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Compound and application thereof

A compound and hydrogenation reaction technology, which is applied in the preparation of rhodium organic compounds, platinum group organic compounds, organic compounds, etc., can solve the problems of low catalytic efficiency, long reaction time, and slow rate-determining steps, so as to improve catalytic efficiency, The effect of saving reaction time and reducing reaction cost

Inactive Publication Date: 2017-11-24
SOUTH UNIVERSITY OF SCIENCE AND TECHNOLOGY OF CHINA
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] The technical problem to be solved by the present invention is to provide a diphosphorus ligand compound of metal rhodium, which can be applied in the field of catalysis, especially to catalyze the hydrogenation reaction of carbon dioxide, and can overcome the problem that the catalyst in the prior art is difficult to recycle and catalyze the hydrogenation reduction of carbon dioxide. problems such as slow step speed, long reaction time, and low catalytic efficiency

Method used

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Examples

Experimental program
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Effect test

Embodiment 1

[0016] Embodiment 1: Catalyst Rh (PCH 2 CF 2 CH 2 P) 2 ] + preparation of

[0017] First, 1,2-dimethoxyfluoromethane was dissolved in glacial acetic acid. Under cooling in an ice-water bath, add a solution of bromine and a small amount of glacial acetic acid into the reaction flask dropwise through a constant-pressure dropping funnel within 3 hours. After reacting at room temperature for 24h, the reaction solution was poured into a 100ml ice-water bath and washed with CH 2 CI 2 Extract three times and separate the organic layer. The organic layer was washed with water and saturated brine, anhydrous MgSO 4 Dry and filter the filtrate to remove CH 2 CI 2 Afterwards, it was distilled under reduced pressure, and the fraction at 178°C and 1 333 Pa was collected to obtain 4-bromo-1,2-dimethoxymethane as a colorless liquid. Under nitrogen protection, 4-bromo-1,2-dimethoxymethane and THF dehydrated and deoxygenated were added into a dry two-necked flask. Slowly add 5.2ml n...

Embodiment 2

[0018] Embodiment 2: Rh (PCH 2 CF 2 CH 2 P) 2 ] + Catalytic carbon dioxide hydrogenation experiment

[0019] The reaction conditions are: solvent: 40mL ethanol; base (Verkade's base): 0.5mmol Catalyst: 0.1mmol Rh(PCH 2 CF 2 CH 2 P) 2 ] + ; Reaction temperature: 85°C; Reaction pressure: H 2 : 4.0MPa; Reaction time 1h. After completion of the reaction, 30.10 mmol of acetic acid was produced, and the conversion number was 1405.

[0020] Catalyst Rh (PCH) prepared in embodiment 1 2 CF 2 CH 2 P) 2 ] + catalytic CO 2 During the hydrogenation reaction, the reaction energy barrier can be reduced to 18.0kcal / mol, which catalyzes CO 2 The energy barrier diagram of the hydrogenation reaction is shown in figure 1 As shown, the electron-withdrawing group on the catalyst ligand leads to the lack of electrons in the metal center, resulting in a decrease in the binding electron ability of hydrogen on the metal, so it is easily taken away by the base, so the activation ener...

Embodiment 3

[0024] Embodiment 3: Catalyst Rh (PCH 2 CH 2 CF 2 CH 2 CH 2 P) 2 ] + preparation of

[0025]First, 1,2-dimethoxyfluoroethane was dissolved in glacial acetic acid. Under cooling in an ice-water bath, add a solution of bromine and a small amount of glacial acetic acid into the reaction flask dropwise through a constant-pressure dropping funnel within 4 hours. After reacting at room temperature for 24h, the reaction solution was poured into a 100ml ice-water bath and washed with CH 2 CI 2 Extract three times and separate the organic layer. The organic layer was washed with water and saturated brine, anhydrous MgSO 4 Dry and filter the filtrate to remove CH 2 CI 2 Afterwards, it was distilled under reduced pressure, and the fraction at 178°C and 1 333 Pa was collected to obtain 4-bromo-1,2-dimethoxyethane as a colorless liquid. Under nitrogen protection, 4-bromo-1,2-dimethoxyethane and THF dehydrated and deoxygenated were added into a dry two-necked flask. Slowly add...

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Abstract

The invention discloses a double-phosphorus coordination compound of metal rhodium. The double-phosphorus coordination compound of the rhodium can be applied to catalysis of a carbon dioxide hydrogenation reaction, a strong sigma electron-drawing group is arranged on a double-phosphorus ligand, and the electron cloud of the rhodium can be increased, so that the speed of the step of catalyzing carbon dioxide hydrogenation reduction by the double-phosphorus coordination compound of the rhodium is increased, the catalytic efficiency is improved, and the reaction time is shortened.

Description

technical field [0001] The invention relates to a compound and its application, in particular to the application of the compound in catalytic carbon dioxide hydrogenation reaction. Background technique [0002] At present, human beings are facing severe energy and environmental problems. Combustion of fossil fuels as the main energy structure produces CO 2 Emissions into the atmosphere aggravate the greenhouse effect and have negative impacts on ecology, economy, and society. Therefore, how to effectively slow down the emission of carbon dioxide is particularly important. CO 2 Absorption and storage technologies are the best way to mitigate CO at scale 2 One of the means of emission, but in the process of desorption, compression, transportation and storage, energy is inevitably consumed. At the same time, CO 2 As a non-toxic, harmless, cheap and easy-to-obtain carbon source, it can replace traditional carbonylation reagents to synthesize high value-added chemical produc...

Claims

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Application Information

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IPC IPC(8): C07F15/00B01J31/24C07C51/00C07C53/02
CPCB01J31/24B01J2231/625B01J2531/0213B01J2531/822C07C51/00C07F15/008C07C53/02
Inventor 党丽倪绍飞
Owner SOUTH UNIVERSITY OF SCIENCE AND TECHNOLOGY OF CHINA
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