Alkane derivatives nitroalkanes

Nitroparaffias (or nitroaLkanes) are derivatives of the alkanes ia which one hydrogen or more is replaced by the electronegative nitro group, which is attached to carbon through nitrogen. The nitroparaffins are isomeric with alkyl nitrites, RONO, which are esters of nitrous acid. The nitro group ia a nitroparaffin has been shown to be symmetrical about the R—N bond axis, and may be represented as a resonance hybrid ... 

Alkalsit is a Ger blasting expi which is described in PATR 2510(1958), p Ger 3 Alkanes, Nitrated Derivatives (Nitrated Aliphatic Hydrocarbons). The first nitro-alkane described in the literature was 1,2-dinitroethane, prepd in Russia by A.Semenov. Since then hundreds of nitroalkanes, some of them explosive, were obtained. The reference given below describes old and new methods of prepn of nitro alkanes. Most of expl nitro alkanes are described in this dictionary under their parent names, such as methane, ethane, propane, etc Ref 0. vonSchickh, AngewChem 62, 547-56 (1950)(Chemie und Technologie der Nitro-alkane)... 

Method of Wakita, Yoshlmoto, Miyamoto, and Watanabe The Wakita et al. method [46] has been derived with a set of 307 liquid compounds, including alkanes, alkenes, alkynes, halogenated alkanes, alkanols, oxoalkanes, alkanones, alkyl alkanoates, alkanethiols, alkanenitriles, nitroalkanes, and substituted benzenes, naphthalenes, and biphenyles. The model equation is... 

The formation of a carbon-carbon bond by reaction of alkylthallium(III) compounds has been described in the a-nitroalkylation of alkanes. The reaction of alkylthallium (129) with nitroalkane anions leads to the nitroalkyl derivatives (130). In this case, radical intermediates generated by electron transfer activation of the carbon-thallium bond are involved in a non-chain substitution process. 

The second most important synthetic application of silyl nitronates in C-C bond-forming reactions is their fluoride-mediated addition to aldehydes. Silyl nitronates from secondary nitroalkanes lead to free nitro aldols such as (4), while those from primary nitro alkanes give silylated products. In contrast to the classical Henry reaction, the silyl variant is highly diastereose-lective with aldehydes, furnishing e yfAro-0-silylated nitro aldols (e.g. 5). It is important that the reaction temperature does not rise above 0 °C, otherwise threo/erythro equilibration takes place. The same erythro-nitio aldol derivatives are available by diastere-oselective protonation of silyloxy nitronates (eq 3) (usually the dr is >20 1), while the nonsilylated fAreo-epimers (R = H, dr = 7 3-20 1) are formed by kinetic protonation of lithioxy lithio nitronates in THF/DMPU (eq 4). Other recent modifications of the nitroaldol addition using titanium nitronates or ClSiRs in situ are less selective. It should also be mentioned that there are recent reports about the enantioselective addition of nitromethane to aldehydes in the presence of rare earth binaphthol complexes. 

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