Nitroacetylenes

Nitroacetylene as dipolarophile in [2 + 3] cycloaddition reactions with allenyl-type three-atom components: DFT computational study

“…Nitroacetylenes belong—because of the presence of a strongly electron withdrawing NO 2 -group—to a class of strongly electrophilic acetylenes. They are relatively unstable, and their physicochemistry is very poorly known [ 1 ].…”

Nitroalkynes: A Unique Class of Energetic Materials

“…6,8,9,11 Jäger mentions a ῦ C≡C of 2165 cm -1 for 2 in a footnote of his thesis, 13 a reference to experiments of his co-worker Verbruggen (the first to synthesize 2), whose work was published in his 1970 Mémoire de Licence 6 and briefly cited again in a reference manual in 1977. 7 Rall' et al give the same number in their review, 27 erroneously referring to Bellamy's book. 34 Terminal alkylalkynes typically exhibit ῦ C≡C = 2140-2100 cm -1 and internal systems 2260-2210 cm -1 .…”

“…The only reported nitroalkyne UV-Vis data (of 3-5) were collected by Jäger in 1969, 13 and summarized again by Rall' et al 27 They consist of one band at ~235-239 nm, associated with a much less intense shoulder at ~290 nm. The primary spectroscopic probe of nitroalkynes has been infrared radiation, and typical bands for all known nitroalkynes (including those previously reviewed) are compiled in Table 1.…”

“…Only a few years later, Motte and Jäger did succeed in oxidizing these compounds to the corresponding nitroalkynes (section 4.2.1). 12,15 Motte, in his 1974 dissertation, 53 tried to effect nitrations of lithiated (e.g., 25), trialkylstannyl- (26), and trialkylsilylalkynes (27)(28)(29)(30)(31) in his attempts to make 3-5, 7, and 32, respectively. Many of these experiments failed, as summarized for nitronium chloride in Scheme 4.…”

“…Thermal decomposition, reduction, bromination, hydrochlorination, hydration, nucleophilic addition, and several cycloadditions have been reviewed previously (primarily featuring 3 as substrate). 13,27 This section describes new aspects of thermal decomposition, nucleophilic addition, and cycloadditions to nitroalkynes.…”