Nitroso Compounds. III. Reactions of Organo-metallic Compounds with Alpha Halo Nitroso Compounds¹

Abstract

Vol. 57 sium oleate at 18,11 except that in previous diagrams boundaries should be raised by a few per cent, to allow for interionic attraction and 100% dissociation of hydrochloric acid. The middle line of the diagram is given from e. m. f. and conductivity data of Figs. 1, 2 and 3. Most of the transition between simple crystalloidal and colloidal electrolytes takes place between 0.05 and 0.15 N for undecyl and lauryl sulfonic acids and in still more dilute solution in myristyl sulfonic acid. Above 0.1 or 0.2 N there can be but little else than colloid and hydrogen ions. The concentration of ionic micelles will be equal to that of the hydrogen ion, the remaining sulfonic acid forming neutral micelles. Summary Hydrogen-ion concentration deduced from con- (11)

The Nitroso Ene Reaction: A Regioselective and Stereoselective Allylic Nitrogen Functionalization of Mechanistic Delight and Synthetic Potential

“…Examples of the various transformations that nitroso compounds undergo are displayed in the form of the rosette in Scheme . As electrophilic species, they undergo additions with enolates (path a), − amines (path b), and Grignard reagents (path c). − With diazomethane, nitrones are formed (path d) and it is well-known that nitroso compounds are good radical scavengers (path e). − The [2+2] (path f) , and [4+2] (path g) − cycloadditions of nitroso compounds are established transformations, as well as the ene reaction (path h). , By the use of chiral nitroso compounds or chiral partner substrates, excellent diastereoselectivities have been obtained in the nitroso aldol reaction (path a), , in [4+2] cycloadditions (path g), ,, and in the ene reaction (path h); the latter shall be discussed in detail in section V.

2 Use of Nitroso Compounds in Organic Synthesis

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“…As electrophilic species, they undergo additions with enolates (path a), [25][26][27] amines (path b), 28 and Grignard reagents (path c). [29][30][31] With diazomethane, nitrones are formed (path d) 32 and it is well-known that nitroso compounds are good radical scavengers (path e). [33][34][35] The [2+2] (path f) 36,37 and [4+2] (path g) [38][39][40][41] cycloadditions of nitroso compounds are established transformations, as well as the ene reaction (path h).…”

Formation ofO-Allyl Oximes by Reaction of Allylzinc Reagents with α-Chloronitroso Compounds

“…10 The reactions were performed by titrating a vigorously stirred THF solution of a-chloronitrosocyclohexane 6a with the allylzinc reagents 15 (Scheme 4, Table 1). The end point was indicated by the disappearance of the blue color of the achloronitroso compound.…”

“…MS (GC-MS) m/z (%) = 167(14), 152(10), 113(14), 96 (17), 85 (19), 55 (100).Anal. Calcd for C10 H 17 NO (167.25): C, 71.81; H, 10.25; N, 8.37.…”