CN106749301A - A kind of preparation method of the new lignans compound of benzo tetrahydrofuran derivatives - Google Patents
A kind of preparation method of the new lignans compound of benzo tetrahydrofuran derivatives Download PDFInfo
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- CN106749301A CN106749301A CN201611088265.7A CN201611088265A CN106749301A CN 106749301 A CN106749301 A CN 106749301A CN 201611088265 A CN201611088265 A CN 201611088265A CN 106749301 A CN106749301 A CN 106749301A
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- tetrahydrofuran derivatives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
Abstract
The invention provides a kind of preparation method of the new lignans compound of benzo tetrahydrofuran derivatives, the method is comprised the following steps：1,4-benzoquinone (BQ), Ce (SO are added in reaction vessel4)2·4H2O and MgSO4, toluene is subsequently adding, alkene is eventually adding, reaction 20 28 hours is stirred at room temperature；Reaction is filtered after terminating using diatomite sand core funnel, and pure product is obtained by upper post separation after being spin-dried for.The preparation method, it is easy, it is with low cost, mild condition and to water and oxygen better tolerance, yield can reach more than 80%, be a kind of new synthetic method of the new lignans compound of benzo tetrahydrofuran derivatives, for the application of such chemicals provides positive exploration.
Description
Technical field
The present invention relates to organic synthesis field, especially, it is related to a kind of new lignans compound of benzo tetrahydrofuran derivatives
Preparation method.
Background technology
Lignanoid is widely existed in the plant of nature, is formed by phenylpropyl alcohol primitive unit cell (C6-C3C) oxidation polymerization
Natural products.The concern of pharmacologist and chemist is enjoyed because of the popularity of the diversity of its structure and bioactivity.Its
In being present in more than 70 kinds of plants, place position is different, or even also has hair in the secretion of plant, the urine of human and animal
It is existing.The new lignans of benzo tetrahydrofuran derivatives used as a kind of important component of lignanoid, but seldom reported by its synthetic method
Road.
Prior art one：Benzofuranone is reduced into benzo tetrahydrofuran by Monte groups with reducing process：
Prior art two：Ellman groups then use wilkinson catalyst direct activation c h bonds, reuse at hydrochloric acid
Manage and then obtain benzo tetrahydrofuran：
Prior art three：Until in recent years, Wuhan University's thunder love culture and education awards seminar carries out catalysis oxidation benzoquinones using HOTf
Benzo tetrahydrofuran is directly generated with styrene：
The complex steps of prior art one, the catalyst of prior art two is with high costs, and the condition of prior art three is more violent, and
It is more sensitive to water and oxygen, reacted in strong acid medium, it is not suitable for the substrate of acid labile, therefore necessary research is new
Benzo tetrahydrofuran derivatives new lignans compound preparation method.
The content of the invention
It is a kind of easy present invention aim at providing, with low cost, mild condition and to water and the benzene of oxygen better tolerance
And the preparation method of the new lignans compound of tetrahydrofuran derivatives, to solve technical problem.
A kind of preparation method of the new lignans compound of benzo tetrahydrofuran derivatives, comprises the following steps：
1,4-benzoquinone (BQ), Ce (SO are added in reaction vessel4)2·4H2O and MgSO4, toluene is subsequently adding, it is eventually adding
Such as the alkene of compound 2.Reaction 20-28 hours is stirred at room temperature；Reaction is carried out after terminating using diatomite sand core funnel
Filtering, pure product is obtained after being spin-dried for by upper post separation.
Specific reaction equation is as follows：
R1=Me, Et, i-Pr, F, Cl, Br, OMe R2=H, Me R3=H, Me.
Preferably, the amount of the material of the addition of described compound 2 is 5-7 times of the amount of the material that 1,4-benzoquinone is added.
Preferably, described Ce (SO4)2·4H2The amount of the material of the addition of O is the 1-3 of the amount of the material that 1,4-benzoquinone is added
Times.
Preferably, described MgSO4Addition material added for 1,4-benzoquinone 5-7 times of amount of material of amount.
The preparation method of the new lignans compound of benzo tetrahydrofuran derivatives of the invention, easy, with low cost, condition temperature
With and to water and oxygen better tolerance, yield can reach more than 80%, be the new lignans compound of benzo tetrahydrofuran derivatives
A kind of new synthetic method, for the application of such chemicals provides positive exploration.
In addition to objects, features and advantages described above, the present invention also has other objects, features and advantages.
The present invention is further detailed explanation below.
Brief description of the drawings
Fig. 1：The hydrogen nuclear magnetic resonance spectrogram of the product of embodiment 1.
Fig. 2：The carbon-13 nmr spectra figure of the product of embodiment 1.
Fig. 3：The hydrogen nuclear magnetic resonance spectrogram of the product of embodiment 2.
Fig. 4：The carbon-13 nmr spectra figure of the product of embodiment 2.
Fig. 5：The hydrogen nuclear magnetic resonance spectrogram of the product of embodiment 3.
Fig. 6：The carbon-13 nmr spectra figure of the product of embodiment 3.
Specific embodiment
Embodiment 1
A kind of preparation method of the new lignans compound of benzo tetrahydrofuran derivatives, comprises the following steps：
32.4mg (0.3mmol) BQ, 363.9mg (0.9mmol) Ce (SO are added in 10ml reaction tubes4)2·4H2O and
216.7mg(1.8mmol)MgSO43ml toluene is added afterwards, is eventually adding the isopropyl alkene benzene of 2.1mmol；It is stirred at room temperature anti-
Answer 24 hours；Reaction is filtered after terminating using diatomite sand core funnel, obtains pure by upper post separation after being spin-dried for
Net product.
Table 1 is the amount of the material that each raw material is adjusted under conditions of embodiment 1, the product yield situation for obtaining：
Table 1：
Product to embodiment 1 makees proton nmr spectra and carbon-13 nmr spectra, respectively obtains Fig. 1 and Fig. 2, thus can push away
The chemical formula of stopping pregnancy thing is：
Embodiment 2
By the R in chemical formula1F is replaced with, remaining preparation condition is constant, and it is common to make proton nmr spectra and nuclear-magnetism to product
The carbon that shakes is composed, and respectively obtains Fig. 3 and Fig. 4, and thus the chemical formula of deducibility product is：
Embodiment 3
By the R in chemical formula1Methyl is replaced with, remaining preparation condition is constant, and make proton nmr spectra and core to product
Magnetic resonance carbon is composed, and respectively obtains Fig. 5 and Fig. 6, and thus the chemical formula of deducibility product is：
The preferred embodiments of the present invention are the foregoing is only, is not intended to limit the invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.It is all within the spirit and principles in the present invention, made any repair
Change, equivalent, improvement etc., should be included within the scope of the present invention.
Claims (5)
1. the preparation method of the new lignans compound of a kind of benzo tetrahydrofuran derivatives, it is characterised in that comprise the following steps：
1,4-benzoquinone, Ce (SO are added in reaction vessel4)2·4H2O and MgSO4, toluene is subsequently adding, it is eventually adding such as compound 2
Alkene, be stirred at room temperature reaction 20-28 hours；Reaction is filtered after terminating using diatomite sand core funnel, is spin-dried for
Going up post separation afterwards can obtain pure product；
The chemical formula of described compound 2 is as follows：
Wherein, R1=Me, Et, i-Pr, F, Cl, Br, OMe R2=H, Me R3=H, Me.
2. the preparation method of the new lignans compound of benzo tetrahydrofuran derivatives as claimed in claim 1, it is characterised in that institute
The amount of the material of the addition of the compound 2 stated is 5-7 times of the amount of the material that 1,4-benzoquinone is added.
3. the preparation method of the new lignans compound of benzo tetrahydrofuran derivatives as claimed in claim 1, it is characterised in that institute
Ce (the SO for stating4)2·4H2The amount of the material of the addition of O is 1-3 times of the amount of the material that 1,4-benzoquinone is added.
4. the preparation method of the new lignans compound of benzo tetrahydrofuran derivatives as claimed in claim 1, it is characterised in that institute
The MgSO for stating4Addition material added for 1,4-benzoquinone 5-7 times of amount of material of amount.
5. the preparation method of the new lignans compound of benzo tetrahydrofuran derivatives as claimed in claim 1, it is characterised in that bag
Include following steps：
0.3mmol 1,4-benzoquinone, 0.9mmolCe (SO are added in 10ml reaction tubes4)2·4H2O and 1.8mmolMgSO4Add afterwards
3ml toluene, is eventually adding the isopropyl alkene benzene of 2.1mmol；Reaction 24 hours is stirred at room temperature；Reaction uses diatom after terminating
Native sand core funnel is filtered, and pure product is obtained by upper post separation after being spin-dried for.
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| CN201611088265.7A CN106749301B (en) | 2016-12-01 | 2016-12-01 | A kind of preparation method of the new lignans compound of benzo tetrahydrofuran derivatives |
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| CN201611088265.7A CN106749301B (en) | 2016-12-01 | 2016-12-01 | A kind of preparation method of the new lignans compound of benzo tetrahydrofuran derivatives |
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| CN106749301A true CN106749301A (en) | 2017-05-31 |
| CN106749301B CN106749301B (en) | 2019-09-24 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4139544A (en) * | 1976-11-26 | 1979-02-13 | Ici Americas Inc. | Oxidative coupling of alkylphenols catalyzed by metal complexes of polyimino acids |
| CN102718773A (en) * | 2012-06-05 | 2012-10-10 | 上海交通大学 | Method for preparing artemisinin through arteannuic acid |
| CN103172645A (en) * | 2012-06-05 | 2013-06-26 | 上海交通大学 | High-efficiency synthesis method of artemisinin |
| CN103193790A (en) * | 2012-06-05 | 2013-07-10 | 上海交通大学 | High-efficiency preparation method of anti-malarial medicine artemisinin |
-
2016
- 2016-12-01 CN CN201611088265.7A patent/CN106749301B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4139544A (en) * | 1976-11-26 | 1979-02-13 | Ici Americas Inc. | Oxidative coupling of alkylphenols catalyzed by metal complexes of polyimino acids |
| CN102718773A (en) * | 2012-06-05 | 2012-10-10 | 上海交通大学 | Method for preparing artemisinin through arteannuic acid |
| CN103172645A (en) * | 2012-06-05 | 2013-06-26 | 上海交通大学 | High-efficiency synthesis method of artemisinin |
| CN103193790A (en) * | 2012-06-05 | 2013-07-10 | 上海交通大学 | High-efficiency preparation method of anti-malarial medicine artemisinin |
Non-Patent Citations (2)
| Title |
|---|
| KAMITANAKA, TOHRU ET AL.: "New synthesis of tetrahydrobenzodifurans by iterative coupling of quinone monoacetals with alkene nucleophiles", 《HETEROCYCLES》 * |
| LINGKUI MENG ET AL.: "Trifluoromethanesulfonic Acid Catalyzed Synergetic Oxidative/[3+2] Cyclization of Quinones with Olefins", 《ANGEW. CHEM. INT. ED.》 * |
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