CN106995428A - A kind of synthetic method of 6H benzos [C] benzopyrans compounds - Google Patents
A kind of synthetic method of 6H benzos [C] benzopyrans compounds Download PDFInfo
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- CN106995428A CN106995428A CN201710354035.9A CN201710354035A CN106995428A CN 106995428 A CN106995428 A CN 106995428A CN 201710354035 A CN201710354035 A CN 201710354035A CN 106995428 A CN106995428 A CN 106995428A
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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
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
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Abstract
The present invention discloses one kind 6HBenzo [C] benzopyrans compounds synthetic method, belong to catalyst preparation technical field, it is characterised in that：Using the diazol shown in formula (I) as raw material, dyestuff sensitising agent is catalyst, in organic solvent, through under nitrogen protection and the irradiation of 3 ~ 100 W green glows, in the h of room temperature ~ 40 DEG C stirring reaction 1 ~ 48, synthesis obtains target product.This method is without metallic catalyst, alkali and part, and reaction condition is gentle, environment-friendly, with low cost, simple to operate, and reaction yield is high, has a good application prospect.
Description
Technical field：
The invention belongs to catalyst preparation field, and in particular to a kind of 6H- benzos [C] benzopyrans compounds
Synthetic method.
Background technology：
6H- benzos [C] chromene be many natural products with physiologically active and drug molecule core skeleton (see
Fig. 1 .1), for example：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.).Simple, the efficient 6H- of development
The preparation method of benzo [C] benzo pyran derivative has great importance.
Several representational 6H- benzos [C] chromene active components of Fig. 1 .1
In recent years, many seminars realized the synthesis of this kind of compound, can be largely classified into following two strategies.
Strategy one：Utilize transition metal-catalyzed synthesis 6H- benzos [C] chromene
Using it is transition metal-catalyzed be synthesize 6H- benzos [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).This kind of method needs expensive transition metal such as palladium etc. as catalyst, and needs addition alkali, part etc. to add
Plus agent, reacting could be carried out at high temperature.In addition, prepared by the substrate of this method also have significant limitation.
Strategy two：Without transition metal-catalyzed synthesis 6H- benzos [C] chromene
The synthesis of 6H- benzos [C] benzopyrans compounds can be also realized without transition metal-catalyzed
(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 seminars were under 254nm ultraviolet lightings, with 2 '-(hydroxymethyl)-[1,1- biphenyl] -2- phenol
For raw material, the synthesis of 6H- benzos [C] chromene is realized, but this method raw material is difficult to prepare, using by the very day of one's doom
System.2015, Jayanta K.Ray et al. halogenated biphenyl classes compound be raw material in DMSO solvents, with the highly basic uncle of 3 equivalents
Butanol potassium has synthesized 6H- benzos [C] chromene as additive at 100 DEG C.Although this method is avoided using expensive transition
Metal still needs highly basic and does additive as catalyst, and could occur at high temperature, therefore obtains its application
Considerable restraint.
The content of the invention：
The present invention is intended to provide a kind of gentle, synthesis 6H- benzos [C] benzopyrans compounds without metal catalytic
New method.
The technical scheme that the present invention takes to achieve the above object is as follows：
A kind of synthetic method of 6H- benzos [C] benzopyrans compounds, it is characterised in that：With the diazonium shown in formula (I)
Salt is raw material, under dyestuff sensitising agent catalytic action, in organic solvent, through nitrogen protection and 3~100W radiation of visible light under, in
Room temperature~40 DEG C stirring reaction, synthesis obtains 6H- benzos [C] benzopyrans compounds shown in formula (II), and reaction scheme 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 material that feeds intake of substrate diazol shown in formula (I) and dyestuff sensitising agent is 1:0.02
~0.001.Described dyestuff sensitising agent be selected from it is following any one：Eosin W or W S (Eosin Y), rhodamine B (Rhodamine B),
Fluorescein (Fluorescein), preferably eosin W or W S (Eosin Y).
In the above method, organic solvent is selected from following one kind：Ethyl acetate, methanol, dimethyl sulfoxide (DMSO), N, N- dimethyl
Formamide, acetonitrile, acetone, preferably acetonitrile.
In the above method, reaction need to be protected through nitrogen, under 3~100W visible ray light irradiations, be reacted 1~48 hour.Institute
It can be white electricity-saving lamp, green LED lamp, preferably blue LED lamp, green LED lamp to state light source.
In the above method, preferred reaction time 12~36 hours, reaction temperature is room temperature.
In the above method, it is 6H- benzos [C] chromene, fluoro- 6H- benzos [C] benzene of 3- to synthesize obtained target compound
And chloro- 6H- benzos [C] chromene of pyrans, 2-, 2- methyl -6H- benzos [C] chromene, 9- methyl -6H- benzos [C] benzene
And chloro- 6H- benzos [C] chromene of pyrans, 9-, 2,9- dimethyl -6H- benzos [C] chromene.
Product structure prepared by the present invention is as follows：
Compared with the preparation method reported, the inventive method has following advantage：
1st, the invention provides under a kind of temperate condition, 6H- benzos [C] chromene is efficiently synthesized under visible ray promotion
The new method of class compound, this method reaction condition as mild as a dove, operate it is very simple.At room temperature by the timing of reactant stirring one
Between product can be obtained with good yield, without heat or flow back.
2nd, reaction cost reduction, condition are more green, and reaction can be carried out under green glow irradiation；Avoid making in course of reaction
With expensive transition-metal catalyst, without adding the additives such as alkali and part, reaction efficient green, cost are substantially reduced.
3rd, by the control to reaction condition, the yield of reaction can be effectively improved.
Embodiment：
The present invention is further explained explanation with reference to specific embodiment, but specific embodiment is merely to illustrate technology
Scheme, protection scope of the present invention is simultaneously confined to this.
Embodiment 1：The embodiment illustrates the preparation of 6H- benzos [C] chromene.
The 10mL reaction tubes of a dried and clean are taken, Arenediazonium salts (59.6mg, 0.2mmol) [formula (1), R is weighed into1=
H,R2=H, R3=H], eosin W or W S (1.4mg, 0.002mmol) adds acetonitrile 2mL with syringe, and system is protected through nitrogen, uses 36W
Green LED lamp irradiates reaction tube, then at room temperature, magnetic agitation 24h, and TLC detects complete to reaction, dilute with ethyl acetate
Release, organic phase is washed 3 times, then organic phase anhydrous sodium sulfate drying after point liquid is spin-dried for concentration, and column chromatographic isolation and purification is obtained
Product, yield is 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) compounds are consistent with document (Tetrahedron 2016,72,1043-1050) report.
Alternative：
Synthetic method be the same as Example 1, difference is：Adjustment reaction dissolvent, catalyst and consumption, light source, reaction temperature, and
Its influence to product yield is counted, 1 is the results are shown in Table.
Table 1：
Embodiment 2：The embodiment illustrates the preparation of fluoro- 6H- benzos [C] chromenes of 3-.
The 10mL reaction tubes of a dried and clean are taken, Arenediazonium salts (63.2mg, 0.2mmol) [formula (1), R is weighed into1=
H,R2=F, R3=H], eosin W or W S (1.4mg, 0.002mmol) adds acetonitrile 2mL with syringe, and system is protected through nitrogen, uses 36W
Green LED lamp irradiates reaction tube, then at room temperature, magnetic agitation 24h, and TLC detects complete to reaction, dilute with ethyl acetate
Release, organic phase is washed 3 times, then organic phase anhydrous sodium sulfate drying after point liquid is spin-dried for concentration, and column chromatographic isolation and purification is obtained
Product, yield is 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- benzos [C] chromenes of 2-.
The 10mL reaction tubes of a dried and clean are taken, Arenediazonium salts (66.4mg, 0.2mmol) [formula (1), R is weighed into1=
Cl,R2=H, R3=H], eosin W or W S (1.4mg, 0.002mmol) adds acetonitrile 2mL with syringe, and system is protected through nitrogen, uses
36W green LED lamps irradiate reaction tube, then at room temperature, magnetic agitation 24h, and TLC is detected to reaction completely, uses ethyl acetate
Dilution, organic phase is washed 3 times, organic phase anhydrous sodium sulfate drying after point liquid, is then spin-dried for concentration, and column chromatographic isolation and purification is obtained
To product, yield is 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 are reported with document (Chem.Commun., 2011,47,9813-9815)
Unanimously.
Embodiment 4：The embodiment illustrates the preparation of 2- methyl -6H- benzos [C] chromene.
The 10mL reaction tubes of a dried and clean are taken, Arenediazonium salts (62.4mg, 0.2mmol) [formula (1), R is weighed into1=
CH3,R2=H, R3=H], eosin W or W S (1.4mg, 0.002mmol) adds acetonitrile 2mL with syringe, and system is protected through nitrogen, uses
36W green LED lamps irradiate reaction tube, then at room temperature, magnetic agitation 24h, and TLC is detected to reaction completely, uses ethyl acetate
Dilution, organic phase is washed 3 times, organic phase anhydrous sodium sulfate drying after point liquid, is then spin-dried for concentration, and column chromatographic isolation and purification is obtained
To product, yield is 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),
(s, 3H) compounds of 7.08 (dd, J=8.2,1.5Hz, 1H), 6.94 (d, J=8.2Hz, 1H), 5.12 (s, 2H), 2.40 with
Document (Tetrahedron 2016,72,1043-1050) report is consistent.
Embodiment 5：The embodiment illustrates the preparation of 9- methyl -6H- benzos [C] chromene.
The 10mL reaction tubes of a dried and clean are taken, Arenediazonium salts (62.4mg, 0.2mmol) [formula (1), R is weighed into1=
H,R2=H, R3=4-CH3], eosin W or W S (1.4mg, 0.002mmol) adds acetonitrile 2mL with syringe, and system is protected through nitrogen,
Reaction tube is irradiated with 36W green LED lamps, then at room temperature, magnetic agitation 24h, TLC is detected to reaction completely, uses acetic acid second
Ester is diluted, and organic phase is washed 3 times, and then organic phase anhydrous sodium sulfate drying after point liquid is spin-dried for concentration, column chromatographic isolation and purification
Product is obtained, yield is 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 compounds are consistent with document (Tetrahedron 2016,72,1043-1050) report.
Embodiment 6：The embodiment illustrates the preparation of chloro- 6H- benzos [C] chromenes of 9-.
The 10mL reaction tubes of a dried and clean are taken, Arenediazonium salts (66.4mg, 0.2mmol) [formula (1), R is weighed into1=
H,R2=H, R3=4-Cl], eosin W or W S (1.4mg, 0.002mmol) adds acetonitrile 2mL with syringe, and system is protected through nitrogen, uses
36W green LED lamps irradiate reaction tube, then at room temperature, magnetic agitation 24h, and TLC is detected to reaction completely, uses ethyl acetate
Dilution, organic phase is washed 3 times, organic phase anhydrous sodium sulfate drying after point liquid, is then spin-dried for concentration, and column chromatographic isolation and purification is obtained
To product, yield is 30%.1H NMR(400MHz,CDCl3) δ 7.70 (dd, J=8.2,1.7Hz, 2H), 7.33-7.24 (m,
2H), (s, 2H) compounds of 7.12-7.07 (m, 2H), 7.02 (dd, J=8.1,1.1Hz, 1H), 5.10 and document
(Tetrahedron Lett.2012,53,7036-7039) report is consistent.
Embodiment 7：The embodiment illustrates the preparation of 2,9- dimethyl -6H- benzos [C] chromene.
The 10mL reaction tubes of a dried and clean are taken, Arenediazonium salts (65.2mg, 0.2mmol) [formula (1), R is weighed into1=
CH3,R2=H, R3=4-CH3], eosin W or W S (1.4mg, 0.002mmol) adds acetonitrile 2mL with syringe, and system is protected through nitrogen
Shield, reaction tube is irradiated with 36W green LED lamps, then at room temperature, magnetic agitation 24h, and TLC is detected to reaction completely, uses acetic acid
Ethyl ester is diluted, and organic phase is washed 3 times, and then organic phase anhydrous sodium sulfate drying after point liquid is spin-dried for concentration, and column chromatography for separation is pure
Change obtains product, and yield is 88%.1H NMR(400MHz,CDCl3)δ7.55-7.48(m,2H),7.11-6.99(m,2H),
(s, 3H) compounds of 6.88 (d, J=8.2Hz, 1H), 5.04 (s, 2H), 2.40 (s, 3H), 2.35 and document
(Tetrahedron Lett.2012,53,7036-7039) report is consistent.
Claims (9)
1. a kind of synthetic method of 6H- benzos [C] benzopyrans compounds, it is characterised in that：With the diazol shown in formula (I)
For raw material, under dyestuff sensitising agent catalytic action, in organic solvent, through under nitrogen protection and radiation of visible light, in room temperature~40
Stirring reaction at a temperature of DEG C, obtains 6H- benzos [C] benzo pyran target product shown in formula (II), and reaction scheme is as follows：
In formula (I) and formula (II)：R1For hydrogen, chlorine, methyl；R2For hydrogen, fluorine；R3For hydrogen, chlorine, methyl.
2. a kind of synthetic method of 6H- benzos [C] benzopyrans compounds as claimed 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- benzos [C] benzopyrans compounds as claimed in claim 1, it is characterised in that：Weight
The ratio between amount for the material that feeds intake of nitrogen salt and dyestuff sensitising agent is 1:0.02~0.001.
4. a kind of synthetic method of 6H- benzos [C] benzopyrans compounds as claimed in claim 1, it is characterised in that：Institute
The dyestuff sensitising agent stated is selected from following one kind：Eosin W or W S, rhodamine B, fluorescein.
5. a kind of synthetic method of 6H- benzos [C] benzopyrans compounds as claimed in claim 1, it is characterised in that：Institute
State reaction dissolvent and be selected from following one kind：Ethyl acetate, methanol, dimethyl sulfoxide (DMSO), N,N-dimethylformamide, acetonitrile, acetone.
6. a kind of synthetic method of 6H- benzos [C] benzopyrans compounds as claimed in claim 1, it is characterised in that：Institute
The power for stating visible ray is 3~100W.
7. a kind of synthetic method of 6H- benzos [C] benzopyrans compounds as claimed in claim 6, it is characterised in that：Institute
It is white electricity-saving lamp, green LED lamp, one kind of blue LED lamp to state visible light source.
8. a kind of synthetic method of 6H- benzos [C] benzopyrans compounds as claimed in claim 1, it is characterised in that：Institute
The reaction time stated is 1~48 hour.
9. a kind of synthetic method of 6H- benzos [C] benzopyrans compounds as claimed in claim 1, it is characterised in that：Institute
The reaction time stated is 12~36 hours, and reaction temperature is room temperature.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115286608A (en) * | 2022-07-25 | 2022-11-04 | 五邑大学 | Benzopyran compound and preparation method thereof |
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2017
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Non-Patent Citations (1)
| Title |
|---|
| JING ZHOU等: "Synthesis of substituted 6H-benzo[c]chromenes: a palladium promoted ring closure of diazonium tetrafluoroborates", 《TETRAHEDRON LETTERS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115286608A (en) * | 2022-07-25 | 2022-11-04 | 五邑大学 | Benzopyran compound and preparation method thereof |
| CN115286608B (en) * | 2022-07-25 | 2024-01-12 | 五邑大学 | Benzopyran compound and preparation method thereof |
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