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Method for photo-induced decarboxylation alkylation of alkyl-active carboxylic ester

A technology of alkyl active carboxylic acid, ester decarboxylation, applied in chemical instruments and methods, preparation of organic compounds, organic chemistry and other directions, can solve the problems of complex synthesis, limited use, expensive photosensitizers, etc. Wide range of compounds and mild reaction conditions

Pending Publication Date: 2022-02-25
UNIV OF SCI & TECH OF CHINA
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Among the known reports, the photocatalytic free radical decarboxylation reaction is the most studied, and the reaction conditions are the mildest. However, the photosensitizer is expensive and the synthesis is complicated, which greatly limits the use of this method.

Method used

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  • Method for photo-induced decarboxylation alkylation of alkyl-active carboxylic ester
  • Method for photo-induced decarboxylation alkylation of alkyl-active carboxylic ester
  • Method for photo-induced decarboxylation alkylation of alkyl-active carboxylic ester

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0079] Reaction formula:

[0080]

[0081] The specific method is as follows: in a 10mL Schlenk reaction tube (Beijing Xinweier Glass Instrument Co., Ltd., F891410 reaction tube, capacity 10mL, grinding port 14 / 20), add redox alkyl active carboxylate (0.3mmol) and lithium sulfide (0.04 mmol). The air in the tube was completely replaced with argon three times, and then 2 mL of N,N-dimethylacetamide (DMA) and free radical acceptor isocyanide (0.2 mmol) were added under an argon atmosphere. The reaction system was continuously stirred at room temperature for 12 hours under the irradiation of a 40W purple LED (427nm) lamp (IKA magnetic stirrer, RCT basic type, stirring speed 500 rpm). After the reaction was completed, the reaction was quenched with saturated NaCl solution, and the reaction solution was repeatedly extracted 3 times with 10 mL of ethyl acetate, and then the combined organic phase was concentrated by rotary evaporation (Swiss Buchi Co., Ltd., BUCHI rotary evapora...

Embodiment 2

[0088] Reaction formula:

[0089]

[0090] The method of embodiment 2 is the same as that of embodiment 1, the difference lies in the kind of redox alkyl active carboxylate shown in the above formula, and the productive rate of embodiment 2 is shown in table 1.

[0091] Utilize nuclear magnetic resonance to carry out the product of embodiment 2 gained 1 H NMR and 13 C NMR analysis.

[0092] Figure 4 It is the product in Example 2 of the present disclosure 1 H NMR nuclear magnetic resonance spectrum.

[0093] Such as Figure 4 as shown, 1 H NMR (400MHz, CDCl3) δ8.52(d, J=8.2Hz, 1H), 8.41(dd, J=8.3, 1.3Hz, 1H), 8.20(d, J=8.2Hz, 1H), 8.05(d ,J=8.2Hz,1H),7.59-7.57(m,4H),3.77-3.28(m,1H),2.01-1.72(m,7H),1.55-1.29(m,3H).

[0094] Figure 5 It is the product in Example 2 of the present disclosure 13 C NMR spectrum.

[0095] Such as Figure 5 as shown, 13 C NMR (101MHz, CDCl 3 )δ165.2, 143.8, 132.9, 129.8, 128.3, 127.0, 126.0, 125.5, 124.6, 123.2, 122.5, 121.7, 41.9, ...

Embodiment 3

[0097] Reaction formula:

[0098]

[0099] The method of Example 3 is the same as that of Example 1, except for the type of free radical acceptor isocyanide shown in the above formula. The yield of Example 3 is shown in Table 1.

[0100] The product obtained in embodiment 3 is carried out nuclear magnetic resonance analysis, and the results are as follows:

[0101] 1 H NMR (400MHz, CDCl 3 )δ8.57(d, J=9.0Hz, 1H), 8.41(dd, J=8.1, 1.5Hz, 1H), 8.21-8.03(m, 1H), 7.98(d, J=2.6Hz, 1H), 7.66-7.53(m,2H),7.41(dd,J=9.1,2.5Hz,1H),3.97(s,3H),1.73(s,9H).

[0102] 13 C NMR (101MHz, CDCl 3 )δ165.7, 157.2, 130.1, 128.2, 127.4, 126.5, 125.4, 124.4, 123.5, 121.1, 119.1, 114.0, 109.7, 55.4, 40.0, 30.9.

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PUM

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Abstract

The invention provides a method for photo-induced decarboxylation alkylation of alkyl-active carboxylic ester. The method comprises the following steps: in the presence of a sulfur salt and an organic solvent, subjecting the alkyl-active carboxylic ester as shown in a formula (1) to reacting with a free radical acceptor as shown in a formula (2) under visible light irradiation so as to obtain alkylation products as shown in a formula (3), wherein the formula (1) is as described in the specification, the formula (2) is Nu, and the formula (3) is Nu-R1. In the formulas, R1 is one selected from substituted or unsubstituted alkyl groups with 1 to 20 carbon atoms or substituted or unsubstituted cycloalkyl groups with 3 to 20 carbon atoms.

Description

technical field [0001] The invention relates to the field of organic compound synthesis, in particular to a method for light-induced decarboxylation and alkylation of alkyl active carboxylic acid esters. Background technique [0002] As an important synthon, alkyl carboxylic acid plays an important role in the field of organic synthesis. Through the decarboxylation reaction, an alkyl anion or an alkyl free radical intermediate can be obtained, and then participate in the subsequent reaction. It is worth mentioning that, compared with the traditional carbonegative heterolytic decarboxylation method, the homolytic free radical decarboxylation method has milder conditions. Among the known reports, the photocatalytic free radical decarboxylation reaction is the most studied, and the reaction conditions are the mildest. However, the photosensitizer is expensive and the synthesis is complicated, which greatly limits the use of this method. Therefore, it is very important to deve...

Claims

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Application Information

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IPC IPC(8): C07D221/12C07D401/04C07D401/14C07D405/04C07D277/64C07D207/16C07D209/48C07C41/18C07C43/205C07C2/86C07C15/52C07C227/16C07C229/18
CPCC07D221/12C07D401/04C07D401/14C07D405/04C07D277/64C07D207/16C07D209/48C07C41/18C07C2/86C07C227/16C07C43/205C07C15/52C07C229/18
Inventor 傅尧秦志伟王光祖
Owner UNIV OF SCI & TECH OF CHINA
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