Chemistry:Fulminic acid

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Fulminic acid
Fulminic acid 3D spacefill.png
Names
IUPAC name
Oxidoazaniumylidynemethane
Identifiers
3D model (JSmol)
1071209
ChEBI
ChEMBL
ChemSpider
772
Properties
HCNO
Molar mass 43.02 g mol−1
Conjugate base Fulminate
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Fulminic acid is an acid with the formula HCNO, more specifically H–C≡N+–O. It is an isomer of isocyanic acid H–N=C=O and of its elusive tautomer cyanic acid H–O–C≡N, and also of isofulminic acid H–O–N+≡C.[1]

Fulminate is the anion [C≡N+–O] or any of its salts. For historical reasons, the fulminate functional group is understood to be –O–N+≡C as in isofulminic acid;[2] whereas the group –C≡N+O is called nitrile oxide.

History

This chemical was known since the early 1800s through its salts and via the products of reactions in which it was proposed to exist,[3] but the acid itself was not detected until 1966.[1]

Structure

Fulminic acid was long believed to have a structure of H–O–N+≡C. It wasn't until the 1966 isolation and analysis of a pure sample of fulminic acid that this structural idea was conclusively disproven.[3] The chemical that actually has that structure, isofulminic acid (a tautomer of the actual fulminic acid structure) was eventually detected in 1988.[3]

The structure of the molecule has been determined by microwave spectroscopy with the following bond-lengths - C-H: 1.027(1)Å, C-N: 1.161(15)Å, N-O: 1.207(15)Å.[4]

Synthesis

A convenient synthesis involves flash pyrolysis of certain oximes. In contrast to earlier syntheses, this method avoids the use of highly explosive metal fulminates.[5]

References

  1. 1.0 1.1 Beck, W.; Feldl, K. (1966). "The Structure of Fulminic Acid, HCNO". Angew. Chem. Int. Ed. Engl. 5 (8): 722–723. doi:10.1002/anie.196607221. 
  2. Wentrup, Curt; Gerecht, Bernd; Laqua, Dieter; Briehl, Horst; Winter, Hans Wilhelm; Reisenauer, Hans Peter; Winnewisser, Manfred (1981). "Organic fulminates, R-O-NC". Journal of Organic Chemistry 46 (5): 1046–1048. doi:10.1021/jo00318a050. 
  3. 3.0 3.1 3.2 Kurzer, Frederick (2000). "Fulminic Acid in the History of Organic Chemistry". Journal of Chemical Education 77 (7): 851–857. doi:10.1021/ed077p851. Bibcode2000JChEd..77..851K. 
  4. Winnewisser, Manfred; Bodenseh, Hans Karl (1967). "Mikrowellenspektrum, Struktur und /-Typ-Dublett-Aufspaltung der HCNO (Knallsäure)". Z. Naturforsch. 22 a (11): 1724–1737. doi:10.1515/zna-1967-1109. Bibcode1967ZNatA..22.1724W. 
  5. Wentrup, Curt; Gerecht, Bernd; Horst, Briehl (1979). "A New Synthesis of Fulminic Acid". Angew. Chem. 18 (6): 467–468. doi:10.1002/anie.197904671.