CN103755630B - 野生葫芦巴碱的新型提取方法 - Google Patents
野生葫芦巴碱的新型提取方法 Download PDFInfo
- Publication number
- CN103755630B CN103755630B CN201310706466.9A CN201310706466A CN103755630B CN 103755630 B CN103755630 B CN 103755630B CN 201310706466 A CN201310706466 A CN 201310706466A CN 103755630 B CN103755630 B CN 103755630B
- Authority
- CN
- China
- Prior art keywords
- trigonelline
- adsorption
- dry
- finished product
- ethanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- WWNNZCOKKKDOPX-UHFFFAOYSA-N N-methylnicotinate Chemical compound C[N+]1=CC=CC(C([O-])=O)=C1 WWNNZCOKKKDOPX-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000011347 resin Substances 0.000 claims abstract description 31
- 229920005989 resin Polymers 0.000 claims abstract description 31
- 238000001179 sorption measurement Methods 0.000 claims abstract description 14
- 239000011265 semifinished product Substances 0.000 claims abstract description 12
- 238000005516 engineering process Methods 0.000 claims abstract description 11
- 238000004440 column chromatography Methods 0.000 claims abstract description 9
- 239000000047 product Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 33
- 238000010828 elution Methods 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 15
- 230000002745 absorbent Effects 0.000 claims description 13
- 239000002250 absorbent Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 10
- 238000005377 adsorption chromatography Methods 0.000 claims description 8
- 230000008878 coupling Effects 0.000 claims description 7
- 238000010168 coupling process Methods 0.000 claims description 7
- 238000005859 coupling reaction Methods 0.000 claims description 7
- 239000000287 crude extract Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 238000007670 refining Methods 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- 238000010898 silica gel chromatography Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000002955 isolation Methods 0.000 claims description 4
- 230000003068 static effect Effects 0.000 claims description 4
- 238000004587 chromatography analysis Methods 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 8
- 238000000746 purification Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000284 extract Substances 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract description 2
- 230000000274 adsorptive effect Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- -1 trigonellines Natural products 0.000 description 4
- 241001164374 Calyx Species 0.000 description 2
- 241001573881 Corolla Species 0.000 description 2
- REFJWTPEDVJJIY-UHFFFAOYSA-N Quercetin Chemical compound C=1C(O)=CC(O)=C(C(C=2O)=O)C=1OC=2C1=CC=C(O)C(O)=C1 REFJWTPEDVJJIY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- WQLVFSAGQJTQCK-UHFFFAOYSA-N diosgenin Natural products CC1C(C2(CCC3C4(C)CCC(O)CC4=CCC3C2C2)C)C2OC11CCC(C)CO1 WQLVFSAGQJTQCK-UHFFFAOYSA-N 0.000 description 2
- 229930182478 glucoside Natural products 0.000 description 2
- 150000008131 glucosides Chemical class 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- OMDQUFIYNPYJFM-XKDAHURESA-N (2r,3r,4s,5r,6s)-2-(hydroxymethyl)-6-[[(2r,3s,4r,5s,6r)-4,5,6-trihydroxy-3-[(2s,3s,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxan-2-yl]methoxy]oxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)[C@H](O)[C@H](O)[C@H](O)O1 OMDQUFIYNPYJFM-XKDAHURESA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 241001643874 Cymbopogon distans Species 0.000 description 1
- SHZGCJCMOBCMKK-UHFFFAOYSA-N D-mannomethylose Natural products CC1OC(O)C(O)C(O)C1O SHZGCJCMOBCMKK-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- PLAPMLGJVGLZOV-UHFFFAOYSA-N Epi-orientin Natural products OC1C(O)C(O)C(CO)OC1C1=C(O)C=C(O)C2=C1OC(C=1C=C(O)C(O)=CC=1)=CC2=O PLAPMLGJVGLZOV-UHFFFAOYSA-N 0.000 description 1
- FWCXELAAYFYCSR-UHFFFAOYSA-N Episamogenin Natural products CC1C(C2(CCC3C4(C)CC(O)C(O)CC4CCC3C2C2)C)C2OC11CCC(C)CO1 FWCXELAAYFYCSR-UHFFFAOYSA-N 0.000 description 1
- 229920000926 Galactomannan Polymers 0.000 description 1
- FWCXELAAYFYCSR-RYKNUXCGSA-N Gitogenin Chemical compound O([C@@H]1[C@@H]([C@]2(CC[C@@H]3[C@@]4(C)C[C@@H](O)[C@H](O)C[C@@H]4CC[C@H]3[C@@H]2C1)C)[C@@H]1C)[C@]11CC[C@@H](C)CO1 FWCXELAAYFYCSR-RYKNUXCGSA-N 0.000 description 1
- ZVWCWPUAQHAINU-UHFFFAOYSA-N Gitogenin Natural products CC1CCC2(CC3OC4C5CCC6CC(O)C(O)CC6(C)C5CCC4(C)C3C2C)OC1 ZVWCWPUAQHAINU-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- SHZGCJCMOBCMKK-JFNONXLTSA-N L-rhamnopyranose Chemical compound C[C@@H]1OC(O)[C@H](O)[C@H](O)[C@H]1O SHZGCJCMOBCMKK-JFNONXLTSA-N 0.000 description 1
- PNNNRSAQSRJVSB-UHFFFAOYSA-N L-rhamnose Natural products CC(O)C(O)C(O)C(O)C=O PNNNRSAQSRJVSB-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- PTNJRKBWIYNFSY-UHFFFAOYSA-N Lirinin-O-methyl-ether Natural products COc1ccc-2c(CC3N(C)CCc4cc(OC)c(OC)c-2c34)c1 PTNJRKBWIYNFSY-UHFFFAOYSA-N 0.000 description 1
- 102000011931 Nucleoproteins Human genes 0.000 description 1
- 108010061100 Nucleoproteins Proteins 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- RBVAFYCFAFADAG-UHFFFAOYSA-N Orientin Natural products OCC1OC(C(O)c2c(O)cc(O)c3C(=O)C=C(Oc23)c4ccc(O)c(O)c4)C(O)C1O RBVAFYCFAFADAG-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- ZVOLCUVKHLEPEV-UHFFFAOYSA-N Quercetagetin Natural products C1=C(O)C(O)=CC=C1C1=C(O)C(=O)C2=C(O)C(O)=C(O)C=C2O1 ZVOLCUVKHLEPEV-UHFFFAOYSA-N 0.000 description 1
- HWTZYBCRDDUBJY-UHFFFAOYSA-N Rhynchosin Natural products C1=C(O)C(O)=CC=C1C1=C(O)C(=O)C2=CC(O)=C(O)C=C2O1 HWTZYBCRDDUBJY-UHFFFAOYSA-N 0.000 description 1
- JMFSHKGXVSAJFY-UHFFFAOYSA-N Saponaretin Natural products OCC(O)C1OC(Oc2c(O)cc(O)c3C(=O)C=C(Oc23)c4ccc(O)cc4)C(O)C1O JMFSHKGXVSAJFY-UHFFFAOYSA-N 0.000 description 1
- GMBQZIIUCVWOCD-WWASVFFGSA-N Sarsapogenine Chemical compound O([C@@H]1[C@@H]([C@]2(CC[C@@H]3[C@@]4(C)CC[C@H](O)C[C@H]4CC[C@H]3[C@@H]2C1)C)[C@@H]1C)[C@]11CC[C@H](C)CO1 GMBQZIIUCVWOCD-WWASVFFGSA-N 0.000 description 1
- RTMWIZOXNKJHRE-UHFFFAOYSA-N Tigogenin Natural products CC1COC2CC(C)(OC12)C3CCC4C5CCC6CC(O)CCC6(C)C5CCC34C RTMWIZOXNKJHRE-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- DWCSNWXARWMZTG-UHFFFAOYSA-N Trigonegenin A Natural products CC1C(C2(CCC3C4(C)CCC(O)C=C4CCC3C2C2)C)C2OC11CCC(C)CO1 DWCSNWXARWMZTG-UHFFFAOYSA-N 0.000 description 1
- 244000250129 Trigonella foenum graecum Species 0.000 description 1
- 235000001484 Trigonella foenum graecum Nutrition 0.000 description 1
- LQSNPVIQIPKOGP-UHFFFAOYSA-N UNPD159785 Natural products OC1C(O)C(O)C(CO)OC1OC1=C(O)C=C(O)C2=C1OC(C=1C=C(O)C(O)=CC=1)=CC2=O LQSNPVIQIPKOGP-UHFFFAOYSA-N 0.000 description 1
- 235000009499 Vanilla fragrans Nutrition 0.000 description 1
- 244000263375 Vanilla tahitensis Species 0.000 description 1
- 235000012036 Vanilla tahitensis Nutrition 0.000 description 1
- MOZJVOCOKZLBQB-UHFFFAOYSA-N Vitexin Natural products OCC1OC(Oc2c(O)c(O)cc3C(=O)C=C(Oc23)c4ccc(O)cc4)C(O)C(O)C1O MOZJVOCOKZLBQB-UHFFFAOYSA-N 0.000 description 1
- 241001123263 Zostera Species 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229930013930 alkaloid Natural products 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- AMSCMASJCYVAIF-QCVMBYIASA-N carpaine Chemical compound O([C@H]1CC[C@@H](CCCCCCCC(=O)O2)N[C@H]1C)C(=O)CCCCCCC[C@H]1N[C@@H](C)[C@@H]2CC1 AMSCMASJCYVAIF-QCVMBYIASA-N 0.000 description 1
- HXFUVYFNBRBBPM-UHFFFAOYSA-N carpaine Natural products CC1(CCCCCCCC(=O)O1)C2CCCN2 HXFUVYFNBRBBPM-UHFFFAOYSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- WQLVFSAGQJTQCK-VKROHFNGSA-N diosgenin Chemical compound O([C@@H]1[C@@H]([C@]2(CC[C@@H]3[C@@]4(C)CC[C@H](O)CC4=CC[C@H]3[C@@H]2C1)C)[C@@H]1C)[C@]11CC[C@@H](C)CO1 WQLVFSAGQJTQCK-VKROHFNGSA-N 0.000 description 1
- 208000002173 dizziness Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229930003944 flavone Natural products 0.000 description 1
- 150000002213 flavones Chemical class 0.000 description 1
- 235000011949 flavones Nutrition 0.000 description 1
- 229930003935 flavonoid Natural products 0.000 description 1
- 150000002215 flavonoids Chemical class 0.000 description 1
- 235000017173 flavonoids Nutrition 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- DFNZYFAJQPLJFI-UHFFFAOYSA-N gentianine Chemical compound O=C1OCCC2=C1C=NC=C2C=C DFNZYFAJQPLJFI-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- MWDZOUNAPSSOEL-UHFFFAOYSA-N kaempferol Natural products OC1=C(C(=O)c2cc(O)cc(O)c2O1)c3ccc(O)cc3 MWDZOUNAPSSOEL-UHFFFAOYSA-N 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 150000002617 leukotrienes Chemical class 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- PEFNSGRTCBGNAN-UHFFFAOYSA-N nephrocizin Natural products OC1C(O)C(O)C(CO)OC1OC1=CC(O)=C2C(=O)C=C(C=3C=C(O)C(O)=CC=3)OC2=C1 PEFNSGRTCBGNAN-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- PLAPMLGJVGLZOV-VPRICQMDSA-N orientin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1C1=C(O)C=C(O)C2=C1OC(C=1C=C(O)C(O)=CC=1)=CC2=O PLAPMLGJVGLZOV-VPRICQMDSA-N 0.000 description 1
- 210000001672 ovary Anatomy 0.000 description 1
- 229960001285 quercetin Drugs 0.000 description 1
- 235000005875 quercetin Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- NWMIYTWHUDFRPL-UHFFFAOYSA-N sapogenin Natural products COC(=O)C1(CO)C(O)CCC2(C)C1CCC3(C)C2CC=C4C5C(C)(O)C(C)CCC5(CCC34C)C(=O)O NWMIYTWHUDFRPL-UHFFFAOYSA-N 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000008925 shengjing Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000001019 trigonella foenum-graecum Nutrition 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- SGEWCQFRYRRZDC-VPRICQMDSA-N vitexin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1C1=C(O)C=C(O)C2=C1OC(C=1C=CC(O)=CC=1)=CC2=O SGEWCQFRYRRZDC-VPRICQMDSA-N 0.000 description 1
- PZKISQRTNNHUGF-UHFFFAOYSA-N vitexine Natural products OC1C(O)C(O)C(CO)OC1OC1=C(O)C=C(O)C2=C1OC(C=1C=CC(O)=CC=1)=CC2=O PZKISQRTNNHUGF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/80—Acids; Esters in position 3
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Medicines Containing Plant Substances (AREA)
Abstract
本发明属于天然有机化学领域，采用超高压提取，具有加热均匀、过程易于控制，无需干燥等预处理，简化了工艺，减少了投资，大大提高了萃取效率；利用大孔树脂吸附一柱层析技术分离纯化葫芦巴碱，对葫芦巴碱的吸附选择性良好，吸附快、解析也快，吸附容量较大，提取方便快捷，生产成本低廉，分离效果明显，提取纯度高，可以通过物理吸附从溶液中有选择地吸附葫芦巴碱，得到含量40％以上的葫芦巴碱半成品和含量90％以上的葫芦巴碱终产品，克服了常规提取率相对较低、提取纯度低的缺点。
Description
技术领域：
本发明属于天然药物提取领域，涉及一种葫芦巴碱的纯化方法，特别是涉及一种利用超高压技术和大孔树脂吸附及柱层析耦联技术富集纯化葫芦巴中葫芦巴碱的方法。
背景技术：
胡芦巴，又名：芸香草《盛京通志》，香草、苦草、苦朵菜、香苜蓿。一年生草本，高40～50厘米。茎丛生，几光滑或被稀疏柔毛。3出复叶，小叶卵状长卵圆形或宽披针形，长1.2～3厘米，宽1～1.5厘米，近先端有锯齿，两面均有稀疏柔毛，小叶柄长1～2毫米，总柄长6～12毫米；托叶与叶柄连合，狭卵形，先端急尖。花无梗，1～2朵腋生：萼筒状，萼齿5，披针形，比花冠短一半，外被长柔毛；花冠蝶形，初为白色，后渐变淡黄色，基部微带紫晕，旗瓣长圆形，先端具缺刻，基部尖楔形，龙骨瓣偏匙形，长仅旗瓣的1／3，翼瓣耳形，雄蕊10，2体；子房无柄，柱头顶生。荚果细长圆筒状，长6～11厘米，宽0.5厘米左右，被柔毛，并具网脉，先端有长尖。种子棕色，长约4毫米。花期4～6月。果期7～8月。我国黑龙江、吉林、辽宁、河北、河南、安徽、浙江、湖北、四川、贵州、云南、陕西、甘肃以及新疆等地有栽培。种子含龙胆宁碱、番木瓜碱、胆碱、胡芦巴碱等生物碱，皂甙元主要是薯蓣皂甙元、雅姆皂甙元和少量芰脱皂甙元、痕量替告皂甙元。尚分离出牡荆素、牡荆素-7-葡萄糖甙、荭草素或异荭草素的***糖甙、黄酮的葡萄糖鼠李糖二糖甙，槲皮素、木犀草素等黄酮类。种子的一般组成为：水分10.30％、灰分3.15％、脂肪7.61％、总蛋白16.97％、总糖3.68％、纤维素6.4％、半纤维素11.98％。脂肪油中固体脂肪酸92.9％、挥发性脂肪酸1.5％、不皂化成分0.9％；卵磷脂6.25％、植物甾醇0.5露。脂肪酸中主要是亚油酸和棕榈酸，并有少量油酸及亚麻酸。蛋白质中核蛋白55％。总糖中主要是半乳糖配甘露聚糖，还含维生素B1-320微克％
葫芦巴碱具有温肾，祛寒，止痛等功效，已引起国际社会的普遍关注。近年来，人们发现天然植物葫芦巴中含有大量的葫芦巴碱，从中提取葫芦巴碱并且取得了可喜进展，原料葫芦巴来源较广。
发明内容：本发明的目的在于克服常规技术提取率相对较低、提取纯度低等缺点，提供一种利用超高压技术和大孔树脂吸附及柱层析耦联技术富集纯化葫芦巴中葫芦巴碱的方法。
为实现上述目的，本发明采用的技术方案是：
一种利用超高压技术和大孔树脂吸附及柱层析耦联技术富集纯化葫芦巴中葫芦巴碱的方法，其步骤如下：
(1)将干葫芦巴粉碎，加入乙酸乙酯，浸泡1小时后放入耐压袋中，在20℃条件下处理，超高压压力在400—500MPA之间，时间在3—5min，回收乙酸乙酯，在60℃～70℃真空干燥得葫芦巴碱粗提物；
(2)将所得葫芦巴碱粗提物用大孔吸附树脂进行吸附，吸附为静态吸附或动态吸附；
(3)用50％～90％不同浓度的乙醇对大孔吸附树脂进行洗脱，用薄层色谱法跟踪检测，收集葫芦巴碱各阶段洗脱液；
(4)将葫芦巴碱各阶段洗脱液浓缩，回收乙醇，得葫芦巴碱半成品，其含量在40％以上；
(5)将所得葫芦巴碱半成品粉末溶于石油醚中，加适量硅胶搅拌，烘干过60—80目筛，干法上样，上工业级柱200—300目硅胶柱层析；
(6)以丙酮、石油醚在1～7∶1条件下进行梯度洗脱，薄层色谱法跟踪检测，收集葫芦巴碱各阶段洗脱液，减压浓缩，回收溶剂；
(7)所得浓缩液在60℃～80℃下进行真空干燥；
(8)将干燥后的产品用75％-90％无水乙醇溶解，浓缩到原体积的十分之一，放置过夜得晶体；分离晶体将剩余物用50％-60％乙醇溶解，再次浓缩，重结晶，如此反复两次，得到精制的葫芦巴碱，其含量在90％以上。
所述的步骤(1)中，干葫芦巴粉碎后过80～100目筛。
所述的步骤(2)中，所用的大孔吸附树脂为NKA-9、D3520、D4006、H103、D4020、AB-8H和NKA-II型树脂中的一种，吸附为静态吸附或动态吸附。
本发明应用超高压技术和大孔吸附技术分离纯化葫芦巴碱，对葫芦巴碱的提取速度快，节省时间，提取率高，利用大孔树脂分离纯化分离效果明显，提取纯度高，可以得到含量40％以上的葫芦巴碱半成品和含量90％以上的葫芦巴碱终产品，克服了常规提取率相对较低、提取纯度低的缺点。
本发明选用理化性质稳定、表面积较大、交换速度较快、机械强度高、抗污染能力强、热稳定性好的大孔吸附树脂，不容于酸、碱及有机媒，对有机物选择性较好，不受无机盐类及强离子低分子化合物存在的影响，可以通过物理吸附从溶液中有选择地吸附葫芦巴碱，吸附快、解析也快，吸附容量较大。
具体实施方式：
实施例1：一种利用超高压技术和大孔树脂吸附及柱层析耦联技术富集纯化葫芦巴中葫芦巴碱的方法其步骤如下：
(1)将1000g干葫芦巴粉碎后过80目筛，加入12倍体积的乙酸乙酯，浸泡1小时后放入耐压袋中，在20℃条件下处理，超高压压力400MPA，时间3min，回收乙酸乙酯，在60℃真空干燥得葫芦巴碱粗提物；
(2)将所得葫芦巴碱粗提物用大孔吸附树脂进行吸附，所用的大孔树脂为D4006型树脂，吸附为静态吸附或动态吸附；
(3)用50％、60％、70％、80％、90％不同浓度的乙醇对大孔吸附树脂进行洗脱，用薄层色谱法跟踪检测，收集葫芦巴碱各阶段洗脱液；
(4)将葫芦巴碱各阶段洗脱液浓缩，回收乙醇，得葫芦巴碱半成品，其含量在41.4％；
(5)将所得葫芦巴碱半成品粉末溶于石油醚，加适量硅胶搅拌，烘干过60目筛，干法上样，上工业级柱200目硅胶柱层析；
(6)以丙酮、石油醚在1∶1、2∶1、3∶1、4∶1、5∶1、6∶1、7∶1条件下进行梯度洗脱，薄层色谱法跟踪检测，收集葫芦巴碱各阶段洗脱液，减压浓缩，回收溶剂；
(7)所得浓缩液在60℃下进行真空干燥；
(8)将干燥后的产品用8倍体积的75％无水乙醇溶解，浓缩到原体积的十分之一，放置过夜得晶体；分离晶体将剩余物用50％无水乙醇溶解，再次浓缩，重结晶，如此反复两次，得到精制的葫芦巴碱3.2g，其含量在91.2％。
实施案例2：一种利用超高压技术和大孔树脂吸附及柱层析耦联技术富集纯化葫芦巴中葫芦巴碱的方法其步骤如下：
(1)将1000g干葫芦巴粉碎后过90目筛，加入14倍体积的乙酸乙酯，浸泡1小时后放入耐压袋中，在20℃条件下处理，超高压压力450MPA，时间4min，回收乙酸乙酯，在60℃真空干燥得葫芦巴碱粗提物；
(2)将所得葫芦巴碱粗提物用大孔吸附树脂进行吸附，所用的大孔树脂为AB-8H型树脂，吸附为静态吸附或动态吸附；
(3)用50％、60％、70％、80％、90％不同浓度的乙醇对大孔吸附树脂进行洗脱，用薄层色谱法跟踪检测，收集葫芦巴碱各阶段洗脱液；
(4)将葫芦巴碱各阶段洗脱液浓缩，回收乙醇，得葫芦巴碱半成品，其含量在40.3％；
(5)将所得葫芦巴碱半成品粉末溶于石油醚，加适量硅胶搅拌，烘干过60目筛，干法上样，上工业级柱200目硅胶柱层析；
(6)以丙酮、石油醚在1∶1、2∶1、3∶1、4∶1、5∶1、6∶1、7∶1条件下进行梯度洗脱，薄层色谱法跟踪检测，收集葫芦巴碱各阶段洗脱液，减压浓缩，回收溶剂；
(7)所得浓缩液在60℃下进行真空干燥；
(8)将干燥后的产品用10倍体积的80％无水乙醇溶解，浓缩到原体积的十分之一，放置过夜得晶体；分离晶体将剩余物用60％无水乙醇溶解，再次浓缩，重结晶，如此反复两次，得到精制的葫芦巴碱4.0g，其含量在92.7％。
实施案例3：一种利用超高压技术和大孔树脂吸附及柱层析耦联技术富集纯化葫芦巴中葫芦巴碱的方法其步骤如下：
(1)将1000g干葫芦巴粉碎后过100目筛，加入16倍体积的乙酸乙酯，浸泡1小时后放入耐压袋中，在20℃条件下处理，超高压压力500MPA，时间5min，回收乙酸乙酯，在60℃真空干燥得葫芦巴碱粗提物；
(2)将所得葫芦巴碱粗提物用大孔吸附树脂进行吸附，所用的大孔树脂为D3520型树脂，吸附为静态吸附或动态吸附；
(3)用50％、60％、70％、80％、90％不同浓度的乙醇对大孔吸附树脂进行洗脱，用薄层色谱法跟踪检测，收集葫芦巴碱各阶段洗脱液；
(4)将葫芦巴碱各阶段洗脱液浓缩，回收乙醇，得葫芦巴碱半成品，其含量在42.1％；
(5)将所得葫芦巴碱半成品粉末溶于石油醚，加适量硅胶搅拌，烘干过60目筛，干法上样，上工业级柱200目硅胶柱层析；
(6)以丙酮、石油醚在1∶1、2∶1、3∶1、4∶1、5∶1、6∶1、7∶1条件下进行梯度洗脱，薄层色谱法跟踪检测，收集葫芦巴碱各阶段洗脱液，减压浓缩，回收溶剂；
(7)所得浓缩液在60℃下进行真空干燥；
(8)将干燥后的产品用10倍体积的90％无水乙醇溶解，浓缩到原体积的十分之一，放置过夜得晶体；分离晶体将剩余物用60％无水乙醇溶解，再次浓缩，重结晶，如此反复两次，得到精制的葫芦巴碱3.6g，其含量为91.9％。
Claims (2)
1.一种利用超高压技术和大孔树脂吸附及柱层析耦联技术富集纯化葫芦巴中葫芦巴碱的方法，其步骤如下：
(1)将干葫芦巴粉碎，加入乙酸乙酯，加入乙酸乙酯的体积为物料粉碎体积的12-16倍，浸泡1小时后放入耐压袋中，在20℃条件下处理，超高压压力在400-500MPA之间，时间在3-5min，回收乙酸乙酯，在60℃～70℃真空干燥得葫芦巴碱粗提物；
(2)将所得葫芦巴碱粗提物用大孔吸附树脂进行吸附，吸附为静态吸附或动态吸附；
(3)用50％～90％不同浓度的乙醇对大孔吸附树脂进行洗脱，用薄层色谱法跟踪检测，收集葫芦巴碱各阶段洗脱液；
(4)将葫芦巴碱各阶段洗脱液浓缩，回收乙醇，得葫芦巴碱半成品，其含量在40％以上；
(5)将所得葫芦巴碱半成品粉末溶于石油醚中，加适量硅胶搅拌，烘干过60-80目筛，干法上样，上工业级柱200-300目硅胶柱层析；
(6)以丙酮、石油醚在1～7：1条件下进行梯度洗脱，薄层色谱法跟踪检测，收集葫芦巴碱各阶段洗脱液，减压浓缩，回收溶剂；
(7)所得浓缩液在60℃～80℃下进行真空干燥；
(8)将干燥后的产品用75％-90％无水乙醇溶解，浓缩到原体积的十分之一，放置过夜得晶体；分离晶体将剩余物用50％-60％乙醇溶解，再次浓缩，重结晶，如此反复两次，得到精制的葫芦巴碱，其含量在90％以上；
所述的步骤(1)中，干葫芦巴粉碎后过80～100目筛；
所述的步骤(2)中，所用的大孔吸附树脂为NKA-9、D3520、D4006、H103、D4020、AB-8H和NKA-II型树脂中的一种，吸附为静态吸附或动态吸附。
2.根据权利要求1所述的利用超高压技术和大孔树脂吸附及柱层析耦联技术富集纯化葫芦巴中葫芦巴碱的方法，其特征是：所述步骤(8)中，加入无水乙醇的体积为干燥后产品的8-10倍。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310706466.9A CN103755630B (zh) | 2013-12-10 | 2013-12-10 | 野生葫芦巴碱的新型提取方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310706466.9A CN103755630B (zh) | 2013-12-10 | 2013-12-10 | 野生葫芦巴碱的新型提取方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103755630A CN103755630A (zh) | 2014-04-30 |
| CN103755630B true CN103755630B (zh) | 2016-05-25 |
Family
ID=50522992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310706466.9A Expired - Fee Related CN103755630B (zh) | 2013-12-10 | 2013-12-10 | 野生葫芦巴碱的新型提取方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103755630B (zh) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106496111A (zh) * | 2016-09-21 | 2017-03-15 | 广东药科大学 | 一种从相思子属植物中制备葫芦巴碱的方法 |
| CN109007959B (zh) * | 2018-09-20 | 2021-02-26 | 云南中烟工业有限责任公司 | 一种葫芦巴净油的高效制备方法及用途 |
| JP7165620B2 (ja) * | 2019-04-24 | 2022-11-04 | 水澤化学工業株式会社 | トリゴネリン吸着剤 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003094948A1 (en) * | 2002-05-10 | 2003-11-20 | Technical Sourcing International, Inc. | Fenugreek seed bio-active compositions and methods for extracting same |
| CN101967121A (zh) * | 2010-06-28 | 2011-02-09 | 南京泽朗医药科技有限公司 | 一种葫芦巴碱的提取工艺 |
| CN102697781A (zh) * | 2011-06-21 | 2012-10-03 | 中国人民解放军第三军医大学第二附属医院 | 胡芦巴碱作为制备防治糖尿病及其并发症药物的应用 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050226948A1 (en) * | 2004-03-02 | 2005-10-13 | Lee Steve S | Methods for enhancing the transport of glucose into muscle |
-
2013
- 2013-12-10 CN CN201310706466.9A patent/CN103755630B/zh not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003094948A1 (en) * | 2002-05-10 | 2003-11-20 | Technical Sourcing International, Inc. | Fenugreek seed bio-active compositions and methods for extracting same |
| CN101967121A (zh) * | 2010-06-28 | 2011-02-09 | 南京泽朗医药科技有限公司 | 一种葫芦巴碱的提取工艺 |
| CN102697781A (zh) * | 2011-06-21 | 2012-10-03 | 中国人民解放军第三军医大学第二附属医院 | 胡芦巴碱作为制备防治糖尿病及其并发症药物的应用 |
Non-Patent Citations (2)
| Title |
|---|
| "胡芦巴药材中胡芦巴碱的提取方法及其含量测定";刘广学等;《中国药品标准》;20150828;第6卷(第4期);第11-14页 * |
| "超高压技术在提取中药有效成分中的应用";贺帅等;《中药材》;20090331;第32卷(第3期);第5.4部分 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103755630A (zh) | 2014-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102451235B (zh) | 油橄榄叶提取物的制备方法 | |
| CN105055527A (zh) | 一种橄榄叶提取物的制备方法 | |
| CN102816066A (zh) | 一种从金银花叶中提取绿原酸和金丝桃苷的方法 | |
| CN102836202A (zh) | 一种甘草地上部分综合开发利用的方法 | |
| CN102617673B (zh) | 一种从胡柚白皮层分离纯化柚皮苷和新橙皮苷的方法 | |
| CN103755630B (zh) | 野生葫芦巴碱的新型提取方法 | |
| CN105713058A (zh) | 一种从金银花叶中同步制备绿原酸和木犀草苷的方法 | |
| CN103130851B (zh) | 一种从萝卜皮中分离制备四种天竺葵素衍生物的方法 | |
| JP5465206B2 (ja) | アクテオシド含量の高い胡麻若葉乾燥末およびそれより得られるエキス粉末 | |
| CN101890084A (zh) | 黑种草子总苷提取物及其制备方法和应用 | |
| CN105175426B (zh) | 一种从四方藤中提取纯化岩白菜素的方法 | |
| CN103554209B (zh) | 从三七中制备人参皂苷Rg1的方法 | |
| CN103113433A (zh) | 一种从巧玲花中提取橄榄苦苷的方法 | |
| CN103342689B (zh) | 从瓜蒌皮中分离纯化木犀草素、芹菜素和香叶木素的方法 | |
| CN101260133B (zh) | 从棉花花瓣中制备金丝桃苷和异槲皮素的方法 | |
| CN102670935B (zh) | 一种从藠头中提取总皂苷的方法 | |
| CN107880084B (zh) | 从凌霄属植物花中提取制备高纯度毛蕊花糖苷的方法 | |
| CN102690359B (zh) | 一种从罗汉果块根中提取淀粉和葫芦素的方法 | |
| CN108743657A (zh) | 一种川西獐牙菜中苷类成分的制备方法 | |
| CN108126000A (zh) | 新鲜三七中三七总皂苷提取制备方法 | |
| CN102796154B (zh) | 一种从茄子皮中分离制备高纯度酰化的飞燕草素衍生物的方法 | |
| CN107602561A (zh) | 利用鸭嘴花制备鸭嘴花碱和牡荆素的方法 | |
| CN101732322B (zh) | 科罗索酸在制备抗抑郁药物中的用途 | |
| CN104211711B (zh) | 一种五味子中分离的化合物及其制备与应用 | |
| CN101926811A (zh) | 络石藤的三萜皂苷类总提取物及其制备方法和用途 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20181119 Address after: 161099 No. 92 Longhua Road, Tiefeng District, Qiqihar City, Heilongjiang Province Patentee after: Heilongjiang Dinghengsheng Pharmaceutical Co.,Ltd. Address before: 165000 Heilongjiang Greater Khingan Range area Jiagedaqi Changhong community Xinyuan District AGA Road North Lin Bei Bei group Patentee before: DAXINGANLING GADOL SPORTS INGREDIENT Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160525 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |