Nitro-olefins

Finally, it is interesting to note that the reduction of nitroethylene, an olefinic nitro-compound having a structure analogous to that of nitrobenzene, leads to acetaldoxime. 

Reaction with -alkylthio nitro olefins. Nitro alkenes bearing an alkylthio or phenylsulfonyl group at the -position undergo addition-elimination reactions with organocopper/zinc reagents to provide functionalized (E)-nitro alkenes. 

This method has had limited application for making aliphatic amines although it assumes increasing importance in view of the commercial availability of the nitroparaffins and the development of processes for their ready conversion to nitro olefins, nitro alcohols, nitro... 

Nitro alcohols ate usually isolated (method 102) but are sometimes dehydrated directly to olefinic nitro compounds as in the preparation of co-nitro-2-vinylthiophene from nitromethane, thiophenecarboxaldehyde, and sodium hydroxide (78% yield). Many substituted /3-nitrostyrenes have been obtained by condensation of nitromethane or nitroethane with substituted benzaldehydes. A methyl group on the benzene ring is sufficiently activated by nitro groups in the orlio or para position to cause condensation with aldehydes. A series of nitrostilbenes has been made in this way from substituted benzaldehydes. ... 

The main index headings for search other than the names of specific compounds are Paraffins nitration of Paraffins, nitro Paraffins, from nitration of— Paraffins, dinitro Hydrocaibons, nitration of Nitration of hydrocarbons Nitration of paraffins Petroleum, nitrogen compounds from Olefins, nitro derivatives and Acetylenes, nitro derivatives. These items are not mutually inclusive, e.g., references under Paraffins, nitration of are not necessarily to be found under Nitration of paraffins. In Chemical Abstracts collective index for 1937 to 1946, there are 19 entries under the first heading and 12 entries under the second only 10 are common to both lists. 

Deuterium gas exchanges rapidly with methanol over Adams platinum catalyst at 35 . The influence of catalyst weight and treatment and of deuterium pressure on this exchange have been studied, as well as the effects of several aromatic, aliphatic, and olefinic nitro and related compounds. All of these nitro compounds reduce the rate of the exchange reaction initially, and the magnitude of such reduction increases with increasing specific rate constant for the platinum catalyzed hydrogenation of these compounds. 

In any of these systems, the methanol exchange and reduction of the nitro or unsaturated compound, as evidenced by absorption of deuterium, are competitive reactions. The kinetics of hydrogenation of these nitro compounds in ethanol over Adams platinum catalyst are similar, being zero order in acceptor and first order in hydrogen pressure (IS). The aromatic and conjugated olefinic nitro compounds have much higher specific rate... 

The group frequencies of aromatic compounds near 1600 cm are excellent for recognizing the presence of aromatic rings in the spectrum of an unknown compound, although some olefinic nitro, amino, and carbonyl compounds can also have bands there. 

Levulinate protecting group for alcohols. 60-90% yieldsj removed by mild reduction,useful for nucleosides. Stable to TFA, 80% HOAc. Compatible with olefin, nitro, ester, acetal functional groups. 

While the direct nitration of aliphatic hydrocarbons enjoys considerable importance in the industrial sphere, in the laboratory it has only limited value since complex mixtures of products are usually formed. Treatment of olefins with dinitrogen tetroxide may lead to dinitroparaffins and mixtures of nitro nitrites. The latter may be oxidized to nitro nitrates or hydrolyzed to nitro alcohols or thermally degraded to olefinic nitro compounds under the reaction conditions. 

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