CN101684112A - Preparation method of 5,6,7,4'-tetramethoxy flavones of scutellarin and aglucone key intermediate thereof - Google Patents
Preparation method of 5,6,7,4'-tetramethoxy flavones of scutellarin and aglucone key intermediate thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- URSUMOWUGDXZHU-UHFFFAOYSA-N 4',5,6,7-tetramethoxyflavone Chemical class C1=CC(OC)=CC=C1C1=CC(=O)C2=C(OC)C(OC)=C(OC)C=C2O1 URSUMOWUGDXZHU-UHFFFAOYSA-N 0.000 title abstract description 8
- DJSISFGPUUYILV-UHFFFAOYSA-N UNPD161792 Natural products O1C(C(O)=O)C(O)C(O)C(O)C1OC(C(=C1O)O)=CC2=C1C(=O)C=C(C=1C=CC(O)=CC=1)O2 DJSISFGPUUYILV-UHFFFAOYSA-N 0.000 title abstract description 3
- NPLTVGMLNDMOQE-UHFFFAOYSA-N carthamidin Natural products C1=CC(O)=CC=C1C1OC2=CC(O)=C(O)C(O)=C2C(=O)C1 NPLTVGMLNDMOQE-UHFFFAOYSA-N 0.000 title abstract description 3
- DJSISFGPUUYILV-ZFORQUDYSA-N scutellarin Chemical compound O1[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1OC(C(=C1O)O)=CC2=C1C(=O)C=C(C=1C=CC(O)=CC=1)O2 DJSISFGPUUYILV-ZFORQUDYSA-N 0.000 title abstract description 3
- 229930190376 scutellarin Natural products 0.000 title abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims abstract description 15
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 claims abstract description 7
- GVSPXQVUXHMUMA-MDWZMJQESA-N (e)-3-(3,5-ditert-butyl-4-hydroxyphenyl)-1-(4-methoxyphenyl)prop-2-en-1-one Chemical compound C1=CC(OC)=CC=C1C(=O)\C=C\C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 GVSPXQVUXHMUMA-MDWZMJQESA-N 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 229930003944 flavone Natural products 0.000 claims description 17
- 150000002213 flavones Chemical class 0.000 claims description 17
- 235000011949 flavones Nutrition 0.000 claims description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- 150000008131 glucosides Chemical class 0.000 claims description 14
- -1 2-hydroxyl-4,5,6-trimethoxy methyl phenyl Chemical group 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 235000014493 Crataegus Nutrition 0.000 claims description 6
- 241001092040 Crataegus Species 0.000 claims description 6
- 229940126214 compound 3 Drugs 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 229930182478 glucoside Natural products 0.000 claims description 5
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 229940125904 compound 1 Drugs 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 150000001788 chalcone derivatives Chemical class 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 229940125782 compound 2 Drugs 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 150000007530 organic bases Chemical class 0.000 claims description 2
- 150000003138 primary alcohols Chemical class 0.000 claims description 2
- 150000003333 secondary alcohols Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 150000003509 tertiary alcohols Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 13
- 238000007243 oxidative cyclization reaction Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- 239000008280 blood Substances 0.000 description 4
- 210000004369 blood Anatomy 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000007039 two-step reaction Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- VTCDZPUMZAZMSB-UHFFFAOYSA-N 3,4,5-trimethoxyphenol Chemical compound COC1=CC(O)=CC(OC)=C1OC VTCDZPUMZAZMSB-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- UORVCLMRJXCDCP-UHFFFAOYSA-N propynoic acid Chemical compound OC(=O)C#C UORVCLMRJXCDCP-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 235000007516 Chrysanthemum Nutrition 0.000 description 1
- 244000189548 Chrysanthemum x morifolium Species 0.000 description 1
- 241000132521 Erigeron Species 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- MXMOTZIXVICDSD-UHFFFAOYSA-N anisoyl chloride Chemical compound COC1=CC=C(C(Cl)=O)C=C1 MXMOTZIXVICDSD-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 229940125692 cardiovascular agent Drugs 0.000 description 1
- 239000002327 cardiovascular agent Substances 0.000 description 1
- 208000026106 cerebrovascular disease Diseases 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 208000011580 syndromic disease Diseases 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- DQFBYFPFKXHELB-VAWYXSNFSA-N trans-chalcone Chemical compound C=1C=CC=CC=1C(=O)\C=C\C1=CC=CC=C1 DQFBYFPFKXHELB-VAWYXSNFSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
The invention relates to a preparation method of 5,6,7,4'-tetramethoxy flavone of scutellarin and aglucone key intermediate thereof. The 5,6,7,4'-tetramethoxy flavones is prepared by utilizing 2-hydroxyl-4,5,6-trimethoxy hypnone as the raw material and comprising a reaction a step and a reaction b step, wherein in the reaction a, 2-hydroxyl-4,5,6-trimethoxy hypnone and p-methoxybenzaldehyde are condensed to prepare a chalcone derivative; and in the reaction b, the chalcone derivative is processed in a oxidative cyclization mode to prepare the 5,6,7,4'-tetramethoxy flavone. The method has the advantages of simple operation steps and high product yield.
Description
Technical field
The present invention relates to compound technology, be specifically related to lamp-dish flower acetic and glucoside thereof unit key intermediate 5,6,7, the preparation method of 4 '-tetramethoxy flavones.
Background technology
Herba Erigerontis has another name called Herba Erigerontis, belongs to the short booth bitter fleabane of chrysanthemum pulse family class plant.Breviscarpine be that separation and Extraction goes out from Herba Erigerontis complete stool plant to contain lamp-dish flower acetic (＞90%), also contain the mixture of a small amount of oil lamp cycle of sixty years element, lamp-dish flower acetic claims scutellarin again.That Breviscarpine has is promoting blood circulation and removing blood stasis, expelling cold and relieving exterior syndrome, the effect of stimulating the circulation of the blood and cause the muscles and joints to relax, dispelling rheumatism, and is usually used in treating cardiovascular and cerebrovascular diseases clinically.
5,6,7,4 '-tetramethoxy flavones is important intermediate (Cui Jianmei etc., " research and development of natural products ", 2003 of preparation cardiovascular agent lamp-dish flower acetic and lamp-dish flower acetic glucoside unit, 15 (3): 255-258), the preparation method of report has following two kinds at present:
1) 3,4,5-trimethoxy phenol and to the anisole acetylenic acid condensation under Vanadium Pentoxide in FLAKES and methylsulfonic acid effect makes.Though this method is single step reaction only, reaction raw materials obtains the anisole acetylenic acid is difficult, also is difficult for preparation.Simultaneously, yield of this step condensation reaction is extremely low, and only about 5%, do not have using value.
2) 2-hydroxyl-4,5,6-trimethoxy methyl phenyl ketone is a raw material, at first generate phenolic ester with the anisoyl chloride reaction, this phenolic ester carries out the Baker-Venkatamah rearrangement reaction and obtains phenol aryl diketone under alkaline condition then, and it heats under the HOAc-NaOAc condition is that cyclization makes 5,6,7,4 '-tetramethoxy flavones.This method is through the three-step reaction operation, and the yield of per step reaction is also good, but operational requirement is more loaded down with trivial details.
Summary of the invention
The object of the present invention is to provide a kind of key intermediate 5,6,7 for preparing lamp-dish flower acetic and glucoside unit thereof, the novel method of 4 '-tetramethoxy flavones, this method operation steps is simple, the product yield height.
Lamp-dish flower acetic of the present invention and glucoside unit key intermediate 5 thereof, 6,7, the preparation method of 4 '-tetramethoxy flavones, be with the 2-hydroxyl-4 shown in the compound 2,5,6-trimethoxy methyl phenyl ketone is a raw material, goes on foot by reaction a and reaction b two to be prepared from, wherein reacting a is by 2-hydroxyl-4,5,6-trimethoxy methyl phenyl ketone and aubepine condensation make the chalcone derivative shown in the compound 3, and reaction b will make 5 shown in the compound 1 behind this chalcone derivative dioxide giving, 6,7,4 '-tetramethoxy flavones, chemical equation is as follows:
Compound 2 compounds 3 compounds 1
Wherein, the reaction solvent in reaction a is selected from lower alcohols, ethers or varsol, can be a kind of or arbitrary combination wherein.
Lower alcohol comprises primary alcohol, secondary alcohol or the tertiary alcohol that C6 is following, as methyl alcohol, ethanol etc.; Can simple ether or mixed ether in the ether solvent, as tetrahydrofuran (THF), dioxane etc.; Common varsol is selected from alkane, alkene, alkynes, naphthenic hydrocarbon, cycloolefin or aromatic hydrocarbon.
Wherein, the temperature of reaction of reaction a is 20-100 ℃; Catalyzer comprises mineral acid (example hydrochloric acid, sulfuric acid etc.), organic acid (as tosic acid etc.) or mineral alkali (as potassium hydroxide, sodium hydroxide etc.) or organic bases (as pyridine, triethylamine etc.).
Wherein, aubepine and 2-hydroxyl-4,5,6-trimethoxy methyl phenyl ketone amount ratio is 1-2.5: 1.
Wherein, the reaction solvent among the reaction b can be dimethyl sulfoxide (DMSO), alcohols (ethylene glycol, propylene glycol etc.), hydro carbons (toluene, dimethylbenzene etc.), ethers (dioxane etc.) or N, and dinethylformamide (DMF) waits other common solvent; Reaction reagent is the mixture of dimethyl sulfoxide (DMSO) and inorganic iodine or its metal-salt; Temperature of reaction is 80-200 ℃.
The invention provides a kind of new synthetic lamp-dish flower acetic and glucoside unit key intermediate 5,6,7 thereof, the method for 4 '-tetramethoxy flavones, this method makes through two-step reaction, and operation steps is simple, and the product yield height has using value preferably.The reaction yield of embodiments of the invention 1 and embodiment 2 is about 85%, the total reaction yield of two-step reaction is about 72%, with preparation lamp-dish flower acetic and glucoside thereof unit key intermediate 5 in the prior art, 6,7, the method of 4 '-tetramethoxy flavones is compared, and not only significantly exceeds single step reaction method (being about about 5%), and apparently higher than the total recovery (being about about 60%) of bibliographical information three-step reaction method.
Embodiment
Specify lamp-dish flower acetic of the present invention and glucoside unit key intermediate 5,6,7 thereof, the preparation method of 4 '-tetramethoxy flavones below by embodiment.Raw material among the present invention (2-hydroxyl-4,5,6-trimethoxy methyl phenyl ketone) is according to bibliographical information method (Duan Xinfang etc., " organic chemistry ", 2003,23 (4): 353-355) preparation.
Embodiment 1: the preparation of phenyl styryl ketone (compound 3)
Take by weighing 11.3g (0.05mol) compound 2,2-hydroxyl-4,5,6-trimethoxy methyl phenyl ketone 7.4g (0.06mol) aubepine places the 250ml round-bottomed flask, adds 150ml methyl alcohol and 22.5g solid KOH, and stirring reaction is 36 hours under the room temperature.Add 200ml water behind the most of methyl alcohol of pressure reducing and steaming, transfer to PH3-4 with concentrated hydrochloric acid then.Separate out red precipitate, fully place after-filtration, precipitation press dry with the little water washing, and 60 ℃ are drying to obtain.Embodiment 1 is that the present invention prepares lamp-dish flower acetic and glucoside unit key intermediate 5 thereof, 6,7, the first step reaction of 4 '-tetramethoxy flavones, be by 2-hydroxyl-4,5,6-trimethoxy methyl phenyl ketone and aubepine condensation make chalcone derivative (compound 3), the first step is reacted to such an extent that compound 3 dry products 14.5 restrain, and reaction yield is about 85%.1HNMR(CDCl3)：δ13.80(s，1H)，δ7.87(s，1H)，δ7.86(s，1H)，δ7.62(d，J＝8.5Hz，2H)，δ6.96(d，J＝8.5Hz，2H)，δ6.31(s，1H)，δ3.94(s，3H)，δ3.92(s，3H)，δ3.88(s，3H)，δ3.86(s，3H)。MS(m/e)：344。
Embodiment 2:5,6,7, the preparation of 4 '-tetramethoxy flavones (compound 1)
Take by weighing 17.2g (0.05mol) compd A 9 and place the 250ml round-bottomed flask, add 50mlDMSO and a little iodine grain, be heated to back flow reaction 30min, then reaction solution is put slightly coldly, added 100ml cold water, fully stir, filter and promptly get compd A 7, be the off-white color crystallization.Embodiment 2 is that the present invention prepares lamp-dish flower acetic and glucoside unit key intermediate 5 thereof, 6,7, the second step reaction of 4 '-tetramethoxy flavones is promptly to make 5,6 behind chalcone derivative (compound 3) dioxide giving that embodiment 1 is made, 7,4 '-tetramethoxy flavones, the reaction of second step obtain compound 1 dry product 14.6 grams, and reaction yield is about 85%.
1HNMR(CDCl
3)：δ7.83(d，J＝9.0Hz，2H)，δ7.01(d，J＝9.0Hz，2H)，δ6.81(s，1H)，δ6.59(s，1H)，δ4.00(s，3H)，δ3.99(s，3H)，δ3.93(s，3H)，δ3.89(s，3H)。MS(m/e)：342。
More than two embodiment illustrated that the present invention prepares lamp-dish flower acetic and glucoside unit key intermediate 5,6,7 thereof, the two-step reaction of 4 '-tetramethoxy flavones, operation steps is simple.Wherein, the yield of two-step reaction is about 85%, therefore total reaction yield is 85% * 85% ≈ 72%, with preparation lamp-dish flower acetic and glucoside thereof unit key intermediate 5 in the prior art, 6,7, the method for 4 '-tetramethoxy flavones is compared, not only significantly exceed single step reaction (being about about 5%), and apparently higher than the total recovery (being about about 60%) of bibliographical information three-step reaction method.
More than to lamp-dish flower acetic provided by the present invention and glucoside thereof unit key intermediate 5,6,7, the preparation method of 4 '-tetramethoxy flavones describes in detail.It is to be noted; the described content of embodiment be for better implement the present invention preferred embodiment; protection scope of the present invention is not limited to the described technical scheme of above-mentioned embodiment; and should be as the criterion with the described flesh and blood of claims, any possible composition, content and technologic change is only otherwise the scope that the flesh and blood that breaks away from claim of the present invention all belongs to the present invention to be protected.
Claims (10)
1, lamp-dish flower acetic and glucoside thereof unit key intermediate 5,6,7, the preparation method of 4 '-tetramethoxy flavones, it is characterized in that, be with the 2-hydroxyl-4,5 shown in the compound 2,6-trimethoxy methyl phenyl ketone is a raw material, be prepared from two steps of reaction b by reaction a, wherein reacting a is by 2-hydroxyl-4,5,6-trimethoxy methyl phenyl ketone and aubepine condensation make the chalcone derivative shown in the compound 3, reaction b will make 5,6,7 shown in the compound 1 behind this chalcone derivative dioxide giving, 4 '-tetramethoxy flavones, chemical equation is as follows:
Compound 2 compounds 3 compounds 1
2, preparation method according to claim 1 is characterized in that, the reaction solvent of reaction a is selected from lower alcohols, ethers or varsol.
3, preparation method according to claim 2 is characterized in that, the lower alcohols solvent comprises primary alcohol, secondary alcohol or the tertiary alcohol that C6 is following.
4, preparation method according to claim 2 is characterized in that, ether solvent is tetrahydrofuran (THF) or dioxane.
5, preparation method according to claim 1 is characterized in that, the temperature of reaction of reaction a is 20-100 ℃.
6, preparation method according to claim 1 is characterized in that, the catalyzer of reaction a comprises mineral acid, organic acid, mineral alkali or organic bases.
7, preparation method according to claim 1 is characterized in that, aubepine and 2-hydroxyl-4,5 among the reaction a, and 6-trimethoxy methyl phenyl ketone amount ratio is 1-2.5: 1.
8, preparation method according to claim 1 is characterized in that, the reaction solvent of reaction b comprises dimethyl sulfoxide (DMSO), alcohols, hydro carbons, ethers or N, dinethylformamide.
9, preparation method according to claim 1 is characterized in that, the reaction reagent of reaction b is the mixture of dimethyl sulfoxide (DMSO) and inorganic iodine or its metal-salt.
10, preparation method according to claim 1 is characterized in that, the temperature of reaction of reaction b is 80-200 ℃.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014015625A1 (en) * | 2012-07-23 | 2014-01-30 | 昆明制药集团股份有限公司 | Method for preparing high purity scutellarin aglycone |
| CN105218606A (en) * | 2015-10-19 | 2016-01-06 | 昆明理工大学 | A kind of method preparing scutellarin |
| CN105439876A (en) * | 2014-09-19 | 2016-03-30 | 四川大学 | 2-hydroxychalcone amine compounds, and preparation method and uses thereof |
| CN105906600A (en) * | 2016-05-20 | 2016-08-31 | 昆明理工大学 | Method for preparing scutellarin |
| CN107759646A (en) * | 2016-08-22 | 2018-03-06 | 昆明龙津药业股份有限公司 | A kind of synthetic method of lamp-dish flower acetic |
-
2008
- 2008-09-27 CN CN200810161468A patent/CN101684112A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014015625A1 (en) * | 2012-07-23 | 2014-01-30 | 昆明制药集团股份有限公司 | Method for preparing high purity scutellarin aglycone |
| CN105439876A (en) * | 2014-09-19 | 2016-03-30 | 四川大学 | 2-hydroxychalcone amine compounds, and preparation method and uses thereof |
| CN105439876B (en) * | 2014-09-19 | 2017-11-07 | 四川大学 | 2 hydroxylated chalcone aminated compounds, preparation method and use |
| CN105218606A (en) * | 2015-10-19 | 2016-01-06 | 昆明理工大学 | A kind of method preparing scutellarin |
| CN105218606B (en) * | 2015-10-19 | 2017-12-01 | 昆明理工大学 | A kind of method for preparing scutellarin |
| CN105906600A (en) * | 2016-05-20 | 2016-08-31 | 昆明理工大学 | Method for preparing scutellarin |
| CN107759646A (en) * | 2016-08-22 | 2018-03-06 | 昆明龙津药业股份有限公司 | A kind of synthetic method of lamp-dish flower acetic |
| CN107759646B (en) * | 2016-08-22 | 2021-07-27 | 昆明龙津药业股份有限公司 | Method for synthesizing scutellarin |
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