Photochemical transformations. 49. Solvent effects on singlet ionic and triplet photoreactions of some bridged polycyclic chlorides: Comparison with ground-state reactions

Autor:	Stanley J. Cristol, Bart J. Vanden Plas
Rok vydání:	1991
Předmět:	chemistry.chemical_compound Allylic rearrangement Acetic acid chemistry Cyclohexane Organic Chemistry Singlet state Solvolysis Physical and Theoretical Chemistry Solvent effects Piperylene Photochemistry Acetonitrile
Zdroj:	Journal of Physical Organic Chemistry. 4:541-546
ISSN:	1099-1395 0894-3230
DOI:	10.1002/poc.610040904
Popis:	Direct irradiations of 2-chloro-6,7 : 8,9-dibenzotricyclo [3.2.2.02,4] nona-6,8-diene (5-Cl) were conducted in cyclohexane, acetic acid and wet acetonitrile. The products are 1-methylfluoranthene (8) in all three solvents, the allylic chlorides 8-chloro-7-methylene-2,3 : 5,6-dibenzobicyclo [2.2.2] octa-2,5-diene (3-Cl) and 7-chloromethyl-2,3 : 5,6-dibenzobicyclo [2.2.2] octa-2,5,7-triene (2-Cl) in acetic acid and acetonitrile and solvolysis product amides in wet acetonitrile. Compound 5-Cl had previously been shown to be the product of triplet sensitization of 2-Cl and 3-Cl, so that the singlet reaction reverses that of the triplet. The formation of 8 from 5-Cl was quenched with piperylene, whereas that of the allylic chlorides was not. Quantum yields of products and singlet lifetimes in the three solvents were measured. The solvent effects are discussed. Deuterium-labeling results on the formation of 5-Cl from 2-Cl and of 8 from 5-Cl are reported.
Databáze:	OpenAIRE
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