NMR Spectroscopic Studies on (exo, endo) C-2 Monosubstituted Norbornene Derivatives

doi:10.11938/cjmr20202880

Abstract

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

CLC Number:

O482.53

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.

Figures/Tables 15

Fig.1

Fig.2

Fig.3

Fig.4

Fig.5

Fig.6

Table 1

Fig.7

Fig.8

Table 2

Fig.9

Fig.10

Fig.11

Table 3

Table 4

References 15

1	SCHLEYER P V R , WILLIAMS J E , BLANCHARD K R . Evaluation of strain in hydrocarbons. The strain in adamantane and its origin[J]. J Am Chem Soc, 1970, 92 (8): 2377- 2386. doi: 10.1021/ja00711a030
2	KOVAČIČ S , SLUGOVC C . Ring-opening metathesis polymerisation derived poly(dicyclopentadiene) based materials[J]. Mater Chem Front, 2020, 4 (8): 2235- 2255. doi: 10.1039/D0QM00296H
3	FERNANDEZ I , BICKELHAUPT F M . Origin of the "Endo Rule" in Diels-Alder reactions[J]. J Comput Chem, 2014, 35 (5): 371- 376. doi: 10.1002/jcc.23500
4	RULE J D , MOORE J S . ROMP reactivity of endo- and exo-dicyclopentadiene[J]. Macromolecules, 2002, 35 (21): 7878- 7882. doi: 10.1021/ma0209489
5	KOICHIRO N , MASAO N . The Synthesis and absolute configuration of optically active tricyclo[4.3.0.03, 8] nonane (Twist-brendane)[J]. Bull Chem Soc Jpn, 1973, 46 (3): 888- 892. doi: 10.1246/bcsj.46.888
6	JANSSEN A J M , KLUNDER A J H , ZWANENBURG B . Enzymatic resolution of norbor(NE)nylmethanols in organic media and an application to the synthesis of (+)- and (−)-endo-norbornene lactone[J]. Tetrahedron, 1991, 47 (29): 5513- 5538. doi: 10.1016/S0040-4020(01)80984-4
7	ZHANG H K , CHAN W H , LEE A W M , et al. Synthesis of chiral sultams and their application as chiral auxiliaries in an asymmetric Diels-Alder reaction[J]. Tetrahedron-Asymmetr, 2005, 16 (4): 761- 771. doi: 10.1016/j.tetasy.2004.12.026
8	CAMPAGNA M , TRZOSS M , BIENZ S . More than a protective group: Synthesis and applications of a new chiral silane[J]. Org Lett, 2007, 9 (19): 3793- 3796. doi: 10.1021/ol071382h
9	KANAO M , OTAKE A , TSUCHIYA K , et al. Stereo-selective synthesis of exo-norbornene derivatives for resist materials[J]. J Photopolym Sci Tech, 2009, 22 (3): 365- 370. doi: 10.2494/photopolymer.22.365
10	KANAO M , OTAKE A , TSUCHIYA K , et al. Stereo-selective synthesis of 5-Norbornene-2-exo-carboxylic scid-rapid isomerization and kinetically selectivehydrolysis[J]. Int J Org Chem, 2012, 2 (1): 26- 30. doi: 10.4236/ijoc.2012.21005
11	DOU M , ZHAO Q , HOU X L , et al. Structural assignment and quantitative analysis for hydrogenation products of anthracene by NMR technology[J]. Chinese J Magn Reson, 2020, doi: 10.11938/cjmr20202849
	窦梦, 赵奇, 侯相林, 等. 蒽加氢产物的结构指认和定量核磁共振分析[J]. 波谱学杂志, 2020, 10 doi: 10.11938/cjmr20202849
12	HORST F. Basic one- and two-dimensional NMR spectroscopy(5^th ed.)[M]. New York, 2010.
13	YIN T P , WANG Z , CHEN Y , et al. An NMR analysis of 10-indol cytochalasin chaetoglobosin F[J]. Chinese J Magn Reson, 2019, 36 (1): 74- 82.
	尹田鹏, 汪泽, 陈阳, 等. 10-吲哚细胞松弛素chaetoglobosin F的NMR解析[J]. 波谱学杂志, 2019, 36 (1): 74- 82.
14	KARPLUS M . Vicinal proton coupling in nuclear magnetic resonance[J]. J Am Chem Soc, 1963, 85 (18): 2870- 2871. doi: 10.1021/ja00901a059
15	薛松. 有机结构分析[M]. 合肥: 中国科学技术大学出版社, 2005.

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 /	+

[1]	KOU Xinhui, ZHANG Yubing. Study on the Enantiomeric Recognition of Chiral Ureas Containing Amino Acid Units [J]. Chinese Journal of Magnetic Resonance, 2025, 42(3): 221-230.
[2]	DU Qunjie. Experimental Study on Accurate Determination of Shale Porosity by Nuclear Magnetic Resonance [J]. Chinese Journal of Magnetic Resonance, 2025, 42(3): 275-284.
[3]	LI Yujiang, ZHAO Wei, TAO Le, LU Bohua, ZHENG Guo, ZHANG Haiyan, GUO Xiaohe, ZHAO Tianzeng. NMR Data Analysis of Acarbose [J]. Chinese Journal of Magnetic Resonance, 2025, 42(2): 184-194.
[4]	SHEN Zhiqiang, DENG Yabo, YANG Peiju, HU Xiaoxue, HUANG Xiaojuan, XU Chuanzhi, SONG Huanling. Design and Application of an in situ NMR Device for Light-Induced Reaction Systems [J]. Chinese Journal of Magnetic Resonance, 2025, 42(1): 22-33.
[5]	XU Xiaojie, CHEN Yan’an, LI Xufei, ZHANG Yuncai, ZHANG Yong, ZHAN Dongkai, PAN Ting. Structural Elucidation of Hybutimibe [J]. Chinese Journal of Magnetic Resonance, 2024, 41(1): 43-55.
[6]	WANG Feng, LIU Tingwei, XU Yajie, YU Peng, WANG Ya, PENG Bowen, YANG Xiaodong. A Miniaturised NMR RF Probe Design with External Field-locking Channel [J]. Chinese Journal of Magnetic Resonance, 2023, 40(3): 332-340.
[7]	WANG Yuanfang,WANG Xiaohua,SHU Chang,ZHANG Xu,LIU Maili,ZENG Danyun. The Aggregation of ATAD2 Bromodomain in Solution [J]. Chinese Journal of Magnetic Resonance, 2023, 40(2): 169-178.
[8]	ZHAO Chang,GONG Zhou. Investigation of Dynamic Structure of Protein Encountering Complex with Paramagnetic NMR [J]. Chinese Journal of Magnetic Resonance, 2023, 40(2): 148-157.
[9]	ZHAN Jianhua,HU Qin,ZHU Qinjun,JIANG Bin,ZHANG Xu,LIU Maili. Track the Conformational Change of Unlabeled Yeast Cytochrome c in Cell Homogenate Using NMR [J]. Chinese Journal of Magnetic Resonance, 2023, 40(1): 22-29.
[10]	CI Jie,YANG Xue,XIN Jiaxiang,WEI Daxiu,YAO Yefeng. Preparation and Lifetime Studies of the Singlet State of Five Spins in Hexene Molecules Used to Guide the Preservation of the Parahydrogen-induced Nuclear Polarization State [J]. Chinese Journal of Magnetic Resonance, 2023, 40(1): 30-38.
[11]	Yun-shan PEI, Cai ZHANG, Xiao-li LIU, Kai CHENG, Ze-ting ZHANG, Cong-gang LI. Inhibition of α-Synuclein Aggregation by the Interaction Between Protein Disulfide Isomerase and α-Synuclein [J]. Chinese Journal of Magnetic Resonance, 2022, 39(4): 381-392.
[12]	Xiao-yang ZHANG, Shou-quan YAO, Jun-cheng XU, Yu JIANG. Magnetic Field Locking System Based on Fluxgate and Time Domain Digital Frequency Discrimination [J]. Chinese Journal of Magnetic Resonance, 2022, 39(4): 448-458.
[13]	Han HU,Wei-yu WANG,Jun XU,Feng DENG. 1, 3-Butadienen Hydrogenation on Supported Pd-Sn Bimetallic Catalysts Investigated by Parahydrogen-induced Polarization [J]. Chinese Journal of Magnetic Resonance, 2022, 39(2): 133-143.
[14]	Qian XU,Lang CHEN,Xiang-ying HU,Cong-gang LI,Yi-xiang LIU,Ling JIANG. The Effect of T69E-mimicked Phosphorylation on the Interaction Between Bcl-2 and Nur77 [J]. Chinese Journal of Magnetic Resonance, 2022, 39(1): 87-95.
[15]	Xiao-qing LIN,Shi-jia DU,Hao-lin ZHAN,Yu-qing HUANG,Zhong CHEN. Two-Dimensional Homonuclear Orthogonal-Pattern Phase-Sensitive J-Resolved NMR Spectroscopy Based on Pure Shifts [J]. Chinese Journal of Magnetic Resonance, 2021, 38(4): 448-459.