Compound nitrobenzene

DNB and 1,3,5-TNB are nitrobenzene compounds that are structurally similar. The only difference in structure between 1,3-DNB and 1,3,5-TNB is the presence of an additional nitro group in 1,3,5- TNB. There is no information on 1,3,5-TNB exposure by the inhalation route. There is also very little information regarding inhalation exposure to 1,3-DNB. 

Another early symptom of exposure to 1,3-DNB is cyanosis due to oxygen deprivation because of the presence of methemoglobin in the blood. These changes are also not specific for 1,3-DNB and may be produced by other nitrobenzene compounds and dinitrobenzene isomers. Therefore, cyanosis is not a good biomarker for 1,3-DNB exposure. 

Exposure. Exposure to 1,3-DNB is currently measured indirectly by determining levels of methemoglobin in the blood (Donovan 1990). However, increased methemoglobin formation is not a specific response to 1,3-DNB exposure and may occur after exposure to other nitrobenzene compounds such as the other two isomers of dinitrobenzene. Determination of methemoglobin levels is widely used and is a reliable detection method. Very few methods are available for direct evaluation of 1,3-DNB levels, and they are not extensively used, probably because of the relatively rapid rate of conversion of 1,3-DNB to its degradation products (Cossum and Rickert 1985). Preliminary data suggested that the formation of adducts of 1,3,5-TNB with tissue DNA and/or with blood proteins may be useful as markers for exposure to 1,3,5-TNB (Reddy et al. 1991). Further research with both 1,3-DNB and 1,3,5-TNB in the area of adduct formation could provide valuable additional information. 

Effect. Cyanosis is also an early symptom of exposure to 1,3-DNB (Okubo and Shigeta 1982) and is a result of oxygen deprivation due to the presence of methemoglobin in the blood. However, it is not specific and may occur after exposure to other nitrobenzene compounds or other non-related chemicals. 

O Brien PJ et al., Toxicity of nitrobenzene compounds towards isolated hepatocytes Dependence on reduction potential, Xenobiotica, 20, 945, 1990. 

Finally, an attempt was made by using Buck and Kobrich s method (ref. 77), which yields phenols by the reaction of lithiated aryl compounds with nitrobenzene. Compound (81) was treated with n-butyllithium at -10010 in THF in the presence of tetramethylethylenediamine followed by the addition of nitrobenzene. The crude products, which were difficult to isolate as phenolic compounds, were immediately methylated with diazomethane in ether solution. The products were subjected to preparative thin layer chromatography, affording two substances. One, obtained from the upper layer, was recrystallized from ethanol as colorless needles. It showed mp 162.5 163.5lC and an optical rotation of [ o ]D -110° (c= 0.14 in CHClj). The other one, isolated from the lower layer, was recrystallized from ethanol as colorless needles. It showed mp 185 — 187"C and an optical rotation of... 

Excited states of ketones (compound I) and positive solvatochromic dyes, e.g. diethylamino p-nitrobenzene (compound II of table VII) or related compounds are more strongly solvated by polar solvents when comparki with apolar ones. The shift of the K a transition of substituted p-nitro enoles as well as the n a transition of ketones are used as empirical polarity scales, a and % of a solvent. The energy shifts of the a a transition of substituted pyridinium-N-phenoIate betaines (compound III) and the charge-transfer absorption... 

Tetralin, Indan and Nitrobenzene Compound Structure-musk Odor Relationship Using... 

Students should carry out the purification by steam distillation of (a) crude nitrobenzene or chlorobenzene, or of (b) crude naphthalene, o-nitrophenol (p. 170) or />-tolunitrile (p. 194) as examples of solid compounds which may also be purified in this way. When the distillation is complete, disconnect the tubing (Fig. 15) between C and D before removing the flame from under D, otherwise the contents of C will be sucked back into D as the latter cools. 

Both aliphatic and aromatic nitro-compounds can be readily reduced in acid solution to the corresponding primary amine. Thus when a mixture of nitrobenzene and tin is treated with hydrochloric acid, the tin dissolves to give stannous chloride, SnCh, which in these circumstances then reacts with more acid to give stannic chloride, SnCl, and the nascent hydrogen produced from... 

Nitrobenzene is an extremely versatile solvent, and may frequently be employed for the crystallisation of compounds which do not dissolve appreciably in the common organic solvents. The vapour is somewhat poisonous, so that recrystaUisations must be carried out in the fume cupboard. After the crystals have been collected, they should be washed with a volatile solvent, such as benzene, alcohol or ether, to remove the excess of nitrobenzene (compare Section 11,32). The only disadvantage of nitrobenzene as a solvent is that it has a pronounced oxidising action at the boihng point. 

Tetrachloroethane is a good solvent for many compounds which dissolve only slightly in the common solvents it is, however, inferior in solvent power to nitrobenzene, but, on the other hand, it does not possess oxidising properties at the boiling point. 

Suspend 0 25 g. of 2 4-dinitrophenylhydrazine in 5 ml. of methanol and add 0-4 0-5 ml. of concentrated sulphuric acid cautiously. FUter the warm solution and add a solution of 0 1-0-2 g. of the carbonyl compound in a small volume of methanol or of ether. If no sohd separate within 10 minutes, dUute the solution carefuUy with 2N sulphuric acid. CoUect the solid by suction filtration and wash it with a little methanol. RecrystaUise the derivative from alcohol, dUute alcohol, alcohol with ethyl acetate or chloroform or acetone, acetic acid, dioxan, nitromethane, nitrobenzene or xylene. 

The commercial product, m.p. 53-55°, may be used. Alternatively the methyl -naphthyl ketone may be prepared from naphthalene as described in Section IV,136. The Friedel - Crafts reaction in nitrobenzene solution yields about 90 per cent, of the p-ketone and 10 per cent, of the a-ketone in carbon disulphide solution at — 15°, the proportions ore 65 per cent, of the a- and 35 per cent, of the p-isomer. With chlorobenzene ns the reaction medium, a high proportion of the a-ketone is also formed. Separation of the liquid a-isomer from the solid p-isomer in Such mixtures (which remain liquid at the ordinary temp>erature) is readily effected through the picrates the picrate of the liquid a-aceto compound is less soluble and the higher melting. 

Nitro compounds. Nitromethane Nitrobenzene ni-Dinitrobenzene. Amides and imides. Acetamide re-Caproamide Acetanilide Benz-anilide Phthalimide. 

Our knowledge of the mechanism of the reaction in this medium comes from an investigation of the nitration of nitrobenzene, /)-chloronitro-benzene and i-nitroanthraquinone. These compounds underwent reaction according to the following rate law ... 

A simple kinetic order for the nitration of aromatic compounds was first established by Martinsen for nitration in sulphuric acid (Martin-sen also first observed the occurrence of a maximum in the rate of nitration, occurrii for nitration in sulphuric acid of 89-90 % concentration). The rate of nitration of nitrobenzene was found to obey a second-order rate law, first order in the concentration of the aromatic and of nitric acid. The same law certainly holds (and in many cases was explicitly demonstrated) for the compounds listed in table 2.3. 

There is increasing evidence that the ionisation of the organic indicators of the same type, and previously thought to behave similarly, depends to some degree on their specific structures, thereby diminishing the generality of the derived scales of acidity. In the present case, the assumption that nitric acid behaves like organic indicators must be open to doubt. However, the and /fp scales are so different, and the correspondence of the acidity-dependence of nitration with so much better than with Hg, that the effectiveness of the nitronium ion is firmly established. The relationship between rates of nitration and was subsequently shown to hold up to about 82 % sulphuric acid for nitrobenzene, />-chloronitrobenzene, phenyltrimethylammonium ion, and p-tolyltrimethylammonium ion, and for various other compounds. ... 

It has already been noted that, as well as alkylbenzenes, a wide range of other aromatic compounds has been nitrated with nitronium salts. In particular the case of nitrobenzene has been examined kinetically. Results are collected in table 4.4. The reaction was kinetically of the first order in the concentration of the aromatic and of the nitronium salt. There is agreement between the results for those cases in which the solvent induces the ionization of nitric acid to nitronium ion, and the corresponding results for solutions of preformed nitronium salts in the same solvent. 

In nitration with nitronium salts in sulpholan, nitrobenzene was substituted in the following proportions 8% ortho, 90% meta and 2% paraf under the same conditions benzylidyne trifluoride yielded 8%, 88% and 4% of 0-, m- and p-nitro compound respectively Both of these aromatic compounds were stated to be io -10 times less reactive than benzene. "... 

The argument for the S 2 process, when the transition from acetic acid as solvent to nitric acid as solvent is considered, is less direct, for because of the experimental need to use less reactive compounds, zeroth-order nitration has not been observed in nitric acid. It can be estimated, however, that a substance such as nitrobenzene would react about 10 faster in first-order nitration in nitric acid than in a solution of nitric acid (7 mol 1 ) in acetic acid. Such a large increase is understandable in terms of the S z mechanism, but not otherwise. 

Table 9.7 contains recent data on the nitration of polychlorobenzenes in sulphuric acid. The data continue the development seen with the diehlorobenzenes. The introduetion of more substituents into these deactivated systems has a smaller effect than predicted. Whereas the -position in ehlorobenzene is four times less reactive than a position in benzene, the remaining position in pentachlorobenzene is about four times more reactive than a position in 1,3,4,5-tetraehlorobenzene. The chloro substituent thus activates nitration, a circumstance recalling the faet that o-chloronitrobenzene is more reactive than nitrobenzene. As can be seen from table 9.7, the additivity prineiple does not work very well with these compounds, underestimating the rate of reaction of pentachlorobenzene by a factor of nearly 250, though the failure is not so marked in the other cases, especially viewed in the circumstance of the wide range of reactivities covered. 

Reductive carbonylation of nitro compounds is catalyzed by various Pd catalysts. Phenyl isocyanate (93) is produced by the PdCl2-catalyzed reductive carbonylation (deoxygenation) of nitrobenzene with CO, probably via nitrene formation. Extensive studies have been carried out to develop the phosgene-free commercial process for phenyl isocyanate production from nitroben-zene[76]. Effects of various additives such as phenanthroline have been stu-died[77-79]. The co-catalysts of montmorillonite-bipyridylpalladium acetate and Ru3(CO) 2 are used for the reductive carbonylation oLnitroarenes[80,81]. Extensive studies on the reaction in alcohol to form the A -phenylurethane 94 have also been carried out[82-87]. Reaction of nitrobenzene with CO in the presence of aniline affords diphenylurea (95)[88]. 

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