation reaction in one or more respects, be completely inert toward the pure sulfonating agent. Several of the solvents mentioned above, for example, ortho—dichlorobenzene, nitrobenzene, chloroform, carbon tetrachloride, methylene chloride, and trichloroethylene, will react with SO3 or its derivatives either by sulfonation or oxidation, in some cases quite easily. Reactive solvents can be employed with little loss if... 

In 1866 Kekule [1291 described the reaction of nitrobenzene with bromine t 250°C which under pressure yielded tetra- and hexabromobenzene [130], thus the replacement of the nitro group by bromine occurred. Later it was found 11311 that chlorobenzene was the main product when acting with chlorine on (nitrobenzene at 375°C in 46 s contact time with only a small proportion of chloronitrobenzenes. The substitution of nitro groups in m-dinitrobenzene by chlorine in gas phase at 200-300°C appears to be a commercial method of manufacturing m-diclilorobenzene [132]. Ponomarenko [133] studied this reaction and found the yield to be 92%. He also stated that aromatic nitro com-jpounds are transformed into chloro derivatives by acting on nitro compounds f with carbon tetrachloride at 220—310°C under pressure. 

Repeat the boiling point determination with the following pure liquids (a) carbon tetrachloride, A.R. (77°) (6) ethylene dibromide (132°) or chlorobenzene (132°) (c) aniline, A.R. (184-6°) and (d) nitrobenzene, A.R. (211°). An air condenser should be used for (c) and (d). Correct the observed boiling points for any appreciable deviation from the normal pressure of 760 mm. Compare the observed boiling points with the values given in parentheses and construct a calibration curve for the thermometer. Compare the latter with the curve obtained from melting point determinations (Section 111,1). 

Solutions of dinitrogen pentoxide have been used in preparative nitrations.Benzene, bromobenzene, and toluene were nitrated rapidly in solutions of the pentoxide in carbon tetrachloride nitrobenzene could not be nitrated under similar conditions, but reacted violently with solid dinitrogen pentoxide. 

Aluminum chloride dissolves readily in chlorinated solvents such as chloroform, methylene chloride, and carbon tetrachloride. In polar aprotic solvents, such as acetonitrile, ethyl ether, anisole, nitromethane, and nitrobenzene, it dissolves forming a complex with the solvent. The catalytic activity of aluminum chloride is moderated by these complexes. Anhydrous aluminum chloride reacts vigorously with most protic solvents, such as water and alcohols. The ability to catalyze alkylation reactions is lost by complexing aluminum chloride with these protic solvents. However, small amounts of these "procatalysts" can promote the formation of catalyticaHy active aluminum chloride complexes. 

Aniline with acetone, benzene, carbon tetrachloride, ethyl ether, n-heptane, methanol, acetonitrile or nitrobenzene. 

NOTE - Petrochemical plants also generate significant amounts of solid wastes and sludges, some of which may be considered hazardous because of the presence of toxic organics and heavy metals. Spent caustic and other hazardous wastes may be generated in significant quantities examples are distillation residues associated with units handling acetaldehyde, acetonitrile, benzyl chloride, carbon tetrachloride, cumene, phthallic anhydride, nitrobenzene, methyl ethyl pyridine, toluene diisocyanate, trichloroethane, trichloroethylene, perchloro-ethylene, aniline, chlorobenzenes, dimethyl hydrazine, ethylene dibromide, toluenediamine, epichlorohydrin, ethyl chloride, ethylene dichloride, and vinyl chloride. 

Goswami and Sarkar3 claimed to have prepared methyl and ethyl fluoroformates by the action of thallium fluoride on the corresponding chloroformates. These fluoroformates were described as powerful lacrimators. We found that no appreciable reaction took place between potassium fluoride and ethyl chloroformate in boiling carbon tetrachloride or nitrobenzene. Ethyl fluoroformate could, however, be readily produced by the action of potassium fluoride on ethyl chloroformate by using the autoclave technique. It was found not to have the lacrimatory properties claimed for it, and was non-toxic in comparison with M.F.A. This non-toxicity was to be expected, as the fluoroformate contains the COF and not the CH2F- group. 

Bawn and Mellish s experiments in other solvents (benzene, carbon tetrachloride, nitrobenzene, methyl acetate, and ethylacetate) produced similar values for the activation enthalpy, with an average Ea = 123.8 kJ mol-1 [323], which corresponds to A t// ,., = 121.0 kJ mol-1. 

White monoclinic crystals density 5.09 g/cm melts at 64°C (triple point) sublimes at 56.6°C critical temperature 232.65°C critical pressure 46 atm critical volume 250 cm /mol reacts with water forming UO2F2 and HF soluble in chloroform, carbon tetrachloride and fluorocarbon solvents soluble in liquid chlorine and bromine dissolves in nitrobenzene to form a dark red solution that fumes in air. 

Almost all electrophilic substitutions known to proceed in solution with isopropylbenzene can also be performed with polystyrene, using solvents such as nitrobenzene, carbon disulfide, or carbon tetrachloride. These substitutions include bromination [42], nitration [43,44], sulfonylation, Friedel-Crafts acylations [45 49], and alkylations... 

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