Structure, conformation, and stereodynamics of N-nitroso-2,4-diaryl-3-azabicyclo[3.3.1]nonanes and N-nitroso-2,4-diaryl-3-azabicyclo[3.3.1]nonan-9-ones

被引:30
作者
Polonski, T [1 ]
Pham, M [1 ]
Milewska, MJ [1 ]
Gdaniec, M [1 ]
机构
[1] ADAM MICKIEWICZ UNIV POZNAN, FAC CHEM, PL-60780 POZNAN, POLAND
关键词
D O I
10.1021/jo9600159
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The variable temperature H-1, C-13, and F-19 NMR spectra were measured for the title N-nitrosamines. The observed unusually law N-N rotation barriers (12-15 kcal/mol) result from a significant deviation of the nitrosamino system from planarity. A pyramidal character of the amino nitrogen was confirmed by the X-ray crystal structures of two compounds and by bathochromic shifts of the n-pi* absorption hands in the UV spectra. The nonplanarity of the nitrosamino moiety is due to the strong pseudoallylic A((1,3)) strain caused by the steric interaction of the NNO group with the neighboring aryl substituents fixed in the equatorial positions of the bicyclic skeleton, In addition, the barriers to the C-C rotation of aryl groups were examined at temperatures lower than required to ''freeze'' the N-N rotation and different Delta G* values were observed for the aryls oriented syn and anti to the nitroso oxygen.
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页码:3766 / 3772
页数:7
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