Acetyl nitrate

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Structural formula
Structural formula of acetyl nitrate
General
Surname Acetyl nitrate
Molecular formula C 2 H 3 NO 4
Brief description

colorless liquid

External identifiers / databases
CAS number 591-09-3
PubChem 11557
ChemSpider 11069
Wikidata Q22668698
properties
Molar mass 105.05 g mol −1
Physical state

liquid

density

1.24 g cm −3

boiling point

22 ° C (70 Torr)

solubility

soluble in acetonitrile, methylene chloride

safety instructions
GHS hazard labeling
no classification available
As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions .

Acetyl nitrate is an organic compound that can be assigned to the group of organic nitrates . It can also be seen as a mixed anhydride of acetic acid and nitric acid . In organic synthesis it is used as a reagent for nitration and oxidation reactions.

history

A first synthesis from dinitrogen pentoxide and acetic anhydride was described in 1907 by Amé Pictet and E. Khotinsky.

Extraction and presentation

The compound is synthesized by reacting concentrated nitric acid with acetic anhydride. Other synthesis variants are the reaction of nitric acid with ketene or the reaction of acetyl chloride with silver nitrate in acetonitrile . An isolation of the pure substance does not take place because the freshly prepared solutions are mostly used as a reagent.

properties

The connection is thermally unstable and tends to decompose explosively when heated. Isolation or even distillation of the compound is not recommended. The controlled thermolysis at 60 ° C leads to nitrogen oxides and tetranitromethane , among other things . In the mixtures of nitric acid and acetic anhydride used for nitrations with a molar excess of acetic anhydride, the compound is in equilibrium with the starting compounds and acetic acid .

In mixtures with a molar excess of nitric acid, nitrous pentoxide is also formed.

Mixtures of nitric acid and acetic anhydride of various compositions tend to undergo a strongly exothermic, explosive decomposition due to the acetyl nitrate they contain. The decomposition kinetics were investigated by means of adiabatic calorimetry. This decomposition is already relevant above 35 ° C, so that storage of such mixtures is not recommended.

use

Acetyl nitrate can be used for the electrophilic nitration of aromatic compounds . With toluene , a mixture of o-, m- and p-nitrotoluene in a ratio of 60: 3: 37 is obtained at room temperature . Biphenyl gives the o- and p-substitution products in a ratio of 58:42. The nitration of naphthalene and pyrene leads to the 1-nitro derivatives, while with 3-fluoroanthracene or phenanthrene the nitration in the 9-position is preferred. CH-acidic compounds such as acetoacetate esters can be nitrated analogously.

Nitration of acetoacetate ester with acetyl nitrate

Alkenes react with acetyl nitrate in an addition reaction to form β-nitroacetates. The addition product 2-nitrocyclohexyl acetate is formed with cyclohexene and 3-nitrocyclohexene is formed after elimination of acetic acid. 4-methylstilbene gives the corresponding addition product.

Addition of acetyl nitrate to 4-methyl stilbene

At temperatures below 0 ° C the targeted oxidation of thioethers to the corresponding sulfoxides succeeds . The corresponding aliphatic nitrates can be obtained in the reaction with alcohols .

Individual evidence

  1. ↑ a b c d e f g h i j Acetyl Nitrate. In: e-EROS Encyclopedia of Reagents for Organic Synthesis . John Wiley and Sons, 1999-2013, accessed August 8, 2013.
  2. ↑ a b c d A. Pictet, E. Khotinsky: About acetyl nitrate. in Chem. Ber. 40, 1907, pp. 1163-1166, doi: 10.1002 / cber.190704001172 .
  3. ↑ This substance has either not yet been classified with regard to its hazardousness or a reliable and citable source has not yet been found.
  4. ↑ HE Folsum, J. Castrillon: The Controlled Oxidation of Organic sulfide to sulfoxide with the help of O-Iodosylbenzoic Acid. In: Synth. Commun. 22, 1992, pp. 1799-1806, doi: 10.1080 / 00397919208020500 .
  5. ↑ Patent DE 849405 (Farbwerke Hoechst, 1952).
  6. ↑ GA Olah, HC Lin, JA Olah, SC Narang: Electrophilic and free radical nitration of benzene and toluene with various nitrating agents. In: Proc. Natl. Acad. Sci. UNITED STATES. 75, 1978, p. 1045.
  7. ↑ W. König: Acetyl nitrate explosion. In: Angew. Chem. 67, 1955, p. 157, doi: 10.1002 / anie.19550670508 .
  8. ↑ a b P. G. Urben: Bretherick's Handbook of Reactive Chemical Hazards. 6th edition. Vol. 1, Butterworth / Heinemann 1999, pp. 283-284.
  9. ^ A b V. Gold, ED Hughes, CK Ingold: Kinetics and mechanism of aromatic nitration. Part V. Nitration by acyl nitrates, particularly by benzoyl nitrate. In: J. Chem. Soc. (Resumed) 1950, pp. 2467-2473, doi: 10.1039 / JR9500002467 .
  10. ^ R. Andreozzi, R. Marotta, R. Sanchirico: Thermal decomposition of acetic anhydride-nitric acid mixtures. In: J. Hazard. Mat. A90, 2002, pp. 111-121, doi: 10.1016 / S0304-3894 (01) 00356-9 .
  11. ↑ H. Burton, PFG Praill: The structure of acyl nitrates. In: J. Chem. Soc. 1955, pp. 729-731, doi: 10.1039 / JR9550000729 .
  12. ↑ E. Hayashi, K. Inana, T Ishikawa: In: Yakugaku Zasshi. 79, 1959, p. 972.
  13. ↑ LI Velichko, OI Kachurin, EY Balabanov: In: Ukr. Khim. Zh. (Russ. Ed.) 49, 1983, p. 1293.
  14. ↑ S. Sifniades: nitration of acetoacetate ester by acetyl nitrate. High yield synthesis of nitroacetoacetate and nitroacetate esters. In: J. Org. Chem. 40, 1975, pp. 3562-3566, doi: 10.1021 / jo00912a020 .
  15. ↑ FG Bordwell, E. Garbisch: nitrate ion with acetyl nitrate. I. The Nature of the Nitrating Agent and the Mechanism of Reaction with Simple Alkenes. In: J. Am. Chem. Soc. 82, 1960, pp. 3588-3598, doi: 10.1021 / ja01499a029 .
  16. ↑ G. Drefahl, H. Crahmer: Investigations on stilbenes, XV. The addition of acetyl nitrate to stilbenes. In: Chem. Ber. 91, 1958, pp. 745-750, doi: 10.1002 / cber.19580910406 .
  17. ↑ G. Drefahl, H. Crahmer: Investigations on stilbenes, XVI. Addition of acetyl nitrate to substituted stilbenes. In: Chem. Ber. 91, 1958, pp. 750-754, doi: 10.1002 / cber.19580910407 .
  18. ↑ R. Louw, HPW Vermeeren, JJA van Asten, WJ Ultee: Reaction of sulphides with acyl nitrates; a simple and rapid method for preparing sulphoxides. In: J. Chem. Soc., Chem. Commun. 1976, pp. 496-497, doi: 10.1039 / C39760000496 .
  19. ^ TG Bonner: Nitration of alcohols at oxygen centers. Part III. The reaction of nitric acid and 2,4-dinitrobenzyl alcohol in acetic anhydride - acetic acid solvent -. In: J. Chem. Soc. 1959, pp. 3908-3913, doi: 10.1039 / JR9590003908 .