CN110483541A - A kind of isopentene group flavone compound and its preparation method and application - Google Patents
A kind of isopentene group flavone compound and its preparation method and application Download PDFInfo
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- CN110483541A CN110483541A CN201910829693.8A CN201910829693A CN110483541A CN 110483541 A CN110483541 A CN 110483541A CN 201910829693 A CN201910829693 A CN 201910829693A CN 110483541 A CN110483541 A CN 110483541A
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- -1 isopentene group flavone compound Chemical class 0.000 title claims abstract description 51
- 229930003944 flavone Natural products 0.000 title claims abstract description 44
- 235000011949 flavones Nutrition 0.000 title claims abstract description 44
- GAMYVSCDDLXAQW-AOIWZFSPSA-N Thermopsosid Natural products O(C)c1c(O)ccc(C=2Oc3c(c(O)cc(O[C@H]4[C@H](O)[C@@H](O)[C@H](O)[C@H](CO)O4)c3)C(=O)C=2)c1 GAMYVSCDDLXAQW-AOIWZFSPSA-N 0.000 title claims abstract description 28
- VHBFFQKBGNRLFZ-UHFFFAOYSA-N vitamin p Natural products O1C2=CC=CC=C2C(=O)C=C1C1=CC=CC=C1 VHBFFQKBGNRLFZ-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 150000002576 ketones Chemical class 0.000 claims abstract description 35
- 241001495452 Podophyllum Species 0.000 claims abstract description 30
- YJGVMLPVUAXIQN-XVVDYKMHSA-N podophyllotoxin Chemical compound COC1=C(OC)C(OC)=CC([C@@H]2C3=CC=4OCOC=4C=C3[C@H](O)[C@@H]3[C@@H]2C(OC3)=O)=C1 YJGVMLPVUAXIQN-XVVDYKMHSA-N 0.000 claims abstract description 30
- 235000013399 edible fruits Nutrition 0.000 claims abstract description 20
- 244000221860 Podophyllum emodi Species 0.000 claims abstract description 19
- 235000010169 Podophyllum emodi Nutrition 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 11
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 235000006708 antioxidants Nutrition 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 88
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 74
- 239000003208 petroleum Substances 0.000 claims description 69
- 238000010828 elution Methods 0.000 claims description 58
- 238000004809 thin layer chromatography Methods 0.000 claims description 57
- HWJHWSBFPPPIPD-UHFFFAOYSA-N ethoxyethane;propan-2-one Chemical compound CC(C)=O.CCOCC HWJHWSBFPPPIPD-UHFFFAOYSA-N 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 43
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 39
- 238000010438 heat treatment Methods 0.000 claims description 39
- 238000010898 silica gel chromatography Methods 0.000 claims description 39
- 238000012360 testing method Methods 0.000 claims description 38
- 239000003795 chemical substances by application Substances 0.000 claims description 36
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- 239000012046 mixed solvent Substances 0.000 claims description 30
- 239000000741 silica gel Substances 0.000 claims description 30
- 229910002027 silica gel Inorganic materials 0.000 claims description 30
- ROAYSRAUMPWBQX-UHFFFAOYSA-N ethanol;sulfuric acid Chemical compound CCO.OS(O)(=O)=O ROAYSRAUMPWBQX-UHFFFAOYSA-N 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- 235000019441 ethanol Nutrition 0.000 claims description 21
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 20
- 239000000284 extract Substances 0.000 claims description 20
- 239000003480 eluent Substances 0.000 claims description 19
- 230000014759 maintenance of location Effects 0.000 claims description 18
- 238000000605 extraction Methods 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 15
- 238000002953 preparative HPLC Methods 0.000 claims description 14
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- 238000004440 column chromatography Methods 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 10
- 239000000499 gel Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- XELZGAJCZANUQH-UHFFFAOYSA-N methyl 1-acetylthieno[3,2-c]pyrazole-5-carboxylate Chemical compound CC(=O)N1N=CC2=C1C=C(C(=O)OC)S2 XELZGAJCZANUQH-UHFFFAOYSA-N 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 239000000469 ethanolic extract Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 8
- WGLUMOCWFMKWIL-UHFFFAOYSA-N dichloromethane;methanol Chemical compound OC.ClCCl WGLUMOCWFMKWIL-UHFFFAOYSA-N 0.000 claims description 7
- FDSGHYHRLSWSLQ-UHFFFAOYSA-N dichloromethane;propan-2-one Chemical compound ClCCl.CC(C)=O FDSGHYHRLSWSLQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002038 ethyl acetate fraction Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 5
- 238000001228 spectrum Methods 0.000 claims description 5
- 241001276404 Arius Species 0.000 claims description 4
- 238000004587 chromatography analysis Methods 0.000 claims description 4
- 244000144730 Amygdalus persica Species 0.000 claims description 2
- 235000006040 Prunus persica var persica Nutrition 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 239000012467 final product Substances 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 235000013305 food Nutrition 0.000 abstract description 5
- 235000013361 beverage Nutrition 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 20
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 18
- 229960001866 silicon dioxide Drugs 0.000 description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 13
- 229960004756 ethanol Drugs 0.000 description 12
- 150000002213 flavones Chemical class 0.000 description 11
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 11
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 238000003919 heteronuclear multiple bond coherence Methods 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- 235000013824 polyphenols Nutrition 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 238000001052 heteronuclear multiple bond coherence spectrum Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical group CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 5
- 201000010099 disease Diseases 0.000 description 5
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 5
- 238000005570 heteronuclear single quantum coherence Methods 0.000 description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- FOGVNFMUZXDMTR-UHFFFAOYSA-N [Mg].Cl Chemical compound [Mg].Cl FOGVNFMUZXDMTR-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 238000000990 heteronuclear single quantum coherence spectrum Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 230000036542 oxidative stress Effects 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical group [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 3
- HHEAADYXPMHMCT-UHFFFAOYSA-N dpph Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1[N]N(C=1C=CC=CC=1)C1=CC=CC=C1 HHEAADYXPMHMCT-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000002114 high-resolution electrospray ionisation mass spectrometry Methods 0.000 description 3
- 230000002000 scavenging effect Effects 0.000 description 3
- SYTWCNXJNPSFQT-UHFFFAOYSA-N 2,2-dimethyl-3,4-dihydropyran Chemical group CC1(C)CCC=CO1 SYTWCNXJNPSFQT-UHFFFAOYSA-N 0.000 description 2
- 208000024827 Alzheimer disease Diseases 0.000 description 2
- 206010011224 Cough Diseases 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 230000007760 free radical scavenging Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- XEYFFTUZUORASQ-UHFFFAOYSA-N 2-[3,4-dihydroxy-2-(3-methylbut-2-enyl)phenyl]-5,7-dihydroxy-3-methoxy-6-(3-methylbut-2-enyl)chromen-4-one Chemical compound CC(=CCC=1C(=C2C(C(=C(OC2=CC=1O)C1=C(C(=C(C=C1)O)O)CC=C(C)C)OC)=O)O)C XEYFFTUZUORASQ-UHFFFAOYSA-N 0.000 description 1
- LVOMAAAYDYWLKU-UHFFFAOYSA-N 3-(2,4-dihydroxy-5-methoxyphenyl)-5,7-dihydroxy-6-(3-methylbut-2-enyl)chromen-4-one Chemical compound C1=C(O)C(OC)=CC(C=2C(C3=C(O)C(CC=C(C)C)=C(O)C=C3OC=2)=O)=C1O LVOMAAAYDYWLKU-UHFFFAOYSA-N 0.000 description 1
- 206010000087 Abdominal pain upper Diseases 0.000 description 1
- 241000227129 Aconitum Species 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 241001115458 Carphophis Species 0.000 description 1
- 208000034656 Contusions Diseases 0.000 description 1
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical group C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 208000029951 Laryngeal disease Diseases 0.000 description 1
- 208000037093 Menstruation Disturbances Diseases 0.000 description 1
- 206010027339 Menstruation irregular Diseases 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 208000018737 Parkinson disease Diseases 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- 206010039966 Senile dementia Diseases 0.000 description 1
- 241000332717 Sinopodophyllum Species 0.000 description 1
- 208000004078 Snake Bites Diseases 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003178 anti-diabetic effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 230000003262 anti-osteoporosis Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 239000003472 antidiabetic agent Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 208000034526 bruise Diseases 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 208000037976 chronic inflammation Diseases 0.000 description 1
- 230000006020 chronic inflammation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000001076 estrogenic effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 208000015122 neurodegenerative disease Diseases 0.000 description 1
- 230000001272 neurogenic effect Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001575 pathological effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
- A23L2/42—Preservation of non-alcoholic beverages
- A23L2/44—Preservation of non-alcoholic beverages by adding preservatives
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
- A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
- A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
- A23L3/3463—Organic compounds; Microorganisms; Enzymes
- A23L3/3544—Organic compounds containing hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
- C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
- C07D311/28—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only
- C07D311/30—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3 with aromatic rings attached in position 2 only not hydrogenated in the hetero ring, e.g. flavones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/22—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4
- C07D311/26—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 4 with aromatic rings attached in position 2 or 3
- C07D311/40—Separation, e.g. from natural material; Purification
-
- C—CHEMISTRY; METALLURGY
- 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
- C07D493/04—Ortho-condensed systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Food Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Nutrition Science (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Medicines Containing Plant Substances (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The present invention relates to isopentene group flavone compounds and its preparation method and application, it can effectively solve the problems, such as the preparation of isopentene group flavone compound and prepare antioxidant, the isopentene group flavone compound is the Chinese podophyllum root ketone Q(sinoflavonoids Q I extracted from Himalayan mayapple fruit), Chinese podophyllum root ketone R(sinoflavonoids R II), Chinese podophyllum root ketone S(sinoflavonoids S III), Chinese podophyllum root ketone T(sinoflavonoids T IV), it can be used for preparing the antioxidant of food or beverage, abundant raw material, preparation method is easy to operate, economic and social benefit is significant.
Description
Technical field
The present invention relates to medicine, especially a kind of isopentene group flavone compound and its system with antioxidant activity
Preparation Method and application.
Background technique
The active oxygen radical that oxidative stress refers to body tissue or generates into the cell has been more than that original oxygen radical makes
With ability or Scavenging activity, redox equilibrium is destroyed, so as to cause the active oxygen radical excessively accumulated is generated in vivo
And its relevant metabolite causes certain detrimental effect to body, thus certain pathological state is presented.Oxidative stress quilt
Be considered the reason of leading to many degenerative diseases, as cancer, chronic inflammation, cardiovascular disease, neurogenic disease, diabetes,
Alzheimer's disease and Parkinson's disease etc..Thus by inhibiting the damage of oxidative stress class to become disease relevant to treatment oxidative stress
One of the important channel of disease.At the same time, in food, the oxidation of nutriment can cause food quality to decline, or even can also
Cause the body of intake person that disease occurs.Therefore, finding safe antioxidant is always grinding for pharmacy and nutrition worker
Study carefully hot spot.
Himalayan mayapple fruit is the drying of Berberidaceae Sinopodophyllum plant Podophyllum emodi var chinense Sinopodophyllum emodi (Wall.) Ying.
Ripening fruits.Podophyllum emodi var chinense is a kind of medicinal plant with long history, just on the books in ancient times Shennong's Herbal: big poison is killed,
Treat cough larynx disease, the tired sense of ailment said due to cold or exposure loses that soul is absurd to see.Do not enter soup.How on the books later history tree is also, is mainly used for Huoxue San "
Knot, dispelling wind and eliminating dampness, worm snake bite, bruise, heart stomachache, cough due to wind-cold evil, irregular menstruation, Aconitum Szechenyianum Gay poisoning, rheumatalgia and gas
The diseases such as pipe inflammation.Than wide, China is mainly distributed on Sichuan, Qinghai, Tibet, Gansu, Shaanxi for Podophyllum emodi var chinense distribution.Himalayan mayapple fruit is as biography
System Tibetan medicine has long medicinal history first recorded in " moon king's medicine examine ".Chemical constitution study shows to mainly contain lignanoid and Huang
Ketone compounds, wherein isopentene group flavone compound is representative active constituent in Himalayan mayapple fruit, is had important and wide
General bioactivity is for example anti-oxidant, antitumor, anti-inflammatory, antibacterial, anti-osteoporosis, prevents senile dementia, anti-diabetic, heart and brain blood
Protection of pipe, estrogen-like etc..But be related to that there is oxidation resistant isopentene group flavone compound and its bioactivity, so far for
It only there are no patent or document report
Summary of the invention
For above situation, for the defect for overcoming the prior art, the purpose of the present invention is just to provide a kind of isopentene group
Flavone compound and its preparation method and application, preparation and the preparation that can effectively solve isopentene group flavone compound are anti-
The problem of oxidant.
The technical solution that the present invention solves is that a kind of isopentene group flavone compound is extracted from Himalayan mayapple fruit
Chinese podophyllum root ketone Q (sinoflavonoids Q I), Chinese podophyllum root ketone R (sinoflavonoids R II), Chinese podophyllum root ketone S
(sinoflavonoids S III), Chinese podophyllum root ketone T (sinoflavonoids T IV), molecular structural formula is respectively as follows:
Preparation method is:
Using 6-9kg of Himalayan mayapple fruit medicinal material as raw material, heated with 2-5 times of raw material weights, the ethyl alcohol that volumetric concentration is 75%-95%
Refluxing extraction 3 times, Extracting temperature is 90-95 DEG C, and each extraction time is 1.5-2 hours, and ethyl alcohol is recovered under reduced pressure and obtains medicinal extract shape second
Alcohol extracting thing is suspended in the distilled water of 2-3.2L, successively respectively extracts 3 with petroleum ether, methylene chloride, ethyl acetate, n-butanol
Secondary, 2-3.2L, time are 1.5-2 hours every time;Ethyl acetate fraction is separated through silica gel column chromatography, successively uses volume ratio
For the petroleum of 100:0,100:5,100:7,100:10,100:30,100:50,100:70,100:100,100:200,0:100
Ether-acetone mixed solvent system carries out gradient elution, 9.1-13L eluents of each gradient, and flow velocity is 10-15mL/min, often
350-500ml volumes are a fraction, collect 260 fractions, each fraction is tested and analyzed through silica gel thin-layer chromatography, thin with GF254
Laminate, respectively using the methylene chloride-methanol of petroleum ether-acetone of volume ratio 1:1 and volume ratio 5:1 as solvent, with volume
As color developing agent, 105 DEG C of 3-5min of heating are closed sulfuric acid-ethanol solution than 10:90 respectively according to thin-layer chromatography testing result
And fraction 1-35, fraction 36-85, fraction 86-104, fraction 105-115, fraction 116-132, fraction 133-144, fraction 145-
157, fraction 158-163, fraction 164-170, fraction 171-182, fraction 183-188, fraction 189-195, fraction 196-204,
Fraction 205-208, fraction 209-234, fraction 235-260, obtain component Fr.1-Fr.16;By component Fr.8 through Sephadex
LH-20 gel column chromatography, methanol elution, flow velocity are 50-70mL/h, and every 8-12mL is a fraction, collects 43 fractions, each
Fraction is tested and analyzed through silica gel thin-layer chromatography, with GF254 lamellae, using methylene chloride-acetone of volume ratio 5:3 as expansion
Agent, using sulfuric acid-ethanol solution of volume ratio 10:90 as color developing agent, 105 DEG C of 3-5min of heating are detected according to thin-layer chromatography and are tied
Fruit, respectively merge fraction 4-7, fraction 8-13, fraction 9-26, fraction 27-33, fraction 34-43, obtain 5 inferior component Fr.8-1,
Fr.8-2,Fr.8-3,Fr.8-4,Fr.8-5;Inferior component Fr.8-4 is purified through preparative high performance liquid chromatography, chromatographic column YMC-
Pack ODS-A, then with volume ratio be the Methanol+Water system elutions of 72:28, flow velocity 7mL/min is collected and is retained
Time is that the chromatographic peak of 36min obtains chemical compounds I;By component Fr.9 through silica gel column chromatography, the petroleum ether-the third of volume ratio 100:30
The elution of ketone mixed solvent, every 10-15mL are a fraction, collect the fraction containing compounds Ⅳ and obtain compounds Ⅳ;By component
Fr.11 is through silica gel column chromatography, petroleum ether-acetone mixed solvent system of volume ratio 100:7,100:10,100:15,100:20
Elution, 50-80mL eluents of each gradient, every 5-8mL are a fraction, collect 40 fractions, each fraction is through silica gel thin-layer
Chromatography tests and analyzes, with GF254 lamellae, respectively using petroleum ether-acetone of volume ratio 5:4 as solvent, with volume ratio 10:
90 sulfuric acid-ethanol solution merges fraction according to thin-layer chromatography testing result as color developing agent, 105 DEG C of 3-5min of heating respectively
1-8, fraction 9-15, fraction 16-31, fraction 32-40, obtain 4 inferior components Fr.11-1, Fr.11-2, Fr.11-3, Fr.11-
4;Inferior component Fr.11-4 is purified through preparative high performance liquid chromatography, is the Methanol+Water system of 80:20 with volume ratio
Elution, chromatographic column are YMC-Pack ODS-A, flow velocity 7mL/min, collect the chromatographic peak that retention time is 69min
Close object III;By component Fr.13 through silica gel column chromatography, volume ratio 100:40 petroleum ether-acetone mixed solution is eluted, and every 3-5mL is
One fraction collects the fraction containing compound ii and obtains compound ii.
Novel isopentene group flavone compound Chinese podophyllum root ketone Q prepared by the present invention with antioxidant activity
(sinoflavonoid Q I), Chinese podophyllum root ketone R (sinoflavonoid R II), Chinese podophyllum root ketone S (sinoflavonoid S III),
Chinese podophyllum root ketone T (sinoflavonoid T IV), can be used for preparing the antioxidant of food or beverage, abundant raw material, preparation side
Method is easy to operate, and economic and social benefit is significant.
Detailed description of the invention
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the compounds of this invention I.
Fig. 2 is the carbon-13 nmr spectra figure of the compounds of this invention I.
Fig. 3 is the HMBC spectrogram of the compounds of this invention I.
Fig. 4 is the hsqc spectrum figure of the compounds of this invention I.
Fig. 5 is the hydrogen nuclear magnetic resonance spectrogram of the compounds of this invention II.
Fig. 6 is the carbon-13 nmr spectra figure of the compounds of this invention II.
Fig. 7 is the HMBC spectrogram of the compounds of this invention II.
Fig. 8 is the hsqc spectrum figure of the compounds of this invention II.
Fig. 9 is the hydrogen nuclear magnetic resonance spectrogram of the compounds of this invention III.
Figure 10 is the carbon-13 nmr spectra figure of the compounds of this invention III.
Figure 11 is the HMBC spectrogram of the compounds of this invention III.
Figure 12 is the hsqc spectrum figure of the compounds of this invention III.
Figure 13 is the hydrogen nuclear magnetic resonance spectrogram of the compounds of this invention IV.
Figure 14 is the carbon-13 nmr spectra figure of the compounds of this invention IV.
Figure 15 is the HMBC spectrogram of the compounds of this invention IV.
Figure 16 is the hsqc spectrum figure of the compounds of this invention IV.
Specific embodiment
It elaborates with reference to embodiments with concrete condition to a specific embodiment of the invention.
The present invention can be provided in the specific implementation by following embodiment.
Embodiment 1
A kind of preparation method of isopentene group flavone compound of the present invention, using Himalayan mayapple fruit medicinal material 9kg as raw material, with
18L, volumetric concentration are 95% ethyl alcohol heating and refluxing extraction 3 times, and Extracting temperature is 95 DEG C, and each extraction time is 1.5 hours, are subtracted
Receipts ethyl alcohol is pushed back, medicinal extract shape ethanol extract is obtained, is suspended in the distilled water of 3.2L, successively with petroleum ether, methylene chloride, acetic acid
Ethyl ester, n-butanol respectively extract 3 times, each 3.2L, and the time is 1.5 hours;By Ethyl acetate fraction through at the beginning of silica gel column chromatography
Step separation, be successively 100:0,100:5 with volume ratio, 100:7,100:10,100:30,100:50,100:70,100:100,
The petroleum ether of 100:200,0:100-acetone mixed solvent system carry out gradient elution, each gradient 13L eluent, and flow velocity is
15mL/min, every 500ml volume are a fraction, collect 260 fractions, each fraction is tested and analyzed through silica gel thin-layer chromatography, use
GF254 lamellae, respectively using the methylene chloride-methanol of petroleum ether-acetone of volume ratio 1:1 and volume ratio 5:1 as solvent,
Using sulfuric acid-ethanol solution of volume ratio 10:90 as color developing agent, 105 DEG C of 3-5min of heating, according to thin-layer chromatography testing result,
Merge fraction 1-35, fraction 36-85, fraction 86-104, fraction 105-115, fraction 116-132, fraction 133-144, stream respectively
Part 145-157, fraction 158-163, fraction 164-170, fraction 171-182, fraction 183-188, fraction 189-195, fraction
196-204, fraction 205-208, fraction 209-234, fraction 235-260 obtain-Fr.16 components of Fr.1;Component Fr.8 is passed through
Sephadex LH-20 gel column chromatography, methanol elution, flow velocity 70mL/h, every 12mL are a fraction, collect 43 fractions, respectively
A fraction is tested and analyzed through silica gel thin-layer chromatography, with GF254 lamellae, using the dichloromethane-acetone of volume ratio 5:3 as expansion
Agent, using sulfuric acid-ethanol solution of volume ratio 10:90 as color developing agent, 105 DEG C of 3-5min of heating are detected according to thin-layer chromatography and are tied
Fruit, respectively merge fraction 4-7, fraction 8-13, fraction 9-26, fraction 27-33, fraction 34-43, obtain 5 inferior component Fr.8-1,
Fr.8-2,Fr.8-3,Fr.8-4,Fr.8-5;Inferior component Fr.8-4 is purified through preparative high performance liquid chromatography, chromatographic column YMC-
Pack ODS-A, then with volume ratio be the Methanol+Water system elutions of 72:28, flow velocity 7mL/min is collected and is retained
Time is that the chromatographic peak of 36min obtains chemical compounds I;By component Fr.9 through silica gel column chromatography, the petroleum ether-the third of volume ratio 100:30
The elution of ketone mixed solvent, every 15mL are a fraction, collect the fraction containing compounds Ⅳ and obtain compounds Ⅳ;By component
Fr.11 is through silica gel column chromatography, petroleum ether-acetone mixed solvent system of volume ratio 100:7,100:10,100:15,100:20
Elution, each gradient 80mL eluent, every 8mL are a fraction, collect 40 fractions, each fraction is examined through silica gel thin-layer chromatography
Analysis is surveyed, with GF254 lamellae, respectively using petroleum ether-acetone of volume ratio 5:4 as solvent, with the sulphur of volume ratio 10:90
Acid-ethanol solution merges fraction 1-8, stream according to thin-layer chromatography testing result as color developing agent, 105 DEG C of 3-5min of heating respectively
Part 9-15, fraction 16-31, fraction 32-40, obtain 4 inferior components Fr.11-1, Fr.11-2, Fr.11-3, Fr.11-4;Subgroup
Part Fr.11-4 is purified through preparative high performance liquid chromatography, is the Methanol+Water system elutions of 80:20, color with volume ratio
Spectrum column is YMC-Pack ODS-A, flow velocity 7mL/min, collects the chromatographic peak that retention time is 69min and obtains compound III;
By component Fr.13 through silica gel column chromatography, volume ratio 100:40 petroleum ether-acetone mixed solution elution, every 5mL is a fraction, is received
Fraction of the collection containing compound ii obtains compound ii.
Embodiment 2
A kind of preparation method of isopentene group flavone compound of the present invention, using Himalayan mayapple fruit medicinal material 6kg as raw material, with
30L, volumetric concentration are 75% ethyl alcohol heating and refluxing extraction 3 times, and Extracting temperature is 90 DEG C, and each extraction time is 2 hours, decompression
Ethyl alcohol is recycled, medicinal extract shape ethanol extract is obtained, is suspended in the distilled water of 2L, successively with petroleum ether, methylene chloride, acetic acid second
Ester, n-butanol respectively extract 3 times, each 2L, and the time is 2 hours;By Ethyl acetate fraction through silica gel column chromatography initial gross separation,
Be successively 100:0,100:5 with volume ratio, 100:7,100:10,100:30,100:50,100:70,100:100,100:200,
The petroleum ether of 0:100-acetone mixed solvent system carries out gradient elution, each gradient 9.1L eluent, flow velocity 10mL/
Min, every 350ml volume are a fraction, collect 260 fractions, each fraction is tested and analyzed through silica gel thin-layer chromatography, use GF254
Lamellae, respectively using the methylene chloride-methanol of petroleum ether-acetone of volume ratio 1:1 and volume ratio 5:1 as solvent, with body
Sulfuric acid-ethanol solution of the product than 10:90 is as color developing agent, 105 DEG C of 3-5min of heating, according to thin-layer chromatography testing result, difference
Merge fraction 1-35, fraction 36-85, fraction 86-104, fraction 105-115, fraction 116-132, fraction 133-144, fraction
145-157, fraction 158-163, fraction 164-170, fraction 171-182, fraction 183-188, fraction 189-195, fraction 196-
204, fraction 205-208, fraction 209-234, fraction 235-260 obtain-Fr.16 components of Fr.1;Component Fr.8 is passed through
Sephadex LH-20 gel column chromatography, methanol elution, flow velocity 50mL/h, every 8mL are a fraction, collect 43 fractions, respectively
A fraction is tested and analyzed through silica gel thin-layer chromatography, with GF254 lamellae, using the dichloromethane-acetone of volume ratio 5:3 as expansion
Agent, using sulfuric acid-ethanol solution of volume ratio 10:90 as color developing agent, 105 DEG C of 3-5min of heating are detected according to thin-layer chromatography and are tied
Fruit, respectively merge fraction 4-7, fraction 8-13, fraction 9-26, fraction 27-33, fraction 34-43, obtain 5 inferior component Fr.8-1,
Fr.8-2,Fr.8-3,Fr.8-4,Fr.8-5;Inferior component Fr.8-4 is purified through preparative high performance liquid chromatography, chromatographic column YMC-
Pack ODS-A, then eluted with volume ratio for the methanol-water mixed solution of 72:28, flow velocity 7mL/min collects retention time
Chemical compounds I is obtained for the chromatographic peak of 36min;By component Fr.9 through silica gel column chromatography, petroleum ether-acetone of volume ratio 100:30 is mixed
Bonding solvent elution, every 10mL are a fraction, collect the fraction containing compounds Ⅳ and obtain compounds Ⅳ;Component Fr.11 is passed through
Silica gel column chromatography, petroleum ether-acetone mixed solvent system elutions of volume ratio 100:7,100:10,100:15,100:20 are each
Gradient 5mL eluent, every 5mL are a fraction, collect 40 fractions, and each fraction is tested and analyzed through silica gel thin-layer chromatography, are used
GF254 lamellae, respectively using petroleum ether-acetone of volume ratio 5:4 as solvent, with sulfuric acid-ethyl alcohol of volume ratio 10:90
Solution is as color developing agent, 105 DEG C of 3-5min of heating, according to thin-layer chromatography testing result, merge respectively fraction 1-8, fraction 9-15,
Fraction 16-31, fraction 32-40 obtain 4 inferior components Fr.11-1, Fr.11-2, Fr.11-3, Fr.11-4;Inferior component
Fr.11-4 is purified through preparative high performance liquid chromatography, is the Methanol+Water system elutions of 80:20, chromatography with volume ratio
Column is YMC-Pack ODS-A, flow velocity 7mL/min, collects the chromatographic peak that retention time is 69min and obtains compound III;By group
Divide Fr.13 through silica gel column chromatography, volume ratio 100:40 petroleum ether-acetone mixed solution elution, every 3mL is a fraction, and collection contains
There is the fraction of compound ii to obtain compound ii.
Embodiment 3
A kind of preparation method of isopentene group flavone compound of the present invention, using Himalayan mayapple fruit medicinal material 8kg as raw material, with
24L, volumetric concentration are 85% ethyl alcohol heating and refluxing extraction 3 times, and Extracting temperature is 92 DEG C, and each extraction time is 1.5 hours, are subtracted
Receipts ethyl alcohol is pushed back, medicinal extract shape ethanol extract is obtained, is suspended in the distilled water of 2.8L, successively with petroleum ether, methylene chloride, acetic acid
Ethyl ester, n-butanol respectively extract 3 times, each 2.8L, and the time is 1.5 hours;By Ethyl acetate fraction through at the beginning of silica gel column chromatography
Step separation, be successively 100:0,100:5 with volume ratio, 100:7,100:10,100:30,100:50,100:70,100:100,
The petroleum ether of 100:200,0:100-acetone mixed solvent system carry out gradient elution, each gradient 11.7L eluent, flow velocity
For 13mLmin-1, every 450ml volume is a fraction, collect 260 fractions, each fraction is tested and analyzed through silica gel thin-layer chromatography,
With GF254 lamellae, respectively using the methylene chloride-methanol of petroleum ether-acetone of volume ratio 1:1 and volume ratio 5:1 as expansion
Agent, using sulfuric acid-ethanol solution of volume ratio 10:90 as color developing agent, 105 DEG C of 3-5min of heating are detected according to thin-layer chromatography and are tied
Fruit, respectively merge fraction 1-35, fraction 36-85, fraction 86-104, fraction 105-115, fraction 116-132, fraction 133-144,
Fraction 145-157, fraction 158-163, fraction 164-170, fraction 171-182, fraction 183-188, fraction 189-195, fraction
196-204, fraction 205-208, fraction 209-234, fraction 235-260 obtain-Fr.16 components of Fr.1;Component Fr.8 is passed through
Sephadex LH-20 gel column chromatography, methanol elution, flow velocity 65mL/h, every 10mL are a fraction, collect 43 fractions, respectively
A fraction is tested and analyzed through silica gel thin-layer chromatography, with GF254 lamellae, using the dichloromethane-acetone of volume ratio 5:3 as exhibition
Agent is opened, using sulfuric acid-ethanol solution of volume ratio 10:90 as color developing agent, 105 DEG C of 3-5min of heating are detected according to thin-layer chromatography
As a result, merging fraction 4-7, fraction 8-13, fraction 9-26, fraction 27-33, fraction 34-43 respectively, 5 inferior component Fr.8- are obtained
1,Fr.8-2,Fr.8-3,Fr.8-4,Fr.8-5;Inferior component Fr.8-4 is purified through preparative high performance liquid chromatography, and chromatographic column is
YMC-Pack ODS-A, then with volume ratio be the Methanol+Water system elutions of 72:28, flow velocity 7mL/min is collected
Retention time is that the chromatographic peak of 36min obtains chemical compounds I;By component Fr.9 through silica gel column chromatography, the petroleum of volume ratio 100:30
Ether-acetone mixed solvent elution, every 12mL are a fraction, collect the fraction containing compounds Ⅳ and obtain compounds Ⅳ;By group
Divide Fr.11 through silica gel column chromatography, petroleum ether-acetone mixed solvent system of volume ratio 100:7,100:10,100:15,100:20
System elution, each gradient 75mL eluent, every 7.5mL are a fraction, collect 40 fractions, each fraction is through silica gel thin-layer
Chromatography tests and analyzes, with GF254 lamellae, respectively using petroleum ether-acetone of volume ratio 5:4 as solvent, with volume ratio
Sulfuric acid-ethanol solution of 10:90 merges as color developing agent, 105 DEG C of 3-5min of heating according to thin-layer chromatography testing result respectively
Fraction 1-8, fraction 9-15, fraction 16-31, fraction 32-40, obtain 4 inferior component Fr.11-1, Fr.11-2, Fr.11-3,
Fr.11-4;Inferior component Fr.11-4 is purified through preparative high performance liquid chromatography, molten for the methanol-water mixing of 80:20 with volume ratio
Agent system elutions, chromatographic column are YMC-Pack ODS-A, flow velocity 7mL/min, collect the chromatographic peak that retention time is 69min and obtain
To compound III;By component Fr.13 through silica gel column chromatography, volume ratio 100:40 petroleum ether-acetone mixed solution is eluted, often
4.5mL is a fraction, collects the fraction containing compound ii and obtains compound ii.
Embodiment 4
In specific implementation, the novel isopentene group flavone compound with antioxidant activity can also be by small by the present invention
Leaf lotus medicinal material 7kg is raw material, and with 28L, volumetric concentration for 75% ethyl alcohol heating and refluxing extraction 3 times, Extracting temperature is 90 DEG C, often
Secondary extraction time be 2 hours, ethyl alcohol is recovered under reduced pressure, obtains medicinal extract shape ethanol extract, is suspended in the distilled water of 2.4L, successively with
Petroleum ether, methylene chloride, ethyl acetate, n-butanol respectively extract 3 times, each 2.4L, and the time is 2 hours;Ethyl acetate is extracted
Position is successively 100:0,100:5 with volume ratio, 100:7,100:10,100:30,100 through silica gel column chromatography initial gross separation:
50, the petroleum ether of 100:70,100:100,100:200,0:100-acetone mixed solvent system carry out gradient elution, Mei Yiti
Degree 10.4L eluent, flow velocity 12mLmin-1, every 400ml volume is a fraction, collects 260 fractions, each fraction warp
Silica gel thin-layer chromatography tests and analyzes, with GF254 lamellae, respectively with petroleum ether-acetone of volume ratio 1:1 and volume ratio 5:1
Methylene chloride-methanol is as solvent, using sulfuric acid-ethanol solution of volume ratio 10:90 as color developing agent, 105 DEG C of heating 3-
5min, according to thin-layer chromatography testing result, merge respectively fraction 1-35, fraction 36-85, fraction 86-104, fraction 105-115,
Fraction 116-132, fraction 133-144, fraction 145-157, fraction 158-163, fraction 164-170, fraction 171-182, fraction
183-188, fraction 189-195, fraction 196-204, fraction 205-208, fraction 209-234, fraction 235-260, obtain
- Fr.16 components of Fr.1;By component Fr.8 through Sephadex LH-20 gel column chromatography, methanol is eluted, flow velocity 55mL/h,
Every 9mL is a fraction, collects 43 fractions, and each fraction tests and analyzes through silica gel thin-layer chromatography, with GF254 lamellae, with body
Dichloromethane-acetone of the product than 5:3 is as solvent, using sulfuric acid-ethanol solution of volume ratio 10:90 as color developing agent, 105
DEG C 3-5min of heating merge fraction 4-7, fraction 8-13, fraction 9-26, fraction 27-according to thin-layer chromatography testing result respectively
33, fraction 34-43 obtain 5 inferior components Fr.8-1, Fr.8-2, Fr.8-3, Fr.8-4, Fr.8-5;Inferior component Fr.8-4 warp
Preparative high-performance liquid chromatographic, chromatographic column is YMC-Pack ODS-A, then is washed with volume ratio for the methanol-water mixed solution of 72:28
De-, flow velocity 7mL/min collects the chromatographic peak that retention time is 36min and obtains chemical compounds I;By component Fr.9 through silicagel column color
Spectrum, petroleum ether-acetone mixed solvent elution of volume ratio 100:30, every 11mL is a fraction, collects the stream containing compounds Ⅳ
Part obtains compounds Ⅳ;By component Fr.11 through silica gel column chromatography, volume ratio 100:7,100:10,100:15,100:20's
Petroleum ether-acetone mixed solvent system elutions, each gradient 70mL eluent, every 7mL are a fraction, collect 40 fractions,
Each fraction is tested and analyzed through silica gel thin-layer chromatography, with GF254 lamellae, is made respectively with the petroleum ether of volume ratio 5:4-acetone
For solvent, using sulfuric acid-ethanol solution of volume ratio 10:90 as color developing agent, 105 DEG C of 3-5min of heating, according to thin-layer chromatography
Testing result, respectively merge fraction 1-8, fraction 9-15, fraction 16-31, fraction 32-40, obtain 4 Arius part Fr.11-1,
Fr.11-2,Fr.11-3,Fr.11-4;Arius part Fr.11-4 is purified through preparative high-performance liquid chromatographic, is 80:20 with volume ratio
Methanol+Water elution, chromatographic column be YMC-Pack ODS-A, flow velocity 7mL/min, collect retention time be
The chromatographic peak of 69min obtains compound III;By component Fr.13 through silica gel column chromatography, volume ratio 100:40 petroleum ether-acetone mixing
Solution elution, every 4mL are a fraction, collect the fraction containing compound ii and obtain compound ii.
The method of the present invention is reliable and stable, easy to operate, embodiment 1-4 products therefrom through UV, IR, NMR spectrum (1H-
NMR、13C-NMR, HSQC, HMBC) and high resolution mass spectrum (HR-ESI-MS) spectral technique be accredited as novel isopentene group flavones
Class compound Chinese podophyllum root ketone Q (sinoflavonoid Q), Chinese podophyllum root ketone R (sinoflavonoid R), Chinese podophyllum root ketone S
(sinoflavonoid S), Chinese podophyllum root ketone T (sinoflavonoid T) has Scavenging activity to DPPH free radical.Related money
Expect as follows:
One, the identification of compound
Chemical compounds I, yellow powder, hydrochloric acid-magnesium powder reaction are positive, and prompt may be flavone compound.HR-ESI-MS
Provide quasi-molecular ion peak m/z 453.1910 [M ﹢ H]+(calcd for C26H29O7, 453.1913, determine that molecular formula is
C26H28O7。 IR(KBr,cm-1) show that the compound has free hydroxyl group (3354cm-1), associate carbonyl (1659cm-1), phenyl ring
(1611 cm-1).UV (λ max) shows that the compound has flavones ol skeleton (262,321nm).1H NMR(500MHz,DMSO-
d6) display two groups of aromatic Coupling System signal δ 6.35 (1H, s), 6.76 (1H, d, J=8.3Hz), 6.74 (1H, d, J=
8.3 Hz), it is respectively belonging to the A ring and B ring of flavones parent nucleus, one five is respectively present in prompting structure and is replaced and 1,2,3,4- tetra-
Substituted benzene ring structural unit.By 2 groups of methene proton signal δ 3.21 (2H, d, J=7.1Hz), 3.24 (2H, d, J=7.3Hz),
Four methyl proton signal δ 1.71 (3H, s), 1.61 (3H, s), 1.34 (3H, s), 1.49 (3H, the s) being connected with quaternary carbon, two
A alkene Hydrogen Proton δ 5.16 (1H, t, J=7.1), 5.03 (1H, t, J=7.3), there are 2 isopentene groups in prompting structure.1
The methoxy proton signal δ 3.56 (3H, s) being connected with olefinic carbon.Five phenolic hydroxyl group proton δ 12.90 (1H, s), 10.81 (1H, s),
9.87 (1H, s), 8.52 (1H, s), wherein δ 12.90 (1H, s) is the 5 phenolic hydroxyl group proton signals to associate with 4 carbonyls.13C
NMR(125 MHz,DMSO-d6) display contains 26 carbon atoms, in addition to 2 groups of isopentene group carbon signal δ 21.4,122.6,
131.1, except 18.1,25.9,26.2,123.3,130.6,17.8,25.7,12 fragrant carbon signals, 1 carbonyl are given
Carbon signal δ 178.5, two olefinic carbon signal δ 159.6,139.0 being connected with oxygen, the above carbon modal data further demonstrate that chemical compounds I
For isopentene group flavones 01 derivatives.HMBC spectrum in, by methene proton signal δ 3.21 (2H, d, J=7.1Hz, H-1 ") with
The long-range correlation of δ 158.5 (C-5), 111.1 (C-6), 162.3 (C-7), δ 3.24 (2H, d, J=7.3Hz, H-1 " ') and δ
The long-range correlation of 123.2 (C-1 '), 128.2 (C-2 '), 143.7 (C-3 ') show that two isopentene groups are connected to flavones
The position C-6 and C-2 ' of parent nucleus.It is remotely related by δ 3.56 (3H, s) and the HMBC of δ 139.0 (C-3), show the methoxy not belonged to
Base is connected to C-3.By chemical compounds I1H NMR、13C NMR signal is belonged to by HSQC, HMBC spectrum (see Table 1).
Therefore chemical compounds I structure be 6,2 '-di (3-methyl-2-butenyl) -5,7,3 ', 4 '-tetrahydroxy-3-
Methoxyflavone is named as Chinese podophyllum root ketone Q (sinoflavonoid Q).
Table 1.NMR(500MHz,DMSO-d6)assignments for I.
Compound ii, yellow powder, hydrochloric acid-magnesium powder reaction are positive, and prompt may be flavone compound.HR-ESI-
MS provides quasi-molecular ion peak m/z 453.1910 [M ﹢ H]+(calcd for C26H29O7, 453.1913), determine that molecular formula is
C26H28O7。IR(KBr,cm-1) show that the compound has free hydroxyl group (3374cm-1), associate carbonyl (1650cm-1), phenyl ring
(1597cm-1).UV (λ max) shows that the compound has flavones ol skeleton (262,321nm).1H NMR(500MHz, DMSO-
d6) two groups of aromatic Coupling System signal δ 6.28 (1H, s) of display, 6.68 (1H, d, J=8.2Hz), 6.72 (1H, d, J=
8.2Hz), it is respectively belonging to the A ring and B ring of flavones parent nucleus, one five is respectively present in prompting structure and is replaced and 1,2,3,4- tetra-
Substituted benzene ring structural unit.By 2 groups of methene proton signal δ 2.54 (2H, t, J=6.8Hz), 1.74 (2H, t, J=6.8Hz),
Methyl proton signal δ 1.30 (6H, s) on two quaternary carbons, there are 12,2- dimethyl dihydropyran rings in prompting structure.By 1
A methene proton signal δ 3.21 (2H, d, J=6.9Hz), two be connected with quaternary carbon methyl proton signal δ 1.34 (3H,
S), 1.50 (3H, s), an alkene Hydrogen Proton δ 5.04 (1H, t, J=6.9), there are 1 isopentene groups in prompting structure.1 with
The connected methoxy proton signal δ 3.48 (3H, s) of olefinic carbon.Three phenolic hydroxyl group signal δ 10.60 (1H, s), 9.75 (1H, s),
8.46 (1H, s), wherein δ 10.60 (1H, s) is 7 phenolic hydroxyl group proton signals.13C NMR(125MHz,DMSO-d6) display contain
There are 26 carbon atoms, in addition to 1 group of 2,2- dimethyl-dihydro pyranyl δ 16.7,30.8,74.7,26.4 (× 2), one group of isoamyl
Alkenyl δ 26.0,122.9,129.9,17.4,25.4, δ 59.4 except a methoxyl group, give 12 fragrant carbon signals, and 1
Carbonyl carbon signals δ 172.0, two company oxygen olefinic carbon signal δ 155.1,140.6, the above carbon modal data further demonstrates that compound ii
For isopentene group flavones 01 derivatives.HMBC spectrum in, by methene proton signal δ 2.54 (2H, t, J=6.8Hz, H-1 ") with
The long-range correlation of δ 154.6 (C-5), 105.0 (C-6), 159.8 (C-7), in conjunction with 7 phenolic hydroxyl group signal δ 10.60 (1H, s)
In the presence of, show dihydropyran ring and flavones parent nucleus C-5 and C-6 it is parallel and.By methene proton signal δ 3.21 (2H, t, J=
6.9Hz, H-1 " ') to δ 121.8 (C-1 '), 127.6 (C-2 '), 143.2 (C-3 ') it is long-range related, show isopentene group connect
It connects in 2 ' positions.It is remotely related by δ 3.56 (3H, s) and the HMBC of δ 140.6 (C-3), show that the methoxyl group not belonged to is connected to
C-3.By compound ii1H NMR、13C NMR signal is belonged to by HSQC, HMBC spectrum (see Table 2).Therefore change
Close object II structure be 5,6- (2,2-dimethyldihydropyrano) -2 '-(3-methyl-2-butenyl) -7,3 ',
4 '-trihydroxy-3-methoxyflavone are named as Chinese podophyllum root ketone R (sinoflavonoid R).
Table 2.NMR(500MHz,DMSO-d6)assignments forⅡ.
Compound III, yellow powder, hydrochloric acid-magnesium powder reaction are positive, and prompt may be flavone compound.HR-ESI-
MS provides quasi-molecular ion peak m/z 453.1912 [M ﹢ H]+(calcd for C26H29O7, 453.1913), determine that molecular formula is
C26H28O7。IR(KBr,cm-1) show that the compound has free hydroxyl group (3524cm-1), associate carbonyl (1651cm-1), phenyl ring
(1604cm-1).UV (λ max) shows that the compound has flavones ol skeleton (261,325nm).1H NMR(500MHz, DMSO-
d6) two groups of aromatic Coupling System signal δ 6.34 (1H, s) of display, 6.73 (1H, d, J=8.4Hz), 6.76 (1H, d, J=
8.4Hz), it is respectively belonging to the A ring and B ring of flavones parent nucleus, one five is respectively present in prompting structure and is replaced and 1,2,3,4- tetra-
Substituted benzene ring structural unit.By 2 groups of methene proton signal δ 2.62 (2H, t, J=6.7Hz), 1.81 (2H, t, J=6.7Hz),
Methyl proton signal δ 1.30 (6H, s) on two quaternary carbons, there are 12,2- dimethyl dihydropyran rings in prompting structure.By 1
A methene proton signal δ 3.25 (2H, d, J=6.9Hz), two be connected with quaternary carbon methyl proton signal δ 1.30 (3H,
S), 1.45 (3H, s), an alkene Hydrogen Proton δ 5.00 (1H, t, J=6.9Hz), there are 1 isopentene groups in prompting structure.1
The methoxy proton signal δ 3.56 (3H, s) being connected with olefinic carbon.Three phenolic hydroxyl group signal δ 13.00 (1H, s), 9.86 (1H, s),
8.56 (1H, s), wherein δ 13.00 (1H, s) is the 5 phenolic hydroxyl group proton signals to associate with 4 carbonyls.13C NMR(125MHz,
DMSO-d6) display contain 26 carbon atoms, in addition to 1 group of 2,2- dimethyl dihydro pyranyl δ 15.7,30.9,76.2,26.3 (×
2), one group of isopentene group δ 25.7,122.8,130.2,17.4,25.4, δ 59.9 except a methoxyl group, gives 12 fragrance
Carbon signal, 1 carbonyl carbon signals δ 178.2, two company oxygen olefinic carbon signal δ 159.7,138.5, the above further table of carbon modal data
Bright compound III is isopentene group flavones 01 derivatives.In HMBC spectrum, by methene proton signal δ 2.62 (2H, t, J=
6.7Hz, H-1 ") to δ 104.4 (C-6), 159.8 (C-7), 94.4 (C-8) it is long-range related, in conjunction with 5 phenolic hydroxyl group signal δ
The presence of 13.00 (1H, s), show 2,2- dimethyl dihydropyran ring and flavones parent nucleus C-6 and C-7 it is parallel and.By methylene
Proton signal δ 3.25 (2H, d, J=6.9Hz, H-1 " ') and δ 121.1 (C-1 '), 127.8 (C-2 '), 143.3 (C-3 ')
It is long-range related, show that isopentene group is connected to 2 ' positions.Remotely related, the table by δ 3.56 (3H, s) and the HMBC of δ 138.5 (C-3)
The bright methoxyl group not belonged to is connected to C-3.By compound III1H NMR、13C NMR signal is carried out by HSQC, HMBC spectrum
Belong to (see Table 3).Therefore the structure of compound III is 6,7- (2,2-dimethyldihydropyrano) -2 '-(3-
Methyl-2-butenyl) -5,3 ', 4 '-trihydroxy-3-methoxyflavone are named as Chinese podophyllum root ketone S
(sinoflavonoid S)。
Table 3.NMR(500MHz,DMSO-d6)assignments forⅢ.
Compounds Ⅳ, yellow powder, hydrochloric acid-magnesium powder reaction are positive, and prompt may be flavone compound.HR-ESI-
MS provides quasi-molecular ion peak m/z 385.1262 [M ﹢ H]+(calcd for C21H21O7, 385.1287), determine that molecular formula is
C21H20O7。IR(KBr,cm-1) show that the compound has free hydroxyl group (3421cm-1), association carbonyl (1655cm-1), phenyl ring
(1617cm-1).UV (λ max) shows that compound tool has flavones ol skeleton (256,345nm).1H NMR(500MHz,
DMSO-d6) display two groups of aromatic Coupling System signal δ 6.40 (1H, s), 7.46 (1H, d, J=2.2Hz), 6.86 (1H,
D, J=8.5Hz), 7.35 (1H, dd, J=8.5,2.2Hz), the A ring and B ring of flavones parent nucleus are respectively belonging to, in prompting structure
One five is respectively present to replace and 1,3,4- trisubstituted benzene ring structure.By 2 groups of methene proton signal δ 2.54 (2H, t, J=
6.7Hz), 1.72 (2H, t, J=6.7Hz), 2 methyl proton signal δ 1.30 (6H, s) being connected with quaternary carbon, shows in structure
There are 1 2,2- dimethyl dihydropyran rings.1 methoxy proton signal δ 3.69 (3H, s) being connected with olefinic carbon.Two phenol
Hydroxyl proton signal δ 10.67 (1H, s), 9.55 (1H, s), 9.29 (1H, s), wherein δ 10.67 (1H, s) is 7 phenolic hydroxyl group matter
Subsignal.13C NMR (125MHz,DMSO-d6) display is containing 21 carbon atoms, in addition to the carbon signal δ 59.2,1 of 1 methoxyl group
Except group 2,2- dimethyl dihydropyran ring carbon signal δ 16.7,30.8,74.8,26.4 (× 2), 12 aromatic carbon letters are given
Number, 1 carbonyl carbon signals δ 172.1, two olefinic carbon signal δ 151.4,139.7 being connected with oxygen, the above carbon modal data is further
Show that compounds Ⅳ is isopentene group flavones 01 derivatives.In HMBC spectrum, by methene proton signal δ 2.54 (2H, d, J=
6.7Hz, H-1 ") to δ 154.5 (C-5), 105.0 (C-6), 159.8 (C-7) it is long-range related, show 2,2- dimethyl dihydro
Pyranoid ring is connected to C-5 and C-6.It is remotely related by δ 3.69 (3H, s) and the HMBC of δ 139.7 (C-3), show not belong to
Methoxyl group be connected to C-3.By compounds Ⅳ1H NMR、13C NMR signal by HSQC, HMBC spectrum belonged to (see
Table 4).Therefore compounds Ⅳ structure be 5,6- (2,2-dimethyldihydropyrano) -7,3 ', 4 ' -
Trihydroxy-3-methoxyflavone is named as Chinese podophyllum root ketone T (sinoflavonoid T).
Table 4.NMR(500MHz,DMSO-d6)assignments forⅣ.
Two, antioxidant activity
With the DPPH solution of dehydrated alcohol configuration 0.1mmol/L, it is kept in dark place.By the DPPH solution of 50 μ L and it is isometric not
Testing sample solution with concentration mixes well, and dark place stands 30min at room temperature, its absorbance is measured at 517nm.DPPH
Free radical scavenging ability IC50Value indicates.As a result see Table 5.
- IV pair of PPH free radical scavenging ability of 5. chemical compounds I of Table
The novel isopentene group flavone compound Chinese podophyllum root ketone Q that the present invention prepares is shown by above-mentioned experiment
(sinoflavonoid Q), Chinese podophyllum root ketone R (sinoflavonoid R), Chinese podophyllum root ketone S (sinoflavonoid S), peach
Seven ketone T (sinoflavonoid T) have Scavenging activity to DPPH free radical, can be used as the antioxidant of food or beverage.
Claims (7)
1. a kind of isopentene group flavone compound, which is characterized in that the compound is the Chinese podophyllum root extracted from Himalayan mayapple fruit
Ketone Q (sinoflavonoids Q I), Chinese podophyllum root ketone R (sinoflavonoids R II), Chinese podophyllum root ketone S
(sinoflavonoids S III), Chinese podophyllum root ketone T (sinoflavonoids T IV), molecular structural formula is respectively as follows:
2. the preparation method of isopentene group flavone compound described in claim 1, which is characterized in that with Himalayan mayapple fruit medicinal material
6-9kg are raw material, with 2-5 times of raw material weights, ethyl alcohol heating and refluxing extraction 3 times that volumetric concentration is 75%-95%, Extracting temperature
It is 90-95 DEG C, each extraction time is 1.5-2 hours, and ethyl alcohol is recovered under reduced pressure and obtains medicinal extract shape ethanol extract, is suspended in 2-3.2L
Distilled water in, successively respectively extract 3 times with petroleum ether, methylene chloride, ethyl acetate, n-butanol, every time 2-3.2L, time be
1.5-2 hours;Ethyl acetate fraction is separated through silica gel column chromatography, be successively 100:0,100:5 with volume ratio, 100:7,
The petroleum ether of 100:10,100:30,100:50,100:70,100:100,100:200,0:100-acetone mixed solvent system into
Row gradient elution, 9.1-13L eluents of each gradient, flow velocity are 10-15mL/min, and every 350-500ml volume is a fraction,
260 fractions are collected, each fraction is tested and analyzed through silica gel thin-layer chromatography, with GF254 lamellae, respectively with volume ratio 1:1's
The methylene chloride-methanol of petroleum ether-acetone and volume ratio 5:1 are as solvent, with sulfuric acid-ethanol solution of volume ratio 10:90
As color developing agent, 105 DEG C of 3-5min of heating merge fraction 1-35, fraction 36-85, stream according to thin-layer chromatography testing result respectively
Part 86-104, fraction 105-115, fraction 116-132, fraction 133-144, fraction 145-157, fraction 158-163, fraction 164-
170, fraction 171-182, fraction 183-188, fraction 189-195, fraction 196-204, fraction 205-208, fraction 209-234,
Fraction 235-260 obtains component Fr.1-Fr.16;By component Fr.8 through Sephadex LH-20 gel column chromatography, methanol is eluted,
Flow velocity is 50-70mL/h, and every 8-12mL is a fraction, collects 43 fractions, and each fraction is tested and analyzed through silica gel thin-layer chromatography,
It is molten with sulfuric acid-ethyl alcohol of volume ratio 10:90 using the dichloromethane-acetone of volume ratio 5:3 as solvent with GF254 lamellae
Liquid merges fraction 4-7, fraction 8-13, stream according to thin-layer chromatography testing result as color developing agent, 105 DEG C of 3-5min of heating respectively
Part 9-26, fraction 27-33, fraction 34-43, obtain 5 inferior components Fr.8-1, Fr.8-2, Fr.8-3, Fr.8-4, Fr.8-5;It is sub-
Component Fr.8-4 is purified through preparative high performance liquid chromatography, and chromatographic column is YMC-Pack ODS-A, then with volume ratio is 72:28's
Methanol+Water system elutions, flow velocity 7mL/min collect the chromatographic peak that retention time is 36min and obtain chemical compounds I;
By component Fr.9 through silica gel column chromatography, petroleum ether-acetone mixed solvent elution of volume ratio 100:30, every 10-15mL is one stream
Part, it collects the fraction containing compounds Ⅳ and obtains compounds Ⅳ;By component Fr.11 through silica gel column chromatography, volume ratio 100:7,
The petroleum ether of 100:10,100:15,100:20-acetone mixed solvent system elutions, 50-80mL eluents of each gradient, often
5-8mL are a fraction, collect 40 fractions, and each fraction is tested and analyzed through silica gel thin-layer chromatography, with GF254 lamellae, difference
Using petroleum ether-acetone of volume ratio 5:4 as solvent, using sulfuric acid-ethanol solution of volume ratio 10:90 as color developing agent, 105
DEG C 3-5min of heating merge fraction 1-8, fraction 9-15, fraction 16-31, fraction 32-according to thin-layer chromatography testing result respectively
40, obtain 4 inferior components Fr.11-1, Fr.11-2, Fr.11-3, Fr.11-4;Inferior component Fr.11-4 is through preparative efficient liquid phase
Chromatogram purification, is the Methanol+Water system elutions of 80:20 with volume ratio, and chromatographic column is YMC-Pack ODS-A, flow velocity
For 7mL/min, collects the chromatographic peak that retention time is 69min and obtain compound III;By component Fr.13 through silica gel column chromatography, body
Product is eluted than 100:40 petroleum ether-acetone mixed solution, and every 3-5mL is a fraction, collects the fraction containing compound ii to obtain the final product
To compound ii.
3. the preparation method of isopentene group flavone compound according to claim 2, which is characterized in that with Himalayan mayapple fruit
Medicinal material 9kg is raw material, and with 18L, volumetric concentration for 95% ethyl alcohol heating and refluxing extraction 3 times, Extracting temperature is 95 DEG C, is extracted every time
Time is 1.5 hours, and ethyl alcohol is recovered under reduced pressure, obtains medicinal extract shape ethanol extract, is suspended in the distilled water of 3.2L, successively with petroleum
Ether, methylene chloride, ethyl acetate, n-butanol respectively extract 3 times, each 3.2L, and the time is 1.5 hours;Ethyl acetate is extracted into portion
Position through silica gel column chromatography initial gross separation, be successively 100:0,100:5 with volume ratio, 100:7,100:10,100:30,100:50,
The petroleum ether of 100:70,100:100,100:200,0:100-acetone mixed solvent system carry out gradient elution, and each gradient is used
13L eluent, flow velocity 15mL/min, every 500ml volume are a fraction, collect 260 fractions, each fraction through silica gel thin-layer
Chromatography tests and analyzes, with GF254 lamellae, respectively with the methylene chloride-of petroleum ether-acetone of volume ratio 1:1 and volume ratio 5:1
Methanol is as solvent, using sulfuric acid-ethanol solution of volume ratio 10:90 as color developing agent, 105 DEG C of 3-5min of heating, according to thin
Layer chromatography testing result, respectively merge fraction 1-35, fraction 36-85, fraction 86-104, fraction 105-115, fraction 116-132,
Fraction 133-144, fraction 145-157, fraction 158-163, fraction 164-170, fraction 171-182, fraction 183-188, fraction
189-195, fraction 196-204, fraction 205-208, fraction 209-234, fraction 235-260 obtain-Fr.16 components of Fr.1;
By component Fr.8 through Sephadex LH-20 gel column chromatography, methanol elution, flow velocity 70mL/h, every 12mL are a fraction, receive
Collect 43 fractions, each fraction is tested and analyzed through silica gel thin-layer chromatography, with GF254 lamellae, with the dichloromethane of volume ratio 5:3
Alkane-acetone is as solvent, using sulfuric acid-ethanol solution of volume ratio 10:90 as color developing agent, 105 DEG C of 3-5min of heating, according to
Thin-layer chromatography testing result merges fraction 4-7, fraction 8-13, fraction 9-26, fraction 27-33, fraction 34-43 respectively, obtains 5
A inferior component Fr.8-1, Fr.8-2, Fr.8-3, Fr.8-4, Fr.8-5;Inferior component Fr.8-4 is pure through preparative high performance liquid chromatography
Change, chromatographic column is YMC-Pack ODS-A, then with volume ratio is the Methanol+Water system elutions of 72:28, and flow velocity is
7mL/min collects the chromatographic peak that retention time is 36min and obtains chemical compounds I;By component Fr.9 through silica gel column chromatography, volume ratio
The petroleum ether of 100:30-acetone mixed solvent elution, every 15mL are a fraction, collect the fraction containing compounds Ⅳ and are changed
Close object IV;By component Fr.11 through silica gel column chromatography, petroleum ether-acetone of volume ratio 100:7,100:10,100:15,100:20
Mixed solvent system elution, each gradient 80mL eluent, every 8mL are a fraction, collect 40 fractions, each fraction is through silicon
Glue thin-layer chromatography tests and analyzes, with GF254 lamellae, respectively using petroleum ether-acetone of volume ratio 5:4 as solvent, with body
Sulfuric acid-ethanol solution of the product than 10:90 is as color developing agent, 105 DEG C of 3-5min of heating, according to thin-layer chromatography testing result, difference
Merge fraction 1-8, fraction 9-15, fraction 16-31, fraction 32-40, obtains 4 inferior components Fr.11-1, Fr.11-2, Fr.11-
3,Fr.11-4;Inferior component Fr.11-4 is purified through preparative high performance liquid chromatography, is mixed with volume ratio for the methanol-water of 80:20
Solvent system elution, chromatographic column are YMC-Pack ODS-A, flow velocity 7mL/min, collect the chromatographic peak that retention time is 69min
Obtain compound III;By component Fr.13 through silica gel column chromatography, volume ratio 100:40 petroleum ether-acetone mixed solution is eluted, often
5mL is a fraction, collects the fraction containing compound ii and obtains compound ii.
4. the preparation method of isopentene group flavone compound according to claim 2, which is characterized in that with Himalayan mayapple fruit
Medicinal material 6kg is raw material, and with 30L, volumetric concentration for 75% ethyl alcohol heating and refluxing extraction 3 times, Extracting temperature is 90 DEG C, is extracted every time
Time be 2 hours, ethyl alcohol is recovered under reduced pressure, obtains medicinal extract shape ethanol extract, is suspended in the distilled water of 2L, successively with petroleum ether,
Methylene chloride, ethyl acetate, n-butanol respectively extract 3 times, each 2L, and the time is 2 hours;By Ethyl acetate fraction through silica gel
Column chromatography initial gross separation is successively 100:0,100:5 with volume ratio, 100:7,100:10,100:30,100:50,100:70,
The petroleum ether of 100:100,100:200,0:100-acetone mixed solvent system carry out gradient elution, and each gradient is eluted with 9.1L
Liquid, flow velocity 10mL/min, every 350ml volume are a fraction, collect 260 fractions, each fraction is examined through silica gel thin-layer chromatography
Analysis is surveyed, with GF254 lamellae, is made respectively with the methylene chloride-methanol of petroleum ether-acetone of volume ratio 1:1 and volume ratio 5:1
For solvent, using sulfuric acid-ethanol solution of volume ratio 10:90 as color developing agent, 105 DEG C of 3-5min of heating, according to thin-layer chromatography
Testing result merges fraction 1-35, fraction 36-85, fraction 86-104, fraction 105-115, fraction 116-132, fraction respectively
133-144, fraction 145-157, fraction 158-163, fraction 164-170, fraction 171-182, fraction 183-188, fraction 189-
195, fraction 196-204, fraction 205-208, fraction 209-234, fraction 235-260 obtain-Fr.16 components of Fr.1;By group
Divide Fr.8 through Sephadex LH-20 gel column chromatography, methanol elution, flow velocity 50mL/h, every 8mL are a fraction, collect 43
Fraction, each fraction are tested and analyzed through silica gel thin-layer chromatography, with GF254 lamellae, with the dichloromethane-acetone of volume ratio 5:3
As solvent, using sulfuric acid-ethanol solution of volume ratio 10:90 as color developing agent, 105 DEG C of 3-5min of heating, according to thin layer color
Testing result is composed, merges fraction 4-7, fraction 8-13, fraction 9-26, fraction 27-33, fraction 34-43 respectively, obtains 5 subgroups
Part Fr.8-1, Fr.8-2, Fr.8-3, Fr.8-4, Fr.8-5;Inferior component Fr.8-4 is purified through preparative high performance liquid chromatography, color
Spectrum column is YMC-Pack ODS-A, then is eluted with volume ratio for the methanol-water mixed solution of 72:28, and flow velocity 7mL/min is received
Integrate retention time and obtains chemical compounds I as the chromatographic peak of 36min;By component Fr.9 through silica gel column chromatography, the stone of volume ratio 100:30
Oily ether-acetone mixed solvent elution, every 10mL are a fraction, collect the fraction containing compounds Ⅳ and obtain compounds Ⅳ;It will
Component Fr.11 is through silica gel column chromatography, petroleum ether-acetone mixed solvent system of volume ratio 100:7,100:10,100:15,100:20
System elution, each gradient 5mL eluent, every 5mL are a fraction, collect 40 fractions, each fraction is through silica gel thin-layer chromatography
It tests and analyzes, with GF254 lamellae, respectively using petroleum ether-acetone of volume ratio 5:4 as solvent, with volume ratio 10:90's
Sulfuric acid-ethanol solution is as color developing agent, 105 DEG C of 3-5min of heating, according to thin-layer chromatography testing result, merge respectively fraction 1-8,
Fraction 9-15, fraction 16-31, fraction 32-40, obtain 4 inferior components Fr.11-1, Fr.11-2, Fr.11-3, Fr.11-4;It is sub-
Component Fr.11-4 is purified through preparative high performance liquid chromatography, is the Methanol+Water system elutions of 80:20 with volume ratio,
Chromatographic column is YMC-Pack ODS-A, flow velocity 7mL/min, collects the chromatographic peak that retention time is 69min and obtains compound III;
By component Fr.13 through silica gel column chromatography, volume ratio 100:40 petroleum ether-acetone mixed solution elution, every 3mL is a fraction, is received
Fraction of the collection containing compound ii obtains compound ii.
5. the preparation method of isopentene group flavone compound according to claim 2, which is characterized in that with Himalayan mayapple fruit
Medicinal material 8kg is raw material, and with 24L, volumetric concentration for 85% ethyl alcohol heating and refluxing extraction 3 times, Extracting temperature is 92 DEG C, is extracted every time
Time is 1.5 hours, and ethyl alcohol is recovered under reduced pressure, obtains medicinal extract shape ethanol extract, is suspended in the distilled water of 2.8L, successively with petroleum
Ether, methylene chloride, ethyl acetate, n-butanol respectively extract 3 times, each 2.8L, and the time is 1.5 hours;Ethyl acetate is extracted into portion
Position through silica gel column chromatography initial gross separation, be successively 100:0,100:5 with volume ratio, 100:7,100:10,100:30,100:50,
The petroleum ether of 100:70,100:100,100:200,0:100-acetone mixed solvent system carry out gradient elution, and each gradient is used
11.7L eluent, flow velocity 13mLmin-1, every 450ml volume is a fraction, and it is thin through silica gel to collect 260 fractions, each fraction
Layer chromatography tests and analyzes, with GF254 lamellae, respectively with the dichloromethane of petroleum ether-acetone of volume ratio 1:1 and volume ratio 5:1
Alkane-methanol is as solvent, using sulfuric acid-ethanol solution of volume ratio 10:90 as color developing agent, 105 DEG C of 3-5min of heating, according to
Thin-layer chromatography testing result merges fraction 1-35, fraction 36-85, fraction 86-104, fraction 105-115, fraction 116-respectively
132, fraction 133-144, fraction 145-157, fraction 158-163, fraction 164-170, fraction 171-182, fraction 183-188,
Fraction 189-195, fraction 196-204, fraction 205-208, fraction 209-234, fraction 235-260 obtain Fr.1-Fr.16
Component;By component Fr.8 through Sephadex LH-20 gel column chromatography, methanol elution, flow velocity 65mL/h, every 10mL are one stream
Part, collect 43 fractions, each fraction tests and analyzes through silica gel thin-layer chromatography, with GF254 lamellae, with the two of volume ratio 5:3
Chloromethanes-acetone is as solvent, using sulfuric acid-ethanol solution of volume ratio 10:90 as color developing agent, 105 DEG C of 3-5min of heating,
According to thin-layer chromatography testing result, merges fraction 4-7, fraction 8-13, fraction 9-26, fraction 27-33, fraction 34-43 respectively, obtain
To 5 inferior components Fr.8-1, Fr.8-2, Fr.8-3, Fr.8-4, Fr.8-5;Inferior component Fr.8-4 is through preparative high-efficient liquid phase color
Spectrum purifying, chromatographic column are YMC-Pack ODS-A, then with volume ratio are the Methanol+Water system elutions of 72:28, flow velocity
For 7mL/min, collects the chromatographic peak that retention time is 36min and obtain chemical compounds I;By component Fr.9 through silica gel column chromatography, volume
Petroleum ether-acetone mixed solvent elution than 100:30, every 12mL is a fraction, collects the fraction containing compounds Ⅳ and obtains
Compounds Ⅳ;By component Fr.11 through silica gel column chromatography, the petroleum ether-the third of volume ratio 100:7,100:10,100:15,100:20
The elution of ketone mixed solvent system, each gradient 75mL eluent, every 7.5mL are a fraction, collect 40 fractions, each fraction
It is tested and analyzed through silica gel thin-layer chromatography, with GF254 lamellae, respectively using petroleum ether-acetone of volume ratio 5:4 as solvent,
Using sulfuric acid-ethanol solution of volume ratio 10:90 as color developing agent, 105 DEG C of 3-5min of heating, according to thin-layer chromatography testing result,
Respectively merge fraction 1-8, fraction 9-15, fraction 16-31, fraction 32-40, obtain 4 inferior component Fr.11-1, Fr.11-2,
Fr.11-3,Fr.11-4;Inferior component Fr.11-4 is purified through preparative high performance liquid chromatography, is the methanol-of 80:20 with volume ratio
Water mixed solvent system elutions, chromatographic column are YMC-Pack ODS-A, flow velocity 7mL/min, and collecting retention time is 69min's
Chromatographic peak obtains compound III;By component Fr.13 through silica gel column chromatography, volume ratio 100:40 petroleum ether-acetone mixed solution is washed
De-, every 4.5mL is a fraction, collects the fraction containing compound ii and obtains compound ii.
6. the preparation method of isopentene group flavone compound according to claim 2, which is characterized in that by Himalayan mayapple fruit
Medicinal material 7kg is raw material, and with 28L, volumetric concentration for 75% ethyl alcohol heating and refluxing extraction 3 times, Extracting temperature is 90 DEG C, is extracted every time
Time is 2 hours, and ethyl alcohol is recovered under reduced pressure, obtains medicinal extract shape ethanol extract, is suspended in the distilled water of 2.4L, successively with petroleum
Ether, methylene chloride, ethyl acetate, n-butanol respectively extract 3 times, each 2.4L, and the time is 2 hours;By Ethyl acetate fraction
Through silica gel column chromatography initial gross separation, be successively 100:0,100:5 with volume ratio, 100:7,100:10,100:30,100:50,
The petroleum ether of 100:70,100:100,100:200,0:100-acetone mixed solvent system carry out gradient elution, and each gradient is used
10.4L eluent, flow velocity 12mLmin-1, every 400ml volume is a fraction, and it is thin through silica gel to collect 260 fractions, each fraction
Layer chromatography tests and analyzes, with GF254 lamellae, respectively with the dichloromethane of petroleum ether-acetone of volume ratio 1:1 and volume ratio 5:1
Alkane-methanol is as solvent, using sulfuric acid-ethanol solution of volume ratio 10:90 as color developing agent, 105 DEG C of 3-5min of heating, according to
Thin-layer chromatography testing result merges fraction 1-35, fraction 36-85, fraction 86-104, fraction 105-115, fraction 116-respectively
132, fraction 133-144, fraction 145-157, fraction 158-163, fraction 164-170, fraction 171-182, fraction 183-188,
Fraction 189-195, fraction 196-204, fraction 205-208, fraction 209-234, fraction 235-260 obtain Fr.1-Fr.16
Component;By component Fr.8 through Sephadex LH-20 gel column chromatography, methanol elution, flow velocity 55mL/h, every 9mL are one stream
Part, collect 43 fractions, each fraction tests and analyzes through silica gel thin-layer chromatography, with GF254 lamellae, with the two of volume ratio 5:3
Chloromethanes-acetone is as solvent, using sulfuric acid-ethanol solution of volume ratio 10:90 as color developing agent, 105 DEG C of 3-5min of heating,
According to thin-layer chromatography testing result, merges fraction 4-7, fraction 8-13, fraction 9-26, fraction 27-33, fraction 34-43 respectively, obtain
To 5 inferior components Fr.8-1, Fr.8-2, Fr.8-3, Fr.8-4, Fr.8-5;Inferior component Fr.8-4 through preparative high-performance liquid chromatographic,
Chromatographic column is YMC-Pack ODS-A, then is eluted with volume ratio for the methanol-water mixed solution of 72:28, flow velocity 7mL/min,
It collects the chromatographic peak that retention time is 36min and obtains chemical compounds I;By component Fr.9 through silica gel column chromatography, volume ratio 100:30's
Petroleum ether-acetone mixed solvent elution, every 11mL are a fraction, collect the fraction containing compounds Ⅳ and obtain compounds Ⅳ;
By component Fr.11 through silica gel column chromatography, petroleum ether-acetone mixed solvent of volume ratio 100:7,100:10,100:15,100:20
System elutions, each gradient 70mL eluent, every 7mL are a fraction, collect 40 fractions, each fraction is through silica gel thin-layer chromatography
Spectrum tests and analyzes, with GF254 lamellae, respectively using petroleum ether-acetone of volume ratio 5:4 as solvent, with volume ratio 10:90
Sulfuric acid-ethanol solution as color developing agent, 105 DEG C of 3-5min of heating merge fraction 1-according to thin-layer chromatography testing result respectively
8, fraction 9-15, fraction 16-31, fraction 32-40 obtain 4 Arius parts Fr.11-1, Fr.11-2, Fr.11-3, Fr.11-4;
Arius part Fr.11-4 is purified through preparative high-performance liquid chromatographic, is eluted with volume ratio for the Methanol+Water of 80:20, chromatography
Column is YMC-Pack ODS-A, flow velocity 7mL/min, collects the chromatographic peak that retention time is 69min and obtains compound III;By group
Divide Fr.13 through silica gel column chromatography, volume ratio 100:40 petroleum ether-acetone mixed solution elution, every 4mL is a fraction, and collection contains
There is the fraction of compound ii to obtain compound ii.
7. isopentene group flavone compound Chinese podophyllum root ketone Q (sinoflavonoids Q I) described in claim 1, peach
Seven ketone R (sinoflavonoids R II), Chinese podophyllum root ketone S (sinoflavonoids S III), Chinese podophyllum root ketone T
(sinoflavonoids T IV) is preparing the application in antioxidant.
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