Method for synthesizing asymmetric disubstituted urea through catalytic oxidation and carbonylation

A disubstituted urea, catalytic oxidation technology, applied in the direction of organic chemical methods, chemical instruments and methods, and the preparation of organic compounds, can solve the problems of poor selectivity of disubstituted urea, difficult post-processing of products, high toxicity of raw materials, etc., to achieve selective High reactivity, wide range of oxidant sources, simple and easy synthesis method

Active Publication Date: 2017-12-01
NANJING NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] The raw materials of the traditional method of synthesizing urea are highly toxic, and a large amount of highly corrosive and polluting chlorine-containing wastes are generated during the reaction, causing serious corrosion of equipment and difficulties in post-processing of products. At the same time, the activity of isocyanate is ve

Method used

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  • Method for synthesizing asymmetric disubstituted urea through catalytic oxidation and carbonylation
  • Method for synthesizing asymmetric disubstituted urea through catalytic oxidation and carbonylation
  • Method for synthesizing asymmetric disubstituted urea through catalytic oxidation and carbonylation

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Experimental program
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Embodiment 1

[0034] Compound 1: Palladium acetate (0.005mmol), amine 1a (0.5mmol), amine 1a' (0.75mmol), triethylamine (0.1mmol), sodium iodide (0.25mmol) and polyethylene glycol were sequentially added to a 25mL reaction flask. Alcohol-400 (2.0g), and introduce an atmospheric pressure of carbon monoxide and oxygen (1:1), react at 25°C for 6h. Cool to room temperature, extract, evaporate the solvent under reduced pressure, and separate by column chromatography to obtain a yield of 81%.

Embodiment 2

[0036]Compound 2: Add palladium chloride (0.005mmol), amine 1b (0.5mmol), amine 1b' (1.0mmol), potassium phosphate (0.1mmol), potassium iodide (0.25mmol) and polyethylene glycol- 400 (2.0g), and introduce an atmospheric pressure of carbon monoxide and oxygen (1:1), and react at 80°C for 12h. Cool to room temperature, extract, evaporate the solvent under reduced pressure, and separate by column chromatography to obtain a yield of 72%.

Embodiment 3

[0038] Compound 3: Add palladium carbon (0.01mmol), amine 1c (0.5mmol), amine 1c' (1.0mmol), triethylenediamine (0.1mmol), sodium iodide (0.25mmol) and polyethylene Diol-600 (2.0g) was introduced into an atmospheric pressure of carbon monoxide and oxygen (1:1), and reacted at 80°C for 12h. Cool to room temperature, extract, evaporate the solvent under reduced pressure, and separate by column chromatography to obtain a yield of 88%.

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Abstract

The invention discloses a novel method for directly synthesizing asymmetric disubstituted urea compounds. The method comprises the step of adding a palladium catalyst into a solvent polyethylene glycol or a polyethylene glycol water solution under the action of alkali, an iodine compound and an oxidant so as to catalyze direct cross coupling reaction of primary amine and carbon monoxide, so as to prepare the asymmetric disubstituted urea compounds. The method for preparing the asymmetric disubstituted urea compounds through the coupling reaction has the advantages that the catalyst is wide in source and environment-friendly; a substrate is wide in source, cheap and easy to process; a carbonyl is stable in source and cheap and does not generate waste; a ligand is not required in the reaction, and the reaction activity is good; reaction conditions are mild, and the reaction selectivity is high; the substrate has good functional group consistency and is wide in application range; and a reaction medium is environment-friendly and can be circularly recycled. The separation yield of a target product can reach up to about 97% under optimized reaction conditions.

Description

technical field [0001] The invention belongs to the field of catalytic synthesis technology and fine chemical synthesis, more specifically, relates to a synthetic method for catalytically synthesizing asymmetric disubstituted urea compounds, which is a method of directly using primary amine compounds, carbon monoxide as carbonyl source and air Or oxygen as an oxidant to cross-coupling to prepare asymmetric disubstituted urea. Background technique [0002] The skeleton structure of unsymmetrical disubstituted urea is widely found in natural products, insecticides, herbicides and medicines, and its synthetic methods have attracted extensive attention because of its wide range of pharmacological and physiological activities. The traditional method of synthesizing asymmetric disubstituted urea is the isocyanate method based on phosgene: although the yield of this reaction is high, this method is due to the high toxicity of raw materials, and a large amount of highly corrosive an...

Claims

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Application Information

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IPC IPC(8): C07B43/00C07C273/18C07C275/30C07C275/36C07C275/38C07C275/40C07C275/26C07C275/24C07C315/04C07C317/42C07C319/20C07C323/36C07D207/34C07D209/08C07D209/40C07D213/643C07D213/75C07D263/48C07D277/48C07D295/192C07D307/82C07D333/36C07D403/12C07D409/12
CPCC07B43/00C07C273/1809C07C315/04C07C319/20C07D207/34C07D209/08C07D209/40C07D213/643C07D213/75C07D263/48C07D277/48C07D295/192C07D307/82C07D333/36C07D403/12C07D409/12C07C275/30C07C275/36C07C275/38C07C275/40C07C323/36C07C317/42C07C275/26C07C275/24
Inventor 韩维杜宏艳王天娇原肖荣
Owner NANJING NORMAL UNIVERSITY
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