Nitroacetylene: HC≡CNO₂

Abstract

Nitroacetylene (1) was prepared by the reaction of NO₂PF₆ with trimethylsilylacetylene. It is stable at room temperature in dilute solution for about a week. The ¹H and ¹³C NMR spectra of nitroacetylene reveal strong ¹H-¹⁴N and ¹³C-¹⁴N spin couplings. Nitroacetylene reacts rapidly with nucleophiles. It gives a 1,4-Diels-Alder adduct with cyclopentadiene. However, its reactions with furan and vinyl ethers produce nitrovinylisoxazoles by a mechanism thought to involve the 1,4-addition of nitroacetylene to the vinyl ether to give a highly strained unsaturated nitrone, followed by fragmentation of the nitrone to vinyl nitrile oxide, then additions of this 1,3-dipolarophile.

Key words

nitroacetylene - alkynes - Diels-Alder reactions - vinyl nitrile oxide - isoxazoles - heterocylcles

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8

We have recently had some success using nitronium triflate, an easily purified material.

15

X-ray data for 10 have been deposited with the Cambridge Crystallographic Data Centre (no. 187049).

19

Ref. [18] ; Table 1.2, p 30.

22

From the ¹⁴N-decoupled, ¹H-coupled spectrum.