CN109096242A - 一种肉豆蔻醚的制备方法及新用途 - Google Patents

一种肉豆蔻醚的制备方法及新用途 Download PDF

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CN109096242A
CN109096242A CN201811007777.5A CN201811007777A CN109096242A CN 109096242 A CN109096242 A CN 109096242A CN 201811007777 A CN201811007777 A CN 201811007777A CN 109096242 A CN109096242 A CN 109096242A
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myristicin
chinese medicine
volatile oil
compound
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杜树山
郭姗姗
耿珠峰
费超
冯怡溪
王杨
曹菊琴
庞雪
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Beijing Normal University
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    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/62—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to atoms of the carbocyclic ring
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    • A01N43/30—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3 with two oxygen atoms in positions 1,3, condensed with a carbocyclic ring

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Abstract

本发明涉及一种用于防治中药材仓储害虫的化合物肉豆蔻醚，其制备方法及其对中药材仓储害虫触杀及驱避活性。本发明的原料丰富，生产工艺简单，生产成本低，对中药材仓储害虫的触杀及驱避等效果较好，有望开发成绿色有机农药。

Description

一种肉豆蔻醚的制备方法及新用途
技术领域
本发明属于中药材仓储生产技术领域，尤其涉及一种肉豆蔻醚的制备方法及用于防治中药材仓储害虫的用途。
背景技术
中药历史悠久，是中华民族数千年来同疾病斗争过程中形成的智慧结晶，以其独特的疗效在美容养生、疾病预防、疑难杂病的治疗方面起到了不可替代的作用，正逐渐被世界认可。近年来，随着中医药在我国医疗体系中地位的不断上升，国家近期相继出台《中医药健康服务发展规划(2015-2020年)》，《中医药发展战略规划纲要(2016-2030 年)》等政策及中国首个自然科学领域诺贝尔奖的获得，极大地推动了中医药国际化的发展。但是，每年我国中药材由于仓储病虫害防治不当已严重影响中医临床的用药安全和中药在国际市场上的竞争力。中药材被虫蛀后形成孔洞，甚至被蛀成粉状，不仅使药材重量减少，也使药材疗效降低甚至丧失，虫粪、虫尸及分泌物会滋生致病菌、霉菌等污染药材，对人体的健康造成威胁。中药材的仓储害虫种类很多，其中药材甲(Stegobium paniceum)、烟草甲(Lasioderma serricorne)和赤拟谷盗(Tribolium castaneum)等为优势种群。据调查，全国常用600多种中药材中约有70％会遭受虫害，每年造成的经济损失达数亿元。
目前中药材仓储病虫害使用硫磺、磷化铝等熏蒸化学防治为主，长期、过量的使用化学农药造成农残超标、害虫抗药性增加及环境污染等问题，带来的中药安全问题也引起了广泛关注。而对抗同贮法是利用具有特殊气味，能起驱虫防霉作用的药材(对抗药材)与易生虫发霉的药材(同贮药材)共存以达防虫防霉的方法，是中药材贮藏与养护经典方法之一，是我国人民长期实践经验积累和总结。受此启发，人们对中药材仓储害虫防治的研究已逐渐转移到从天然植物中找寻抗虫成分，开发绿色防护剂，也是符合世界绿色环保的潮流趋势，对促进中医药事业可持续发展及国际化具有重要的意义。
假黄皮(Clausena excavata Burm.f.)为芸香科黄皮属植物，多省地均产。假黄皮种子当中含有肉豆蔻醚，试验表明其具有高效、低毒绿色安全的特性，对中药材仓储害虫具有很好的防治效果。本发明提供一种原料丰富，生产工艺简单，生产成本低的肉豆蔻醚提取制备方法，并将制备出的肉豆蔻醚用于中药材仓储病虫害防治。
发明内容
本发明的目的在于提供一种肉豆蔻醚的制备方法及用于防治中药材仓储害虫的用途。
本发明的目的还在于提供上述化合物的制备方法，通过该方法，可得到用于防治中药材仓储害虫的效果显著、工艺简单的化合物。
本发明提供了防治中药材仓贮害虫的化合物的制备方法，由以下步骤组成：
1、挥发油提取：取假黄皮种子，粉碎后置挥发油提取器中，采用水蒸气蒸馏法提取5～ 7h，以无水硫酸钠干燥处理，即得挥发油。挥发油存储于冰箱保鲜室4℃备用。挥发油出油率为0.1～0.3％。
2、化合物分离：假黄皮种子挥发油8～20ml，经正相硅胶柱层析，采用石油醚，石油醚-乙酸乙酯，乙酸乙酯依次梯度洗脱分段，回收溶剂，获得25个馏分段，馏分段9经正相硅胶柱层析分离，得到化合物肉豆蔻醚1.5～5.0g。
该方法工艺简单，适合工业化生产，生产成本低。
本发明的目的还在于提供肉豆蔻醚防治中药材仓储害虫的新用途。将肉豆蔻醚用于对中药材仓储害虫烟草甲、赤拟谷盗等的防治，有极好的触杀及驱避活性。
肉豆蔻醚用于对中药材仓储害虫的使用方法为：本产品可以进行空仓喷洒，直接毒杀仓虫；或在储存药材时进行驱避防虫。
附图说明
图1肉豆蔻醚化学结构式
图2肉豆蔻醚1H-NMR谱图
图3肉豆蔻醚13C-NMR谱图
图4肉豆蔻醚EI-MS谱图
具体实施方式
为了更清晰说明发明目的和技术方案，借助下述实施例进一步详述。
实施例：
1、挥发油提取：取假黄皮种子，粉碎后置挥发油提取器中，采用水蒸气蒸馏法提取6h，以无水硫酸钠干燥处理，即得挥发油。挥发油存储于冰箱保鲜室4℃备用。挥发油出油率为 0.24％。
2、化合物分离：假黄皮挥发油10ml，经正相硅胶柱层析，采用正己烷，正己烷-乙酸乙酯，乙酸乙酯依次梯度洗脱分段，回收溶剂，获得25个馏分段，馏分段9经正相硅胶柱层析分离，得到化合物肉豆蔻醚2.5g。
3、结构鉴定：肉豆蔻醚
淡黄色油，C11H12O3；ESI-MS m/z:192.0[M]+；1H-MNR(500MHz,CDCl3)δ(ppm):3.32(2H,d,J＝6.5Hz,1-CH2),3.91(3H,s,3′-OCH3),5.09(2H,m,3-CH2),5.95(2H,s, O-CH2-O),5.96(1H,m,2-H),6.38(1H,s,6’-H),6.41(1H,s,2′-H)；13C-NMR(125MHz, CDCl3)δ(ppm):40.2(C-1),56.6(-OCH3),101.2(O-CH2-O),102.7(C-6′),107.8(C-2 ′),115.8(C-3),133.5(C-1′),134.6(C-4′)137.3(C-2),143.5(C-3′),148.8(C-5 ′)。将该化合物的核磁数据与文献[1]报道的1H-NMR和13C-NMR数据进行比较，确定化合物为肉豆蔻醚。
4、作用效果试验研究：
4.1触杀活性测试
肉豆蔻醚对赤拟谷盗和中药材甲的触杀活性的测试参照文献所述方法[2]：将羽化一周左右的成虫从培养瓶中取出，制备5个不同浓度的肉豆蔻醚正己烷稀释液，用移液枪点滴0.5μL 于试虫的前胸背板上(置于冰袋上操作)，处理后放入直径2.5cm，高5.5cm玻璃瓶中，正己烷为对照组，每个浓度重复5次，每个重复10头试虫。处理组与对照组置于温度为(29 ±1)℃，相对湿度为(75±5)％的恒温培养箱中培养24h，观察和记录试虫的死亡情况，计算LD50。LD50值按文献方法[3]采用Probit(IBM SPSS V20.0)分析计算。
实验用药：本发明实施例1的化合物；
阳性对照药：除虫菊酯；
结果见表1。
表1肉豆蔻醚对赤拟谷盗和烟草甲的触杀活性
4.2驱避活性测试
肉豆蔻醚对赤拟谷盗和烟草甲的的驱避活性的测试参照文献所述方法[4]，将直径为9cm 的圆形滤纸从中间裁为两半，用移液枪吸取500μL肉豆蔻醚正己烷稀释液(设定5个浓度： 78.63、15.73、3.15、0.63和0.31nL/cm2，每个浓度5次重复)滴于其中一半滤纸上，另一半用空白溶剂处理作为对照，自然晾干30s，用固体胶相向粘贴在培养皿底部(皿壁涂上聚四氟乙烯)。把20头试虫倒入培养皿中央，观察记录2h和4h时处理与对照滤纸上试虫的分布情况，计算驱避率PR(％)，公式如下：
PR(％)＝[(Nc-Nt)/(Nc+Nt)]×100
Nc是空白对照滤纸上试虫的数量，Nt是给药组滤纸上试虫的数量。
实验用药：本发明实施例1的化合物；
阳性对照药：避蚊胺；
结果见表2、表3。
表2肉豆蔻醚在2h对中赤拟谷盗和烟草甲的驱避率(PR％±SE)
表3肉豆蔻醚在4h对赤拟谷盗和烟草甲的驱避率(PR％±SE)
结论：以上实验结果显示，本发明化合物对防治中药材仓储害虫中药材甲、赤拟谷盗等具有极好的防治效果。
以上描述了本发明优选实施方式，然其并非用以限定本发明。本领域技术人员对在此公开的实施方案可进行不偏离本发明范畴和精神的改进和变化。
综上所述，本发明具有以下优点：
1、本发明方法，原料丰富，生产工艺简单，生产成本低。
2、本发明用途用于中药材仓储害虫的防治，对中药材仓储害虫赤拟谷盗、烟草甲等有极好的触杀及驱避活性。
3、本发明用途具有高效绿色安全的特性，有望开发成绿色防护剂。
参考文献
[1]Passreiter,C.M.,Akhtar,Y.and Isman,M.B.2005.Insecticidal activityof the essential oil of Ligusticum mutellina roots.Zeitschrift furNaturforschung C-A Journal of Biosciences.60,411–414.
[2]Liu,Z.L.,Ho,S.H.,1999.Bioactivity of the essential oil extractedfrom Evodia rutaecarpa Hook f.et Thomas against the grain storage insects,Sitophilus zeamais Motsch.and Tribolium castaneum(Herbst).Journal of StoredProducts Research,35,317–328.
[3]Sakuma,M.Probit analysis of preference data,1998.AppliedEntomology and Zoology,33,339–347.
[4]Zhang,J.S.,Zhao,N.N.,Liu,Q.Z.,Liu,Z.L.,Du,S.S.,Zhou,L.,Deng,Z.W.,2011.Repellent constituents of essential oil of Cymbopogon distans aerialparts against two stored-product insects.Journal of agricultural and foodchemistry,59,9910–9915.

Claims (2)

1.一种用于防治中药材仓储害虫的化合物肉豆蔻醚的制备方法，其特征在于，包括以下步骤：
1)挥发油提取：取假黄皮种子，粉碎后置挥发油提取器中，采用水蒸气蒸馏法提取5-7h，以无水硫酸钠干燥处理，即得挥发油。挥发油存储于冰箱保鲜室4℃备用。
2)化合物分离：假黄皮种子挥发油8-20ml，经正相硅胶柱层析，采用正己烷，正己烷-乙酸乙酯，乙酸乙酯依次梯度洗脱分段，回收溶剂，获得25个馏分段，馏分段9经正相硅胶柱层析分离，得到化合物肉豆蔻醚1.5-5.0g。
2.权利要求1所述的化合物肉豆蔻醚在防治中药材仓储害虫中的应用。
CN201811007777.5A 2018-08-31 2018-08-31 一种肉豆蔻醚的制备方法及新用途 Pending CN109096242A (zh)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115399324A (zh) * 2022-10-10 2022-11-29 天津农学院 一种τ-杜松醇的制备方法及用途
CN115399324B (zh) * 2022-10-10 2024-03-12 天津农学院 一种τ-杜松醇的制备方法及用途

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Application publication date: 20181228