Structural studies in azolylmethanes
Structural studies in azolylmethanes
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唑基甲烷的结构研究
DOI：
10.1002/ps.2780150314
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发表时间：
1984
期刊：
影响因子：
--
通讯作者：
P. Walker
中科院分区：
文献类型：
--
作者：
N. Anderson;S. Branch;R. Loeffler;B. Mann;I. W. Nowell;P. Walker
比较了几种杀菌剂偶氮甲烷的晶体结构。在苄化合物[1-aryl-4 4-dimethyl-2——(1、2、4-triazol-1-yl) pentan-3-ones,相应的pentan-3-ols,和1 - (4-chlorophenyl) 3 - (2-fluorophenyl) 2(1、2、4-triazol-1-yl) propan-1-one],和叔丁基苄组(或4-chlorophenyl组)是反式,而在类似的含苯氧基的化合物[1 - (4-chlorophenoxy) 3, 3-dimethyl-1 -(1、2、4-triazol-1-yl) butan-2-one和相应的butan-2-ol],叔丁基组织反式苯三唑和偏转含苯氧基的集团。由核磁共振光谱测定的耦合常数表明，某些化合物有一个主要的溶液构象。在两种化合物中，红外光谱观察到分子内氢键，支持了核磁共振的发现。对于一些化合物，晶体和溶液的构象似乎非常相似，而在另一些化合物中，它们却截然不同。对苯和苯氧基化合物的对映体的相对活性的已发表的数据进行了讨论，但在两个系列的对映体的相对活性的差异不能轻易合理化。结果表明，不同的对映体在活性位点的结合方式不同。
The crystal structures of a number of fungicidal azolylmethanes are compared. In the benzyl compounds [1-aryl-4,4-dimethyl-2-(1,2,4-triazol-1-yl)pentan-3-ones, the corresponding pentan-3-ols, and 1-(4-chlorophenyl)-3-(2-fluorophenyl)-2-(1,2,4-triazol-1-yl)propan-1-one], the benzyl and tert-butyl groups (or 4-chlorophenyl group) are trans, whereas in the analogous phenoxy compounds [1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one and the corresponding butan-2-ol], the tert-butyl groups are trans to the triazole and gauche to the phenoxy group. Coupling constants, determined by nuclear magnetic resonance (n.m.r.) spectroscopy, suggest that for some compounds there is one dominant solution conformation. Intramolecular hydrogen bonding, observed by infrared spectroscopy in two of the compounds, supports the findings by n.m.r. For some compounds, the crystal and solution conformations appear to be very similar, whereas in others they are quite different. Published data on the relative activity of the enantiomers of the benzyl- and phenoxy-compounds are discussed, but differences in the relative activity of enantiomers in the two series cannot be readily rationalised. It is concluded that different enantiomers may have different modes of binding at the active site.