Optical Rotatory Dispersion Studies. LXXXV.1 Circular Dichroism and Optical Rotatory Dispersion of the Nitrite and Nitro Chromophores2
Optical Rotatory Dispersion Studies. LXXXV.1 Circular Dichroism and Optical Rotatory Dispersion of the Nitrite and Nitro Chromophores2
复制标题
旋光色散研究。
DOI：
10.1021/ja00901a036
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发表时间：
1963
影响因子：
15
通讯作者：
E. Bunnenberg
中科院分区：
文献类型：
--
作者：
C. Djerassi;H. Wolf;E. Bunnenberg
对一系列含亚硝酸根和硝基发色团的甾体化合物进行了平行旋光色散、圆二色性和紫外吸收的测量。亚硝酸根基团在350-400 µ区域表现出多个ORD Cotton效应和CD曲线，这很容易使它们自己成为相应羟基官能团的立体化学分配-其他光学活性发色团，如饱和羰基官能团，没有复杂性。用硝基发色团获得了特别有指导意义的结果，其中ORD和CD测量大大澄清了有关电子跃迁的位置，这些跃迁常常隐藏在其他发色团（如羰基官能团）的存在下，并且常常不能用紫外光谱检查检测到。在目前的研究中，ORD或CD提供了基本相同的信息，尽管偶尔一种或另一种方法似乎更适合检测重叠的吸收带。3~ 5比较了C= S_3或C= O_3 ~（4-）有机化合物旋光色散和圆二色性测量的相对优势。6发色团或联苯和联萘的固有不对称发色团。5得出的结论是，虽然大多数结构和立体化学
Parallel optical rotatory dispersion, circular dichroism, and ultraviolet absorption measurements have been conducted on a series ofsteroids containing the nitrite and nitro chromophores. The nitrite grouping exhibits multiple ORD Cotton effects and CD curves in the 350-400 µ region, which lend themselves readily to stereochemical assignments of the corresponding hydroxyl function—other optically active chromophores such as saturated carbonyl functions offering no complications. Particularly instructive results were obtained with the nitro chromophore, where ORD and CD measurements clarify greatly the location of the relevant electronic transitions, which are often hidden in thepresence of other chromophores, such as the carbonyl func-tion, and whichfrequently cannot be detected by ultraviolet spectral examination. In the present studies either ORD or CD offered essentially the same information, although occasionally one or the other method appeared to be preferable in the detection of overlapping absorption bands.In three earlier articles, 3~ 5 we have compared the relative advantages of optical rotatory dispersion and circular dichroism measurements among organic com-pounds possessing the C= S3 or C= 03’4· 6 chromophores or the inherently dissymmetric chromophore of the biphenyls and binaphthyls. 5 It was concluded that, while for the majority of structural and stereochemical