CN103936704B - A kind of method preparing chrysin - Google Patents

A kind of method preparing chrysin Download PDF

Info

Publication number
CN103936704B
CN103936704B CN201410137766.4A CN201410137766A CN103936704B CN 103936704 B CN103936704 B CN 103936704B CN 201410137766 A CN201410137766 A CN 201410137766A CN 103936704 B CN103936704 B CN 103936704B
Authority
CN
China
Prior art keywords
chrysin
dimethoxychalcone
hydroxyl
reaction
solid
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
Application number
CN201410137766.4A
Other languages
Chinese (zh)
Other versions
CN103936704A (en
Inventor
杨健
刘漫
张楫
杨波
韩彬
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kunming University of Science and Technology
Original Assignee
Kunming University of Science and Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kunming University of Science and Technology filed Critical Kunming University of Science and Technology
Priority to CN201410137766.4A priority Critical patent/CN103936704B/en
Publication of CN103936704A publication Critical patent/CN103936704A/en
Application granted granted Critical
Publication of CN103936704B publication Critical patent/CN103936704B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

The invention discloses a kind of method preparing chrysin.The method of the invention comprises step 1,1,3,5-trimethoxy-benzene synthesizes 2 '-hydroxyl-4 with styracin under boron trifluoride diethyl etherate catalysis ', 6 '-dimethoxychalcone; Step 2,2 '-hydroxyl-4 ', 6 '-dimethoxychalcone generates 5,7-dimethoxy flavone under iodine catalysis; Step 3,5,7-dimethoxy flavones generate chrysin through full demethylation.The present invention improves the synthesis yield of chrysin for the preparation of the method for chrysin, and synthesis step reduces, and has raw material cheap and easy to get, is easy to control, easy and simple to handle, has very high prospects for commercial application.

Description

A kind of method preparing chrysin
Technical field
The present invention relates to pharmaceutical synthesis field, be specifically related to a kind of method preparing chrysin.
Background technology
Chrysin (5,7-dihydroxy-2-phenyl-4 h-chromen-4- one), English name chrysin, be present in seed, the stem skin of Bignoniaceae plant oroxylum indicum [Oroxylum indicum (L.) Vent.], the heart wood of pinaceae plant western white pine (Pinus mon-ticola Dougl.), in the various plants such as the heart wood of bristlecone pine (P.aristata Engelm.), its chemical structural formula is as follows.
Modern pharmacology research show, chrysin has pharmacologically active effect widely, such as antitumor action (M. C á rdenas, et al., bioorg. Med. Chem., 2006,14,2966); Anti-allergic effects (F. L. Pearce, et al., j. Allergy Clin. Immun., 1984,73,819); Anti-inflammatory action (H. Cho, et al.. pharmacol. Res., 2004,49,37); Antivirus action (J.-H. Lee, et al., korean Journal of Pharmacognosy., 1999,30,34); Resisting pathogenic microbes effect (K. Suresh Babu, et al., bioorg. Med. Chem. Lett., 2006,16,221) and hypoglycemic activity (J.-S. Shin, et al, med. Chem. Lett., 1999,9,869.) etc.Use using chrysin as the medicine of main active ingredient is existing in many countries and regions.With chrysin be arrive first compound carry out multiple derivative that structural modification obtains also show have comparatively than quite or more excellent pharmacologically active effect (F. Yang, et al, bioorg. Med. Chem. Lett., 2013,23,5544.).
Usually, the acquisition of current chrysin is mainly extracted and is obtained from plant material.But due to the finiteness of natural plant resource, and wherein chrysin content is also on the low side, makes to obtain chrysin in a large number with this method and be restricted.But, be one by chemical process synthesis and obtain the fabulous approach of chrysin in a large number, successively have scholar to be studied exploitation to this method.Xiao Jinxia etc. are with 1,3,5-trimethoxy-benzene is starting raw material, by being obtained by reacting intermediate 2 with Acetyl Chloride 98Min. generation good fortune gram, 4,6-trimethoxy methyl phenyl ketone, then obtains β-propanedione with methyl benzoate in sodium methoxide catalyzed lower condensation, and last demethylation closes ring and obtains chrysin (CN 102127044).But raw material Acetyl Chloride 98Min. poor stability, in operation or the Shi Yifen that is heated explain phosgene and the hydrogen chloride gas of severe toxicity, be unfavorable for safety in production, and last demethylation cyclization process produces a large amount of spent acid.In addition in another section of patent documentation; Wu Yonglong etc. (CN 102010393) are raw material with Benzoyl chloride; ethyl benzoylacetate is obtained with methyl aceto acetate condensation under condensing agent catalysis; then under elevated temperature in vacuo, chrysin is obtained with Phloroglucinol mixing condensation reaction; but this reaction must be carried out in a vacuum; require higher to production unit, Phloroglucinol price is more expensive.It is raw material with Phloroglucinol that minister in ancient times phoenix tail feathers etc. (CN 1475487) report a kind of, first there is Hoesch with excess chlorine acetonitrile and be obtained by reacting intermediate 2,4,6-trihydroxy--α-chloro-methyl phenyl ketone, after it becomes phenyl styryl ketone with benzaldehyde under alkaline environment, by cyclization and dehydrochlorination generate chrysin in the basic conditions.But this method Hoesch long reaction time, operation has inconvenience, and need with a large amount of HCl gas, and equipment corrosion is serious, and requires that equipment is higher, is unfavorable for amplifying and produces.Document Med. Chem. Res.; 20; 838 – 846; report in 2011 with 2; 4,6-trihydroxy-acetophenone is raw material, obtains 2-hydroxyl-4 with methyl-sulfate selective protection; after 6-dimethoxy-acetophenone; under become ester, alkaline environment with Benzoyl chloride, be rearranged to β-propanedione, cyclization under acetic acid/sulfuric acid nitration mixture catalysis again, final demethylation obtains chrysin; this method route is long; synthesis total recovery and efficiency all not high, the methyl-sulfate used has strong toxicity and corrodibility, and raw material not easily obtains; and price is costly, be unsuitable for for the production of.
Summary of the invention
The present invention is intended to provide a kind of easier, method of preparing chrysin efficiently, and the method adopts commercially available cheap raw material, achieves the complete synthesis of chrysin, synthesis total recovery and efficiency are improved all greatly by only three-step reaction.
The method preparing chrysin of the present invention, concrete steps are as follows:
(1) with 1,3,5-trimethoxy-benzene and styracin for raw material, with boron trifluoride diethyl etherate catalyzed reaction synthesis 2 '-hydroxyl-4 ', 6 '-dimethoxychalcone;
(2) 2 '-hydroxyls-4 ', the cyclization under iodine/DMSO condition of 6 '-dimethoxychalcone, generates 5,7-dimethoxy flavone;
Namely (3) 5,7-dimethoxy flavones demethylating under pyridine hydrochloride process generates chrysin;
The chemical reactive synthesis route that the present invention relates to is:
The concrete operations of the inventive method are as follows:
(1) be that raw material is placed in flask with 1,3,5-trimethoxy-benzene and styracin, 1, the blending ratio of 3,5-trimethoxy-benzene and styracin is mol ratio 1:1 ~ 1:2, boron trifluoride diethyl etherate is added in raw material, under temperature of reaction is 80 ~ 120 DEG C of conditions after condensing reflux reaction 3 ~ 5h, be cooled to room temperature to filter, obtain crystal, crystal is placed in aqueous ethanolic solution reflux 2 ~ 3h, obtain safran clear liquor, add activated carbon decolorizing and filter; Separate out yellow solid after cooling, after filtration, washing leaching cake drying, obtain 2 '-hydroxyl-4 ', 6 '-dimethoxychalcone, wherein the addition of boron trifluoride diethyl etherate is 5 ~ 15 times of 1,3,5-trimethoxy-benzene mole number;
(2) by 2 '-hydroxyl-4 ', 6 '-dimethoxychalcone is dissolved in DMSO solution, adds iodine, is warming up to 80-140 DEG C of backflow 3-6h, is cooled to room temperature, then reaction solution is poured into the NaHSO that mass percent concentration is 2% 3in solution, leach solid after abundant stirring, after dry, obtain pale yellow powder shape crystal 5,7-dimethoxy flavone with dehydrated alcohol recrystallization, wherein 2 '-hydroxyl-4 ', the blending ratio of 6 '-dimethoxychalcone and iodine is 10:1-20:1 (mol ratio);
(3) by 5, the mol ratio of 7-dimethoxy flavone and pyridine hydrochloride is the ratio of 1:5-1:15,5,7-dimethoxy flavone is added in pyridine hydrochloride, after stirring reaction 4-6h, mixture is let cool to room temperature at 180-220 DEG C, add water, separate out solid, filter after fully stirring, collect solid, dry after fully washing solid with distilled water, after ethyl alcohol recrystallization, obtain chrysin.
The present invention significantly simplify the synthetic route of chrysin for the preparation of the method for chrysin, improves synthesis yield and the efficiency of chrysin, has raw material cheap and easy to get, and synthesis step reduces, and is easy to control, easy and simple to handle, has very high prospects for commercial application.
The compound that the method for the invention is finally prepared passes through magnetic resonance detection, prove that its structure is consistent with chrysin structure, and synthesize total recovery and be up to about 62.6% after testing, significant raising has been had compared with existing synthesis yield, obtained chrysin detects through HPLC method, purity reaches more than 98%, and quality is higher.
Embodiment
The method preparing chrysin disclosed by the invention, those skilled in the art can be easy to realize with reference to teachings herein operation.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the art, the method of the invention is described by following instance, related personnel obviously can in the scope not departing from content of the present invention, connotation to method as herein described to realize the technology of the present invention.Within these similar replacements and change also should be placed in the claim of the application's patent.
It is as follows that this prepares the concrete implementation content of chrysin:
embodiment 1:
(1) 2 '-hydroxyl-4 ', the synthesis of 6 '-dimethoxychalcone
Take 4.2g 1,3,5-trimethoxy-benzene (0.025mol) and 3.7g styracin (0.025mol) adds in dry round-bottomed flask, then add 15.0mL boron trifluoride diethyl etherate, band drying tube 80 DEG C of condensing refluxes.After reaction 3h, stop being heated to room temperature, separate out red needle crystal, leach crystal.Crystal to be added in 100mL aqueous ethanolic solution reflux 2.5 hours, obtain safran clear liquor, add activated carbon decolorizing and filter.Wash out yellow solid after cooling, after filtration, washing leaching cake drying, obtain 5.35g 2 '-hydroxyl-4 ', 6 '-dimethoxychalcone, yield 75.4%.
Structural parameter 1h NMR (400 MHz, DMSO-d 6), δ: 3.83 (s, 3H, OCH 3-4 '), 3.91 (s, 3H, OCH 3-6 '), 6.14 (d, J=1.6 Hz, 1H, H-3 '), 6.17 (d, J=1.6 Hz, 1H, H-5 '), 7.45 – 7.49 (m, 3H, H-3,4,5), 7.65 (d, 1H, J=16 Hz, H-α), 7.72 – 7.74 (m, 2H, H-2,6), 7.78 (d, J=16 Hz, 1H, H-β), 13.41 (s, 1H, OH-2 ').
The synthesis of (2) 5,7-dimethoxy flavones
Take 5.7g(0.02 mol) 2 '-hydroxyl-4 ', the synthesis of 6 '-dimethoxychalcone, adds after 30 mL DMSO dissolve completely, adds 0.13g iodine, be warming up to 80 DEG C of reaction 4h hour under room temperature.Be chilled to room temperature, then reaction solution poured into 200mL 2% NaHSO 3solution, leaches solid after fully stirring, and obtains pale yellow powder shape crystal 4.79g 5,7-dimethoxy flavone, yield 84.9% after dry with dehydrated alcohol recrystallization.
Structural parameter 1h NMR (400 MHz, DMSO-d6), δ: 3.83 (s, 3H, OCH3-7), 3.90 (s, 3H, OCH3-5), 6.50 (d, 1H, J=2.4 Hz, H-8), 6.76 (s, 1H, H-3), 6.85 (d, 1H, J=2.4 Hz, H-6), 7.56 (m, 3H, H-4 ', 5 ', 6 '), 8.03 (m, 2H, H-2 ', 3 ').
(3) synthesis of chrysin
Take the synthesis of 2.8g (0.01 mol) 5,7-dimethoxy flavones, put in 50mL reaction flask, add 5.7g pyridine hydrochloride.With after air in nitrogen replacement bottle, mixture is heated to 180 DEG C, after stirring reaction 4 h, mixture is let cool to room temperature, add water, separate out a large amount of solid, filter after fully stirring, collect solid, fully wash rear drying with water, solid obtains chrysin 2.1g after ethyl alcohol recrystallization, and yield is 82.7%.
Structural parameter: 1h NMR (400 MHz, DMSO-d 6), δ: 6.23 (d, 1H, J=2.0 Hz, H-6), 6.53 (d, 1H, J=2.0 Hz, H-8), 6.97 (s, 1H, H-3), 7.55 – 7.62 (m, 3H, H-4 ', 5 ', 6 '), 8.06 (m, 2H, H-2 ', 3 '), 10.94 (s, 1H, OH-5), 12.83 (s, 1H, OH-7).
embodiment 2:
(1) 2 '-hydroxyl-4 ', the synthesis of 6 '-dimethoxychalcone
Take 4.2g 1,3,5-trimethoxy-benzene (0.025mol) and 5.5g styracin (0.0375mol) adds in dry round-bottomed flask, then add 30.0mL boron trifluoride diethyl etherate, band drying tube 100 DEG C of condensing refluxes.After reaction 4h, stop being heated to room temperature, separate out red needle crystal, leach crystal.Crystal to be added in 100mL aqueous ethanolic solution reflux 2.5 hours, obtain safran clear liquor, add activated carbon decolorizing and filter.Wash out yellow solid after cooling, after filtration, washing leaching cake drying, obtain 5.79g 2 '-hydroxyl-4 ', 6 '-dimethoxychalcone, yield 81.6%.
The synthesis of (2) 5,7-dimethoxy flavones
Take 5.7g(0.02 mol) 2 '-hydroxyl-4 ', the synthesis of 6 '-dimethoxychalcone, adds after 30 mL DMSO dissolve completely, adds 0.17g iodine, be warming up to 120 DEG C of reaction 5h under room temperature.Be chilled to room temperature, then reaction solution poured into 200mL 2% NaHSO 3solution, leaches solid after fully stirring, and obtains pale yellow powder shape crystal 5.0 g 5,7-dimethoxy flavone, yield 88.6% after dry with dehydrated alcohol recrystallization.
(3) synthesis of chrysin
Take the synthesis of 2.8g (0.01 mol) 5,7-dimethoxy flavones, put in 50mL reaction flask, add 11.5g pyridine hydrochloride.With after air in nitrogen replacement bottle, mixture is heated to 200 DEG C, after stirring reaction 5 h, mixture is let cool to room temperature, add water, separate out a large amount of solid, filter after fully stirring, collect solid, fully wash rear drying with water, solid obtains chrysin 2.2g after ethyl alcohol recrystallization, and yield is 86.7%.
embodiment 3:
(1) 2 '-hydroxyl-4 ', the synthesis of 6 '-dimethoxychalcone
Take 4.2g 1,3,5-trimethoxy-benzene (0.025mol) and 7.4g styracin (0.050mol) adds in dry round-bottomed flask, then add 45.0mL boron trifluoride diethyl etherate, band drying tube 120 DEG C of condensing refluxes.After reaction 5h, stop being heated to room temperature, separate out red needle crystal, leach crystal.Crystal to be added in 100mL aqueous ethanolic solution reflux 2.5 hours, obtain safran clear liquor, add activated carbon decolorizing and filter.Wash out yellow solid after cooling, after filtration, washing leaching cake drying, obtain 6.1g 2 '-hydroxyl-4 ', 6 '-dimethoxychalcone, yield 85.9%.
The synthesis of (2) 5,7-dimethoxy flavones
Take 5.7g(0.02 mol) 2 '-hydroxyl-4 ', the synthesis of 6 '-dimethoxychalcone, adds after 30mL DMSO dissolves completely, adds 0.25g iodine, be warming up to 140 DEG C of reaction 6h under room temperature.Be chilled to room temperature, then reaction solution poured into 200mL 2% NaHSO 3solution, leaches solid after fully stirring, and obtains pale yellow powder shape crystal 5.1 g 5,7-dimethoxy flavone, yield 90.1% after dry with dehydrated alcohol recrystallization.
(3) synthesis of chrysin
Take the synthesis of 2.8g (0.01 mol) 5,7-dimethoxy flavones, put in 50mL reaction flask, add 17.4g pyridine hydrochloride.With after air in nitrogen replacement bottle, mixture is heated to 220 DEG C, after stirring reaction 6 h, mixture is let cool to room temperature, add water, separate out a large amount of solid, filter after fully stirring, collect solid, fully wash rear drying with water, solid obtains chrysin 2.1g after ethyl alcohol recrystallization, and yield is 82.6%.

Claims (1)

1. prepare a method for chrysin, it is characterized in that carrying out as follows:
(1) with 1,3,5-trimethoxy-benzene and styracin for raw material, with boron trifluoride diethyl etherate catalyzed reaction synthesis 2 '-hydroxyl-4 ', 6 '-dimethoxychalcone;
(2) 2 '-hydroxyls-4 ', the cyclization under iodine/DMSO condition of 6 '-dimethoxychalcone, generates 5,7-dimethoxy flavone;
Namely (3) 5,7-dimethoxy flavones demethylating under pyridine hydrochloride process generates chrysin;
Synthetic route is as follows:
；
The concrete operations of described step (1) are as follows: be that raw material is placed in flask with 1,3,5-trimethoxy-benzene and styracin, 1, the blending ratio of 3,5-trimethoxy-benzene and styracin is mol ratio 1:1-1:2, boron trifluoride diethyl etherate is added in raw material, under temperature of reaction is 80 ~ 120 DEG C of conditions after condensing reflux reaction 3-5h, be cooled to room temperature to filter, obtain crystal, crystal is placed in aqueous ethanolic solution reflux 2-3h, obtain safran clear liquor, add activated carbon decolorizing and filter; Separate out yellow solid after cooling, after filtration, washing leaching cake drying, obtain 2 '-hydroxyl-4 ', 6 '-dimethoxychalcone, wherein the addition of boron trifluoride diethyl etherate is 5-15 times of 1,3,5-trimethoxy-benzene mole number;
The concrete operations of described step (2) are as follows: by 2 '-hydroxyl-4 ', 6 '-dimethoxychalcone is dissolved in DMSO solution, adds iodine, is warming up to 80-140 DEG C of backflow 3-6h, be cooled to room temperature, then reaction solution poured into the NaHSO that mass percent concentration is 2% 3in solution, after fully stirring, leach solid, after dry, obtain pale yellow powder shape crystal 5,7-dimethoxy flavone, wherein 2 '-hydroxyl-4 with dehydrated alcohol recrystallization ', the blending ratio of 6 '-dimethoxychalcone and iodine is mol ratio 10:1-20:1;
The concrete operations of described step (3) are as follows: by 5, the mol ratio of 7-dimethoxy flavone and pyridine hydrochloride is the ratio of 1:5-1:15,5,7-dimethoxy flavone is added in pyridine hydrochloride, after stirring reaction 4-6 h, mixture is let cool to room temperature at 180-220 DEG C, add water, separate out solid, filter after fully stirring, collect solid, dry after fully washing solid with distilled water, after ethyl alcohol recrystallization, obtain chrysin.
CN201410137766.4A 2014-04-08 2014-04-08 A kind of method preparing chrysin Expired - Fee Related CN103936704B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410137766.4A CN103936704B (en) 2014-04-08 2014-04-08 A kind of method preparing chrysin

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410137766.4A CN103936704B (en) 2014-04-08 2014-04-08 A kind of method preparing chrysin

Publications (2)

Publication Number Publication Date
CN103936704A CN103936704A (en) 2014-07-23
CN103936704B true CN103936704B (en) 2015-09-30

Family

ID=51184616

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410137766.4A Expired - Fee Related CN103936704B (en) 2014-04-08 2014-04-08 A kind of method preparing chrysin

Country Status (1)

Country Link
CN (1) CN103936704B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105237503B (en) * 2015-10-19 2017-10-27 昆明理工大学 A kind of method for preparing baicalein
CN107759551B (en) * 2016-08-22 2021-10-01 昆明龙津药业股份有限公司 Method for synthesizing scutellarin aglycone

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009065141A1 (en) * 2007-11-15 2009-05-22 The General Hospital Corporation Methods and compositions for reducing skin damage
CN102465158A (en) * 2010-11-19 2012-05-23 苏州宝泽堂医药科技有限公司 Method for preparing chrysin
CN102793712A (en) * 2012-09-07 2012-11-28 天津医科大学 Application of chrysin in preparation of medicaments for treating autoimmune and inflammatory diseases

Also Published As

Publication number Publication date
CN103936704A (en) 2014-07-23

Similar Documents

Publication Publication Date Title
CN101941999B (en) Method for preparing scutellarin
NZ539819A (en) Compositions and therapeutic methods involving isoflavones and analogues thereof
CN101735190B (en) Method for preparing baicalein
CN103570661B (en) Natural product Rubraflavone category-A is like thing and its preparation method and application
CN101891728A (en) Scutellarein derivative as well as preparation method and application thereof
CN105237503B (en) A kind of method for preparing baicalein
CN103936704B (en) A kind of method preparing chrysin
CN101824017A (en) Method for preparing scutellarin aglycone
KR100565423B1 (en) A manufacturing process of Isoflavan or Isoflavene derivatives
CN104529973A (en) Synthetic method for polysubstituted baicalein derivatives
CN101735229A (en) Tetrahydroisoquinoline compounds and preparation method and application thereof
CN105218499B (en) A kind of method for preparing Scutellarein
CN106279083B (en) A kind of furocoumarin analog derivative and preparation method thereof
CN102731459B (en) Scutellarin aglycone Mannich derivatives, and preparation method and application thereof
CN104311518B (en) A kind of preparation method of 6-methyl scutellarin genin
CN101186563A (en) 3,5-dimethoxyl or 3,5-dihydroxy diphenylethene compounds and preparation method thereof
CN101003530B (en) Method for preparing perfluoroalkyl group sulfonyl isoflavone of possessing anticarcinogenesis
CN105566233A (en) Preparation method of erlotinib intermediate
CN110498744A (en) A kind of preparation method of 1- ethyl -3- nitrobenzene
CN102060832A (en) Method for compounding baicalein derivative
CN102516215A (en) Preparation method of C-glucoside containing saturated cyclohexane structure
CN101143861B (en) B ring 4'-single substituted flavone compounds, preparation method and use
CN103936707B (en) A kind of method preparing mango aglycone
CN110183371A (en) A kind of preparation process of zafirlukast intermediate
CN104072362A (en) Synthesis process for antiviral chemical compound protocatechuic acid

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
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20150930

Termination date: 20210408

CF01 Termination of patent right due to non-payment of annual fee