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Preparation method of 4-aryl coumarin-3-phosphonate derivatives

A technology for aryl coumarin and aryl propynoic acid aryl ester, which is applied in the field of coumarin derivatives, can solve the problems of small scope of application and long reaction time, and achieves short reaction time, high yield, and high reaction time. mild effects

Inactive Publication Date: 2013-08-21
SUZHOU UNIV
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AI Technical Summary

Problems solved by technology

[0005] In the above technical scheme, the substrates of many reactions are difficult to obtain, resulting in a small scope of application of the reaction, and the reaction conditions are strict (anhydrous and oxygen-free conditions are required), the yield is 23-67%, and the reaction time is relatively long (18 hours)

Method used

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  • Preparation method of 4-aryl coumarin-3-phosphonate derivatives
  • Preparation method of 4-aryl coumarin-3-phosphonate derivatives
  • Preparation method of 4-aryl coumarin-3-phosphonate derivatives

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Example 1: Synthesis of 4-phenyl-2H-benzopyran-2-one-3-phosphonate

[0032] Using 3-phenylpropiolic acid phenyl ester and dimethyl phosphite as raw materials, the reaction formula is as follows:

[0033]

[0034] (1) Add 0.22 g (1 mmol) of phenyl 3-phenylpropiolate, 0.11 g (1 mmol) of dimethyl phosphite, 0.1 g of K-OMS-2 and methanol (30 mL) into the reaction flask , 20°C reaction;

[0035] (2) TLC tracking reaction until completely finished;

[0036] (3) The crude product obtained after the reaction was separated by column chromatography (petroleum ether: ethyl acetate = 4:1) to obtain the target product (yield 75%).

[0037] 1 H NMR (400 MHz, CDCl 3 ): δ 7.60 (t, J = 7.59 Hz, 1H, ArH), 7.55 ? 7.50 (m, 3H, ArH), 7.38 (d, J = 8.30 Hz, 1H, ArH), 7.36 ? 7.30 (m, 3H, ArH), 7.18 (t, J = 7.16 Hz, 1H, ArH), 7.06 (d, J = 7.95 Hz, 1H, ArH), 3.60 ? 3.59 ( m, 3H, CH 3 ), 3.57 ? 3.55 ( m, 3H, CH 3 );HRMS (EI): m / z (%) calcd. for C 17 h 15 o 5 P, 330.0657, ...

Embodiment 2

[0038]Example 2: Synthesis of 4-phenyl-2H-benzopyran-2-one-3-phosphonate

[0039] With phenyl 3-phenylpropiolate and diethyl phosphite as raw materials, the reaction formula is as follows:

[0040]

[0041] (1) Add 0.22 g (1 mmol) of phenyl 3-phenylpropiolate, 0.21 g (1.5 mmol) of diethyl phosphite, 0.05 g of K-OMS-2 and ethanol (30 mL) into the reaction flask , 40°C reaction;

[0042] (2) TLC tracking reaction until complete completion;

[0043] (3) The crude product obtained after the reaction was separated by column chromatography (petroleum ether: ethyl acetate = 4:1) to obtain the target product (yield 82%).

[0044] 1 H NMR (300 MHz, CDCl 3 ): δ 7.55 ? 7.45 (m, 3H, ArH), 7.38 (s, 1H, ArH), 7.34 ? 7.28 (m, 2H, ArH), 7.12 (d, J = 6.7 Hz, 2H, ArH), 6.97 (d, J = 8.6 Hz, 1H, ArH), 4.15 ? 4.00 (m, 2H, CH 2 ), 4.0 ? 3.82 (m, 2H, CH 2 , 1.11 (m, 6H, CH 3 ); HRMS (EI, M + ): calcd for C 19 h 19 o 5 P 358.0971, found 358.1043.

Embodiment 3

[0045] Example 3: Synthesis of 4-(4-methylphenyl)-2H-benzopyran-2-one-3-phosphonate

[0046] Using 3-(4-methylphenyl)phenyl propiolate and diethyl phosphite as raw materials, the reaction formula is as follows:

[0047]

[0048] (1) Add 0.24 g (1 mmol) of 3-(4-methylphenyl) phenyl propiolate, 0.28 g (2 mmol) of diethyl phosphite, and 0.1 g of K-OMS-2 into the reaction flask React with acetonitrile (30 mL) at 50°C;

[0049] (2) TLC tracking reaction until complete completion;

[0050] (3) The crude product obtained after the reaction was separated by column chromatography (petroleum ether: ethyl acetate = 4:1) to obtain the target product (yield 87%).

[0051] 1 H NMR (300 MHz, CDCl 3 ): δ 7.52 (s, 1H, ArH), 7.35 ? 7.24 (m, 3H, ArH), 7.20 ? 7.04 (m, 4H, ArH), 4.10-4.00 (m ,2H, CH 2 ), 3.96 ? 3.84 (m, 2H, CH 2 ), 2.40 (s, 3H, CH 3 ), 1. 08 (m, 6H, CH 3 ); HRMS (EI, M + ): calcd for C 20 h 21 o 5 P 372.1127, found 372.1205 。

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Abstract

The invention discloses a preparation method of 4-aryl coumarin-3-phosphonate derivatives, which is characterized comprising the following steps: adding one of 3-aryl propiolic acid aryl ester derivatives, one of phosphite esters and a manganite octahedral molecular sieve into a solvent; and carrying out a reaction at a temperature of 20-150 DEG C so as to obtain a 4-aryl coumarin-3-phosphonate derivative. According to the invention, 3-aryl propiolic acid aryl ester derivatives are used as a starting material, so that raw materials are easily obtained and diverse in type; products obtained by using the method disclosed by the invention is diverse in type, both can be directly used, and can be applied to other further reactions; and the method is short in synthetic route, mild in reaction conditions, simple in reaction operation and post-treatment process, and high in yield.

Description

technical field [0001] The invention relates to a coumarin derivative, in particular to the preparation of a 4-aryl coumarin-3-phosphonate derivative. Background technique [0002] Coumarin derivatives are a very important class of natural products with a wide range of physiological activities. Organic phosphine compounds are closely related to life phenomena. Therefore, the synthesis of 3-phosphonate-substituted coumarin derivatives is of great value. It has been reported in the literature that coumarin-3-phosphonate derivatives have strong alkylation properties and cell activity in vivo (Elzbieta Budzisz, Elzbieta Brzezinska, Urszula Krajewska, Marek Rozalski, European Journal of Medicinal Chemistry 2003, 38, 597- 603). [0003] In the prior art, there are only few reports on the synthesis of several coumarin-3-phosphates (see: 1. Charles N. Robinson and John F. Addison Journal of Organic Chemistry, 1966, 31, 4325; 2 .Rajendra K. Singh and Michael D.Rogers Journal of Het...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/655A61P35/00A61P35/02
Inventor 邹建平季云飞潘向强王璐曹晓慧
Owner SUZHOU UNIV
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