Chinese Journal of Magnetic Resonance >
Structural Elucidation and Quantitative Analysis of Hydrogenation Products of Anthracene by NMR Spectroscopy
Received date: 2020-08-24
Online published: 2020-09-24
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.
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 . DOI: 10.11938/cjmr20202849
| 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. |
| 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. |
| 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. |
| 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. |
| 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. |
| 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. |
| 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. |
| 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. |
| 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. |
| 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. |
| 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. |
| 16 | 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 , CASTA?AR 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. |
| 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. |
| 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, |
| 19 | 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. |
| 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. |
| 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. |
| 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. |
| 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. |
| 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. |
| 25 | 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. |
| 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. |
| 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. |
| 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. |
| 31 | WANG M , HUI Y H , ZHANG X H , et al. Oxidation of tetrahydrofuran[J]. Progress in Chemistry, 2013, 25 (7): 1158- 1165. |
| 31 | 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. |
/
| 〈 |
|
〉 |