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COX and CC is affected by the amount of the internal energy
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ozonation involving the DC operates under our conditions
of low temperatures while it might not be operative at higher
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(iv) Failed formation of SOZ in the ozonation of 2,3-dimethylbut-
2-ene
The gas phase ozonation of (CH ) C᎐C(CH ) carried out at
᎐
3
2
3 2
Ϫ40 ЊC does not yield secondary tetramethylethene ozonide but
only acetone (major product) and acetone diperoxide together
with a C4H8O and two other minor products. These findings are
in keeping with other unsuccessful attempts to prepare second-
ary tetramethylethene ozonide in the gas phase at low6,39 or
atmospheric41 pressure, in solution,7c in silica gel42 and in cryo-
genic matrices.43 We note, however, that the successful form-
ation of secondary tetramethylethene ozonide occurs on the
surface of polyethene particles, when restricted migration of
the adsorbed CC and COX is believed44 to overwhelm low
reactivity of the CC in intramolecular cyclization with COX.
The absence of secondary tetramethylethene ozonide among
the products of the gas-phase ozonation of tetramethylethene
is thus confirming the failure of secondary tetramethylethene
ozonide formation in the solution phase.
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Conclusions
The use of complementary combination of GC–FTIR and
GC–MS techniques provides unequivocal evidence that sec-
ondary ozonides are products of ozonation of alkenes in the
gas phase.
The SOZ yields from primary alkenes (RHC᎐CH ) decrease
as the temperature is increased from Ϫ40 to 20 ЊC, while
᎐
2
those from secondary alkenes (trans-RHC᎐CHR) are almost
᎐
unaffected within this temperature range. The stereoselectivity
for the formation of trans-secondary ozonides from trans-
RHC᎐CHR possessing Me, Et and Pri is similar to that earlier
᎐
observed for the ozonation in solution. The data show that the
geminate CO and COX components can bimolecularly react
into SOZ without the stabilizing effect of solvent and they
give definite support to earlier held opinions that the complete
Criegee mechanism can be extended to the gas-phase.
The unambiguous determination of the SOZs as products of
alkenes ozonation in the gas phase reported in this work also
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Acknowledgements
This research was supported under Grant No. HRN-2078, C12-
223, US-Israel Cooperative Development Research Program,
Office of the Science Advisor, US Agency for International
Development, and under Grant No. 104/96/0472 of the Grant
Agency of the Czech Republic.
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