Nitro compounds, determination

Reduction of a nitrosamine to a secondary amine. Proceed as for a nitro compound. Determine the solubility of the residue after evaporation of the ether and also its behaviour towards benzenesulphonyl (or p-toluenesulphonyl) chloride. 

Krull IS, Ding XD, Selavka C, et al. 1984. Explosives and other nitro compounds determined by liquid chromatography with photolysis-electrochemical detection. Methodological Surveys in Biochemistry and Analysis 14 365-366. 

Dissociation Constants of a NxraiBBR of Nitro Compounds Determined BY Gilbert, Laxton, and Prideadx at 25°... 

The observed tendency in the dual reactivity of C02 radical anion may he rationalized by the reduction potential of the substrate. An electron transfer mechanism is observed for those substituted benzenes which are reduced by the hydrated electron with diffusion-controlled rates. For substrates showing lower reactivity towards the hydrated electron, i.e. which are more difficult to reduce, C02 addition is the preferred reaction channel. These observations are in line with studies reporting the reduction of nitro compounds by a-hydroxyalkyl radicals, where the redox potential of the nitro compound determines the probability of radical addition or electron transfer." ... 

Comparison of data for the nitration of alkyl- and halogenobenzenes with those for the related p-nitro-compounds supports the view that the rate of nitration of highly electron-deficient systems is determined by polarizability factors which enhance the reactivity of the substituted by comparison with that of the unsubstituted system. 

The overall reactivity of the 4- and 5-positions compared to benzene has been determined by competitive methods, and the results agreed with kinetic constants established by nitration of the same thiazoles in sulfuric acid at very low concentrations (242). In fact, nitration of alkylthiazoles in a mixture of nitric and sulfuric acid at 100°C for 4 hr gives nitro compounds in preparative yield, though some alkylthiazoles are oxidized. Results of competitive nitrations are summarized in Table III-43 (241, 243). For 2-alkylthiazoles, reactivities were too low to be measured accurately. 

Analytical and Test Methods. o-Nitrotoluene can be analyzed for purity and isomer content by infrared spectroscopy with an accuracy of about 1%. -Nitrotoluene content can be estimated by the decomposition of the isomeric toluene diazonium chlorides because the ortho and meta isomers decompose more readily than the para isomer. A colorimetric method for determining the content of the various isomers is based on the color which forms when the mononitrotoluenes are dissolved in sulfuric acid (45). From the absorption of the sulfuric acid solution at 436 and 305 nm, the ortho and para isomer content can be deterrnined, and the meta isomer can be obtained by difference. However, this and other colorimetric methods are subject to possible interferences from other aromatic nitro compounds. A titrimetric method, based on the reduction of the nitro group with titanium(III) sulfate or chloride, can be used to determine mononitrotoluenes (32). Chromatographic methods, eg, gas chromatography or high pressure Hquid chromatography, are well suited for the deterrnination of mononitrotoluenes as well as its individual isomers. Freezing points are used commonly as indicators of purity of the various isomers. 

Of the four possible oxazolopyridines, two have been studied with respect to quatemization reactions. Frazer and Tittensor prepared 2-alkyl- and 2-aryl-oxazolo[4,5-c]pyridines (105 Y = H) and converted them into methiodides, the structures of which have not been determined. Subsequently Takahashi et al. prepared the corresponding 5-methyl (105 Y = Me) and 2-methyl-5-nitro compounds and... 

Reactions of nitro compounds with chiral imines have only recently been described. Either chiral 1-phenylethylamine (auxiliary) or the glyceraldehyde acetonide aldehyde was used as the chiral precursors of the imines 66 and 68, which reacted with 3-mesyloxynitropropane to give the 3-nitropyrrolidines dl)-67 and 69, respectively, with good diastereoselectivity. In fact, both products were obtained (almost) exclusively as trans diastereomers with high level of asymmetric induction, but the configurations of the newly formed stereocenters were not determined [44] (Scheme 13). N-Boc imines can be formed... 

The taste of various amino acids, sugars, and aliphatic nitro compounds was studied, and it was concluded that the distance over which this hydrogen atom migrates, to give a second tautomeric form, determines the sweetness. In the case of saccharin, the sweetness was explained as due to two tautomeric forms. 

Reduction of monocyclic aromatic nitro compounds has been demonstrated (a) with reduced sulfur compounds mediated by a naphthoquinone or an iron porphyrin (Schwarzenbach et al. 1990), and (b) by Fe(II) and magnetite produced by the action of the anaerobic bacterium Geobacter metallireducens (Heijman et al. 1993). Quinone-mediated reduction of monocyclic aromatic nitro compounds by the supernatant monocyclic aromatic nitro compounds has been noted (Glaus et al. 1992), and these reactions may be signihcant in determining the fate of aromatic nitro compounds in reducing environments (Dunnivant et al. 1992). 

Aromatic nitro and nitroso compounds are easily reduced at carbon and mercury electrodes. Other nitro compounds such as nitrate esters, nitramines, and nitrosamines are also typically easily reduced. The complete reduction of a nitro compound consists of three two-electron steps (nitro-nitroso-hydroxylamine-amine). Since most organic oxidations are only two-electron processes, higher sensitivity is typically found for nitro compounds. Several LCEC based determination of nitro compounds have been reported... 

In some respects this is a trivial application. In order to select a protective glove for a new nitro compound, all we would do in practice would be to check to see what material provides good protection against known nitro compounds and assume that this material would be appropriate we do not need a computer to tell us how to do this. But the reason that the procedure in this case is simple is that we already have a means to group compounds by noting the presence or absence of particular functional groups. If the link between structure and protective material were subtler, a more sophisticated way to determine the appropriate material would be required. 

Among the natively fluorescent compounds determined by the POCL reaction are PAHs in different matrices such as coal tar [100] and biomass emissions [101], and amino-PAHs in shale oil, coal oil, and coal gasifier tar [102], Nitro-PAHs have no fluorescent properties, but have been reduced online (either pre-or postcolumn) to the corresponding amino-PAHs [103], The two fluorescent drugs dipyridamole and benzydamine have been determined in rat plasma by... 

An example of this situation is provided by the reduction of the bis-nitro compound shown in Scheme 1.3 in a polar solvent where A ° is indeed equal to (1ZT/F) In 4 as soon as n = 3.67 Temperature-dependent determination of AE° showed that an entropic effect is dealt with effectively. 

The same reaction can be applied, not only to the aromatic parent substances, the hydrocarbons, but also to all their derivatives, such as phenols, amines, aldehydes, acids, and so on. The nitration does not, however, always proceed with the same ease, and therefore the most favourable experimental conditions must be determined for each substance. If a substance is very easily nitrated it may be done with nitric acid sufficiently diluted with water, or else the substance to be nitrated is dissolved in a resistant solvent and is then treated with nitric acid. Glacial acetic acid is frequently used as the solvent. Substances which are less easily nitrated are dissolved in concentrated or fuming nitric acid. If the nitration proceeds with difficulty the elimination of water is facilitated by the addition of concentrated sulphuric acid to ordinary or fuming nitric acid. When nitration is carried out in sulphuric acid solution, potassium or sodium nitrate is sometimes used instead of nitric acid. The methods of nitration described may be still further modified in two ways 1, the temperature or, 2, the amount of nitric acid used, may be varied. Thus nitration can be carried out at the temperature of a freezing mixture, at that of ice, at that of cold water, at a gentle heat, or, finally, at the boiling point. Moreover, we can either employ an excess of nitric acid or the theoretical amount. Small scale preliminary experiments will indicate which of these numerous modifications may be expected to yield the best results. Since nitro-compounds are usually insoluble or sparingly soluble in water they can be precipitated from the nitration mixture by dilution with water. 

In respect of their properties, conditions of rearrangement, and reactions, we simply refer to what was said about the keto-enol change. Here, also, the bromine method enables the points of equilibrium to be determined quantitatively. The oldest and most important example of desmotropy in nitro-compounds was found in phenylnitromethane,... 

It has been found that a good correlation exists between Bordwell s pKa values and heats of deprotonation ( AHq) determined in DMSO7. In particular, when nitro compounds were considered together with ketones, they generated the following good (r = 0.993) linear correlation ... 

A semiconductor sensor-based instrument was described for determination of the composition and concentrations of vapors of organic nitro compounds and nitrogen dioxide in the atmosphere. Four organic semiconductor sensors [e.g. aluminum phthalocyanine fluoride (222a)] were tested in conjunction with platinized platinum preconcentrators sensitivity is to ppm levels of nitrobenzene450. 

Nitropropanoyl esters of glucose from the roots of Lotus pendunculatus Cav. were determined by analysis of nitrate released on alkaline hydrolysis. This method was validated for quantitation of both total nitro compounds in ethanolic extracts and for individual components from TLC separations557. 

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