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Novel method for realizing visible light catalytic asymmetric oxidation by using micro reactor

A micro-reactor and micro-channel reactor technology, applied in the field of flow chemistry, can solve problems such as safety hazards, photocatalytic reaction amplification and production limitations, and achieve the effects of process safety, effective continuity and amplification, and mild reaction conditions.

Active Publication Date: 2019-10-25
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] According to the Bouguer-Lambert-Beer law, the photocatalytic reaction will be significantly limited when using the "volume scale-up" strategy for scale-up production
In addition, the introduction of air or oxygen in the photocatalytic oxidation reaction system will cause great safety hazards in actual production.

Method used

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  • Novel method for realizing visible light catalytic asymmetric oxidation by using micro reactor
  • Novel method for realizing visible light catalytic asymmetric oxidation by using micro reactor
  • Novel method for realizing visible light catalytic asymmetric oxidation by using micro reactor

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0021] Embodiment 1: Preparation of 2-hydroxyl-1-indanone-2-formic acid adamantyl

[0022]

[0023] Weigh 0.031g (0.1mmol) 1-indanone-2-carboxylate adamantyl (Ia-1), 0.0077g (0.01mmol, 10mol%) catalyst PTC-1, in 20mL test tube, add 10mL toluene, solid dissolves completely , recorded as a bottle; another configuration of 50% K 2 HPO 4 The solution is denoted as bottle b. The temperature of the entire reaction system is controlled at 20°C. The organic phase in bottle a is pumped in at a rate of 1.5mL / min from pump A, and the alkaline solution in bottle b is pumped in at a rate of 1.5mL / min from pump B. The flow rate of oxygen (oxygen content 99.99%) was 3 mL / min, the reaction pressure was 1 bar, the light source was white light, and the residence time was 90 min. The starting material was completely converted and the organic phase was worked up to give the oxidation product IIa-1 (0.031 g, 95% yield, 82% ee). 1 H NMR (400MHz, Chloroform-d) δ7.79 (d, J = 7.7Hz, 1H), 7.65 (t...

Embodiment 2

[0024] Example 2: Preparation of 2-hydroxy-1-indanone-2-formic acid adamantyl process enlarged 10 times volume

[0025]

[0026] Weigh 0.31g (1mmol) 1-indanone-2-carboxylate adamantyl (Ia-1), 0.077g (0.1mmol, 10mol%) catalyst PTC-1, in 200mL test tube, add 100mL toluene, solid dissolves completely, Recorded as a bottle; another 50% K 2 HPO 4The solution is denoted as bottle b. The temperature of the entire reaction system is controlled at 20°C. The organic phase in bottle a is pumped in at a rate of 1.5mL / min from pump A, and the alkaline solution in bottle b is pumped in at a rate of 1.5mL / min from pump B. The flow rate of oxygen (oxygen content 99.99%) was 3 mL / min, the reaction pressure was 1 bar, the light source was white light, and the residence time was 90 min. The starting material was completely converted and the organic phase was worked up to give the oxidation product IIa-1 (0.31 g, 95% yield, 82% ee).

Embodiment 3

[0027] Example 3: Preparation of 5-chloro-2-hydroxyl-1-indanone-2-carboxylic acid adamantyl

[0028]

[0029] Weigh 0.0344g (0.1mmol) 5-chloro-1-indanone-2-formic acid adamantyl (Ia-2), 0.0008g (0.001mmol, 1mol%) catalyst PTC-2, in 200mL test tube, add 100mL adjacent Xylene, the solid is completely dissolved, recorded as a bottle; another 20% K 2 HPO 4 The solution is denoted as bottle b. The temperature of the entire reaction system is controlled at 10°C. The organic phase in bottle a is pumped in at a rate of 0.5mL / min from pump A, and the alkaline solution in bottle b is pumped in at a rate of 0.5mL / min from pump B. The air flow rate was 1mL / min, the reaction pressure was 0bar (atmospheric pressure), the light source was 300nm LEDs, and the residence time was 5min. The starting material was completely converted and the organic phase was worked up to give the oxidation product IIa-2 (0.0339 g, 94% yield, 80% ee).

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Abstract

The invention belongs to the field of flow chemistry, and provides a novel method for realizing visible light catalytic asymmetric oxidation by using a micro reactor. According to the method, a chiralbeta-hydroxy-beta-dicarbonyl compound is prepared continuously by the asymmetric photocatalytic oxidation of a beta-dicarbonyl compound with oxygen as an oxidizing agent under the conditions of visible light, a phase transfer catalyst derived from cinchona base and without additional photosensitizers or photosensitizer group introduction. The reaction temperature is -15-30 DEG C, the reaction residence time is 5-200 min, and the 100% substrate conversion rate can be immediately achieved and enantioselectivity greater than 70% can further be achieved. The method has the advantages of mild reaction conditions, continuous reaction, the catalyst provided with dual functionalization of chiral catalyst center and photosensitive center, no amplification effect and easy industrialization.

Description

technical field [0001] The invention belongs to the field of flow chemistry and relates to a new method for realizing visible light catalytic asymmetric oxidation by utilizing a microreactor. Background technique [0002] At present, visible light has been applied to the synthesis of chiral α-hydroxy-β-dicarbonyl compounds, which are ubiquitous in nature, especially methyl indanone carboxylate as an important intermediate of indoxacarb has attracted much attention. In 2012, we reported the use of cinchona base phase transfer catalyst, using tetraphenylporphyrin (TPP) as a photosensitizer to activate oxygen in the air under visible light to catalyze the asymmetric photocatalytic oxidation of β-dicarbonyl compounds (Chem .Asian.J.2012,7,2019-2023). Subsequently, patent CN106045985A and patent CN107899611A respectively reported a combination of an organic visible light catalyst and a chiral organic catalyst to form a bifunctional organometallic catalyst or a bifunctional organ...

Claims

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Application Information

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IPC IPC(8): C07C67/31C07C69/757C07C69/013C07C69/017C07D211/16C07C231/12C07C235/82C07B53/00B01J31/02B01J19/00
CPCB01J19/0093C07C67/31C07D211/16C07C231/12C07B53/00B01J31/0244C07C2602/08C07C2603/74C07B2200/07C07C2602/10C07C69/757C07C69/013C07C69/017C07C235/82
Inventor 孟庆伟唐晓飞冯世豪赵静喃武玉峰宋博恽磊
Owner DALIAN UNIV OF TECH
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