Nitroarenes phase

Staggered conformation, 94 molecular model of, 94 Stannous chloride, reaction with nitroarenes, 928 Starch, 1—>4- -links in, 1000 structure of, 1000 Stationary phase, chromatography and, 432... 

Considerable attention has been directed to the formation of nitroarenes that may be formed by several mechanisms (a) initial reaction with hydroxyl radicals followed by reactions with nitrate radicals or NO2 and (b) direct reaction with nitrate radicals. The first is important for arenes in the troposphere, whereas the second is a thermal reaction that occurs during combustion of arenes. The kinetics of formation of nitroarenes by gas-phase reaction with N2O5 has been examined for naphthalene (Pitts et al. 1985a) and methylnaphthalenes (Zielinska et al. 1989) biphenyl (Atkinson et al. 1987b,c) acephenanthrylene (Zielinska et al. 1988) and for adsorbed pyrene (Pitts et al. 1985b). Both... 

Nitroarenes were formed under laboratory conditions when PAH reacted with gas-phase OH radical (in presence of NO ) and N2O540 45. The atmospheric nitroarene formation rate depends upon the concentration of the individual species N2O5-NO3-NO2 An analogous reaction sequence occurs when PAH reacts in N2O5-NO3-NO2 systems46. Naphthalene reacts with NO3 radical forms NO3-naphthalene adduct, which dissociates or reacts with NO2 to form nitronaphthalene and other products as shown in Figure 6. 

Table 3 shows the atmospheric lifetime for eleven PAH with respect to gas-phase reaction with OH and NO3 radicals, O3 and N2O5. This was calculated from the estimated and calculated rate constants. It is evident that most of the nitroarenes formed under ambient atmospheric conditions were produced by reaction of PAH with OH. The PAH reaction with NO3 radical was also considered as an important step because it resulted in the formation of nitroarenes from the N2O5 reaction with gas-phase PAH. 

Viologen salts act as one-electron phase-transfer agents and, in conjunction with sodium dithionite which regenerates the bipyridinium radical cation, they have been used for the debromination of 1,2-dibromoalkanes to yield alkenes in variable yields [13-15]. Nitroarenes are reduced to anilines in high yield (>90%) under similar conditions [16], whereas conjugated nitroalkenes are converted into the oximes of the saturated ketones [17] saturated aliphatic nitro compounds are not reduced by this process. 

Nitroarenes are reduced to anilines (>85%) under the influence of metal carbonyl complexes. In a two-phase system, the complex hydridoiron complex [HFe,(CO)u]2-is produced from tri-iron dodecacarbonyl at the interface between the organic phase and the basic aqueous phase [7], The generation of the active hydridoiron complex is catalysed by a range of quaternary ammonium salts and an analogous hydrido-manganese complex is obtained from dimanganese decacarbonyl under similar conditions [8], Virtually no reduction occurs in the absence of the quaternary ammonium salt, and the reduction is also suppressed by the presence of carbon monoxide [9], In contrast, dicobalt octacarbonyl reacts with quaternary ammonium fluorides to form complexes which do not reduce nitroarenes. 

In many respects the apparently analogous reduction of nitroarenes with triruthenium dodecacarbonyl under basic phase-transfer conditions is superior to that of the iron carbonyl-mediated reductions. However, the difference in the dependence of the two processes on the concentration of the aqueous sodium hydroxide and the pressure of the carbon monoxide suggests that they may proceed by different mechanisms. Although the iron-based system is most effective under dilute alkaline conditions in the absence of carbon monoxide, the use of 5M sodium hydroxide is critical for the ruthenium-based system, which also requires an atmosphere of carbon monoxide [11]. The ruthenium-based reduction has been extended to the... 

Method A (using iron complexes) Fe,(CO)12 (0.25 g, 0.5 mmol) and the nitroarene (l.O mmol) in PhH (I0 ml) are stirred for 2 h with TEBA-CI (0.02 g, 0.I mmol) in aqueous NaOH (lM, I0 ml) at room temperature. The organic phase is separated and filtered through silica to give the aniline. 

The nitroarene (5 mmol) in dry THF (10 ml) is added dropwise to TEA-HFe3(CO)l0 (3.0 g, 5 mmol) in dry THF (30 ml) and the mixture is heated at 50°C for 2 h and then cooled and acidified with aqueous HC1 (5M). The acidic solution is washed with Et20 (2 x 25 ml) and the aqueous phase is then made alkaline with aqueous NaOH (5M) and extracted with Et20 (3 x 25 ml). The combined extracts are dried (Na2S04) and evaporated under vacuum to give the aniline. 

Quaternary ammonium salts aid the transfer of the hypophosphite anion in the palladium-catalysed reduction of, for example, alkynes to alkenes, nitroarenes to aminoarenes, and in the hydrogenolysis of tetrazolyl aryl ethers to phenols [12-14], It has been demonstrated that the hydrogenolysis is ineffective when preformed tetra-n-butylammonium hypophosphite is employed in a dry homogenous organic solvent [13, 14], For optimum hydrogen transfer, the concentration of hypophosphite relative to the substrate must be controlled at a low level and this is most effectively accomplished with a two-phase system. 

Concentrations of the gaseous nitroarenes, 1- and 2-nitronaphthalene, and 3-nitrobiphenyl in these 18 samples were determined concurrently with the PAHs, in this case sampling with a Teflon-impregnated glass fiber filter (TIGF)/polyurethane foam (PUF) apparatus (Fig. 10.4). The PUF plugs quantitatively trapped the gas-phase nitroaromatics, but not naphthalene and biphenyl and several 3-ring PAHs. 

In a laboratory environmental chamber study of the gas-phase photooxidation of naphthalene and phenan-threne, Sasaki and co-workers (1997b) found two products, 2-nitronaphthalene and 2-nitrodibenzopyranone (XI), that displayed significant genotoxicity in the MCL-5 human cell assay. This finding emphasized the importance of atmospheric reactions in forming mutagens, since the concentrations of such compounds are relatively high in ambient air compared to those expected for nitroarenes directly emitted from primary combustion sources (see Section F). 

Overall, while the combinations of substrate effects, ambient NOz levels, and other gas-particle phenomena preclude a definitive answer, the formation of significant amounts of nitroarenes in heterogeneous particle-phase N02-PAH, atmospheric reactions seems unlikely, e.g., much slower than photooxidation or ozonolysis. This conclusion also applies to heterogeneous reactions of N205 with particle-bound PAHs on diesel and wood soot (Kamens and co-workers, 1990 see also Pitts et al., 1985c, 1985d, 1985e). 

As we have seen, key nitroarenes found in extracts of ambient particulate matter are 1-nitropyrene (1-N02-Py), predominant in primary combustion emissions, and 2-nitrofluoranthene and 2-nitropyrene, major products of gas-phase atmospheric reactions. Here we focus simply on their atmospheric fates as particle-bound species participating in heterogeneous decay processes. Formation of such nitro-PAHs in gas-phase reactions is addressed in Section F. 

F. REACTIONS OF GAS-PHASE PAHs ATMOSPHERIC FORMATION OF MUTAGENIC NITROARENES... 

Products (and their mutagenicities) of the gas-phase reactions of these and other 2- to 4-ring PAHs (fluorene, naphthalene, etc.) carried out under simulated atmospheric conditions should be consistent with the nitroarenes and nitro-PACs that have been identified in ambient air. This criterion has been well established over the years in environmental chamber studies conducted in several laboratories (e.g., see reviews by Atkinson and Arey, 1994 and Arey, 1998a articles by Kamens et al., 1994 Fan et al., 1995 Feilberg et al., 1999a and references therein). 

Arey, J., B. Zielinska, R. Atkinson, and S. M. Aschmann, Nitroarene Products from the Gas-Phase Reactions of Volatile Polycyclic Aromatic Hydrocarbons with the OH Radical and N205, Int. J. Chem. Kinet., 21, 775-799 (1989b). 

Ciccioli, P., A. Cecinato, R. Cabella, and E. Brancaleoni, The Contribution of Gas-Phase Reactions to the Nitroarene Fraction of Molecular Weight 247 Present in Carbon Particles Sampled in... 

Acceptor-substituted haloarenes have been successfully used to O-arylate phenols by aromatic nucleophilic substitution (Table 7.14). The most common arylating agents are 2-fluoro-l-nitroarenes, 2-halopyridines, 2-halopyrimidines, and 2-halotriazines. When sufficiently reactive haloarenes are used, the reaction proceeds smoothly with either the arylating agent or the phenol linked to the support. The thallium(III) nitrate catalyzed arylation of phenols with aryl iodides has been used for macrocycli-zations on solid phase [184], Burgess and co-workers have developed a solid-phase synthesis of 3-turri mimetics based on ring-closure by aromatic nucleophilic substitution (Entry 4, Table 7.14 see also Table 10.5). Phenols, alkylamines, and thiols have been successfully used as nucleophiles for this type of macrocyclization [185],... 

Selective reduction to hydroxylamine can be achieved in a variety of ways the most widely applicable systems utilize zinc and ammonium chloride in an aqueous or alcoholic medium. The overreduction to amines can be prevented by using a two-phase solvent system. Hydroxylamines have also been obtained from nitro compounds using molecular hydrogen and iridium catalysts. A rapid metal-catalyzed transfer reduction of aromatic nitroarenes to N-substituted hydroxylamines has also been developed the method employs palladium and rhodium on charcoal as catalyst and a variety of hydrogen donors such as cyclohexene, hydrazine, formic acid and phosphinic acid. The reduction of nitroarenes to arylhydroxyl-amines can also be achieved using hydrazine in the presence of Raney nickel or iron(III) oxide. ... 

---