Phosphamide derivative as well as preparation method and catalytic application thereof

A technology of phosphoramide and derivatives, which is applied in the catalytic application of phosphoramide derivatives in rearrangement reactions, and in the field of rapid and efficient preparation of phosphoramide derivatives and their one-pot method, which can solve the problems of poor catalyst activity, long reaction time, high Reaction temperature and other issues, to achieve the effect of simplified operation, less dosage, and improved synthesis yield

Active Publication Date: 2020-04-14
WANHUA CHEM GRP CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] In summary, although a variety of catalysts have been used in the rearrangement reaction with allyl alcohol and 2-alkoxypropylene, the activity of these catalysts is generally poor, requiring higher reaction temperatures and longer reaction times. to complete the reaction

Method used

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  • Phosphamide derivative as well as preparation method and catalytic application thereof
  • Phosphamide derivative as well as preparation method and catalytic application thereof
  • Phosphamide derivative as well as preparation method and catalytic application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0042] Synthesis of diphenylmethylsulfonylphosphoramidate

[0043] In nitrogen, add 4-dimethylaminopyridine (0.18g, 1.5mmol), dichloroethane (40mL), triethylamine (30.36g, 0.3mol) and phosphorus oxychloride ( 7.67g, 0.05mol), start stirring, put the three-necked bottle into a normal temperature water bath, then slowly add phenol (9.41g, 0.1mol) in dichloroethane (20mL) solution dropwise, after the dropwise addition is complete, continue stirring at room temperature for 2 hours . Finally, a solution of methanesulfonamide (4.76g, 0.05mol) in dichloroethane (20mL) was added dropwise. After the dropwise addition, the water bath was removed, and the three-neck flask was placed in an oil bath, and heated to reflux for 2 hours until the reaction was complete. Post-treatment, the reaction solution was lowered to room temperature, quenched with water, separated phases, and the organic phase was washed 2 to 3 times with 4M hydrochloric acid to remove 4-dimethylaminopyridine and triethy...

Embodiment 2

[0045] Synthesis of diphenyl ethylsulfonylphosphoramidate

[0046] In nitrogen, add 4-pyrrolidinylpyridine (0.37g, 2.5mmol), dichloroethane (40mL), triethylamine (30.36g, 0.3mol) and phosphorus oxychloride ( 7.67g, 0.05mol), start stirring, put the three-neck bottle into a normal temperature water bath, then slowly add phenol (9.65g, 0.1025mol) in dichloroethane (20mL) solution dropwise, after the addition is complete, continue stirring at room temperature for 2 hours . Finally, a solution of ethanesulfonamide (5.46 g, 0.05 mol) in dichloroethane (20 mL) was added dropwise. After the dropwise addition, the water bath was removed, and the three-necked flask was placed in an oil bath, and heated to reflux for 2 hours until the reaction was complete. Post-treatment, the reaction solution was lowered to room temperature, quenched with water, phase separation, the organic phase was washed 2 to 3 times with 4M hydrochloric acid to remove 4-pyrrolidinylpyridine and triethylamine in ...

Embodiment 3

[0048] Synthesis of diphenyl tosylphosphoramidate

[0049] In nitrogen, add 4-dimethylaminopyridine (0.18g, 1.5mmol), dichloroethane (40mL), diisopropylethylamine (45.24g, 0.35mol) and three Phosphorus oxychloride (7.67g, 0.05mol), start stirring, put the three-necked bottle into a normal temperature water bath, then slowly add dropwise a solution of phenol (9.41g, 0.1mol) in dichloroethane (20mL), after the dropwise addition is complete, continue to The reaction was stirred for 2 hours. Finally, a dichloroethane (20 mL) solution of p-toluenesulfonamide (8.56 g, 0.05 mol) was added dropwise. After the dropwise addition, the water bath was removed, and the three-necked flask was placed in an oil bath, and heated to reflux for 2 hours until the reaction was complete. Post-treatment, the reaction solution was lowered to room temperature, quenched with water, separated phases, and the organic phase was washed 2 to 3 times with 4M hydrochloric acid to remove 4-dimethylaminopyridin...

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Abstract

The invention provides a phosphamide derivative, a preparation method thereof and application of the phosphamide derivative in catalytic rearrangement reaction, the structural formula of the phosphamide is shown in the specification, R1 is independently selected from aryl and heteroaryl, and R2 is selected from alkyl, alkenyl, alkynyl, aryl and heteroaryl. The preparation method of the phosphamidecompound is obtained by one-pot reaction of phosphorus oxychloride, phenol and sulfonamide, and compared with a known literature report method, the preparation method has the advantages that the operation is simplified, and the synthesis yield is increased. The phosphamide compound is easily dissolved in an organic solvent, has very strong acidity, can be used for catalyzing rearrangement reaction, and is successfully applied to the rearrangement reaction between allyl alcohol and 2-alkoxy propylene to quickly and efficiently synthesize a gamma, delta-unsaturated ketone product.

Description

technical field [0001] The invention belongs to the fields of fine chemicals and flavors and fragrances, and in particular relates to a phosphoramide derivative and a one-pot rapid and efficient preparation method thereof, and the catalytic application of the obtained phosphoramide derivative in a rearrangement reaction. Background technique [0002] γ, δ-unsaturated ketones widely exist in natural products and fine chemicals, such as methyl heptenone, which has a fresh fruity aroma and is a food flavor allowed by the national standard. At the same time, methyl heptenone is still important Synthetic intermediates can be used to synthesize fine chemicals with great economic value such as linalool, linalyl acetate, vitamin A and vitamin E. Geranyl acetone, farnesyl acetone, etc. are also typical γ, δ-unsaturated ketones, which also have very important applications. [0003] As early as 1967, Saucy et al. found that in the presence of a catalytic amount of phosphoric acid, all...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F9/24B01J31/02C07C45/51C07C49/203
CPCC07F9/2483C07F9/242B01J31/0271C07C45/513C07C49/203
Inventor 沈稳黄文学张永振宋军伟王延斌杨宗龙
Owner WANHUA CHEM GRP CO LTD
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