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Method of preparing 1,2,4-triphenylbenzene in supercritical CO2

A carbon dioxide, triphenylbenzene technology, applied in chemical instruments and methods, organic chemistry, hydrocarbons, etc., can solve the problems of few reports on alkyne cycloaddition, high reaction temperature, high pressure, long reaction time, etc. , to achieve the effect of high yield, short reaction time and high selectivity

Inactive Publication Date: 2016-06-15
INNER MONGOLIA UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

In recent years, the use of supercritical carbon dioxide as a reaction medium has penetrated into almost all basic organic reactions, but there are relatively few reports on the research work on alkyne cycloaddition
At present, the reported alkyne trimerization reaction in supercritical carbon dioxide uses relatively expensive catalysts, and requires the use of co-solvents. The reaction temperature and pressure are also relatively high, and the required reaction time is also relatively long.

Method used

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  • Method of preparing 1,2,4-triphenylbenzene in supercritical CO2

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Add 0.2ml, 1.82mmol of phenylacetylene and 47mg, 0.14mmol of dicobalt octacarbonyl into a 50ml reaction vessel lined with polytetrafluoroethylene, and put in a suitable magnet. Use CO 2 The air was replaced twice, the reactor was preheated in an oil bath at 50°C for 20 minutes, and carbon dioxide was pumped in to 8MPa. Turn on the stirring, raise the temperature of the reactor to 80°C, and react for 8 hours.

[0029] After the reaction, the reactor was cooled to room temperature. Slowly vent the carbon dioxide to atmospheric pressure. The autoclave was washed with dichloromethane, and the entire reaction mixture was collected into a 100 ml round bottom flask. The excess solvent dichloromethane was distilled off under reduced pressure to obtain a crude product. The crude product was separated by column chromatography (200-300 mesh silica gel) using petroleum ether and dichloromethane (V / V=2:1) ​​as the eluent to obtain white solids 1, 2, 4 with a purity of more than ...

Embodiment 2

[0031] Add 0.2ml, 1.82mmol of phenylacetylene and 47mg, 0.14mmol of dicobalt octacarbonyl into a 50ml reaction vessel lined with polytetrafluoroethylene, and put in a suitable magnet. Use CO 2 The air was replaced twice, the reactor was placed in an oil bath at 50°C to preheat for 20 minutes, and carbon dioxide was pumped in to 10MPa. Turn on the stirring, raise the temperature of the reactor to 100°C, and react for 10 hours.

[0032] The post-treatment process was the same as in Example 1 to obtain white solid 1,2,4-triphenylbenzene with a purity greater than 99%, and the isolated yield was 70%.

Embodiment 3

[0034] Add 0.2ml, 1.82mmol of phenylacetylene and 47mg, 0.14mmol of dicobalt octacarbonyl into a 50ml reaction vessel lined with polytetrafluoroethylene, and put in a suitable magnet. Use CO 2 Replace the air twice, preheat the reactor, and pump carbon dioxide to 12MPa. Turn on the stirring, raise the temperature of the reactor to 120°C, and react for 12 hours.

[0035] The post-treatment process was the same as in Example 1, and a white solid 1,2,4-triphenylbenzene with a purity greater than 99% was obtained with an isolated yield of 60%.

[0036] Identification of 1,2,4-triphenylbenzene:

[0037] Infrared spectrum data IR(KBr)v / cm -1 : 3080, 3054, 3025 (v CH , Ph), 1599, 1472, 1450 (v C＝C , Ph), 759, 697 (γ CH , Ph).

[0038] NMR data: 1 HNMR (500MHz, CDCl 3 , TMS): δ7.66-7.16 (m, 18H, Ph); 13 CNMR (125MHz, CDCl 3 , TMS): δ140.44, 140.06, 139.94, 139.54, 139.32, 138.50 (centeralPh), 130.07, 128.86, 128.83, 128.38, 127.79, 126.89, 126.86, 126.39, 126.10, 125.48, 12...

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Abstract

A method of preparing 1,2,4-triphenylbenzene in supercritical CO2 includes the following steps: 1) successively adding a raw material, phenylacetylene, and a catalyst, octacarbonyl dicobalt, into a reaction kettle, and feeding CO2 gas to dispel the air in the kettle; 2) pre-heating the reaction kettle and pumping liquid CO2 thereinto, heating the reaction kettle and starting stirring to increase the temperature in the kettle, and continuously stirring the materials until the reaction is finished; 3) cooling the reaction kettle to room temperature, slowly release the CO2, decompressing the reactor to normal pressure, and fully washing the reaction kettle with dichloromethane; and 4) concentrating, separating and purifying the wash liquid to prepare the product. With the low-cost octacarbonyl dicobalt as the catalyst, the method is carried out in a green solvent supercritical CO2 without any organic solvent as additives, and the product, 1,2,4-triphenylbenzene, can be prepared at high selectivity. The method is short in reaction time, is low in reaction temperature and pressure and is high in yield.

Description

technical field [0001] The invention relates to the technical field of organic synthesis, in particular to a method for preparing 1,2,4-triphenylbenzene in supercritical carbon dioxide. Background technique [0002] Benzene and its derivatives are important chemical raw materials, and the transition metal-catalyzed [2+2+2] cycloaddition reaction of alkynes is an important method for the synthesis of multi-substituted benzene derivatives. This method can simultaneously construct multiple C-C bonds through a one-step reaction, and convert linear compounds into cyclic compounds. All are well tolerated. Most of these reactions are carried out in organic solvents such as tetrahydrofuran, dioxane, and benzene. Traditional organic solvents are volatile and highly toxic, which will pollute the environment and do not conform to the current development path of green chemistry. [0003] Supercritical carbon dioxide fluid is cheap, non-toxic, non-combustible, easy to separate, recycla...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C2/48C07C15/14
CPCC07C2/48C07C15/14Y02P20/141Y02P20/52Y02P20/54
Inventor 王亚琦尹强索全伶韩利民
Owner INNER MONGOLIA UNIV OF TECH
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