Structural Elucidation and Quantitative Analysis of Hydrogenation Products of Anthracene by NMR Spectroscopy

doi:10.11938/cjmr20202849

Abstract

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

CLC Number:

O482.53

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.

Figures/Tables 7

Fig.1

Fig.2

Fig.3

Fig.4

Table 1

Table 2

Fig.5

References 31

1	YUAN T , MARSHALL W D . Catalytic hydrogenation of polycyclic aromatic hydrocarbons over palladium/gamma-Al₂O₃ under mild conditions[J]. J Hazard Mater, 2005, 126 (1-3): 149- 157. doi: 10.1016/j.jhazmat.2005.06.022
2	FANG D , WANG G , LIU M J , et al. Combined selective hydrogenation and catalytic cracking process for efficient conversion of heavy cycle oil to high octane number gasoline[J]. Ind Eng Chem Res, 2019, 58 (43): 19752- 19759. doi: 10.1021/acs.iecr.9b03896
3	JACINTO M J , SANTOS O H C F , LANDERS R , et al. On the catalytic hydrogenation of polycyclic aromatic hydrocarbons into less toxic compounds by a facile recoverable catalyst[J]. Appl Catal B-Environ, 2009, 90 (3, 4): 688- 692.
4	PETRUKHINA N N , VINNIKOVA M A , MAKSIMOV A L . Production of high-density jet and diesel fuels by hydrogenation of highly aromatic fractions[J]. Russ J Appl Chem, 2018, 91, 1223- 1254. doi: 10.1134/S1070427218080013
5	KOTANIGAWA T , YAMAMOTO M , YOSHIDA T . Selective nuclear hydrogenation of naphthalene, anthracene and coal-derived oil over Ru supported on mixed oxide[J]. Appl Catal A-Gen, 1997, 164 (1, 2): 323- 332.
6	PINILLA J L , GARCíA A B , PHILIPPOT K , et al. Carbon-supported Pd nanoparticles as catalysts for anthracene hydrogenation[J]. Fuel, 2014, 116, 729- 735. doi: 10.1016/j.fuel.2013.08.067
7	PAL S , MUKHERJEE M , PODDER D , et al. A highly regioselective 6-endo-aryl radical cyclisation: stereocontrolled synthesis of trans-octa hydroanthracenes[J]. J Chem Soc Chem Commun, 1991, 22, 1591- 1593.
8	JACINTO M J , WIZBIKI M , JUSTINO L C , et al. Platinum-supported mesoporous silica of facile recovery as a catalyst for hydrogenation of polyaromatic hydrocarbons under ultra-mild conditions[J]. J Sol-Gel Sci Techn, 2015, 77 (2): 298- 305. doi: 10.1007/s10971-015-3854-6
9	BAIKENOV M I , MEIRAMOV M G , KHALIKOVA Z S , et al. Catalytic hydrogenation of anthracene in ethanol[J]. Solid Fuel Chem, 2016, 50 (4): 256- 259. doi: 10.3103/S0361521916040029
10	JACINTO M J , GONZALES M G , ZANATO A F S , et al. Rh nanoparticles grafted on mesoporous silica support as a high-efficiency catalyst for Anthracene hydrogenation[J]. Sustain Chem Pharm, 2017, 6, 90- 95. doi: 10.1016/j.scp.2017.10.002
11	KALENCHUK A N , KOKLIN A E , BOGDAN V I , et al. Hydrogenation of anthracene and dehydrogenation of perhydroanthracene on Pt/C catalysts[J]. Russ J Phys Chem A, 2018, 92 (4): 663- 668. doi: 10.1134/S0036024418040106
12	大连理工大学. 一种工业蒽选择加氢-氧化耦合制均苯四甲酸二酐的方法与流程: 中国, 10375903[P], 2018-10-12
13	大连理工大学. 一种蒽选择加氢制对称八氢蒽的方法与流程: 中国, 10316649[P], 2018-09-28
14	BOTTOMLEY P A . NMR imaging techniques and applications: a review[J]. Rev Sci Instrum, 1982, 53 (9): 1319- 1337. doi: 10.1063/1.1137180
15	MCKENZIE J S , DONARSKI J A , WILSON J C , et al. Analysis of complex mixtures using high-resolution nuclear magnetic resonance spectroscopy and chemometrics[J]. Prog Nucl Mag Res Sp, 2011, 59 (4): 336- 359. doi: 10.1016/j.pnmrs.2011.04.003
16	WANG L M , QIU R C , HUANG S H . Quantitative analysis of active ingredients in compound acetylsalicylic acid tablets by DOSY[J]. Chinese J Magn Reson, 2016, 33 (3): 415- 421.
	王丽敏, 仇汝臣, 黄少华. 复方乙酰水杨酸片中有效成分的DOSY技术分析[J]. 波谱学杂志, 2016, 33 (3): 415- 421.
17	DAL POGGETTO G , CASTAñAR L , MORRIS G A , et al. A new tool for NMR analysis of complex systems: selective pure shift TOCSY[J]. RSC Adv, 2016, 6 (102): 100063- 100066. doi: 10.1039/C6RA22807K
18	MACKINNON N , WHILE P T , KORVINK J G . Novel selective TOCSY method enables NMR spectral elucidation of metabolomic mixtures[J]. J Magn Reson, 2016, 272, 147- 157. doi: 10.1016/j.jmr.2016.09.011
19	YAN K , BAI Z W , HUANG S H . NMR signal separation of ionic liquids by poly(sodium-p-styrenesulfonate)-assisted chromatographic NMR spectroscopy[J]. Chinese J Magn Reson, 2019,
	严葵, 柏正武, 黄少华. 利用聚(苯乙烯磺酸钠)辅助的DOSY技术分析离子液体[J]. 波谱学杂志, 2019,
20	LYU Z X , YUE F , YAN X Y , et al. Combination of DOSY and 1D selective gradient TOCSY: Versatile NMR tools for identify the mixtures from glycerol hydrogenolysis reaction[J]. Fuel Process Technol, 2018, 171, 117- 123. doi: 10.1016/j.fuproc.2017.11.011
21	MA H , PEDERSEN C M , ZHAO Q , et al. NMR analysis of the Fischer-Tropsch wastewater: Combination of 1D selective gradient TOCSY, 2D DOSY and qNMR[J]. Anal Chim Acta, 2019, 1066, 21- 27. doi: 10.1016/j.aca.2019.04.007
22	ZHAO Q , LIU Y , MA H , et al. Combination of pure shift NMR and chemical shift selective filters for analysis of Fischer-Tropsch waste-water[J]. Anal Chim Acta, 2020, 1110, 131- 140. doi: 10.1016/j.aca.2020.03.014
23	LYU Z X , GAO F E , WEN L Z , et al. DOSY Plus Selective TOCSY: An efficient NMR combination for analyzing hydrogenation/hydrogenolysis mixtures of biomass-derived platform compounds[J]. Energ Fuels, 2018, 32 (3): 3551- 3558. doi: 10.1021/acs.energyfuels.7b03992
24	RUNDLOF T , MATHIASSON M , BEKIROGLU S , et al. Survey and qualification of internal standards for quantification by ¹H NMR spectroscopy[J]. J Pharmaceut Biomed, 2010, 52 (5): 645- 651. doi: 10.1016/j.jpba.2010.02.007
25	ZHANG F F , SHEN W B , XU K B , et al. A proton nuclear magnetic resonance method for quantitative analysis of ticagrelor[J]. Chinese J Magn Reson, 2020, 37 (2): 216- 223.
	张芬芬, 沈文斌, 徐开兵, 等. 定量核磁共振氢谱测定新药替格瑞洛[J]. 波谱学杂志, 2020, 37 (2): 216- 223.
26	TAVERNIER D , ANTEUNIS M J O . Stereochemical aspects of proton chemical shifts. X-the slow exchange ¹H NMR spectrum of cis-transoid-cis-perhydroanthracene and of cis-decalin[J]. Organ Magn Reson, 1982, 18 (2): 109- 111. doi: 10.1002/mrc.1270180213
27	BARJAT H , MORRIS G , SMART S , et al. High-resolution diffusion-ordered 2D spectroscopy (HR-DOSY)-A new tool for the analysis of complex mixtures[J]. J Magn Reson B, 1995, 108 (2): 170- 172. doi: 10.1006/jmrb.1995.1118
28	JR C S J . Diffusion ordered nuclear magnetic resonance spectroscopy: principles and applications[J]. Prog Nucl Mag Res Sp, 1999, 34 (3, 4): 203- 256.
29	FACKE T , BERGER S . Application of pulsed field gradients in an improved selective TOCSY experiment[J]. J Magn Reson A, 1995, 113 (2): 257- 259. doi: 10.1006/jmra.1995.1090
30	LI W Y , ZHENG H , YE C P , et al. Effect of the intermolecular hydrogen bond between carbazole and N, N-dimethylformamide/isopropanolamine on the solubility of carbazole[J]. Energ Fuels, 2012, 26 (10): 6316- 6322. doi: 10.1021/ef301240t
31	WANG M , HUI Y H , ZHANG X H , et al. Oxidation of tetrahydrofuran[J]. Progress in Chemistry, 2013, 25 (7): 1158- 1165.
	王猛, 惠永海, 张雪华, 等. 四氢呋喃的氧化[J]. 化学进展, 2013, 25 (7): 1158- 1165.

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	/	/

[1]	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.
[2]	Xiao-li CHEN,Tian-qiao YONG,Cheng CHEN,Juan FU,Jia-mei MO,Qiu-cheng SU. Physical and Chemical Properties of Silicone Electrolyte Materials Evaluated by Nuclear Magnetic Resonance Technology [J]. Chinese Journal of Magnetic Resonance, 2021, 38(3): 291-300.
[3]	HUANG Shan-shan, YAO Ye-feng, LI Peng, HE Pei-zhong. Quantum Chemical Calculation and Simulation of HSQC Experiments in Liquid-State NMR [J]. Chinese Journal of Magnetic Resonance, 2021, 38(1): 32-42.
[4]	WANG Rui-di, XU Bei-bei, SONG Yan-hong, WANG Xue-lu, YAO Ye-feng. Methanol-Water Interaction in Photocatalytic Methanol Reforming ─ An Operando NMR Study [J]. Chinese Journal of Magnetic Resonance, 2021, 38(1): 43-57.
[5]	ZHOU Zhong-gao, XIE Qian, YUAN Yang-yang, LI Jing, LU Dong-liang, CHEN Zheng-wang. An NMR Study of Chiral Glucopyranosyl-Based N-Heterocyclic Carbene-Palladium(II)-Pyridine Complex [J]. Chinese Journal of Magnetic Resonance, 2020, 37(4): 505-514.
[6]	WANG Si-hong, ZHANG Jing-dong, YIN Xiu-mei, LI Dong-hao, KAN Yu-he, HU Wei. NMR Assignments of 6-(4-chlorophenoxy)-tetrazolo[5,1-a]phthalazine [J]. Chinese Journal of Magnetic Resonance, 2020, 37(3): 390-398.
[7]	YANG Yi-ning, WANG Xue-lu, YAO Ye-feng. The Effects of Reaction Environment on Photocatalytic Methanol Reforming Studied by Operando Nuclear Magnetic Resonance Spectroscopy [J]. Chinese Journal of Magnetic Resonance, 2020, 37(1): 104-113.
[8]	LIN Xiao-qing, LI Hong, ZHAN Hao-lin, DU Shi-jia, HUANG Yu-qing, CHEN Zhong. High-Resolution Pure Shift NMR Spectroscopy and Its Applications [J]. Chinese Journal of Magnetic Resonance, 2019, 36(4): 425-436.
[9]	LIU Ji-hong, JIN Kun, WANG Ping, LUO Gen. An NMR Study on Esculetin and It's Derivatives [J]. Chinese Journal of Magnetic Resonance, 2019, 36(3): 341-349.
[10]	LI Hong-wei, YUAN Zhi-liang, XIA Bin. Determination of Apparent Protein Molecular Weight in Solution by Diffusion Ordered NMR Spectroscopy [J]. Chinese Journal of Magnetic Resonance, 2018, 35(3): 280-286.
[11]	HUANG Jun-lin, YU Yi-hua. Effects of Digital Resolution on Diffusional Dimension in DOSY Experiments [J]. Chinese Journal of Magnetic Resonance, 2018, 35(3): 287-293.
[12]	MA Lin-ge, LONG Yin-hua. Determination of Aromatic Carbon Mole Ratio in Oil Samples by Quantitative ¹³C NMR Spectroscopy with DFSS Methodology [J]. Chinese Journal of Magnetic Resonance, 2017, 34(1): 8-15.
[13]	WANG Li-min, QIU Ru-chen, HUANG Shao-hua. Quantitative Analysis of Active Ingredients in Compound Acetylsalicylic Acid Tablets by DOSY [J]. Chinese Journal of Magnetic Resonance, 2016, 33(3): 415-421.
[14]	HE Bao-jiang1， XU Xiu-juan1， YANG Wei-ping1， ZHANG Wen-juan1， WU Rui3， HUANG Shao-hua2， YANG Ying2， BAI Zheng-wu3. Progresses in Matrixed Chromatographic NMR [J]. Chinese Journal of Magnetic Resonance, 2015, 32(4): 699-706.
[15]	WU Rui1，BAI Zheng-wu1，YANG Ying2，HUANG Shao-hua2. Evaluation of Separation Performance of Polydimethylsiloxane-Matrixed Chromatography by NMR [J]. Chinese Journal of Magnetic Resonance, 2015, 32(3): 511-517.