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Visible light catalyzed saturated carbon-hydrogen bond direct oxidizing method

一种碳氢键、可见光的技术，应用在化学仪器和方法、有机化学方法、有机氧化等方向，能够解决活性低、性质不太稳定过氧化物等问题，达到反应效率高、性质稳定、成本低廉的效果

Active Publication Date: 2017-06-13
SHANGHAI TECH UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Due to the high bond energy of this type of carbon-hydrogen bond, which makes its activity low, the existing methods usually require noble transition metal catalysis, and use peroxides with less stable properties, and usually require higher temperatures and pressures

Method used

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  • Visible light catalyzed saturated carbon-hydrogen bond direct oxidizing method
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  • Visible light catalyzed saturated carbon-hydrogen bond direct oxidizing method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] A method for direct oxidation of saturated carbon-hydrogen bonds catalyzed by visible light, the specific steps are:

[0022] Into 2 mL of ethylbenzene (106 mg, 1 mmol) in acetonitrile solution, bubbling oxygen for 20 min to oxygen saturation, adding 1 mol% cerium complex cerium trichloride (2.4 mg, 0.01 mmol) and 2 mol% additive tetrabutylammonium chloride (5.5mg, 0.02mmol), at room temperature (25°C), under the conditions of blue LED light (wavelength 380nm-550nm), make ethylbenzene and oxygen under the action of cerium complexes and additives Carry out reaction 2h, make the carbon-hydrogen bond oxidation of ethylbenzene obtain oxidation product acetophenone, reaction equation is as follows:

[0023]

[0024] After stopping the reaction, dichloromethane was added to dilute, washed with water and saturated brine successively, dried, and separated by column chromatography to obtain the product acetophenone (108mg, 90% yield), and the data characterized by H NMR were ...

Embodiment 2

[0026] A method for direct oxidation of saturated carbon-hydrogen bonds catalyzed by visible light, the specific steps are:

[0027] Into 2 mL of cyclohexane (85 mg, 1 mmol) in acetonitrile solution, oxygen was passed through for 20 min to oxygen saturation, and 1 mol% of cerium complex cerium trichloride (2.4 mg, 0.01 mmol) and 2 mol% of additive tetrabutyl chloride were added After ammonium (5.5mg, 0.02mmol), at room temperature (25°C), under the condition of blue LED light (wavelength 380nm-550nm), make cyclohexane and oxygen in the complex of cerium and additives Under the effect, carry out reaction 5h, make the carbon-hydrogen bond oxidation of cyclohexane obtain oxidation product cyclohexanol, and reaction equation is as follows:

[0028]

[0029] After stopping the reaction, dichloromethane was added to dilute, washed with water and saturated brine successively, dried, and separated by column chromatography to obtain the product cyclohexanol (88 mg, 88% yield). The ...

Embodiment 3

[0031] A method for direct oxidation of saturated carbon-hydrogen bonds catalyzed by visible light, the specific steps are:

[0032] Oxygen was passed through 2 mL of cyclohexane (85 mg, 1 mmol) in acetonitrile solution for 20 min to oxygen saturation, and 2 mol % cerium complex cerium nitrate (8.7 mg, 0.02 mmol) and 4 mol % additive tetrabutylammonium bromide ( 12.9mg, 0.04mmol), at room temperature (25°C), under the condition of blue LED light (wavelength 380nm-550nm) irradiation, make cyclohexane and oxygen under the action of cerium complexes and additives Carry out reaction 48h, make the carbon-hydrogen bond oxidation of cyclohexane obtain oxidation product cyclohexanone, and reaction equation is as follows:

[0033]

[0034] After stopping the reaction, dichloromethane was added to dilute, washed with water and saturated brine successively, dried, and separated by column chromatography to obtain the product cyclohexanone (80 mg, 82% yield). The data characterized by ...

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Abstract

The invention provides a visible light catalyzed saturated carbon-hydrogen bond direct oxidizing method which is characterized by comprising the following step of performing a reaction on an organic compound and an oxidizing reagent in the presence of a cerium complex in a visible light irradiating condition to oxidize a saturated carbon-hydrogen bond of the organic compound to obtain an oxidized product. According to the method provided by the invention, the reaction is only performed at room temperature, so that the catalytic efficiency is high; energy required by an activating reaction is provided by means of visible light, so that the method is a more mild and green activating mode; and meanwhile, the used catalyst is low in cost, and the used oxidizing reagent is more stable in property, the industrial utilization cost is low, and the practicality of a catalytic system is high; meanwhile, pollution caused by heavy transition metals, peroxides and the like can be avoided.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a visible-light catalyzed method for efficiently oxidizing saturated carbon-hydrogen bonds in organic compounds by utilizing cerium complexes. Background technique [0002] The direct oxidation of carbon-hydrogen bonds in organic compounds has always been a research hotspot in the field of catalysis. This synthetic strategy can directly construct the widely existing carbon-hydrogen bonds into expected functional groups (hydroxyl, carbonyl, amine, etc.), and can use cheap starting materials in the synthesis of high value-added drug molecules or their intermediates, significantly Shortening the synthetic route has broad application prospects in industry. Due to the high bond energy of this type of carbon-hydrogen bond, which makes its activity low, the existing methods usually require noble transition metal catalysis, and use peroxides with less stable properties, and ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C49/78C07C45/36C07C35/08C07C29/50C07C49/403C07C45/33C07C22/04C07C17/14C07C281/02C07C69/63C07C67/307C07C69/716C07C67/313C07C49/67C07C17/10C07C23/18
CPCC07C17/10C07C17/14C07C29/50C07C45/33C07C45/36C07C67/307C07C67/313C07C281/02C07C49/78C07C35/08C07C49/403C07C22/04C07C69/63C07C69/716C07C49/67C07C23/18C07B33/00
Inventor 左智伟胡安华
Owner SHANGHAI TECH UNIV
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