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A kind of method for preparing spiro ring 2 azidoindoline

A technology for indole and azide group, which is applied in the field of preparing spirocyclic 2-azidoindoline, can solve problems such as harmful by-products, and achieves the effects of simple operation, mild reaction conditions and easy preparation.

Inactive Publication Date: 2017-12-19
INST OF CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Traditional methods of introducing azide compounds are Sandmeyer reactions, copper-catalyzed coupling reactions of aryl halides or aryl boronic acids with sodium azide or azidotrimethylsilane, which generate unwanted by-products

Method used

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  • A kind of method for preparing spiro ring 2 azidoindoline
  • A kind of method for preparing spiro ring 2 azidoindoline
  • A kind of method for preparing spiro ring 2 azidoindoline

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0053] Example 1. Compounds preparation of

[0054] 1) According to figure 1 Shown synthetic route prepares the indole raw material shown in I-a, and concrete operation is as follows:

[0055] Add compound 1 (3.10g, 17.8mmol), DCM (89.0mL) successively in the reactor, then add Et successively 3 N (8.2mL, 58.8mmol), TsCl (3.80g, 19.6mmol) were stirred overnight at room temperature, spin-dried, and column chromatography gave the product shown in formula 2-a.

[0056] The product shown in formula 2-a (2.95g, 9.0mmol) was dissolved in acetonitrile (27.0mL), DBU (0.273g, 1.8mmol) and compound 3 (1.68g, 12.0mmol) were added successively, stirred overnight at room temperature, and Column chromatography after drying afforded 2.20 g of the product represented by formula I-a as a white solid, 61% yield.

[0057] The results of structural confirmation are as follows: 1 H NMR (400MHz, CDCl 3 )δ8.22-8.05(m,1H),7.73(d,J=8.0Hz,2H),7.41(d,J=7.6Hz,1H),7.37-7.15(m,5H),4.96(t,J =5.6Hz, 1...

Embodiment 2

[0063] Example 2. Compounds preparation of

[0064] 1) According to image 3 Shown synthetic route prepares the indole raw material shown in I-b, concrete operations are as follows:

[0065] In the reactor, add p-methylphenylhydrazine hydrochloride 4 (3.16g, 20.0mmol) successively, 4%H 2 SO 4 (30.0mL), N,N-dimethylacetamide (DMAC) (30.0mL), the reactor was placed at 100 ° C and stirred, dihydropyranyl ether (2.4mL, 26.0mmol) was added, and after 2h of reaction, the The reaction solution was cooled to room temperature, extracted with diethyl ether (3×40.0 mL), and the obtained organic phase was dried over anhydrous magnesium sulfate, filtered and spin-dried. The resulting product was dissolved in dichloromethane (40.0 mL), the reactor was placed at 0 ° C, and then Et 3 N (7.0mL, 50.0mmol), TsCl (1.90g, 10.0mmol) was stirred at 0°C overnight, and the product shown in 5 was obtained by column chromatography after spinning to dryness.

[0066] Add p-toluenesulfonamide (0.41...

Embodiment 3

[0074] Example 3. Compounds preparation of

[0075] 1) According to Figure 5 The shown synthetic route prepares the indole raw material shown in I-c, and concrete operation is as follows:

[0076] In the reactor, add p-methoxyphenylhydrazine hydrochloride 6 (0.454g, 2.6mmol), 4%H 2 SO 4 (3.0mL), N,N-dimethylacetamide (DMAC) (3.0mL), put the reactor at 60°C and stir, add compound 7 (0.474mL, 2.0mmol), react for 2h, and cool the reaction solution Return to room temperature, extract with dichloromethane (3×6.0 mL), dry the obtained organic phase over anhydrous magnesium sulfate, filter and spin dry, and obtain the product shown in 2-c by column chromatography.

[0077] The product shown in formula 2-c (0.684g, 2.0mmol) was dissolved in acetonitrile (6.0mL), DBU (0.304g, 2.0mmol) and compound 3 (0.364g, 2.6mmol) were added successively, stirred overnight at room temperature, and vortexed Column chromatography after drying gave 0.375 g of the product represented by formula I...

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Abstract

The present invention provides a method for preparing the compound represented by formula III or formula IV. The method comprises: in an inert atmosphere, reacting the indole represented by formula I or formula II with a precursor capable of providing an azide group and ammonium cerium nitrate to obtain the product. In formula I, formula II, formula III and formula IV, R1 is selected from the following at least one: hydrogen, C1-C5 alkyl, C1-C5 alkoxy, F, Br and Cl; X is O or TsN , Ts represents p-toluenesulfonyl; R2 is C1-C5 alkyl. The precursor is sodium azide or trimethylsilyl azide; the molar ratio of the indole shown in the formula I or formula II to the precursor and ammonium cerium nitrate is 1:1-3:2-6 in sequence . The present invention adopts a simple method to introduce azide into organic molecules, that is, indoles with different structures are used as raw materials, and under the action of precursors that can provide azide groups and cerium ammonium nitrate, the spiro ring 2 is effectively prepared. ‑Azidoindoline. The method of the invention has the advantages of easy preparation of raw materials, mild reaction conditions, simple and convenient operation, and the highest yield can reach 94%.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a method for preparing spirocyclic 2-azidoindoline. Background technique [0002] Organic azides are important preparation intermediates that can be easily converted into nitrogen-containing compounds, especially nitrogen-containing heterocycles in some drugs. Azides have a wide range of applications in materials science, polymer chemistry, medicinal chemistry, and biology. In addition, azides have important biological activities. Traditional methods for introducing azides are Sandmeyer reactions, copper-catalyzed coupling reactions of aryl halides or aryl boronic acids with sodium azide or azidotrimethylsilane, which generate unwanted by-products. Contents of the invention [0003] The purpose of this invention is to provide a new method for preparing spirocyclic 2-azidoindoline. [0004] The method for preparing spirocyclic 2-azidoindoline provided by the presen...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D491/107
Inventor 史一安李静刘懋田华
Owner INST OF CHEM CHINESE ACAD OF SCI
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