Estrogen photoaffinity labels. 1. Chemical and radiochemical synthesis of hexestrol diazoketone and azide derivatives; photochemical studies in solution.
Estrogen photoaffinity labels. 1. Chemical and radiochemical synthesis of hexestrol diazoketone and azide derivatives; photochemical studies in solution.
复制标题
雌激素光亲和标签。
作者：
J. Katzenellenbogen;H. N. Myers;H. J. Johnson;R. Kempton;K. Carlson
两种光敏雌激素衍生物，己雌酚重氮酮丙醚 (5) 和己雌酚叠氮化物 (8a)，已以放射性标记形式合成，并研究了它们在溶液中的光化学行为。根据改进的合成程序，以良好的收率制备了放射性标记的化合物；它们很稳定，比活度在 50-100 Ci/mmol 范围内，放射化学纯度超过 95%。使用更简单的模型系统苯基重氮酮丙醚来研究重氮酮丙醚基团的光化学行为。该化合物在甲醇中于 254 nm 处直接照射，产生 33% 的插入产物（甲氧基酮）和 67% 的 Wolff 重排产物（酯）。 [3H]己雌醇重氮酮丙醚(5)在甲醇中的辐射主要产生非极性光产物（推测是甲氧基酮和酯）；然而，在水介质中照射会产生大量游离己雌酚（52%）。叠氮化己雌酚 (8a) 在甲醇或水中光解，以低产率产生相应的胺，这是唯一可识别的光产物。
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 diazoketoprophyl 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.