The photochemistry of six pregna-1, 4-dien-3, 20-diones has been compared and found to involve both the cyclohexadienone moiety in ring A and the isolated ketone at C-20. The two reactions take place proportionally to the fraction of light absorbed by each chromophore. The cross-conjugated ketone absorbs predominantly or exclusively at both 254 and 366 nm and undergoes the 'lumi' rearrangement to bicyclo[3.1.0]hex-3-en-2-one. The quantum yield of reaction diminished somewhat with increasing the wavelenght of excitation. A much stronger lowering is caused by halogen substitution in position 9 (by a factor of 3 for F, >50 for Cl), apparently due to a shortened triplet lifetime caused by heavy atom effect. At 310 nm both chromophores absorb to a comparable degree and both may react. Reaction at C20 ketone involves either quite efficient cleavage (C17-C20) for compounds bearing an acetal or hydroxyl function at C17, or less effective (by a factor of ca. 10) hydrogen abstraction from the 18-methyl group in the other cases (finally resulting in Norrish II fragmentation or Yang cyclization). The results allow generalizing how the substitution pattern surrounding each chromophore affects the photoreactivity at that site and the competition between the two modes, allowing predicting the photochemistry of this family of anti-inflammatory drugs.

General Patterns in the Photochemistry of Pregna-1, 4-dien-3, 20-diones

RICCI, ANDREA;FASANI, ELISA;MELLA, MARIELLA;ALBINI, ANGELO
2003

Abstract

The photochemistry of six pregna-1, 4-dien-3, 20-diones has been compared and found to involve both the cyclohexadienone moiety in ring A and the isolated ketone at C-20. The two reactions take place proportionally to the fraction of light absorbed by each chromophore. The cross-conjugated ketone absorbs predominantly or exclusively at both 254 and 366 nm and undergoes the 'lumi' rearrangement to bicyclo[3.1.0]hex-3-en-2-one. The quantum yield of reaction diminished somewhat with increasing the wavelenght of excitation. A much stronger lowering is caused by halogen substitution in position 9 (by a factor of 3 for F, >50 for Cl), apparently due to a shortened triplet lifetime caused by heavy atom effect. At 310 nm both chromophores absorb to a comparable degree and both may react. Reaction at C20 ketone involves either quite efficient cleavage (C17-C20) for compounds bearing an acetal or hydroxyl function at C17, or less effective (by a factor of ca. 10) hydrogen abstraction from the 18-methyl group in the other cases (finally resulting in Norrish II fragmentation or Yang cyclization). The results allow generalizing how the substitution pattern surrounding each chromophore affects the photoreactivity at that site and the competition between the two modes, allowing predicting the photochemistry of this family of anti-inflammatory drugs.
File in questo prodotto:
Non ci sono file associati a questo prodotto.

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11571/106836
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus ND
  • ???jsp.display-item.citation.isi??? ND
social impact