The Formation of Highly Oxidized Multifunctional Products in the Ozonolysis of Cyclohexene

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• 作者：Matti P. Rissanen ; Theo Kurt茅n ; Mikko Sipil盲 ; Joel A. Thornton ; Juha Kangasluoma ; Nina Sarnela ; Heikki Junninen ; Solvejg J酶rgensen ; Simon Schallhart ; Maija K. Kajos ; Risto Taipale ; Monika Springer ; Thomas F. Mentel ; Taina Ruuskanen ; Tuukka Pet盲j盲 ; Douglas R. Worsnop ; Henrik G. Kjaergaard ; Mikael Ehn
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：November 5, 2014
• 年：2014
• 卷：136
• 期：44
• 页码：15596-15606
• 全文大小：528K
• ISSN：1520-5126

文摘

The prompt formation of highly oxidized organic compounds in the ozonolysis of cyclohexene (C₆H₁₀) was investigated by means of laboratory experiments together with quantum chemical calculations. The experiments were performed in borosilicate glass flow tube reactors coupled to a chemical ionization atmospheric pressure interface time-of-flight mass spectrometer with a nitrate ion (NO₃^{鈥?/sup>)-based ionization scheme. Quantum chemical calculations were performed at the CCSD(T)-F12a/VDZ-F12//蠅B97XD/aug-cc-pVTZ level, with kinetic modeling using multiconformer transition state theory, including Eckart tunneling corrections. The complementary investigation methods gave a consistent picture of a formation mechanism advancing by peroxy radical (RO₂) isomerization through intramolecular hydrogen shift reactions, followed by sequential O₂ addition steps, that is, RO₂ autoxidation, on a time scale of seconds. Dimerization of the peroxy radicals by recombination and cross-combination reactions is in competition with the formation of highly oxidized monomer species and is observed to lead to peroxides, potentially diacyl peroxides. The molar yield of these highly oxidized products (having O/C > 1 in monomers and O/C > 0.55 in dimers) from cyclohexene ozonolysis was determined as (4.5 卤 3.8)%. Fully deuterated cyclohexene and cis-6-nonenal ozonolysis, as well as the influence of water addition to the system (either H₂O or D₂O), were also investigated in order to strengthen the arguments on the proposed mechanism. Deuterated cyclohexene ozonolysis resulted in a less oxidized product distribution with a lower yield of highly oxygenated products and cis-6-nonenal ozonolysis generated the same monomer product distribution, consistent with the proposed mechanism and in agreement with quantum chemical modeling.}