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$^{13}C-^{1}H$ Coupling Constant as a Criterion for the Presence of $pi$ Bridging in Substituted 9-Benzonorbornenyl Cation
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  • $^{13}C-^{1}H$ Coupling Constant as a Criterion for the Presence of $pi$ Bridging in Substituted 9-Benzonorbornenyl Cation
  • $^{13}C-^{1}H$ Coupling Constant as a Criterion for the Presence of $pi$ Bridging in Substituted 9-Benzonorbornenyl Cation
저자명
Ryu. Gweon-Young,Shin. Jung-Hyu
간행물명
Bulletin of the Korean Chemical Society
권/호정보
1993년|14권 5호|pp.546-548 (3 pages)
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대한화학회
파일정보
정기간행물|ENG|
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이 논문은 한국과학기술정보연구원과 논문 연계를 통해 무료로 제공되는 원문입니다.
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기타언어초록

The discrete structure of substituted 9-benzonorbornenyl cation 3a and 3c was studied using the empirical ${Delta}$J equation which was developed by Kelly and coworker$^5$. The ${Delta}$J values of substituted 9-benzonorbornenyl cations were obtained from p-methyl-6,7-dimethyl benzonorbornen-9-yl (3a) and 9-methyl-6,7-dimethyl benzonorbonen-9-yl (3c) cations under stable ion conditions, and were compared with those of the corresponding ketone analog; these cations were generated by dissolving the corresponding carbinols in superacid at -120$^{circ}$C and the nmr spectra taken at -60$^{circ}$C~-90$^{circ}$C. The ${Delta}$J values are 8.7 Hz for the bridgehead carbons in cation 3c and 3.1 Hz for cation 3b. The ${Delta}$J values at C5,8 in fused benzene ring are 14.3 Hz for cation 3c and 8.7 Hz for cation 3a. The excellent correlation of the ${Delta}$J values with 1$^9F$ chemical shifts of p-fluorophenyl-6,7-dimethylbenzonorbornenyl cation (3d) indicate that ${Delta}$J value is a reliable probe to charge density at adjacent cationic carbon. These NMR parameters strongly support that the symmetrically ${pi}$-bridged nonclassical structure (type 2) of substituted 9-benzonorbornenyl cations in stable ion conditions.