REACTIONS OF CYCLOPENTANONE,
γ
ꢀBUTYROLACTONE
309
between these carbonyl compounds and their carbonꢀ
ylated analogues I–VI
6. Brinkevich, S.D. and Shadyro, O.I., High Energy
Chem., 2008, vol. 42, no. 4, p. 255.
.
7
. Brinkevich, S.D. and Shadyro, O.I., Bioorg. Med.
Chem. Lett., 2008, vol. 18, no. 24, p. 6448.
Compounds VII and VIII alter the ratio of radiaꢀ
tionꢀchemical yields of ethanol in favor of AA, acting
8. Brinkevich, S.D. and Shadyro, O.I., High Energy
Chem., 2009, vol. 43, no. 6, p. 435.
as an oxidant in reactions with ꢀHER, like most carꢀ
α
bonyl compounds. However, despite the presence of
the carbon–carbon double bond conjugated with the
carbonyl group, VII and VIII are mild oxidants, a fact
that is probably due to the increase of electron density
on the carbonyl group by electronꢀdonating substituꢀ
9. Brinkevich, S.D. and Shadyro, O.I., High Energy
Chem., 2011, vol. 45, no. 2, p. 93.
1
0. Brinkevich, S.D., Boreko, E.I., Savinova, O.V., Pavꢀ
lova, N.I., and Shadyro, O.I., Bioorg. Med. Chem.
Lett.,2012, vol. 22, no. 7, p. 2424.
ents at С2 and С3. No products of ꢀHER addition to
α
VI and VIII have been detected by gas chromatograꢀ
phy–mass spectrometry; hence, the presence of
hydroxy or methoxy groups as substituents at the douꢀ
11. Shadyro, O.I. and Kisel’, R.M., High Energy Chem.
,
2007, vol. 41, no. 5, p. 318.
ble carbon–carbon bond imposes steric constraints on 12. Von Sonntag, C., FreeꢀRadicalꢀInduced DNA Damage
and Its Repair, Berlin: Springer, 2006.
the addition of
α
ꢀHER.
1
3. Sosnovskaya, A.A., Sladkova, A.A., Dobridenev, I.S.,
and Shadyro, O.I., High Energy Chem., 2009, vol. 43,
no. 6, p. 431.
CONCLUSIONS
1
4. Yurkova, I., Kisel, M., Arnhold, J., and Shadyro, O.,
The interaction of ascorbic acid and its carbonyꢀ
lated cyclic analogues with ꢀHER generated during
radiationꢀinduced transformations of deaerated ethaꢀ
nol have been studied in the continuous radiolysis
Chem. Phys. Lipids, 2005, vol. 134, no. 1, p. 41.
α
15. Shadyro, O.I., Free Radical Res., 2002, vol. 36, no. 8,
p. 859.
mode. The test compounds, except
oxidize ꢀHER as indicated by a change in the ratio
γ
ꢀbutyrolactone, 16. Grintsevich, I.B. and Shadyro, O.I., High Energy
Chem., 2005, vol. 39, no. 3, p. 137.
α
between the yields of the main radiolysis products of
deaerated ethanol in favor of acetaldehyde. It has been
shown that the principal mechanism of radiolytic
1
7. Brinkevich, S.D., Sverdlov, R.L., Lagutin, P.Yu., and
Shadyro, O.I., High Energy Chem., 2011, vol. 45, no. 5,
p. 380.
transformations of
pounds VI and IV is the addition of
α
,
β
ꢀunsaturated carbonyl comꢀ
18. Brinkevich, S.D., Samovich, S.D., and Shadyro, O.I.,
α
ꢀHER to the carꢀ
High Energy Chem., 2011, vol. 45, no. 6, p. 532.
bon–carbon double bond. The process follows the
1
9. Samovich, S.N., Brinkevich, S.D., Edimecheva, I.P.,
and Shadyro, O.I., J. Radiat. Phys. Chem., 2014 (in
press).
shortꢀchain mechanism in the case of IV and has a
1
greater chain length for VI. The H NMR and GC–
MS studies showed that the products of C ꢀ and C ꢀ
2
3
addition of
formed in a ratio of 1.3 : 1. Unlike
carbonyl compounds IV and VI, ascorbic and 5,6ꢀ
isopropylidenylꢀ2,3ꢀ ꢀdimethylꢀLꢀascorbic acid are 21. Mashkovskii, M.D., Lekarstvennye sredstva (Medicinal
weaker oxidants of
α
ꢀHER in the case of 2(5H)ꢀfuranone are 20. Brinkevich, S.D., Ostrovskaya, N.I., Parkhach, M.E.,
Samovich, S.N., and Shadyro, O.I., Free Radical Res.
012, vol. 46, no. 3, p. 295.
,
α
, ꢀunsaturated
β
2
Oꢀ
O
αꢀHER and do not form hydroxyꢀ
Products), Moscow: Novaya Volna, 2010.
ethylation products by radiolysis in deaerated ethanol.
22. Ulrich, D., Z. Lebensm. Unters. Forsc, vol. 200, no. h.
1995, p. 217.
2
3. Freeman, G.R., Radiation Chemistry of Ethanol: A
Review of Data on Yields, Reaction Rate Parameters, and
Spectral Properties of Transients, Washington: NBS,
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Translated by S. Zatonsky
HIGH ENERGY CHEMISTRY
Vol. 48
No. 5
2014