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Method for greenly synthesizing 5-hydroxy-5-alkyl disubstituted barbituric acid derivative by amine catalysis of air oxidation

A technology of dimethyl barbituric acid and air oxidation, applied in the direction of organic chemistry, etc., to achieve the effects of easy control and realization, mild reaction conditions and low reaction cost

Inactive Publication Date: 2018-11-30
HENAN UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

In general, the key methods to achieve the synthesis of these compounds involve harmful oxidants or transition metals or metal oxides and additives (phosphine as reducing agent), which is the disadvantage of the above schemes

Method used

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  • Method for greenly synthesizing 5-hydroxy-5-alkyl disubstituted barbituric acid derivative by amine catalysis of air oxidation
  • Method for greenly synthesizing 5-hydroxy-5-alkyl disubstituted barbituric acid derivative by amine catalysis of air oxidation
  • Method for greenly synthesizing 5-hydroxy-5-alkyl disubstituted barbituric acid derivative by amine catalysis of air oxidation

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Example 1 Preparation of substrate

[0026] (1) Preparation of 5-aryl-1,3-dimethylbarbituric acid, the reaction equation is:

[0027]

[0028] Specific steps are as follows:

[0029] a. Add a stir bar, CuI (5.0 mol%), 2-picolinic acid (10.0 mol%), and Cs to a dry three-necked flask in sequence 2 CO 3 (3.0 mmol) and aryl iodide (solid) (1.0 mmol), then replaced with nitrogen three times to remove the air in the reaction flask. Add anhydrous 1,4-dioxane (2.0mmol) and diethyl malonate (0.3mL) to the reaction flask, then seal the reaction flask and place it in a preheated oil bath at 70℃. The reaction process was monitored by layer chromatography (TLC) and cooled to room temperature after the reaction. After the reaction, the reaction solution was separated and extracted with ethyl acetate (20 mL×3) and saturated ammonium chloride solution (10 mL). Anhydrous Na for organic layer 2 SO 4 (3g) Dry, filter, and concentrate. The crude product is subjected to rapid column separation...

Embodiment 2

[0036] Example 2 Oxidation reaction of 5-aryl-1,3-dimethylbarbituric acid derivatives

[0037] (1) 5-aryl-1,3-dimethylbarbituric acid oxidation, the reaction equation is:

[0038]

[0039] Specific steps are as follows:

[0040] Combine hexamethyleneimine (HMTA) (2mol%), N,N-dimethylformamide (DMF) (0.3mL) and 5-aryl-1,3-dimethylbarbituric acid (11a -11g) (0.2mmol) was added to the reaction flask, and then stirred at room temperature (25°C), the reaction was monitored by TLC, and the reaction process is shown in reaction scheme 1. After the reaction, the target product (12a-12g) was obtained directly by silica gel column chromatography (petroleum ether / ethyl acetate=5 / 1).

[0041]

[0042] (2) 5-benzyl-1,3-dimethylbarbituric acid oxidation, the reaction equation is:

[0043]

[0044] Specific steps are as follows:

[0045] The N,N-diethylethylamine (Et 3 N) (10mol%), tetrahydrofuran (THF) (0.4mL) and 5-benzyl-1,3-dimethylbarbituric acid (13a-13h) (0.2mmol) were added to the reaction fl...

Embodiment 3

[0050] Example 3 Screening of oxidation reaction conditions for 5-aryl-1,3-dimethylbarbituric acid derivatives

[0051] Select 5-phenyl-1,3-dimethylbarbituric acid as the model substrate to screen the reaction conditions of α-CH hydroxylation. The reaction process is shown in Reaction Route 4, and the selection of reaction conditions is shown in Table 1 below. . Firstly, 20mol% DMAP was selected as the catalyst, and the solvent was initially explored. It was found that when DMF was the solvent, the reaction effect was the best. The reaction only required 12h to achieve the complete conversion of the raw materials and produce the target product 12a (97%) (Table 1 Record in 1). For other solvents, when the reaction time is extended to 24h, the complete conversion of the raw materials still cannot be achieved, resulting in a relatively low yield (records 2-9 in Table 1). When toluene or dichloromethane is selected as the solvent, the reaction time is also controlled at 24h, and th...

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Abstract

The invention relates to the field of oxidative synthesis, and in particular, relates to a 5-hydroxy-5-alkyl disubstituted barbituric acid derivative greenly synthesized by amine catalysis of air oxidation and a method thereof. The amine-catalyzed oxidation reaction of a 5-substituted 1,3-dimethylbarbituric acid derivative is studied; reaction catalysts and solvents are screened, hydroxylation ofalpha-C-H of 5-aryl or benzyl substituted barbituric acid compounds is found out to be realized through catalytic reaction under different conditions. The method has the following characteristics: (1)air is used as the source of hydroxyl functional groups, so the requirements of green development are met; (2) easily available and cheap alkali R3N rather than expensive metal catalysts is used; and(3) stoichiometric harmful phosphine compounds are prevented from being used as additives and reductants.

Description

Technical field [0001] The present invention relates to the field of oxidation synthesis, in particular to a 5-hydroxy-5-hydrocarbyl disubstituted barbituric acid derivative and a method thereof that are green synthesized by amine-catalyzed air oxidation. Background technique [0002] The oxidation reaction is a relatively important reaction in organic synthesis. Through this reaction, hydrocarbons can be converted into valuable oxygen-containing products, which can be used as raw materials for the chemical and pharmaceutical industries. In these oxidation processes, the α-CH of α-substituted carbonyl compounds is hydroxylated to obtain quaternary carbon α-hydroxycarbonyl compounds. This type of reaction has gained more and more attention in synthetic chemistry because of its quaternary carbon α- The hydroxyl functional group is the central element of natural products and some drug molecules. In addition, such quaternary α-hydroxycarbonyl compounds are used as effective photoini...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D239/60C07D239/62
CPCC07D239/60C07D239/62
Inventor 汪游清完颜东艳张永娜刘颖
Owner HENAN UNIVERSITY
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