Nitro compounds, aliphatic 1.1- dinitro compound

Aliphatic gem-dinitro compounds can be prepared by anodic oxidation of a nitro-paraffin in aqueous alkaline solution in the presence of an excess of N02 [201]. Yields are considerably better when Ag" is the oxidizing agent [202], so that an indirect oxidation process involving the generation of Ag" " at an Ag anode was found to give excellent results [203]. 

Aliphatic nitro compounds are hydrolyzed, with the formation of nitrous acid, which can be detected easily. The reaction is also given with aromatic o- and p-dinitro compounds containing a labile nitro group (3). 

Silver nitrate/sodium nitrite sodium hydroxide 1,1-Dinitro compounds from aliphatic nitro compounds 

Olefin synthesh. Komblum ei a . have described a new synthesis of tetrasubsti-tuted olefins from vicinal dinitro compounds. There are several methods for conversion of aliphatic and alicyclic nitro compounds into nic-dinitro compounds, the most useful of which is a procedure of Seigle and Hass. A nitroparafhn is converted into (he lithium salt (I) by treatment with lithium methoxidc and this is then treated with bromine to form a bromonilro compound (2). Reaction of (2) with a second equivalent of the nitro-R.. NO,,  

Both the Henry reaction and the reverse demethylolation are synthetically useful in the chemistry of polynitroaliphatic compounds. The Henry reaction is commonly used to mask the natural chemistry of an aliphatic nitro or terminal em-dinitro group by removing the acidic a -proton(s). In Section 1.7 we discussed the conversion of Q ,ty-dinitroalkanes to their bis-methylol derivatives before subjecting them to oxidative nitration and subsequent demethylolation with base, a procedure which results in the formation of Q ,Q , y, y-tetranitroalkanes.  

For aromatic or heteroaromatic monoaldehydes, ArCHO, an efficient procedure has been developed for synthesis of 1,3-dinitro compounds [132]. Rather than in situ reduction of O2, the O2 reduction is carried out in a divided cell with the aliphatic nitro compound as the solvent. Charge corresponding to 0.5 F with respect to the aldehyde is passed through the cell, the current is switched off 

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