Nitroso compounds 2-nitrostyrene

Nitrosamines, 1074, 1076 Nitrosobenzene, 629, 630 Nitroso compounds, table of, 1085 p-Nitroso derivatives, 660 N-Nitrosodiethylamine, 426 N-Nitrosodimethylamine, 426 p-Nitrosodimetlivlaniline, 562,573 N-Nitrosoethylaniline, 570 N-Nitrosomethylaniline, 562. 563, 570 p-Nitroso-N-methylanOine, 563, 574 Nitrosomethylurea. 968, 969 a-Nitroso-(3-naphthol, 958 (3-Nitrostyrene, 709, 717 a(3-Nonenoic acid, 405, 468 -Nonoic acid. 487... 

The reduction of an a, i3-unsaturated nitro compound [29], such as /3-nitrostyrene (V), occurs in two steps. The first reduction of (V) is a four-electron reaction that yields phenylacetaldoxime (VI) the reaction has been formulated as a reduction of the nitro group followed by a rearrangement of the unsaturated hydroxylamine (VII), but might also be regarded as a 1,4-reduction of the intermediate unsaturated nitroso compound. There is no conclusive evidence for either route, but the former has been chosen here, as the protonation of the heteroatom would be expected to be faster than protonation of the carbon atom ... 

Nitrosative cyclization, 547 Nitroso compounds, 97-98 Nitrosolysis, 422 N-Ni tro so-N-methylurea, 159 /3-Nitrostyrene, 422 Nitrosyl chloride, 422-423 Nitrosyl tetrafluoroborate, 226 cr-Nitrotriphenylmethane, 272 Nitroxides, 455-456 Nitroxyl radicals, 110 Nonactic acid, 106,107 Nonactin, 106, 625... 

In the presence of 3 equivalents of ) -nitrostyrene (15a) 2-methoxy-l,3-butadiene (61) reacted to afford the nitroso acetals 64 and 65, and at 15 kbar and 50 °C the conversion of the starting compounds was complete within 18 h (Scheme 9.24). 

Attempted reactions of 7d with Ru3(CO)i2 in order to isolate a possible nitrene complex intermediately formed were unsuccessful [9], Thus, we can only speculate about the reaction mechanism. Formation of a nitrene complex analogous to compound 4 is a reasonable hypothesis. However, when the carbonylation of some organic nitro derivatives was conducted in c/.y-cyclooctene as solvent and with Ru3(CO)i2 as catalyst, nitrones have been detected among the products [14]. Under these conditions, the intermediate nitroso derivative reacts with the alkene solvent to yield the corresponding nitrone. The reaction of nitroso derivatives with alkenes is in fact one of the methods for the preparation of nitrones [28]. Thus it could be that in the case of the carbonylation of ortho-nitrostyrenes, the reaction follows the path depicted in Scheme 4 ... 

---