CN102757446A - Synthesis method of pyranocoumarin derivatives - Google Patents
Synthesis method of pyranocoumarin derivatives Download PDFInfo
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- CN102757446A CN102757446A CN2012102651296A CN201210265129A CN102757446A CN 102757446 A CN102757446 A CN 102757446A CN 2012102651296 A CN2012102651296 A CN 2012102651296A CN 201210265129 A CN201210265129 A CN 201210265129A CN 102757446 A CN102757446 A CN 102757446A
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- SOQSCSUCGCDSLS-UHFFFAOYSA-N NC(OC(c1ccccc1O1)=C(C2c(ccc(Cl)c3)c3Cl)C1=O)=C2C#N Chemical compound NC(OC(c1ccccc1O1)=C(C2c(ccc(Cl)c3)c3Cl)C1=O)=C2C#N SOQSCSUCGCDSLS-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a green synthesis method of pyranocoumarin derivatives disclosed as Formula (4a) in the following reaction equation. According to the synthesis method, by using DBU-type ionic liquid disclosed as Formula (b) in the following reaction equation as a catalyst, aromatic aldehyde disclosed as Formula (1a), malononitrile disclosed as Formula (2a) and 4-hydroxycoumarin disclosed as Formula (3a) which are used as raw materials react in water under the promoting action of microwaves to obtain the target products. The operational method disclosed by the invention is simple and environment-friendly, and has the advantages of mild reaction conditions and the like; and the products can be easily separated, and the catalyst can be recycled. The reaction equation is as follows.
Description
Technical field
The present invention relates to the compound method of a kind of pyrans and coumarin derivatives.
Background technology
In recent years, the synthetic of pyrans and tonka bean camphor and verivate thereof causes people's extensive concern always, duplicates reagent, suppresses uterotonic pharmacophore and the multiple drug effect opposing of potential counter-rotating reagent because have plenty of potential inhibition Measles virus in them; Also having some verivates is to stop the same human leukaemia cell of [3H] thymidine (HL-60) bonded reagent; Also have some to have the activity that stimulates brain, antimycotic and antimicrobial is active in addition according to bibliographical information.Along with the continuous expansion of pyrans and tonka bean camphor and verivate Application Areas thereof, also more and more to the research of their compound methods.Wherein M.K.Jitender is that catalyzer backflow compound method in water is considered to one of a kind of convenient and economic method (Tetrahedron with DBU; 2011; 66:5637-5641), but catalyzer DBU in water easily hydrolysis lose catalytic activity, can not recycle; Hong-Juan Wang utilize vulkacit H for catalyzer reflux in ethanol synthesizing pyran and coumarin derivatives (Monatsh.Chem., 2010,141:1107-1112).Exist catalyst levels big and be difficult to recycling in the prior synthesizing method; Product yield is low, long reaction time, factor such as environmental pollution is big; Mostly use volatile organic solvent in most of method simultaneously; Like ethanol, acetonitrile etc., these solvents not only have harm to environment in the use, and also have certain toxicity.Therefore, invention pyrans and coumarin derivatives compound method simple and high-efficiency environment friendly seems particularly important.
Summary of the invention
Big for solving in existing preparation pyrans and the coumarin derivatives technology catalyst levels; Catalyzer is not easy to reclaim long reaction time, some reaction needed high temperature; To a series of problems such as environment is unfriendly; Advocate a kind of green more, synthetic theory efficiently simultaneously, the objective of the invention is to disclose a kind of is catalyzer with [DBU] [Ac] ionic liquid, in water solvent with the compound method of promoted pyrans of UW and coumarin derivatives.This method reaction conditions is gentle, and easy and simple to handle, building-up process is environmentally friendly, the product separate easily, and productive rate is high with purity, and the reaction times is short, and the reaction system of ionic liquid and water formation can directly recycle, and need not characteristics such as processing.
For reaching the purpose of invention, the technical scheme that the present invention adopts is following:
The compound method of a kind of pyrans and coumarin derivatives; The structural formula of said pyrans and coumarin derivatives is shown in the formula in the reaction equation 1 (4a); Described compound method is to be substrate with the raw materials such as 4 hydroxy coumarin shown in the third two eyeballs shown in the aromatic aldehyde shown in the structural formula in the reaction equation 1 (1a), the formula (2a) and the formula (3a), is catalyzer with [DBU] [Ac] ionic liquid shown in the formula (b), in water solvent; Under room temperature ultrasonic 5～20 minutes; Reacting liquid filtering gets filter cake, filter cake through ethyl alcohol recrystallization, be drying to obtain described pyrans and coumarin derivatives
Reaction equation is following:
R in the said structure formula
1Be hydrogen, chlorine, nitro, aldehyde radical, methoxyl group; R
2Be hydrogen, methyl.
The amount of substance of aromatic aldehyde of the present invention, the third two eyeballs and 4 hydroxy coumarin is than being 1:1: (1.0～1.2), said [DBU] [Ac] ionic-liquid catalyst is 0.5 with aromatic aldehyde amount of substance ratio: (50～150), ratio of greater inequality is 0.5:100.
The ultrasonic response time of the present invention is 5～20 minutes.
Ultrasonic response temperature of the present invention is 20～40 ℃, and ultrasonic power input is 400W.
After reaction of the present invention finished, reaction solution obtained solid product through after filtering, and the filtrating that contains the dissolved catalyzer can directly recycle.
[DBU] of the present invention [Ac] ionic liquid is a catalyzer, UW promote down in water the main beneficial effect of synthesizing pyran and coumarin derivatives be embodied in following aspect:
1) to replace traditional organic bases, solid alkali be catalyzer to [DBU] [Ac] ionic liquid; Dissolving each other with water forms the homogeneous response system, improves catalytic effect, and reaction finishes the back ionic liquid aqueous solution and can directly reuse; Do not need special processing, product yield is unaffected;
2) be reaction solvent with water, reduce cost, reduce environmental pollution;
3) UW promotes reaction, and the reaction times is short, and is easy and simple to handle, and yield and product purity are high.
To sum up, the compound method of a kind of pyrans according to the invention and coumarin derivatives is a kind of green synthesis method, is suitable for suitability for industrialized production.
The practical implementation method
Below in conjunction with specific embodiment the present invention is further described, but protection scope of the present invention is not limited in this.
Embodiment 1
With [DBU] [Ac] ionic liquid (0.125mmol), phenyl aldehyde (25mmol), the third two eyeballs (25mmol); 4 hydroxy coumarin (27.5mmol), deionized water 15mL joins in this reaction vessel successively, places in the UW container; Ultrasonic reaction 10 minutes (ultrasonic power input 400W) under room temperature, mixed solution filters, ethyl alcohol recrystallization; Dry pure products, the yield 94% of getting.
Characterization data:
1H NMR (200MHz, DMSO-d
6): δ 4.45 (s, 1H), 7.23-7.31 (m, 4H), 7.42-7.17 (m, 4H), 7.31 (br s, 2H), 7.40-7.54 (m, 2H), 7.69 (t, J=6.4Hz), 7.90 (d, J=7.8Hz);
13C NMR (62.5MHz, DMSO-d
6) 160.0,158.7,154.0,152.8,144.0,133.6,129.2 (2C), 127.8 (2C), 125.3,123.1,119.9,117.2,113.6,104.7,58.6,37.6.
Embodiment 2:
With [DBU] [Ac] ionic liquid (0.125mmol), 4-chlorobenzaldehyde (25mmol), the third two eyeballs (25mmol); 4 hydroxy coumarin (27.5mmol), deionized water 15mL joins in this reaction vessel successively, places in the UW container; Ultrasonic response 10 minutes (ultrasonic power input 400W) under room temperature, mixed solution filters, ethyl alcohol recrystallization; Dry pure products, the yield 96% of getting.
Characterization data:
1H NMR (200MHz, DMSO-d
6): δ 4.49 (s, 1H), 7.29-7.40 (m, 4H), 7.49 (br s, 2H), 7.54-7.74 (m, 2H), 7.88-8.55 (m, 2H);
13C NMR (62.5MHz, DMSO-d
6): 160.1,158.6,154.2,152.9,142.9,133.6,129.1 (2C), 127.8 (2C), 125.3,123.2,119.9,117.2,113.6,104.1,58.2,37.1.
Embodiment 3:
With [DBU] [Ac] ionic liquid (0.125mmol), 3-chlorobenzaldehyde (25mmol), the third two eyeballs (25mmol); 4 hydroxy coumarin (27.5mmol), deionized water 15mL joins in this reaction vessel successively, places in the UW container; Ultrasonic response 10 minutes (ultrasonic power input 400W) under room temperature, mixed solution filters, ethyl alcohol recrystallization; Dry pure products, the yield 90% of getting.
Characterization data
1H NMR (200MHz, DMSO-d
6): δ 4.51 (s, 1H), 7.26-7.35 (m, 4H), 7.45 (br s, 2H), 7.47-7.54 (m, 2H), 7.68-7.76 (m, 2H), 7.78-7.82 (m, 2H);
13CNMR (62.5MHz, DMSO-d
6): 160.2,158.7,154.4,152.9,146.5,134.3,132.0,129.3,128.3,127.9,127.3,125.3,123.1,119.7,117.2,113.7,103.9,58.1,37.4.
Embodiment 4:
With [DBU] [Ac] ionic liquid (0.125mmol), 2-chlorobenzaldehyde (25mmol), the third two eyeballs (25mmol); 4 hydroxy coumarin (27.5mmol), deionized water 15mL joins in this reaction vessel successively, places in the UW container; Ultrasonic response 10 minutes (ultrasonic power input 400W) under room temperature, mixed solution filters, ethyl alcohol recrystallization; Dry pure products, the yield 91% of getting.
Characterization data:
1H NMR (200MHz, DMSO-d
6): δ 4.97 (s, 1H), 7.24-7.33 (m, 4H), 7.45 (br s, 2H), 7.47-7.54 (m, 3H), 7.68-7.76 (m, 2H), 7.71 (dd, J=8.4,2.0Hz, 1H), 7.90 (dd, J=7.8,1.4,1H);
13CNMR (62.5MHz, DMSO-d
6): 160.1,158.8,154.7,152.9,140.9,133.7,133.1,131.3,130.3,129.5,128.4,125.4,123.2,119.5,117.3,113.5,103.6,57.2,35.0.
Embodiment 5:
With [DBU] [Ac] ionic liquid (0.125mmol), 4-methoxybenzaldehyde (25mmol), the third two eyeballs (25mmol); 4 hydroxy coumarin (27.5mmol), deionized water 15mL joins in this reaction vessel successively, places in the UW container; Ultrasonic response 10 minutes (ultrasonic power input 400W) under room temperature, mixed solution filters, ethyl alcohol recrystallization; Dry pure products, the yield 89% of getting.
Characterization data:
1H NMR (200MHz, DMSO-d
6): δ 3.72 (s, 3H), 4.39 (s, 1H), 6.86 (d, J=8.8Hz, 2H), 7.18 (d, J=8.8Hz; 2H), 7.37 (br s, 2H), 7.44-7.53 (m, 2H), 7.76 (t, J=6.4Hz, 2H); 7.90 (dd, J=8.0,1.6,1H), 7.90 (dd, J=7.8,1.4Hz, 1H);
13CNMR (62.5MHz, DMSO-d
6): 160.2,159.0,158.6,153.8,152.8,136.1,133.5,129.5 (2C), 125.3,123.1,119.9,117.2,114.5 (2C), 113.7,104.9,58.9,55.7,36.9.
Embodiment 6:
With [DBU] [Ac] ionic liquid (0.125mmol), 3-methoxybenzaldehyde (25mmol), the third two eyeballs (25mmol); 4 hydroxy coumarin (27.5mmol), deionized water 15mL joins in this reaction vessel successively, places in the UW container; Ultrasonic response 10 minutes (ultrasonic power input 400W) under room temperature, mixed solution filters, ethyl alcohol recrystallization; Dry pure products, the yield 92% of getting.
Characterization data:
1H NMR (200MHz, DMSO-d
6): δ 3.73 (s, 3H), 4.43 (s, 1H), 6.80-6.83 (m, 3H), 7.24 (t, J=8.0Hz, 1H), 7.42 (br s, 2H), 7.44-7.54 (m, 2H), 7.73 (t, J=6.4Hz, 1H), and 7.91d, J=8.0,1H);
13CNMR (62.5MHz, DMSO-d
6): 160.2,159.9,158.7,154.1,152.8,145.6,133.6,130.3,125.3,123.1,120.4,119.9,117.2,114.6,113.6,112.7,104.5,58.6,55.7,37.6.
Embodiment 7:
With [DBU] [Ac] ionic liquid (0.125mmol), 2-methoxybenzaldehyde (25mmol), the third two eyeballs (25mmol); 4 hydroxy coumarin (27.5mmol), deionized water 15mL joins in this reaction vessel successively, places in the UW container; Ultrasonic response 10 minutes (ultrasonic power input 400W) under room temperature, mixed solution filters, ethyl alcohol recrystallization; Dry pure products, the yield 93% of getting.
Characterization data:
1H NMR (200MHz, DMSO-d
6): δ 3.71 (s, 3H), 4.71 (s, 1H), 6.91 (t, J=7.8Hz, 1H), 6.98 (d; J=8.4MHz, 1H), 7.1 (d, J=6.4Hz, 1H), 7.18-7.22 (m, 2H), 7.25 (brs; 2H), 7.44-7.53 (m, 2H), 7.68-7.71 (m, 1H), 7.90 (d, J=7.3Hz, 1H);
13CNMR (62.5MHz, DMSO-d
6): 160.2,159.2,157.8,154.7,152.8,133.4,131.4,129.8,129.1,125.3,122.9,121.2,120.0,119.9,117.2,113.7,112.5,103.9,57.6,56.4,32.9.
Embodiment 8:
With [DBU] [Ac] ionic liquid (0.125mmol), 4-nitrobenzaldehyde (25mmol), the third two eyeballs (25mmol); 4 hydroxy coumarin (27.5mmol), deionized water 15mL joins in this reaction vessel successively, places in the UW container; Ultrasonic response 10 minutes (ultrasonic power input 400W) under room temperature, mixed solution filters, ethyl alcohol recrystallization; Dry pure products, the yield 94% of getting.
Characterization data:
1H NMR (200MHz, DMSO-d
6): 4.69 (s, 1H), 7.46-7.56 (m, 4H), 7.58 (br s, 2H), 7.70-7.75 (m, 1H), 7.89-7.94 (m, 1H), 8.19 (d, J=8.8Hz, 1H);
13CNMR (62.5MHz, DMSO-d
6): 160.2,158.7,154.6,152.9,151.4,147.3,133.8,129.9 (2C), 125.4,124.4 (2C), 123.3,119.6,117.3,113.6,103.5,57.5,37.5.
Embodiment 9:
With [DBU] [Ac] ionic liquid (0.125mmol), 3-nitrobenzaldehyde (25mmol), the third two eyeballs (25mmol); 4 hydroxy coumarin (27.5mmol), deionized water 15mL joins in this reaction vessel successively, places in the UW container; Ultrasonic response 10 minutes (ultrasonic power input 400W) under room temperature, mixed solution filters, ethyl alcohol recrystallization; Dry pure products, the yield 95% of getting.
Characterization data:
1H NMR (200MHz, DMSO-d
6): 4.73 (s, 1H), 7.45-7.54 (m, 2H), 7.59 (br s, 2H), 7.62-7.69 (m, 2H), 7.73-7.83 (m, 1H), 7.89-7.94 (m, 1H), 8.10-8.14 (m, 2H);
13CNMR (62.5MHz, DMSO-d
6): 160.3,158.8,154.6,152.9,148.5,146.1,135.4,133.8,130.7,125.4,123.3,123.1,122.9,119.6,117.3,113.6,103.5,57.6,37.4.
Embodiment 10:
With [DBU] [Ac] ionic liquid (0.125mmol), 2-nitrobenzaldehyde (25mmol), the third two eyeballs (25mmol); 4 hydroxy coumarin (27.5mmol), deionized water 15mL joins in this reaction vessel successively, places in the UW container; Ultrasonic response 10 minutes (ultrasonic power input 400W) under room temperature, mixed solution filters, ethyl alcohol recrystallization; Dry pure products, the yield 90% of getting.
Characterization data:
1H NMR (200MHz, DMSO-d
6): 5.24 (s, 1H), 7.43-7.53 (m, 4H), 7.56 (br s, 2H), 7.62-7.65 (m, 1H), 7.68-7.72 (m, 1H), 7.90 (d, J=7.8Hz, 2H);
13CNMR (62.5MHz, DMSO-d
6): 160.4,159.3,154.3,152.9,149.9,138.0,134.4,133.8,131.9,129.1,125.4,124.7,123.3,119.4,117.3,113.5,103.9,56.8,32.3.
Embodiment 11:
With [DBU] [Ac] ionic liquid (0.125mmol), 2,4 dichloro benzene formaldehyde (25mmol); The third two eyeballs (25mmol), 4 hydroxy coumarin (27.5mmol), deionized water 15mL join in this reaction vessel successively; Place in the UW container, ultrasonic response 10 minutes (ultrasonic power input 400W) under room temperature, mixed solution filters; Ethyl alcohol recrystallization, dry pure products, the yield 93% of getting.
Characterization data:
1H NMR (200MHz, DMSO-d
6): 4.97 (s, 1H), 7.36-7.38 (m, 2H), 7.46-7.50 (m, 2H), 7.55 (brs, 2H), 7.58-7.59 (m, 1H), 7.69-7.73 (m, 1H), 7.88-7.92 (m, 1H);
13CNMR (62.5MHz, DMSO-d
6): 160.1,158.1,154.8,152.9,140.1,134.0,133.8,133.1,132.8,129.5,128.6,125.4,123.2,119.3,117.3,113.5,103.2,56.7,34.6.
Embodiment 12:
With [DBU] [Ac] ionic liquid (0.125mmol), terephthalaldehyde (12.5mmol), the third two eyeballs (25mmol); 4 hydroxy coumarin (27.5mmol), deionized water 15mL joins in this reaction vessel successively, places in the UW container; Ultrasonic response 10 minutes (ultrasonic power input 400W) under room temperature, mixed solution filters, ethyl alcohol recrystallization; Dry pure products, the yield 89% of getting.
264～266 ℃ of characterization data: Mp.
1H NMR (200MHz, DMSO-d
6): 4.42 (s, 2H), 7.19 (s, 4H), 7.39 (br s, 4H), 7.42-7.52 (m, 4H), 7.61-7.71 (m, 2H), 7.89 (d, J=7.8Hz, 2H);
13C NMR (62.5MHz, DMSO-d
6): 160.3,158.8,154.1,152.8,142.7,133.6,128.4 (4C), 125.3,123.1,119.9,117.3,113.6,104.7,58.6,37.2.
Embodiment 13:
With [DBU] [Ac] ionic liquid (0.125mmol), 3,4-dimethoxy benzaldehyde (25mmol); The third two eyeballs (25mmol), 4 hydroxy coumarin (27.5mmol), deionized water 15mL join in this reaction vessel successively; Place in the UW container, ultrasonic response 10 minutes (ultrasonic power input 400W) under room temperature, mixed solution filters; Ethyl alcohol recrystallization, dry pure products, the yield 92% of getting.
Characterization data:
1H NMR (200MHz, DMSO-d
6): 3.72 (s, 6H), 4.41 (s, 1H), 6.76 (d, J=2.0Hz, 2H), 6.84-6.90 (m, 2H), 7.35 (br s, 2H), 7.44-7.53 (m, 2H), 7.68-7.72 (m, 1H), 7.88-7.91 (m, 1H);
13C NMR (62.5MHz, DMSO-d
6): 160.2,158.6,153.8,152.8,149.2,148.7,136.5,133.5,125.3,123.1,120.4,119.9,117.2,113.7,112.6,104.8,58.9,56.2 (2C), 37.2.
Embodiment 14:
With [DBU] [Ac] ionic liquid (0.125mmol), phenyl aldehyde (25mmol), the third two eyeballs (25mmol); 4-hydroxyl-8-methylcoumarin (27.5mmol), deionized water 15mL joins in this reaction vessel successively, places in the UW container; Ultrasonic response 10 minutes (ultrasonic power input 400W) under room temperature, mixed solution filters, ethyl alcohol recrystallization; Dry pure products, the yield 90% of getting.
Characterization data:
1H NMR (200MHz, DMSO-d
6): 2.35 (s, 3H), 4.45 (s, 1H), 7.23-7.39 (m, 6H), 7.42 (br s, 2H), 7.59 (d, J=6.8Hz, 1H), 7.75 (d, J=7.8Hz, 1H);
13C NMR (62.5MHz, DMSO-d
6): 160.1,158.7,154.3,151.1,144.1,134.5,129.2 (2C), 128.3 (2C), 127.8,126.2,124.8,120.8,113.3,104.4,58.6,37.6,15.7.
Embodiment 15:
With [DBU] [Ac] ionic liquid (0.125mmol), phenyl aldehyde (25mmol), the third two eyeballs (25mmol); 4-hydroxyl-7-methylcoumarin (27.5mmol), deionized water 15mL joins in this reaction vessel successively, places in the UW container; Ultrasonic response 10 minutes (ultrasonic power input 400W) under room temperature, mixed solution filters, ethyl alcohol recrystallization; Dry pure products, the yield 91% of getting.
Characterization data:
1H NMR (200MHz, DMSO-d
6): 2.44 (s, 3H), 4.42 (s, 1H), 7.22-7.35 (m, 8H), 7.38 (br s, 2H), 7.78 (d, J=7.8Hz, 1H);
13C NMR (62.5MHz, DMSO-d
6): 160.4,158.7,154.3,152.9,144.6,144.1,129.2 (2C), 128.3 (2C), 127.8,126.4,122.8,119.9,117.2,111.1,103.7,58.7,37.6,21.9.
Embodiment 16:
With [DBU] [Ac] ionic liquid (0.125mmol), phenyl aldehyde (25mmol), the third two eyeballs (25mmol); 4-hydroxyl-6-Methylcoumarin (27.5mmol), deionized water 15mL joins in this reaction vessel successively, places in the UW container; Ultrasonic response 10 minutes (ultrasonic power input 400W) under room temperature, mixed solution filters, ethyl alcohol recrystallization; Dry pure products, the yield 93% of getting.
Characterization data:
1H NMR (200MHz, DMSO-d
6): 2.42 (s, 3H), 4.43 (s, 1H), 7.22-7.31 (m, 4H), 7.32 (d, J=3.8Hz, 2H), 7.37 (br s, 2H), 7.53 (dd, J=2.0,8.8Hz, 2H), 7.37 (s, 1H);
13C NMR (62.5MHz, DMSO-d
6): 160.2,158.8,154.1,152.8,151.0,144.1,142.2,134.7,133.6,129.1,128.4,128.3,125.3,123.1,119.9,117.3,104.7,58.5,37.6,21.2.
Embodiment 17:DBU and [DBU] [Ac] ionic liquid recycle
With embodiment 2 is example, respectively with DBU and the ionic liquid-catalyzed reaction of [DBU] [Ac], after reaction finishes; Reacting liquid filtering, the filtrating that contains the dissolved catalyzer directly recycles as catalystic converter system, can directly be used for reacting after adding raw material and small amount of deionized water according to proportioning raw materials next time; React according to embodiment 2 steps, during reaction system circulation 8 times, the ionic liquid-catalyzed reaction yield of [DBU] [Ac] is still more than 94%; And after the DBU secondary circulation yield below 30%; Show that DBU meets the water posthydrolysis, catalytic activity reduces, and gained is following table as a result:
| Cycle index | Product yield (%) (DBU catalysis) | Product yield (%) (ionic liquid-catalyzed) |
| 1 | 94 | ?96 |
| 2 | 28 | ?96 |
| 3 | - | ?95 |
| 4 | - | ?95 |
| 5 | - | ?96 |
| 6 | - | ?95 |
| 7 | - | ?94 |
| 8 | - | ?94 |
Claims (7)
1. the compound method of pyrans and coumarin derivatives; The structural formula of said pyrans and coumarin derivatives is shown in (4a) in the reaction equation 1; It is characterized in that described compound method is is substrate with the 4 hydroxy coumarin raw material shown in the third two eyeballs shown in the aromatic aldehyde shown in the formula in the reaction equation 1 (1a), the formula (2a) and the formula (3a), is catalyzer with the DBU type ionic liquid shown in the formula (b), in water solvent; Under room temperature ultrasonic 10～20 minutes; Reaction finishes after-filtration and gets crude product, through ethyl alcohol recrystallization, be drying to obtain described pyrans and coumarin derivatives
Reaction formula is following:
R in the reaction equation 1
1Be hydrogen, chlorine, nitro, aldehyde radical, methoxyl group; R
2Be hydrogen, methyl.
2. the compound method of pyrans as claimed in claim 1 and coumarin derivatives is characterized in that described DBU type ionic-liquid catalyst is designated as [DBU] [Ac], and its structure is shown in the formula in the reaction equation 1 (b).
3. like the compound method of described pyrans of claim 1～2 and coumarin derivatives; The amount of substance that it is characterized in that described aromatic aldehyde, the third two eyeballs and 4 hydroxy coumarin is than being 1:1: (1.0～1.2), said DBU type ionic-liquid catalyst is 0.5 with aromatic aldehyde amount of substance ratio: (50～150).
4. like the compound method of described pyrans of claim 1～3 and coumarin derivatives, it is characterized in that the described ultrasonic reaction time is 5～20 minutes.
5. like the compound method of described pyrans of claim 1～4 and coumarin derivatives, it is characterized in that described ultrasonic reaction temperature is 20～40 ℃.
6. like the compound method of described pyrans of claim 1～3 and coumarin derivatives, it is characterized in that described reaction finishes after, reacting liquid filtering obtains pyrans and coumarin derivatives, the filtrating that contains the dissolved catalyzer can directly continue to use more than 8 times.
7. like the compound method of described pyrans of claim 1～3 and coumarin derivatives; It is characterized in that described compound method specifically comprises the steps: aromatic aldehyde, the third two eyeballs, 4 hydroxy coumarin compounds and catalyzer [DBU] [Ac] are joined in the reaction vessel; Add deionized water 15mL; At room temperature in ultrasound reactor ultrasonic 5～20 minutes (power input 400W), reaction finishes after-filtration and gets solid, after recrystallization, drying, gets title product; The amount of substance of said aromatic aldehyde, the third two eyeballs and 4 hydroxy coumarin is than being 1:1: (1.0～1.2), said DBU type ionic-liquid catalyst is 0.5 with aromatic aldehyde amount of substance ratio: (50～150).
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| CN105801595A (en) * | 2016-05-17 | 2016-07-27 | 安徽工业大学 | Method for catalytically preparing 4,5-dihydropyran[c]chromene derivative |
| CN107098914A (en) * | 2017-05-18 | 2017-08-29 | 江苏理工学院 | A kind of chromene simultaneously [3 ', 4 ':5,6] pyrans simultaneously [2,3 b] quinoline and its preparation method and application |
| CN108218883A (en) * | 2016-12-22 | 2018-06-29 | 精华制药集团南通有限公司 | A kind of simultaneously [2,3-b] quinoline and its synthesis technology and the application in anti-tumor aspect of pyrans |
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| US11141402B2 (en) | 2017-06-05 | 2021-10-12 | National University Of Singapore | Compounds useful in inhibiting human trefoil factor 3 |
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| CN105801595A (en) * | 2016-05-17 | 2016-07-27 | 安徽工业大学 | Method for catalytically preparing 4,5-dihydropyran[c]chromene derivative |
| CN105801595B (en) * | 2016-05-17 | 2018-03-20 | 安徽工业大学 | The method that one kind catalysis prepares 4,5 dihydropyran [c] 1-benzopyran derivatives |
| CN108218883A (en) * | 2016-12-22 | 2018-06-29 | 精华制药集团南通有限公司 | A kind of simultaneously [2,3-b] quinoline and its synthesis technology and the application in anti-tumor aspect of pyrans |
| CN108218882A (en) * | 2016-12-22 | 2018-06-29 | 精华制药集团南通有限公司 | A kind of simultaneously [2,3-b] quinoline and preparation method thereof and the application in anti-tumor aspect of pyrans |
| CN107098914A (en) * | 2017-05-18 | 2017-08-29 | 江苏理工学院 | A kind of chromene simultaneously [3 ', 4 ':5,6] pyrans simultaneously [2,3 b] quinoline and its preparation method and application |
| US11141402B2 (en) | 2017-06-05 | 2021-10-12 | National University Of Singapore | Compounds useful in inhibiting human trefoil factor 3 |
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