Indene, photodimerization

The photodimerizations of other indene derivatives are shown below 124 ... 

Indene does not photodimerize unless sensitized,259 whereas acenaphthylene, 16, does so when irradiated directly.280-261 Although it is believed that this reaction involves triplets, the mechanism(s) must be somewhat unusual since the stereochemistry is controlled by the reaction solvent. 

Photodimerization of the stilbene chromophore in small or medium ring systems is highly dependent upon the ring size. Indeno[2,l-a]indene (5) yields a 1 2 mixture of head-to-head head-to-tail dimers 28 and 29 (eq. 12) upon irradiation in... 

The photocyclodimerization of JV-vinylcarbazole, which was reported by Ledwith and Shirota, can be accounted for by this mechanism [71-73]. A chain process is involved in this photoreaction, and the quantum yield exceeds unity (the maximum quantum yield is 66). The hole transfer from the cyclobutane radical cation to a neutral JV-vinylcarbazole is a key reaction for the chain process. Similar photodimerizations of electron-rich alkenes such as aryl vinyl ethers [74-76], indenes [29, 77, 78], styrenes [79-80] and enamines [71] have been reported by several groups. The DCA-sensitized photodimerization of phenyl vinyl ether gives cis- and trans-1,2-diphenoxycyclobutanes. This photoreaction also involves a chain process although the chain length is short [75]. 

In its deprotonated form, cinnamic acid already presents some prerequisites of surfactants and is easily incorporated in reversed micelles, as demonstrated bySawaki and co-workers " " and others.Then-results support the view that increased local concentration and alignment can be achieved at micellar interfaces. Substantially higher conversion of cinnamate to its photodimers is observed upon irradiation of reversed micelles formed by laurylammonium or hexadecyltrimethylammonium cinnamate in carbon tetrachloride. The photoproducts are mainly the P- and 5-truxinates, consistent with the requirements imposed by the assembly for the formation of contact ion pairs. Unfortunately, these are also the main products observed by Reiser upon irradiation of ethyl cinnamate (albeit in different proportions). Interestingly, however, the observed dimer distribution varies as a function of added water that is proposed to He near the ion pair interface. Similar results were also obtained for indene-2-carboxylate and using sodium dodecyl sulfate microemulsions in water. " The photodimerization of coumarin in micelles has been investigated by Ramamurthy and co-workers. ... 

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See also in sourсe #XX -- [ ]

See also in sourсe #XX -- [ ]

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