CN104529973A - Synthetic method for polysubstituted baicalein derivatives - Google Patents

Synthetic method for polysubstituted baicalein derivatives Download PDF

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Publication number
CN104529973A
CN104529973A CN201410746519.4A CN201410746519A CN104529973A CN 104529973 A CN104529973 A CN 104529973A CN 201410746519 A CN201410746519 A CN 201410746519A CN 104529973 A CN104529973 A CN 104529973A
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polysubstituted
substituted
reaction
baicalein
chloride
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刘湘
朱洁莲
李炜
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Jiangnan University
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Jiangnan University
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    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)

Abstract

The invention discloses a synthetic method for a kind of polysubstituted baicalein derivatives shown as a formula I, and in the formula I, R1, R2 and R3 are H, hydroxyl, alkyl, alkoxy and the like. By modifying baicalein B-ring skeleton, the baicalein derivatives are synthesized, which are substantially improved in dissolvability, anticancer activity and other aspects compared with baicalein. The method employs substituted benzaldehyde and 3,4,5-trimethoxyphenol as basic raw materials, and the B-ring polysubstituted baicalein derivatives are prepared through 3 steps. The method concretely comprises performing condensation reaction on the substituted benzaldehyde and an acid anhydride under the effect of an alkali catalyst, so as to obtain substituted cinnamic acid, and further synthesizing substituted cinnamoyl chloride, performing acylation reaction on the substituted cinnamoyl chloride and 3,4,5-trimethoxyphenolunder the effect of a catalyst, so as to obtain a chalcone compound, and performing cyclization reaction on the chalcone compound under the effect of a catalyst, so as to obtain the corresponding polysubstituted baicalein derivative. The method is simple in technology, abundant in raw materials, high in yield, good in product purity and low in cost, and has wide application prospect.

Description

A kind of synthetic method of polysubstituted Scutellarein derivative
Technical field
The present invention relates to a kind of synthetic method of polysubstituted Scutellarein derivative, belong to the technical field of organic synthesis.
Background technology
Scutellarin is the main active ingredient of baikal skullcap root; there is antibacterial, antiviral, anti-inflammatory, anti-oxidant, scavenging activated oxygen, anticancer, antitumor, anti-freezing, multiple physiologically active and the pharmacological action such as antithrombus formation and protection liver, cardiovascular and cerebrovascular, neurone; but scutellarin solvability is bad, limit its application in field of medicaments.In order to improve these shortcomings and expand its range of application, people transform its structure, have synthesized a series of Scutellarein derivative, these derivatives in water-soluble, fat-soluble and anticancer etc. all comparatively scutellarin have greatly improved.
Bibliographical information (J.Med.Chem, 2004,47,5555-5566), obtain a series of Scutellarein derivative by carrying out alkylation to scutellarin A ring, enhance it and suppress P-glycoprotein 170 active, active testing result shows that these compounds have certain cytotoxicity; Bibliographical information (Acta Pharmaceutica Sinica, 1997,32,140-143) two benzyl oxide analog derivatives are separately had to have certain HIV (human immunodeficiency virus)-resistant activity.Also the methylamine Scutellarein derivative having patent (Chinese Patent Application No. 02111185.5) to report the replacement of 8-position has stronger arrestin kinase c (PKC) and the activity of inhibiting HIV HIV/ III B.But it is few about modifying to obtain the bibliographical information with stronger pharmacological action to scutellarin B ring skeleton.Invention describes the synthetic method of the cyclosubstituted novel Scutellarein derivative of a class B.
Summary of the invention
The present invention essentially discloses that a class abundant raw material, productive rate are high, the synthetic method of the simple polysubstituted Scutellarein derivative of technique, it is characterized in that first with substituted benzaldehyde and diacetyl oxide synthesis substituted cinnamic acid, to go forward side by side one-step synthesis substituted cinnamoyl chloride, then by substituted cinnamoyl chloride and 3,4,5-trimethoxy phenol synthesizes polysubstituted chalcone compounds, and finally synthesis obtains polysubstituted Scutellarein derivative, and the step of employing is as follows:
(1) substituted benzaldehyde and diacetyl oxide reflux 1 ~ 3h under basic catalyst effect, and after reaction terminates, extraction, obtains phenyl ring there is multiple substituent styracin.The substituted cinnamic acid obtained is dissolved in (the consumption of every mol substrate in 1 ~ 3L organic solvent, lower same), under nitrogen and ice-water bath condition with the halogenating agent of one of thionyl chloride, oxalyl chloride at N, dinethylformamide or N, accelerine catalysis generation halogenating reaction, after reaction 2 ~ 4h, separation and purification obtains substituted cinnamoyl chloride.
(2) be dissolved in 1 ~ 3L organic solvent by substituted cinnamoyl chloride and 3,4,5-trimethoxy phenol, reflux 0.5 ~ 2h under catalyst action, separation and purification obtains the chalcone compounds such as formula II.R in formula II 1, R 2, R 3can be hydrogen, hydroxyl, alkyl, alkoxyl group etc.
(3) be dissolved in 3 ~ 5L organic solvent by such as formula the chalcone compounds shown in II, reflux 2 ~ 5h under catalyst action, precipitation is separated out in ice-water bath cooling, obtains such as formula the polysubstituted Scutellarein derivative shown in I, the R in formula I through separation and purification 1, R 2, R 3can be hydrogen, hydroxyl, alkyl, alkoxyl group etc.
Below be namely the basic synthetic method of raw 5,6, the 7-trimethoxy Scutellarein derivatives replaced of B environment-development disclosed in this invention.
Organic solvent in the present invention can select toluene, ether, normal hexane, sherwood oil, tetrahydrofuran (THF), one of ethyl acetate and methyl-sulphoxide.Wherein step (2) used catalyst can be one of Eorontrifluoride etherate, Aluminum chloride anhydrous, and the reaction times is 0.5 ~ 2h.Wherein step (3) used catalyst can be one of elemental iodine, Potassium Iodate, and the reaction times is 2 ~ 5h.
Embodiment
Further illustrate flesh and blood of the present invention with example below, but they are not construed as limiting the invention.
Embodiment 1:4'-methyl-5,6,7-trimethoxy scutellarin
17mL (150mmol) p-tolyl aldehyde is added, 19mL (200mmol) diacetyl oxide, 10g salt of wormwood, reflux 1.5h in flask.With ethyl acetate (3 × 250mL) extraction, concentrated after organic over anhydrous dried over sodium sulfate, must to tolyl acrylic acid (20g, 82%) after ethyl alcohol recrystallization.
16.3g (100mmol) is added to tolyl acrylic acid, 80mL CH in flask 2cl 2, at N 2the lower ice-water bath holding temperature of using of protection, at 0 ~ 5 DEG C, instills 9.5mL (130mmol) SOCl 2and a small amount of dry DMF, under 0 ~ 5 DEG C of condition, react 2h.Decompression steams solvent and namely obtains methylcinnamoyl chloride (13.5g, 82%).
13g (80mmol) is added to methylcinnamoyl chloride, 12.9g (70mmol) 3,4,5-trimethoxy phenol, 80mL BF in flask 3-Et 2o, reflux 30min, cool to room temperature separates out precipitation.Filter, precipitation washed with diethylether obtains thick product, and normal hexane and ethyl acetate (V/V=3:1) recrystallization, obtain 6'-hydroxy-4-methyl-2', 3', 4'-trimethoxy cinnamophenone (18.4g, 80%).
16.4g (50mmol) 6'-hydroxy-4-methyl-2' is added, 3', 4'-trimethoxy cinnamophenone, 150mL DMSO, 0.75g (3mmol) I in flask 2, reflux 2h, precipitation is separated out in ice-water bath cooling.Filter, by the resolution of precipitate that obtains in ethyl acetate, with 10% sodium thiosulfate solution washing (3 × 250mL), ester layer anhydrous sodium sulfate drying, decompression steams solvent and obtains thick product, obtains yellow solid 4'-methyl-5,6 with ethyl alcohol recrystallization, 7-trimethoxy scutellarin (14.7g, 90%).
The preparation of embodiment 2:4', 5,6,7-tetramethoxy scutellarin
18.2mL (150mmol) aubepine is added, 19mL (200mmol) diacetyl oxide, 8g anhydrous acetic acid potassium, reflux 2h in flask.Adding 15g sodium carbonate makes solution be slight alkalinity, carry out wet distillation till distillate is without oil droplet, add proper amount of active carbon and boil 5 ~ 10min, suction filtration while hot, in filtrate, add 30mL concentrated hydrochloric acid, make solution be obvious acidity, separate out a large amount of solid, suction filtration obtains p-methoxycinnamic acid (23g, 85%).
17.8g (100mmol) p-methoxycinnamic acid is added, 80mL CH in flask 2cl 2, at N 2the lower ice-water bath holding temperature of using of protection, at 0 ~ 5 DEG C, instills 9.5mL (130mmol) SOCl 2and a small amount of dry DMF, under 0 ~ 5 DEG C of condition, react 2.5h.Decompression steams solvent and namely obtains methoxycinnamate acyl chlorides (17g, 85%).
16.1g (80mmol) is added to methoxycinnamate acyl chlorides, 12.9g (70mmol) 3,4,5-trimethoxy phenol, 80mL BF in flask 3-Et 2o, reflux 45min, cool to room temperature separates out precipitation.Filter, precipitation washed with diethylether obtains thick product, obtains 6'-hydroxyl-2' after sherwood oil and ethyl acetate (V/V=3:1) recrystallization, 3', 4', 4-tetramethoxy cinnamophenone (19.6g, 85%).
17.2g (50mmol) 6'-hydroxyl-2' is added, 3', 4', 4-tetramethoxy cinnamophenone, 150mLDMSO, 0.75g (3mmol) I in flask 2, reflux 2.5h, precipitation is separated out in ice-water bath cooling.Filter, by the resolution of precipitate that obtains in ethyl acetate, with 10% sodium thiosulfate solution washing (3 × 250mL), ester layer anhydrous sodium sulfate drying, decompression steams solvent and obtains thick product, be separated with silica gel column chromatography, normal hexane and ethyl acetate (V/V=7:3) are eluent, obtain brown solid 4', 5,6,7-tetramethoxy scutellarin (16g, 93%).
The preparation of embodiment 3:3', 5,6,7-tetramethoxy scutellarin
18.2mL (150mmol) NSC 43794 is added, 19mL (200mmol) diacetyl oxide, 8g anhydrous acetic acid potassium, reflux 3h in flask.With ethyl acetate (3 × 250mL) extraction, concentrated after organic over anhydrous dried over sodium sulfate, obtain meta-methoxy styracin (21.4g, 80%) after ethyl alcohol recrystallization.
17.8g (100mmol) meta-methoxy styracin is added, 80mL CH in flask 2cl 2, at N 2the lower ice-water bath holding temperature of using of protection, at 0 ~ 5 DEG C, instills 9.5mL (130mmol) SOCl 2and a small amount of dry DMF, under 0 ~ 5 DEG C of condition, react 3h.Decompression steams solvent and namely obtains meta-methoxy cinnamyl chloride (17g, 80%).
16.1g (80mmol) meta-methoxy cinnamyl chloride is added, 12.9g (70mmol) 3,4,5-trimethoxy phenol, 80mL BF in flask 3-Et 2o, reflux 1h, cool to room temperature separates out precipitation.Filter, precipitation washed with diethylether obtains thick product, obtains 6'-hydroxyl-2' after sherwood oil and ethyl acetate (V/V=3:1) recrystallization, 3,3', 4'-tetramethoxy cinnamophenone (21g, 80%).
17.2g (50mmol) 6'-hydroxyl-2' is added, 3,3', 4'-tetramethoxy cinnamophenone, 150mLDMSO, 0.75g (3mmol) I in flask 2, reflux 3h, precipitation is separated out in ice-water bath cooling.Filter, by the resolution of precipitate that obtains in ethyl acetate, with 10% sodium thiosulfate solution washing (3 × 250mL), ester layer anhydrous sodium sulfate drying, decompression steams solvent and obtains thick product, obtains brown solid 3' with ethyl alcohol recrystallization, 5,6,7-tetramethoxy scutellarin (18g, 88%).
The preparation of embodiment 4:4'-nitro-5,6,7-trimethoxy scutellarin
22.7g (150mmol) paranitrobenzaldehyde is added, 19mL (200mmol) diacetyl oxide, 10g salt of wormwood, reflux 2h in flask.With toluene (3 × 250mL) extraction, concentrated after organic over anhydrous dried over sodium sulfate, must to nitrocinnamic acid (24g, 82%) after ethyl alcohol recrystallization.
15g (100mmol) is added to nitrocinnamic acid, 80mL CH in flask 2cl 2, at N 2the lower ice-water bath holding temperature of using of protection, at 0 ~ 5 DEG C, instills 9.5mL (130mmol) SOCl 2and a small amount of dry DMF, under 0 ~ 5 DEG C of condition, react 3.5h.Decompression steams solvent and namely obtains nitrocinnamyl acyl chlorides (18g, 85%).
16.9g (80mmol) is added to nitrocinnamyl acyl chlorides, 12.9g (70mmol) 3,4,5-trimethoxy phenol, 80mL BF in flask 3-Et 2o, reflux 1.5h, cool to room temperature separates out precipitation.Filter, precipitation washed with diethylether obtains thick product, obtains 6'-hydroxyl-2' after sherwood oil and ethyl acetate (V/V=7:3) recrystallization, 3', 4'-trimethoxy-4-nitro cinnamophenone (23g, 78%).
18g (50mmol) 6'-hydroxyl-2' is added, 3', 4'-trimethoxy-4-nitro cinnamophenone, 150mL DMSO, 0.75g (3mmol) I in flask 2, reflux 2h, precipitation is separated out in ice-water bath cooling.Filter, by the resolution of precipitate that obtains in ethyl acetate, with 10% sodium thiosulfate solution washing (3 × 250mL), ester layer anhydrous sodium sulfate drying, decompression steams solvent and obtains thick product, be separated with silica gel column chromatography, normal hexane and ethyl acetate (V/V=3:1) are eluent, obtain orange solids 4'-nitro-5,6,7-trimethoxy scutellarin (16g, 85%).
The preparation of embodiment 5:3'-hydroxyl-5,6,7-trimethoxy scutellarin
18.3g (150mmol) m-hydroxybenzaldehyde is added, 19mL (200mmol) diacetyl oxide, 8g anhydrous acetic acid potassium, reflux 3h in flask.With ethyl acetate (3 × 250mL) extraction, concentrated after organic over anhydrous dried over sodium sulfate, hydroxycinnamic acid (21g, 85%) between obtaining after ethyl alcohol recrystallization.
Hydroxycinnamic acid between 16.4g (100mmol) is added, 80mL CH in flask 2cl 2, at N 2the lower ice-water bath holding temperature of using of protection, at 0 ~ 5 DEG C, instills 9.5mL (130mmol) SOCl 2and a small amount of dry DMF, under 0 ~ 5 DEG C of condition, react 4h.Decompression steams solvent and namely obtains a hydroxy cinnamate acyl chlorides (15.5g, 85%).
Hydroxy cinnamate acyl chlorides between 14.6g (80mmol) is added, 12.9g (70mmol) 3,4,5-trimethoxy phenol, 80mL BF in flask 3-Et 2o, reflux 30min, cool to room temperature separates out precipitation.Filter, precipitation washed with diethylether obtains thick product, obtains 3,6'-dihydroxyl-2' after normal hexane and ethyl acetate (V/V=3:1) recrystallization, 3', 4'-trimethoxy cinnamophenone (19.7g, 85%).
16.5g (50mmol) 3,6'-dihydroxyl-2' is added, 3', 4'-trimethoxy cinnamophenone, 150mLDMSO, 0.75g (3mmol) I in flask 2, reflux 5h, precipitation is separated out in ice-water bath cooling.Filter, by the resolution of precipitate that obtains in ethyl acetate, with 10% sodium thiosulfate solution washing (3 × 250mL), ester layer anhydrous sodium sulfate drying, decompression steams solvent and obtains thick product, obtains yellow solid 3'-hydroxyl-5,6 with ethyl alcohol recrystallization, 7-trimethoxy scutellarin (15.3g, 93%).

Claims (3)

1. the synthetic method of a polysubstituted Scutellarein derivative, it is characterized in that first with substituted benzaldehyde and diacetyl oxide synthesis substituted cinnamic acid, to go forward side by side one-step synthesis substituted cinnamoyl chloride, then by substituted cinnamoyl chloride and 3,4,5-trimethoxy phenol synthesizes polysubstituted chalcone compounds, and last cyclization obtains polysubstituted Scutellarein derivative, and its step is as follows:
Step (1): substituted benzaldehyde first carries out condensation reaction with diacetyl oxide under the effect of anhydrous acetic acid potassium, back flow reaction 1 ~ 3h, separation and purification obtains substituted cinnamic acid, again with the halogenating agent of one of thionyl chloride, oxalyl chloride at N, under dinethylformamide or DMA catalysis, halogenating reaction occurs, temperature of reaction is 0 ~ 5 DEG C, reaction times is 2 ~ 4h, and separation and purification obtains polysubstituted cinnamyl chloride;
Step (2): substituted cinnamoyl chloride under catalyst action with 3,4,5-trimethoxy phenol generation acylation reaction, 3, the molar ratio of 4,5-trimethoxy phenol and substituted cinnamoyl chloride is 1:1 ~ 1:1.5, and separation and purification obtains polysubstituted chalcone compounds;
Step (3): chalcone compounds carries out self ring-closure reaction under catalyst action, separation and purification obtains polysubstituted Scutellarein derivative.
2. the method preparing Scutellarein derivative according to claim 1, is characterized in that: wherein step (2) described catalyzer can be one of Eorontrifluoride etherate, Aluminum chloride anhydrous, and the described reaction times is 0.5 ~ 2h.
3. the method preparing Scutellarein derivative according to claim 1, is characterized in that: wherein step (3) described catalyzer can be one of elemental iodine, Potassium Iodate, and the described reaction times is 2 ~ 5h.
CN201410746519.4A 2014-12-09 2014-12-09 Synthetic method for polysubstituted baicalein derivatives Pending CN104529973A (en)

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Cited By (5)

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CN107759551A (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 breviscapine B aglycone
CN110698810A (en) * 2019-06-28 2020-01-17 江西瀚泰新材料科技有限公司 High-toughness, anti-ultraviolet-absorption and flame-retardant epoxy resin composition and preparation thereof
CN111349068A (en) * 2020-03-30 2020-06-30 中国药科大学 Organic synthesis method of scutellarein
CN111826014A (en) * 2020-07-17 2020-10-27 浙江乐酷厨具有限公司 Non-stick pan with modified tetrafluoroethylene coating and preparation method thereof
CN116162077A (en) * 2023-02-28 2023-05-26 苏州普瑞森生物科技有限公司 Baicalein derivative and preparation method and application thereof

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107759551A (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 breviscapine B aglycone
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
CN110698810A (en) * 2019-06-28 2020-01-17 江西瀚泰新材料科技有限公司 High-toughness, anti-ultraviolet-absorption and flame-retardant epoxy resin composition and preparation thereof
CN110698810B (en) * 2019-06-28 2022-07-05 江西瀚泰新材料科技有限公司 High-toughness, anti-ultraviolet-absorption and flame-retardant epoxy resin composition and preparation thereof
CN111349068A (en) * 2020-03-30 2020-06-30 中国药科大学 Organic synthesis method of scutellarein
CN111826014A (en) * 2020-07-17 2020-10-27 浙江乐酷厨具有限公司 Non-stick pan with modified tetrafluoroethylene coating and preparation method thereof
CN111826014B (en) * 2020-07-17 2021-09-03 浙江乐酷厨具有限公司 Non-stick pan with modified tetrafluoroethylene coating and preparation method thereof
CN116162077A (en) * 2023-02-28 2023-05-26 苏州普瑞森生物科技有限公司 Baicalein derivative and preparation method and application thereof
CN116162077B (en) * 2023-02-28 2024-02-02 苏州普瑞森生物科技有限公司 Baicalein derivative and preparation method and application thereof

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Application publication date: 20150422