Conine J W
J Pharm Sci. 1975 May;64(5):777-81. doi: 10.1002/jps.2600640509.
Mestranol (17alpha-ethynylestradiol 3-methyl ether), when placed on a carrier such as powdered silica gel and exposed to the atmosphere, is converted to a yellow product. The compound formed was shown to be 1alpha-ethynyltetrahydro-1beta-hydroxy4 - (2 - hydroxy - 5 - methoxy - 3 - nitrophenethyl) - 7a - methyl-5(4H)-indanone. The 3-methyl ethers of three other steroids having aromatic A rings yielded products of a similar type. Identical compounds were prepared from the respective steroids by treatment with nitrating agents in acetic acid. This reaction in acetic acid is light catalyzed. An independent synthesis of a model compound, 6-(2-hydroxy-5-methoxy-3-nitrophenyl)-3-hexanone, established the position of the constituents on the aromatic ring as well as the location of the carbonyl. The mechanism proposed for the formation of these products is an initial oxidation of the 1-substituted tetralin to form a hydroperoxide, which is ionically decomposed to form a ketophenol. The phenol is then nitrated in the ortho-position.
炔雌醇甲醚（17α-乙炔基雌二醇3-甲醚）置于硅胶粉等载体上并暴露于空气中时，会转化为黄色产物。所形成的化合物经证明是1α-乙炔基四氢-1β-羟基-4-（2-羟基-5-甲氧基-3-硝基苯乙基）-7a-甲基-5（4H）-茚满酮。另外三种具有芳香A环的甾体的3-甲醚也生成了类似类型的产物。通过在乙酸中用硝化剂处理相应的甾体，制备出了相同的化合物。乙酸中的这一反应是光催化的。对模型化合物6-（2-羟基-5-甲氧基-3-硝基苯基）-3-己酮进行的独立合成确定了芳香环上各成分的位置以及羰基的位置。为这些产物的形成所提出的机制是，首先将1-取代的四氢萘氧化形成氢过氧化物，该氢过氧化物经离子分解形成酮酚。然后酚在邻位被硝化。
