Conformational studies of aliphatic secondary ozonides (propene, 1-butene and 1-heptene) by means of FTIR spectroscopy

• Authors: Ruta Bariseviciute , Justinas Ceponkus , Alytis Gruodis , Valdas Sablinskas
• Languages of publication: EN

Abstracts

EN

Ozonization reaction of simple alkenes was studied by means of FT infrared absorption gas spectroscopy. The reaction was performed at 95 K in neat films of the reactants. IR absorption spectra of the gaseous products were recorded. The spectra were analyzed combining experimental results with theoretical calculations performed at B3LYP 6-311++G (3df, 3pd) level. We found that among all theoretically predicted conformers of propene secondary ozonide, only one which has the O-O half-chair configuration for the five membered ring and the radical attached in the equatorial position was present in the sample. Samples of 1-butene and 1-heptene secondary ozonides consist from two conformers of very similar energy (ΔH=0.3 kJ/mol). The most stable conformer for both ozonides is the one with O-O half-chair configuration of the five membered ring and the radical attached in equatorial position and the aliphatic chain in gauche position. The second stable conformer has the aliphatic chain in anti position.

Keywords

EN

Ozonization; conformational analysis; secondary ozonides; IR spectroscopy

• Publisher: De Gruyter Open
• Journal: Open Chemistry
• Year: 2006
• Volume: 4
• Issue: 4
• Pages: 578-591

Dates

published

1 - 12 - 2006

online

1 - 12 - 2006

Contributors

author

Ruta Bariseviciute

• Department of General Physics and Spectroscopy, Vilnius University, Vilnius, 01513, Lithuania

author

Justinas Ceponkus

• Department of General Physics and Spectroscopy, Vilnius University, Vilnius, 01513, Lithuania

author

Alytis Gruodis

• Department of General Physics and Spectroscopy, Vilnius University, Vilnius, 01513, Lithuania

author

Valdas Sablinskas

• Department of General Physics and Spectroscopy, Vilnius University, Vilnius, 01513, Lithuania

References

• [1] R.D. Suenram and F.J. Lovas: “Dioxirane. Its synthesis, microwave spectrum, structure and dipole moment”, J. Am. Chem. Soc., Vol. 100(16), (1978), pp. 5117–5122. http://dx.doi.org/10.1021/ja00484a034[Crossref]
• [2] R. Fajgar, J. Vitek, Y. Haas and J. Pola: “Formation of secondary ozonides in the gas phase low-temperature ozonation of primary and secondary alkenes”, J. Chem. Soc. Perk. Trans 2, (1999), pp. 239–248. [Crossref]
• [3] R. Atkinson, E.C. Tuazon and S.M. Aschmann: “Products of the gas-phase reactions of O3 with alkenes”, Environ. Sci. Technol., Vol. 29(7), (1995), pp. 1860–1866. [WoS][Crossref]
• [4] P. Neeb, O. Horie, G.K. Moortgat: “Formation of secondary ozonides in the gas-phase ozonolysis of simple alkenes”, Tetrahedron Lett., Vol. 37(52), (1996), pp. 9297–9300. http://dx.doi.org/10.1016/S0040-4039(97)82946-2[Crossref]
• [5] N.L. Bauld, J.A. Thompson, C.E. Hudson and P.S. Bailey: “Stereospecificity in ozonide and cross-ozonide formation”, J. Am. Chem. Soc., Vol. 90(7), (1968), pp. 1822–1830. http://dx.doi.org/10.1021/ja01009a026[Crossref]
• [6] P.S. Bailey and T.M. Ferrell: “Mechanism of ozonolysis. A more flexible stereochemical concept”, J. Am. Chem. Soc., Vol. 100(3), (1978), pp. 899–905. http://dx.doi.org/10.1021/ja00471a040[Crossref]
• [7] C.W. Gillies and R.L. Kuczkowski: “Mechanism of ozonolysis. Microwave spectrum, structure, and dipole moment of ethylene ozonide”, J. Am. Chem. Soc., Vol. 94(18), (1972), pp. 6337–6343. http://dx.doi.org/10.1021/ja00773a014[Crossref]
• [8] R.P. Lattimer, R.L. Kuczkowski and C.W Gillies: “Mechanism of ozonolysis. (a) Microwave spectra, structures, and dipole moments of propylene and trans-2-butene ozonides. (b) Orbital symmetry analysis”, J. Am. Chem. Soc., Vol. 96(2), (1974), pp. 348–358. http://dx.doi.org/10.1021/ja00809a006[Crossref]
• [9] P. Klaeboe: “Conformational studies by vibrational spectroscopy: a review of various methods”, Vib. Spectrosc., Vol. 9(1), (1995), pp. 3–17. http://dx.doi.org/10.1016/0924-2031(94)00058-O[Crossref]
• [10] M.S. Johnson, F. Hegelund and B. Nelander: “The v 5 band of HClO4”, J. Mol. Spectrosc., Vol. 190(2), (1998), pp. 269–273. http://dx.doi.org/10.1006/jmsp.1998.7588
• [11] R.W. Larsen, F. Hegelund and B. Nelander: “Studies of intermolecular vibrations in hydrogen-bonded molecular complexes for the gas phase using synchrotron radiation source”, Mol. Phys. Vol. 102(16–17), (2004), pp. 1743–1747. http://dx.doi.org/10.1080/00268970412331287142[Crossref]
• [12] M.G. Loudon: Organic chemistry, 4th ed., Oxford University Press, 2002.
• [13] E.C. Tuazon, S.M. Aschmann, J. Arey and R. Atkinson: “Products of the gas-phase reactions of O3 with a series of methyl-substituted ethenes”, Environ. Sci. Technol., Vol. 31(10), (1997), pp. 3004–3009. http://dx.doi.org/10.1021/es970258y[Crossref]
• [14] R.S. Disselkamp and M. Dupuis: “A temperature-dependent study of the ozonolysis of propene”, J. Atmos. Chem., Vol. 40, (2001), pp. 231–245. http://dx.doi.org/10.1023/A:1012239827705[Crossref]
• [15] L. Andrews, C. K. Kohlmiller: “Infrared spectra and photochemistry of the primary and secondary ozonides of propene, trans-2-butene and methylpropene in solid argon”, J. Phys. Chem., Vol. 86(23), (1982), pp. 4548–4557. http://dx.doi.org/10.1021/j100220a020[Crossref]

Identifiers

DOI

10.2478/s11532-006-0031-3