THE DETERMINATION OF HYDROXYLATED NATURAL PRODUCTS

7-[(氯甲酰基)甲氧基]-4-甲基香豆素1 伯羟基和仲羟基的荧光标记。我们有 开发的合成程序允许克规模的生产 1是高纯度的，我们已经对这种酸性氯化物进行了彻底的表征 通过质谱学和多核多维核 磁共振光谱学。试剂1与A反应平稳 各种伯羟基和仲羟基化合物，使 相应的酯类。 尽管1的衍生物很容易从反相高效液相色谱柱上洗脱出来， 用毛细管气相色谱/质谱法分析这些化合物均不成功。 但分子量最低的材料由于挥发性有限。 虽然有报道称在考试中使用了CI和FAB MS 对于结构相似的化合物，我们发现EI(70 EV)MS提供了 最广泛的化学结构指示。所有衍生品 给出一个独特的分子离子(相对丰度100%-12%)，离子 在189，表明7-甲氧基-4-甲基香豆素 半个月。分子一氧化碳(CO)的损失是不可预测的。 最后，对于那些具有合适结构的化合物 酯的酒精部分，发生麦克拉弗蒂重排， 从而产生m/z为234的特征离子。

7-[(Chlorocarbonyl)methoxy]-4-methylcoumarin 1 has been proposed for fluorescent labeling of primary and secondary hydroxyl groups. We have developed synthetic procedures which allow the gram-scale production of 1 in high purity and we have thoroughly characterized this acid chloride by mass spectrometry and multinuclear and multi-dimensional nuclear magnetic resonance spectroscopy. Reagent 1 reacts smoothly with a variety of primary and secondary hydroxyl compounds to give the corresponding esters. Although derivatives of 1 readily elute from reversed-phase HPLC columns, analyses of these compounds by capillary GC/MS were unsuccessful for all but the lowest molecular weight materials due to limited volatility. Although there are reports of the use of CI and FAB MS in the examination of compounds of similar structure, we find that EI (70 eV) MS provides the most extensive indication of chemical structure. All derivatives give a distinctive molecular ion (relative abundance 100%-12%), and ions at 189 which are indicative of the 7- carbonylmethoxy-4-methylcoumarin moiety. Loss of molecular carbon monoxide (CO) occurs unpredictably. Finally, for those compounds possessing a suitable structure in the alcohol portion of the ester, the McLafferty Rearrangement occurs, leading to a characteristic ion at m/z 234.