外型和内型C-2位单取代降冰片烯衍生物的核磁共振波谱研究

doi:10.11938/cjmr20202880

摘要/Abstract

摘要：

C-2位单取代降冰片烯衍生物中降冰片烯环存在各向异性，且多数为外型和内型异构体的混合物，导致其结构解析困难.针对这一问题，本文在制备了单一构型的C-2位羧基和羟甲基取代的降冰片烯衍生物的基础上，利用¹H NMR、DEPT135、¹H-¹H COSY、¹H-¹³C HMQC、¹H-¹H NOESY谱和相应的耦合裂分信息，对外型-5-降冰片烯-2-羧酸、内型-5-降冰片烯-2-羧酸、外型-5-降冰片烯-2-甲醇和内型-5-降冰片烯-2-甲醇的¹H和¹³C NMR信号进行归属，并探讨了降冰片烯衍生物的取代基种类及空间构型对¹H NMR化学位移的影响.

关键词: 5-降冰片烯-2-羧酸, 5-降冰片烯-2-甲醇, 构型异构体, 核磁共振(NMR), 结构归属

Abstract:

The ¹H NMR spectra of C-2 monosubstituted norbornene and its derivatives are usually difficult to assign due to the anisotropy effect of norbornene ring and being a mixture of exo- and endo- isomers. Based on the preparation of configurationally pure C-2 substituted norbornene derivatives, this study assigned the ¹H and ¹³C NMR signals of exo-5-norbornene-2-carboxylic acid, endo-5-norbornene-2-carboxylic acid, exo-5-norbornene-2-methanol and endo-5-norbornene-2-methanol by combined use of ¹H NMR, DEPT135, ¹H-¹H COSY, ¹H-¹³C HMQC and ¹H-¹H NOESY spectroscopy, and corresponding coupling constants. The effects of norbornene derivatives' C-2 substituents and their configurations on ¹H NMR chemical shifts of the compunds were also investigated.

Key words: 5-norbornene-2-carboxylic acid, 5-norbornene-2-methanol, configurational isomer, nuclear magnetic resonance (NMR), structural assignment

中图分类号:

O482.53

王子豪,徐赫,汪涛,杨善中,丁运生,魏海兵. 外型和内型C-2位单取代降冰片烯衍生物的核磁共振波谱研究[J]. 波谱学杂志, 2021, 38(3): 323-335.

Zi-hao WANG,He XU,Tao WANG,Shan-zhong YANG,Yun-sheng DING,Hai-bing WEI. NMR Spectroscopic Studies on (exo, endo) C-2 Monosubstituted Norbornene Derivatives[J]. Chinese Journal of Magnetic Resonance, 2021, 38(3): 323-335.

图/表 15

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参考文献 15

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Position	δ_C	δ_H (J/Hz)	¹H-¹H COSY	¹H-¹³C HMQC
1	46.7	3.11 (1H, m)	H-6, 7a, 7b	+
2	43.1	2.27 (1H, m)	H-3a, 3b	+
3a b	30.3	1.96 (1H, dt, J₁=11.4 Hz, J₂=3.0 Hz) 1.40 (1H, m)	H-2, 3b, 4 H-2, 3a, 4	+
4	41.7	2.94 (1H, m)	H-3a, 3b, 5, 7a, 7b	+
5	138.1	6.15 (1H, dd, J₁=5.4 Hz, J₂=3.0 Hz)	H-4, 6	+
6	135.7	6.12 (1H, dd, J₁=5.4 Hz, J₂=3.0 Hz)	H-1, 5	+
7a b	46.4	1.39 (1H, d, J=8.4 Hz) 1.54 (1H, d, J=8.4 Hz)	H-1, 4, 7b H-1, 4, 7a	+
8	182.7	11.61 (1H, br)	/	/

Position	δ_C	δ_H (J/Hz)	¹H -¹H COSY	¹H-¹³C HMQC
1	45.7	3.23 (1H, m)	H-2, 6, 7a, 7b	+
2	43.2	3.00 (1H, dt, J₁=9.6 Hz, J₂=J₃=4.2 Hz)	H-1, 3a, 3b	+
3a b	29.1	1.92 (1H, ddd, J₁=12.0 Hz, J₂=9.0 Hz, J₃=3.6 Hz) 1.40 (1H, ddd, J₁=12.0 Hz, J₂=4.2 Hz, J₃=2.4 Hz)	H-2, 3b, 4 H-2, 3a, 4	+
4	42.5	2.92 (1H, m)	H-3a, 3b, 5, 7a, 7b	+
5	137.9	6.21 (1H, dd, J₁=6.0 Hz, J₂=3.0 Hz)	H-4, 6	+
6	132.5	6.00 (1H, dd, J₁=6.0 Hz, J₂=3.0 Hz)	H-1, 5	+
7a b	49.7	1.45 (1H, ddd, J₁=8.4 Hz, J₂=4.2 Hz, J₃=2.4 Hz) 1.29 (1H, d, J=8.4 Hz)	H-1, 4, 7b H-1, 4, 7a	+
8	181.1	11.29 (1H, br)	/	/

Position	δ_C	δ_H (J/Hz)	¹H -¹H COSY	¹H-¹³C HMQC
1	43.3	2.75 (1H, m)	H-6, 7a, 7b	+
2	41.9	1.62 (1H, m)	H-3a, 3b, 8a, 8b	+
3a b	29.5	1.11 (1H, dt, J₁=12.0 Hz, J₂=J₃=4.2 Hz) 1.25 (1H, ddd, J₁=12.0 Hz, J₂=8.4 Hz, J₃=2.4 Hz)	H-2, 3b, 4 H-2, 3a, 4	+
4	41.5	2.82 (1H, m)	H-3a, 3b, 5, 7a, 7b	+
5	136.8	6.07 (1H, dd, J₁=6.0 Hz, J₂=3.0 Hz)	H-4, 6	+
6	136.4	6.11 (1H, dd, J₁=6.0 Hz, J₂=3.0 Hz)	H-1, 5	+
7a b	44.9	1.29 (1H, d, J₁=9.0 Hz) 1.34 (1H, d-quint, J₁=9.0 Hz, J₂=1.8 Hz)	H-1, 4, 7b H-1, 4, 7a	+
8a b 8β	67.5	3.53 (1H, dd, J₁=10.8 Hz, J₂=8.4 Hz) 3.70 (1H, dd, J₁=10.8 Hz, J₂=6.6 Hz) 1.49 (1H, s)	H-2, 8b H-2, 8a /	+

Position	δ_C	δ_H (J/Hz)	¹H -¹H COSY	¹H-¹³C HMQC
1	43.6	2.93 (1H, m)	H-2, 6, 7a, 7b	+
2	41.7	2.29 (1H, m)	H-1, 3a, 3b, 8a, 8b	+
3a b	28.8	1.82 (1H, ddd, J₁=12.0 Hz, J₂=9.0 Hz, J₃=3.6 Hz) 0.52 (1H, ddd, J₁=12.0 Hz, J₂=4.2 Hz, J₃=2.4 Hz)	H-2, 3b, 4 H-2, 3a, 4	+
4	42.2	2.81 (1H, m)	H-3a, 3b, 5, 7a, 7b	+
5	137.4	6.14 (1H, dd, J₁=6.0 Hz, J₂=3.0 Hz)	H-4, 6	+
6	132.1	5.95 (1H, dd, J₁=6.0 Hz, J₂=3.0 Hz)	H-1, 5	+
7a b	49.5	1.45 (1H, dm, J₁=8.4 Hz) 1.27 (1H, d, J₁=8.4 Hz)	H-1, 4, 7b H-1, 4, 7a	+
8a b 8β	66.5	3.26 (1H, dd, J₁=10.2 Hz, J₂=8.4 Hz) 3.40 (1H, dd, J₁=10.2 Hz, J₂=6.6 Hz) 1.42 (1H, s)	H-2, 8b H-2, 8a /	+

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