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Method for preparing aromatic cross-coupled compound

A cross-coupling and compound technology, which is applied in the field of preparation of aromatic cross-coupling compounds, can solve problems such as difficult access to aryl diazonium salts, limited application of coupling reactions, sensitivity to heat and light, and achieves low cost and low substrate Stable, well tolerated effect

Active Publication Date: 2013-08-07
PEKING UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, in the prior art, aryl diazonium salts are not easy to obtain, difficult to purify, and difficult to store. They are also sensitive to heat and light, and cannot react at higher temperatures, which limits the Application of Coupling Reaction

Method used

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  • Method for preparing aromatic cross-coupled compound
  • Method for preparing aromatic cross-coupled compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Synthesis of 4-methoxybiphenyl

[0030] Add 182mg (i.e. 1.2mmol) p-methoxyphenylboronic acid, 23mg (i.e. 0.025mmol) Pd 2 (dba) 3 , 35mg (ie 0.15mmol) P (furyl) 3 , 2ml DMF. Then weigh 93mg (i.e. 1mmol) of aniline and 113mg (i.e. 1.1mmol) of tert-butyl nitrite in a long tube type reaction bottle, add 2ml of DMF, stir and inject into the Schlenk bottle with a needle, and the system is heated at 80°C React for 8 hours, concentrate after the reaction, and use petroleum ether as the eluent for column chromatography purification to obtain 4-methoxybiphenyl, whose structure is shown in the following formula:

[0031]

[0032] The compound is a white solid with a yield of 81%, and its NMR data are as follows:

[0033] 1 H NMR (400MHz, CDCl 3 )δ7.56~7.51(m, 4H), 7.43~7.39(m, 2H), 7.31~7.28(m, 1H), 6.99~6.96(m, 2H), 3.84(s, 3H); 13 C NMR (100MHz, CDCl 3 )δ 159.1, 140.8, 133.7, 128.7, 128.1, 126.7, 126.6, 114.2, 55.3.

Embodiment 2

[0035] Synthesis of 4-methyl 4'-methoxybiphenyl

[0036] Add 182mg (i.e. 1.2mmol) p-methoxyphenylboronic acid, 23mg (i.e. 0.025mmol) Pd 2 (dba) 3 , 35mg (ie 0.15mmol) P (furyl) 3 , 2ml DMF. Then take by weighing 107mg (i.e. 1mmol) p-toluidine and 113mg (i.e. 1.1mmol) tert-butyl nitrite in the long tube type reaction bottle, add 2ml DMF, inject in the Schlenk bottle with needle after stirring, system is at 80 React at ℃ for 8 hours, concentrate after reaction, and use petroleum ether as eluent for column chromatography purification to obtain 4-methyl-4'-methoxybiphenyl, whose structure is shown in the following formula:

[0037]

[0038] The compound is a yellow solid with a yield of 77%, and its NMR data are as follows:

[0039] 1 H NMR (400MHz, CDCl 3 )δ7.50(d, 2H, J=8.8Hz), 7.44(d, 2H, J=8.1Hz), 7.22(d, 2H, J=7.9Hz), 6.96(d, 2H, J=8.8Hz) , 3.83(s, 3H), 2.34(s, 3H); 13 C NMR (100MHz, CDCl 3 ) 158.9, 137.9, 136.3, 133.7, 129.4, 127.9, 126.5, 114.1, 55.3, 21.0.

Embodiment 3

[0041] Synthesis of 4-Chloro4'-Methoxybiphenyl

[0042] Add 182mg (i.e. 1.2mmol) p-methoxyphenylboronic acid, 23mg (i.e. 0.025mmol) Pd 2 (dba) 3 , 35mg (ie 0.15mmol) P (furyl) 3 , 2ml DMF. Then take by weighing 128mg (i.e. 1mmol) p-chloroaniline and 113mg (i.e. 1.1mmol) tert-butyl nitrite in the long tube type reaction flask, add 2ml DMF, inject in the Schlenk bottle with needle after stirring, system is at 80 React at ℃ for 8 hours, concentrate after the reaction, and use petroleum ether as the eluent for column chromatography purification to obtain 4-chloro-4'-methoxybiphenyl, whose structure is shown in the following formula:

[0043]

[0044] The compound is a yellow solid with a yield of 75%, and its NMR data are as follows:

[0045] 1 H NMR (400MHz, CDCl 3 )δ7.48(d, 2H, J=6.3Hz), 7.46(d, 2H, J=6.1Hz), 7.37(d, 2H, J=8.7Hz), 6.97(d, 2H, J=8.9Hz) , 3.84(s, 3H); 13 C NMR (100MHz, CDCl 3 ) δ 159.3, 139.2, 132.6, 132.4, 128.8, 127.9, 127.9, 114.3, 55.3.

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Abstract

The invention discloses a method for preparing an aromatic cross-coupled compound. In the method, under a water-free and oxygen-free condition, aromatic amine and aromatic boric acid react in an organic solvent under the action of alkyl nitrite and palladium, which serve as a catalyst, and an organophosphorus ligand to form the aromatic cross-coupled compound. Compared with the coupling of aromatic diazonium tetrafluoroborate and aromatic boric acid, the method has the advantages that: the reaction of aromatic amine for forming a diazonium salt is accomplished by one step of coupling; the diazonium salt is not needed to be separated; the reaction efficiency is high; and the cost is low. In addition, the method has the characteristics of stable substrate and wide adaptability, has high tolerance and adaptability to functional groups and can be widely used for preparing aromatic cross-coupled compounds.

Description

technical field [0001] The invention belongs to the field of organic synthesis, in particular to a preparation method of an aromatic cross-coupling compound. Background technique [0002] Palladium-catalyzed cross-coupling reactions are an important method for the synthesis of organic compounds. Classical name reactions such as Suzuki-Miyaura reaction, Sonogashira coupling reaction, etc., were reported in 1996 and 1997 for the coupling reaction using aryl diazonium salt as electrophile. In 2001, Andrus et al. reported the coupling reaction of aromatic diazonium salts and aromatic boronic acids at lower temperatures (0°C to room temperature). However, in the prior art, aryl diazonium salts are not easy to obtain, difficult to purify, and difficult to store. They are also sensitive to heat and light, and cannot react at higher temperatures, which limits the Application of coupling reactions. Contents of the invention [0003] The purpose of the present invention is to pro...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07B37/00C07C43/205C07C41/30C07C43/225C07C69/78C07C67/343C07C69/63C07C255/54C07C253/30C07D333/20
Inventor 莫凡洋邱頔江玉波张艳王剑波
Owner PEKING UNIV
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