Aromatic compounds nitrobenzene

Misc. aromatic compounds (nitrobenzene tetraphenyltin) accumulator column 6 47-89 74 6-24 13 d... 

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. 

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. "... 

A further consequence of association of acylating agents with basic compounds is an increase in the bulk of the reagent, and greater resistance to attack at the more stericaHy hindered positions of aromatic compounds. Thus acylation of chrysene and phenanthrene in nitrobenzene or in carbon disulfide occurs to a considerable extent in an outer ring, whereas acylation of naphthalene leads to extensive reaction at the less reactive but stericaky less hindered 2-position. 

Organic Reactions. Nitric acid is used extensively ia iadustry to nitrate aHphatic and aromatic compounds (21). In many iastances nitration requires the use of sulfuric acid as a dehydrating agent or catalyst the extent of nitration achieved depends on the concentration of nitric and sulfuric acids used. This is of iadustrial importance ia the manufacture of nitrobenzene and dinitrotoluene, which are iatermediates ia the manufacture of polyurethanes. Trinitrotoluene (TNT) is an explosive. Various isomers of mononitrotoluene are used to make optical brighteners, herbicides (qv), and iasecticides. Such nitrations are generally attributed to the presence of the nitronium ion, NO2, the concentration of which iacreases with acid strength (see Nitration). 

Tnflic acid is an excellent catalyst for the nitration of aromatic compounds [.S7]. In a mixture with nitnc acid, it forms the highly electrophilic nitronium inflate, which can be isolated as a white crystalline solid Nitronium inflate is a powerful nitrating reagent in inert organie solvents and in tnflic acid or sulfuric acid. It nitrates benzene, toluene, chlorobenzene, nitrobenzene, m-xylene, and benzotn-fluoride quantitatively in the temperature range of-110 to 30 °C with exeeptionally high positional selectivity [87],... 

Pyridine lies near one extreme in being far less reactive than benzene toward substitution by electrophilic reagents. In this respect it resembles strongly deactivated aromatic compounds such as nitrobenzene. It is incapable of being acylated or alkylated under Friedel-Crafts conditions, but can be sulfonated at high temperature. Electrophilic substitution in pyridine, when it does occur, takes place at C-3. 

Aromatic hydrocarbons, like paraffin hydrocarbons, react by substitution, but by a different reaction mechanism and under milder conditions. Aromatic compounds react by addition only under severe conditions. For example, electrophilic substitution of benzene using nitric acid produces nitrobenzene under normal conditions, while the addition of hydrogen to benzene occurs in presence of catalyst only under high pressure to... 

The heat of decomposition (238.4 kJ/mol, 3.92 kJ/g) has been calculated to give an adiabatic product temperature of 2150°C accompanied by a 24-fold pressure increase in a closed vessel [9], Dining research into the Friedel-Crafts acylation reaction of aromatic compounds (components unspecified) in nitrobenzene as solvent, it was decided to use nitromethane in place of nitrobenzene because of the lower toxicity of the former. However, because of the lower boiling point of nitromethane (101°C, against 210°C for nitrobenzene), the reactions were run in an autoclave so that the same maximum reaction temperature of 155°C could be used, but at a maximum pressure of 10 bar. The reaction mixture was heated to 150°C and maintained there for 10 minutes, when a rapidly accelerating increase in temperature was noticed, and at 160°C the lid of the autoclave was blown off as decomposition accelerated to explosion [10], Impurities present in the commercial solvent are listed, and a recommended purification procedure is described [11]. The thermal decomposition of nitromethane under supercritical conditions has been studied [12], The effects of very high pressure and of temperature on the physical properties, chemical reactivity and thermal decomposition of nitromethane have been studied, and a mechanism for the bimolecular decomposition (to ammonium formate and water) identified [13], Solid nitromethane apparently has different susceptibility to detonation according to the orientation of the crystal, a theoretical model is advanced [14], Nitromethane actually finds employment as an explosive [15],... 

The ease with which the sulphonic group enters into aromatic compounds depends on the nature of the substituents present, just as it does in nitration. Benzene is rather difficult to sulphonate, toluene and naphthalene are somewhat more easy, phenols and amines very easy. The sulphonation of nitrobenzene or the further sulphonation of the benzene sulphonic acids proceeds with more difficulty, and the action of the sulphuric acid must here be intensified by increasing its S03-content. 

A method with LOQ at ppt levels was developed based on LLE followed by GC-AFID for the determination of trace concentrations of nitrobenzene, l-chloro-2-nitrobenzene and synthetic fragrances such as musk xylene (223) and musk ketone (224). The method was applied to study the distribution of these compounds in environmental samples of North Sea waters460. GC with atomic emission detection (AED) has been successfully applied to the determination of nitro musks in human adipose tissues, at ppb concentration levels. A clean-up procedure for nonpolar substances and element-specific detection with AED enabled for the first time target screening analysis for lipophilic nitro aromatic compounds. The lack of sensitivity of AED was compensated by higher concentrations of the extracts... 

Shimizu N, Yasui Y, Matsumoto N. 1983. Structural specificity of aromatic compounds with special reference to mutagenic activity in Salmonella typhimurium - a series of chloro- or fluoro-nitrobenzene derivatives. Mutat Res 116 217-238. 

X - and especially X -phosphorins are electron-rich aromatic compounds, comparable with aniline, whereas pyridine and pyridinium ions are electron-poor and are comparable to nitrobenzene. Many chemical properties can be easily understood once this fact is taken into account. 

The fluorination of other activated aromatic compounds, such as anisole and phenol, undergo monofluorination mainly in the ortho and para positions, whereas the fluorination of deactivated aromatics, such as nitrobenzene, trifluoromethylbenzene and benzoic acid, give predominantly the corresponding meta fluoro-derivatives which is consistent with a typical electrophilic substitution process. Also, fluoro-, chloro- and bromo-benzenes are deactivated with respect to benzene itself but are fluorinated preferentially in the ortho and para positions [139]. At higher temperatures, polychlorobenzenes undergo substitution and addition of fluorine to give chlorofluorocyclohexanes [136]. 

This type of duality of action is presumably present in other situations, such as the Fries rearrangement (78), the Friedel-Crafts reaction with acid chlorides (65) or acid anhydrides (21), and the catalytic chlorination of nitrobenzene (17). In these reactions it appears that the uncoordinated Lewis acid is the effective catalyst. The same situation is illustrated by recent work on aromatic amination (32, 33) and halogenation (57, 58, 71) and seems to be general feature of Lewis acid-catalyzed electrophilic reactions of aromatic compounds containing suitable donor groups. 

Nitrogen dioxide was used in mixtures with such combustibles as paraffin (without aromatic compounds), carbon disulphide or nitrobenzene. These substances were used in the proportions necessary to give complete decomposition into C02, H20 and N2, thus permitting full utilization of the oxygen present in the nitrogen dioxide. To prevent the solidification of nitrobenzene at low temperatures a binary combustible constituent, e.g. a mixture of nitrobenzene with carbon disulphide, was used. 

The nucleophilic displacement of halogens in aromatic compounds by fluorine is aided by utilizing an appropriate catalyst. Polymer-supported aminopyridinium salts have been found to be versatile catalysts for the synthesis of aryl fluorides. The advantage of the catalyst is that it can be recycled and used again. l-Chloro-4-nitrobenzene (3) is converted to l-fluoro-4-nitrobenzene (4) in 71 % isolated yield using this method. The catalyst used has the structure 5.91... 

Though safer than the decomposition of pure, solid diazonium tetrafluoroborates, dediazoni-ation of these compounds mixed with inert solid salts cannot be scaled up to a large extent since heat exchange through large quantities of powdered solids rapidly becomes difficult. Thus, dediazoniation of arenediazonium tetrafluoroborates suspended in inert fluids is an alternative proposition.13105 141 175-219 220 In addition to the safety improvement, lower quantities of tar are formed using this technique. The inert fluid can be ligroin,143 petroleum ether,147 Decalin,3 or simple aromatic compounds,1-3,5,131-221 such as toluene, xylene, biphenyl, nitrobenzene,177 or quinoline. Simple esters have also been used as solvents in the dediazoniation... 

Selection of an appropriate solvent for Friedel-Crafts acylation is an important question since solvents are known to affect regioselectivities.8,9 In many cases acylation is carried out in an excess of the reacting aromatic compound. Aromatics, however, are poor solvents for most Lewis acids and therefore, they merely serve as diluent in biphase systems. Carbon disulfide is a reasonably good solvent just as dichloromethane and dichloroethane. Although AICI3 is insoluble in chlorinated hydrocarbons, they dissolve many of the complexes formed between acyl halides and AICI3. Nitrobenzene and nitromethane are also suitable solvents. Moreover, the 1 1 addition complexes they form with AICI3 allow acylations to be performed under mild conditions often without side reactions. 

Aromatic nitro compounds nitrobenzene, nitrotoluene, dinitrobenzene, dinitrotoluene, trinitrotoluene, nitroanisoles and nitrophenetoles, dinitroanisoles and dinitrophenetoles, nitrophenols etc. 

A somewhat related report in which equally impressive selectivity and yield (60—90%) were obtained Cacou and Wolf have studied the low temperature direct fluorination of aromatic compounds in CC13 F (100). They have established that under appropriate conditions molecular fluorination proceeds on substituted benzenes and tolulenes with similar selectivity and orientation as has been commonly observed for other halogens. For example reaction with nitrobenzene gives 80% meta substitution and reaction with tolulene gives 60% ortho substitution. The conversions were reported in this study and found to average 0.01%. 

Substituted aromatic compounds are named using the suffix -benzene. Thus, C6H5Br is bromobenzene, C6H5CH3 is methylbenzene (also called toluene), C6H5N02 is nitrobenzene, and so on. Disubstituted aromatic compounds are named using one of the prefixes ortho-, meta-, or para-. An ortho- or o-disubstituted benzene has its two substituents in a 1,2 relationship on the ring a meta- or m-disubstituted benzene has its two substituents in a 1,3 relationship and a para- or p-disubstituted benzene has its substituents in a 1,4 relationship. When the benzene ring itself is a substituent, the name phenyl (pronounced fen-nil) is used. 

The action of fuming nitric acid transforms benzene and its homologues (toluene, xylene) into nitro-compounds (nitrobenzene, etc.), which remain in the acid liquid, from which the mineral oil is subsequently separated. The liquid is then diluted with as much water and the solution neutralised with caustic soda solution and extracted with ether. The ethereal liquid (dried with a few granules of caldum chloride and filtered) is evaporated at a gentle heat and the residue weighed. If tar oils are present, this residue will consist of a reddish-brown oily liquid, heavier than water and with the odour characteristic of aromatic nitro-derivatives. The weight found, divided by 1-15 (mean sp. gr. of aromatic nitro-compounds), will give the volume. 

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