药学学报

Position	1		2
1′	-	134.3		-	134.2
2′	6.67 (1H, s)	113.1	6.68 (1H, s)	113.0
3′	-	148.7	-	148.5
4′	-	145.6	-	145.5
5′	6.69 (1H, d, J = 8.0 Hz)	116.0	6.70 (1H, d, J = 8.0 Hz)	115.8
6′	6.59 (1H, d, J = 8.0 Hz)	121.8	6.60 (1H, d, J = 8.0 Hz)	121.6
1	-	154.7	-	154.6
2	5.83 (1H, d, J = 8.9 Hz)	106.7	5.83 (1H, d, J = 8.9 Hz)	106.5
3	2.82 (1H, overlap)	35.3	2.82 (1H, overlap)	35.1
4	5.83 (1H, d, J = 8.9 Hz)	106.1	5.83 (1H, d, J = 8.9 Hz)	106.0
5	-	155.7	-	155.6
6	2.57 (2H, t, J = 7.4 Hz)	28.6	2.57 (2H, t, J = 7.4 Hz)	28.8
7	1.60 (2H, t, J = 7.4 Hz)	31.4	1.62 (2H, t, J = 7.0 Hz)	29.2
8	1.37 (2H, q, J = 7.5 Hz)	23.2	1.34 (2H, overlap)	29.7
9	0.94 (3H, t, J = 7.3 Hz)	14.2	1.34 (2H, overlap)	32.6
10	2.82 (3H, s)	31.6	1.34 (2H, overlap)	23.5
11	-	-	0.92 (2H, t, J = 7.0 Hz)	14.2
12	-	-	2.82 (3H, s)	31.2
-OCH₃	3.79 (3H, s)	56.3	3.80 (3H, s)	56.1

Position	1		2
1′	-	134.3		-	134.2
2′	6.67 (1H, s)	113.1	6.68 (1H, s)	113.0
3′	-	148.7	-	148.5
4′	-	145.6	-	145.5
5′	6.69 (1H, d, J = 8.0 Hz)	116.0	6.70 (1H, d, J = 8.0 Hz)	115.8
6′	6.59 (1H, d, J = 8.0 Hz)	121.8	6.60 (1H, d, J = 8.0 Hz)	121.6
1	-	154.7	-	154.6
2	5.83 (1H, d, J = 8.9 Hz)	106.7	5.83 (1H, d, J = 8.9 Hz)	106.5
3	2.82 (1H, overlap)	35.3	2.82 (1H, overlap)	35.1
4	5.83 (1H, d, J = 8.9 Hz)	106.1	5.83 (1H, d, J = 8.9 Hz)	106.0
5	-	155.7	-	155.6
6	2.57 (2H, t, J = 7.4 Hz)	28.6	2.57 (2H, t, J = 7.4 Hz)	28.8
7	1.60 (2H, t, J = 7.4 Hz)	31.4	1.62 (2H, t, J = 7.0 Hz)	29.2
8	1.37 (2H, q, J = 7.5 Hz)	23.2	1.34 (2H, overlap)	29.7
9	0.94 (3H, t, J = 7.3 Hz)	14.2	1.34 (2H, overlap)	32.6
10	2.82 (3H, s)	31.6	1.34 (2H, overlap)	23.5
11	-	-	0.92 (2H, t, J = 7.0 Hz)	14.2
12	-	-	2.82 (3H, s)	31.2
-OCH₃	3.79 (3H, s)	56.3	3.80 (3H, s)	56.1

Position	δ_H	δ_C
1′		133.9
2′	6.69 (1H, s)	111.0
3′		146.4
4′		143.7
5′	6.81 (1H, d, J = 8.0 Hz)	114.3
6′	6.67 (1H, d, J = 8.0 Hz)	120.9
1	2.67, 2.61 (2H, m)	31.4
2	1.73 (2H, m)	40.0
3	3.84 (1H, overlap)	72.4
4	1.60, 1.50 (2H, overlap)	43.0
5	3.84 (1H, overlap)	73.4
6	1.44 (2H, overlap)	38.4
7	1.24 (2H, overlap)	25.3
8	1.24 (2H, overlap)	29.6
9	1.24 (2H, overlap)	29.5
10	1.24 (2H, overlap)	29.3
11	1.24 (2H, overlap)	31.9
12	1.24 (2H, overlap)	22.9
13	0.85 (3H, t, J = 6.7 Hz)	14.1
14
-OCH₃	3.86 (3H, s)	55.9

Position	δ_H	δ_C
1′		133.9
2′	6.69 (1H, s)	111.0
3′		146.4
4′		143.7
5′	6.81 (1H, d, J = 8.0 Hz)	114.3
6′	6.67 (1H, d, J = 8.0 Hz)	120.9
1	2.67, 2.61 (2H, m)	31.4
2	1.73 (2H, m)	40.0
3	3.84 (1H, overlap)	72.4
4	1.60, 1.50 (2H, overlap)	43.0
5	3.84 (1H, overlap)	73.4
6	1.44 (2H, overlap)	38.4
7	1.24 (2H, overlap)	25.3
8	1.24 (2H, overlap)	29.6
9	1.24 (2H, overlap)	29.5
10	1.24 (2H, overlap)	29.3
11	1.24 (2H, overlap)	31.9
12	1.24 (2H, overlap)	22.9
13	0.85 (3H, t, J = 6.7 Hz)	14.1
14
-OCH₃	3.86 (3H, s)	55.9

Position	δ_H	δ_C
1′	-	134.0
2′	6.76 (1H, s)	113.3
3′	-	148.9
4′	-	145.8
5′	6.67 (1H, d, J = 8.0 Hz)	116.1
6′	6.60 (1H, d, J = 8.0 Hz)	121.8
1	2.75 (2H, m)	30.3
2	2.75 (2H, m)	45.2
3	-	210.4
4	2.62 (2H, m)	46.6
5	4.39 (1H, m)	48.0
6	1.45 (2H, m)	33.1
7	1.22 (2H, overlap)	26.9
8	1.22 (2H, overlap)	32.5
9	1.27 (2H, overlap)	23.6
10	0.88 (3H, t, J = 6.8 Hz)	14.3
11	-	177.7
12	2.27 (2H, m)	32.4
13	1.91 (2H, m)	19.1
14	3.24 (2H, m)	44.2
-OCH₃	3.82 (3H, s)	56.4

Position	δ_H	δ_C
1′	-	134.0
2′	6.76 (1H, s)	113.3
3′	-	148.9
4′	-	145.8
5′	6.67 (1H, d, J = 8.0 Hz)	116.1
6′	6.60 (1H, d, J = 8.0 Hz)	121.8
1	2.75 (2H, m)	30.3
2	2.75 (2H, m)	45.2
3	-	210.4
4	2.62 (2H, m)	46.6
5	4.39 (1H, m)	48.0
6	1.45 (2H, m)	33.1
7	1.22 (2H, overlap)	26.9
8	1.22 (2H, overlap)	32.5
9	1.27 (2H, overlap)	23.6
10	0.88 (3H, t, J = 6.8 Hz)	14.3
11	-	177.7
12	2.27 (2H, m)	32.4
13	1.91 (2H, m)	19.1
14	3.24 (2H, m)	44.2
-OCH₃	3.82 (3H, s)	56.4

干姜中五个新的姜辣素类化合物

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张晓娟 ¹ , 王彦志 ¹^,²^,^* , 李曼倩 ¹ , 宋志敏 ¹ , 郭燕 ¹ , 胡雪雨 ¹ , 冯卫生 ¹^,²^,^*

药学学报 | 研究论文 2020,55(10): 2421-2427

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药学学报 | 研究论文 2020, 55(10): 2421-2427

干姜中五个新的姜辣素类化合物

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张晓娟¹, 王彦志¹^,²^,^*, 李曼倩¹, 宋志敏¹, 郭燕¹, 胡雪雨¹, 冯卫生¹^,²^,^*

作者信息

1.河南中医药大学药学院, 河南郑州 450046

2.呼吸疾病诊疗与新药研发河南省协同创新中心, 河南郑州 450046

通讯作者:

*王彦志, Tel:86-371-65962746, E-mail:wangyzlb@126.com;

冯卫生, Tel:86-371-65680011, E-mail:fwsh@hactcm.edu.cn

Five new gingerol compounds from Zingiberis Rhizoma

Xiao-juan ZHANG¹, Yan-zhi WANG¹^,²^,^*, Man-qian LI¹, Zhi-min SONG¹, Yan GUO¹, Xue-yu HU¹, Wei-sheng FENG¹^,²^,^*

Affiliations

1. School of Pharmacy, Henan University of Chinese Medicine, Zhengzhou 450046, China

2. Respiratory Disease Diagnosis and Treatment and New Drug Development Henan Collaborative Innovation Center, Zhengzhou 450046, China

出版时间: 2020-10-12 doi: 10.16438/j.0513-4870.2020-0538

文章导航

摘要

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运用Diaion HP-20、Sephadex LH-20、硅胶、半制备高效液相等多种色谱分离技术分离纯化研究干姜中化学成分，利用理化性质及MS和NMR波谱学技术鉴定了5个姜辣素类化合物：4-（2-丁基-6-甲基-4H-吡喃-4-基）-2-甲氧基苯酚（1）、4-（2-己基-6-甲基-4H-吡喃-4-基）-2-甲氧基苯酚（2）、1-（4-羟基-3-甲氧基苯基）十三烷-3，5-二醇（3）、[10]-gingerdiol（4）和1-[1-（4-羟基-3-甲氧基苯基）-3-氧代-5-基]吡咯烷-2-酮（5a、5b），化合物1~3、5a、5b均为新化合物。

关键词

干姜 / 姜辣素 / 波谱技术 / 分离鉴定

Abstract

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We separated and purified five chemical constituents of dried ginger by Diaion HP-20, Sephadex LH-20, silica gel and semi-preparative high performance liquid chromatography. Five gingerols were identified by physicochemical properties and MS and NMR spectroscopy techniques:4-(2-butyl-6-methyl-4H-pyran-4-yl)-2-methoxyphenol (1), 4-(2-hexyl-6-methyl-4H-pyran-4-yl)-2-methoxyphenol (2), 1-(4-hydroxy-3-methoxyphenyl)tridecane-3, 5-diol (3), [10]-gingerdiol (4) and 1-[1-(4-hydroxy-3-methoxy phenyl)-3-oxodecan-5-yl]pyrrolidin-2-one (5a, 5b). Compounds 1-3, 5a, 5b are new compounds.

Key words

Zingiberis Rhizoma / gingerol / spectrum technology / isolation and identification

引用本文

张晓娟, 王彦志, 李曼倩, 宋志敏, 郭燕, 胡雪雨, 冯卫生. 干姜中五个新的姜辣素类化合物. 药学学报, 2020 , 55 (10) : 2421 -2427 . DOI: 10.16438/j.0513-4870.2020-0538

Xiao-juan ZHANG, Yan-zhi WANG, Man-qian LI, Zhi-min SONG, Yan GUO, Xue-yu HU, Wei-sheng FENG. Five new gingerol compounds from Zingiberis Rhizoma[J]. Acta Pharmaceutica Sinica, 2020 , 55 (10) : 2421 -2427 . DOI: 10.16438/j.0513-4870.2020-0538

正文

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干姜为姜科姜属植物姜(Zingiber offinicinale Rosc.)的干燥根茎^[1], 是一种用途广泛的药食两用的中药材^{[2, 3]}。主要产区为热带亚洲地区, 中国境内的姜科植物主要分布在西南部至东南部各省区, 其中云南省种类最多^[4]。味辛、性热, 归脾、胃、肾、心、肺经, 具有温中散寒、回阳通脉等功效^[5-7]。干姜中主要含有挥发油类、姜辣素类及二苯基庚烷类化学成分。现代药理学研究表明, 干姜中姜辣素具有镇痛抗炎、抗肿瘤、抗溃疡、抗缺氧、改善局部血液循环、止呕等多种药理作用^[8-14]。为明确干姜中姜辣素成分, 需对干姜中辣味成分进行系统研究。本实验采用Diaion HP-20、Sephadex LH-20、硅胶、半制备高效液相等多种色谱分离技术从干姜乙酸乙酯提取物中分离得到5个姜辣素成分, 分别是: 4-(2-丁基-6-甲基-4H-吡喃-4-基)-2-甲氧基苯酚(1)、4-(2-己基-6-甲基-4H-吡喃-4-基)-2-甲氧基苯酚(2)、1-(4-羟基-3-甲氧基苯基)十三烷-3, 5-二醇(3)、^[10]-gingerdiol (4)和1-[1-(4-羟基-3-甲氧基苯基)-3-氧代-5-基]吡咯烷-2-酮(5), 化合物1~3、5a、5b均为新化合物。结构见图 1。

结果与讨论

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化合物1 黄色油状液体, 易溶于甲醇及氯仿, UV (MeOH) λ_max (logε): 202 nm (1.09)、224 nm (0.49)、281 nm (0.09); $\left[ \alpha \right]_{\rm{D}}^{20}$-0.335 (c 0.810, MeOH)。HR-ESI-MS [M+H]⁺ m/z 275.164 1 (Calcd. 275.164 2), 提示化合物1的分子式为C₁₇H₂₂O₃, 不饱和度为7。遇FeCl₃显色剂显蓝色, 提示此化合物中含有酚羟基。分析其¹H NMR (500 MHz, CD₃OD)谱(表 1), 在低场区存在一组ABX耦合系统的苯环氢质子信号[δ_H 6.69 (1H, d, J = 8.0 Hz, H-5′), δ_H 6.67 (1H, s, H-2′), δ_H 6.59 (1H, d, J = 8.0 Hz, H-6′)]; 2个不饱和双键氢信号δ_H 5.83 (2H, d, J = 8.9 Hz, H-2, H-4); 1个甲氧基氢信号δ_H 3.79 (3H, s, -OCH₃); 2个甲基氢信号δ_H 2.82 (3H, s, H-10)及δ_H 0.94 (3H, t, J = 7.3 Hz, H-9); 1个次甲基氢信号δ_H 2.82 (1H, overlap, H-3); 3个亚甲基[δ_H 2.57 (2H, t, J = 7.4 Hz, H-6), δ_H 1.60 (2H, t, J = 7.4 Hz, H-7), δ_H 1.37 (2H, q, J = 7.5 Hz, H-8)]。根据¹³C NMR (125 MHz, CD₃OD)共发现17个碳信号, 其中δ_C 155.7 (C-5), δ_C 154.7 (C-1), δ_C 106.7 (C-2), δ_C 106.1 (C-4)为两个不饱和双键的碳信号; δ_C 148.7 (C-3′), δ_C 145.6 (C-4′), δ_C 134.3 (C-1′), δ_C 121.8 (C-6′), δ_C 116.0 (C-5′), δ_C 113.1 (C-2′)为苯环上的特征碳信号; δ_C 56.3为甲氧基碳信号; δ_C 35.3 (C-3)为次甲基碳信号; δ_C 31.6 (C-10)及δ_C 14.2 (C-9)为甲基碳信号; δ_C 31.4 (C-7), δ_C 28.6 (C-6), δ_C 23.2 (C-8)为亚甲基碳信号。化合物1的¹H-¹H COSY谱(图 2)中, 可观察到δ_H 2.57 (H-6)与δ_H 1.60 (H-7)的相关, δ_H 1.60 (H-7)与δ_H 1.37 (H-8)的相关, δ_H 1.37 (H-8)与δ_H 0.94 (H-9)的相关关系, 可推断存在四碳链。分析HSQC谱, 进一步确定C-H的数据归属。结合HMBC谱发现, δ_H 6.67 (H-2′)与δ_C 35.3 (C-3)相关及δ_H 6.59 (H-6′)与δ_C 35.3 (C-3)相关并结合氢谱ABX耦合系统的苯环可推断C-1′与C-3相连。根据δ_H 5.83 (H-2)/δ_C 106.1 (C-4)相关, δ_H 2.82 (H-3)与δ_C 134.3 (C-1′)、δ_C 154.7 (C-1)、δ_C 106.7 (C-2)相关; δ_H 5.83 (H-4)与δ_C 155.7 (C-5)相关并结合δ_C 155.7 (C-5)、δ_C 154.7 (C-1)的化学位移表明存在吡喃环。δ_H 2.82 (H-10)与δ_C 154.7 (C-1)、δ_C 106.7 (C-2)相关, 推断C-10与吡喃环C-1位相连。依据δ_H 2.57 (H-6)与δ_C 106.1 (C-4)、δ_C 155.7 (C-5)、δ_C 31.4 (C-7)、δ_C 23.2 (C-8)相关; δ_H 1.60 (H-7)与δ_C 23.2 (C-8)、δ_C 14.2 (C-9)相关并结合¹H-¹H COSY谱进一步确定C-6与C-7、C-7与C-8、C-8与C-9连接次序, 推断四碳链位于吡喃环C-5位上。化合物1含有一个手性中心, 经手性柱分析(CHIRALCEL IC手性柱, 环己烷:异丙醇=97:3, t = 13.019 min)确定化合物1为光学纯。为了确定化合物1的绝对构型, 采取量子化学计算的方法进行, 由于化合物1中侧链对CD的贡献不大, 却会产生多个构象增加量子化学计算的任务量, 因此对简化的化合物1 (即1a, 图 3)采用量子化学计算的方法[B3LYP-SCRF/6-31G (d, p)//B3LYP/6-31G (d, p), MeOH]计算了3S的ECD谱, 结果表明计算的ECD谱与化合物1的实验值吻合较好(图 3), 故确定化合物1的构型为3S, 综上所述, 化合物1为姜辣素类化合物, 故确定化合物1结构为4-(2-丁基-6-甲基-4H-吡喃-4-基)-2-甲氧基苯酚(1)。

化合物2 黄色油状液体, 易溶于甲醇及氯仿, UV (MeOH) λ_max (logε): 203 nm (1.63)、224 nm (0.80)、281 nm (0.15); IR谱显示该化合物结构中含有羟基(3 417 cm^-1)和双键及苯环(1 652、1 517 cm^-1); $\left[ \alpha \right]_{\rm{D}}^{20}$-0.914 (c 0.322, MeOH)。HR-ESI-MS [M+H]⁺ m/z 303.195 5 (Calcd. 303.195 5), 化合物2的分子式为C₁₉H₂₆O₃, 不饱和度为7。遇FeCl₃显色剂显蓝色, 提示此化合物中含有酚羟基。其¹H NMR (500 MHz, CD₃OD)谱与¹³C NMR (125 MHz, CD₃OD)数据(表 1)显示与化合物1相似, 仅在碳链长度不同, 故同为姜辣素类化合物。其氢谱数据如下, δ_H 6.70 (1H, d, J = 8.0 Hz, H-5′), δ_H 6.68 (1H, s, H-2′), δ_H 6.60 (1H, d, J = 8.0 Hz, H-6′), δ_H 5.83 (2H, d, J = 8.9 Hz, H-2, H-4), δ_H 3.80 (3H, s, -OCH₃), δ_H 2.82 (3H, s, H-12), δ_H 0.92 (3H, t, J = 7.0 Hz, H-11), δ_H 2.82 (1H, overlap, H-3), δ_H 2.57 (2H, t, J = 7.4 Hz, H-6), δ_H 1.62 (2H, t, J = 7.0 Hz, H-7), δ_H 1.34 (6H, overlap, H-8, H-9, H-10);根据¹³C NMR (125 MHz, CD₃OD)共发现19个碳信号, 数据如下δ_C 155.6 (C-5), δ_C 154.6 (C-1), δ_C 106.5 (C-2), δ_C 106.0 (C-4), δ_C 148.5 (C-3′), δ_C 145.5 (C-4′), δ_C 134.2 (C-1′), δ_C 121.6 (C-6′), δ_C 115.8 (C-5′), δ_C 113.0 (C-2′), δ_C 56.1 (-OCH₃), δ_C 35.1 (C-3), δ_C 31.2 (C-12), δ_C 14.2 (C-11), δ_C 32.6 (C-9), δ_C 29.7 (C-8), δ_C 29.2 (C-7), δ_C 28.8 (C-6), δ_C 23.5 (C-10)。分析HSQC谱, 进一步确定C-H的数据归属。结合HMBC谱(图 2)发现, 观察到δ_H 6.68 (H-2′)与δ_C 35.1 (C-3)相关; δ_H 6.60 (H-6′)与δ_C 35.1 (C-3)相关并结合氢谱ABX耦合系统的苯环可推断C-1′与C-3相连。δ_H 2.82 (H-3)与δ_C 134.2 (C-1′)、δ_C 154.6 (C-1)、δ_C 106.5 (C-2)相关; δ_H 5.83 (H-2)与δ_C 106.0 (C-4)相关; δ_H 5.83 (H-4)与δ_C 155.6 (C-5)相关并结合δ_C 155.6 (C-5)、δ_C 154.6 (C-1)的化学位移表明存在吡喃环, 依据δ_H 2.82 (H-12)与δ_C 154.6 (C-1)、δ_C 106.5 (C-2)相关, 推断C-12与C-1相连。δ_H 2.57 (H-6)与δ_C 106.0 (C-4), δ_C 155.6 (C-5), δ_C 29.7 (C-8)相关; δ_H 1.62 (H-7)与δ_C 32.6 (C-9)相关; δ_H 0.92 (H-11)与δ_C 32.6 (C-9)、δ_C 23.5 (C-10)相关并结合化合物2的¹H-¹H COSY谱(图 2), δ_H 2.57 (H-6)与δ_H 1.62 (H-7)相关、δ_H 1.62 (H-7)与δ_H 1.34 (H-8)相关、δ_H 1.34 (H-8)与δ_H 1.34 (H-9)相关、δ_H 1.34 (H-10)与δ_H 0.92 (H-11)相关进一步确定C-6与C-7、C-7与C-8、C-8与C-9、C-9与C-10、C-10与C-11连接次序, 推断六碳链位于吡喃环C-5位上。其绝对构型采用与化合物1类似的方法确定为3S, 综上所述, 确定化合物2结构为4-(2-己基-6-甲基-4H-吡喃-4-基)-2-甲氧基苯酚(2)。

化合物3 无色油状物, 易溶于甲醇、氯仿及乙酸乙酯, UV (MeOH) λ_max (logε): 203 nm (1.55)、281 nm (0.15); $\left[ \alpha \right]_{\rm{D}}^{20}$-3.041 (c 0.082, MeOH)。HR-ESI-MS [M+H]⁺ m/z 339.241 5 (Calcd. 339.249 1), 提示化合物3的分子式为C₂₀H₃₄O₄, 不饱和度为4。遇FeCl₃显色剂显蓝色, 提示此化合物中含有酚羟基。其¹H NMR (500 MHz, CD₃OD)谱与¹³C NMR (125 MHz, CD₃OD)数据(表 2)显示与化合物4相似, 较化合物4少一个碳, 故同为姜辣素类化合物。在芳香区存在3个氢质子信号, [δ_H 6.81 (1H, d, J = 8.0 Hz, H-5′), δ_H 6.69 (1H, s, H-2′), δ_H 6.67 (1H, d, J = 8.0 Hz, H-6′)]为ABX系统; 1个甲氧基氢信号和2个次甲基氢信号[δ_H 3.84 (5H, overlap, -OCH₃, H-3, H-5)]; 10个亚甲基氢信号[δ_H 2.67, 2.61(2H, m, H-1), δ_H 1.73 (2H, m, H-2), δ_H 1.60、1.50 (2H, overlap, H-4), δ_H 1.44 (2H, overlap, H-6), δ_H 1.24 (12H, overlap, H-7, H-8, H-9, H-10, H-11, H-12)]; 1个甲基氢信号[δ_H 0.85 (3H, t, J = 6.7 Hz, H-13)]。根据¹³C NMR (125 MHz, CDCl₃)共发现20个碳信号, 其中δ_C 146.4 (C-3′), δ_C 143.7 (C-4′), δ_C 133.9 (C-1′), δ_C 120.9 (C-6′), δ_C 114.3 (C-5′), δ_C 111.0 (C-2′)为苯环上碳信号; δ_C 73.4 (C-5), δ_C 72.4 (C-3)均为次甲基碳信号, 化学位移值偏低场, 推测应与吸电子基相连; δ_C 55.9 (-OCH₃)为甲氧基碳信号; δ_C 43.0 (C-4), δ_C 40.0 (C-2), δ_C 38.4 (C-6), δ_C 31.9 (C-11), δ_C 31.4 (C-1), δ_C 29.6 (C-8), δ_C 29.5 (C-9), δ_C 29.3 (C-10), δ_C 25.3 (C-7), δ_C 22.9 (C-12)均为亚甲基碳信号; δ_C 14.1 (C-13)为碳链末端甲基碳信号。综上所述, 以上数据与化合物4对照基本一致, 仅碳原子个数不同, 并结合质谱数据确定其结构, 故确定化合物3结构为1-(4-羟基-3-甲氧基苯基)十三烷-3, 5-二醇(3)。

化合物5 无色油状物, 易溶于甲醇, IR谱显示该化合物结构中含有羟基(3 337 cm^-1)和羰基(1 673 cm^-1); $\left[ \alpha \right]_{\rm{D}}^{20}$-4.062 (c 0.100, MeOH)。HR-ESI-MS [M+H]⁺ m/z 362.232 6 (Calcd. 362.232 6), 提示化合物5的分子式为C₂₁H₃₁NO₄, 不饱和度为7。遇FeCl₃显色剂显蓝色, 提示此化合物中含有酚羟基。分析其¹H NMR (500 MHz, CD₃OD)谱(表 3), 在芳香区存在3个氢质子信号[δ_H 6.76 (1H, s, H-2′), δ_H 6.67 (1H, d, J = 8.0 Hz, H-5′), δ_H 6.60 (1H, d, J = 8.0 Hz, H-6′)]为ABX系统; 1个甲氧基氢信号δ_H 3.82 (3H, s, -OCH₃); 1个次甲基氢信号δ_H 4.39 (1H, m, H-5); 10个亚甲基氢信号[δ_H 3.24 (2H, m, H-14), δ_H 2.75 (4H, m, H-1, H-2), δ_H 2.62 (2H, m, H-4), δ_H 2.27 (2H, m, H-12), δ_H 1.91 (2H, m, H-13), δ_H 1.45 (2H, m, H-6), δ_H 1.27 (2H, overlap, H-9), δ_H 1.22 (4H, overlap, H-7, H-8)]和1个甲基氢信号δ_H 0.88 (3H, t, J = 6.8 Hz, H-10)。根据¹³C NMR (125 MHz, CD₃OD)共发现21个碳信号, 其中1个碳信号被氘代甲醇溶剂峰覆盖, 可根据HSQC确定。δ_C 210.4 (C-3)为酮羰基; δ_C 177.7 (C-11)为内酰胺羰基; δ_C 148.9 (C-3′), δ_C 145.8 (C-4′), δ_C 134.0 (C-1′), δ_C 121.8 (C-6′), δ_C 116.1 (C-5′), δ_C 113.3 (C-2′)为苯环上的特征碳信号; δ_C 56.4为甲氧基碳信号; δ_C 48.0 (C-5)为次甲基碳信号; δ_C 46.6 (C-4), δ_C 45.2 (C-2), δ_C 32.4 (C-12), δ_C 33.1 (C-6), δ_C 32.5 (C-8), δ_C 44.2 (C-14), δ_C 30.3 (C-1), δ_C 26.9 (C-7), δ_C 23.6 (C-9), δ_C 19.1 (C-13)为亚甲基碳信号; δ_C 14.3 (C-10)为甲基碳信号。分析HSQC谱, 进一步确定C-H的数据归属。根据化合物5的HMBC谱(图 4)中, 观察到δ_H 6.76 (H-2′)与δ_C 30.3 (C-1)、δ_C 121.8 (C-6′)、δ_C 145.8 (C-4′)相关, δ_H 6.60 (H-6′)与δ_C 30.3 (C-1)、δ_C 113.3 (C-2′)、δ_C 145.8 (C-4′)相关进一步证实苯环为ABX耦合系统, 根据δ_H 2.75 (H-1)与δ_C 45.2 (C-2)、δ_C 210.4 (C-3)、δ_C 134.0 (C-1′)相关, δ_H 2.62 (H-4)与δ_C 210.4 (C-3)、δ_C 48.0 (C-5)、δ_C 33.1 (C-6)相关, δ_H 4.39 (H-5)与δ_C 33.1 (C-6)相关, δ_H 1.45 (H-6)与δ_C 32.5 (C-8)相关, δ_H 0.88 (H-10)与δ_C 32.5 (C-8)、δ_C 23.6 (C-9)相关可推断C-1与C-1′相连, 并结合化合物5的¹H-¹H COSY谱(图 4)显示, δ_H 2.62 (H-4)与δ_H 4.39 (H-5)相关, δ_H 4.39 (H-5)与δ_H 1.45 (H-6)相关, δ_H 1.45 (H-6)与δ_H 1.22 (H-7)相关, δ_H 1.27 (H-9)与δ_H 0.88 (H-10)相关可推断为十碳链, 根据化合物5的¹H-¹H COSY谱(图 4)显示, δ_H 2.27 (H-12)与δ_H 1.91 (H-13)相关, δ_H 1.91 (H-13)与δ_H 3.24 (H-14)相关, 结合HMBC谱, 根据δ_H 1.91 (H-13)与δ_C 177.7 (C-11)、δ_C 32.4 (C-12)、δ_C 44.2 (C-14)相关确定了五元内酰胺的结构并根据C-5位氢谱及碳谱数据, 推断内酰胺片段连接在C-5位上。注意到化合物5含有一个手性中心, 经手性柱分析(CHIRALCEL AD-H手性柱, 环己烷:异丙醇=9:1, t_a = 15.832 min, t_b = 18.972 min)确定化合物5为消旋体, 通过手性拆分, 分离成化合物5a及5b。为了确定化合物5a及5b的绝对构型, 采取量子化学计算的方法进行, 由于化合物5中侧链对CD的贡献不大, 却会产生多个构象增加量子化学计算的任务量, 因此对简化的化合物5 (即5A, 图 5)采用量子化学计算的方法[B3LYP-SCRF/6-31G(d, p)//B3LYP/6-31G(d, p), MeOH]计算了5S的ECD谱, 结果表明计算的ECD谱与化合物5a的实验值吻合较好(图 5), 故确定化合物5的一对对映体的构型分别为5S及5R, 即5a及5b的构型为分别为5S及5R, 综上所述, 化合物5为姜辣素类化合物, 故确定化合物5结构为1-[1-(4-羟基-3-甲氧基苯基)-3-氧代-5-基]吡咯烷-2-酮。

实验部分

收起

TripleTOF 6600型高效液相色谱-四极杆飞行时间高分辨质谱联用仪(AB SCIEX); LC3000型半制备高效相色谱仪(赛普锐思公司); Bruker AM-500MHz核磁共振谱用超导核磁共振仪, TMS做内标; Thermo Nicolet IS10红外光谱仪(Thermo Scientific, USA); Rudolph AP-Ⅳ型旋光仪(Rudolph, USA); Thermo EVO300紫外分光光度计(Thermo Scientific, USA); 1260 1nfinity Ⅱ高效液相色谱仪; RE-5210A型旋转蒸发仪(上海亚荣生化仪器厂); N-1100型旋转蒸发仪(东京理化仪器有限公司); Sephadex LH-20 (Parmacia Biotech公司); SMB100-20/45型反相柱色谱材料RP-1 (日本富士公司); 硅胶正相色谱填料(青岛海洋化工厂); Kromasil 100-5 C18 column型分析色谱柱; CHIRALCEL IC及AD-H手性柱; 色谱纯及分析纯试剂(天津四友精细化学品有限公司)。

干姜购自安徽亳州, 产地为四川省宜宾市, 经河南中医药大学董诚明教授鉴定为姜科草本植物姜Z. offccinale Rosc.的干燥根茎。保存于河南中医药大学中药化学提取分离实验室, 标本号: BS631005。

1 提取分离

取干姜50 kg, 粉碎成粗粉后用乙酸乙酯(200 L)浸泡1 h, 之后回流提取(75 ℃, 3×200 L×1.5 h), 45 ℃水浴减压浓缩得总提物稠膏4 kg。总提物用60%的乙醇溶解后, 经Diaion HP-20大孔吸附树脂色谱柱, 依次用60%乙醇、80%乙醇、95%乙醇梯度洗脱, 收集后减压浓缩得到相应的部位(Fr.1~Fr.3)。然后将组分Fr.1 (1.5 kg)上硅胶柱(100~200目), 流动相采用二氯甲烷/甲醇梯度洗脱, 分为7段(Fr.1.1~Fr.1.7)。组分Fr.1.1 (500 g)再次过硅胶柱(200~300目), 流动相采用石油醚/丙酮梯度洗脱, 划分为9小段(Fr.1.1.1~Fr.1.1.9)。将组分Fr.1.1.6 (198 g)再过硅胶柱(100~200目), 流动相采用石油醚/乙酸乙酯梯度洗脱, 得到7个组分(Fr.1.1.6.1~Fr.1.1.6.7)。随后以甲醇为洗脱剂, 组分Fr.1.1.6.3 (19 g)经过Sephadex LH-20柱色谱, 得到5个组分(Ⅰ~Ⅴ)。组分Ⅲ通过半制备型HPLC (210 nm, 254 nm)在YMC HPLC柱(双波长紫外检测器203 nm、254 nm, 250 mm×10 mm, 5 μm, 流速3 mL·min^-1)进行纯化得到化合物2 (16.1 mg, 82%甲醇水溶液, t_R = 34.651 min)和化合物5 (5.0 mg, MeOH/H₂O, 79%, t_R = 28.665 min); 组分Ⅳ通过半制备型HPLC在YMC HPLC柱(流速3 mL·min^-1)进行纯化得到化合物1 (40.5 mg, MeOH/H₂O, 65%, t_R = 23.109 min); 组分Fr.1.1.6.6 (25 g)经过Sephadex LH-20柱色谱, 得到5个组分(a~e)。组分a通过半制备型HPLC在YMC HPLC柱(流速3 mL·min^-1)进行纯化得到化合物4 (16.6 mg, 65%甲醇水溶液, t_R = 20.031 min); 组分b通过半制备型HPLC在YMC HPLC柱(流速3 mL·min^-1)进行纯化得到化合物3 (4.1 mg, 58%甲醇水溶液, t_R = 25.643 min)。

2 数据归属

化合物1 黄色油状液体, 易溶于甲醇及氯仿, 遇FeCl₃显色剂显蓝色, $\left[ \alpha \right]_{\rm{D}}^{20}$-0.335 (c 0.810, MeOH)。HR-ESI-MS [M+H]⁺ m/z 275.164 1 (Calcd. 275.164 2), 化合物1的分子式为C₁₇H₂₂O₃。UV (MeOH) λ_max (logε) 202 nm (1.09)、224 nm (0.49)、281 nm (0.09); ¹H NMR (500 MHz, CD₃OD)和¹³C NMR (125 MHz, CD₃OD)数据见表 1。

化合物2 黄色油状液体, 易溶于甲醇及氯仿, 遇FeCl₃显色剂显蓝色, $\left[ \alpha \right]_{\rm{D}}^{20}$-0.914 (c 0.322, MeOH)。HR-ESI-MS [M+H]⁺ m/z 303.195 5 (Calcd. 303.195 5), 化合物2的分子式为C₁₉H₂₆O₃。UV (MeOH) λ_max (logε) 203 nm (1.63)、224 nm (0.80)、281 nm (0.15); IR (MeOH) ν_max: 3 417、1 652、1 517 cm^-1; ¹H NMR (500 MHz, CD₃OD)和¹³C NMR (125 MHz, CD₃OD)数据见表 1。

化合物3 无色油状物, 易溶于甲醇、氯仿及乙酸乙酯, 遇FeCl₃显色剂显蓝色, $\left[ \alpha \right]_{\rm{D}}^{20}$-3.041 (c 0.082, MeOH)。HR-ESI-MS [M+H]⁺ m/z 339.249 1 (Calcd. 339.249 1), 提示化合物3的分子式为C₂₀H₃₄O₄。UV (MeOH) λ_max (logε) 203 nm (1.55)、281 nm (0.15); ¹H NMR (500 MHz, CDCl₃)和¹³C NMR (125 MHz, CDCl₃)数据见表 2。

化合物4 无色油状物, 易溶于甲醇、氯仿及乙酸乙酯, 遇FeCl₃显色剂显蓝色。HR-ESI-MS [M+Na]⁺m/z 375.245 0 (Calcd. 375.350 6), 分子式为C₂₁H₃₆O₄。¹H NMR (500 MHz, CDCl₃) δ_H 6.84 (1H, d, J= 8.2 Hz, H-5′), 6.73 (1H, s, H-2′), 6.71 (1H, d, J = 8.2 Hz, H-6′), 3.99 (2H, overlap, H-3, H-5), 3.89 (3H, s, -OCH₃), 2.73、2.64 (2H, m, H-1), 1.85、1.76 (2H, m, H-2), 1.66 (2H, overlap, H-4), 1.54、1.44 (2H, overlap, H-6), 1.24 (14H, overlap, H-6, H-7, H-8, H-9, H-10, H-11, H-12, H-13), 0.85 (3H, t, J = 6.7 Hz, H-14)。¹³C NMR (125 MHz, CDCl₃) δ_C 146.4 (C-3′), 143.7 (C-4′), 133.9 (C-1′), 120.9 (C-6′), 114.3 (C-5′), 111.0 (C-2′), 69.7 (C-5), 69.0 (C-3), 55.9 (-OCH₃), 42.3 (C-4), 39.4 (C-2), 37.5 (C-6), 32.0 (C-12), 31.9 (C-1), 29.6 (C-8), 29.6 (C-9), 29.6 (C-10), 29.3 (C-11), 25.8 (C-7), 22.7 (C-13), 14.1 (C-14)。以上数据与文献^[15]对照基本一致, 同为姜辣素类化合物, 故确定化合物4为^[10]-gingerdiol (4)。

化合物5a 无色油状物, 易溶于甲醇, 遇FeCl₃显色剂显蓝色, $\left[ \alpha \right]_{\rm{D}}^{20}$-18.323 (c 0.024, MeOH)。HR-ESI-MS [M+H]⁺ m/z 362.232 6 (Calcd. 362.232 6), 提示化合物5的分子式为C₂₁H₃₁NO₄。UV (MeOH) λ_max (logε) 203 nm (1.36)、282 nm (0.11); IR (MeOH) ν_max: 3 362、1 669、1 449 cm^-1; ¹H NMR (500 MHz, CD₃OD)和¹³C NMR (125 MHz, CD₃OD)数据见表 3。

化合物5b 无色油状物, 易溶于甲醇, 遇FeCl₃显色剂显蓝色, $\left[ \alpha \right]_{\rm{D}}^{20}$-4.507 (c 0.026, MeOH)。UV (MeOH) λ_max (logε) 203 nm (1.42)、282 nm (0.12); IR (MeOH) ν_max: 3 337、1 673、1 452 cm^-1; ¹H NMR (500 MHz, CD₃OD)和¹³C NMR (125 MHz, CD₃OD)数据见表 3。

作者贡献:王彦志、张晓娟、冯卫生设计研究; 张晓娟、李曼倩、宋志敏、郭燕和胡雪雨进行了研究并分析了数据; 王彦志给出了关于论文写作的建议, 张晓娟写了论文。所有作者都阅读并批准了最后的手稿。

利益冲突:作者声明不存在利益冲突。

基金

收起

河南中医药大学科技创新团队项目资助(2015XCXTD02)
河南省高等学校重点科研项目计划(19A360012)

参考文献

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文献

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2020年第55卷第10期

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doi: 10.16438/j.0513-4870.2020-0538

接收时间：2020-04-13
首发时间：2026-01-23
出版时间：2020-10-12

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收稿日期：2020-04-13
修回日期：2020-07-17

基金

河南中医药大学科技创新团队项目资助(2015XCXTD02)

河南省高等学校重点科研项目计划(19A360012)

作者信息

1.河南中医药大学药学院, 河南郑州 450046

2.呼吸疾病诊疗与新药研发河南省协同创新中心, 河南郑州 450046

通讯作者:

*王彦志, Tel:86-371-65962746, E-mail:wangyzlb@126.com;

冯卫生, Tel:86-371-65680011, E-mail:fwsh@hactcm.edu.cn

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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Position	1		2
1′	-	134.3		-	134.2
2′	6.67 (1H, s)	113.1	6.68 (1H, s)	113.0
3′	-	148.7	-	148.5
4′	-	145.6	-	145.5
5′	6.69 (1H, d, J = 8.0 Hz)	116.0	6.70 (1H, d, J = 8.0 Hz)	115.8
6′	6.59 (1H, d, J = 8.0 Hz)	121.8	6.60 (1H, d, J = 8.0 Hz)	121.6
1	-	154.7	-	154.6
2	5.83 (1H, d, J = 8.9 Hz)	106.7	5.83 (1H, d, J = 8.9 Hz)	106.5
3	2.82 (1H, overlap)	35.3	2.82 (1H, overlap)	35.1
4	5.83 (1H, d, J = 8.9 Hz)	106.1	5.83 (1H, d, J = 8.9 Hz)	106.0
5	-	155.7	-	155.6
6	2.57 (2H, t, J = 7.4 Hz)	28.6	2.57 (2H, t, J = 7.4 Hz)	28.8
7	1.60 (2H, t, J = 7.4 Hz)	31.4	1.62 (2H, t, J = 7.0 Hz)	29.2
8	1.37 (2H, q, J = 7.5 Hz)	23.2	1.34 (2H, overlap)	29.7
9	0.94 (3H, t, J = 7.3 Hz)	14.2	1.34 (2H, overlap)	32.6
10	2.82 (3H, s)	31.6	1.34 (2H, overlap)	23.5
11	-	-	0.92 (2H, t, J = 7.0 Hz)	14.2
12	-	-	2.82 (3H, s)	31.2
-OCH₃	3.79 (3H, s)	56.3	3.80 (3H, s)	56.1

Position

δ_H

δ_C

δ_H

δ_C

1′

134.3

134.2

2′

6.67 (1H, s)

113.1

6.68 (1H, s)

113.0

3′

148.7

148.5

4′

145.6

145.5

5′

6.69 (1H, d, J = 8.0 Hz)

116.0

6.70 (1H, d, J = 8.0 Hz)

115.8

6′

6.59 (1H, d, J = 8.0 Hz)

121.8

6.60 (1H, d, J = 8.0 Hz)

121.6

154.7

154.6

5.83 (1H, d, J = 8.9 Hz)

106.7

5.83 (1H, d, J = 8.9 Hz)

106.5

2.82 (1H, overlap)

35.3

2.82 (1H, overlap)

35.1

5.83 (1H, d, J = 8.9 Hz)

106.1

5.83 (1H, d, J = 8.9 Hz)

106.0

155.7

155.6

2.57 (2H, t, J = 7.4 Hz)

28.6

2.57 (2H, t, J = 7.4 Hz)

28.8

1.60 (2H, t, J = 7.4 Hz)

31.4

1.62 (2H, t, J = 7.0 Hz)

29.2

1.37 (2H, q, J = 7.5 Hz)

23.2

1.34 (2H, overlap)

29.7

0.94 (3H, t, J = 7.3 Hz)

14.2

1.34 (2H, overlap)

32.6

2.82 (3H, s)

31.6

1.34 (2H, overlap)

23.5

0.92 (2H, t, J = 7.0 Hz)

14.2

2.82 (3H, s)

31.2

-OCH₃

3.79 (3H, s)

56.3

3.80 (3H, s)

56.1

Position	δ_H	δ_C
1′		133.9
2′	6.69 (1H, s)	111.0
3′		146.4
4′		143.7
5′	6.81 (1H, d, J = 8.0 Hz)	114.3
6′	6.67 (1H, d, J = 8.0 Hz)	120.9
1	2.67, 2.61 (2H, m)	31.4
2	1.73 (2H, m)	40.0
3	3.84 (1H, overlap)	72.4
4	1.60, 1.50 (2H, overlap)	43.0
5	3.84 (1H, overlap)	73.4
6	1.44 (2H, overlap)	38.4
7	1.24 (2H, overlap)	25.3
8	1.24 (2H, overlap)	29.6
9	1.24 (2H, overlap)	29.5
10	1.24 (2H, overlap)	29.3
11	1.24 (2H, overlap)	31.9
12	1.24 (2H, overlap)	22.9
13	0.85 (3H, t, J = 6.7 Hz)	14.1
14
-OCH₃	3.86 (3H, s)	55.9

Position

δ_H

δ_C

1′

133.9

2′

6.69 (1H, s)

111.0

3′

146.4

4′

143.7

5′

6.81 (1H, d, J = 8.0 Hz)

114.3

6′

6.67 (1H, d, J = 8.0 Hz)

120.9

2.67, 2.61 (2H, m)

31.4

1.73 (2H, m)

40.0

3.84 (1H, overlap)

72.4

1.60, 1.50 (2H, overlap)

43.0

3.84 (1H, overlap)

73.4

1.44 (2H, overlap)

38.4

1.24 (2H, overlap)

25.3

1.24 (2H, overlap)

29.6

1.24 (2H, overlap)

29.5

1.24 (2H, overlap)

29.3

1.24 (2H, overlap)

31.9

1.24 (2H, overlap)

22.9

0.85 (3H, t, J = 6.7 Hz)

14.1

-OCH₃

3.86 (3H, s)

55.9

Position	δ_H	δ_C
1′	-	134.0
2′	6.76 (1H, s)	113.3
3′	-	148.9
4′	-	145.8
5′	6.67 (1H, d, J = 8.0 Hz)	116.1
6′	6.60 (1H, d, J = 8.0 Hz)	121.8
1	2.75 (2H, m)	30.3
2	2.75 (2H, m)	45.2
3	-	210.4
4	2.62 (2H, m)	46.6
5	4.39 (1H, m)	48.0
6	1.45 (2H, m)	33.1
7	1.22 (2H, overlap)	26.9
8	1.22 (2H, overlap)	32.5
9	1.27 (2H, overlap)	23.6
10	0.88 (3H, t, J = 6.8 Hz)	14.3
11	-	177.7
12	2.27 (2H, m)	32.4
13	1.91 (2H, m)	19.1
14	3.24 (2H, m)	44.2
-OCH₃	3.82 (3H, s)	56.4

Position

δ_H

δ_C

1′

134.0

2′

6.76 (1H, s)

113.3

3′

148.9

4′

145.8

5′

6.67 (1H, d, J = 8.0 Hz)

116.1

6′

6.60 (1H, d, J = 8.0 Hz)

121.8

2.75 (2H, m)

30.3

2.75 (2H, m)

45.2

210.4

2.62 (2H, m)

46.6

4.39 (1H, m)

48.0

1.45 (2H, m)

33.1

1.22 (2H, overlap)

26.9

1.22 (2H, overlap)

32.5

1.27 (2H, overlap)

23.6

0.88 (3H, t, J = 6.8 Hz)

14.3

177.7

2.27 (2H, m)

32.4

1.91 (2H, m)

19.1

3.24 (2H, m)

44.2

-OCH₃

3.82 (3H, s)

56.4