Method for preparing 3-sulfonyl coumarin compound

A technology of sulfonyl coumarin and compounds, which is applied in the field of preparation of 3-sulfonyl coumarin compounds, can solve problems such as bad odor and unfavorable operation and use, achieve low cost, avoid the use of sulfonyl chloride intermediates, and use raw materials easy-to-achieve effects

Active Publication Date: 2016-10-26
FUDAN UNIV
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  • Abstract
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  • Claims
  • Application Information

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Problems solved by technology

The oxidation method requires the use of some strong oxidants, and the sulfur-co

Method used

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  • Method for preparing 3-sulfonyl coumarin compound
  • Method for preparing 3-sulfonyl coumarin compound

Examples

Experimental program
Comparison scheme
Effect test

Example Embodiment

[0021] Example 1

[0022] Ia

[0023] Add DABCO to the reaction tube one by one . (SO 2 ) 2 (2.0 equivalents), phenyl phenylpropiolate (0.2 mmol), aryl diazonium salt (1.2 equivalents) and 1,2-dichloroethane (2 mL), under the protection of inert gas nitrogen or argon, in Stir at 40~60°C for 0.5-1.0 hours, until TLC detects the complete reaction, the reaction solution is directly concentrated and separated by column chromatography to obtain the corresponding 3-sulfonylcoumarin compound Ia.

[0024] 1 H NMR (400 MHz, CDCl 3 )δ8.01 (d, J = 8.0 Hz, 2H), 7.57-7.61 (m, 4H), 7.50 (t, J = 8.0 Hz,2H), 7.33-7.35 (m, 2H), 7.15 (s, 1H), 7.01 (d, J = 7.6Hz, 1H), 6.90 (d, J = 8.4Hz, 1H), 2.45 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ159.6, 155.8, 153.9, 146.8, 140.3, 133.5, 132.7, 129.6, 129.1, 129.0, 128.5, 128.0, 127.4, 126.1, 124.5, 117.8, 116.8, 21.8; HRMS calcd for C 22 H 17 O 4 S(M + +H): 377.0842, found: 377.0830.

Example Embodiment

[0025] Example 2

[0026] Ib

[0027] Add DABCO to the reaction tube one by one . (SO 2 ) 2 (2.0 equivalents), phenyl phenylpropiolate (0.2 mmol), aryl diazonium salt (1.2 equivalents) and 1,2-dichloroethane (2 mL), under the protection of inert gas nitrogen or argon, in Stir at 40~60°C for 0.5-1.0 hours, until TLC detects the complete reaction, the reaction solution is directly concentrated and separated by column chromatography to obtain the corresponding 3-sulfonylcoumarin compound Ib.

[0028] 1 H NMR (400 MHz, CDCl 3 )δ8.02 (d, J = 7.6 Hz, 2H), 7.58-7.64 (m, 2H), 7.51 (t, J = 7.6 Hz, 2H), 7.40 (d, J = 8.0 Hz, 2H), 7.34 (d, J = 8.4 Hz, 1H), 7.18-7.26 (m, 3H), 7.09 (d, J = 8.0Hz, 1H), 2.51 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 159.9, 155.5, 153.8, 140.2, 139.2, 134.5, 133.5, 129.9, 129.4, 129.0, 128.8, 128.5, 127.4, 125.8, 124.7, 120.3, 116.7, 21.5; HRMS calcd forC 22 H 17 O 4 S(M + +H): 377.0842, found: 377.0841.

Example Embodiment

[0029] Example 3

[0030] Ic

[0031] Add DABCO to the reaction tube one by one . (SO 2 ) 2 (2.0 equivalents), phenyl phenylpropiolate (0.2 mmol), aryl diazonium salt (1.2 equivalents) and 1,2-dichloroethane (2 mL), under the protection of inert gas nitrogen or argon, in Stir at 40~60°C for 0.5-1.0 hours, until TLC detects the complete reaction, the reaction solution is directly concentrated and separated by column chromatography to obtain the corresponding 3-sulfonyl coumarin compound Ic.

[0032] 1 H NMR (400 MHz, CDCl 3 )δ 8.00 (d, J = 7.6 Hz, 2H), 7.60-7.67 (m, 2H), 7.52 (t, J = 8.0 Hz, 2H), 7.30-7.37 (m, 5H), 7.23 (t, J = 8.0 Hz, 1H), 7.05(d, J = 8.0 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 163.2 (d, 1 J F = 248.3), 158.5, 155.3, 153.8, 140.0, 134.8, 133.7, 129.6 (d, 2 J F =21.5 Hz), 129.5, 129.0, 128.6, 128.2, 126.2, 124.9, 120.0, 116.9, 115.5 (d, 2 J F =22.0 Hz);HRMS calcdfor C 21 H 14 FO 4 S(M + +H): 381.0591, found: 381.0588.

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Abstract

The invention belongs to the technical field of organic chemistry, and particularly relates to a method for preparing a 3-sulfonyl coumarin compound. According to the method, arenediazonium salt, phenyl ester phenylpropiolate and DABCO.(SO2)2 react in an organic solvent to prepare the 3-sulfonyl coumarin compound. The structure of the compound is represented through the 1 H NMR, 13 C NMR, HRMS and single crystal x-ray diffraction analysis methods and determined. According to the method, under very mild and simple conditions, DABCO.(SO2)2 serves as a sulfur dioxide source, sulfur acylation reaction is achieved directly, and the 3-sulfonyl coumarin compound is built. Raw materials in the reaction are easy to obtain, cost is low, use of a sulfonyl chloride intermediate in a traditional synthesis method is avoided, and the method can be suitable for large-scale preparation and has very good application prospects.

Description

technical field [0001] The invention belongs to the technical field of organic chemistry, and in particular relates to a preparation method of 3-sulfonyl coumarin compounds. Background technique [0002] The coumarin skeleton is one of the common heterocyclic structures, which widely exists in a variety of natural products and drug molecules with significant biological activities. For example, umbelliferide in rue, escin in chinensis and angelica lactone in lovage all have a coumarin skeleton; the coumarin compound warfarin (Wafarin) is a widely used Medical clinical anticoagulant; Calanolide A extracted from the plant Populus euphratica exhibits very good HIV-1 reverse transcriptase inhibitory activity, and is a potential anti-AIDS drug. Coumarin compounds also play an important role in the fields of dyes and materials. The industrialized coumarin fluorescent dyes include Disperse Yellow 184, Disperse Yellow 232, Solvent Red 196 and Disperse Red 277, etc. Its derivatives...

Claims

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Application Information

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IPC IPC(8): C07D311/16C07D311/12
Inventor 郑旦庆吴劼
Owner FUDAN UNIV
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