Journal of Organic Chemistry Research
Vol.05 No.04(2017), Article ID:22981,5 pages
10.12677/JOCR.2017.54021

Studies on Chemical Constituents from the Style of Zea mays

Ling Zhang, Tiandong Zhang, Weiyao Hu, Baokun Zhu, Bo Cai, Qianxu Yang, Wei Zhao, Yinliang Zhao

R&D Center, China Tobacco Yunnan Industrial Co., Ltd, Kunming Yunnan

Received: Nov. 21st, 2017; accepted: Dec. 3rd, 2017; published: Dec. 11th, 2017

ABSTRACT

In order to discovery activity ingredients, the chemical component of style of Zea mays was studied. Chemical constituents of style of Zea mays were isolated by silica gel, sephadex LH-20, and Rp-18 column chromatography. And their structures were elucidated by spectral methods. Twelve compounds were isolated, and their structures were identified as 7-hydroxy-4’-methoxyisoflavone (1), chrysoeriol-6-C-α-boivinopyranosyl-7-O-β-glucopyranoside (2), stigmasta-4-en-3β, 6β-diol (3), 7α-hydroxysitosterol (4), daucosterol plamitate (5), 7α-hydroxysitosterol-3-O-β-D-glucopyranoside (6), palmitic acid (7), daucosterol (8), p-hydroxycinnamic acid (9), vanillic acid (10), soya-cere- broside I (11), β-sitosterol (12). Above all compounds were obtained from this plant for the first time.

Keywords:Zea mays, Chemical Constituents, Isolation, Identification

云南糯玉米龙须的化学成分研究

张玲,张天栋,胡巍耀,朱保昆,蔡波,杨干栩,赵蔚,赵英良

云南中烟工业有限责任公司,云南 昆明

收稿日期:2017年11月21日;录用日期:2017年12月3日;发布日期:2017年12月11日

摘 要

本论文研究了云南产的糯玉米的化学成分。采用正相硅胶、凝胶及反相材料进行化合物的分离和纯化,采用IR、NMR、MS等现代波谱分析鉴定化合物的结构。结果:从云南产的糯玉米中分离得到个12化合物,它们分别为:7-羟基-4’-甲氧基异黄酮(1)、柯伊利素-6-C-β-波伊文糖-7-O-β-葡萄糖苷(2)、豆甾-4-烯-3β,6β-二醇(3)、7α-羟基谷甾醇(4)、胡萝卜苷棕榈酸酯(5)、7α-羟基谷甾醇-3-O-β-D-葡萄糖苷(6)、棕榈酸(7)、胡萝卜苷(8)、对羟基桂皮酸(9)、香草酸(10)、大豆脑苷I (11)和 β-谷甾醇(12),以上化合物为首次从该植物中分离得到。

关键词 :糯玉米,化学成分,分离,鉴定

Copyright © 2017 by authors and Hans Publishers Inc.

This work is licensed under the Creative Commons Attribution International License (CC BY).

http://creativecommons.org/licenses/by/4.0/

1. 引言

糯玉米龙须是农作物糯玉米(Zea mays)的花序,糯玉米是普通玉米发生突变再经人工选育而成的新类型,营养丰富,口感好,具有防癌抗癌的功效,是天然的营养保健食品 [1] 。基于其较好的营养价值,在云南地区广泛种植,其玉米须产量很大,作为常用的中药资源,民间以玉米须煮水服用治疗水肿、高血压和糖尿病,无毒副作用,具有一定的疗效。相关药理研究表明玉米须有抗癌、降血压、降血糖、增强免疫功能和抑制黄曲霉毒素等作用 [2] 。基于以上,本课题组首次对云南产糯玉米须的化学成分进行了研究,从中分离得到12化合物,它们分别为:7-羟基-4’-甲氧基异黄酮(1)、柯伊利素-6-C-β-波伊文糖-7-O-β-葡萄糖苷(2)、豆甾-4-烯-3β,6β-二醇(3)、7α-羟基谷甾醇(4)、胡萝卜苷棕榈酸酯(5)、7α-羟基谷甾醇-3-O-β-D-葡萄糖苷(6)、棕榈酸(7)、胡萝卜苷(8)、对羟基桂皮酸(9)、香草酸(10)、大豆脑苷I (11)和β-谷甾醇(12)。以上化合物为首次从该植物中分离得到。

2. 仪器与材料

柱层析和薄层层析硅胶板购自于青岛海洋化工厂;RP-18反相材料为Merck公司生产;葡聚糖凝胶Pharmadex LH-20为安法玛西亚技术上海有限公司生产;质谱数据由Agilent G3250AA LC/MSD TOF质谱仪测定;NMR在Bruker AV-500型核磁共振波谱仪测定(TMS为内标,δ为ppm,J为Hz)。

植物样品糯玉米须于2016年8月收购于云南西双版纳;标本保存于云南中烟工业有限责任公司技术中心(标本号:2016-zl-1)。

3. 提取与分离

2.0 kg阴干粉碎后的糯玉米须经60%的乙醇室温提取48 h,重复3次,过滤回收乙醇得到总浸膏(320 g)。浸膏用水分散后依次用石油醚、氯仿、乙酸乙酯和正丁醇萃取,得到石油醚提取物(85 g),氯仿提取物(34 g),乙酸乙酯提取物(51 g)和正丁醇提取物(90 g)。

氯仿提取物(34 g)经硅胶柱层析梯度洗脱[氯仿–甲醇(99:1-6:1)],等量接收并合并相同组分得到5个部分(Fr.A1-Fr.A5)。Fr.A2经硅胶柱层析经硅胶柱层析[石油醚–丙酮(4:1)]洗脱得到化合物5 (25 mg)。Fr.A3经硅胶柱层析[石油醚–丙酮(3:1)]洗脱得到化合物6 (20 mg)和7 (8 mg)。Fr.A5经硅胶柱层析[石油醚–丙酮(2:1)]洗脱得到化合物8 (15 mg)、10 (19 mg)、11 (28 mg)和12 (35 mg)。

乙酸乙酯部分(51 g)经硅胶柱层析[氯仿–甲醇(100:1-4:1)]梯度洗脱,等量接收并合并相同部分得到7个部分(Fr.B1-Fr.B7)。Fr.B2 (1.4 g)经硅胶柱层析[石油醚–丙酮(2: 1)]洗脱得到化合物9 (10 mg)。

正丁醇部分(90 g)经D101大孔吸附树脂脱糖得到浸膏(61 g),经硅胶柱层析[氯仿–甲醇–甲酸 (95:5:1-30:10:1)]梯度洗脱,等量接收并合并相同组分得到7个部分(Fr.C1-Fr.C7)。Fr.C2 (4.1 g)经聚酰胺柱层析[水:甲醇(1:0-0:1)]、Rp18反相硅胶柱层析[水:甲醇 (2:1-1:2)]和凝胶柱层析(甲醇)得到化合物1 (5 mg)和3 (6 mg)。Fr.C3 (1.2 g)经硅胶柱层析[氯仿–甲醇(6:1)]洗脱得到化合物4 (11 mg)。Fr.C5 (1.1 g)经硅胶柱层析[氯仿–甲醇(5:1)]洗脱得到化合物2 (11 mg)。

4. 结构鉴定

化合物1:白色针状结晶(甲醇)。1H NMR (400 MHz, MeOD) δ:8.29 (1H, s, H-2),7.51 (2H, d, J = 8.2, H-2’, 6’),6.89 (2H, d, J = 8.4, H-3’, 5’),7.95 (1H, d, J = 8.8, H-5),6.90 (1H, dd, J = 8.8, 2.0, H-6),6.83 (1H, s, H-8),3.73 (3H, s, 4-OCH3)。13C NMR (100 MHz, MeOD) δ:151.2 (C-2),121.1 (C-3),172.5 (C-4),114.8 (C-4a),125.6 (C-5),113.5 (C-6),160.4 (C-7),100.4 (C-8),155.2 (C-8a),122.9 (C-1'),128.5 (C-2'),111.3 (C-3'),157.2 (C-4'),111.3 (C-5'),128.2 (C-6'),53.0 (4-OCH3)。以上数据与文献 [3] 报道一致,鉴定化合物1为刺芒柄花素(7-羟基-4’-甲氧基异黄酮).

化合物2:黄色无定形粉末,1H NMR (400 MHz, pyridine-d5) δ:7.55 (1H, d, J = 8.4 Hz, H-6'),7.52 (1H, s, H-2'),7.20 (1H, s, H-8),7.00 (1H, d, J = 8.4 Hz, H-5'),6.87 (1H, s, H-3),6.25 (1H, d, J = 12.2 Hz, H-1),5.42 (1H, d, J = 7.6 Hz, H-1'),3.56 (3H, s, 3'-OCH3),1.43 (3H, d, J = 6.6 Hz, H-6);13C NMR (100 MHz, pyridine-d5) δ:164.1 (C-2),103.9 (C-3),183.0 (C-4),159.1 (C-5),113.9 (C-6),163.5 (C-7),95.1 (C-8),156.8 (C-9),105.9 (C-10),122.0 (C-1'),110.0 (C-2'),148.5 (C-3'),152.0 (C-4'),116.2 (C-5'),120.6 (C-6'),65.8 (C-1),31.4 (C-2),67.8 (C-3),71.1 (C-4),71.9 (C-5),17.2 (C-6),103.2 (C-1'),74.7 (C-2'),77.0 (C-3'),70.9 (C-4'),79.2 (C-5'),61.3 (C-6'),55.4 (3'-OCH3)。以上数据与文献 [4] 报道一致,鉴定化合物2为柯伊利素-6-C-β-波伊文糖-7-O-β-葡萄糖苷。

化合物3:白色无定形粉末,1H NMR (400 MHz, CDCl3) δ:5.81 (1H, brs, H-4),4.39 (1H, brs, H-6),4.38 (1H, brs, H-3),1.40 (3H, s, H-19),0.93 (3H, d, J = 6.2 Hz, H-21),0.75 (3H, s, H-18);13C NMR (100 MHz, CDCl3) δ:36.8 (C-1),29.3 (C-2),73.2 (C-3),129.0 (C-4),146.9 (C-5),67.2 (C-6),29.9 (C-7),55.8 (C-8),36.2 (C-9),37.1 (C-10),40.0 (C-11),39.5 (C-12),42.7 (C-13),56.5 (C-14),24.9 (C-15),29.5 (C-16),56.0 (C-17),12.1 (C-18),21.5 (C-19),29.2 (C-20),18.7 (C-21),34.0 (C-22),26.1 (C-23),45.9 (C-24),30.2 (C-25),19.6 (C-26),19.9 (C-27),23.4 (C-28),11.9 (C-29)。以上数据与文献 [5] 报道一致,鉴定化合物3为豆甾-4-烯-3β,6β-二醇。

化合物4:白色无定形粉末,1H NMR (400 MHz, CDCl3) δ:5.65 (1H, d, J = 5.2 Hz, H-6),3.91 (1H, m, H-7),3.62 (1H, m, H-3),1.06 (3H, s, H-19),0.95 (3H, d, J = 6.2 Hz, H-21),0.74 (3H, s, H-18);13C NMR (100 MHz, CDCl3) δ:37.4 (C-1),31.8 (C-2),71.9 (C-3),42.5 (C-4),146.8 (C-5),124.5 (C-6),65.9 (C-7),37.6 (C-8),42.8 (C-9),37.9 (C-10),21.3 (C-11),39.6 (C-12),42.7 (C-13),49.9 (C-14),24.9 (C-15),28.8 (C-16),56.4 (C-17),12.3 (C-18),18.7 (C-19),36.6 (C-20),19.4 (C-21),34.3 (C-22),29.7 (C-23),46.5 (C-24),26.6 (C-25),19.3 (C-26),20.2 (C-27),23.5 (C-28),12.6 (C-29)。以上数据及显色与文献 [5] 报道一致,鉴定化合物4为7α-羟基谷甾醇。

化合物5:白色无定形粉末,1H NMR (400 MHz, CDCl3) δ:5.30 (1H, brs, H-6),4.32 (1H, d, J = 7.2 Hz, H-1'),0.95 (3H, s, H-19),0.65 (3H, s, H-18);13C NMR (100 MHz, CDCl3) δ:37.2 (C-1),28.1 (C-2),79.5 (C-3),38.8 (C-4),140.3 (C-5),122.0 (C-6),31.8 (C-7),31.8 (C-8),50.1 (C-9),36.7 (C-10),21.0 (C-11),39.6 (C-12),42.3 (C-13),56.6 (C-14),24.7 (C-15),28.5 (C-16),56.1 (C-17),11.7 (C-18),19.4 (C-19),36.1 (C-20),18.8 (C- 21),34.0 (C-22),26.2 (C-23),45.8 (C-24),29.1 (C-25),19.6 (C-26),19.0 (C-27),23.0 (C-28),11.9 (C-29),101.2 (C-1'),73.3 (C-2'),76.2 (C-3'),70.2 (C-4'),73.7 (C-5'),63.3 (C-6'),174.1 (C-1),34.2 (C-2),24.8 (C-3),29.2~30.2 (C-4-13),31.8 (C-14),22.6 (C-15),14.1 (C-16)。以上数据与文献 [6] 报道一致,鉴定化合物5为胡萝卜苷棕榈酸酯。

化合物6:白色无定形粉末,1H NMR (400 MHz, CD3OD) δ:5.59 (1H, d, J = 5.2 Hz, H-6),4.40 (1H, d, J = 7.6 Hz, H-1'),3.68 (2H, m, H-3, 7),1.03 (3H, s, H-19),0.99 (3H, d, J = 6.6 Hz, H-21),0.75 (3H, s, H-18);13C NMR (100 MHz, CD3OD):38.6 (C-1),30.9 (C-2),79.9 (C-3),40.2 (C-4),146.8 (C-5),125.7 (C-6),66.3 (C-7),39.3 (C-8),43.8 (C-9),39.4 (C-10),22.3 (C-11),41.2 (C-12),43.7 (C-13),50.9 (C-14),25.5 (C-15),29.8 (C-16),57.7 (C-17),12.8 (C-18),19.2 (C-19),37.9 (C-20),19.8 (C-21),35.5 (C-22),30.8 (C-23),47.7 (C-24),27.6 (C-25),19.8 (C-26),20.7 (C-27),24.6 (C-28),12.4 (C-29),102.8 (C-1'),75.5 (C-2'),78.4 (C-3'),71.9 (C-4'),78.6 (C-5'),63.2 (C-6')。以上数据与文献 [7] 报道一致,鉴定化合物6为7α-羟基谷甾醇-3-O-β-D-葡萄糖苷。

化合物7:白色无定形粉末,1H NMR (400 MHz, CDCl3) δ:2.35 (2H, t, J = 7.4 Hz, H-2),2.06 (2H, m, H-3),1.65 (2H, m, H-4),1.27 (2H, m, H-15),0.90 (2H, t, J = 7.4 Hz, H-16),1.33 (20H, m, H-5-14);13C NMR (100 MHz, CDCl3) δ:179.2 (C-1),33.2 (C-2),31.1 (C-3),29.0 (C-4-13),24.0 (C-14),24.0 (C-15),21.9 (C-16)。以上数据与文献 [6] 报道一致,鉴定化合物7为棕榈酸。

化合物8:白色无定形粉末,1H NMR (400 MHz, pyridine-d5) δ:5.31 (1H, brs, H-6),5.00 (1H, d, J = 7.4Hz, H-1'),1.01 (3H, d, J = 5.4 Hz, H-21),0.90 (3H, s, H-19),0.85 (6H, d, J = 6.6 Hz, H-26, 27),0.63 (3H, s, H-18);13C NMR (100 MHz, pyridine-d5) δ:37.9 (C-1),28.8 (C-2),79.1 (C-3),39.9 (C-4),141.4 (C-5),122.4 (C-6),32.7 (C-7),32.6 (C-8),50.9 (C-9),37.5 (C-10),21.8 (C-11),40.6 (C-12),42.9 (C-13),57.4 (C-14),25.0 (C-15),26.9 (C-16),56.8 (C-17),12.7 (C-18),20.5 (C-19),36.9 (C-20),19.5 (C-21),34.7 (C-22),23.9 (C-23),46.7 (C-24),30.7 (C-25),19.9 (C-26),19.8 (C-27),29.9 (C-28),12.5 (C-29),103.1 (C-1'),75.8 (C-2'),78.9 (C-3'),72.2 (C-4'),78.6 (C-5'),63.2 (C-6')。以上数据与文献 [6] 报道一致,鉴定化合物8为胡萝卜苷。

化合物9:黄色粉末,1H NMR (400 MHz, DMSO-d6) δ:7.55 (2H, d, J = 8.4 Hz, H-2, 6),7.53 (1H, d, J = 15.6 Hz, H-7),6.82 (2H, d, J = 8.2 Hz, H-3, 5),6.34 (1H, d, J = 16.0 Hz, H-8)。13C NMR (100 MHz, DMSO-d6) δ:124.9 (C-1),129.1 (C-2, 6),115.0 (C-3, 5),158.8 (C-4),143.4 (C-7),114.6 (C-8),167.2 (C-9)。以上数据与文献 [8] 报道一致,鉴定化合物9为对羟基桂皮酸。

化合物10:淡黄色粉末,1H NMR (400 MHz, DMSO-d6) δ:12.33 (1H, s, COOH),7.68 (1H, s, 4-OH),3.72 (3H, s, OCH3),6.73 (1H, dd, J = 6.6, 2.4 Hz, H-5),7.35 (1H, dd, J = 6.6, 2.2 Hz, H-6),7.32 (1H, d, J = 2.2 Hz, H-2)。13C NMR (100 MHz, DMSO-d6) δ:168.2 (COOH),56.3 (OCH3),122.6 (C-1),113.7 (C-2),148.3 (C-3),152.2 (C-4),116.1 (C-5),124.3 (C-6)。以上数据与文献 [8] 报道一致,鉴定化合物10为香草酸。

化合物11:白色粉末,1H NMR (400 MHZ, pyridine-d5) δ:5.94 (1H, dd, J = 16.0, 11.0 Hz, H-4),5.48 (1H, d, J = 16.0 Hz, H-5),5.47 (1H, m, H-9),5.26 (1H, m, H-8),4.88 (1H, dd, J = 11.0, 5.4 Hz, H-1),4.46 (1H, m, H-2′),4.16 (1H, m, H-3),3.54 (1H, m, H-2),0.83 (6H, t, J = 5.4 Hz, H-18, 16′);13C NMR (100 MHz, pyridine-d5) δ:72.0 (C-1),55.1 (C-2),72.8 (C-3),131.7 (C-4),132.6 (C-5),33.4 (C-6),32.6 (C-7),130.3 (C-8),132.3 (C-9),33.1 (C-10),29.6~30.2 (C-11-16),23.4 (C-17),14.8 (C-18);176.2 (C-1′),72.8 (C-2′),36.1 (C-3′),25.8 (C-4′),29.6~30.0 (C-5-15′),14.7 (C-16′),106.2 (C-1′′),75.6 (C-2′′),79.1 (C-3′′),70.9 (C-4′′),79.0 (C-5′′),63.2 (C-6′′)。以上数据与文献 [6] 报道一致,鉴定化合物11鉴定为大豆脑苷I。

化合物12:白色针尖(氯仿),1H NMR (400 MHz, CDCl3) δ:3.61 (1H, m H-3),5.45 (1H, m, H-6),0.77 (3H, s, 18-CH3),1.11 (3H, s, 19-CH3),1.02 (3H, J = 6.4 Hz, 21-CH3)。1H NMR (100 MHz, CDCl3) δ:37.7 (C-1),32.1 (C-2),72.3 (C-3),42.7 (C-4),141.1 (C-5),122.2 (C-6),32.3 (C-7),32.3 (C-8),51.6 (C-9),36.9 (C-10),21.5 (C-11),40.1 (C-12),42.8 (C-13),57.2 (C-14),24.7 (C-15),28.8 (C-16),56.4 (C-17),12.5 (C-18),19.8 (C-19),36.6 (C-20),19.2 (C-21),34.5 (C-22),26.5 (C-23),46.3 (C-24),30.2 (C-25),20.3 (C-26),19.5 (C-27),23.6 (C-28),12.5 (C-29)。以上数据与文献 [9] 报道一致,鉴定化合物12为β-谷甾醇。

5. 结论

通过现代分离技术手段,从云南产糯玉米须中分离得到12个化合物,它们分别为:7-羟基-4’-甲氧基异黄酮(1)、柯伊利素-6-C-β-波伊文糖-7-O-β-葡萄糖苷(2)、豆甾-4-烯-3β,6β-二醇(3)、7α-羟基谷甾醇(4)、胡萝卜苷棕榈酸酯(5)、7α-羟基谷甾醇-3-O-β-D-葡萄糖苷(6)、棕榈酸(7)、胡萝卜苷(8)、对羟基桂皮酸(9)、香草酸(10)、大豆脑苷I (11)和β-谷甾醇(12)。以上化合物为首次从云南产糯玉米须中分离得到,为开发利用云南产糯玉米须提供科学依据。

致谢

本研究工作得到了云南中烟工业有限责任公司科技项目(2017CP04)的经费支持。

文章引用

张 玲,张天栋,胡巍耀,朱保昆,蔡 波,杨干栩,赵 蔚,赵英良. 云南糯玉米龙须的化学成分研究
Studies on Chemical Constituents from the Style of Zea mays[J]. 有机化学研究, 2017, 05(04): 159-163. http://dx.doi.org/10.12677/JOCR.2017.54021

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