|Title||THE NOVEL SOLID-STATE AND SOLUTION PHASE PHOTOCHEMISTRY OF DIMETHYL 9-CHLOROMETHYL-9,10-DIHYDRO-9,10-ETHENOANTHRACENE-11,12-DICARBOXYLATE|
|Publication Type||Journal Article|
|Year of Publication||1991|
|Authors||Chen, JX, Pokkuluri, PR, Scheffer, JR, Trotter, J|
|Journal||Journal of Photochemistry and Photobiology a-Chemistry|
|Type of Article||Article|
Although the triplet excited state behavior of dimethyl 9-chloromethyl-9,10-dihydro-9,10-ethenoanthracene-11,12-dicarboxylate (5) is normal, di-pi-methane photorearrangement to a 4:1 mixture of regioisomers 6 and 7, its singlet excited state reactivity is unusual and involves the formation of the novel photoproducts 8 and 9. The mechanism by which these products are formed is thought to involve photorearrangement to the 1,4-biradical 10 followed by a non-concerted chlorine atom migration. Photoproducts 8 and 9 are more prevalent in solid state photolyses compared with those carried out in solution, a result that may be related to a favorable (4.28 angstrom) intermolecular C...Cl contact in crystals of 5.
|URL||<Go to ISI>://A1991FJ78100004|