9(11)-tetraene-3,12,17-triol (6). With higher concentrations of H(2)O(2), the novel secoestra-1(10),2,4-trien-9-one derivative 7 was obtained from 2. Theoretical calculations suggested that the peculiar behavior of 2 may be due to the generation of a relatively stable radical intermediate at C(9), which would then be converted to the reactive quinone methide 8. The chemistry described in this paper appears to be
用
过氧化物酶/ H(2)O(2)系统氧化4-硝基-17β-
雌二醇(1)通过
苯氧基自由基偶联得到对称的C(2)-连接的二聚体(3)。2-硝基17β-
雌二醇(2)的相似氧化反应(其中硝基与芳环共面)产生9α-和9β-羟基-2-硝基-17β-
雌二醇(4a,b)(17beta) -2-nitroestra-1(10),2,4,9(11)-
丁烯-3,17
-二醇(5)和(12alpha,17beta)-2-nitroestra-1(10),2,4, 9(11)-四烯-3,12,17-三醇(6)。随着更高浓度的H(2)O(2),新型secoestra-1(10),2,4-trien-9-one衍
生物7从2获得。理论计算表明2的特殊行为可能是由于会在C(9)处生成相对稳定的自由基中间体,然后将其转化为反应性醌甲基化物8。