Preparation method of 3,3'-diindolyl acetate

A technology of indole acetate and indole derivatives, which is applied in the field of preparation of 3,3'-diindole acetate compounds, can solve the problems of harsh reaction conditions, high toxicity in use, and cumbersome steps, etc. Achieve the effects of less reaction steps, easy operation and environmental friendliness

Inactive Publication Date: 2019-04-05
LANZHOU UNIVERSITY
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AI Technical Summary

Problems solved by technology

[0015] This method raw material is cheap and easy to get, and productive rate is high, but needs to use the relatively expensive catalyst tris (4-bromophenyl) amine hexachloroantimonate (TBPA +. ), and the amount of catalyst used is as high as 20mol%, so the synthesis cost is higher, and it is not suitable for large-scale raw material preparation
[0016] In summary, although several methods for the synthesis of 3,3'-diindolyl acetate have been reported, the current methods still have obvious deficiencies, such as cumbersome steps, low yields, and poor reaction conditions. Harshness, use of highly toxic reagents, expensive catalysts and large dosages, etc., these problems seriously restrict the further application of the above method

Method used

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  • Preparation method of 3,3'-diindolyl acetate
  • Preparation method of 3,3'-diindolyl acetate
  • Preparation method of 3,3'-diindolyl acetate

Examples

Experimental program
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Effect test

Embodiment 1

[0036] Embodiment 1: the preparation of 3,3'-diindole ethyl acetate

[0037]

[0038] In a 25 mL flask, dissolve 193 mg (1 mmol) (4-methylphenyl) ethyl aminoacetate in 5.0 mL ethanol, then add 246 mg (2.1 mmol) indole, 6.9 mg (1 mol%) eosin Y, 0.11mL (1.5eq) of trifluoroacetic acid was stirred at room temperature for 12 hours under the irradiation of a 26W energy-saving lamp. Then add saturated sodium bicarbonate solution to quench the reaction, extract with ethyl acetate, dry over anhydrous sodium sulfate, evaporate the solvent under reduced pressure, column chromatography (petroleum ether / ethyl acetate=4:1) to obtain 312mg of product, yield 98 %. Pale red solid. 1 H NMR (400MHz, CDCl 3 ): δ8.00(s,2H),7.65(d,J=8.0Hz,2H),7.28(d,J=8.2Hz,2H),7.19(m,2H),7.10(m,2H),6.96 (d, J=2.4Hz, 2H), 5.51(s, 1H), 4.23(q, J=7.1Hz, 2H), 1.27(t, J=7.1Hz, 3H). 13 C NMR (100MHz, CDCl 3 ): δ173.9, 136.2, 126.5, 123.5, 121.9, 119.4, 119.1, 113.2, 111.3, 61.2, 40.5, 14.1.

Embodiment 2

[0039] Embodiment 2: the preparation of 3,3'-diindole acetic acid benzyl ester

[0040]

[0041] In a 25mL flask, dissolve 271mg (1mmol) benzyl (4-methoxyphenyl)aminoacetate in 5.0mL 1,2-dichloroethane, then add 246mg (2.1mmol) indole, 10.2mg ( 1mol%) rose bengal, 0.087mL (1.5eq) phosphoric acid, and stirred at room temperature for 10 hours under the irradiation of a 5W blue LED light. Then add saturated sodium bicarbonate solution to quench the reaction, extract with ethyl acetate, dry over anhydrous sodium sulfate, evaporate the solvent under reduced pressure, column chromatography (petroleum ether / ethyl acetate=4:1) to obtain 346mg product, yield 91 %. Pale yellow solid. 1 H NMR (400 MHz, acetone-d 6):δ7.95(s,2H),7.50(d,J=7.6Hz,2H),7.29-6.97(m,13H),5.51(s,1H),5.11(s,2H). 13 C NMR (100MHz, acetone-d 6 ): δ172.7, 136.9, 136.5, 128.2, 128.0, 127.8, 126.9, 123.6, 121.3, 119.1, 118.7, 113.1, 111.3, 66.0, 40.7.

Embodiment 3

[0042] Embodiment 3: Preparation of 3,3'-diindole allyl acetate

[0043]

[0044] In a 25mL flask, dissolve 221mg (1mmol) (4-methoxyphenyl) allyl aminoacetate in 5.0mL acetonitrile, then add 246mg (2.1mmol) indole, 4.8mg (1mol%) rhodamine 6G , 315mg (1.5eq) of citric acid, stirred at room temperature for 12 hours under sunlight irradiation. Then add saturated sodium bicarbonate solution to quench the reaction, extract with ethyl acetate, dry over anhydrous sodium sulfate, evaporate the solvent under reduced pressure, column chromatography (petroleum ether / ethyl acetate=4:1) to obtain 307mg product, yield 93 %. red solid. 1 H NMR (400MHz, CDCl 3 ): δ 7.86(s,2H),7.51(d,J=8.0Hz,2H),7.17-7.03(m,4H),6.81(s,2H),5.81(m,1H),5.44(s,1H ),5.17-5.04 (m,2H),4.55(m,2H). 13 C NMR (100MHz, CDCl 3 )δ172.7, 136.9, 132.7, 126.8, 123.7, 121.3, 119.0, 118.8, 117.1, 113.1, 111.4, 64.8, 40.7.

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Abstract

A 3,3'-diindolyl acetate compound and a derivative thereof are discovered to have extensive activities of immunity resistance, inflammation resistance, edema inhibition and the like. Meanwhile, The 3,3'-diindolyl acetate compound is also an important intermediate raw material which belongs to the field of organic preparation. The compound can be used for synthesizing multiple bioactive molecules with 3,3'-bis-indolymethane structure, and has quite high organic synthesis application value. The invention provides a quite simple preparation method of a visible light catalyzed 3,3'-diindolyl acetate compound. The preparation method comprises the following specific steps: taking a glycine derivative and an indole derivative as raw materials, taking an organic photosensitizer (eosin Y, rose-bengal or rhodamine 6G) as a photocatalyst, reacting for 10-30 h at the room temperature under illumination of visible light, and separating and purifying to obtain a product. Compared with the prior art,the preparation method has the advantages of simple steps, high yield, cheap and easily obtained raw materials and catalysts, zero metal, mild reaction condition, simplicity in reaction operation andthe like, and is more suitable for pilot scale-up and large-scale preparation of the 3,3'-diindolyl acetate compound.

Description

technical field [0001] The invention belongs to the technical field of organic preparation, and in particular relates to a preparation method of a 3,3'-diindolyl acetate compound. Background technique [0002] 3,3'-Diindolyl acetate compounds and their derivatives such as Soritin B(bis-(1H-indol-3-yl)-acetic acid methyl ester), Soritin C(bis-2,2-(1 -methyl-indol-3-yl) acetic acidmethyl ester), Soritin D (bis-2,2-(1-methyl-indol-3-yl) acetic acid) etc. have been found to have a wide range of anti-immune, anti-inflammatory and inhibitory Edema and other activities (U.S. Pat. No. 20010056112, 6444697, 6323233). At the same time, 3,3'-diindolyl acetate compounds also belong to a class of important intermediate raw materials in the category of organic preparation, and this type of compound can be used to synthesize a variety of drugs containing 3,3'-diindolylmethane structure Molecules, alkaloid natural products and biologically active intermediates, for example, can be used in...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D209/18C07D209/22
CPCC07D209/18C07D209/22
Inventor 张元杨枭荣周煌李瀛
Owner LANZHOU UNIVERSITY
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