CN106749301B - 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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- CN106749301B CN106749301B CN201611088265.7A CN201611088265A CN106749301B CN 106749301 B CN106749301 B CN 106749301B CN 201611088265 A CN201611088265 A CN 201611088265A CN 106749301 B CN106749301 B CN 106749301B
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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 present invention provides a kind of preparation methods of the new lignans compound of benzo tetrahydrofuran derivatives, method includes the following steps: 1,4-benzoquinone (BQ), Ce (SO are added in the reaction vessel4)2·4H2O and MgSO4, toluene is then added, is eventually adding alkene, reaction 20-28 hours is stirred at room temperature；Reaction is filtered after terminating using diatomite sand core funnel, and pure product can be obtained in upper post separation after being spin-dried for.The preparation method, it is easy, it is low in cost, mild condition and good to water and oxygen tolerance, yield can achieve 80% or more, is the new synthetic method of one kind of the new lignans compound of benzo tetrahydrofuran derivatives, provides positive exploration for the application of such chemicals.
Description
Technical field
The present invention relates to organic synthesis fields, particularly, are related to a kind of new lignans compound of benzo tetrahydrofuran derivatives
Preparation method.
Background technique
Lignanoid widely exists in the plant of nature, is as made of phenylpropyl alcohol primitive unit cell (C6-C3C) oxidation polymerization
Natural products.By the concern of pharmacologist and chemist due to the popularity of the diversity of its structure and bioactivity.Its
It is present in more than 70 kinds plants, place position is different, or even also has hair in the secretion of plant, the urine of human and animal
It is existing.A kind of important component of the new lignans of benzo tetrahydrofuran derivatives as lignanoid, synthetic method are but seldom reported
Road.
Benzofuranone is reduced into benzo tetrahydrofuran with reduction method by one: Monte group of the prior art:
Two: Ellman group of the prior art then uses wilkinson catalyst direct activation c h bond, reuses at hydrochloric acid
It manages and then obtains benzo tetrahydrofuran:
The prior art three: until in recent years, Wuhan University's thunder love culture and education awards seminar and carries out catalysis oxidation benzoquinones using HOTf
Benzo tetrahydrofuran is directly generated with styrene:
One complex steps of the prior art, two catalyst of the prior art is with high costs, and three condition of the prior art is more violent, and
It is more sensitive to water and oxygen, it is reacted in strong acid medium, is not suitable for the substrate of acid labile, therefore necessary research is new
Benzo tetrahydrofuran derivatives new lignans compound preparation method.
Summary of the invention
It is low in cost it is an object of that present invention to provide a kind of simplicity, mild condition and the benzene good to water and oxygen 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, comprising the following steps:
1,4-benzoquinone (BQ), Ce (SO are added in the reaction vessel4)2·4H2O and MgSO4, toluene is then added, 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 can be obtained in upper post separation after being spin-dried for.
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 substance of the addition of the compound 2 is 5-7 times of the amount for the substance that 1,4-benzoquinone is added.
Preferably, the Ce (SO4)2·4H2The amount of the substance of the addition of O is the 1-3 of the amount for the substance that 1,4-benzoquinone is added
Times.
Preferably, the MgSO4The amount of substance of addition be 5-7 times of amount of the substance that 1,4-benzoquinone is added.
The preparation method of the new lignans compound of benzo tetrahydrofuran derivatives of the invention, easy, low in cost, condition temperature
With and to water and oxygen tolerance it is good, yield can achieve 80% or more, be the new lignans compound of benzo tetrahydrofuran derivatives
One kind new synthetic method, be such chemicals using providing positive exploration.
Other than objects, features and advantages described above, there are also other objects, features and advantages by the present invention.
The present invention is further detailed explanation below.
Detailed description of the invention
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, comprising the following steps:
32.4mg (0.3mmol) BQ, 363.9mg (0.9mmol) Ce (SO is added in 10ml reaction tube4)2·4H2O and
216.7mg(1.8mmol)MgSO43ml toluene is added later, is eventually adding the isopropyl alkene benzene of 2.1mmol；It is stirred at room temperature anti-
It answers 24 hours；Reaction is filtered after terminating using diatomite sand core funnel, and upper post separation can be obtained pure after being spin-dried for
Net product.
Table 1 is to adjust the amount of the substance of each raw material, obtained product yield situation under conditions of embodiment 1:
Table 1:
Nuclear magnetic resonance spectroscopy and carbon-13 nmr spectra are made to the product of embodiment 1, respectively obtain Fig. 1 and Fig. 2, thus can be pushed away
The chemical formula of stopping pregnancy object are as follows:
Embodiment 2
By the R in chemical formula1F is replaced with, remaining preparation condition is constant, and it is total to make nuclear magnetic resonance spectroscopy and nuclear-magnetism to product
The carbon that shakes is composed, and respectively obtains Fig. 3 and Fig. 4, thus the chemical formula of deducibility product are as follows:
Embodiment 3
By the R in chemical formula1Methyl is replaced with, remaining preparation condition is constant, and makees nuclear magnetic resonance spectroscopy and core to product
Magnetic resonance carbon spectrum, respectively obtains Fig. 5 and Fig. 6, thus the chemical formula of deducibility product are as follows:
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (4)
1. a kind of preparation method of the new lignans compound of benzo tetrahydrofuran derivatives, which comprises the following steps:
1,4-benzoquinone, Ce (SO are added in the reaction vessel4)2·4H2O and MgSO4, toluene is then added, 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
Pure product can be obtained in upper post separation afterwards；
The chemical formula of the 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 described in claim 1, which is characterized in that institute
The amount of the substance of the addition for the compound 2 stated is 5-7 times of the amount for the substance that 1,4-benzoquinone is added.
3. the preparation method of the new lignans compound of benzo tetrahydrofuran derivatives as described in claim 1, which is characterized in that institute
Ce (the SO stated4)2·4H2The amount of the substance of the addition of O is 1-3 times of the amount for the substance that 1,4-benzoquinone is added.
4. the preparation method of the new lignans compound of benzo tetrahydrofuran derivatives as described in claim 1, which is characterized in that institute
The MgSO stated4The amount of substance of addition be 5-7 times of amount of the substance that 1,4-benzoquinone is added.
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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 CN106749301A (en) | 2017-05-31 |
| CN106749301B true 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 |
|---|
| New synthesis of tetrahydrobenzodifurans by iterative coupling of quinone monoacetals with alkene nucleophiles;Kamitanaka, Tohru ET AL.;《Heterocycles》;20151023;第93卷(第1期);第295-309页 * |
| Trifluoromethanesulfonic Acid Catalyzed Synergetic Oxidative/[3+2] Cyclization of Quinones with Olefins;Lingkui Meng et al.;《Angew. Chem. Int. Ed.》;20131231;第52卷;第10195-10198页 * |
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