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19.1.2 Product Subclass 2: Nitrile Sulfides

DOI: 10.1055/sos-SD-019-00002

Kanemasa, S.Science of Synthesis, (20041934.

Since the first indirect evidence for the existence of a nitrile sulfide (benzonitrile sulfide) in 1970,[‌117‌] these compounds, generated as transient species and reactive intermediates, have become important in organic chemistry. Although much less stable than the corresponding nitrile oxides, to the extent that their isolation in the pure state is not possible, they undergo 1,3-dipolar cycloaddition reactions in solution, providing routes to several classes of heterocycles accessible only with difficulty by other means.[‌118‌,‌119‌] They are usually generated in situ, in the presence of a suitable dipolarophile, by thermal decomposition of a five-membered heterocycle containing a CNS unit. The method of choice generally involves the thermolysis of a 1,3,4-oxathiazol-2-one. Chemical trapping reactions provide the strongest evidence for the existence of nitrile sulfides as spectroscopic studies are limited by the instability of nitrile sulfides at room temperature. However, both benzonitrile sulfide and acetonitrile sulfide have been detected by IR and UV spectroscopy when they are generated photolytically in a cold matrix, or when the gas-phase pyrolysis products are condensed onto a cold window at very low temperatures using matrix isolation techniques. Nitrile sulfides are assumed to readily lose sulfur at normal temperatures, or when they are photolyzed at very low temperatures. Allowing a nitrile sulfide to warm above 173°C certainly results in desulfuration.[‌118‌] The parent compound thiofulminic acid and other simple nitrile sulfide derivatives have been generated and identified as neutral molecules in the gas phase by neutralizationreionization mass spectroscopy (NRMS),[‌119‌‌123‌] as have some of the corresponding selenides.

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