CN108047242A - The method that epoxide and acid anhydrides are extracted from fig - Google Patents
The method that epoxide and acid anhydrides are extracted from fig Download PDFInfo
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- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
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- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/42—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms in positions 2 and 4
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
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Abstract
The present invention relates to a kind of methods that epoxide and acid anhydrides are extracted from fig, comprise the following steps：First, fig fruit is taken to prepare 70% ethanol extract；2nd, medicinal extract extracting in water obtains ethyl acetate extract；3rd, ethyl acetate extract silica gel column separating purification merges similar compositions and obtains fraction section 1 10 after elution；4th, compound I and II are afforded in fraction section 1, compound III is afforded in fraction section 3, compounds Ⅳ is afforded in fraction section 5, compound V and VI, VII and VIII are afforded in fraction section 4.8 compound I VIII that the present invention is extracted from fig, wherein compound I, IV, V, VI, VII, VIII is noval chemical compound, it is and isolated from the fruit of fig for the first time, to disclose the special high-quality potential that fig antitumaous effect provides the scientific evidence of new evidence-based medicine EBM and fig is developed as functional food and anticancer accesary foods.
Description
Technical field
The present invention relates to active ingredient extractive technique fields in fig, and in particular to epoxy compound is extracted from fig
The method of object and acid anhydrides.
Background technology
Ficus is in Moraceae（Moraceae）Ficus（Ficus）Shrub or dungarunga.Wherein French Blanc is auspicious
Gram, the figs such as early Huang in Xinjiang, Maryia, the red and Japanese purple fruit of middle peasant, be that China's fig introduces that cultivate popularization wider
Improved seeds belong to summer and autumn fruit dual-purpose kind.The kind Arles salami sausage, the tree vigo(u)r golden mean of the Confucian school, fruit is larger, unique in taste, and flavor is fragrant
Sweet tea, almost no disease and pests harm, is the optimal seeds for producing green fruit.Though China's fig cultivation history is long, systematically open
Exhibition fig medicine-food two-purpose ingredient and technical research work are started late.The research work of fig is proceeded by from the beginning of the eighties
Since, as scientists from all over the world are to the progress of fig fruit research work, especially to fig medical value and health value
Progressively understanding and the progress for treating cancer, people is made to have new understanding to the economic value of fig.This
Invention thinks that many foods are both food and drug based on integration of drinking and medicinal herbs theoretical research, i.e. traditional Chinese medicine, and food and drug are similary
The effect of being capable of's the succession of disease preventing and treating, probing into the people's " to eat as medicine, to eat for medicine " ingredient makes the common of wherein Chinese medicine and food
Active ingredient or efficacy factor are the basis of regimen, and can be used for preventing and curing diseases.
The content of the invention
The object of the present invention is to provide a kind of methods that epoxide and acid anhydrides are extracted from fig.
The present invention is in order to solve the above technical problems, used technical solution is：Epoxide is extracted from fig
With the method for acid anhydrides, comprise the following steps：
It Step 1: taking fig fruit, is freeze-dried after section, is then with mass concentration by lyophilized dried fruit at ambient temperature
70% ethyl alcohol cold soaking, ultrasound assisted extraction and filtering, after separation of solid and liquid, solid residue air-dries and repeats above-mentioned cold soaking, ultrasound is auxiliary
Extraction and filter operation 2-3 times are helped, then filter liquor is merged, is stood overnight, lower sediment is filtered off, supernatant is evaporated dense
70% ethanol extract is obtained after contracting, it is spare；
Step 2: 70% ethanol extract that step 1 is obtained is dissolved in water to transparent, then refrigerates and display under the conditions of -4 DEG C,
Refrigeration removes insoluble matter after displaying, and obtained clear liquid is extracted respectively with petroleum ether and ethyl acetate, Ran Hou
Less than 50 DEG C are concentrated under reduced pressure into obtain corresponding medicinal extract, spare；
Step 3: the ethyl acetate extract that step 2 is taken to obtain, after being dissolved again with ethyl acetate, with silica gel column separating purification,
Wet method loading, it is 15 then to use volume ratio successively:1、13:1、10:1、9:1、7:1、7:3、5:4、1:1、3:7、4:5、1:7、1:9
Petroleum ether and ethyl acetate gradient, the fraction afforded analyzed using TLC, merges similar fraction, there are
The fraction section 1-8 arrived, it is spare；
Step 4: the fraction section 1 that step 3 obtains is separated with normal pressure column chromatography, hexamethylene is selected in gradient elution agent：
Ethyl acetate 10:1、8:2、6：4 and 1：1 is used as gradient elution agent to elute separation successively, merges and collects 10 parts of fraction, by fraction
It places at room temperature, then will have solid that 1-3 fractions are precipitated and be filtered, and obtain a yellow solid powdered compounds I（Furan
It mutters cumarin）；Through small silicagel column hexamethylene after fraction 5-9 merging：Ethyl acetate 8:2、6：4 and 1：1 is purified by flash, and removal is molten
Yellow transparent colloidal cpd II is obtained after agent drying（3- methyl, 7- formyl ester groups, 4- hydroxyl pyranocoumarins）, compound I
Structural formula with II is as follows：
；
The fraction section 3 that step 3 obtains is separated with normal pressure column chromatography, gradient elution agent is followed successively by volume ratio as 9:1、
7:1 and 7:3 chloroform-methanol, gradient elution collects fraction in the process, and fraction is placed at room temperature, through eluant, eluent
For 7：The fraction that 1 chloroform-methanol elutes has solid precipitation, and the fraction for having solid to be precipitated is centrifuged to obtain white
Solid obtains compound III after white solid is recrystallized（Cupreol）, the structural formula of compound III is as follows：
The fraction section 5 that step 3 obtains is separated with normal pressure column chromatography, gradient elution agent is followed successively by volume ratio as 9:1、
7:3、1:1 and 3:7 hexamethylene：Acetone soln, gradient elution collects fraction in the process, and fraction is placed at room temperature, passes through
Eluant, eluent is 3:7 hexamethylene：The fraction that acetone soln elutes has solid precipitation, and the fraction for having solid to be precipitated is centrifuged
White residule and mother liquor are obtained, is concentrated to dryness clear solution after filtering, obtains faint yellow gluey compounds Ⅳ（Bicyclic [2,
2,2] furans -2,5- rings intramolecular anhydride）, the structural formula of compounds Ⅳ is as follows：
；
The fraction section 7 that step 3 obtains is separated with normal pressure column chromatography, gradient elution agent is followed successively by 10:1、9:1、7:3、
1:1 and 3:7 hexamethylene：It is placed at room temperature after acetone soln, constantly collection fraction and by fraction, it is found that it is solid fraction 3-11 has
Body washes out, and the fraction merging for having solid to be precipitated is centrifuged to obtain white solid, by chloroform and recrystallizing methanol, obtains same
Enantiomers compound V（5,6- is double【1', 1 "-diisopropyl alkyl】- cyclohexene oxide groups -2,3- two【2,2,1】- cycloheptane diformazan
Anhydride rings intramolecular anhydride）And VI（5,6- is double【1', 1 "-diisopropyl alkyl】- cyclohexene oxide groups -2,3- two【2,2,1】- cycloheptane diformazan
The outer acid anhydride of anhydride rings）；Mother liquor after filtering is continued to place, secondary crystallization is precipitated, and is collected solid and is merged, is drenched with chloroform repeatedly
It washes, obtains white solid powder shape isomer compound VII（5,6- pairs-【1'- amylenes -3', 1 " -（4 "-methyl）- penta
Alkene -3 "】- cyclohexene oxide groups -2,3- two【2,2,1】- cycloheptane dioctyl phthalate anhydro ring intramolecular anhydride）And VIII（5,6- pairs-【1'- amylenes-
3', 1"-（4 "-methyl）- amylene -3 "】- cyclohexene oxide groups -2,3- two【2,2,1】The outer acid anhydride of-cycloheptane dioctyl phthalate anhydro ring）, chemical combination
The structural formula of object V, VI, VII and VIII are as follows：
；
The further optimization of the method for epoxide and acid anhydrides is extracted from fig as the present invention：It will in the step 1
Lyophilized dried fruit is 70% ethyl alcohol cold soaking with the mass concentration of 10-20 times of its weight.
The further optimization of the method for epoxide and acid anhydrides is extracted from fig as the present invention：The step 2
Middle ethanol extract adds 10-20 times of water dissolution to transparent, and then 12h is displayed in refrigeration under the conditions of -4 DEG C.
Advantageous effect
8 compound I-VIII that the present invention is extracted from fig, wherein compound II, IV, V, VI, VII, VIII are
Noval chemical compound and isolated from the fruit of fig for the first time.The structure of these compounds is except compound III is in plant
Beyond common cupreol, compound I and II are coumarin kind compound, belong to the natural materials with antibacterial activity, are changed
It is anhydride compound to close object IV, V, VI, VII and VIII, and document report is also the tool cytotoxic activity in Chinese medicine source and suppression cancer
They coexist in fig medicine-food two-purpose fruit the related class of compounds of gene Pdcd4 expression, and find to coexist in through separation
The ethyl acetate extract of the extract, this Key Information composition information of the extract part material composition group.Therefore
The invention is using to disclose, fig antitumaous effect provides the scientific evidence of new evidence-based medicine EBM and fig is eaten as functionality
Product and the potential of anticancer accesary foods exploitation.
Description of the drawings
Fig. 1 is the nuclear magnetic resonance spectroscopy of compound I；
Fig. 2 is the nuclear magnetic resonance spectroscopy of compound II；
Fig. 3 is the carbon-13 nmr spectra of compound II；
Fig. 4 is the nuclear magnetic resonance spectroscopy of compound III；
Fig. 5 is the nuclear magnetic resonance spectroscopy of compound IV；
Fig. 6 is the carbon-13 nmr spectra of compound IV；
The carbon-13 nmr spectra DEPT that Fig. 7 is compound IV is composed；
Fig. 8 is the nuclear magnetic resonance spectroscopy of compound V and VI；
Fig. 9 is the carbon-13 nmr spectra of compound V and VI；
The carbon-13 nmr spectra DEPT that Figure 10 is compound V and VI is composed；
Figure 11 is the nuclear magnetic resonance spectroscopy of compound VII and VIII；
Figure 12 is the carbon-13 nmr spectra of compound VII and VIII；
The carbon-13 nmr spectra DEPT that Figure 13 is compound VII and VIII is composed.
Specific embodiment
Further technical scheme is illustrated below in conjunction with specific embodiment.
Embodiment 1：
The method that epoxide and acid anhydrides are extracted from fig：
Step 1: take 13kg after the section of fig Blanc Rake kind fruit, freeze-drying；Lyophilized dried fruit is used under room temperature
The mass concentration of 10-20 times of its weight is 70% ethyl alcohol cold soaking, ultrasound assisted extraction and filtering, after separation of solid and liquid, solid residue
After air-drying, repetition above-mentioned cold soaking 2-3 times；Filter liquor is merged, is stood overnight, filters off lower sediment, then supernatant evaporates
Concentration；70% ethanol extract is obtained, it is spare；
Step 2: it is transparent 10-20 times of water to be added to be dissolved to the leaching paste that step 1 obtains, then refrigerated under the conditions of -4 DEG C old
12h is put, refrigeration removes insoluble matter after displaying, and obtained clear liquid is extracted respectively with petroleum ether, ethyl acetate；So
Corresponding medicinal extract is concentrated under reduced pressure into below 50 DEG C afterwards, it is spare；
Step 3: it is mostly that pigment is given up to take step 2 oil ethereal extract, step 2 ethyl acetate extract is taken, with ethyl acetate again
After dissolving, with silica gel column separating purification.TLC selects petroleum ether：Ethyl acetate normal pressure column chromatography is separated, gradient elution.It is wet
Method loading, it is 15 then to use volume ratio successively:1、13:1、10:1、9:1、7:1、7:3、5:4、1:1、3:7、4:5、1:7、1:9 Hes
The petroleum ether and ethyl acetate gradient of ethyl acetate extract；The fraction afforded is analyzed using TLC, merges phase
Like fraction, the fraction section 1-10 that is obtained is spare；
Step 4: the fraction section 1 that step 3 obtains is separated with normal pressure column chromatography, hexamethylene is selected in gradient elution agent：
Ethyl acetate 10:1、8:2、6：4 and 1：1 is used as gradient elution agent to elute separation successively, merges and collects 10 parts of fraction, by fraction
It places at room temperature, then will have solid that 1-3 fractions are precipitated and be filtered, and obtain a yellow solid powdered compounds I
（36.0mg）, it is accredited as furocoumarin（As shown in Fig. 1 nuclear magnetic resonance spectroscopies）；Through the small silica gel band of column after fraction 5-9 merging
Hexane：Ethyl acetate 8:2、6：4 and 1：1 is purified by flash, and yellow transparent colloidal cpd II is obtained after removing solvent seasoning
(24.3mg), it is a noval chemical compound that compound II, which is pushed off, is named as 3- methyl, 7- formyl ester groups, 4- hydroxyls pyrans perfume
Legumin（As shown in nuclear magnetic resonance spectroscopy and the carbon spectrum of Fig. 2 and 3）；
The fraction section 3 that step 3 is obtained（Petroleum ether：Ethyl acetate 10:1-9:1）It is separated with normal pressure column chromatography, ladder
Degree eluant, eluent is followed successively by volume ratio as 9:1、7:1 and 7:3 chloroform-methanol, gradient elution collect fraction in the process, and will
Fraction is placed at room temperature, is 7 through eluant, eluent：The fraction that 1 chloroform-methanol elutes has solid precipitation, will have solid
The fraction of precipitation is centrifuged to obtain white solid, and white solid powder, i.e. compound III are obtained after white solid is recrystallized
(39.0mg) is accredited cupreol（As shown in Fig. 4 nuclear magnetic resonance spectroscopies）；
The fraction section 5 that step 3 is obtained（Petroleum ether：Ethyl acetate 9:1-7:3）It is separated with normal pressure column chromatography, gradient
Eluant, eluent is followed successively by volume ratio as 9:1、7:3、1:1 and 3:7 hexamethylene：Acetone soln, gradient elution collect fraction in the process,
And place fraction at room temperature, it is 3 through eluant, eluent:The fraction that 7 chloroform-methanol elutes has solid precipitation, will have
The fraction that solid is precipitated is centrifuged to obtain White residule and mother liquor, is concentrated to dryness clear solution after filtering, i.e., sterling
Compounds Ⅳ (17.6mg)；Be estimated to be by Spectrum Analysis there are one noval chemical compound, be named as bicyclic [2,2,2] furans-
2,5- ring intramolecular anhydrides（As shown in nuclear magnetic resonance spectroscopy and the carbon spectrum of Fig. 5-7）；
The fraction section 4 that step 3 is obtained（Petroleum ether：Ethyl acetate 5:4、1:1、3:7、4:5-0:1）With normal pressure column chromatography into
Row separation, gradient elution agent are followed successively by 10:1、9:1、7:3、1:1 and 3:7 hexamethylene：Acetone soln, after constantly collecting fraction
And place fraction at room temperature, it is found that fraction 3-11 has solid wash-off.The fraction merging for having solid to be precipitated centrifuge
To white solid；By chloroform and recrystallizing methanol to get to white solid powder compound isomers V and VI (27.0mg)；
Mother liquor after filtering is continued to place, secondary crystallization is precipitated, and is collected solid and is merged, is eluted with chloroform repeatedly, you can obtain shallow
Yellow solid powder compounds isomers VII and VIII (13.4mg).Through infrared spectrum and spectral analysis of the nuclear magnetic resonance, compound
V and VI, VII and VIII are noval chemical compound, they are named as respectively：5,6- is double【1', 1 "-diisopropyl alkyl】- epoxy oneself
Alkyl -2,3- two【2,2,1】- cycloheptane dioctyl phthalate anhydro ring intramolecular anhydride（V）And 5,6- are double【1', 1 "-diisopropyl alkyl】- epoxy oneself
Alkyl -2,3- two【2,2,1】The outer acid anhydride of-cycloheptane dioctyl phthalate anhydro ring（VI）；5,6- pairs-【1'- amylenes -3', 1 " -（4 "-methyl）-
Amylene -3 "】- cyclohexene oxide groups -2,3- two【2,2,1】- cycloheptane dioctyl phthalate anhydro ring intramolecular anhydride（VII）With 5,6- it is double-【1'- amylenes-
3', 1"-（4 "-methyl）- amylene -3 "】- cyclohexene oxide groups -2,3- two【2,2,1】The outer acid anhydride of-cycloheptane dioctyl phthalate anhydro ring
（VIII）, as shown in the nuclear magnetic resonance map of Fig. 8-13.
Embodiment 2：
The method that epoxide and acid anhydrides are extracted from fig：
Step 1: take 9kg after the early yellow kind fruit section in fig Xinjiang, freeze-drying；Lyophilized dried fruit is used under room temperature
The mass concentration of 10-20 times of its weight is 70% ethyl alcohol cold soaking, ultrasound assisted extraction and filtering, after separation of solid and liquid, solid residue
After air-drying, repetition above-mentioned cold soaking 2-3 times；Filter liquor is merged, is stood overnight, filters off lower sediment, then supernatant evaporates
Concentration；70% ethanol extract is obtained, it is spare；
Step 2: it is transparent 10-20 times of water to be added to be dissolved to the leaching paste that step 1 obtains, then refrigerated under the conditions of -4 DEG C old
12h is put, refrigeration removes insoluble matter after displaying, and obtained clear liquid is extracted respectively with petroleum ether, ethyl acetate；So
Corresponding medicinal extract is concentrated under reduced pressure into below 50 DEG C afterwards, it is spare；
Step 3: it is mostly that pigment is given up to take step 2 oil ethereal extract.Step 2 ethyl acetate extract is taken, with ethyl acetate again
After dissolving, with silica gel column separating purification.TLC selects petroleum ether：Ethyl acetate normal pressure column chromatography is separated, gradient elution.It is wet
Method loading, it is 15 then to use volume ratio successively:1、13:1、10:1、9:1、7:1、7:3、5:4、1:1、3:7、4:5、1:7、1:9 Hes
The petroleum ether and ethyl acetate gradient of ethyl acetate extract；The fraction afforded is analyzed using TLC, merges phase
Like fraction, the fraction section 1-8 that is obtained is spare；
Step 4: the fraction section 1 that step 3 obtains is separated with normal pressure column chromatography, hexamethylene is selected in gradient elution agent：
Ethyl acetate 10:1、8:2、6：4 and 1：1 is used as gradient elution agent to elute separation successively, merges and collects 10 parts of fraction, by fraction
It places at room temperature, then will have solid that 1-3 fractions are precipitated and be filtered, and obtain a yellow solid powdered compounds I
（28.9mg）, it is accredited as furocoumarin（As shown in Fig. 1 nuclear magnetic resonance spectroscopies）；Through the small silica gel band of column after fraction 5-9 merging
Hexane：Ethyl acetate 8:2、6：4 and 1：1 is purified by flash, and yellow transparent colloidal cpd II is obtained after removing solvent seasoning
(19.7mg), it is a noval chemical compound that compound II, which is pushed off, is named as 3- methyl, 7- formyl ester groups, 4- hydroxyls pyrans perfume
Legumin；
The fraction section 3 that step 3 is obtained（Petroleum ether：Ethyl acetate 10:1-9:1）It is separated with normal pressure column chromatography, ladder
Degree eluant, eluent is followed successively by volume ratio as 9:1、7:1 and 7:3 chloroform-methanol, gradient elution collect fraction in the process, and will
Fraction is placed at room temperature, is 7 through eluant, eluent：The fraction that 1 chloroform-methanol elutes has solid precipitation, will have solid
The fraction of precipitation is centrifuged to obtain white solid, and white solid powder, i.e. compound III are obtained after white solid is recrystallized,
Identified cupreol (30.0mg)；
The fraction section 5 that step 3 is obtained（Petroleum ether：Ethyl acetate 9:1-7:3）It is separated with normal pressure column chromatography, gradient
Eluant, eluent is followed successively by volume ratio as 9:1、7:3、1:1 and 3:7 hexamethylene：Acetone soln, gradient elution collect fraction in the process,
And place fraction at room temperature, it is 3 through eluant, eluent:The fraction that 7 chloroform-methanol elutes has solid precipitation, will have
The fraction that solid is precipitated is centrifuged to obtain White residule and mother liquor, is concentrated to dryness clear solution after filtering, i.e., sterling
Compounds Ⅳ (12.5mg)；Be estimated to be by Spectrum Analysis there are one noval chemical compound, be named as bicyclic [2,2,2] furans-
2,5- ring intramolecular anhydrides
The fraction section 4 that step 3 is obtained（Petroleum ether：Ethyl acetate 5:4、1:1、3:7、4:5-0:1）With normal pressure column chromatography into
Row separation, gradient elution agent are followed successively by 10:1、9:1、7:3、1:1 and 3:7 hexamethylene：Acetone soln, after constantly collecting fraction
And place fraction at room temperature, it is found that fraction 3-11 has solid wash-off.The fraction merging for having solid to be precipitated centrifuge
To white solid；By chloroform and recrystallizing methanol to get to white solid powder compound isomers V and VI (15.0mg)；
Mother liquor after filtering is continued to place, secondary crystallization is precipitated, and is collected solid and is merged, is eluted with chloroform repeatedly, you can obtain shallow
Yellow solid powder compounds isomers VII and VIII (9.4mg).Through infrared spectrum and spectral analysis of the nuclear magnetic resonance, compound V
It is noval chemical compound with VI, VII and VIII, they are named as respectively：5,6- is double【1', 1 "-diisopropyl alkyl】- oxepane
Base -2,3- two【2,2,1】- cycloheptane dioctyl phthalate anhydro ring intramolecular anhydride（V）And 5,6- are double【1', 1 "-diisopropyl alkyl】- oxepane
Base -2,3- two【2,2,1】The outer acid anhydride of-cycloheptane dioctyl phthalate anhydro ring（VI）；5,6- pairs-【1'- amylenes -3', 1 " -（4 "-methyl）- penta
Alkene -3 "】- cyclohexene oxide groups -2,3- two【2,2,1】- cycloheptane dioctyl phthalate anhydro ring intramolecular anhydride（VII）With 5,6- it is double-【1'- amylenes-
3', 1"-（4 "-methyl）- amylene -3 "】- cyclohexene oxide groups -2,3- two【2,2,1】The outer acid anhydride of-cycloheptane dioctyl phthalate anhydro ring
（VIII）.
Embodiment 3：
The method that epoxide and acid anhydrides are extracted from fig：
Step 1: take 15kg after the red kind fruit section of fig middle peasant, freeze-drying；Lyophilized dried fruit is used it under room temperature
The mass concentration of 10-20 times of weight is 70% ethyl alcohol cold soaking, ultrasound assisted extraction and filtering, after separation of solid and liquid, solid residue wind
After dry, repetition above-mentioned cold soaking 2-3 times；Filter liquor is merged, is stood overnight, filters off lower sediment, then supernatant evaporation is dense
Contracting；70% ethanol extract is obtained, it is spare；
Step 2: it is transparent 10-20 times of water to be added to be dissolved to the leaching paste that step 1 obtains, then refrigerated under the conditions of -4 DEG C old
12h is put, refrigeration removes insoluble matter after displaying, and obtained clear liquid is extracted respectively with petroleum ether, ethyl acetate；So
Corresponding medicinal extract is concentrated under reduced pressure into below 50 DEG C afterwards, it is spare；
Step 3: it is mostly that pigment is given up to take step 2 oil ethereal extract.Step 2 ethyl acetate extract is taken, with ethyl acetate again
After dissolving, with silica gel column separating purification.TLC selects petroleum ether：Ethyl acetate normal pressure column chromatography is separated, gradient elution.It is wet
Method loading, it is 15 then to use volume ratio successively:1、13:1、10:1、9:1、7:1、7:3、5:4、1:1、3:7、4:5、1:7、1:9 Hes
The petroleum ether and ethyl acetate gradient of ethyl acetate extract；The fraction afforded is analyzed using TLC, merges phase
Like fraction, the fraction section 1-10 that is obtained is spare；
Step 4: the fraction section 1 that step 3 obtains is separated with normal pressure column chromatography, hexamethylene is selected in gradient elution agent：
Ethyl acetate 10:1 and 8:2 gradient elution separation successively, merge and collect fraction, and fraction is placed at room temperature, there is solid analysis
Go out, then the fraction for having solid to be precipitated is filtered, obtains solid chemical compound powder I (38.2mg), be accredited as furans perfume
Legumin.Further 8:After the liquid drying of 2 fractions, a yellow transparent jelly is obtained, TLC analyses are sterling, through wave spectrum
It analyzes and identifies as compound ii (22.1mg).It is a noval chemical compound that compound II, which is pushed off, is named as 3- methyl, 7- formyls
Ester group, 4- hydroxyl pyranocoumarins.
The fraction section 3 that step 3 is obtained（Petroleum ether：Ethyl acetate 10:1-9:1）Divided with normal pressure column chromatography
From gradient elution agent is followed successively by volume ratio as 9:1、7:1 and 7:3 chloroform-methanol, gradient elution is collected in the process to be evaporated
Point, and fraction is placed at room temperature, it is 7 through eluant, eluent：The fraction that 1 chloroform-methanol elutes has solid precipitation, will
There is the fraction that solid is precipitated to be centrifuged to obtain white solid, white solid powder is obtained after white solid is recrystallized, that is, is changed
Object III is closed, is accredited cupreol (42.0mg)；
The fraction section 5 that step 3 is obtained（Petroleum ether：Ethyl acetate 9:1-7:3）It is separated with normal pressure column chromatography, gradient
Eluant, eluent is followed successively by volume ratio as 9:1、7:3、1:1 and 3:7 hexamethylene：Acetone soln, gradient elution collect fraction in the process,
And place fraction at room temperature, it is 3 through eluant, eluent:The fraction that 7 chloroform-methanol elutes has solid precipitation, will have
The fraction that solid is precipitated is centrifuged to obtain White residule and mother liquor, is concentrated to dryness clear solution after filtering, i.e., sterling
Compounds Ⅳ (18.2mg)；Be estimated to be by Spectrum Analysis there are one noval chemical compound, be named as bicyclic [2,2,2] furans-
2,5- ring intramolecular anhydrides
The fraction section 4 that step 3 is obtained（Petroleum ether：Ethyl acetate 5:4、1:1、3:7、4:5-0:1）With normal pressure column chromatography into
Row separation, gradient elution agent are followed successively by 10:1、9:1、7:3、1:1 and 3:7 hexamethylene：Acetone soln, after constantly collecting fraction
And place fraction at room temperature, it is found that fraction 3-11 has solid wash-off.The fraction merging for having solid to be precipitated centrifuge
To white solid；By chloroform and recrystallizing methanol to get to white solid powder compound isomers V and VI (27.9mg)；
Mother liquor after filtering is continued to place, secondary crystallization is precipitated, and is collected solid and is merged, is eluted with chloroform repeatedly, you can obtain shallow
Yellow solid powder compounds isomers VII and VIII (12.0mg).Through infrared spectrum and spectral analysis of the nuclear magnetic resonance, compound
V and VI, VII and VIII are noval chemical compound, they are named as respectively：5,6- is double【1', 1 "-diisopropyl alkyl】- epoxy oneself
Alkyl -2,3- two【2,2,1】- cycloheptane dioctyl phthalate anhydro ring intramolecular anhydride（V）And 5,6- are double【1', 1 "-diisopropyl alkyl】- epoxy oneself
Alkyl -2,3- two【2,2,1】The outer acid anhydride of-cycloheptane dioctyl phthalate anhydro ring（VI）；5,6- pairs-【1'- amylenes -3', 1 " -（4 "-methyl）-
Amylene -3 "】- cyclohexene oxide groups -2,3- two【2,2,1】- cycloheptane dioctyl phthalate anhydro ring intramolecular anhydride（VII）With 5,6- it is double-【1'- amylenes-
3', 1"-（4 "-methyl）- amylene -3 "】- cyclohexene oxide groups -2,3- two【2,2,1】The outer acid anhydride of-cycloheptane dioctyl phthalate anhydro ring
（VIII）.
The above described is only a preferred embodiment of the present invention, not make limitation in any form to the present invention, though
So the present invention is disclosed above with preferred embodiment, however is not limited to the present invention, any to be familiar with this professional technology people
Member, without departing from the scope of the present invention, when the technology contents using the disclosure above make a little change or modification
For the equivalent embodiment of equivalent variations, as long as being without departing from technical solution of the present invention content, technical spirit pair according to the invention
Any simple modification, equivalent change and modification that above example is made, in the range of still falling within technical solution of the present invention.
Claims (3)
1. the method for epoxide and acid anhydrides is extracted from fig, it is characterised in that：Comprise the following steps：
It Step 1: taking fig fruit, is freeze-dried after section, is then with mass concentration by lyophilized dried fruit at ambient temperature
70% ethyl alcohol cold soaking, ultrasound assisted extraction and filtering, after separation of solid and liquid, solid residue air-dries and repeats above-mentioned cold soaking, ultrasound is auxiliary
Extraction and filter operation 2-3 times are helped, then filter liquor is merged, is stood overnight, lower sediment is filtered off, supernatant is evaporated dense
70% ethanol extract is obtained after contracting, it is spare；
Step 2: 70% ethanol extract that step 1 is obtained is dissolved in water to transparent, then refrigerates and display under the conditions of -4 DEG C,
Refrigeration removes insoluble matter after displaying, and obtained clear liquid is extracted respectively with petroleum ether and ethyl acetate, Ran Hou
Less than 50 DEG C are concentrated under reduced pressure into obtain corresponding medicinal extract, spare；
Step 3: the ethyl acetate extract that step 2 is taken to obtain, after being dissolved again with ethyl acetate, with silica gel column separating purification,
Wet method loading, it is 15 then to use volume ratio successively:1、13:1、10:1、9:1、7:1、7:3、5:4、1:1、3:7、4:5、1:7、1:9
Petroleum ether and ethyl acetate gradient, the fraction afforded analyzed using TLC, merges similar fraction, there are
The fraction section 1-8 arrived, it is spare；
Step 4: the fraction section 1 that step 3 obtains is separated with normal pressure column chromatography, hexamethylene is selected in gradient elution agent：
Ethyl acetate 10:1、8:2、6：4 and 1：1 is used as gradient elution agent to elute separation successively, merges and collects 10 parts of fraction, by fraction
It places at room temperature, then will have solid that 1-3 fractions are precipitated and be filtered, and obtain a yellow solid powdered compounds I；It evaporates
Divide after 5-9 merging through small silicagel column hexamethylene：Ethyl acetate 8:2、6：4 and 1：1 is purified by flash, and is obtained after removing solvent seasoning
Yellow transparent colloidal cpd II；
The fraction section 3 that step 3 obtains is separated with normal pressure column chromatography, gradient elution agent is followed successively by volume ratio as 9:1、
7:1 and 7:3 chloroform-methanol, gradient elution collects fraction in the process, and fraction is placed at room temperature, through eluant, eluent
For 7：The fraction that 1 chloroform-methanol elutes has solid precipitation, and the fraction for having solid to be precipitated is centrifuged to obtain white
Solid obtains compound III after white solid is recrystallized；
The fraction section 5 that step 3 obtains is separated with normal pressure column chromatography, gradient elution agent is followed successively by volume ratio as 9:1、
7:3、1:1 and 3:7 hexamethylene：Acetone soln, gradient elution collects fraction in the process, and fraction is placed at room temperature, passes through
Eluant, eluent is 3:7 hexamethylene：The fraction that acetone soln elutes has solid precipitation, and the fraction for having solid to be precipitated is centrifuged
White residule and mother liquor are obtained, is concentrated to dryness clear solution after filtering, obtains faint yellow gluey compounds Ⅳ；
The fraction section 7 that step 3 obtains is separated with normal pressure column chromatography, gradient elution agent is followed successively by 10:1、9:1、7:3、
1:1 and 3:7 hexamethylene：It is placed at room temperature after acetone soln, constantly collection fraction and by fraction, it is found that it is solid fraction 3-11 has
Body washes out, and the fraction merging for having solid to be precipitated is centrifuged to obtain white solid, by chloroform and recrystallizing methanol, obtains same
Enantiomers compound V and VI；Mother liquor after filtering is continued to place, secondary crystallization is precipitated, and is collected solid and is merged, uses repeatedly
Chloroform elutes, and obtains white solid powder shape isomer compound VII and VIII.
2. the method for epoxide and acid anhydrides is extracted from fig as described in claim 1, it is characterised in that：The step
By lyophilized dried fruit with the mass concentration of 10-20 times of its weight it is 70% ethyl alcohol cold soaking in one.
3. the method for epoxide and acid anhydrides is extracted from fig as described in claim 1, it is characterised in that：The step
Ethanol extract adds 10-20 times of water dissolution to transparent in two, and then 12h is displayed in refrigeration under the conditions of -4 DEG C.
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| CN110981921A (en) * | 2019-12-26 | 2020-04-10 | 湖南华诚生物资源股份有限公司 | Continuous method for synchronously extracting multiple effective components from figs |
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| CN1124738A (en) * | 1994-05-23 | 1996-06-19 | 大日本油墨化学工业株式会社 | 7-glycosyloxybenzopyran derivative and antiallergic agent containing the derivative as active ingredient |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110981921A (en) * | 2019-12-26 | 2020-04-10 | 湖南华诚生物资源股份有限公司 | Continuous method for synchronously extracting multiple effective components from figs |
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