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A diradical mechanism described here includes an extremely short-lived diradical or diradicaloid for which O-O and C-C bonds cleave in a concerted, but not simultaneous, manner. (1b, 1g)
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note
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The chemiluminescent (CL) decomposition of hydroxyphenyl-substituted dioxetanes has been proposed to proceed by the CIEEL (10) (chemically initiated electron exchange luminescence) mechanism, where an initially formed radical ion pair annihilates by back-electron transfer (BET) to give an excited aromatic carbonyl compound. However, the question of whether such a CL reaction includes BET as a fundamental process is still being argued and remains unclear. Therefore, we have recently been using the term CTID, which includes CIEEL and other CT-induced mechanisms.
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Although dihydrofurans 2a - c with allylic hydrogen(s) could undergo "ene" reaction as well as 1,2-addition of singlet oxygen, the formation of allylic hydroperoxides was not observed. (15) Dihydrofuran 2e underwent selectively 1,2-addition, though dioxetane 1e was obtained as a mixture including 20-40% of decomposition product 9e.
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77953015070
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TBAF-triggered decomposition of a hydroxyphenyl-substituted dioxetane is consecutive, comprising initial deprotonation giving an oxidophenyl-substituted dioxetane and its subsequent CTID so that the rate of the decomposition of dioxetane depends on both TBAF concentration and the substrate. However, the rate of decomposition followed pseudo-first-order kinetics independent of the TBAF concentration when an excess of fluoride concentration (TBAF/dioxetane > ca. 200) was used. Such a kinetic analysis has been well documented for siloxyphenyl-subsituted dioxetane by Adam et.al. (19)
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CL was estimated based on the value 0.29 for the chemiluminescent decomposition of 3-adamantylidene-4-methoxy-4-(3-oxidophenyl)- 1,2-dioxetane in a TBAF/DMSO system. (19)
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a = 2.1 for 2-(benzoxazol-2-yl)phenol and 4.3 for 2-(benzimidazol-2-yl)phenol.
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Solvation with acetonitrile molecules clustered around the oxido group of 1 should also participate in the change of entropy term for the CTID: solvation of the oxido group would be weaker as the size of R increases and the increase in mobility of solvent molecules would not be as large in going from 1a to 1d.
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