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Method for preparing polysubstituted indole from aryl hydrazine and alkyne

A kind of technology of aryl hydrazine and alkyne, applied in the field of catalytic synthesis of fine chemical products

Active Publication Date: 2014-04-30
TSINGHUA UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Therefore, it is still a great challenge to design and develop more efficient and green indole synthesis methods

Method used

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  • Method for preparing polysubstituted indole from aryl hydrazine and alkyne
  • Method for preparing polysubstituted indole from aryl hydrazine and alkyne
  • Method for preparing polysubstituted indole from aryl hydrazine and alkyne

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Experimental program
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Effect test

Embodiment 1

[0049] Weigh successively the phenylhydrazine hydrochloride (R 1 is H) (0.5mmol), 106.9mg belongs to the diphenylacetylene of formula III (R 2 and R 3 Both are phenyl) (0.6mmol), 7.7mg catalyst [Cp*RhCl 2 ] 2 (2.5mol%) and 54.0mg alkali potassium acetate (0.55mmol) in a 25mL sealed tube containing a magnetic stirrer, vacuum-filled with nitrogen for three cycles. Under nitrogen protection, 72.1 mg of additive isobutyraldehyde (1.0 mmol) and 2.5 mL of solvent methanol were added. Seal the sealed tube, put it into an oil bath at 80° C. and stir for 12 hours to carry out the alkyne cyclization reaction based on carbon-hydrogen bond activation. After the reaction was completed, column separation was performed to obtain 111.4 mg of a white solid, and the isolated yield of the target product 2,3-diphenylindole was 83%.

[0050] figure 1 and figure 2 The proton nuclear magnetic resonance spectrum and carbon spectrum of the product prepared in this embodiment are respectively, ...

Embodiment 2

[0052] Weigh successively the p-methylphenylhydrazine hydrochloride (R 1 is methyl) (0.5mmol), 106.9mg belongs to the diphenylacetylene of formula III (R 2 and R 3 Both are phenyl) (0.6mmol), 7.7mg[Cp*RhCl 2 ] 2 (2.5mol%) and 54.0mg potassium acetate (0.55mmol) in a 25mL sealed tube containing a magnetic stirrer, vacuum-filled with nitrogen for three cycles. 72.1 mg of isobutyraldehyde (1.0 mmol) and 2.5 mL of methanol were added under nitrogen protection. Seal the sealed tube, put it into an oil bath at 80°C and stir for 12 hours. After the reaction was completed, column separation was performed to obtain 129.4 mg of a white solid, and the isolated yield of the target product 5-methyl-2,3-diphenylindole was 91%.

Embodiment 3

[0054] Take by weighing 79.3mg m-methylphenylhydrazine hydrochloride (R 1 is methyl) (0.5mmol), 106.9mg belongs to the diphenylacetylene of formula III (R 2 and R 3 Both are phenyl) (0.6mmol), 7.7mg[Cp*RhCl 2 ] 2 (2.5mol%) and 54.0mg potassium acetate (0.55mmol) in a 25mL sealed tube containing a magnetic stirrer, vacuum-filled with nitrogen for three cycles. 72.1 mg of isobutyraldehyde (1.0 mmol) and 2.5 mL of methanol were added under nitrogen protection. Seal the sealed tube, put it into an oil bath at 80°C and stir for 12 hours. After the reaction was completed, column separation was performed to obtain 111.6 mg of a white solid, and the isolated yield of the target product 6-methyl-2,3-diphenylindole was 79%.

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Abstract

The invention discloses a method for preparing polysubstituted indole. The method comprises the following step: carrying out alkyne cyclization reaction based on hydrocarbon chain activation on aryl hydrazine hydrochloride disclosed as Formula II, alkyne disclosed as Formula III, catalyst, alkali and additives to obtain the compound disclosed as Formula I. The accessible raw materials are subjected to on-pot reaction to generate orientating group in situ in the reaction without presetting the orientating group on the substrate. After the cyclization reaction, the orientating group is automatically removed, and the obtained NH indole can be conveniently derived to obtain the N-substituted indole and has favorable compatibility with multiple substituent groups; no additional oxidizer and strong acid or strong alkali are needed in the reaction; the atomic economical efficiency is high; and although the catalyst is not cheap, the addition amount is small.

Description

technical field [0001] The invention belongs to the field of catalytic synthesis of fine chemical products, and relates to a method for preparing multi-substituted indoles from arylhydrazines and alkynes. Background technique [0002] Indole is a nitrogen-containing aromatic heterocycle, and its derivatives are widely found in nature [(a) Joule, J.A.; Mills, K., Heterocyclic Chemistry, 5th ed.; Wiley-Blackwell: West Sussex, United Kingdom, 2010. (b) Eicher, T.; Hauptmann, S.; Speicher, A. The Chemistry of Heterocycles: Structure, Reactions, Syntheses, and Applications, 2nd ed.; Wiley-VCH GmbH & Co. KGaA: Weinheim, Germany, 2003.]. Tryptophan containing an indole ring is an essential amino acid for mammals, and indole acetic acid (auxin) is one of the most important endogenous hormones in plants. In organisms, tryptophan can be converted into 5-hydroxytryptamine (5-HT, serotonin) containing an indole ring, which is a neurotransmitter and vasoactive substance widely present i...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D209/08C07D209/12C07D209/10
CPCC07D209/08C07D209/10C07D209/12
Inventor 华瑞茂郑李垚
Owner TSINGHUA UNIV
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