Estrogen Photoaffinity Labels. 1. Chemical and Radiochemical Synthesis of Hexestrol Diazoketone and Azide Derivatives; Photochemical Studies in Solution

John A. Katzenellenbogen, Harvey N. Myers, Howard J. Johnson, Robert J. Kempton, Kathryn E. Carlson

Research output: Contribution to journalArticlepeer-review

Abstract

Two photosensitive estrogen derivatives, hexestrol diazoketopropyl ether (5) and hexestrol azide (8a), have been synthesized in radiolabeled form, and their photochemical behavior in solution has been studied. The radiolabeled compounds were prepared in good yields according to improved synthetic procedures; they are stable and were obtained with specific activities in the range of 50-100 Ci per mmol and radiochemical purities in excess of 95%. A simpler model system, phenyl diazoketopropyl ether, was used to study the photochemical behavior of the diazoketopropyl ether group. Direct irradiation of this compound at 254 nm in methanol led to 33% insertion product (methoxyketone) and 67% Wolff rearrangement product (ester). Irradiation of [3H]hexestrol diazoketopropyl ether (5) in methanol gives mainly nonpolar photoproducts (presumed to be the methoxy ketone and ester); however, irradiation in aqueous medium leads to large amounts of free hexestrol (52%). Photolysis of hexestrol azide (8a) in either methanol or water gives the corresponding amine in low yield as the only identifiable photoproduct.

Original languageEnglish (US)
Pages (from-to)1964-1970
Number of pages7
JournalBiochemistry
Volume16
Issue number9
DOIs
StatePublished - May 1 1977

ASJC Scopus subject areas

  • Biochemistry

Fingerprint

Dive into the research topics of 'Estrogen Photoaffinity Labels. 1. Chemical and Radiochemical Synthesis of Hexestrol Diazoketone and Azide Derivatives; Photochemical Studies in Solution'. Together they form a unique fingerprint.

Cite this