CN-121976206-A - Electrochemical synthesis method of allyl N, O-acyl acetal and derivative thereof

Abstract

The invention discloses an electrochemical synthesis method of allyl N, O-acyl acetal and derivatives thereof, which takes N-cyclopropyl benzamide compounds and alcohol compounds as raw materials, takes a carbon electrode as an anode, takes a metal electrode as a cathode, takes tetrabutylammonium fluoride as electrolyte, and reacts at 0-40 ℃ under 8-20 mA current to obtain the allyl N, O-acyl acetal and derivatives thereof. The method has the advantages of simple and easily obtained raw materials, simple operation, good substrate applicability, green and economical property and mild reaction conditions, and opens up a new way for synthesizing the allyl N, O-acyl acetal and the derivatives thereof.

Inventors

• MA HAOJIE
• HE YUMENG
• GUO CUI
• CHENG XIAOMIN
• ZHANG YUQI

Assignees

• 延安大学

Dates

Publication Date

20260505

Application Date

20260206

Claims (5)

1. 1. An electrochemical synthesis method of allyl N, O-acyl acetal and derivatives thereof is characterized in that N-cyclopropyl benzamide compounds shown in a formula 1 are added into alcohol compounds shown in a formula 2, a carbon electrode is used as an anode, a metal electrode is used as a cathode, tetrabutylammonium fluoride is used as an electrolyte, and the allyl N, O-acyl acetal or derivatives thereof shown in a formula 3 are obtained through reaction at 0-40 ℃ under the current of 8-20 mA; Wherein R 1 represents any one of phenyl, furyl, naphthyl, C 1 ～C 6 alkyl and C 3 ～C 6 cycloalkyl, or 1-5 substituted phenyl groups selected from C 1 ～C 4 alkyl, C 1 ～C 4 alkoxy, halogen, phenyl, trifluoromethyl, nitro and cyano, and R 2 represents any one of H, C 1 ～C 4 alkyl.
2. 2. The electrochemical synthesis method of allyl N, O-acyl acetal and derivatives thereof according to claim 1, wherein the ratio of the molar amount of the N-cyclopropyl benzamide compound to the volume of the alcohol compound is 1 mmol:50-150 mL.
3. 3. The electrochemical synthesis method of allyl N, O-acyl acetal and its derivatives according to claim 1, wherein the reaction is carried out at room temperature for 1-5 hours under a current of 15-20 mA.
4. 4. The method for electrochemical synthesis of allyl N, O-acyl acetals and derivatives thereof according to claim 1, wherein the metal electrode is any one of Pt, fe and Ni electrodes.
5. 5. The electrochemical synthesis method of allyl N, O-acyl acetal and derivatives thereof according to claim 1, wherein the electrolyte is added in an amount 1-2 times the molar amount of the N-cyclopropyl benzamide compound.

Description

Electrochemical synthesis method of allyl N, O-acyl acetal and derivative thereof Technical Field The invention belongs to the technical field of organic synthesis, relates to synthesis of allyl N, O-acyl acetal and derivatives thereof, and in particular relates to synthesis of allyl N, O-acyl acetal and derivatives thereof under the action of electrocatalysis by using N-cyclopropyl benzamide compounds and alcohol compounds as raw materials. Background The allyl N, O-acyl acetal molecule contains allyl and acetal structural units, the allyl has carbon-carbon double bond, can generate various reactions such as addition, oxidation and the like, and the acetal part is connected with other groups through nitrogen atoms and oxygen atoms, so that the compound has unique chemical properties and reactivity. Allyl N, O-acyl acetals and derivatives thereof are a class of organic compounds having specific structures that play a critical role in pharmaceutical chemistry, since they not only play an important role in the biological activity of drug-related molecules, but also have the potential to be the basis for the construction of various nitrogen-containing compounds, including pederin, psymberin and zampanolide, and the like. Currently, synthesis studies on allylic N, O-acyl acetals have focused on developing innovative synthetic methods. Taking the study of the Wen group of topics (Organic Letters 2013, 16 (1), 10-13) as an example, they proposed the use of a titanium-mediated condensation reaction between an amide and acrolein. Although the method can construct the skeleton of the allyl N, O-acyl acetal, the method only obtains one allyl N, O-acyl acetal, has poor substrate applicability, adopts a metal catalyst, increases the reaction cost and pollutes the environment. As is known, the organic electrochemical synthesis is a green synthesis tool, and uses a clean reagent of traceless electron to replace a traditional oxidant and a reducing agent, so that the reactant loses and loses electrons at an electrode/solution interface to generate oxidation-reduction reaction, thereby avoiding the use of exogenous transition metal, chemical oxidant or reducing agent, reducing material consumption, reducing environmental pollution and having high atomic economic efficiency. In addition, the reaction rate and the chemical selectivity can be effectively regulated and controlled by changing the electrolysis mode or adjusting the current/voltage, and the reaction is controlled by the on/off mode. In addition, many electrochemical reactions are easy to amplify, and have certain industrialization potential. The organic chemistry synthesis condition is mild, green and sustainable, and meets the development requirement of green chemistry, so that the organic chemistry synthesis method becomes one of the most sustainable methods in modern organic chemistry. Disclosure of Invention The invention aims to provide a method for synthesizing allyl N, O-acyl acetal and derivatives thereof by electrochemical one-step, which has the advantages of low-cost and easily available raw materials, simple operation, atom economy, green and high efficiency and good substrate applicability. The electrochemical synthesis method of the allyl N, O-acyl acetal and the derivative thereof comprises the steps of adding an N-cyclopropyl benzamide compound shown in a formula 1 into an alcohol compound shown in a formula 2, taking a carbon electrode as an anode, a metal electrode as a cathode, and tetrabutylammonium fluoride as an electrolyte, and reacting at 0-40 ℃ under 8-20 mA current to obtain the allyl N, O-acyl acetal or the derivative thereof shown in the formula 3, wherein the reaction formula is as follows: Wherein R 1 represents any one of phenyl, furyl, naphthyl, C 1～C6 alkyl and C 3～C6 cycloalkyl, or 1-5 substituted phenyl groups selected from C 1～C4 alkyl, C 1～C4 alkoxy, halogen, phenyl, trifluoromethyl, nitro and cyano, and R 2 represents any one of H, C 1～C4 alkyl. In the above synthesis method, the ratio of the molar amount of the N-cyclopropylbenzamide compound to the volume of the alcohol compound is preferably 1 mmol:50 to 150 mL. In the above synthesis method, it is preferable to react at a current of 15 to 20 mA for 1 to 5 hours at room temperature. In the above synthesis method, the metal electrode is preferably any one of Pt, fe, and Ni electrodes. In the above synthesis method, the electrolyte is preferably added in an amount of 1 to 2 times the molar amount of the N-cyclopropylbenzamide compound. The beneficial effects of the invention are as follows: According to the invention, an electrochemical synthesis method is adopted, cyclopropylamide compounds and alcohol compounds are used as raw materials, a carbon electrode is used as an anode, a metal electrode is used as a cathode, tetrabutylammonium fluoride is used as an electrolyte, and the allyl N, O-acyl acetal and derivatives thereof can be synthesized in one step in a green and eff