Matrix isolation study of the early intermediates in the ozonolysis of selected vinyl ethers

Abstract

The Criegee mechanism of the ozonolysis reaction of vinyl ethers has been observed by matrix isolation FTIR spectroscopy.

Atmospheric Chemistry of 2-Methoxypropene and 2-Ethoxypropene: Kinetics and Mechanism Study of Reactions with Ozone

“…In conclusion, the four types of Criegee intermediates formed in the ozonolysis of 2-MPE can undergo a variety of further reactions, and all possible pathways are summarized in Scheme 1. As can be seen in Scheme 1, the reaction of 2-MPE with O 3 pursued by O 3 electrophilic addition on the double bond and accordingly led to the formation of the primary ozonide, which has been proved to form in similar reactions in our previous study [57]. Primary ozonide could rapidly decompose by two pathways: the first one is decomposition to CH 3 C(O)OCH 3 and HCHO.…”

“…A reaction mechanism is proposed for this reaction, based on the reaction products identified and previous mechanism studies of unsaturated compounds [2,25,28,42]. As can be seen in Scheme 1, the reaction of 2-MPE with O3 pursued by O3 electrophilic addition on the double bond and accordingly led to the formation of the primary ozonide, which has been proved to form in similar reactions in our previous study [57]. Primary ozonide could rapidly decompose by two pathways: the first one is decomposition to CH3C(O)OCH3 and a Criegee intermediate ([CH2OO]*), and the second is the formation of another Criegee intermediate ([CH3OC(CH3)OO]*) and HCHO.…”

“…Primary ozonide could rapidly decompose by two pathways: the first one is decomposition to CH3C(O)OCH3 and a Criegee intermediate ([CH2OO]*), and the second is the formation of another Criegee intermediate ([CH3OC(CH3)OO]*) and HCHO. The rates of these two pathways were rapid and the products were barely detected by matrix isolation technique [57]. Both Criegee intermediates could undergo collisional stabilization and thus are formed in either excited or stabilized forms, resulting in a total of four decomposition channels for the reaction.…”

Identification of the early intermediates formed in ozonolysis of cis-2-butene and limonene: a theoretical and matrix isolation study

“…This can be partly attributed to the shortcomings of current experimental instruments on detecting the short-lived substances. Currently, matrix isolation 17,18 has been becoming one of the most popular techniques to investigate short-lived substances [19][20][21][22][23][24][25] including CIs. 20,21,24 In the matrix isolation system, the concerned reaction systems are trapped in argon matrix at temperatures lower to $14 K, allowing for very short mixing time.…”

“…Currently, matrix isolation 17,18 has been becoming one of the most popular techniques to investigate short-lived substances [19][20][21][22][23][24][25] including CIs. 20,21,24 In the matrix isolation system, the concerned reaction systems are trapped in argon matrix at temperatures lower to $14 K, allowing for very short mixing time. Thus, the short-lived substances can be isolated and stabilized by the matrix molecules around.…”