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Preparation method of palladium-catalyzed aryl alkyne

A technology catalyzed by aryl alkynes and palladium, which is applied in the preparation of organic compounds, halogenated hydrocarbons, and carbon-based compounds. The effect of activity, good tolerance and mild reaction conditions

Inactive Publication Date: 2019-05-10
SHAOXING UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

For highly active aryl iodides and aryl bromides, they can successfully participate in the reaction under the catalysis of metal Pd, Cu, Fe and other compounds. However, aryl iodides and bromides are not ideal due to their high price. Arylating reagents
In comparison, aryl chlorides have obvious advantages in price as arylation reagents, but due to their poor activity and high bond energy, the reactions using aryl chlorides as substrates are full of challenges. Among them, only extremely low yields were obtained for electron-rich aryl chlorides

Method used

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  • Preparation method of palladium-catalyzed aryl alkyne
  • Preparation method of palladium-catalyzed aryl alkyne
  • Preparation method of palladium-catalyzed aryl alkyne

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] In a reaction flask, add phenylpropiolic acid (1.0mmol), benzenesulfonyl chloride (1.1mmol), catalyst (0.05mmol), ligand (0.1mmol), base (1.5mmol) and 1mL solvent, and stir under air atmosphere , and then heated to 80°C for reaction. After 12 hours of reaction, TLC monitored the reaction to be complete, cooled to room temperature, filtered off the solid, added 1 mL of water and extracted three times with ether (3 mL each time), combined the extracts, and dried over anhydrous sodium sulfate. , after spin-drying the solvent, use the mixed solvent of petroleum ether and ethyl acetate as the eluent for column separation to obtain the product. The reaction formula, reaction conditions and reaction results are shown in Table 1.

[0031] The reaction condition and reaction result of table 1 embodiment 1

[0032]

[0033]

Embodiment 2

[0035] In the reaction flask, add substituted alkynoic acid (1.0mmol), p-methoxybenzenesulfonyl chloride (1.1mmol), Pd(OAc) 2(0.05mmol), phen (0.1mmol), K 2 CO 3 (1.5mmol) and 1mLDMF were stirred under an air atmosphere, then heated to 80°C for reaction, after 12 hours of reaction, TLC monitored that the reaction was complete, cooled to room temperature, filtered off the solid, added 1mL of water and extracted three times with ether (each 3mL), the combined extracts were dried over anhydrous sodium sulfate, and the solvent was spin-dried, and the mixed solvent of petroleum ether and ethyl acetate was used as the eluent for column separation to obtain the product. The reaction formula and reaction result are as follows:

[0036]

Embodiment 3

[0038] In a reaction flask, add phenylpropiolic acid (1.0 mmol), substituted benzenesulfonyl chloride (1.1 mmol), Pd(OAc) 2 (0.05mmol), phen (0.1mmol), K 2 CO 3 (1.5mmol) and 1mL DMF, stirred under air atmosphere, then heated to 80 ° C for reaction, after 12 hours of reaction, TLC monitored the reaction was complete, down to room temperature, filtered off the solid, added 1mL of water and extracted three times with diethyl ether (each 3 mL times), combined the extracts, dried over anhydrous sodium sulfate, spin-dried the solvent, and carried out column separation with a mixed solvent of petroleum ether and ethyl acetate as the eluent to obtain the product. The reaction formula and reaction result are as follows:

[0039]

[0040] Some product characterization data

[0041] 1,2-bis(4-methoxyphenyl)ethyne(2a):White solid,mp:146-149℃. 1 H NMR (400MHz, CDCl 3 )δ7.48(d, J=8.8Hz, 4H), 6.86(d, J=8.8Hz, 4H), 3.81(s, 6H). 13 C NMR (100MHz, CDCl 3 )δ159.4, 132.9, 124.4, 115.7,...

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Abstract

The invention discloses a preparation method of palladium-catalyzed aryl alkyne. The preparation method includes the steps of subjecting substituted acetylenic acid and aryl sulfonyl chloride to decarboxylation coupling reaction in an organic solvent under the action of a catalyst, a ligand and alkali, and carrying out treatment after the reaction to obtain the aryl alkyne. Raw materials used in the preparation method are cheap and easy to obtain, and the reaction and the post-treatment operations are simple; side reactions are few, and the yield of the obtained product is high.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a preparation method of palladium-catalyzed aryl alkynes. Background technique [0002] Alkyne derivatives play an important role in organic synthesis. Many natural products, drug molecules, and polymeric materials contain alkyne structures or are synthesized from simple alkyne compounds. Therefore, a large number of methods for synthesizing alkyne derivatives It came into being. The classic Sonogashira coupling is one of the most commonly used synthetic methods, that is, under the co-catalysis of palladium and copper, aryl halides and terminal alkynes undergo coupling reactions to obtain disubstituted alkyne compounds (R. Chinchilla and C. Nájera, Chem. Rev., 2007, 107, 874.). However, the classic Sonogashira coupling reaction requires copper salts as auxiliary catalysts to complete the reaction. The alkynyl copper intermediates produced during the reaction are ver...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C1/32C07C15/54C07C41/30C07C43/215C07C201/12C07C205/37C07C205/06C07C17/263C07C25/18C07C22/04C07C45/68C07C49/796C07C67/343C07C69/76C07C43/225C07B37/04
Inventor 赵保丽
Owner SHAOXING UNIVERSITY
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