破骨风中木脂素类化合物的分离鉴定及抗氧化活性

doi:10.7503/cjcu20180159

摘要/Abstract

摘要：

以破骨风(Jasminum lanceolarium Roxb.)为研究对象, 采用硅胶柱和Sephadex LH-20凝胶柱层析等手段, 从中分离获得7个木脂素类化合物: Jasminlanoside A(1)、 (+)-环橄榄树脂素(2)、丁香脂素-4-O-β-D-葡萄糖苷(3)、 (+)-环橄榄树脂素-6-O-β-D-葡萄糖苷(4)、 (+)-环橄榄树脂素-4'-O-β-D-葡萄糖苷(5)、橄榄素4″-O-β-D-葡萄糖苷(6)和丁香脂素-4,4'-O-双-β-D-葡萄糖苷(7), 其中化合物1为新化合物, 化合物3~6均为首次从本属植物中分离得到. 利用一维核磁共振谱(1D NMR)、二维核磁共振谱(2D NMR)和高分辨电喷雾电离质谱(HR-ESI-MS)对化合物1的结构进行了鉴定. 抗氧化活性测试结果表明, 化合物1, 2, 4和5表现出一定的抗氧化活性, 化合物5的1,1-二苯基-2-三硝基苯肼(DPPH)清除活性最强, IC₅₀值为(0.148±0.005) μmol/L.

关键词: 破骨风, 木脂素类, 抗氧化活性

Abstract:

Using silica and Sephadex LH-20 column chromatographies, seven lignans, Jasminlanoside A(1),(+)-cycloolivil(2), syringaresinol-4-O-β-D-glucopyranoside(3), (+)-cycloolivil-6-O-β-D-glucopyranoside(4), (+)-cycloolivil-4'-O-β-D-glucopyranoside(5), (-)-olivil-4″-O-β-D-glucopyranoside(6) and syringare-sinol-4,4'-O-bis-β-D-glucopyranoside(7) were isolated from the extracts of Jasminum lanceolarium. Compound 1 was first found and compounds 3—6 were isolated from the Jasminum genus for the first time. The structure of compound 1 was determined by various spectral techniques. Compounds 1, 2, 4 and 5 exhibited antioxidant activity in the 1,1-diphenyl-2-picrylhydrazyl(DPPH) assay, with the highest activity in compound 5[(0.148±0.005) μmol/L].

Key words: Jasminum lanceolarium, Lignan, Antioxidant activity

中图分类号:

O629.9

TrendMD:

王雁冰, 张辉, 杨峻山, 陈炳鹏, 孙佳明. 破骨风中木脂素类化合物的分离鉴定及抗氧化活性. 高等学校化学学报, 2018, 39(9): 1942.

WANG Yanbing,ZHANG Hui,YANG Junshan,CHEN Bingpeng,SUN Jiaming. Isolation, Identification and Antioxidant Activity of Lignans in Jasminum lanceolarium^†. Chem. J. Chinese Universities, 2018, 39(9): 1942.

图/表 5

参考文献 21

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C atom	δ_H(J/Hz)	Key NOESY	δ_C	Key HMBC
1	—		126.3(C)
2	6.70 brs		106.7(CH)	C7
3	—		147.1(C)
4	—		147.6(C)
5	—		147.1(C)
6	6.70 brs		106.7(CH)	C7
7	4.63 brs		87.6(CH)	C1, C2, C6, C9, C8',C9'
8	3.56 m	7'-H, 9'-H	60.9(CH)	C1, C7'
9	4.36d(7.6)	8'-H	97.2(CH)	C7, C7', C8'
1'	—		131.6(C)
2'	6.81 dd(8.0,1.2)		118.5(CH)	C7'
3'	—		135.0(C)
4'	—		146.0(C)
5'	6.76 d(8.0)		115.2(CH)	C1', C3'
6'	6.97 d(1.2)		110.0(CH)	C2', C4', C7'
7'	4.69d(6.0)	8-H	85.1(CH)	C8, C9, C2', C6',C9'
8'	3.28 m	9-H, 9'-H	58.7(CH)	C7, C9, C1'
9'	4.36d(7.6)	8-H, 8'-H	98.5(CH)	C7, C8, C7'
1″	4.30 d(7.6)		98.5(CH)	C9
2″	3.86 m		72.3(CH)
3″	2.94 m		77.1(CH)
4″	2.82 m		73.3(CH)
5″	2.94 m		69.8(CH)
6″	1.22 d(6.4)		15.6(CH₃)
3,5-ArOCH₃	3.74 s		56.0(CH₃)	C3, C5
4'-ArOCH₃	3.79 s		55.6(CH₃)	C4'
4-ArOH	8.94 brs			C4
3'-ArOH	8.20 brs			C3'

C atom	δ_H(J/Hz)	Key NOESY	δ_C	Key HMBC
1	—		126.3(C)
2	6.70 brs		106.7(CH)	C7
3	—		147.1(C)
4	—		147.6(C)
5	—		147.1(C)
6	6.70 brs		106.7(CH)	C7
7	4.63 brs		87.6(CH)	C1, C2, C6, C9, C8',C9'
8	3.56 m	7'-H, 9'-H	60.9(CH)	C1, C7'
9	4.36d(7.6)	8'-H	97.2(CH)	C7, C7', C8'
1'	—		131.6(C)
2'	6.81 dd(8.0,1.2)		118.5(CH)	C7'
3'	—		135.0(C)
4'	—		146.0(C)
5'	6.76 d(8.0)		115.2(CH)	C1', C3'
6'	6.97 d(1.2)		110.0(CH)	C2', C4', C7'
7'	4.69d(6.0)	8-H	85.1(CH)	C8, C9, C2', C6',C9'
8'	3.28 m	9-H, 9'-H	58.7(CH)	C7, C9, C1'
9'	4.36d(7.6)	8-H, 8'-H	98.5(CH)	C7, C8, C7'
1″	4.30 d(7.6)		98.5(CH)	C9
2″	3.86 m		72.3(CH)
3″	2.94 m		77.1(CH)
4″	2.82 m		73.3(CH)
5″	2.94 m		69.8(CH)
6″	1.22 d(6.4)		15.6(CH₃)
3,5-ArOCH₃	3.74 s		56.0(CH₃)	C3, C5
4'-ArOCH₃	3.79 s		55.6(CH₃)	C4'
4-ArOH	8.94 brs			C4
3'-ArOH	8.20 brs			C3'

Compd.	Appearance	m. p. /℃	MS, m/z
2	White solid	170—172	399[M+Na]⁺, 377[M+H]⁺
3	White solid	268—270	603[M+Na]⁺
4	White solid	193—195	561[M+Na]⁺, 539[M+H]⁺
5	White solid	190—192	561[M+Na]⁺, 539[M+H]⁺
6	White solid	175—177	561[M+Na]⁺, 539[M+H]⁺
7	White solid	270—272	765[M+Na]⁺

Compd.	Appearance	m. p. /℃	MS, m/z
2	White solid	170—172	399[M+Na]⁺, 377[M+H]⁺
3	White solid	268—270	603[M+Na]⁺
4	White solid	193—195	561[M+Na]⁺, 539[M+H]⁺
5	White solid	190—192	561[M+Na]⁺, 539[M+H]⁺
6	White solid	175—177	561[M+Na]⁺, 539[M+H]⁺
7	White solid	270—272	765[M+Na]⁺

Compd.		¹H NMR(400 MHz, DMSO-d₆ ), δ
2	8.36(1H, s, 4'-OH), 8.73(1H, s, 4-OH), 6.65(1H, d, J=1.6 Hz, 2-H), 6.70(1H, d, J=8.0 Hz, 5-H), 6.52(1H, dd, J=8.0, 1.6 Hz, 6-H),3.84(1H, d, J=11.6 Hz, 7-H), 1.88(1H, dt, J=11.6, 3.7 Hz, 8-H), 3.62(1H, m, 9-H), 3.37(1H, m, 9-H), 6.55(1H, s, 2'-H), 6.05(1H, s, 5'-H), 3.09(1H, d, J=16.5 Hz, 7'-H), 2.43(1H, d, J=16.5 Hz, 7'-H), 3.60(1H, m, 9'-H), 3.37(1H, m, 9'-H), 3.73(6H, s, 3, 3'-OCH₃)		136.9(C1), 113.4(C2), 147.3(C3), 144.7(C4), 115.3(C5), 121.8(C6) ,43.7(C7), 45.6(C8), 59.0(C9),132.0(C1'), 112.3(C2'), 145.7(C3'), 143.8(C4'), 116.1(C5'), 125.1(C6'), 39.5(C7'), 72.9(C8'), 68.0(C9'), 55.6(3-OCH₃), 55.5(3'-OCH₃)
3	6.66(2H, s, 2,6-H), 6.60(2H, s, 2',6'-H), 4.66(1H, d, J=4.2 Hz, 7-H), 4.60(1H, d, J=4.2 Hz, 7'-H), 4.18(2H, t, J=13.2, 6.6 Hz, 9_e, 9'_e-H), 3.89(2H, dd, J=13.2, 6.6 Hz, 9_a, 9'_a-H), 3.10(2H, m, 8, 8'-H), 3.75(12H, s, 4-OCH₃), 4.87(1H, d, J=5.4 Hz, 1″-H)		131.3(C1,1'), 103.7(C2, 6, 2', 6'), 152.6(C3, 5), 147.9(C3', 5'), 137.1(C4), 134.8(C4'), 85.3(C7), 85.0(C7'), 53.6(C8), 53.5(C8'), 71.2(C9), 71.1(C9'), 102.6(C1″), 74.1(C2″), 76.5(C3″), 69.9(C4″), 77.2(C5″), 60.9(C6″), 56.4(3, 5-OCH₃), 56.0(3', 5'-OCH₃)
4	8.73(1H, brs, 4'-OH), 6.65(1H, d, J=0.8 Hz, 2'-H), 6.71(1H, d, J=8.0 Hz, 5'-H), 6.53(1H, dd, J=8.0, 0.8 Hz, 6'-H), 6.63(1H, brs, 8-H), 6.32(1H, brs, 5-H), 3.90(1H, d, J=11.6 Hz, 4-H) 1.96(1H, d, J=11.6 Hz, 3-H), 2.48(1H, d, J=17.2 Hz, 1_a-H), 3.15(1H, d, J=17.2 Hz, 1_b-H), 4.26(1H, d, J=8.0 Hz, 1'-H), 3.71(6H, s, 7, 3'-OCH₃)		40.0(C1), 73.0(C 2), 69.2(C2_a), 45.3(C3), 59.0(C3_a), 43.3(C4), 116.4(C5), 144.2(C6) ,146.8(C7), 112.7(C8), 128.1(C9), 132.1(C10), 136.5(C1'), 113.4(C2'), 147.3(C3'), 146.8(C4'), 115.3(C5'), 121.7(C6'), 100.7(C1″), 73.0(C2″), 76.9(C3″), 69.2(C4″), 77.0(C5″), 60.1(C6″), 55.6(7-OCH₃), 55.7(3'-OCH₃)
5	8.77(1H, brs, 6-OH), 6.65(1H, d, J=0.8 Hz, 2'-H), 6.68(1H, d, J=8.0 Hz, 5'-H), 6.53(1H, dd, J=8.0, 0.8 Hz, 6'-H), 6.63(1H, brs, 8-H), 6.32(1H, brs, 5-H),3.89(1H, d, J=12.0 Hz, 4-H), 1.95(1H, d, J=11.2 Hz, 3-H), 2.48(1H, d, J=14.0 Hz, 1_a-H), 3.17(1H, d, J=14.0 Hz, 1_b-H), 4.85(1H, d, J=7.2 Hz, 1'-H), 3.74(6H, s, 7, 3'-OCH₃)		39.5(C1), 72.9(C2), 69.2(C2_a), 45.2(C3), 58.9(C3_a), 43.2(C4), 116.4(C5), 145.6(C6),147.3(C7), 113.4(C8), 132.1(C9), 128.1(C10), 134.4(C1'), 114.7(C2'),148.1(C3'), 146.8(C4'), 116.4(C5'), 122.2(C6'),100.2(C1″), 73.0(C2″), 76.8(C3″), 69.7(C4″), 76.9(C5″), 60.6(C6″), 55.6(7-OCH₃), 55.7(3'-OCH₃)
6	8.78(1H, brs, 4'-OH), 7.03(1H, d, J=1.6 Hz, 2'-H), 6.70(1H, d, J=8.4 Hz, 5'-H), 6.80(1H, dd, J=8.4, 1.6 Hz, 6'-H), 6,91(1H, d, J=1.6 Hz, 2″-H), 6.96(1H, d, J=8.4 Hz, 5″-H), 6.75(1H, dd, J=8.4, 1.6 Hz, 6″-H), 3.63(1H, d, J=9.2 Hz, 5_a-H), 2.75(1H, d, J=14.0 Hz, 4_a-H), 2.88(1H, d, J=14.0 Hz, 4_b-H), 4.59(1H, d, J=7.2 Hz, 2-H), 2.14(1H, dd, J=12.8, 2.0 Hz, 3-H), 3.55(1H, m, 3_a-H), 3.65(1H, m, 3_b-H), 4.85(1H, d, J=7.2 Hz, 1″'-H), 3.74(6H, s, 3', 3″-OCH₃)		83.3(C2), 60.6(C3), 58.9(C3_a),80.5(C4), 39.5(C4_a), 134.4.1(C1'), 111.0(C2'), 146.8(C3'), 145.6(C4'), 115.3(C5'), 119.1(C6'),132.1(C1″), 115.0(C2″),147.3(C3″), 144.9(C4'), 114.7(C5″), 121.7(C6″), 100.7(C1″'), 73.0(C2″'), 76.9(C3″'), 69.2(C4″'), 76.9(C5″'), 60.1(C6″'), 55.6(3'-OCH₃), 55.7(3″-OCH₃)
Compd.		¹H NMR(400 MHz, DMSO-d₆ ), δ			¹³C NMR(100 MHz, DMSO-d₆ ), δ
7	6.66(4H, s, 2, 6, 2', 6'-H), 4.67(2H, d, J=3.2 Hz, 7, 7'-H), 4.19(2H, dd, J=9.0, 6.0 Hz, 9_e, 9'_e-H), 3.82(2H, dd, J=9.0, 6.0 Hz, 9_a, 9'_a-H), 3.76(12H, s, 4-OMe), 3.03(2H, m, 8, 8-H') 4.89(2H, m, 1″,1″'-H)			133.7(C1,1'), 104.2(C2, 6, 2', 6'), 152.6(C3, 5, 3', 5'), 137.1(C4, 4'), 85.1(C7, 7'), 53.6(C8, 8'), 71.3(C9, 9'), 102.7(C1″, 1″'), 74.1(C2″, 2″'), 76.5(C3″, 3″'), 69.9(C4″, 4″'), 77.2(C5″, 5″'), 60.9(C6″, 6″'), 56.4(3, 5, 3', 5'-OMe)