CN106995428B - A kind of synthetic method of 6H- benzo [C] benzopyrans compounds - Google Patents
A kind of synthetic method of 6H- benzo [C] benzopyrans compounds Download PDFInfo
- Publication number
- CN106995428B CN106995428B CN201710354035.9A CN201710354035A CN106995428B CN 106995428 B CN106995428 B CN 106995428B CN 201710354035 A CN201710354035 A CN 201710354035A CN 106995428 B CN106995428 B CN 106995428B
- Authority
- CN
- China
- Prior art keywords
- benzo
- synthetic method
- formula
- benzopyrans compounds
- reaction
- 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.)
- Active
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
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The present invention discloses one kind 6HBenzo [C] benzopyrans compounds synthetic method; belong to catalyst preparation technical field; it is characterized by: using diazonium salt shown in formula (I) as raw material; dyestuff photosensitizer is catalyst; in organic solvent; through being stirred to react 1 ~ 48 h in room temperature ~ 40 DEG C, synthesis obtains target product under nitrogen protection and the irradiation of 3 ~ 100 W green lights.This method is not necessarily to metallic catalyst, alkali and ligand, and reaction condition is mild, environmental-friendly, low in cost, easy to operate, and reaction yield is high, has a good application prospect.
Description
Technical field:
The invention belongs to catalyst preparation fields, and in particular to a kind of 6H- benzo [C] benzopyrans compounds
Synthetic method.
Background technique:
6H- benzo [C] chromene be many natural products with physiological activity and drug molecule core skeleton (see
Fig. 1 .1), such as: sonchus oleraceus rod method extract (Alternethanoxins A, E), hemp main active
(J.Agric.Food Chem.,2009,57,6656-6660；J.Agric.Food Chem.2015,63,1196-1199；
J.Nat.Prod.,2009,72,906-911；J.Med.Chem.,2013,56,3904-3921.).Develop simple, efficient 6H-
The preparation method of benzo [C] benzo pyran derivative has great importance.
Several representative 6H- benzo [C] chromene active components of Fig. 1 .1
In recent years, many seminars realized the synthesis of this kind of compound, can be mainly divided into following two strategy.
Strategy one: transition metal-catalyzed synthesis 6H- benzo [C] chromene is utilized
Using it is transition metal-catalyzed be synthesize 6H- benzo [C] chromene conventional method (Pure
Appl.Chem.1991,63,419-422；Chem.Rev.1995,95,2457-2483；Chem.Rev.2002,102,1359-
1470；Org.Lett.,2011,13,3242-3245；CN 102633582 A；Tetrahedron Lett.2012,53,
7036-7039).Such methods need expensive transition metal such as palladium etc. to be used as catalyst, and need to be added alkali, ligand etc. and add
Add agent, reaction just can be carried out at high temperature.In addition, the substrate preparation of this method also has significant limitation.
Strategy two: it is not necessarily to transition metal-catalyzed synthesis 6H- benzo [C] chromene
Without the transition metal-catalyzed synthesis for being also able to achieve 6H- benzo [C] benzopyrans compounds
(J.Am.Chem.Soc.1991,113,7676-7684；RSC Advances 2015,5,50174-50177), but both at home and abroad
Report it is seldom.1991, Wan seminar was under 254nm ultraviolet lighting, with 2 '-(hydroxymethyls)-[1,1- biphenyl] -2- phenol
For raw material, the synthesis of 6H- benzo [C] chromene is realized, but this method raw material is not easy to prepare, using by the very day of one's doom
System.2015, Jayanta K.Ray et al. halogenated biphenyl class compound was raw material in DMSO solvent, with the highly basic uncle of 3 equivalents
Butanol potassium has synthesized 6H- benzo [C] chromene at 100 DEG C as additive.Although this method is avoided using expensive transition
For metal as catalyst, however, there remains highly basic to do additive, and could occur at high temperature, therefore obtains its application
Considerable restraint.
Summary of the invention:
The present invention is intended to provide a kind of mild, without metal catalytic synthesis 6H- benzo [C] benzopyrans compounds
New method.
The technical solution that the present invention takes to achieve the above object is as follows:
A kind of synthetic method of 6H- benzo [C] benzopyrans compounds, it is characterised in that: with diazonium shown in formula (I)
Salt is raw material, under dyestuff photosensitizer catalytic action, in organic solvent, and through under nitrogen protection and 3~100W radiation of visible light, in
Room temperature~40 DEG C are stirred to react, and synthesis obtains 6H- benzo [C] benzopyrans compounds shown in formula (II), and reaction route is such as
Under:
In formula (I) and formula (II): R1For hydrogen, chlorine, methyl；R2For hydrogen, fluorine；R3For hydrogen, chlorine, methyl.
Further it is provided in:
In the above method, the ratio between amount for the substance that feeds intake of substrate diazonium salt shown in formula (I) and dyestuff photosensitizer is 1:0.02
~0.001.The dyestuff photosensitizer be selected from it is following any one: eosin Y (Eosin Y), rhodamine B (Rhodamine B),
Fluorescein (Fluorescein), preferably eosin Y (Eosin Y).
In the above method, organic solvent one kind selected from the following: ethyl acetate, methanol, dimethyl sulfoxide, N, N- dimethyl
Formamide, acetonitrile, acetone, preferably acetonitrile.
In the above method, reaction need to react 1~48 hour under the irradiation of 3~100W visible light light through nitrogen protection.Institute
Stating light source can be white energy-saving lamp, green LED lamp, blue LED lamp, preferably green LED lamp.
In the above method, preferred reaction time 12~36 hours, reaction temperature was room temperature.
In the above method, the target compound synthesized is 6H- benzo [C] chromene, fluoro- 6H- benzo [C] benzene of 3-
And chloro- 6H- benzo [C] chromene of pyrans, 2-, 2- methyl -6H- benzo [C] chromene, 9- methyl -6H- benzo [C] benzene
And chloro- 6H- benzo [C] chromene of pyrans, 9-, 2,9- dimethyl -6H- benzo [C] chromene.
Product structure prepared by the present invention is as follows:
Compared with reported preparation method, the method for the present invention is had several advantages that
1, the present invention provides under a kind of temperate condition, 6H- benzo [C] chromene is efficiently synthesized under visible light promotion
The new method of class compound, this method reaction condition as mild as a dove, operation it is very simple.At room temperature by one timing of reactant stirring
Between can obtain product with good yield, without heating or reflux.
2, reaction cost reduction, condition are more green, and reaction can carry out under green light irradiation；It avoids making in reaction process
With expensive transition-metal catalyst, does not have to plus the additives such as alkali and ligand, reaction efficient green, cost substantially reduce.
3, by the control to reaction condition, the yield of reaction can be effectively improved.
Specific embodiment:
Explanation is further explained to the present invention combined with specific embodiments below, but specific embodiment is merely to illustrate technology
Scheme, protection scope of the present invention are simultaneously confined to this.
Embodiment 1: the embodiment illustrates the preparation of 6H- benzo [C] chromene.
The 10mL reaction tube for taking a dried and clean is weighed into Arenediazonium salts (59.6mg, 0.2mmol) [formula (1), R1=
H,R2=H, R3=H], acetonitrile 2mL is added with syringe in eosin Y (1.4mg, 0.002mmol), and system uses 36W through nitrogen protection
Green LED lamp irradiates reaction tube, and then at room temperature, for 24 hours, TLC is detected to fully reacting magnetic agitation, dilute with ethyl acetate
It releases, organic phase is washed 3 times, and organic phase is dry with anhydrous sodium sulfate after liquid separation, is then spin-dried for being concentrated, column chromatographic isolation and purification obtains
Product, yield 90%.1H NMR(400MHz,CDCl3) δ 7.77 (dd, J=7.7,1.6Hz, 1H), 7.73 (d, J=7.7Hz,
1H), 7.41 (td, J=7.7,1.2Hz, 1H), 7.31 (td, J=7.5,1.2Hz, 1H), 7.29-7.24 (m, 1H), 7.18
(dd, J=7.5,0.6Hz, 1H), 7.09 (td, J=7.6,1.2Hz, 1H), 7.03 (dd, J=8.1,1.1Hz, 1H), 5.15
(s, 2H) compound and document (Tetrahedron 2016,72,1043-1050) report are consistent.
Alternative:
With embodiment 1, difference is synthetic method: adjustment reaction dissolvent, catalyst and dosage, light source, reaction temperature, and
Its influence to product yield is counted, the results are shown in Table 1.
Table 1:
Embodiment 2: the embodiment illustrates the preparation of fluoro- 6H- benzo [C] chromene of 3-.
The 10mL reaction tube for taking a dried and clean is weighed into Arenediazonium salts (63.2mg, 0.2mmol) [formula (1), R1=
H,R2=F, R3=H], acetonitrile 2mL is added with syringe in eosin Y (1.4mg, 0.002mmol), and system uses 36W through nitrogen protection
Green LED lamp irradiates reaction tube, and then at room temperature, for 24 hours, TLC is detected to fully reacting magnetic agitation, dilute with ethyl acetate
It releases, organic phase is washed 3 times, and organic phase is dry with anhydrous sodium sulfate after liquid separation, is then spin-dried for being concentrated, column chromatographic isolation and purification obtains
Product, yield 80%.1H NMR(400MHz,CDCl3) δ 7.75-7.59 (m, 2H), 7.38 (t, J=7.7Hz, 1H), 7.29
(dd, J=7.5,0.9Hz, 1H), 7.15 (d, J=7.4Hz, 1H), 6.87-6.62 (m, 2H), 5.13 (s, 2H) compounds
It is consistent with document (Tetrahedron 2016,72,1043-1050) report.
Embodiment 3: the embodiment illustrates the preparation of chloro- 6H- benzo [C] chromene of 2-.
The 10mL reaction tube for taking a dried and clean is weighed into Arenediazonium salts (66.4mg, 0.2mmol) [formula (1), R1=
Cl,R2=H, R3=H], acetonitrile 2mL is added with syringe in eosin Y (1.4mg, 0.002mmol), and system is used through nitrogen protection
36W green LED lamp irradiates reaction tube, and then at room temperature, for 24 hours, TLC is detected to fully reacting magnetic agitation, uses ethyl acetate
Dilution, organic phase are washed 3 times, and organic phase is dry with anhydrous sodium sulfate after liquid separation, are then spin-dried for being concentrated, column chromatographic isolation and purification obtains
To product, yield 72%.1H NMR (400MHz, Chloroform-d) δ 7.59 (d, J=2.6Hz, 1H), 7.55 (d, J=
7.6Hz, 1H), 7.32 (t, J=7.6Hz, 1H), 7.23 (dt, J=7.6,1.0Hz, 1H), 7.06-7.10 (m, 2H), 6.84
(d, J=8.6Hz, 1H), 5.10 (s, 2H) compounds and document (Chem.Commun., 2011,47,9813-9815) are reported
Unanimously.
Embodiment 4: the embodiment illustrates the preparation of 2- methyl -6H- benzo [C] chromene.
The 10mL reaction tube for taking a dried and clean is weighed into Arenediazonium salts (62.4mg, 0.2mmol) [formula (1), R1=
CH3,R2=H, R3=H], acetonitrile 2mL is added with syringe in eosin Y (1.4mg, 0.002mmol), and system is used through nitrogen protection
36W green LED lamp irradiates reaction tube, and then at room temperature, for 24 hours, TLC is detected to fully reacting magnetic agitation, uses ethyl acetate
Dilution, organic phase are washed 3 times, and organic phase is dry with anhydrous sodium sulfate after liquid separation, are then spin-dried for being concentrated, column chromatographic isolation and purification obtains
To product, yield 90%.1H NMR(400MHz,CDCl3) δ 7.73 (d, J=7.7Hz, 1H), 7.58 (d, J=1.6Hz,
1H), 7.41 (t, J=8.2Hz, 1H), 7.31 (td, J=7.5,1.1Hz, 1H), 7.18 (dd, J=7.5,0.6Hz, 1H),
7.08 (dd, J=8.2,1.5Hz, 1H), 6.94 (d, J=8.2Hz, 1H), 5.12 (s, 2H), 2.40 (s, 3H) compounds with
Document (Tetrahedron 2016,72,1043-1050) report is consistent.
Embodiment 5: the embodiment illustrates the preparation of 9- methyl -6H- benzo [C] chromene.
The 10mL reaction tube for taking a dried and clean is weighed into Arenediazonium salts (62.4mg, 0.2mmol) [formula (1), R1=
H,R2=H, R3=4-CH3], acetonitrile 2mL is added with syringe in eosin Y (1.4mg, 0.002mmol), system through nitrogen protection,
Reaction tube is irradiated with 36W green LED lamp, then at room temperature, for 24 hours, TLC is detected to fully reacting magnetic agitation, with acetic acid second
Ester dilution, organic phase are washed 3 times, and organic phase is dry with anhydrous sodium sulfate after liquid separation, are then spin-dried for being concentrated, column chromatographic isolation and purification
Obtain product, yield 95%.1H NMR(400MHz,CDCl3) δ 7.76 (dd, J=7.6,1.6Hz, 1H), 7.55 (s, 1H),
7.28-7.24 (m, 1H), 7.14-7.06 (m, 3H), 7.02 (dd, J=8.0,1.2Hz, 1H), 5.12 (s, 2H), 2.44 (s,
3H) the compound and document (Tetrahedron 2016,72,1043-1050) report are consistent.
Embodiment 6: the embodiment illustrates the preparation of chloro- 6H- benzo [C] chromene of 9-.
The 10mL reaction tube for taking a dried and clean is weighed into Arenediazonium salts (66.4mg, 0.2mmol) [formula (1), R1=
H,R2=H, R3=4-Cl], acetonitrile 2mL is added with syringe in eosin Y (1.4mg, 0.002mmol), and system is used through nitrogen protection
36W green LED lamp irradiates reaction tube, and then at room temperature, for 24 hours, TLC is detected to fully reacting magnetic agitation, uses ethyl acetate
Dilution, organic phase are washed 3 times, and organic phase is dry with anhydrous sodium sulfate after liquid separation, are then spin-dried for being concentrated, column chromatographic isolation and purification obtains
To product, yield 30%.1H NMR(400MHz,CDCl3) δ 7.70 (dd, J=8.2,1.7Hz, 2H), 7.33-7.24 (m,
2H), 7.12-7.07 (m, 2H), 7.02 (dd, J=8.1,1.1Hz, 1H), 5.10 (s, 2H) compounds and document
(Tetrahedron Lett.2012,53,7036-7039) report is consistent.
Embodiment 7: the embodiment illustrates the preparation of 2,9- dimethyl -6H- benzo [C] chromene.
The 10mL reaction tube for taking a dried and clean is weighed into Arenediazonium salts (65.2mg, 0.2mmol) [formula (1), R1=
CH3,R2=H, R3=4-CH3], acetonitrile 2mL is added with syringe in eosin Y (1.4mg, 0.002mmol), and system is protected through nitrogen
Shield irradiates reaction tube with 36W green LED lamp, and then at room temperature, for 24 hours, TLC is detected to fully reacting magnetic agitation, uses acetic acid
Ethyl ester dilution, organic phase are washed 3 times, and organic phase is dry with anhydrous sodium sulfate after liquid separation, are then spin-dried for being concentrated, column chromatography for separation is pure
Change obtains product, yield 88%.1H NMR(400MHz,CDCl3)δ7.55-7.48(m,2H),7.11-6.99(m,2H),
6.88 (d, J=8.2Hz, 1H), 5.04 (s, 2H), 2.40 (s, 3H), 2.35 (s, 3H) compounds and document
(Tetrahedron Lett.2012,53,7036-7039) report is consistent.
Claims (7)
1. a kind of synthetic method of 6H- benzo [C] benzopyrans compounds, it is characterised in that: with diazonium salt shown in formula (I)
For raw material, under dyestuff photosensitizer catalytic action, in organic solvent, through under nitrogen protection and radiation of visible light, in room temperature~40
It is stirred to react at a temperature of DEG C, it is as follows to obtain 6H- benzo [C] benzo pyran target product, reaction route shown in formula (II):
In formula (I) and formula (II): R1For hydrogen, chlorine, methyl；R2For hydrogen, fluorine；R3For hydrogen, chlorine, methyl；
Described dyestuff photosensitizer one kind selected from the following: eosin Y, rhodamine B, fluorescein；
Described reaction dissolvent one kind selected from the following: ethyl acetate, dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, third
Ketone.
2. a kind of synthetic method of 6H- benzo [C] benzopyrans compounds as described in claim 1, it is characterised in that: system
The target product structure obtained is as follows:
3. a kind of synthetic method of 6H- benzo [C] benzopyrans compounds as described in claim 1, it is characterised in that: weight
The ratio between amount for the substance that feeds intake of nitrogen salt and dyestuff photosensitizer is 1:0.02~0.001.
4. a kind of synthetic method of 6H- benzo [C] benzopyrans compounds as described in claim 1, it is characterised in that: institute
The power for stating visible light is 3~100W.
5. a kind of synthetic method of 6H- benzo [C] benzopyrans compounds as claimed in claim 4, it is characterised in that: institute
Visible light source is stated as white energy-saving lamp, green LED lamp, one kind of blue LED lamp.
6. a kind of synthetic method of 6H- benzo [C] benzopyrans compounds as described in claim 1, it is characterised in that: institute
The reaction time stated is 1~48 hour.
7. a kind of synthetic method of 6H- benzo [C] benzopyrans compounds as described in claim 1, it is characterised in that: institute
The reaction time stated is 12~36 hours, and reaction temperature is room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710354035.9A CN106995428B (en) | 2017-05-18 | 2017-05-18 | A kind of synthetic method of 6H- benzo [C] benzopyrans compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710354035.9A CN106995428B (en) | 2017-05-18 | 2017-05-18 | A kind of synthetic method of 6H- benzo [C] benzopyrans compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106995428A CN106995428A (en) | 2017-08-01 |
| CN106995428B true CN106995428B (en) | 2019-05-24 |
Family
ID=59434896
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710354035.9A Active CN106995428B (en) | 2017-05-18 | 2017-05-18 | A kind of synthetic method of 6H- benzo [C] benzopyrans compounds |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106995428B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115286608B (en) * | 2022-07-25 | 2024-01-12 | 五邑大学 | Benzopyran compound and preparation method thereof |
-
2017
- 2017-05-18 CN CN201710354035.9A patent/CN106995428B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| Synthesis of substituted 6H-benzo[c]chromenes: a palladium promoted ring closure of diazonium tetrafluoroborates;Jing Zhou等;《Tetrahedron Letters》;20121023;第53卷;参见第7037页表1第4行 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106995428A (en) | 2017-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Egami et al. | Concise synthesis of oxindole derivatives bearing a 3-trifluoroethyl group: Copper-catalyzed trifluoromethylation of acryloanilides | |
| CN103274917B (en) | Method for catalyzing and synthesizing benzil derivatives from alkali type copper fluoride | |
| CN104447599B (en) | A kind of tetrazole heterogeneous ring compound and preparation method thereof | |
| CN109053625A (en) | A kind of preparation method replacing benzothiazole C2 alkyl derivative | |
| CN105384788A (en) | Tildipirosin preparation method | |
| CN106995428B (en) | A kind of synthetic method of 6H- benzo [C] benzopyrans compounds | |
| CN113620891A (en) | Method for preparing quinoxaline-2-ketone derivative by controllable catalysis | |
| CN106892800A (en) | A kind of preparation method and application of unactivated alkene hydrogen trifluoromethylation | |
| CN106146334A (en) | 2,3-diaryl-2-propargyl amide groups-3-arylamino methyl propionate derivant and its preparation method and application | |
| CN105330560A (en) | Enzalutamide intermediate preparation method | |
| Lin et al. | A green and transition-metal-free light-mediated trifluoromethylation reaction of coumarins | |
| CN103467386B (en) | Aryl pyrimidine ortho-position monocyano compounds and synthesis method thereof | |
| CN110128385A (en) | A kind of quercetin derivative and its synthetic method by lauroyl chloride chemical modification | |
| CN103374049B (en) | One prepares 5,6, the method for 4 '-trihydroxyflavone-7-0-D-glucuronic acid | |
| CN106977488B (en) | A kind of preparation method of 6H- benzo [C] chromene and its derivative | |
| CN104774171A (en) | 3-amino-3-hydroxymethyl oxoindole and 3-hydroxyl-3-hydroxymethyl oxoindole derivative, and preparation methods and applications thereof | |
| CN102219792A (en) | Novel method for preparing prasugrel | |
| CN109020895B (en) | Synthesis method of metal-catalyzed 1-benzylamino-substituted benzimidazole | |
| CN106810508A (en) | A kind of method that iron catalysis multi-component reaction synthesizes benzo [1,4] oxygen azatropylidene compound | |
| CN104761600B (en) | Synthesis and uses of beta-1-imidazole-2,3,4,6-tetrahydroxy-D-glucopyranose bromide | |
| Zheng et al. | A convenient and efficient one-pot conversion of peimisine into cyclopamine | |
| CN104803895A (en) | Method for preparing sulfinic acid ester from phenylsulfonyl methyl isocyanide | |
| CN110903304A (en) | Okadaic acid derivative and preparation method thereof | |
| CN103130702A (en) | Method for synthesizing 3-substituted indole and 2,3-disubstituted indole | |
| CN110305083B (en) | Process for preparing 5-chloromethyl furfural from fructose |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |