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Synthesis method of (E)-3-subunit substituted phthalide compounds

A synthetic method and compound technology, applied in the -3- field, can solve the problems of toxicity, high reaction temperature, and unavailable raw materials, and achieve the effects of less catalyst consumption, simple reaction raw materials, and simple operation

Active Publication Date: 2017-08-25
SHAANXI NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, these methods have some shortcomings in varying degrees, including raw materials that are not easy to obtain, poisonous carbon monoxide gas, and high reaction temperature.

Method used

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  • Synthesis method of (E)-3-subunit substituted phthalide compounds
  • Synthesis method of (E)-3-subunit substituted phthalide compounds
  • Synthesis method of (E)-3-subunit substituted phthalide compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0013] Preparation of (E)-tert-butyl-2-(4-methyl-3-oxoisobenzofuran-1(3H)-ylidene)acetate of the formula

[0014]

[0015] Add 13.6mg (0.1mmol) o-toluic acid, 14.5μL (0.1mmol) tert-butyl acrylate, 2.3mg (0.00375mmol) pentamethylcyclopentadienyl rhodium dichloride, 41mg (0.15mmol) of silver carbonate, 1.4mg (0.01mmol) of cuprous oxide, and 0.5mL of toluene were stirred and reacted at 105°C for 1.5 hours in a closed system, cooled to room temperature after the reaction, and filtered through a column chromatography silica gel column to remove Salt and catalyst, separated by TLC to give (E)-tert-butyl-2-(4-methyl-3-oxoisobenzofuran-1(3H)-ylidene)acetate, which The rate is 71%, and the structural characterization data are as follows:

[0016] 1 H NMR (400MHz, CDCl 3 ):δ(ppm)=8.86(d,J=7.9Hz,1H),7.65(t,J=7.8Hz,1H),7.44(d,J=7.5Hz,1H),6.07(s,1H), 3.81(s,3H),2.69(s,3H);

[0017] 13 C NMR (100MHz, CDCl 3 ): δ (ppm) = 166.0, 165.7, 157.8, 139.6, 136.3, 134.9, 134.4, 125.63, 123....

Embodiment 2

[0020] Preparation of (E)-tert-butyl-2-(4-phenoxy-3-oxoisobenzofuran-1(3H)-ylidene)acetate of the following structural formula

[0021]

[0022] In Example 1, the o-toluic acid used was replaced with equimolar 2-phenoxybenzoic acid, and the other steps were the same as in Example 1 to obtain (E)-tert-butyl-2-(4-phenoxy Base-3-oxoisobenzofuran-1(3H)-ylidene) acetate, its yield is 75%, and the structural characterization data are as follows:

[0023] 1 H NMR (400MHz, CDCl 3 ): δ (ppm) = 8.64 (d, J = 7.8Hz, 1H), 7.56 (t, J = 8.1Hz, 1H), 7.35 (t, J = 7.6Hz, 2H), 7.19-7.16 (m, 1H ), 7.06(d, J=7.8Hz, 2H), 6.86(s, 1H), 6.02(s, 1H), 1.48(s, 9H);

[0024] 13 C NMR (100MHz, CDCl 3 ): δ (ppm) = 164.8, 163.2, 156.6, 156.4, 154.7, 138.3, 136.9, 130.1, 125.3, 121.9, 120.6, 119.5, 114.7, 104.6, 81.5, 28.2;

[0025] HRMS(ESI)m / z:C 20 h 18 o 5 ,[M+Na] + , The theoretical value is 361.1052; the measured value is 361.1054.

Embodiment 3

[0027] Preparation of (E)-tert-butyl-2-(4-ethyl-3-oxoisobenzofuran-1(3H)-ylidene)acetate of the following structural formula

[0028]

[0029] In Example 1, the o-toluic acid used is replaced with equimolar 2-ethylbenzoic acid, and other steps are the same as in Example 1 to obtain (E)-tert-butyl-2-(4-ethyl- 3-oxoisobenzofuran-1(3H)-ylidene) acetate, its yield is 74%, and the structural characterization data are as follows:

[0030] 1 H NMR (400MHz, CDCl 3 ):δ(ppm)=8.87(d,J=7.9Hz,1H),7.69(t,J=7.8Hz,1H),7.47(d,J=7.6Hz,1H),6.03(s,1H), 3.13(q, J=7.5Hz, 2H), 1.55(s, 9H), 1.29(t, J=7.6Hz, 3H);

[0031] 13 C NMR (100MHz, CDCl 3 ): δ (ppm) = 165.8, 165.0, 156.9, 145.8, 136.8, 135.1, 132.5, 125.7, 123.2, 103.7, 81.3, 28.2, 24.3, 14.8;

[0032] HRMS(ESI)m / z:C 16 h 18 o 4 ,[M+Na] + , The theoretical value is 297.1103; the measured value is 297.1104.

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Abstract

The invention discloses a synthesis method of (E)-3-subunit substituted phthalide compounds. The method uses pentamethyl cyclopentadienyl rhodium dichloride as a catalyst, and a series of (E)-3-subunit substituted phthalide compounds is simply, conveniently and efficiently synthesized in a one-step mode through carboxyl ortho-position C-H key functionalization based cascade cyclization reaction between aromatic carboxylic acid and an acrylic compound. The synthesis method has the advantages that raw materials are simple and easy to obtain, the catalyst dosage is small, operation is simple, reaction conditions are mild and the like.

Description

technical field [0001] The present invention relates to a kind of synthetic method of (E)-3-subunit substituted phthalide compound, be specifically related to a kind of use pentamethylcyclopentadienyl rhodium dichloride as catalyst, through aromatic carboxylic acid and acrylic acid ester A tandem cyclization reaction based on the functionalization of the carboxyl-ortho-position C—H bond occurs between the compounds, and a method for synthesizing (E)-3-subunit phthalide compounds in one step is simple and efficient. Background technique [0002] 3-subunit substituted phthalides show a wide range of biological activities in clinical applications, for example, they show good performance in anti-AIDS, anti-diabetes, antispasmodic, anti-allergic etc. (Bioorg.Med.Chem.Lett 2007, 17:4972-4976; Chem.Pharm.Bull.2008, 56:1264-1269; Bioorg.Med.Chem.Lett.2013, 23:5614-5618). So far, many methods have been reported in the literature to construct the framework of 3-subunit substituted ph...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D307/88B01J31/22
CPCB01J31/2295B01J2531/0263B01J2531/822C07D307/88
Inventor 石先莹韩文静王嘉妮
Owner SHAANXI NORMAL UNIV
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