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题名: 狗筋蔓、短瓣花及三种木兰科植物的化学成分研究
作者: 程永现
学位类别: 博士
答辩日期: 2000
授予单位: 中国科学院昆明植物研究所
授予地点: 中国科学院昆明植物研究所
导师: 周俊
学位专业: 植物学
中文摘要: 本论文主要由三部分组成。第一部分共二章,详细论述了石竹科二种植物狗筋蔓(Cucubalus baccifer)及短瓣花(Brachystemma calycinum)中新化合物的结构解析;第二部分分三章,分别介绍了对木兰科三种植物云南拟单性木兰(Parakmeria yunnanensis)、粗梗木莲(Manglietia crassipes)及壮丽含笑(Michelia lacei)的化学成分研究的情况;论文的第三部分综述了木兰科7属22种植物木脂体类成分的研究进展。利用植物化学的各种材料及方法(包括常压、低压硅胶柱层析,真空液相层析,制备薄层层析,D_(101)大孔树脂,Diaion HP 20,MCI-gel CHP 20P SephadexLH-20及Rp-18等),从以上五种植物中共分离得到105个单体化合物(重复者未计入),鉴定了其中65个,19个为新化合物,已鉴定的化合物结构类型涉及降倍半萜及其苷、倍半萜、吡咯烷酮及其过氧化物、植物蜕皮甾酮(C_(19),C_(27),C_(28))及其苷、黄酮醇及其苷、苯丙素、木脂素及其苷、芳环取代物、生物碱、植物环肽等。一、二种石竹科植物的化学成分研究1.狗筋蔓的化学成分研究作为石竹科植物化学研究的继续,我们对采自云南的石竹科植物狗筋蔓进行了系统化学研究,从其全草的乙醇提取物中共分离得到30个单体成分,鉴定了6个新奇化合物,即狗筋蔓醇(cucubalsol,1),狗筋蔓内酯(cucubalactone,2),drummondol 3-0-β.D-glueopyranoside(3),狗筋蔓二醇(cucubaldiol,4),狗筋蔓内酰胺(cucubalactam,5),6-methoxypiperidin-2-one(6);除上述化合物外,还鉴定了1 3个已知化合物,即5,7(E)-megastigmadiene-3β,4α,9ξ-triol(7),drummondol(8),ecdysterone(9),24(28)-ecdysterone A(10),22-deoxyecdysterone(11),25-hydroxypanuosterone(12),暗红牛膝甾酮(rubrosterone,13),2,22一dideoxyecdysterone 3.glucoside(14),5,7,4'-三羟基黄酮(5,7,4'-trihydroxyflavone,15),松柏酸(4-hydroxy-3-methoxybenzopropanyl acid,16),4一羟基苯甲醛(4一hydroxybenzoaldehyde,17),4-羟基苯甲酸(4-hydroxybenzoic acid,18)及pterolactam(19)。化合物1-6为新成分,其中化合物1-4为4个新奇的降倍半萜衍生物,化合物5为1个新奇的吡咯烷酮类过氧化物;对化合物4进行了X-ray晶体衍射分析;从β-紫罗兰醇类似物开始,对降倍半萜衍生物提出了生物合成途径假设;用三氧化铬氧化的方法对几个降倍半萜类化合物进行了化学转化和沟通,制备了3个新的衍生物;本植物检测到了环肽的存在,由于量微,我们未进行分离,但在用茚三酮试剂追踪分离环肽的过程中,偶然发现有一类内酰胺化合物不需经矿酸水解,而在硅胶板上遇茚三酮试剂加热即可呈现阳性(红色)反应,这与一般的内酰胺化合物需水解后才与茚三酮显色是不同的,经分析认为此类化合物的显色机理可能与内酰胺环中氮的另一邻位具有偕氧取代基,易于开环使胺基暴露有关。目前还未见到文献上有此类化合物遇茚三酮试剂加热即可显色的报道,由此提示与茚三酮试剂显阳性反应的不仅有氨基酸、直链肽,可能还有此类酰胺。2.短瓣花的化学成分研究短瓣花为一民间草药,具有祛风除湿、利尿、强筋骨之功能,从其根的乙醇提取物中共分离得到32个单体成分,鉴定了其中17个,分别为短瓣花环肽A-E(braehystemin A-E,1-5),短瓣花啶A-E(braehystemidine A-E,6-10),5".乙酰短瓣花啶D(5"-acetylbraehystemidine D,11),短瓣花苷A(braehystemoside A,12),L-焦谷氨酸甲酯(methyl L-pyroglutamate,13),腺嘌呤核苷(adenosine,14),2一吡咯甲酸(2-minaline,15),吡咯-2-羧酸.3'-糠酯(3'-furfuryl-pyrrole-2-earboxylate,16)及α-D.乙基葡萄糖苷(ethyl α-D-glueopyranoside,17)。化合物1-5为5个新的环八肽,化合物6-11为6个结构新奇的生物碱(其中化合物11为一新的人工产物),化合物12为一新的2-吡咯甲酸的葡萄糖酯苷;对短瓣花环肽E(brachystemin E)进行了X-ray晶体衍射分析;化合物4即短瓣花环肽D(brachystemin D)含有一不常见氨基酸,即硫氧化蛋氨酸,在核磁共振谱中,惟独此氨基酸呈现对峰,比例约为3:2,其原因可能与此氨基酸中亚砜的锥形结构在溶液中的旋转受阻从而引起对映异构有关,当然这需要进一步证明。但是应该指出硫氧化蛋氨酸在石竹科是首次发现。这类硫氧化蛋氨酸组成的环肽在番荔枝科植物中已有发现,这一点似乎能进一步证明周俊研究员提出的石竹科是由番荔枝科进化而来的观点。二、三种木兰科植物的化学成分研究1.云南拟单性木兰的化学成分研究从云南拟单性木兰干燥嫩枝的乙醇提取物中共分离得到20个单体化合物,鉴定了其中13个,分别为云南拟单性木兰素A(parakmerin.A,1),eupomatenoid-7(2),eupomatenoid-5(3),(+)-isolariciresinol(4),(+)-5'-methoxyisolariciresinol(5),lingueresinol(6),(+)-isolariciresinol 9-O-β-D-glucopyranoside(7),丁香苷(syringin,8),槲皮素(quercetin,9),芦丁(rutin,10),棕榈酸一1一甘油酯(palmitic acid-2,3-dihydroxy-propanenyl ester,11),二十三烷酸一1一甘油酯(tricosanoic acid-2,3一dihydroxy-propanenyl ester,12)及蜡酸-1一甘油酯(cerotic acid-2,3-dihydroxy-propanenyl ester,13)。其中化合物1为一新的eupomatene型木脂素,其他已知化合物均为首次从该植物中分到。2.粗梗木莲的化学成分研究从粗梗木莲干燥嫩枝的乙醇提取物中共分离得到15个成分,鉴定了其中10个,分别为原儿茶醛(protocatechualdehyde,1),4-羟基苯甲醛(4-hydroxybenzoaldehyde,2),3,5-二甲氧基-4-羟基-苯甲醛(3,5-dimethoxy-4-hydroxybenzoaldehyde,3),香草醛(vanillin,4),2,5-二甲氧基苯醌(2,5-dimethoxybenzoquinone,5),松柏醛(coniferylaldehyde,6),丁香醛(syringaldehyde,7),丁香苷(syringin,8),(+)-syringaresinol(9)及cryptomeridiol(10)。化合物1-10均系首次从该植物中分到的已知结构,这些结构虽然较简单,但似乎支持木莲属是木兰科中较为原始的属的主张;另活性筛选试验表明化合物5具有中等抗细菌活性。3.壮丽含笑的化学成分研究从壮丽含笑干燥嫩枝的乙醇提取物中共分离得到12个成分,鉴定了其中6个,分别为(十)一alloaromadendrane-4β-10β-diol(1),D-aromadendrane-4β-10α-diol(2),spathulenol(3),sarthenolide(4),11,13-dehydrolanuginolide(5)及丁香苷(syringin,6)。化合物1-6均为首次从该植物中分到的已知化合物,其中化合物1及2分别为alloaromadendrane及aromadendrane型倍半萜,在含笑属植物中尚属首次发现。论文的最后部分对木兰科7属22种植物的木脂体类成分从化合物名称、分子式、分子量、旋光、熔点、生物活性、来源及参考文献等方面进行了综述。
英文摘要: The thesis is mainly composed of three parts. The first part including two chapters is about detailed structural elucidation of new compounds from two Caryophyllaceae plants, Cucubalus baccifer and Brachystemma calycinum. The second part involving three chapters deals with chemical constituents from Parakmeria yunnanensis, Manglietia crassipes and Michelia lacei, which all belong to Magnoliaceae family. The chemotaxonomy of Magnoliaceae plants is also briefly discussed in this part. The last part reviews the progress of lignans and neolignans from 7 genera and 22 species of Magnoliaceae plants. Systematic phytochemical investigations on above-mentioned five plants led to the isolation of 105 compounds, 65 of which were identified, and about 19 compounds are new ones. The elucidated structures covered norsesquiterpenes and their glycosides, sesquiterpenes, pyrrolidones and their peroxidates, phytoecdysterones (C_(19), C_(27) and C_(28)) derivatives, flavonol, lignans, aromatic derivatives, alkaloids and phytocyclopeptides etc. 1. Study on ehemical consfituents of Caryophyllaceae 1.1 Chemical constituents from Cucubalus baccifer As a continued study of Caryophyllaceae cyclopeptides and also a systematic research on other constituents, two Caryophyllaceae plants C. baccifer and B. calycinum were investigated. From the former plant 30 compounds were isolated, and 19 of them were elucidated as cucubalsol (1), cucubalactone (2), dmmmondol 3-O-β-D-glucopyranoside (3) , cucubaldiol (4) , cucubalactam ( 5 ) , 6- methoxy-piperidin-2-one (6), 5,7(E)-megastigmadiene-3β,4α,9ξ-triol (7), drummondol (8), ecdysterone (9), 24(28)-ecdysterone A (10), 22-deoxyecdysterone (11), 25-hydroxypanuosterone (12), mbrosterone (13), 2, 22-dideoxyecdysterone 3-glucoside (14), 5,7,4'-trihydroxyflavone (15),4-hydroxy-3-methoxybenzopropanyl acid (16) , 4-hydroxybenzoaldehyde (17) , 4-hydroxybenzoic acid (18) and pterolactam (19) respectively as summarized in Fig. 1. Compounds 1-6 are new ones. Compounds 1-4 are novel norsesquiterpenes, we proposed their biosynthetic pathway starting from β-ionol analogs; Using chromium trioxide as oxidizer chemical translations between these compounds were performed (see Part 1 Chapter 1 Section 3). Besides, nine compounds from essential oil of the whole plants were identified qualitatively and quantitatively by GC/MS analyses. In this plant we also discovered cyclopeptides, we couldn't obtained them due to their low #phi#ontent. However in the course of screening cyclopeptides, we accidentally found that pyrrolidones bearing an oxygen substituent at the neighboring position of nitrogen show positive reaction to ninhydrin reagent (normally negative reaction should be reasonable), the possible reason may be due to this kind of compound is readily hydrolyzed when heated on silica gel plate (Lewis acid). To date we don't find such report in literatures. This phenomenon suggests us that not only amino acids, peptides but also this kind of amides show positive reaction to ninhydrin reagent. 1.2 Chemical constituents from Brachystemma calycinum B. calycinum is a folk medicine used for rheumatism, from the ethanol extract of it's roots 32 compounds were isolated, 17 of which were determined as brachystemin A-E (1-5) , brachystemidine A-E (6-10) , 5"-acetylbrachystemidine D (11) , brachystemoside A (12), methyl L-pyroglutamate ( 13 ), adenosine (14), 2-minaline (15), 3'-fuffuryl-pyrrole-2-carboxylate (16) and Ethyl α-D-glucopyranoside (17) respectively as are listed in Fig. 2. Compounds 1-5 are new octacyclopeptides; Compounds 6-11 are novel alkaloids with three cycles linked by single bond which may freely rotate; Another new compound namely 12 is a glycoside combined by glucose and 2-minaline through ester bond; Compound 4 is an octacyclopeptide containing an unusual amino acid namely S-oxomethionine, in it's ~1H and ~(13)C spectra only S-oxomethionine exhibited pairs of peaks, the ratio is 3:2, the reason maybe results from rotation hindrance of sulfoxide functionality. Such a phenomenon has been found in annosquamosin A, which further confirmed that Caryophyllaceae is relative to Annonaceae proposed by Prof. Jun Zhou; The crystal structure analysis of compound 5 was achieved by X-ray diffraction. 2. Study on chemical constituents of Magnoliaceae 2.1 Chemical constituents from Parakmeria yunnanensis The thesis discussed the chemical studies of three Magnoliaceae plants under the support of national nature science foundation, from the ethanol extract of the dried branches of P. yunnanensis 20 compounds were isolated and 13 of them were identified as parakmerin A (1), eupomatenoid-7 (2), eupomatenoid-5 (3), (+)- isolariciresinol (4), (+)-5'-methoxyisolariciresinol (5), lingueresinol (6), (+)- isolariciresinol 9-O-β-D-glucopyranoside (7), syringin (8) , quercetin (9) , mtin (10) , palmitic acid-2,3-dihydroxy-propanenyl ester (11) , tricosanoic acid-2,3- dihydroxy-propanenyl ester (12) and cerotic acid-2,3-dihydroxy-propanenyl ester (13) respectively which are presented in Fig. 3. Compound 1 is a new eupomatene-type lignan; Other known compounds were all first isolated from this plant. 2.2 Chemical constituents from Manglietia crassipes Phytochemical investigation on the ethanol extract of the dried branches of M. crassipes led to the isolation of 15 compounds, the structures of 10 ones were determined as protocatechualdehyde (1), 4-hydroxybenzoaldehyde (2), 3, 5- dimethoxy-4-hydroxybenzoaldehyde (3), vanillin (4), 2,5-dimethoxybenzoquinone (5), coniferylaldehyde (6), syringaldehyde (7), syringin (8), (+)-syringaresinol (9) and cryptomeridiol (10) respectively as are outlined in Fig. 4. These known compounds are all first isolated from the plant; Their chemotaxonomy is briefly discussed; Compound 5 shows moderately antibacteria activity. 2.3 Chemical constituents from Michelia lacei From the ethanol extract of the dried branches of M. lacei 12 compounds were obtained, 6 of which were identified as (+)-alloaromadendrane-4β-10β-diol (1), D- aromadendrane-4β-10α-diol (2), spathulenol (3), parthenolide (4), 11,13- dehydrolanuginolide (5) and syringin (6) respectively as are showed in Fig. 5. All these compounds were the first isolation from this plant, and compounds 1 and 2 were first found in Michelia genus. The end part of the thesis reviews the progress of lignans and neolignans from Magnoliaceae in aspects of compound name, molecular weight, molecular formular, optical rotation, melting point, bioactivity, source and reference.
语种: 中文
内容类型: 学位论文
URI标识: http://ir.kib.ac.cn/handle/151853/514
Appears in Collections:昆明植物所硕博研究生毕业学位论文_学位论文

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