Criegee intermediate stabilization

Solvent effects on relative stability and electronic and molecular structure of carbonyl oxide (Criegee) intermediates in ozonolysis have been analysed by ab initio... 

Table 6.10 gives the ranges of observed yields of the stabilized Criegee intermediates at 1 atm pressure in air and at room temperature. Clearly, significant decomposition of the intermediates occurs under typical tropospheric conditions. 

TABLE 6.10 Yields of Stabilized Criegee Intermediates at Room Temperature and 1 atm Air ... 

While it is often assumed that only the stabilized form of the Criegee intermediate undergoes such reactions, Moortgat and co-workers (Horie et al., 1994) have suggested that in the ethene reaction, it is the excited form that reacts with water vapor to form the acid, while the reaction of the stabilized Criegee intermediate leads to a hydroxyhydroperoxide, corresponding to reaction (48b). 

The H atoms formed in reaction 15a can react with 02 (reaction 11) to form H02. The stabilized Criegee intermediate (CH200) can participate in further reactions, some of which will result in the formation of peroxy radicals. Larger alkenes react with ozone to produce organic peroxy radicals. 

The following simplified reaction scheme represents the formation of compound X via the reaction of HCHO with the thermally stabilized entity of the Criegee intermediate CH200 [123] ... 

Two recent papers have dealt with the stability of the Criegee intermediate ,... 

The energy rich Criegee intermediates ROC HOO and HC°HOO° may thermally stabilize, rearrange, react or decompose to form other stable compoimds. 

Hasson, A.S., Orzechowska, G., Paulson, S.E. Production of stabilized Criegee intermediates and peroxides in the gas phase ozonolysis of alkenes 1. Ethene, trans-2-butene, and 2,3-dimethyl-2-butene. J. Geophys. Res. 106, 34131-34142 (2001)... 

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