5-O-caffeoylquinic acid and cinamic acid from Gleditschia australis Hemsl (Caesalpiniaceae)

Journal of Chemistry, Vol. 45 (Special issue), P. 127 - 130, 2007<br /> <br /> <br /> 5-O-caffeoylquinic acid and cinamic acid from<br /> Gleditschia australis Hemsl., (Caesalpiniaceae)<br /> Received 15 October 2007<br /> NGUYEN THI HONG VAN, PHAN VAN KIEM, CHAU VAN MINH, NGUYEN THE DUNG<br /> Institute of Natural Products Chemistry, Vietnamese Academy of Science and Technology<br /> <br /> SUMMARY<br /> From the methanolic extract of the leaves of Gleditschia australis Hemsl., (Caesalpiniaceae)<br /> 5-O-caffeoylquinic acid (1) and cinnamic acid (2) have been isolated. Their structures were<br /> deduced from the spectral evidence and comparison with the literature.<br /> <br /> <br /> I - INTRODUCTION 2. General experimental procedures<br /> <br /> Gleditschia australis Hemsl., belongs to Melting points were determined using an<br /> Electro thermal IA-9200. The IR spectra were<br /> family Caesalpiniaceae and is wildly distributed<br /> obtained on a Hitachi 270-30 type spectrometer<br /> in Vietnam. The fruits are used to produce<br /> with KBr discs. Optical rotations were<br /> soaps, shampoo, medicinal drugs, and local<br /> determined on a Jasco DIP-1000 KUY<br /> people can sell them for income. It has been<br /> polarimeter. The electrospray ionization (ESI)<br /> used in traditional medicine for various diseases<br /> mass spectra were obtained using an AGILENT<br /> such as inflammation, kidney stone, and<br /> 1100 LC-MSD Trap spectrometer. The 1H-NMR<br /> diabetes mellitus…[1, 2]. The fruits contain<br /> (500 MHz) and 13C-NMR (125 MHz) spectra<br /> numbers of triterpenes and flavonoids [2].<br /> were recorded on a Bruker AM500 FT-NMR<br /> However, no studies on chemical constituents<br /> spectrometer and TMS was used as an internal<br /> and bioactivity of the leaves has been carried<br /> standard. Column chromatography (CC) was<br /> out.<br /> performed on silica gel (Kieselgel 60, 70 - 230<br /> As a part of our study on this plant [3, 4], mesh and 230 - 400 mesh, Merck) and YMC<br /> we report herein the isolation and the structural RP-18 resins.<br /> elucidation of 5-O-caffeoylquinic acid (1) and<br /> cinnamic acid (2) from the leaves. 3. Extraction and isolation<br /> Dried leaves of G. australis (5.0 kg) were<br /> II - EXPERIMENTAL powdered and then extracted three times with<br /> MeOH. The MeOH extract (70 g) was<br /> 1. Plant material suspended in water and partitioned in turn with<br /> The leaves of G. australis Hemsl. were n-hexane, chloroform, ethyl acetate, and n-<br /> collected in Tam Dao Mountain, Vinh Phuc BuOH to obtain n-hexane, chloroform, ethyl<br /> province, Vietnam and was identified by Dr acetate, and n-BuOH fraction. The n-BuOH<br /> Tran Huy Thai, Institute of Ecology and fraction (8.0 g) was chromatographed on silica<br /> Biological Resources, VAST. A voucher of gel column using CHCl3-MeOH-H2O (30:10:1)<br /> specimen was deposited at Institute of Natural and on YMC column using MeOH-H2O (2:1) to<br /> Products Chemistry (INPC), VAST. yield compounds 1 (18 mg) and 2 (65 mg).<br /> <br /> 127<br />  5-O-caffeoylquinic acid (1): Colorless caffeoyl unit and 7 carbons of the quinic acid.<br /> needles; IR (KBr) max cm-1: 3440 (OH), 1725 The substituted benzene ring was confirmed at<br /> (C=O), 1445 (C=C), 1055 (C-O-C); ESI-MS 115.56, 116.82, 123.14, 127.81, 146.81 and<br /> m/z: 355 [M+H]+; 353 [M-H]- (C16H18O9); 1H- 149.19, a double bond at 116.69 and 146.99<br /> NMR (500 MHz, CD3OD+D2O) and 13C-NMR and a carboxyl carbon at 169.55. The presence<br /> (125 MHz, CD3OD+D2O): see Table 1. of a quinic acid unit was confirmed at 181.03<br /> Cinnamic acid (2): Colorless needles; IR (C=O), 72.31, 72.40, 74.79 (CH), 38.84 and<br /> (KBr) max cm-1: 3432 (OH), 1714 (C=O), 1445 40.38 (CH2), and a tertiary carbon bearing<br /> (C=C); ESI-MS m/z: 149 [M+H]+; 353 [M-H]- oxygen atom at 77.77. These evidence<br /> (C9H8O2); 1H-NMR (500 MHz, CDCl3+CD3OD) suggested the molecular formula of 1 as<br /> and 13C-NMR (125 MHz, CDCl3+CD3OD), see C16H18O9, which was further confirmed by the<br /> table 1. ESI-MS with the appearance of the quasi ion<br /> peaks at 355 [M+H]+ (positive); 353 [M-H]-<br /> III - RESULTS AND DISCUSSION (negative). All the NMR assignments were<br /> deduced from HSQC and HMBC spectra and<br /> Repeated column chromatography on silica shown in table 1.<br /> gel and YMC RP-18 of the n-BuOH fraction of The key HMBC correlations of 1 were<br /> G. australis give compounds 1 and 2 as shown in Fig. 2. In the HMBC spectrum, H-5 (<br /> colorless needles. The IR spectrum of 1 5.37) correlated to C-9' ( 169.55). This<br /> exhibited the presence of OH, C =O and C=C, evidence confirmed that the caffeoyl unit linked<br /> C-O-C groups at 3440, 1725, 1445 and 1055 to C-5 of the quinic acid by ester linkage.<br /> cm-1, respectively. The 1H-NMR showed a Furthermore, the NMR data of 1 were compared<br /> 1,2,3-substituted benzene ring at 6.70 (1H, dd, to those of 5-O-caffeoylquinic acid and found to<br /> J = 2.0, 9.0 Hz), 6.85 (1H, d, J = 9.0 Hz) and match well [5]. This compound had been<br /> 7.11 (1H, d, J = 2.0 Hz); a double bond with reported to have insecticide activity, inhibits<br /> trans configuration at 6.32 (1H, d, J = 16.0 development of Spodoptera litura larvae,<br /> Hz) and 7.62 (1H, d, J = 16.0 Hz), and a quinic inhibitor of glucose 6-phosphate translocase,<br /> acid at 2.00-5.37 ppm. The 13C-NMR showed shows antiviral (HSV-1), antioxidant activities<br /> signals of 16 carbons including 9 carbons of the and scavenging effect on DPPH radical.<br /> <br /> <br /> O OH<br /> <br /> 9'<br /> O 8'<br /> 7' 2' 3'<br /> 8 9<br /> OH 6<br /> 1' 4' OH COOH<br /> 5 7<br /> 6' 5' 4<br /> 7 4<br /> 1<br /> O OH 2<br /> 2<br /> 1 3<br /> 2<br /> OH OH<br /> 1<br /> Figure 1: Structures of 1 and 2<br /> <br /> The 1H-NMR spectrum of 2 displayed the 130.33 (CH), a carbonyl carbon and the double<br /> resonances due to the signals of a benzene ring bond were assigned at 169.56, 117.91 and<br /> ( 7.37-7.53, 5H) and a trans double bond at 145.74, respectively. These evidence together<br /> 6.43 (1H, J = 16.0 Hz) and 7.71 (1H, J = 16.0 with the appearance of the quasi ion peaks at<br /> Hz). The 13C-NMR spectrum showed the signals 149 [M+H]+ and 147 [M-H]- in the ESI-MS led<br /> of 9 carbons, including a benzene ring at 134.31 to the structure of 2 as cinnamic acid, which was<br /> (C), 128.12 (2 x CH), 128.84 (2 x CH) and reported as an anaesthetic, anthelmintic,<br /> 128<br /> phytotoxic, cell differentiation inducer, and protein isoprenylation inhibitor.<br /> <br /> O OH<br /> <br /> O 9'<br /> 8'<br /> 7' 2' 3'<br /> <br /> OH 1' 4' OH<br /> 6' 5'<br /> 7 6 4<br /> O<br /> 2 5 OH<br /> 3<br /> 1<br /> <br /> <br /> OH OH<br /> H C<br /> <br /> Figure 2: HMBC correlations of 1<br /> <br /> Table 1: The NMR data of 1 and 2<br /> 1 2<br /> C a,b a,c d,b d,c<br /> C H C H<br /> <br /> 1 77.77 - 134.31 -<br /> 2 38.84 2.11 (m); 2.14 (m) 128.12 7.53 (m)<br /> 3 72.82 4.17 (dd, J = 6.5, 3.5 Hz) 128.84 7.38 (m)*<br /> 4 74.79 3.74 (dd, J = 3.5, 10.0 Hz) 130.33 7.38 (m)*<br /> 5 72.67 5.37 (m) 128.84 7.38 (m)*<br /> 6 40.38 2.00 (m); 2.18 (m) 128.12 7.53 (m)<br /> 7 181.03 - 145.74 7.72 (d, J = 16.0 Hz)<br /> 1' 127.81 - 117.91 6.43 (d, J = 16.0 Hz)<br /> 2' 115.31 7.11 (d, J = 2.0 Hz) 169.56 -<br /> 3' 146.41 -<br /> 4' 149.19 -<br /> 5' 115.48 6.85 (d, J = 9.0 Hz)<br /> 6' 123.14 6.70 (dd, J = 2.0, 9.0 Hz)<br /> 7' 146.99 7.62 (d, J = 16.0 Hz)<br /> 8' 116.69 6.32 (d, J = 16.0 Hz)<br /> 9' 169.55 -<br /> a<br /> Measured in CD3OD&D2O, b125 MHz, c500 MHz, dMeasured in CDCl3&CD3OD; Chemical shift ( ) in ppm,<br /> *Overlapped signals.<br /> <br /> Acknowledgments: The authors would like to Dictionary. Medicinal Publishing House,<br /> thank Dr Tran Huy Thai, Institute of Ecology (1997).<br /> and Biological Resources, VAST for the plant 2. D. H. Bich, D. Q. Trung, B. X. Chuong, N.<br /> identification. T. Dong, D. T. Dam, P. V. Hien, V. N. Lo,<br /> P. D. Mai, P. K. Man, D. T. Nhu, N. Tap,<br /> REFERENCES and T. Toan, The medicinal plants and<br /> animals of Vietnam, Hanoi Science and<br /> 1. V. V. Chi, Vietnamese Medical Plant<br /> 129<br />  Technology Publisher, 1st edition, Hanoi, Dung. Flavonoid constituents from<br /> Vol. II. pp. 635 - 636 (2004). Gleditschia australis Hemsl.,<br /> 3. P. V. Kiem, N. T. H. Van, P. K. Tiep, C. V. (Caesalpiniaceae), Journal of Pharmacy<br /> Minh, L. M. Huong, N. D. Tomasi, A. (Vietnamese), submitted (2007).<br /> Braca. Journal of Pharmacy (Vietnamese), 5. L. C. Lin, Y. C. Kuo, and C. J. Chou.<br /> Vol. 372 (4), 33 - 36 (2007). Journal of Natural Products, Vol. 62(3), 405<br /> 4. N. T. H. Van, P. V. Kiem, C. V. Minh, N. T. - 408 (1999).<br /> <br /> <br /> <br /> <br /> 130<br />