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Method for synthesizing symmetrical urea compound

A technology for compounds and nitro compounds, applied in the preparation of organic compounds, chemical instruments and methods, preparation of urea derivatives, etc., can solve the problems of complex post-processing, high price, unfriendly environment, etc., and achieves low reaction process difficulty, The effect of simple operation and low equipment investment

Inactive Publication Date: 2013-02-13
LIAONING UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In recent years, it has been reported to use transition metals to catalyze carbon monoxide carbonylation of amine compounds, most of which are Mn, Au, Rh, Ru, etc., and the price is relatively expensive
Researcher Lu Shiwei and Dr. Wang Xiaofang from Dalian Institute of Chemical Physics proposed that selenium catalyzes the carbonylation of aniline to urea in the presence of nitrobenzene at atmospheric pressure, but the solvent used is DMF. The existence of the solvent makes the post-treatment more complicated and unfriendly to the environment.
The method of synthesizing symmetrical urea in carbon monoxide with aromatic amine as raw material under pure solvent-free normal pressure condition has not been reported

Method used

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  • Method for synthesizing symmetrical urea compound
  • Method for synthesizing symmetrical urea compound
  • Method for synthesizing symmetrical urea compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] Add aniline (200mmol), nitrobenzene (40mmol), selenium powder (2mmol), and DBU (10mmol) into a 100ml three-neck flask equipped with a stirring bar and a condenser tube, continue to feed carbon monoxide, and heat to Stir and react at 95oC for 6 hours, after cooling to room temperature, switch carbon monoxide to air and stir for 0.5-1 hour, filter, wash with water, recrystallize with ethanol, and vacuum dry to obtain the target product diphenylurea.

[0025] The product has a purity of 100% and a yield of 40% as measured by proton nuclear magnetic resonance spectroscopy.

[0026]

[0027] white crystals; 1 H NMR ((CD 3 ) 2 SO; 300MHz) 8.656(2H,s,NH)7.436-7.469 (4H, d, Ar skeleton 1, 5, 6, 10 ), 7.252-7.305 (4H, t, ArH skeleton, 2, 4, 7, 9) , 6.941-6.994 (2H, t, ArH skeleton, 3,8) .

Embodiment 2

[0029] Add aniline (200mmol), selenium powder (2mmol), and DBU (10mmol) into a 100ml three-necked flask equipped with a stirring bar and a condenser tube, continuously feed carbon monoxide and oxygen, and heat to 95oC under normal pressure to react with stirring for 6 hours , after cooling to room temperature, switch carbon monoxide and oxygen to air and stir for 0.5-1 hour, filter, wash with water, recrystallize with ethanol, and dry in vacuum to obtain the target product diphenylurea.

[0030] The purity of the product measured by proton nuclear magnetic resonance is 100%, and the separation yield is 28%.

Embodiment 3

[0032] Only change reaction temperature, other conditions are with embodiment 1, and result is as table 1.

[0033] Table 1

[0034]

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Abstract

The invention relates to a method for synthesizing a symmetrical urea compound. According to the technical scheme, the method comprises the following steps of: based on aromatic amines or fatty amines as raw materials, selenium as a catalyst, a nitro-compound or oxygen as an oxidant, and organic base as a promoter or without adding any promoter, continuously introducing carbon monoxide, and reacting at the temperature of 50 to 120 DEG C under normal pressure for 5 to 7 hours; and cooling to room temperature, stirring by replacing carbon monoxide with air, filtering, washing and performing ethanol recrystallization to obtain a target product. According to the method, the symmetrical urea compound is prepared under normal pressure without a solvent through a carbonyl reaction. The product has the selectivity of 100 percent and the separation yield of more than 20 percent. The method is easy, convenient and safe in operation and readily available in raw materials and has high environment friendliness, the catalyst and the mother solution can be recycled, and the products are easily separated.

Description

technical field [0001] The invention relates to the synthesis of symmetric urea compounds, in particular to a method for synthesizing symmetric urea by taking amine compounds as raw materials and utilizing carbon monoxide to catalyze selenium under normal pressure and reaction without solvent. Background technique [0002] Urea compounds are a class of compounds with a wide range of uses, so they play a very important role in both industrial applications and life science research. Since the molecular structure of urea contains differently substituted peptide bonds (—CONH—), most of them have biological activity, and can be used as antioxidants in gasoline, corrosion inhibitors, etc., and can be used as herbicides, insecticides, etc. in pesticides. Plant growth regulators and fungicides are important pharmaceutical intermediates in medicine. The traditional method for synthesizing ureas is to utilize the phosgene method to carbonylate amines [Bigi, F.; Maggi, R.; Sartori, G....

Claims

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Application Information

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IPC IPC(8): C07C273/18C07C275/28C07C275/34C07C275/30C07C275/26C07C275/24
CPCY02P20/584
Inventor 刘晓智耿斌张欣刘士枕全凤玲杨龙兰诗龙高扬
Owner LIAONING UNIVERSITY
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