Eclipsed ground-state conformations of the tert-butyl-X bond in N-tert-butoxy- and N-neopentyl-2,2,6,6-tetramethylpiperidine. X-ray crystal structure determinations and molecular mechanics calculations
作者:J. Edgar Anderson、Derek A. Tocher、John E. T. Corrie、Lodovico Lunazzi
DOI:10.1021/ja00062a012
日期:1993.5
X-ray crystallographic studies of derivatives of N-methoxy- and N-tert-butoxy-2,2,6,6-tetramethylpiperidine show that as expected the N-O bond is staggered with respect to the C-H bonds of the methoxy group in the former case, yet it eclipses a C-methyl bond of the tert-butyl group in the latter case. Molecular mechanics calculations confirm this and show that likewise the preferred conformation of
N-甲氧基-和 N-叔丁氧基-2,2,6,6-四甲基哌啶衍生物的 X 射线晶体学研究表明,正如预期的那样,NO 键相对于前者中甲氧基的 CH 键是交错的在后一种情况下,它使叔丁基的 C-甲基键黯然失色。分子力学计算证实了这一点,并表明同样优选的 N-新戊基-2,2,6,6-四甲基哌啶构象的 CH 2 与叔丁基键重叠,而在相应的 N-乙基化合物中,CH 2 与甲基键是交错的。报告了所有这些分子的四甲基环己基类似物和轴向构象的计算