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Method for preparing 3-allyl-3-hydroxy oxindole

A technology of hydroxyl oxidation and allyl group, applied in the direction of organic chemistry, etc., can solve the problems of narrow application range of substrates, limited reaction substrates, and difficult source of raw materials, etc., to achieve convenient post-processing procedures, convenient recycling, and low price Effect

Inactive Publication Date: 2011-05-25
EAST CHINA NORMAL UNIV
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  • Abstract
  • Description
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  • Application Information

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Problems solved by technology

[0006]2) Allyl addition reaction to isatin catalyzed by transition metal palladium: This reaction needs to use expensive palladium(II) acetate as catalyst, and the catalytic amount The requirement is 5 mol%; three equivalents of triethylborane need to be added; the reaction requires strict anhydrous and oxygen-free operation, and the operation is complicated; and the reaction substrate is limited to isatin that is protected and does not contain halogen groups , narrow substrate range
[0007]3) Allyl addition reaction of isatin catalyzed by transition metal iridium: the reaction uses 2.5 mol% metal iridium complex as catalyst; reaction conditions It needs to be strictly anhydrous and oxygen-free, and the temperature is 60-100oC; it needs to add additives such as isopropanol, cesium carbonate and 3-nitro-4-cyanobenzyl alcohol, and the operation is complicated; isatin
[0009]5) Preparation of Claisen rearrangement of 2-allyloxindole: This reaction not only has rare raw materials, but also has low yield and many by-products; rearrangement An equivalent amount of organic base needs to be used; the reaction conditions are relatively harsh, and the temperature needs to range from room temperature to 110 degrees; the substrate range is narrow
[0010]6) Preparation by addition reaction of isatin and allyl Grignard reagent: This reaction needs to use six times equivalent of allyl Grignard reagent equivalent to the substrate, the operation Requires strict anhydrous and oxygen-free, and incompatibility with Grignard reagent-sensitive functional groups such as nitro, ester, etc., narrow substrate range
[0011] In summary, although 3-allyl-3-hydroxyoxindole A is an important intermediate with a wide range of uses, the existing synthetic methods not only Strict operation is required, the source of raw materials is not easy, the production cost is high, and the scope of substrate application is narrow, which makes large-scale production face many difficulties

Method used

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  • Method for preparing 3-allyl-3-hydroxy oxindole
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  • Method for preparing 3-allyl-3-hydroxy oxindole

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038] 3-allyl-3-hydroxyindole 1 Synthesis:

[0039]

[0040] In a 10.0 mL reaction flask, add mercury(II) trihydrate perchlorate [Hg(ClO 4 ) 2 ·3H 2 O, 1.8 mg, 0.004 mmol], isatin I-1 (58.8 mg, 0.40 mmol), anhydrous dichloromethane (2.0 mL), allyltrimethylsilane Ⅱ (127.0 mu L, 0.80 mmol), stirred at room temperature, TLC detected that the raw materials had basically reacted, stopped the reaction, transferred the reaction solution to a 100 mL round bottom flask, diluted with 30 mL ethyl acetate, added 10 drops of concentrated hydrochloric acid dropwise, and continued to stir for 5- After 10 minutes, TLC point plate found that there was only one product point, the organic phase was washed once with saturated sodium bicarbonate solution, once with saturated brine, and spin-dried for column chromatography, the eluent was (acetone / dichloromethane=1 / 10), get the product 1 As a white solid 71.8 mg, yield 95%. 1 H NMR (400 MHz, DMSO- d 6 ): 10.21 (s, 1H), 7.27-7.25 (m,...

Embodiment 2

[0042] 3-allyl-3-hydroxy-5-chloroindole 2 Synthesis:

[0043]

[0044] Add mercury(II) trifluoromethanesulfonate [Hg(OTf) 2 ,2.0 mg, 0.004 mmol], 5-chloroisatin I-2 (71.2 mg, 0.40 mmol), anhydrous tetrahydrofuran (3.0 mL), allyltrimethylsilane Ⅱ (127.0 mu L, 0.80 mmol), stirred at 0°C, TLC detected that the reaction of the raw materials was basically complete, the reaction was stopped, the reaction solution was transferred to a 100 mL round bottom flask, diluted with 20 mL ethyl acetate, added dropwise with 10 drops of concentrated hydrochloric acid, and continued to stir for 5 -10 minutes, after the TLC point plate found that there was only one product point, the organic phase was washed once with saturated sodium bicarbonate solution, once with saturated brine, and spin-dried for column chromatography, the eluent was (acetone / dichloromethane=1 / 10), get the product 2 As a white solid 85.6 mg, yield 97%. 1 H NMR (400 MHz, DMSO- d 6 ): d 10.38 (s, 1H), 7.29 (s, ...

Embodiment 3

[0046] 3-allyl-3-hydroxy-5-nitrooxindole 3 Synthesis:

[0047]

[0048] Add indium(III) perchlorate octahydrate [In(ClO 4 ) 3 ·8H 2 O, 22.0 mg, 0.04 mmol], 5-nitroisatin I-3 (76.9 mg, 0.40 mmol), anhydrous chloroform (3.0 mL), allyltrimethylsilane Ⅱ (127.0 mu L, 0.80 mmol), stirred at 40°C, TLC detected that the raw materials were basically reacted, stopped the reaction, transferred the reaction solution to a 100 mL round bottom flask, diluted with 30 mL ethyl acetate, added 8 drops of concentrated hydrochloric acid, and continued to stir for 5- After 10 minutes, the TLC point board found that there was only one product point, and the organic phase was washed once with saturated sodium bicarbonate solution, once with saturated brine, and spin-dried for column chromatography, and the eluent was (acetone / dichloromethane=1 / 10), get the product 3 It is 89.0 mg of white solid, and the yield is 95%. 1 H NMR (400 MHz, DMSO- d 6): d 10.99 (s, 1H), 8.20-8.18 (m, 1H), 8....

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Abstract

The invention discloses a method for preparing 3-allyl-3-hydroxy oxindole, which comprises the following steps of: adding a catalyst, solvent, isatin and silicane in a reaction bulb, stirring at the specific temperature, performing thin layer chromatography (TLC) detection until the isatin disappears, adding ethyl acetate for diluting, dripping concentrated hydrochloric acid, stirring continuously at the room temperature for half an hour, washing once sequentially by using solution of saturated sodium hydrogen carbonate and saturated saline solution, drying an organic phase by using anhydrous magnesium sulfate, and performing column chromatographic separation to obtain the 3-allyl-3-hydroxy oxindole. Various reagents used in the method can be obtained commercially, and have wide sources of raw materials and low cost; the used catalyst has a good catalytic effect and helps to reduce cost and also helps to simplify a process, reduce cost, facilitate aftertreatment process and reduce pollution to the environment.

Description

technical field [0001] The invention belongs to the technical field of organic compound technology application, and specifically relates to a method for preparing 3-allyl-3-hydroxyindole from isatin and allylsilane. Background technique [0002] 3-allyl-3-hydroxyindole A is a class of important pharmaceutical and chemical intermediates with high application value. Starting from this type of synthetic building block, some natural products and drug molecules with strong biological activity can be easily synthesized (see the formula below), such as Convolutamydine A, B or E, 3-Hydroglucoisatisin , Donaxaridine , CPC-1, Flutraminol , Dioxibrassinine wait. [0003] [0004] Currently, 3-allyl-3-oxindole can be synthesized by the following methods: [0005] 1) Barbier reaction of isatin and allyl bromide with indium participation: This reaction requires the use of equivalent indium powder, the reaction substrate is limited to isatin without any substituents, and the ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D209/38
Inventor 周剑曹中艳
Owner EAST CHINA NORMAL UNIV
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