Silyl Nitronates in Organic Synthesis. Silylation of Secondary Nitro Compounds. Preparation of Nitroso Compounds and alpha,beta-Unsaturated Aldehydes.

Synthesis, reactions, and properties of oxygen-nitrogen-oxygen systems

“…46,56,58,61,65,[71][72][73]79 In 1972 Ioffe and co-workers80 suggested using the silyl esters of nitronic acids as a 1,3-dipolar component, which unlike their alkyl analogues is stable and retains the ability of cycloaddition to olefins. [81][82][83][84][85][86][87][88][89][90][91][92] The intramolecular reactions of the nitronate group with double bonds are known too. For instance, the interaction of tetranitromethane with one of the double bonds of hexa-1,5-diene gives a nitronic ester which is then added to the other double bond forming bicyclic compound 2 (Scheme l).…”

Conjugated nitrosoalkenes

“…Previously this route for the construction of a nitroso group has been realised during ring opening in N-trimethylsilyloxyisoxazolidines. 41,71 III. Structure and physical properties of nitrosoalkenes As was to be expected, stable nitrosoalkenes, the properties of which are listed in Table 1, have been characterised most comprehensively by spectroscopic data.…”

“…Previously this route for the construction of a nitroso group has been realised during ring opening in N-trimethylsilyloxyisoxazolidines. 41,71…”

“…IR spectra of nitrosoalkenes contain two absorption bands in the region 1420 ± 1660 cm 71 . A band in the range 1420 ± 1480 cm 71 corresponds to the stretching vibrations of the N=O bond (for 2,2-di-tert-butylnitrosoethylene 1c 7 this band occurs at 1485 cm 71 ). The same region contains the absorption bands for the N=O bonds in other monomeric nitroso compounds.…”

“…The same region contains the absorption bands for the N=O bonds in other monomeric nitroso compounds. 72 The absorption at shorter wavelengths (1500 ± 1600 cm 71 ) was assigned to stretching vibrations of the C=C bond. 8 In the 1 H NMR spectra of the compounds 1b and 1f (see Table 1), the vinylic protons account for signals at d 9.13 ppm 6 and 8.68 ppm, 10 respectively.…”