Nitrosation Reactions of Primary Vinylamines. Possible Divalent Carbon Intermediates¹

Stereoselective synthesis of racemic grandisol

“…Then 2.37 g (0.01 mol) of 2 {vide infra) was added; the addition of ammonia gas below the surface at a moderate rate was started immediately. Periodically, 0.1-ml samples were withdrawn, diluted with 5 ml of water, adjusted to pH 9 with NH4OH, and extracted with CHCls (5 ml). The extracts were analyzed by glc;5 the results are presented in Figure 1.…”

Allene Oxide Intermediates: Vinylidene Carbene Addition to Carbonyl Compounds

“…Most of the products isolated by column chromatography were noncrystalline, but three crystalline side-products were often isolated: the secondary amine 13d, 9,9'-biformyl-9,9'-bifluorenyl (17) and fluorenone. 13d has been suggested by Curtin et al (9) to arise from insertion of the carbene 10 in the N H bond of 9. He also proposed that 17 could be formed by initial nitrosation of the 9-carbon atom of 9-(aminomethy1ene)-fluorene followed by loss of nitric oxide to give a radical which dimerizes to give the imine of 17 and thence 17 itself by hydrolysis during work-up.…”

Alkenediazonium Salts: A New Chapter of Classical Organic Chemistry

“…Regarding the two structural possibilities, namely an addition complex (2) or a diazonium chelate (3) with salt character, measurement of the electrical conductivity in liquid sulfur dioxide provides evidence in favor of (3). Boron trichloride and boron trifluoride also combine with dicarbonyl diazo compounds, to form 2 : 1 addition products, for which Fahr and Hormann[gl suggest structures analogous to the complex (2).…”

“…In the presence of hydrogen chloride and antimony pentachloride, diazomalonic ester does not add a proton, but reacts with two molecules of the Lewis acid[' 'I. Regarding the two structural possibilities, namely an addition complex (2) or a diazonium chelate (3) with salt character, measurement of the electrical conductivity in liquid sulfur dioxide provides evidence in favor of (3).…”