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In organic chemistry, a nitrate ester is an organic functional group with the formula R−ONO₂, where R stands for any organyl group. They are the esters of nitric acid and alcohols. A well-known example is nitroglycerin, which is not a nitro compound, despite its name.

Synthesis and reactions

Nitrate esters are typically prepared by condensation of nitric acid and the alcohol: For example, the simplest nitrate ester, methyl nitrate, is formed by reaction of methanol and nitric acid in the presence of sulfuric acid:

${\displaystyle {\ce {CH3OH + HNO3 -> CH3ONO2 + H2O}}}$

Formation of a nitrate ester is called a nitrooxylation (less commonly, nitroxylation).

Most commonly, "mixed acid" (nitric and sulfuric acids) are used, but in the 1980s production of the nitrocellulose with magnesium nitrate as a dehydrating agent was started in the US. In laboratory, phosphoric acid and phosphorus pentoxide or acetic acid and its anhydride may be used for the same purpose, or the nitroxylation can be conducted in anhydrous conditions (such as dichloromethane or chloroform).

Explosive properties

The thermal decomposition of nitrate esters mainly yields the gases molecular nitrogen (N₂) and carbon dioxide. The considerable chemical energy of the detonation is due to the high strength of the bond in molecular nitrogen. This stoichiometry is illustrated by the equation for the detonation of nitroglycerin.

Illustrative of the highly sensitive nature of some organic nitrates is Si(CH₂ONO₂)₄. A single crystal of this compound detonates even upon contact with a teflon spatula and in fact made full characterization impossible. Another contributor to its exothermic decomposition (inferred from much safer in silico experimentation) is the ability of silicon in its crystal phase to coordinate to two oxygen nitrito groups in addition to regular coordination to the four carbon atoms. This additional coordination would make formation of silicon dioxide (one of the decomposition products) more facile.

Medical use

The nitrate esters isosorbide dinitrate (Isordil) and isosorbide mononitrate (Imdur, Ismo, Monoket, Mononitron) are converted in the body to nitric oxide, a potent natural vasodilator. In medicine, these esters are used as a medicine for angina pectoris (ischemic heart disease).

Related compounds

Acetyl nitrate is a nitrate anhydride, being derived from the condensation of nitric and acetic acids.

References

1. Snyder, H. R.; Handrick, R. G.; Brooks, L. A. (1942). "Imidazole". Organic Syntheses; Collected Volumes, vol. 3, p. 471.
2. Boschan, Robert; Merrow, Raymond T.; van Dolah, Robert W. (1955-06-01). "The Chemistry of Nitrate Esters". Chemical Reviews. 55 (3): 485–510. doi:10.1021/cr50003a001. ISSN 0009-2665.
3. Alvin P. Black & Frank H. Babers. "Methyl nitrate". Organic Syntheses; Collected Volumes, vol. 2, p. 412.
4. Liu, Jiping (2019-03-06). Nitrate Esters Chemistry and Technology. Springer. ISBN 978-981-13-6647-5.
5. Heinze, T.; Liebert, T. (2012-01-01), Matyjaszewski, Krzysztof; Möller, Martin (eds.), "10.05 - Celluloses and Polyoses/Hemicelluloses", Polymer Science: A Comprehensive Reference, Amsterdam: Elsevier, pp. 83–152, ISBN 978-0-08-087862-1, retrieved 2024-11-11
6. The Sila-Explosives Si(CH₂N₃)₄ and Si(CH₂ONO₂)₄: Silicon Analogues of the Common Explosives Pentaerythrityl Tetraazide, C(CH₂N₃)₄, and Pentaerythritol Tetranitrate, C(CH₂ONO₂)₄Thomas M. Klapötke, Burkhard Krumm, Rainer Ilg, Dennis Troegel, and Reinhold Tacke J. Am. Chem. Soc.; 2007 doi:10.1021/ja071299p
7. Sila-Explosives Offer A Better Bang Stephen K. Ritter Chemical & Engineering News May 7 2007Link

• Functional groups
• Nitrate esters