- Email: [email protected]
A new 3-(3,4-methylenedioxyphenyl)-propane-1,2-diol glycoside from the roots of Cinnamomum camphora
Available online at www.sciencedirect.com
Chinese Chemical Letters 22 (2011) 954–956 www.elsevier.com/locate/cclet
A new 3-(3,4-methylenedioxyphenyl)-propane-1,2-diol glycoside from the roots of Cinnamomum camphora Rui Jiang Zhong a, Lin You Wu a, Wei Xiong a, Er Lei Xie a, Guo Ping Zhou a,*, Dong Ming Zhang b b
a Jiangxi Provical Institute for Drug and Food Control, Nanchang 330029, China Institute of Materia Medica, Chinese Academy of Medical Sciences and Peking Union Medical College (Key Laboratory of Bioactive Substances and Resources Utilization of Chinese Herbal Medicine, Ministry of Education), Beijing 100050, China
Received 15 October 2010 Available online 18 May 2011
Abstract A new 3-(3,4-methylenedioxyphenyl)-propane-1,2-diol glycoside, named cinnamomdiol A (1), together with two known compounds, 3-(3,4-methylenedioxyphenyl)-propane-1,2-diol (2) and taxifolin (3), was isolated from the roots of Cinnamomum camphora. Their structures were determined on the basis of spectroscopic evidences. Compounds 2 and 3 were isolated from the title plant for the first time. # 2011 Guo Ping Zhou. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved. Keywords: Cinnamomum camphora; 3-(3,4-Methylenedioxyphenyl)-propane-1,2-diol glycoside; Cinnamomdiol A
Cinnamomum camphora (L.) Presl is a Chinese medicinal plant widespread in China and has long been prescribed in traditional medicine for treatment of inflammation-related diseases, such as rheumatism, sprins, bronchitis and muscle pains [1]. Previous investigations on the roots of C. camphora have led to the isolation of several tannins [2], organic acids [3] and monoterpenoids [4]. Phytochemical investigation on alcoholic extracts of the roots of C. camphora resulted in the isolation of a new compound named cinnamomdiol A (1) and two known compounds. Their structures were determined on the basis of spectroscopic evidences, including IR, MS, 1D and 2D NMR spectral data. We report herein the isolation and structural elucidation of 1. The roots of C. camphora were collected from Jiangxi province of China, and authenticated by Professor Gui-Ping Yuan of Jiangxi Provical Institute for Drug and Food Control of the People’s Republic of China. A voucher specimen (no. 20090816) has been deposited in Jiangxi Provincial Institute for Drug and Food Control. The powdered dried roots of C. camphora (20 kg) were extracted with 70% EtOH two times by heating, and the gum (1 kg) obtained by concentrating the 70% EtOH extract in vacuo was partitioned with petroleum ether, CHCl3, EtOAc and n-BuOH successively. The n-BuOH extract (150 g) was fractionated via HP-20 macroporous resin column chromatography, eluted with MeOH–H2O (0:100 to 100:0, v/v) to afford the new compound 1 (300 mg) and two known compounds 2 and 3 Fig. 1.
* Corresponding author. E-mail addresses: [email protected] (G.P. Zhou), [email protected] (D.M. Zhang). 1001-8417/$ – see front matter # 2011 Guo Ping Zhou. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved. doi:10.1016/j.cclet.2011.01.031
[()TD$FIG]
R.J. Zhong et al. / Chinese Chemical Letters 22 (2011) 954–956
O
2
3
7
9
8
OH
1
10 O
955
O
6
4
OH
1'
5
2'
O
3'
5' O
5''
6''
O
HO 4''
6'
OH 4'
1''
3''
OH
2''
HO HO
Fig. 1. Structure of compound 1.
Compound 1 was obtained as a yellow crystal, mp 104–105 8C. ½a20 D 40:4 (c 0.43, MeOH). UV (MeOH) lmax (log e): 285 (1.87), 233 (1.83) nm. The IR spectrum indicated the presence of hydroxyl (3386 cm1) and methyl (1491 cm1). The negative ESIMS of 1 gave a quasi-molecular ion peak at m/z 503.1 [MH], while the positive ESIMS exhibited [M+Na]+ at m/z 527.2. The HRESIMS displayed a quasi-molecular ion at m/z 527.1021 [M+Na]+ (calcd. for C22H32NaO13 527.1034), indicating the molecular formula of 1 as C22H32O13. The 1H NMR spectrum of 1 showed signals of ABX-type aromatic protons at d 6.91 (brs, 1H, H-2), d 6.77 (d, 1H, J = 8.0 Hz, H-5), d 6.72 (brd, 1H, J = 8.0 Hz, H-6) and a methylenedioxy group at d 5.94 (d, 2H, J = 2.5 Hz, H-10). In the aliphatic region, the observation of two anomeric protons at d 4.21 (H-10 ) and 4.56 (H-100 ) and corresponding carbons at d 102.4 (H-10 ) and 101.0 (H-100 ) in NMR spectra (Table 1) suggested the existence of two sugar units. The propane chain was defined in the 1H NMR spectrum by a double doublets at d 2.71 (dd, 2H, J = 14.0, 6.0 Hz, H-7), three multiple signals at d 3.69 (m, 1H, H-8), 3.37 (m, 1H, H-9a), 3.27 (m, 1H, H-9b). This aliphatic part was confirmed in the 13C NMR spectrum by two methylene signals at d 36.7 and 62.9 and a methine peak at d 81.6. The acid hydrolysis of 1 afforded glucose and a rhamnose. The large coupling constant (8.0 Hz) of the anomeric proton at d 4.21 revealed that the glucose was the bconfiguration, while the small coupling constant (1.5 Hz) of the anomeric proton at d 4.56 indicated that the rhamnose was the a-configuration. GC analysis established the D- and L-configuration of the moieties, respectively [5]. The 13C NMR spectrum displayed a signal at d 100.6, which was assigned to methylenedioxy carbon [6], and six aromatic carbons, some of them being superimposed (d 147.0, 145.4, 132.2, 122.2, 110.2, 107.9), suggesting that there was an aromatic ring in the structure of 1. In HMBC spectrum of 1 (Fig. 2), a series of HMBC correlations from H-7 to C-1, C2, C-6, C-8, and C-9, from H-8 to C-7, C-9, C-1, C-10 , from H-9 to C-7, C-8. The HMBC cross peaks noted for H-7 and/ Table 1 The 1H NMR (500 MHz) and Position 1 2 3 4 5 6 7 8 9 10 Glucose 10
13
C NMR (125 MHz) spectral data of compound 1 (DMSO-d6, d).
dH (mult., J in Hz) 6.91 (brs, 1H)
6.77 6.72 2.71 3.69 3.37 3.27 5.94
(d, 1H, 8.0) (brd, 1H, 8.0) (dd, 2H, 14.0, 6.0) (m, 1H) (m, 1H) (m, 1H) (d, 2.5, 2H)
4.21 (d, 8.0, 1H)
dC 132.2 110.2 147.0 145.4 107.9 122.2 36.7 81.6 62.9 100.6 102.4
Position
dH (mult., J in Hz) 20 30 40 50 60
Rhamnose 100 200 300 400 500 600
2.96 3.15 3.00 3.11 3.80 3.36
(m, 1H) (m, 1H) (m, 1H) (m, 1H) (brd, 1H, 5.0) (m, 1H)
4.56 3.39 3.61 3.18 3.36 1.11
(1.5, 1H) (m, 1H) (m, 1H) (m, 1H) (m, 1H) (d, 3H, 6.5)
dC 73.5 76.6 70.4 75.3 67.3
101.0 70.7 70.4 72.1 68.4 18.0
[()TD$FIG] 956
R.J. Zhong et al. / Chinese Chemical Letters 22 (2011) 954–956
O
9
8
OH
1
10 O
7
2
3
O
6
4 5
OH
1'
2'
O
3'
5' 6' O
OH 4'
OH
5''
6''
O
HO 4''
HO
3''
1'' 2'' OH
Fig. 2. Key HMBC (H ! C) correlations of compound 1.
or C-7 and other surrounding positions (Fig. 1) showed the link between the propane chain and the aromatic ring. In addition linkage information on the two sugar units was obtained on the basis of the 13C NMR and HMBC spectra. The presence of a downfield methylene signal at d 67.3 (C-60 ) in the 13C NMR spectrum indicated the attachment of the a0 L-rhamanopyranosyl moiety at C-6 of the b-D-glucopyranosyl moiety, and this was further confirmed by the HMBC 00 0 correlation from H-1 to C-6 , HMBC correlations between H-10 and C-8 indicated the attachment of the b-D-glucose moiety at C-8 of the propane chain. The acid hydrolysis of 1 yielded 3-(3,4-methylenedioxyphenyl)-propane-1,2-diol. The optical rotation {½a20 D þ 33:5 (c 0.92, CHCl3)} for 3-(3,4-methylenedioxyphenyl)-propane-1,2-diol was similar to (2R)-3-phenylpropane-1,2-diol that reported in the literature [7]. Therefore, the configuration at C-8 was determined to be R on the data of the ORD of (2R)-3-phenylpropane-1,2-diol. In light of the evidence mentioned above, the structure of 1 was established as 8R-O-[a-L-rhamanopyranosyl (1 ! 6)-b-D-glucopyranosyl]-3-(3,4-methylenedioxyphenyl)-propane-1,2-diol, named cinnamomdiol A. The structures of known compounds 2 and 3 were determined as 3-(3,4-methylenedioxyphenyl)-propane-1,2- diol [8] and taxifolin [9], respectively, by detailed spectroscopic analysis and comparison of their spectral data with reported values in the literatures. Acknowledgments We are grateful to the Department of Instrumental Analysis, Institute of Materia Medica, Chinese Academy of Medical Sciences and Peking Union Medical College for NMR measurements. References [1] [2] [3] [4] [5] [6] [7] [8] [9]
H.J. Lee, E.A. Hyun, W.J. Yoon, J. Ethnopharmacol. 103 (2006) 208. Y.C. Shen, Foreign Med. Sci. (TCM Section) 4 (1982) 51. N.K. Hirao, Ichushi 227 (1967) 138. G.F. Zhang, C.J. Chen, Z.P. Chen, J. Plant Resour. Environ. 1 (2008) 24. J. Kinijo, K. Araki, K. Fukui, Chem. Pharm. Bull. 40 (1992) 3269. G. Comet, D.P. Allais, A.J. Chulia, et al. Phytochemistry 44 (1997) 1170. M. Kapur, A. Khartulyari, M.E. Maier, Org. Lett. 8 (2006) 1632. Y. Li, F. Wang, X.P. Cao, Acta Chim. Sinica 2 (2003) 281. Y.Y. Zhou, D. Wang, F. Guan, Lishizhen Med. Mater. Med. Res. 10 (2007) 2642.
Chinese Chemical Letters 22 (2011) 954–956 www.elsevier.com/locate/cclet
A new 3-(3,4-methylenedioxyphenyl)-propane-1,2-diol glycoside from the roots of Cinnamomum camphora Rui Jiang Zhong a, Lin You Wu a, Wei Xiong a, Er Lei Xie a, Guo Ping Zhou a,*, Dong Ming Zhang b b
a Jiangxi Provical Institute for Drug and Food Control, Nanchang 330029, China Institute of Materia Medica, Chinese Academy of Medical Sciences and Peking Union Medical College (Key Laboratory of Bioactive Substances and Resources Utilization of Chinese Herbal Medicine, Ministry of Education), Beijing 100050, China
Received 15 October 2010 Available online 18 May 2011
Abstract A new 3-(3,4-methylenedioxyphenyl)-propane-1,2-diol glycoside, named cinnamomdiol A (1), together with two known compounds, 3-(3,4-methylenedioxyphenyl)-propane-1,2-diol (2) and taxifolin (3), was isolated from the roots of Cinnamomum camphora. Their structures were determined on the basis of spectroscopic evidences. Compounds 2 and 3 were isolated from the title plant for the first time. # 2011 Guo Ping Zhou. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved. Keywords: Cinnamomum camphora; 3-(3,4-Methylenedioxyphenyl)-propane-1,2-diol glycoside; Cinnamomdiol A
Cinnamomum camphora (L.) Presl is a Chinese medicinal plant widespread in China and has long been prescribed in traditional medicine for treatment of inflammation-related diseases, such as rheumatism, sprins, bronchitis and muscle pains [1]. Previous investigations on the roots of C. camphora have led to the isolation of several tannins [2], organic acids [3] and monoterpenoids [4]. Phytochemical investigation on alcoholic extracts of the roots of C. camphora resulted in the isolation of a new compound named cinnamomdiol A (1) and two known compounds. Their structures were determined on the basis of spectroscopic evidences, including IR, MS, 1D and 2D NMR spectral data. We report herein the isolation and structural elucidation of 1. The roots of C. camphora were collected from Jiangxi province of China, and authenticated by Professor Gui-Ping Yuan of Jiangxi Provical Institute for Drug and Food Control of the People’s Republic of China. A voucher specimen (no. 20090816) has been deposited in Jiangxi Provincial Institute for Drug and Food Control. The powdered dried roots of C. camphora (20 kg) were extracted with 70% EtOH two times by heating, and the gum (1 kg) obtained by concentrating the 70% EtOH extract in vacuo was partitioned with petroleum ether, CHCl3, EtOAc and n-BuOH successively. The n-BuOH extract (150 g) was fractionated via HP-20 macroporous resin column chromatography, eluted with MeOH–H2O (0:100 to 100:0, v/v) to afford the new compound 1 (300 mg) and two known compounds 2 and 3 Fig. 1.
* Corresponding author. E-mail addresses: [email protected] (G.P. Zhou), [email protected] (D.M. Zhang). 1001-8417/$ – see front matter # 2011 Guo Ping Zhou. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved. doi:10.1016/j.cclet.2011.01.031
[()TD$FIG]
R.J. Zhong et al. / Chinese Chemical Letters 22 (2011) 954–956
O
2
3
7
9
8
OH
1
10 O
955
O
6
4
OH
1'
5
2'
O
3'
5' O
5''
6''
O
HO 4''
6'
OH 4'
1''
3''
OH
2''
HO HO
Fig. 1. Structure of compound 1.
Compound 1 was obtained as a yellow crystal, mp 104–105 8C. ½a20 D 40:4 (c 0.43, MeOH). UV (MeOH) lmax (log e): 285 (1.87), 233 (1.83) nm. The IR spectrum indicated the presence of hydroxyl (3386 cm1) and methyl (1491 cm1). The negative ESIMS of 1 gave a quasi-molecular ion peak at m/z 503.1 [MH], while the positive ESIMS exhibited [M+Na]+ at m/z 527.2. The HRESIMS displayed a quasi-molecular ion at m/z 527.1021 [M+Na]+ (calcd. for C22H32NaO13 527.1034), indicating the molecular formula of 1 as C22H32O13. The 1H NMR spectrum of 1 showed signals of ABX-type aromatic protons at d 6.91 (brs, 1H, H-2), d 6.77 (d, 1H, J = 8.0 Hz, H-5), d 6.72 (brd, 1H, J = 8.0 Hz, H-6) and a methylenedioxy group at d 5.94 (d, 2H, J = 2.5 Hz, H-10). In the aliphatic region, the observation of two anomeric protons at d 4.21 (H-10 ) and 4.56 (H-100 ) and corresponding carbons at d 102.4 (H-10 ) and 101.0 (H-100 ) in NMR spectra (Table 1) suggested the existence of two sugar units. The propane chain was defined in the 1H NMR spectrum by a double doublets at d 2.71 (dd, 2H, J = 14.0, 6.0 Hz, H-7), three multiple signals at d 3.69 (m, 1H, H-8), 3.37 (m, 1H, H-9a), 3.27 (m, 1H, H-9b). This aliphatic part was confirmed in the 13C NMR spectrum by two methylene signals at d 36.7 and 62.9 and a methine peak at d 81.6. The acid hydrolysis of 1 afforded glucose and a rhamnose. The large coupling constant (8.0 Hz) of the anomeric proton at d 4.21 revealed that the glucose was the bconfiguration, while the small coupling constant (1.5 Hz) of the anomeric proton at d 4.56 indicated that the rhamnose was the a-configuration. GC analysis established the D- and L-configuration of the moieties, respectively [5]. The 13C NMR spectrum displayed a signal at d 100.6, which was assigned to methylenedioxy carbon [6], and six aromatic carbons, some of them being superimposed (d 147.0, 145.4, 132.2, 122.2, 110.2, 107.9), suggesting that there was an aromatic ring in the structure of 1. In HMBC spectrum of 1 (Fig. 2), a series of HMBC correlations from H-7 to C-1, C2, C-6, C-8, and C-9, from H-8 to C-7, C-9, C-1, C-10 , from H-9 to C-7, C-8. The HMBC cross peaks noted for H-7 and/ Table 1 The 1H NMR (500 MHz) and Position 1 2 3 4 5 6 7 8 9 10 Glucose 10
13
C NMR (125 MHz) spectral data of compound 1 (DMSO-d6, d).
dH (mult., J in Hz) 6.91 (brs, 1H)
6.77 6.72 2.71 3.69 3.37 3.27 5.94
(d, 1H, 8.0) (brd, 1H, 8.0) (dd, 2H, 14.0, 6.0) (m, 1H) (m, 1H) (m, 1H) (d, 2.5, 2H)
4.21 (d, 8.0, 1H)
dC 132.2 110.2 147.0 145.4 107.9 122.2 36.7 81.6 62.9 100.6 102.4
Position
dH (mult., J in Hz) 20 30 40 50 60
Rhamnose 100 200 300 400 500 600
2.96 3.15 3.00 3.11 3.80 3.36
(m, 1H) (m, 1H) (m, 1H) (m, 1H) (brd, 1H, 5.0) (m, 1H)
4.56 3.39 3.61 3.18 3.36 1.11
(1.5, 1H) (m, 1H) (m, 1H) (m, 1H) (m, 1H) (d, 3H, 6.5)
dC 73.5 76.6 70.4 75.3 67.3
101.0 70.7 70.4 72.1 68.4 18.0
[()TD$FIG] 956
R.J. Zhong et al. / Chinese Chemical Letters 22 (2011) 954–956
O
9
8
OH
1
10 O
7
2
3
O
6
4 5
OH
1'
2'
O
3'
5' 6' O
OH 4'
OH
5''
6''
O
HO 4''
HO
3''
1'' 2'' OH
Fig. 2. Key HMBC (H ! C) correlations of compound 1.
or C-7 and other surrounding positions (Fig. 1) showed the link between the propane chain and the aromatic ring. In addition linkage information on the two sugar units was obtained on the basis of the 13C NMR and HMBC spectra. The presence of a downfield methylene signal at d 67.3 (C-60 ) in the 13C NMR spectrum indicated the attachment of the a0 L-rhamanopyranosyl moiety at C-6 of the b-D-glucopyranosyl moiety, and this was further confirmed by the HMBC 00 0 correlation from H-1 to C-6 , HMBC correlations between H-10 and C-8 indicated the attachment of the b-D-glucose moiety at C-8 of the propane chain. The acid hydrolysis of 1 yielded 3-(3,4-methylenedioxyphenyl)-propane-1,2-diol. The optical rotation {½a20 D þ 33:5 (c 0.92, CHCl3)} for 3-(3,4-methylenedioxyphenyl)-propane-1,2-diol was similar to (2R)-3-phenylpropane-1,2-diol that reported in the literature [7]. Therefore, the configuration at C-8 was determined to be R on the data of the ORD of (2R)-3-phenylpropane-1,2-diol. In light of the evidence mentioned above, the structure of 1 was established as 8R-O-[a-L-rhamanopyranosyl (1 ! 6)-b-D-glucopyranosyl]-3-(3,4-methylenedioxyphenyl)-propane-1,2-diol, named cinnamomdiol A. The structures of known compounds 2 and 3 were determined as 3-(3,4-methylenedioxyphenyl)-propane-1,2- diol [8] and taxifolin [9], respectively, by detailed spectroscopic analysis and comparison of their spectral data with reported values in the literatures. Acknowledgments We are grateful to the Department of Instrumental Analysis, Institute of Materia Medica, Chinese Academy of Medical Sciences and Peking Union Medical College for NMR measurements. References [1] [2] [3] [4] [5] [6] [7] [8] [9]
H.J. Lee, E.A. Hyun, W.J. Yoon, J. Ethnopharmacol. 103 (2006) 208. Y.C. Shen, Foreign Med. Sci. (TCM Section) 4 (1982) 51. N.K. Hirao, Ichushi 227 (1967) 138. G.F. Zhang, C.J. Chen, Z.P. Chen, J. Plant Resour. Environ. 1 (2008) 24. J. Kinijo, K. Araki, K. Fukui, Chem. Pharm. Bull. 40 (1992) 3269. G. Comet, D.P. Allais, A.J. Chulia, et al. Phytochemistry 44 (1997) 1170. M. Kapur, A. Khartulyari, M.E. Maier, Org. Lett. 8 (2006) 1632. Y. Li, F. Wang, X.P. Cao, Acta Chim. Sinica 2 (2003) 281. Y.Y. Zhou, D. Wang, F. Guan, Lishizhen Med. Mater. Med. Res. 10 (2007) 2642.