CN107987112B - Preparation method of afzelin derivative - Google Patents
Preparation method of afzelin derivative Download PDFInfo
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- CN107987112B CN107987112B CN201810047582.7A CN201810047582A CN107987112B CN 107987112 B CN107987112 B CN 107987112B CN 201810047582 A CN201810047582 A CN 201810047582A CN 107987112 B CN107987112 B CN 107987112B
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- cercidiphyllum japonicum
- beta
- methoxy
- afzerin
- glucosyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H17/00—Compounds containing heterocyclic radicals directly attached to hetero atoms of saccharide radicals
- C07H17/04—Heterocyclic radicals containing only oxygen as ring hetero atoms
- C07H17/06—Benzopyran radicals
- C07H17/065—Benzo[b]pyrans
- C07H17/07—Benzo[b]pyran-4-ones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
- C07H1/08—Separation; Purification from natural products
Abstract
The invention belongs to the field of efficient preparation of secondary metabolic components with high added values of trees, and particularly relates to an afzerin derivative which is never reported in literature, namely 8-methoxy-4 '-O-beta-D-glucosyl afzerin, and a method for preparing the 8-methoxy-4' -O-beta-D-glucosyl afzerin from xylem saplings of cercidiphyllum japonicum by combining processes such as solution extraction, gradient extraction of solvents with different polarities, chromatographic separation and the like. The preparation method provided by the invention has the characteristics of easily available raw materials, simple and efficient preparation process, high purity of target products and the like.
Description
Technical Field
The invention belongs to the field of efficient preparation of secondary metabolic components with high added values of trees, and particularly relates to an afzerin derivative which is never reported in literature, namely 8-methoxy-4 '-O-beta-D-glucosyl afzerin, and a method for preparing the 8-methoxy-4' -O-beta-D-glucosyl afzerin from xylem saplings of cercidiphyllum japonicum by combining processes such as solution extraction, gradient extraction of solvents with different polarities, chromatographic separation and the like. The preparation method provided by the invention has the characteristics of easily available raw materials, simple and efficient preparation process, high purity of target products and the like.
Background
The third class of wiggly-leaved tree species, Cercidiphyllum japonicum (Cercidiphyllum japonicum), among plants of the genus Nectria (Cercidiphyllaceae), is commonly known as Cercis chinensis leaf trees or mother-son trees, and is now mainly distributed in China, and cultivated in some regions of the countries of Korea, Japan, and the like. The cercidiphyllum japonicum is a unisexual heterotrophic plant, flowers of the cercidiphyllum japonicum have no perianth, flowers and leaves open simultaneously or earlier than leaves, and flowers are purple red and have 1 bud. The male inflorescence is generally 4 clusters, nearly has no stem, and stamens are 15-20; the female inflorescences generally cluster in 2-6 flowers with total stems. Liangxiang trees are now classified as national second-level important protection wild plants in China (Jin, et al., PloS ONE, 2017, 12 (5): e 0178382; Zhanying, Likefeng, Shaanxi forestry science and technology, 2009, (1): 53-54; Manchester, et al., Journal of Systematics and Evolution, 2009, 47 (1): 1-42). The medical effects of good antioxidation, anti-inflammation, hair growth promotion, antibiosis, ice nucleus resistance and the like of various organs such as bark, branches and leaves of the oriental paperbush are achieved, and the medical effects are widely applied to prevention and treatment of folk traditional medicines or related diseases in many countries in Asia for many years (Towatari, et al, Planta Medica, 2002, 68: 995-998; Tada & Sakurai, Phytochemistry, 1991, 30 (4): 1119-1120; Wang, et al, Planta, 2012, 235: 747-759). Until now, some researchers at home and abroad have studied sporadically the secondary metabolic chemical components of the bark, leaves, xylem heartwood and other organ parts of the Nepeta didyma (Bae & Kim, Journal of the Korea Wood Science and Technology, 2017, 45 (3): 250-257; Guan, et al, Ecological information, 2016, 33, 51-56; Lee, et al, Journal of Korea Wood Science and Technology, 2016, 44 (4): 551-558; Mitsuma et al, Proc. 1991, 41 (2): 209-212), and until now, the research on the secondary metabolic components in the xylem sapwood of Nepeta dida has not been systematically developed.
The invention prepares 8-methoxy-4' -O-beta-D-glucosyl afzerumoside which is never reported in documents from xylem sapwood saplings of the cercidiphyllum japonicum by a method combining solution extraction, gradient extraction of solvents with different polarities, chromatographic separation and the like.
Disclosure of Invention
The invention aims to provide an afzelin derivative which has never been reported in the literature, namely 8-methoxy-4 '-O-beta-D-glucosyl afzelin, and the corresponding English name of the compound is 8-methoxy-zelin-4' -O-beta-D-glucopyranoside.
The second purpose of the invention is to provide a method for efficiently preparing 8-methoxy-4' -O-beta-D-glucosyl afzerin from xylem sapwood of cercidiphyllum japonicum.
The technical scheme of the invention is summarized as follows:
the following structural formula is 8-methoxy-4' -O-beta-D-glucosyl afzerin:
the afuroside derivative is light yellow powder, and the molecular formula of the afuroside derivative is C28H32O16The chemical name is 8-methoxy-4 '-O-beta-D-glucosyl afungin, and the corresponding English name is 8-methoxyafzelin-4' -O-beta-D-glucopyranoside. Through search, the afzerin derivative is a new compound which has never been reported in the literature.
The method for preparing 8-methoxy-4' -O-beta-D-glucosyl afzerin from xylem sapwood of cercidiphyllum japonicum sequentially comprises the following characteristic steps:
(1) taking a dried woody saplings of the cercidiphyllum japonicum as a raw material, crushing the raw material, adding a petroleum ether-ethanol-water solution with the volume ratio of 1: 3: 6 according to the mass ratio of the raw material liquid of 1: 2-1: 6, extracting at normal temperature or by heating or ultrasonic-assisted extraction for 1-8 times, filtering or centrifuging the extracting solution to remove insoluble substances, and drying under reduced pressure to obtain a crude woody saplings of the cercidiphyllum japonicum;
(2) adding water with the mass 0.5-3 times of that of the crude extract of the xylem sapwood of the cercidiphyllum japonicum, stirring, and then sequentially extracting with petroleum ether, normal hexane, chloroform and ethyl acetate;
(3) vacuum drying the ethyl acetate extractive solution under reduced pressure to obtain extract of wood sapwood of Cercidiphyllum japonicum;
(4) separating and refining the extract of the woody saplings ethyl acetate of the cercidiphyllum japonicum by chromatography to obtain 8-methoxy-4' -O-beta-D-glucosyl afungoside.
For the above preparation methods, it is to be noted that:
in the step (1), the plant raw material for extraction is xylem sapwood of cercidiphyllum japonicum;
in the step (1), the solution for extraction is a petroleum ether-ethanol-water solution with the volume ratio of 1: 3: 6;
in the step (4), the chromatographic separation method is one or more of gel chromatography, silica gel chromatography, high performance liquid chromatography and high-speed counter-current chromatography.
The preparation method provided by the invention has the characteristics of easily available raw materials, simple and efficient preparation process, high purity of target products and the like.
Detailed Description
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative, not limiting, and are not intended to limit the invention to these specific embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all modifications, alternatives, and equivalents as may be included within the scope of the claims.
Example 1: preparation of 8-methoxy-4' -O-beta-D-glucosyl afzerin from xylem sapwood of cercidiphyllum japonicum
(1) Taking a dried woody saplings of the cercidiphyllum japonicum as a raw material, crushing, adding a petroleum ether-ethanol-water solution with the volume ratio of 1: 3: 6 according to the mass ratio of the material liquid of 1: 3, extracting at normal temperature for 4 times, filtering an extracting solution to remove insoluble substances, and drying under reduced pressure to obtain a crude woody saplings of the cercidiphyllum japonicum;
(2) adding water with the mass 1 time of that of the crude extract of the xylem sapwood of the cercidiphyllum japonicum, stirring, and then sequentially extracting with petroleum ether, n-hexane, chloroform and ethyl acetate;
(3) vacuum drying the ethyl acetate extractive solution under reduced pressure to obtain extract of wood sapwood of Cercidiphyllum japonicum;
(4) separating and refining the extract of the woody saplings ethyl acetate of the cercidiphyllum japonicum by silica gel chromatography and high performance liquid chromatography to obtain the 8-methoxy-4' -O-beta-D-glucosyl afuroide.
Example 2: preparation of 8-methoxy-4' -O-beta-D-glucosyl afzerin from xylem sapwood of cercidiphyllum japonicum
(1) Taking dried xylem sapwood raw material of the cercidiphyllum japonicum, crushing, adding petroleum ether-ethanol-water solution with the volume ratio of 1: 3: 6 according to the mass ratio of the material liquid of 1: 4, heating and extracting for 3 times, centrifuging to remove insoluble substances, and drying under reduced pressure to obtain a crude extract of the xylem sapwood of the cercidiphyllum japonicum;
(2) adding water with the mass 1.5 times of that of the crude extract of the xylem sapwood of the cercidiphyllum japonicum, stirring, and then sequentially extracting with petroleum ether, n-hexane, chloroform and ethyl acetate;
(3) vacuum drying the ethyl acetate extractive solution under reduced pressure to obtain extract of wood sapwood of Cercidiphyllum japonicum;
(4) separating and refining the extract of the woody saplings ethyl acetate of the cercidiphyllum japonicum by silica gel chromatography and gel chromatography to obtain 8-methoxy-4' -O-beta-D-glucosyl afuroside.
The chemical structure of the afzerin derivative is analyzed:
with the help of a melting point tester, the melting point of the afzerin derivative is 239-241 ℃, and the optical rotation is measured
21.2 ° (c, 0.5, MeOH). In Positive fast atom bombardment mass spectrum Positive FAB-MS experiments, the [ M + K ] of the compound]Is M/z 663, [ M + Na [ ]]Are M/z 647, [ M + H [ + ]]M/z 625, combined with other experimental data, revealed that the molecular formula of the afzeolin derivative of the invention is C28H32O16. The African glycosides derivative is prepared by dissolving in deuterated dimethyl sulfoxide (DMSO-d)6) In a solvent1H (600MHz) and13the C (150MHz) NMR spectrum data are shown in Table 1. According to the chemical-physical data of the compound, in particular it1H and13c NMR data information shows that the compound contains 8-methoxy-afzelin (8-methoxyafzelin) which is a flavonol glycoside compound that methoxy and O-alpha-L-rhamnosyl are respectively connected to C-8 and C-3 positions of A ring. Other chemical, physical and nuclear magnetic resonance experimental data of the compound also fully indicate that the afzerin derivative molecule is also connected with an O-beta-D-glucosyl unit (O-beta-D-glucose). Through the multi-bond hydrocarbon relation (HMBC), the heteronuclear multiple quantum relation (HMQC) and other two-dimensional maps of the compound, the O-beta-D-glucosyl unit of the compound is deduced to be combined at the C-4' position of the B ring of the afungside. Based on the above information, the chemical formula of the compound was analytically determined to be 8-methoxy-4' -O- β -D-glucosylaafungin, which isThe corresponding English name is 8-methoxyafzelin-4' -O-beta-D-glucopyranoside.
TABLE 1 preparation of the compound 8-methoxy-4' -O-beta-D-glucosylaafungin1H (600MHz) and13c (150MHz) NMR data (DMSO-d)6)
Example 3: preparation of 8-methoxy-4' -O-beta-D-glucosyl afzerin from xylem sapwood of cercidiphyllum japonicum
(1) Taking a dried woody saplings of the cercidiphyllum japonicum saplings raw material, crushing, adding a petroleum ether-ethanol-water solution with the volume ratio of 1: 3: 6 according to the mass ratio of the material liquid of 1: 5, carrying out ultrasonic-assisted extraction for 2 times, filtering an extracting solution to remove insoluble substances, and drying under reduced pressure to obtain a crude woody saplings of the cercidiphyllum japonicum;
(2) adding water with the mass 2 times of that of the crude extract of the xylem sapwood of the cercidiphyllum japonicum, stirring, and then sequentially extracting with petroleum ether, n-hexane, chloroform and ethyl acetate;
(3) vacuum drying the ethyl acetate extractive solution under reduced pressure to obtain extract of wood sapwood of Cercidiphyllum japonicum;
(4) separating and refining the extract of the woody saplings ethyl acetate of the cercidiphyllum japonicum by silica gel chromatography and high-speed counter-current chromatography to obtain 8-methoxy-4' -O-beta-D-glucosyl afuroside.
Claims (2)
1. A preparation method of an afzerin derivative, namely 8-methoxy-4' -O-beta-D-glucosyl afzerin, is characterized by sequentially comprising the following steps:
(1) taking a dried woody saplings of the cercidiphyllum japonicum as a raw material, crushing the raw material, adding a petroleum ether-ethanol-water solution with the volume ratio of 1: 3: 6 according to the mass ratio of the raw material liquid of 1: 2-1: 6, extracting at normal temperature or by heating or ultrasonic-assisted extraction for 1-8 times, filtering or centrifuging the extracting solution to remove insoluble substances, and drying under reduced pressure to obtain a crude woody saplings of the cercidiphyllum japonicum;
(2) adding water with the mass 0.5-3 times of that of the crude extract of the xylem sapwood of the cercidiphyllum japonicum, stirring, and then sequentially extracting with petroleum ether, normal hexane, chloroform and ethyl acetate;
(3) vacuum drying the ethyl acetate extractive solution under reduced pressure to obtain extract of wood sapwood of Cercidiphyllum japonicum;
(4) separating and refining the extract of the woody saplings ethyl acetate of the cercidiphyllum japonicum by chromatography to obtain 8-methoxy-4' -O-beta-D-glucosyl afungoside.
2. The method as claimed in claim 1, wherein the chromatography is one or more selected from the group consisting of gel chromatography, silica gel chromatography, high performance liquid chromatography, and high speed counter current chromatography.
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| JP3988839B2 (en) * | 1996-09-19 | 2007-10-10 | 日本製粉株式会社 | Glycerophosphate dehydrogenase inhibitor |
| CN102343083A (en) * | 2011-10-17 | 2012-02-08 | 中国科学院成都生物研究所 | Antivirus composition medicament |
| CN105259268A (en) * | 2015-10-30 | 2016-01-20 | 上海杏灵科技药业股份有限公司 | Detection method for fingerprint chromatogram of flavonoid and organic acid components in ginkgo biloba extract and application of detection method |
| CN106916193A (en) * | 2017-03-31 | 2017-07-04 | 河南大学 | A kind of method that afzclin is extracted in the leaf from cercis |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3988839B2 (en) * | 1996-09-19 | 2007-10-10 | 日本製粉株式会社 | Glycerophosphate dehydrogenase inhibitor |
| CN102343083A (en) * | 2011-10-17 | 2012-02-08 | 中国科学院成都生物研究所 | Antivirus composition medicament |
| CN105259268A (en) * | 2015-10-30 | 2016-01-20 | 上海杏灵科技药业股份有限公司 | Detection method for fingerprint chromatogram of flavonoid and organic acid components in ginkgo biloba extract and application of detection method |
| CN106916193A (en) * | 2017-03-31 | 2017-07-04 | 河南大学 | A kind of method that afzclin is extracted in the leaf from cercis |
Non-Patent Citations (2)
| Title |
|---|
| Deep supercooling xylem parenchyma cells of katsura tree (Cercidiphyllum japonicum) contain flavonol glycosides exhibiting high anti-ice nucleation activity;JUN KASUGA;《Plant Cell and Environment》;20081231;第31卷;全文 * |
| 连香树树皮化学成分的研究;王静蓉;《植物学报》;19991231;第41卷(第2期);全文 * |
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