蒽加氢产物的结构指认和定量核磁共振分析

doi:10.11938/cjmr20202849

摘要/Abstract

摘要：

本文利用多种液体核磁共振（NMR）技术，综合分析了在三个不同反应条件下蒽催化加氢反应获得的产物混合物.利用二维扩散排序谱（DOSY）和一维选择性激发谱（selTOCSY）确定了产物中含有的二氢蒽、四氢蒽、对称八氢蒽和非对称八氢蒽；利用¹H NMR、¹³C NMR、DEPT135、¹H-¹H COSY、¹H-¹³C HSQC实验对二氢蒽、四氢蒽和对称八氢蒽的¹H和¹³C NMR信号进行了详细归属；利用定量核磁共振氢谱（QNMR）计算得到了蒽的转化率和产物的选择性.本研究可用于指导优化催化反应条件，提高产物对称八氢蒽的选择性，同时为稠环类芳烃催化加氢产物的分析提供系统的NMR技术方案.

关键词: 液体核磁共振, 结构指认, 二维扩散排序谱(DOSY), 一维选择性激发谱(selTOCSY), 定量核磁共振氢谱(QNMR), 蒽催化加氢

Abstract:

Three product mixtures of anthracene catalytic hydrogenation under different catalytic conditions were analyzed by nuclear magnetic resonance (NMR) spectroscopy. Dihydroanthracene, tetrahydroanthracene, symmetric octahydroanthracene, and asymmetric octahydroanthracene were successfully detected with diffusion-ordered spectroscopy (DOSY) and one-dimension selective gradient total correlation spectroscopy (selTOCSY) techniques. The ¹H and ¹³C NMR signals of dihydroanthracene, tetrahydroanthracene and symmetric octahydroanthracene were assigned by ¹H NMR, ¹³C NMR, DEPT135, ¹H-¹H COSY, ¹H-¹³C HSQC. The conversion of anthracene and selectivity of the products were calculated by quantitative ¹H NMR (QNMR). The results demonstrated that NMR is a versatile and powerful tool to guide and optimize catalytic reaction conditions for increasing the selectivity of symmetrical octahydroanthracene. The present research provides a systematic NMR analysis scheme for polycyclic aromatic hydrocarbons catalytic hydrogenation.

Key words: liquid-state nuclear magnetic resonance, structural assignment, DOSY, selTOCSY, QNMR, anthracene catalytic hydrogenation

中图分类号:

O482.53

窦梦雨,赵奇,侯相林,刘雷,唐明兴,王英雄. 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, 2021, 38(2): 239-248.

Meng-yu DOU,Qi ZHAO,Xiang-lin HOU,Lei LIU,Ming-xing TANG,Ying-xiong WANG. Structural Elucidation and Quantitative Analysis of Hydrogenation Products of Anthracene by NMR Spectroscopy[J]. Chinese Journal of Magnetic Resonance, 2021, 38(2): 239-248.

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化合物	分子结构	原子编号	δ_C	δ_H (J/Hz)	HSQC	¹H-¹H COSY
二氢蒽		1/4/5/8	127.4	7.29 (4H, dd, J=5.5/3.4)	+	H-2/3/6/7
		2/3/6/7	126.1	7.19 (4H, dd, J=5.6/3.3)	+	H-1/4/5/8
		9/10	36.1	3.93 (4H, s)	+	/
		11/12/13/14	136.8	/	/	/
四氢蒽		1/4	124.9	7.34 (2H, dd, J=6.3/3.2)	+	H-2/3
		2/3	127.0	7.70 (2H, dd, J=6.2/3.3)	+	H-1/4
		6/7	23.4	1.86 (4H, m)	+	H-5/8
		5/8	29.9	2.97 (4H, m)	+	H-6/7
		9/10	126.6	7.53 (2H, s)	+	/
		11/12	136.2	/	/	/
		13/14	136.1	/	/	/
对称八氢蒽		1/4/5/8	29.0	2.70 (8H, m)	+	H-2/3/6/7
		2/3/6/7	23.4	1.77 (8H, m)	+	H-1/4/5/8
		9/10	129.7	6.78 (2H, s)	/	/
		11/12/13/14	129.5	/	/	/
蒽*		1/4/5/8	128.2	8.00 (4H, dd, J=6.4/3.3)	+	H-2/3/6/7
		2/3/6/7	125.4	7.45 (4H, dd, J=6.6/3.3)	+	H-1/4/5/8
		9/10	126.2	8.42 (2H, s)	+	/
		11/12/13/14	131.7	/	/	/

	化合物	DHA	THA	sym-OHA	(cis+trans) OHA	AN	吡嗪
	分子量	180.09	182.11	186.14	186.14	178.08	80.04
	积分范围	7.27~7.32	7.68~7.73	6.78~6.80	7.02~7.10	8.41~8.44	8.58~8.61
	质子数	4	2	2	4	2	4
样品1	含量/mg	1.59	1.34	0.20	0	0	0.18
	选择性/%	50.73	42.80	6.47	/	/	/
	转化率/%	/	/	/	/	100	/
	相对偏差/%	0.82	2.18	1.93	/	/	/
样品2	含量/mg	0.62	1.33	0.08	0.07	0.06	0.18
	选择性/%	29.39	63.28	3.74	3.59	/	/
	转化率/%	/	/	/	/	92.27	/
	相对偏差/%	1.37	0.20	1.69	7.41	2.62	/
样品3	含量/mg	2.98	0.22	2.99	1.84	0	0.18
	选择性/%	37.29	2.70	36.93	23.08	/	/
	转化率/%	/	/	/	/	100	/
	相对偏差/%	2.11	4.28	1.78	2.37	/	/

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