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Method used for synthesizing heterocycle substituted multi-fluoro arene through defluorination and hydrogenation and controlled by phosphine ligand

A phosphine ligand and hydrogenation technology, which is applied in the chemical industry and can solve problems such as unstable hydrogenation of intermediates

Active Publication Date: 2016-09-07
JIANGNAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Although this method provides an effective and simple way to synthesize less fluorinated aromatics, the method he showed is only limited to the synthesis of monofluorodefluorination products, which may be due to the instability of the intermediate hydrogenation of the metal catalyst they selected. reason

Method used

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  • Method used for synthesizing heterocycle substituted multi-fluoro arene through defluorination and hydrogenation and controlled by phosphine ligand
  • Method used for synthesizing heterocycle substituted multi-fluoro arene through defluorination and hydrogenation and controlled by phosphine ligand
  • Method used for synthesizing heterocycle substituted multi-fluoro arene through defluorination and hydrogenation and controlled by phosphine ligand

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Embodiment 1

[0034] For rhodium catalyzed dehydrofluorination, the inventor proposes conjecture ( figure 1 ): ethanol is used as a hydrogen source, and the hydrogen on the ethanol is transferred to metal rhodium through a hydrogenation reaction to form a metal rhodium hydride. The rhodium hydride is then used as a catalytic intermediate for dehydrofluorination to complete the dehydrofluorination reaction. During this period, through the control of ligands, monofluorodehydrofluorination products or bisdehydrofluorination products are selectively obtained.

[0035] Therefore, the rhodium complex ([Cp*RhCl 2 ] 2 , [(COD)RhCl] 2 ) as a catalyst to explore the optimal reaction conditions for dehydrofluorination. 2-Perfluorophenylpyridine as a model substrate for the reaction. Pinacol diboronic acid ester was added to the reaction system as a fluorine atom capture agent. Ethanol was used as the reaction solution, the reaction temperature was set at 90° C., and the reaction time was 12 h. ...

Embodiment 2

[0041] Example 2: Mono dehydrofluorination

[0042] After exploring the reaction conditions, the inventors investigated the applicability of the reaction using the conditions.

[0043] Firstly, a series of nitrogen-containing heterocyclic substituted polyfluorinated aromatic hydrocarbons were synthesized, such as figure 2 shown.

[0044] Using DPPE as a ligand, the monodehydrofluorination reaction was studied ( image 3 ). Wherein the reaction conditions are as follows: Compound 1 (0.25mmol), [(COD)RhCl] 2 (0.0125mmol), DPPE (0.025mmol), AgBF 4 (0.025mmol), B 2 pin 2 (0.5mmol), KOAc (0.5mmol), solvent (toluene:ethanol=4:1) 2.0mL.

[0045] It was found that the substrates substituted with perfluorobenzene could be separated to obtain the target product in higher yield ( Figure 4 3a, 3a', 3b, 3c, 3g, 3h, 3k, 3i). Among them, 3b and 3c, in the presence of C-X (C, F) at the ortho position of the pyridine ring, the reaction still maintains a good yield. When the ortho p...

Embodiment 3

[0046] Example 3: Double dehydrofluorination

[0047] Using Xant-phos as the phosphine ligand, the applicability of this method to double defluorination reactions was investigated ( Figure 5 ). Wherein the reaction conditions are as follows: Compound 1 (0.25mmol), [(COD)RhCl] 2 (0.0125mmol), Xant-phos(0.025mmol), AgBF 4 (0.025mmol), B 2 pin 2 (0.5mmol), KOAc (0.5mmol), solvent (toluene:ethanol=4:1) 2.0mL.

[0048] The reaction is similar to that of monodehydrofluorination. It is worth mentioning that when using image 3 When the monofluorinated defluorinated product (compound 3) in is used as a raw material to obtain double defluorinated product, the yield ratio Figure 6 The listed yields are slightly higher.

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Abstract

The invention discloses a method for synthesizing heterocycle substituted multi-fluoro arene through defluorination and hydrogenation and controlled by a phosphine ligand, and belongs to the technical field of chemical engineering. Cheap heterocycle substituted perfluoroarene is used as a raw material, ethyl alcohol high in hydrogen content and nontoxic is used for replacing traditional silane as a hydrogen source, and a monofluoro substitution product or a difluoro substitution product is selectively obtained through phosphine ligand control. A potential novel raw material is provided for the field of modern industry by the method, and the leading-edge research strategy in the field is developed.

Description

technical field [0001] The invention relates to a method for synthesizing heterocyclic substituted polyfluorinated aromatic hydrocarbons through defluorination controlled by a phosphine ligand, and belongs to the technical field of chemical industry. Background technique [0002] Over the past few decades, scientists have shown that fluoroorganic compounds play an increasingly important role in many fields of chemistry and modern life. However, as the demand for fluorine-containing substances is increasing, the method for synthesizing organic fluorides is becoming more and more difficult to meet. Some simple fluoroaromatic compounds have been synthesized on a large scale. However, the large-scale synthesis of fluorine-substituted arene compounds at special positions is limited by the nature of fluorine-containing blocks, and it is extremely dependent on finding a suitable synthesis method. It has always been a good way to synthesize less fluorinated aromatics from perfluor...

Claims

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Application Information

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IPC IPC(8): C07D213/26C07D213/61C07D213/30C07D213/38C07D215/12C07D215/14C07D241/42C09K11/06
CPCC07D213/26C07D213/30C07D213/38C07D213/61C07D215/12C07D215/14C07D241/42C09K11/06C09K2211/1029C09K2211/1044
Inventor 丁玉强陈建平黄东阳
Owner JIANGNAN UNIV
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