Method using manganese dioxide to catalyze trifluoromethylation of arenes or heterocyclic arenes

A technology of trifluoromethylation and heterocyclic aromatic hydrocarbons, which is applied in the field of catalytic organic synthesis, can solve the problems of high pollution and high cost, and achieve the effect of simple reaction process, cost reduction and large-scale industrial production

Inactive Publication Date: 2017-06-13
FUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] The object of the present invention is to provide a kind of MnO 2 An organic synthesis method that catalyzes the trifluoromethylation of aromatic hydrocarbons or heterocyclic aromatic hydrocarbons. The system is simple, the reaction conditions are mild, and the cost is low, which solves the problems of high pollution and high cost in the current industrial preparation.

Method used

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  • Method using manganese dioxide to catalyze trifluoromethylation of arenes or heterocyclic arenes
  • Method using manganese dioxide to catalyze trifluoromethylation of arenes or heterocyclic arenes
  • Method using manganese dioxide to catalyze trifluoromethylation of arenes or heterocyclic arenes

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Example 1 (The substrate is benzene as an example)

[0027] (1) Weigh 0.2mmol of manganese dioxide as the catalyst and 0.5mmol of sodium trifluoromethanesulfinate as the source of trifluoromethyl. After mixing in the reactor, add 1mL of acetonitrile as solvent and 0.5mL of reactant benzene, and seal Parafilm

[0028] (2) After placing the reactor in an ultrasonic cleaning machine with 50KHz ultrasonic treatment for 30s, connect the reactor to an air balloon and place it in a heat-collecting thermostatic magnetic stirrer at 50°C for 24h;

[0029] (3) Centrifuge after the reaction is complete, and pass the supernatant through the column to obtain pure trifluorotoluene and then measure 19 F NMR spectrum (see figure 1 ).

Embodiment 2

[0030] Example 2 (The substrate is benzene as an example)

[0031] (1) Weigh 0.2mmol of manganese dioxide as the catalyst and 0.5mmol of sodium trifluoromethanesulfinate as the source of trifluoromethyl. After mixing in the reactor, add 1mL of acetonitrile as the solvent and 0.5mL of benzene, and seal with the sealing film ;

[0032] (2) Put the reactor in an ultrasonic cleaning machine after 50KHz ultrasonic treatment for 30s, connect the reactor to an air balloon, and place it in a heat-collecting thermostatic magnetic stirrer for 24 hours at 25℃, 40℃, and 50℃. ,60℃;

[0033] (3) Centrifuge after the reaction is complete, and detect the supernatant by GC (product volume has been calibrated);

[0034] The result is displayed (see figure 2 ), as the reaction temperature increases, the yield increases gradually, but not infinitely, reaching the highest at 50°C.

Embodiment 3

[0036] (1) Weigh 10-20mg sodium trifluoromethanesulfinate as 1, 2 respectively. The thermogravimetric test results are shown in air and nitrogen atmosphere image 3 Curve in 1,2;

[0037] (2) Weigh a mixture of 10 mg of sodium trifluoromethanesulfinate and 10 mg of manganese dioxide for thermogravimetric test under air atmosphere, the results are shown in image 3 Curve 3 in

[0038] (3) The test results show that the decomposition temperature of trifluoromethyl source sodium trifluoromethanesulfinate is 150-190℃, which is much higher than the required temperature of 50℃ for the reaction.

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Abstract

The invention discloses a method using manganese dioxide to catalyze trifluoromethylation of arenes or heterocyclic arenes. According to the method, the manganese dioxide serves as a catalyst, sodium trifluoromethanesulfinate serves as a source of trifluoromethyl groups, acetonitrile serves as a solvent, the trifluoromethylation of the arenes or the heterocyclic arenes is conducted at the low-temperature atmospheric condition. According to the method, the materials are cheap and easy to obtain, the reaction condition is mild, environmental pollution is low, products are easy to separate, the situation is avoided that highly-corrosive and highly-toxic fluorinated reagents are used in current industrial trifluoromethylation reactions, and the method has potential industrial application value.

Description

Technical field [0001] The invention belongs to the technical field of catalytic organic synthesis, and specifically relates to a MnO 2 Catalytic method for trifluoromethylation of aromatic or heterocyclic aromatic hydrocarbons. Background technique [0002] The use of heterogeneous catalysts has attracted much attention due to the problems of difficult recovery of the catalyst, high cost of chemicals, and introduction of impurities when using homogeneous catalysts. [0003] Manganese dioxide is a metallic manganese compound with brown-black or black color. It is a positive tetravalent in an intermediate valence state. It has both oxidizing and reducing properties, and is easily oxidized to hexavalent manganese under alkaline conditions. Under acidic conditions, it can be reduced to divalent manganese. Manganese dioxide is an environment-friendly, cheap and easy-to-obtain transition metal oxide. It has unique physical and chemical properties, which make it an important position in...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C17/32C07C22/08
CPCC07C17/32C07C22/08
Inventor 员汝胜邵鸿鸽李铭铭王乐乐
Owner FUZHOU UNIV
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