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Method for regiodisperse nucleophilic functionalization of olefin under base catalysis

A nucleophilic function, base-catalyzed technology, applied in chemical instruments and methods, preparation of organic compounds, organic chemistry, etc., can solve the problem of no way to achieve regioselectivity, suitable for one or a few kinds of olefin substrates Narrow range and other issues, to achieve high atomic utilization, mild conditions, and reduce emissions

Pending Publication Date: 2021-08-20
NANJING UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0020] In summary, although the functionalization of olefins can be achieved by using these two methods, there are still some unavoidable problems.
Although metal-catalyzed functionalization of olefins can achieve regioselectivity, the catalysts used are relatively expensive and the reaction conditions are harsh. Not only is the range of olefin substrates tested narrow, but it can only be applied to one or a few nucleophiles
Non-metal catalyzed functionalization, although its reaction cost is low and the reaction conditions are mild, there is no way to achieve regioselectivity, and the range of olefin substrates is narrow, and it can only be applied to one or a few nucleophiles
No cost-effective, easy-to-use method for regiodispersed nucleophilic functionalization of alkenes

Method used

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  • Method for regiodisperse nucleophilic functionalization of olefin under base catalysis
  • Method for regiodisperse nucleophilic functionalization of olefin under base catalysis
  • Method for regiodisperse nucleophilic functionalization of olefin under base catalysis

Examples

Experimental program
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Effect test

Embodiment 1

[0045] A method for the regiodispersion nucleophilic functionalization of alkenes under base catalysis, comprising the steps of:

[0046] S1-1. Add 1.61 g of N-phenylbut-3-enamide, 165 mg of cesium carbonate, and 1.52 g of propanethiol in an orderly manner to a dry 50 ml round-bottomed flask containing a magnetic stirrer. The N-phenyl The molar ratio of but-3-enamide, cesium carbonate and propanethiol is 1:0.05:1;

[0047] S2-1. Insert a condensing reflux tube at the mouth of the bottle, and vigorously stir the mixture in a preheated 60°C oil bath for 6 hours, and the reaction is complete;

[0048] S3-1. Purify through a silica gel column to obtain pure N-phenyl-3-(propylthio)butyramide.

[0049] It can be seen through detection and calculation that the weight of the obtained N-phenyl-3-(propylthio)butyramide is 2.25 g, and the yield is 95%.

Embodiment 2

[0051] A method for the regiodispersion nucleophilic functionalization of alkenes under base catalysis, comprising the steps of:

[0052] S1-2. Add 1.61 g of N-phenylbut-3-enamide, 42 mg of sodium bicarbonate, 1.52 g of propanethiol, and the N-benzene The molar ratio of but-3-enamide, sodium bicarbonate and propanethiol is 1:0.05:1;

[0053] S2-2. Insert a condensing reflux tube at the mouth of the bottle, and vigorously stir the mixture in a preheated 60°C oil bath for 6 hours, and the reaction is complete;

[0054] S3-2. Purify through a silica gel column to obtain pure N-phenyl-4-(propylthio)butyramide.

[0055] It can be seen through detection and calculation that the weight of the obtained N-phenyl-4-(propylthio)butanamide is 2.13 g, and the yield is 90%.

Embodiment 3

[0057] A method for the regiodispersion nucleophilic functionalization of alkenes under base catalysis, comprising the steps of:

[0058] S1-3, add N-phenylbut-3-enamide 1.61g, cesium carbonate 165mg, 2-thiophene methyl mercaptan 2.60g orderly in the dry 50ml round bottom flask that contains magnetic stirring bar, described The molar ratio of N-phenylbut-3-enamide, cesium carbonate and 2-thiophene methyl mercaptan is 1: 0.05: 2;

[0059] S2-3. Insert a condensing reflux tube at the mouth of the bottle, and vigorously stir the mixture in a preheated 80°C oil bath for 12 hours, and the reaction is complete;

[0060] S3-3. Purify by silica gel column to obtain pure 3-((furan-2-ylmethyl)thio)-N-phenylbutyramide.

[0061] It can be seen through detection and calculation that the weight of the obtained 3-((furan-2-ylmethyl)thio)-N-phenylbutyramide is 2.64 g, and the yield is 96%.

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Abstract

The invention discloses a method for regiodisperse nucleophilic functionalization of alkene under base catalysis, which belongs to the technical field of organic chemistry and comprises the steps of placing alkene, alkali and a nucleophilic reagent in a reaction device for reflux reaction to obtain a crude product; and then carrying out low-pressure rotary evaporation to remove the solvent in the reaction liquid, and purifying to obtain a pure product, wherein the nucleophilic reagent is a nucleophilic reagent containing any one of boron, carbon, nitrogen, oxygen, silicon, phosphine and sulfur heteroatoms. The method has the characteristics of high atom utilization rate, high chemical selectivity, high regioselectivity, high yield, mild reaction conditions and simple reaction and post-treatment purification process, the range of olefin substrates is wider, the olefin substrates can react with a wide range of nucleophilic reagents, and meanwhile, the raw materials are simple and easy to obtain, the production cost is lower, the operation is simple, and the method is suitable for industrial large-scale production.

Description

technical field [0001] The invention relates to the technical field of organic chemistry, in particular to a method for regiodispersive nucleophilic functionalization of alkenes under base catalysis. Background technique [0002] Catalytic regioselective addition of alkenes to polynuclear reagents has emerged as an important synthetic route to construct carbon-heteroatom bonds, offering one of the most direct and atom-economical methods for synthesizing existing starting materials and drugs to date. So far, there is no universal method for the regioselective addition of alkenes to various nucleophiles. So far, the organic synthesis methods of nucleophilic addition of alkenes and nucleophiles can be roughly summarized into the following two categories: (A). Free radical type addition strategies carried out by various free radical initiators, which mainly generate reaction Additive products of Markovnikov rules. E.g: [0003] (1) Fadeyi, O. Org. Lett. 2015, 17, 5756-5759. ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C319/18C07C319/28C07C323/52C07D307/38C07D333/18C07F9/53
CPCC07C319/18C07C319/28C07D307/38C07D333/18C07F9/5325C07C323/52
Inventor 吴晓进赵耀陈日志
Owner NANJING UNIV OF TECH