Aliphatic nitro compounds table

On the basis of their investigations of nearly 35 nitro compounds, Komblum, Ungnade and Smiley have distinguished the vibrations of primary, secondary and tertiary nitro groups in aliphatic nitro compounds (Table 23). 

A study of closely related compounds, however, often reveals secondary influences on nitrogen chemical shifts. Poranski and Moniz ° have shown that the chemical shifts of aliphatic nitro-compounds (Table III) depend on the inductive effect of substituent groups. Simple empirical rules for the prediction of chemical shifts in the system R R R CN02 have been devised, where R = H, NO2, Cl or alkyl.The contribution of the shift from CH3, RCH2 and Cl are additive and, with a further modification of the expression—... 

The physical properties of a number of aliphatic nitro compounds are listed in Table IV,16B. 

TABLE 30. MM27 calculated condensed-phase heats of formation for aliphatic nitro compounds... 

Aliphatic nitro compounds are converted into the corresponding carbonyl derivatives (Table 10.16) using sodium chlorite under basic conditions in the presence of a... 

Let us compare HFC data from Table 1.1. Aliphatic nitro compounds produce anion-radicals, in which an unpaired electron spends its time on the nitro group completely. In the nitrobenzene... 

Aliphatic nitro compounds are reduced to various products, in all the published examples, only C-F bonds at a-positions are reduced, while the nitro group can be reduced in two steps. Catalytic hydrogenation of primary nitro compounds over palladium transforms them to the corresponding isonitroso compounds, i. e. oximes, while secondary nitro groups are converted into amines (Table 4). The reduction with Raney nickel alloy converts all types of nitro compounds into the corresponding amines, e. g. formation of 14.136... 

The following are data in ethanol [4] which illustrate the effect of lengthening the conjugated system in aliphatic unsaturated compounds Table (13). Kochany and Piotrowska [10] examined the ultraviolet-spectra of a number of nitroalkenes. Their w — tt were observed between 360 and 420 run. The ultraviolet absorption spectra of nitroethylene, nitropropenes and nitro methane have been taken and interpreted with the Pariser-Parr-Pople self-consistent field — MO calculation. The absorption bands it it are in good agreement with calculated values [11]. 

Table 3.5. rr Transitions of Aliphatic Nitro Compounds (RNO3)... 

A third class of compounds comprising aldehydes, ketones, aliphatic nitro compounds, and esters is characterized by absorption maxima in the near-UV region. But they have intensities so low that they are useful only under special circumstances i.e., acetone has a very low molecular extinction coefficient (a) at its wavelength maximum of 270 nm. By way of comparison, a moderately strong bond would have an e of 1000-10 0001 mol cm and values as high as 100 0001 mol cm are not uncommon. Table 1 lists some common chromophoric groups. 

Recently, the oxidation of primary aliphatic amines to the corresponding nitro compounds has also been achieved using the catalyst system based on zirconium tetra tert-butoxide and tert-butyl hydroperoxide in a molecular sieve (50-98% yield) (Eqs. 2.56 and 2.57 and Table... 

While primary aliphatic amines are converted to nitro compounds on reaction with ozone these reactions are accompanied by numerous by-products.Such side-reactions are largely suppressed by first dissolving the amine onto silica gel followed by passing a stream of 3 % ozone in oxygen through the solid at -78 °C under anhydrous conditions, where yields of between 60 and 70 % are reported. This route has been used to synthesize the energetic cyclopropane (65) from the diamine (64) (Table 1.7). ... 

Primary, secondary and tertiary aliphatic amines are efficiently converted to nitro compounds in 80-90 % yield with dimethyldioxirane, a reagent prepared from the reaction of oxone (2KHSO5-KHSO4-K2SO4) with buffered acetone. Dimethyldioxirane (DMDO) has been used for the synthesis of 1,3,5,7-tetranitroadamantane (71) from the corresponding tetraamine as the tetrahydrochloride salt (70) and is an improvement over the initial synthesis using permanganate anion (Table 1.7). ° Oxone is able to directly convert some aromatic amines into nitro compounds. 

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