Method for preparing 3-allyl-3-hydroxy oxindole

A kind of hydroxyl oxidation, allyl technology, applied in the direction of organic chemistry, etc., can solve the problems of narrow substrate application range, harsh reaction conditions, difficult source of raw materials, etc., to achieve the effect of convenient post-processing procedures, mild operating conditions and low price

CN102070509BInactive Publication Date: 2012-10-10EAST CHINA NORMAL UNIV
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Patent Information

Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Publication Date
2012-10-10
Estimated Expiration
Not applicable · inactive patent

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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 anhydrousmagnesium 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.
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Description

Technical field

[0001] The present invention is the field of organic compound process application technology, which specifically involves a class of category from red and algly alkanes. Background technique

[0002] The 3-hydroxyl oxygen oxidation 吲哚 A is an important pharmaceutical and chemical intermediate, which has high application value.Starting through this type of synthetic block can easily synthesize some natural products and drug molecules with strong biological activity (see the following), such as Convolutamydine A, B or E, 3-Hydroglucoisatisin ,, Donaxaridine , CPC-1, Flutraminol ,, DioxibrasSinine wait.

[0003]

[0004] At present, the 3-ethyl-3-hydroxyl oxidation can be synthesized by the following methods:

[0005] 1) Barbier reaction of the redness of 靛 1 1 1 1 1: The reaction needs to be used as a pink of the equivalent, and the reaction substrate is limited to the red without any replacement base, and the reaction requires the addition of 1.5 times the amount...

Examples

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....