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Isolation and Identification of Two Novel Condensed Aromatic Lactones from Zhundong Subbituminous Coal Xing-shun Cong, Zhi-Min Zong, Min Li, Yin Zhou, Shiqiu Gao, and Xian-Yong Wei Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/ef501851y • Publication Date (Web): 06 Nov 2014 Downloaded from http://pubs.acs.org on November 10, 2014
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Isolation and Identification of Two Novel Condensed Aromatic Lactones from Zhundong Subbituminous Coal Xing-Shun Cong,†,‡ Zhi-Min Zong,*,† Min Li,§ Yin Zhou,† Shi-Qiu Gao, and Xian-Yong Wei† ‖
†
Key Laboratory of Coal Processing and Efficient Utilization, Ministry of Education, China
University of Mining & Technology, Xuzhou 221116, Jiangsu, China ‡
Department of Chemistry, Zaozhuang University, Zaozhuang 277160, Shandong, China
§
State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao 266555,
Shandong, China ‖
State Key Laboratory of Multi-phase Complex Systems, Institute of Process Engineering, Chinese
Academy of Sciences, Beijing 100190, China ABSTRACT: Zhundong subbituminous coal was extracted with isometric carbon disulfide (CDS) and acetone mixed solvent (IMCDSAMS) to obtain the extract (EM). EM was fractionated with petroleum ether (PE), CDS, methanol, acetone, IMCDSAMS, and tetrahydrofuran to obtain the sub-extracts 1 to 6 (ES1 to ES6), respectively. ES2 was sequentially eluted with PE, 30%, 50%, and 70% CDS/PE mixed solvents through a silica gel-packed column to obtain eluted fractions 1-4 (EF1-EF4). A series of condensed aromatic lactones (CALs) were detected in EF4. Among them, 5H-phenanthro[1,10,9-cde]chromen-5-one and 4H-benzo[5,10]anthra[1,9,8-cdef]chromen-4-one, were further isolated as nearly pure compounds by gelatin column chromatography and identified by gas chromatography/mass spectrometry, atmospheric solid analysis probe/time-of-flight mass spectrometry, Fourier transform infrared spectrometry, 1H nuclear magnetic resonance spectrometry, and 1H-1H correlation spectrometry. Main fragmental ions in the mass spectrum of each CAL are formed by successive losses of 28 (CO) and 29 (-CHO) u from the molecular ion. An effective way to isolate CALs from low-rank coals was provided in this paper. 1. INTRODUCTION Organooxygen compounds (OOCs) in low-rank coals significantly impact on the coal properties ACS Paragon Plus Environment
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and conversion, such as spontaneous combustion,1,2 dewatering (or moisture re-absorption),3,4 hydrogenolysis,5,6 and alcoholysis.7-9 Therefore, detailed understanding of OOCs in the coals is the important base for efficient utilization of the coals. Many efforts were made to determine the types and relative contents (RCs) of oxygen functionalities in coals by inseparable analyses10-13 and destructive analyses (e.g., pyrolysis).14,15 However, inseparable methods cannot provide the precise structure of OOCs in coals and destructive methods only reflect the destroyed structures of OOCs. Some OOCs were enriched from coals with separable and non-destructive methods16-19 and their structures were identified at the molecular level. For example, fatty acid amides,20 methyl alkanones,21 and long-chain normal alkanals22 were enriched as group components, and two bis(2-ethylheptyl)benzenedicarboxylates23 and two methyl alkanoates18 were isolated as nearly pure compounds in our laboratory. A series of long-chain fatty acids were enriched from coals24 and an oxygen-containing aromatic compound with 8 rings was isolated from Yubari coal.25 In this paper, we present our preliminary results about the isolation and identification of two novel condensed aromatic lactones (CALs), i.e., 5H-phenanthro[1,10,9-cde]chromen-5-one (4) and 4H-benzo[5,10]anthra[1,9,8-cdef]chromen-4-one (9), from Zhundong subbituminous coal (ZSBC) and discuss their possible formation pathways. 2. EXPERIMENTAL SECTION 2.1. Extraction and Column Chromatographic Separation. ZSBC was collected from Zhundong coalfield, Changji, Xinjiang, China and pulverized to pass through a 200-mesh sieve (particle size < 74 µm). The contents of carbon, hydrogen, and oxygen of ZSBC on a dry and ash-free basis (daf) are 75.23, 3.18, and 20.33 wt%, respectively. As Figures SI1-SI3 in the Supporting Information show, ca. 1 kg of vacuum-dried ZSBC was extracted 97 times with isometric carbon disulfide (CDS) and acetone mixed solvent (IMCDSAMS) at room temperature to obtain the
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extracts 1-97 (E1-E97), which were sequentially incorporated to obtain the mixed extracts 1 to 5 (EM1-EM5). Each extract was fractionally extracted with petroleum ether (PE, bp 60-90oC), CDS, methanol, acetone, IMCDSAMS, and tetrahydrofuran in a Soxhlet extractor to obtain the sub-extracts ES1-ES6, respectively. ES2 was dissolved in IMCDSAMS and then mixed with proper amount of silica gel (SG, 100-200 mesh) under ultrasonic irradiation for 10 min followed by solvent removal. The resulting mixture of ES2 and SG was transferred into a SG-packed column (5 cm internal diameter and 80 cm height) and sequentially eluted with PE, 30%, 50%, and 70% (volume ratio) CDS/PE mixed solvents to obtain the eluted fractions 1-4 (EF1-EF4), respectively. As mentioned above, EF4 was eluted with trichloromethane/PE/ethyl acetate mixed solvent with the volume ratio of 4:2:1 in a SG-packed column (2 cm internal diameter and 60 cm height) to obtain the eluted sub-fractions 1-42 (ESF1-ESF42). ESF25 and ESF28 were eluted with isometric trichloromethane/methanol mixed solvent in two Sephadex LH-20 gelatin-packed columns (1 cm internal diameter and 25 cm height) to obtain ESF25a and ESF28a, respectively. Two tan powders, i.e., compounds 4 and 9, were obtained from ESF25a and ESF28a by solvent removal, respectively. 2.2. Characterization Methods. Gas chromatography/mass spectrometry (GC/MS) analysis was performed on a Hewlett-Packard 6890/5973 gas chromatograph/mass spectrometer equipped with a HP-5MS capillary column (60.0 m length, 250 µm internal diameter, and 0.25 µm film thickness) and quadrupole mass analyzer (33~550 u) in electron impact mode at 70 eV. The injection and ion source temperatures were set at 250 and 230 oC, respectively. The column was heated from 60 to 300 oC at a rate of 30 oC/min and then held at 300 oC for 50 min. Atmospheric solid analysis probe/time-of-flight mass spectrometry (ASAP/TOF-MS) analysis was conducted with an IonSense ASAP/Agilent 6210 TOF mass spectrometer equipped with an atmosphere pressure chemical ionization source. The hot nitrogen stream and drying gas temperatures were set
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to 250 and 350 oC, respectively. The mass range was set from 55 to 1000 u. Fourier transform infrared (FTIR) spectra were recorded on a Nicolet Magna IR-560 spectrometer using KBr pellets with a resolution of 4 cm-1 in the measuring range of 4000–400 cm-1. Proton nuclear magnetic resonance (1H NMR) and 1H-1H correlation spectroscopy (COSY) spectra were recorded on a Bruker AV-500 spectrometer (500 MHz) in CDCl3 at 25 oC. 3. RESULTS AND DISCUSSION 3.1. Identification of CALs. As Figures 1, 2, and SI4 in the Supporting Information show, in total, ten organic compounds, including seven CALs (peaks 1-4 and 6-9) with 4-6 rings, dinaphtho[1,2-b:1',2'-d]furan (peak 5), 3-methylstigmastane (peak 7), and a condensed aromatic ketone (peak 10), were enriched into EF4. We tried to isolate all of the CALs as pure compounds from EF4, but only 3.2 mg (3.4 µg/g coal, daf) of compound 4 and 3.1 mg (3.3 µg/g coal, daf) of compound 9 were obtained by SG column chromatography (CC) and subsequent gelatin CC. The RCs of compounds 4 and 9 are ca. 92% and 95% in ESF25a and ESF28a, respectively. The mass spectrum of compound 9 is almost the same as that of compound 6 and similar to that of compound 8, implying that compounds 6 and 8 should be isomers of compound 9. The base peaks of compounds 4 and 9 are the molecular ions (MIs). The peaks at m/z 213 and 242 of compound 4 and those at m/z 237 and 266 of compound 9 show the same losses of 28 (CO) and 29 (-CHO) u from the MI. Hence, compounds 4 and 9 should have a similar structure. As Figure 2 shows, the monoisotopic masses of compounds 4 and 9, determined by ASAP/TOF-MS, are 270.06823 and 294.06816, respectively. The molecular formulae of compounds 4 (C19H10O2) and 9 (C21H10O2) could be calculated based on the monoisotopic mass and relative abundance of the MI and isotopic peaks with MassHunter Workstation. These facts indicate that compounds 4 and 9 should be CALs with 5 and 6 aromatic rings, respectively.
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FTIR data listed in Table 1 provide further evidence that both compounds 4 and 9 have an ester group. Compound 9 has absorbances at nearly the same bands of C=O and Ccarbonyl-O as those of compound 4, but has a lower wavenumber (shift ca. 15 cm-1) of O-Caryl vibration compared to compound 4. We infer that the shift could be caused by the increase of the ring A (cf. Figure 2) in compound 9. In addition, the stretching and bending vibrations of Caryl-H bond and stretching vibrations of C C bond are also observed in FTIR spectra. The results from 1H NMR analysis (cf. Figures SI8 to SI11 in the Supporting Information and Table 2) indicate that there are 10 protons in compounds 4 and 9. According to the above multiple analyses, compounds 4 and 9 are 5H-phenanthro[1,10,9-cde]chromen-5-one and 4H-benzo[5,10]anthra[1,9,8-cdef]chromen-4-one, respectively. 1H-1H COSY spectra shown in Figures SI12 and SI13 in the Supporting Information further confirm that the structural identification of compounds 4 and 9 is reasonable. Oxidation of chrysene with hydrogen peroxide-acetic acid and ceric ammonium sulfate could produce 5H-naphtho[1,2-c]chromen-5-one26 and 6H-dibenzo[c,h]chromen-6-one (1),27 respectively. As an isomer of compound 4, 5H-chryseno[4,5-bcd]pyran-5-one was synthesized and its mutagenicity was tested.28 Then it was detected in contaminated soil29 and sediment.30 Perylo[1,12-b,c,d]pyranone (8) was also detected in the sediment.30 Togo et al.31 provided a method to prepare γ- and δ-lactones from the corresponding carboxylic acids and synthesized 6H-benzo[c]chromen-6-one in a good yield. However, to our knowledge, no report was issued on the isolation and identification of compounds 4 and 9 from any coals and sediments, and even on their synthesis. 3.2. Possible Formation Pathways of CALs. CALs were rarely reported previously and their origin in coals is unknown. However, they should not be original compounds in coal-forming plants. There are at least four possible formation pathways of CALs. First, they are possibly produced from
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the oxidation of corresponding condensed arenes (CAs), i.e., compounds 4 and 9 could be produced from benzo[e]pyrene and benzo[ghi]perylene, respectively. There should be many other undiscovered isomers of compounds 4 and 9 in ZSBC if they are produced from the oxidation of CAs. Alternative possible precursors of CALs are a series of aromatic ethers, e.g., 3H-perylo[1,12-b,c,d]pyran shown in Figure SI15 in the Supporting Information was detected in ZSBC and is seemingly more labile to be oxidized than CAs. On the other hand, they are possibly formed from the corresponding carboxylic acids.31 In addition, lactonization of some bifunctional aromatics, which contain both carboxylic and phenolic hydroxy groups, is also a possible geochemical pathway for CAL formation. Hence, CALs could be a class of important compounds for the research on organic geochemistry and molecular coal chemistry, and their formation processes need further investigation. 3.3. Extraction Mechanism of CALs from Coals. IMCDSAMS is an effective synergic solvent like CDS/N-methy-2-pyrrolidinone mixed solvent32-34 and can extract more soluble organic matter from coals effectively than other commonly-used solvents. Non-polar organic compounds (e.g., n-alkanes and arenes with 1-4 rings) with low molecular mass in EM could be preferentially extracted out with PE. Hence, CALs tended to be enriched into ES2 by subsequent extraction with CDS due to the strong π−π interaction between CDS and CAL molecules.20,22 4. CONCLUSION Seven CALs with 4-6 rings were detected in EF4. Among them, compounds 4 and 9 were isolated as nearly pure compounds and identified by GC/MS, ASAP/TOF-MS, FTIR, 1H NMR, and 1H-1H COSY. Fractional extraction and subsequent column chromatographic separation proved to be an effective approach for isolating CALs from ZSBC. CDS is an effective solvent to enrich CALs due to the strong π−π interaction between CDS and CAL molecules. Main fragmentation rule of CALs
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in mass spectrometer is successive losses of 28 (CO) and 29 (-CHO) u from the MI (base peak). Aromatic lactone could be an important form of oxygen functionality in coals and CALs should be a class of potential value-add chemicals. ASSOCIATED CONTENT Supporting Information Nomenclature, proximate and ultimate analyses (Table SI1), fractional extraction (Figures SI1 and SI3), column chromatographic separation (Figure SI2), mass spectra and possible compounds identified according to GC/MS analysis (Table SI2, Figures SI4-SI6, SI14, and SI15), FTIR spectra (Figure SI7), and NMR spectra (Figures SI8-SI13). This material is available free of charge via the Internet at http://pubs.acs.org. ACKNOWLEDGMENTS This work was subsidized by Natural Basic Research Program of China (Grant 2011CB201302), the Fund from Natural Science Foundation of China for Innovative Research Group (Grant 51221462), National Natural Science Foundation of China (Grant 51074153), the Key Project of Coal Joint Fund form Natural Science Foundation of China and Shenhua Group Co., Ltd. (Grant 51134021), Strategic Chinese-Japanese Joint Research Program (Grant 2013DFG60060), the Fundamental Research Funds for the Doctoral Program of Higher Education (Grant 20120095110006) and from Zaozhuang University, and a Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions. AUTHOR INFORMATION Corresponding Author *Telephone: +86 516 83995916. E-mail:
[email protected]. Notes
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The authors declare no competing financial interest. REFERENCES (1) Lopez, D.; Sanada, Y.; Mondragon, F. Fuel 1998, 77 (14), 1623–1628. (2) Ogunsola, O. I.; Mikula, R. J. Fuel 1991, 70 (2), 258–261. (3) Allardice, D. J.; Chaffee, A. L.; Jackson, W. R.; Marshall, M. Water in Brown Coal and Its Removal. In Advances in the Science of Victorian Brown Coal; Li, C. Z., Ed.; Elsevier: Amsterdam, 2004; pp 85–133. (4) Ogunsola, O. I. Fuel Process. Technol. 1993, 34 (1), 73–81. (5) Szladow, A. J.; Given, P. H. Am. Chem. Soc., Div. Fuel Chem., Prepr. 1978, 23 (4), 161–168. (6) Mae, K.; Song, C.; Shimada, M.; Miura, K. Energy Fuels 1998, 12 (5), 975–980. (7) Lu, H. Y.; Wei, X. Y.; Yu, R.; Peng, Y. L.; Qi, X. Z.; Qie, L. M.; Wei, Q.; Lv, J.; Zong, Z. M.; Zhao, W.; Zhao, Y. P.; Ni, Z. H.; Wu, L. Energy Fuels 2011, 25 (6), 2741–2745. (8) Makabe, M.; Ouchi, K. Fuel Process. Technol. 1979, 2 (2), 131–141. (9) Ross, D. S.; Blessing, J. E. Am. Chem. Soc., Div. Fuel Chem., Prepr. 1977, 22 (1), 208–213. (10) Murata, S.; Hosokawa, M.; Kidena, K.; Nomura, M. Fuel Process. Technol. 2000, 67 (3), 231–243. (11) Petersen, H. I.; Rosenberg, P.; Nytoft, H. P. Int. J. Coal Geol. 2008, 74 (2), 93–113. (12) Ruberto, R. G.; Cronauer, D. C. Oxygen and Oxygen Functionalities in Coal and Coal Liquids. In Organic Chemistry of Coal; American Chemical Society (ACS): Washington, D.C., 1978; ACS Symposium Series, Vol. 71, Chapter 3, pp 50–70. (13) Yoshida, T.; Tokuhashi, K.; Narita, H.; Hasegawa, Y.; Maekawa, Y. Fuel 1984, 63 (2), 282–284. (14) Charland, J. P.; Macphee, J. A.; Giroux, L.; Price, J. T.; Khan, M. A. Fuel Process. Technol. 2003, 81 (3), 211–221. (15) Macphee, J. A.; Charland, J. P.; Giroux, L. Fuel Process. Technol. 2006, 87 (4), 335–341. (16) Cong, X. S.; Zong, Z. M.; Zhou, Y.; Li, M.; Wang, W. L.; Li, F. G.; Zhou, J.; Fan, X.; Zhao, Y. P.; Wei, X. Y. Energy Fuels 2014, 28 (10), 6694–6697. (17) Cong, X. S.; Zong, Z. M.; Wei, Z. H.; Li, Y.; Fan, X.; Zhou, Y.; Li, M.; Zhao, Y. P.; Wei, X. Y. Energy Fuels 2014, DOI: 10.1021/ef501105n. (18) Liu, Z. W.; Wei, X. Y.; Zong, Z. M.; Li, J. N.; Xue, J. Q.; Chen, X. F.; Chen, F. J. Energy
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Fuels 2010, 24 (4), 2784–2786. (19) Sun, L. B.; Wei, X. Y.; Liu, X. Q.; Zong, Z. M.; Li, W. Energy Fuels 2009, 23 (10), 5284–5286. (20) Ding, M. J.; Zong, Z. M.; Zong, Y.; Ou-Yang, X. D.; Huang, Y. G.; Zhou, L.; Wang, F.; Cao, J. P.; Wei, X. Y. Energy Fuels 2008, 22 (4), 2419–2421. (21) Zhou, J.; Zong, Z. M.; Chen, B.; Yang, Z. S.; Li, P.; Lu, Y.; Yue, X. M.; Cong, X. S.; Wei, Y. B.; Wang, Y. G.; Fan, X.; Zhao, Y. P.; Wei, X. Y. Energy Sources, Part A 2013, 35 (23), 2218–2224. (22) Cong, X. S.; Zong, Z. M.; Zhou, Y.; Li, M.; Zhao, Y. P.; Fan, X.; Wei, X. Y. J. Fuel Chem. Technol. 2014, 42 (3), 257–261. (23) Liu, Z. W.; Zong, Z. M.; Li, J. N.; Chen, C. F.; Jiang, H.; Peng, Y. L.; Xue, J. Q.; Yang, X. L.; Zheng, Y. X.; Zhou, X.; Xie, R. L.; Wei, X. Y. Energy Fuels 2008, 23 (1), 588–590. (24) Řezanka, T. J. Chromatogr. A 1992, 627 (1–2), 241–245. (25) Ouchi, K.; Imuta, K. Fuel 1973, 52 (3), 171–173. (26) Copeland, P. G.; Dean, R. E.; Mcneil, D. J. Chem. Soc. (R) 1961, 1232–1238. (27) Balanikas, G.; Hussain, N.; Amin, S.; Hecht, S. S. J. Org. Chem. 1988, 53 (5), 1007–1010. (28) Amin, S.; Hecht, S. S.; Lavoie, E.; Hoffmann, D. J. Med. Chem. 1979, 22 (11), 1336–1340. (29) Lundstedt, S.; Haglund, P.; Öberg, L. Environ. Toxicol. Chem. 2003, 22 (7), 1413–1420. (30) Lübcke-von Varel, U.; Bataineh, M.; Lohrmann, S.; Löffler, I.; Schulze, T.; Flückiger-Isler, S.; Neca, J.; Machala, M.; Brack, W. Environ. Int. 2012, 44, 31–39. (31) Togo, H.; Muraki, T.; Yokoyama, M. Tetrahedron Lett. 1995, 36 (39), 7089–7092. (32) Iino, M.; Kumagai, J.; Ito, O. J. Fuel Soc. Jpn 1985, 64 (3), 210–212. (33) Zong, Z. M.; Peng, Y. L.; Qin, Z. H.; Liu, J. Z.; Wu, L.; Wang, X. H.; Liu, Z. G.; Zhou, S. L.; Wei, X. Y. Energy Fuels 2000, 14 (3), 734–735. (34) Iino, M.; Takanohashi, T.; Ohsuga, H.; Toda, K. Fuel 1988, 67 (12), 1639–1647.
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100
4
EF4
80 60 40
9
78
5
3
2
1
20
10 6
0 100 80
4 RC: 58%
ESF25
4 RC: 92%
ESF25a
60
Relative abundance (%)
40 20 0 100 80 60 40 20 0 100 80
9 RC: 62%
ESF28
9 RC: 95%
ESF28a
60 40 20 0 100 80 60 40 20 0 10
15
25
20
30
35
40
50
45
Retention time (min)
Figure 1. Total ion chromatograms of EF4, ESF25, ESF28, ESF25a, and ESF28a. 100
4, EI
60 40
observed
calculated
270
100
100
271
21.1
272
2.4
- CHO.
9,
EI
63 74
39
116.6 93.6 121 135
- CO
observed
calculated
294
100
100
21.1
295
23.4
23.3
2.5
296
3.1
3.0
- CHO.
187
224
i
O
=[M+H]+ - H =271.07606-1.00783 =270.06823
f
60
a b
observed:
h
O
g
O
f
d
e
120
150
180
210
240
270
300 30
248
monoisotopic mass
A
e
90
211
295.07599
i
O
g
266 187
APCI j
calculated: 270.06808
h
0 30
observed:
c
j
40 20
9,
monoisotopic mass
b a
60
79
40 271.07606
4, APCI
80
- CO
237 118.5 133 147 118.3
242 163
294
relative aboundance (%) m/z
213
20 0 100
270
relative aboundance (%) m/z
80
Relative abundance (%)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
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=[M+H]+ - H =295.07599-1.00783 =294.06816
calculated: 294.06808
c d
90
120
150
180
210
240
270
m/z
Figure 2. Mass spectra of compounds 4 and 9 from GC/MS (upper) and ASAP/TOF-MS (lower) analyses.
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Table 1. FTIR Data of Compounds 4 and 9 wavenumber (cm-1) compound 4
assignmenta
compound 9
3054 3049 1733 1732 1597 1595 1264 1263 1227 1212 1103, 1027 1059 807, 745, 724 835, 759, 729 a ν, stretching vibration; δ, bending vibration.
Caryl-H, ν C=O, ν C C, ν Ccarbonyl-O, ν O-Caryl, ν Caryl-H, δ(In-plane) Caryl-H, δ
intensity weak strong medium medium medium medium medium
Table 2. Possible Assignment of 1H NMR Spectra of Compounds 4 and 9 carbon atom* a b c d e f g h i j * As shown in Figure 2.
δH compound 4
compound 9
8.49 7.85 7.61 8.67 7.98 8.99 7.77 8.70 8.70 7.77
8.24 7.88 8.22 8.06 8.81 9.04 7.98 8.65 8.02 8.02
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