8-羟基香叶醇、8-羟基橙花醇、8-羟基芳樟醇及其衍生物的制备与表征大马士革玫瑰中几种化学成分的研究
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摘要
单萜类化合物是由2个异戊烯单位构成,含10个碳原子的化合物类群,是植物挥发油的主要成分。单萜类化合物按骨架结构可以分为链状型和环状型两大类。链状单萜的含氧衍生物,如8-羟基香叶醇、8-羟基橙花醇和8-羟基芳樟醇等,多具有较强的生物活性和浓郁的香气,是医药、化妆品和食品工业的重要原料。同时,8-羟基香叶醇还是单萜类化合物及药用价值广泛的单萜吲哚类生物碱,如利血平、喜树碱等生物合成的关键中间体。本研究的内容之一就是分别以香叶醇、橙花醇及芳樟醇为原料,经SeO2和t-BuOOH氧化、NaBH4还原得到三个二醇化合物,为8-羟基香叶醇、8-羟基橙花醇及8-羟基芳樟醇,然后利用乙酰化反应及苯甲酰化反应分别制备了这三个二醇化合物的乙酰化及苯甲酰化衍生物。进一步以GC-EI-MS及LC-ESI-MS研究了所合成化合物的色谱和质谱性质。结果显示,以GC-MS表征这些化合物时不能得到它们的分子离子峰,而在LC-MS方法中则可以清楚地观察到这些化合物分子离子峰的信号。这些工作为研究植物中的单萜类化合物的生物合成提供了重要的工具。
玫瑰(Rosa)为蔷薇科蔷薇属植物,在全世界范围内种植很广,主要分布于北半球,以保加利亚、土耳其、摩洛哥、法国、俄罗斯等国家为主,我国亦有栽培。玫瑰的品种繁多,其中大马士革玫瑰(Rosa damascena)中富含单萜类化合物,本研究内容之二是以陕西渭南产的大马士革玫瑰花为研究对象,采用溶剂萃取法,柱层析分离法分离大马士革玫瑰花中的化学成分,并且利用GC/MS分析寻找出大马士革玫瑰花中的8-羟基香叶醇和8-羟基芳樟醇这两个含氧单萜衍生物,同时在研究过程中亦分离出了两个化合物。这些工作为大马士革玫瑰花中主要香气成分的分析提供了一种新的方法,也为研究大马士革玫瑰花中萜类化合物的生物合成途径提供了重要的基础。
Monoterpenes have two prenyl units in structure, containing 10 carbon atoms. They are the main components of plant volatile oil. According to the skeleton structures, monoterpenes can be divided into two types:acyclic type and cyclic-type. Oxygen-containing monoterpene derivatives, such as 8-hydroxygeraniol,8-hydroxynerol and 8-hydroxylinalool, etc. have strong biological activity and are rich in aroma, they are the important materials of pharmaceutical, cosmetic and food industries. Moreover,8-hydroxygeraniol is not only a key intermediate of monoterpene biosynthesis, but also plays a critical role in the biosynthetic pathway for the monoterpene-indole alkaloids, such as reserpine and camptothecin which have wide ranges of medicinal values. In this study we synthesized three oxygen-containing acyclic monoterpene derivatives by oxidation of geraniol, nerol and linalool with SeO2/ter-buty hydroperoxide, then reduction with NaBH4. 8-hydroxygeraniol, 8-hydroxynerol and 8-hydroxylinalool were obtained by this strategy. The acetylated and benzoylated derivatives of these alcohols were prepared by respective acetylation and benzoylation. Furthermore, all these compounds were characterized by GC-EI-MS and LC-ESI-MS respectively and the results showed that only in ESI-MS, the signals of molecular ions of these compounds were able to be clearly observed. This effort provides a useful tool for the study of biosynthesis of monoterpenoids in plants.
Rose (Rosa) belongs to the family of the Rosaceae and is planted world widely, mainly in the northern hemispheric countries, such as Bulgaria, Turkey, Morocco, France, Russia, etc. It is also cultivated in our country. There are many kinds of roses among which Rosa damascena contains abundant monoterpenes. What we used in this study is the R. damascena planted in Weinan, Shaanxi Province. The flowers of plant were extrcated with organic solvents, isolated with solica gel chromatography and the fractions that might contain the oxidized acyclic monoterpenes, eg.8-hydroxygeraniol,8-hydroxynerol and 8-hydroxylinalool, were analysed with GC-MS to find out where they located. In the course of the study, two more compounds were also purified and elucidated. The work has not only provided a new method for the determination of the main aromatic components of Rosa damascena, but also built up an important foundation for the study of biosynthesis of monoterpenoids in the plant
玫瑰(Rosa)为蔷薇科蔷薇属植物,在全世界范围内种植很广,主要分布于北半球,以保加利亚、土耳其、摩洛哥、法国、俄罗斯等国家为主,我国亦有栽培。玫瑰的品种繁多,其中大马士革玫瑰(Rosa damascena)中富含单萜类化合物,本研究内容之二是以陕西渭南产的大马士革玫瑰花为研究对象,采用溶剂萃取法,柱层析分离法分离大马士革玫瑰花中的化学成分,并且利用GC/MS分析寻找出大马士革玫瑰花中的8-羟基香叶醇和8-羟基芳樟醇这两个含氧单萜衍生物,同时在研究过程中亦分离出了两个化合物。这些工作为大马士革玫瑰花中主要香气成分的分析提供了一种新的方法,也为研究大马士革玫瑰花中萜类化合物的生物合成途径提供了重要的基础。
Monoterpenes have two prenyl units in structure, containing 10 carbon atoms. They are the main components of plant volatile oil. According to the skeleton structures, monoterpenes can be divided into two types:acyclic type and cyclic-type. Oxygen-containing monoterpene derivatives, such as 8-hydroxygeraniol,8-hydroxynerol and 8-hydroxylinalool, etc. have strong biological activity and are rich in aroma, they are the important materials of pharmaceutical, cosmetic and food industries. Moreover,8-hydroxygeraniol is not only a key intermediate of monoterpene biosynthesis, but also plays a critical role in the biosynthetic pathway for the monoterpene-indole alkaloids, such as reserpine and camptothecin which have wide ranges of medicinal values. In this study we synthesized three oxygen-containing acyclic monoterpene derivatives by oxidation of geraniol, nerol and linalool with SeO2/ter-buty hydroperoxide, then reduction with NaBH4. 8-hydroxygeraniol, 8-hydroxynerol and 8-hydroxylinalool were obtained by this strategy. The acetylated and benzoylated derivatives of these alcohols were prepared by respective acetylation and benzoylation. Furthermore, all these compounds were characterized by GC-EI-MS and LC-ESI-MS respectively and the results showed that only in ESI-MS, the signals of molecular ions of these compounds were able to be clearly observed. This effort provides a useful tool for the study of biosynthesis of monoterpenoids in plants.
Rose (Rosa) belongs to the family of the Rosaceae and is planted world widely, mainly in the northern hemispheric countries, such as Bulgaria, Turkey, Morocco, France, Russia, etc. It is also cultivated in our country. There are many kinds of roses among which Rosa damascena contains abundant monoterpenes. What we used in this study is the R. damascena planted in Weinan, Shaanxi Province. The flowers of plant were extrcated with organic solvents, isolated with solica gel chromatography and the fractions that might contain the oxidized acyclic monoterpenes, eg.8-hydroxygeraniol,8-hydroxynerol and 8-hydroxylinalool, were analysed with GC-MS to find out where they located. In the course of the study, two more compounds were also purified and elucidated. The work has not only provided a new method for the determination of the main aromatic components of Rosa damascena, but also built up an important foundation for the study of biosynthesis of monoterpenoids in the plant
引文
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[12]LEES. Fumigation toxicity of monoterpenoids to several stored product insects[J]. Journal of Stored Products Research,2003,39(1):77-85
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[16]涂胜豪,陈哲.雷公藤治疗类风湿关节炎的现状和存在的问题[J].中国中西医结合研究,2009, 1 (1):42-44
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[18]Schalk M., Clark A., Miles R. B., et al. Redirection of cytosolic or plastidic isoprenoid precursors elevates terpene production in plants[J]. Nat Biotechnol,2006,24(11):1441-1447
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