A-Nitrotoluene

Fig. 6.13 Highly repeatability separation and detection of DNT from nitrotoluene and DNT mixtures. SPME extractions are performed at room temperature, (a) Nitrotoluene extraction time 3 s, DNT extraction time 20 s. (b) Nitrotoluene extraction time 1 s, DNT extraction time 30 s. DNT peak emerges at approximately 40 s. Curves are vertically shifted for clarity...

Of numerous other preparations for which nitrile oxides have been invoked as intermediates, one of the most synthetically useful is that developed by Shimizu et al. which employs alkyl esters of a-nitroalkanoic acids as precursors <87BCJ1948). The method is suitable for aliphatic, amide, and ester derivatives, and involves themolysis in an inert solvent to generate the nitrile oxide with con-commitant expulsion of carbon dioxide and alkanol. Other reactions leading to furoxans via nitrile oxides include treatment of a-bromo-a-nitrotoluene with triphenylphosphine <84TL2029), nitrosation... 

The possibility of using of aliphatic alcohols as hydrogen donors for the catalytic transfer reduction of nitro group over MgO was examined. Catalytic hydrogen transfer was found to be effective and selective method for reduction of nitrobenzene, A-nitrotoluene, A-chloronitrobenzene, 4-nitro-m-xylene, 3-nitro-styrene, 3-nitrobenzaldehyde, 1-nitropropane, and 1-nitrobutane. Conversion of starting nitro compound into desired product depended on the alcohol used as a donor. Adsorption of reactant and catalyst deactivation were studied by esr. New aspects of a role of one-electron donor sites in hydrogen transfer over MgD were demonstrated. 

Since the trinitrotoluene isomers are formed as a result of the nitration of m- ni-trotoluene, W. W. Jones and Russel [9] undertook the task of determining to what extent the presence of m- nitrotoluene in mononitrotoluene lowers the melting point of a- nitrotoluene. The authors nitrated mixtures of m- and p- nitrotoluenes (Table 61). 

The addition of the anion of a-bromo-a-nitrotoluene (564) to cyclohexene gave the hexahydro derivative (565) of 3-phenyl-l,2-benzisoxazole (75TL2131). An unusual hexahydro derivative (566) was produced by the bis addition of benzonitrile A-oxide to benzoquinone (67AHC(8)277). 

For liquid benzyldifluoramine and a-nitrotoluene, the corresponding value (from solely experimental measurements) of 835 is -14.6 3.7 kJ mol". We close the comparison with a discussion of the thermochemistry of )V,yV,, lV -tetrafluoro-1,1-heptanediamine. The enthalpy of formation of 1,1-dinitroheptane is seemingly absent but we know the value for 1,1-dinitropentane, -216.9 1.3 kJ mol". To correct for the two liquid-phase CH2 groups is easy prior experience (e.g. ref. 34) shows that each contributes ca. -25 kJ mol" resulting in a value of ca. -267 kJ mol". Alternatively, we can use our earlier derived equation [7],... 

The enaminate anions produced by deprotonating a- and 7-alkylpyridines can participate in a wide range of reactions, " being closely analogous to enolate anions. Similar side-chain carbanion formation is seen in ortho- but not me/a-nitrotoluene. Side-chain metallation of 2-/-butylcarbonylamino-4-methylpyridine proceeds at room temperature. ... 

The reaction of benzyl bromides with silver nitrite (72) has been studied. The ratio of the products, benzyl nitrite and a-nitrotoluenes, as well as the reaction rates, are intimately related to the structure of the benzyl bromide. The softer electrophiles tend to react preferentially with the softer nitrogen of the base. 

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