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A method for synthesizing α-hydroxyl-β-dicarbonyl compounds using water as a solvent

A compound, dicarbonyl technology, applied in the field of organic synthesis, can solve problems such as unsuitable for production and application, harsh reaction conditions, cumbersome operation, etc., and achieve the effects of broad production and application prospects, simple post-treatment, and good reaction effect

Active Publication Date: 2021-04-16
XINXIANG MEDICAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

So far, there have been many methods to obtain such compounds. Davis first reported the method of using Davis reagent to obtain α-oxo-β-ketoester compounds in 1981 (Tetrahedron Lett.1981, 22, 4385-4388) , but the method is cumbersome to operate, the reaction conditions are relatively harsh, the use of chemical doses of chiral oxidants, the cost is high, and it is not suitable for production applications

Method used

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  • A method for synthesizing α-hydroxyl-β-dicarbonyl compounds using water as a solvent
  • A method for synthesizing α-hydroxyl-β-dicarbonyl compounds using water as a solvent
  • A method for synthesizing α-hydroxyl-β-dicarbonyl compounds using water as a solvent

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Experimental program
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Effect test

Embodiment 1

[0019] Preparation of Methyl 2-Hydroxy-1-indanone-2-carboxylate Ia-1

[0020]

[0021] Weigh 0.1mmol 1-indanone-2-carboxylic acid methyl ester IIa-1, add 5mol% tetrabutylammonium bromide, 0.2mol cumyl hydroperoxide (mass fraction is 85%), put into 10mL single-port reaction tube, add 2 mL of pure water, and stir the reaction at 60°C. After reacting for 12 hours, the mixture was extracted twice with ethyl acetate, washed once with water, dried over anhydrous sodium sulfate, filtered, and spin-dried. The crude product was separated by column chromatography (petroleum ether: ethyl acetate = 25:1, v / v) to obtain the hydroxylated product 2-hydroxy-1-indanone-2-carboxylic acid methyl ester Ia-1 (22mg, yield 91% ); 1 H NMR (400MHz, Chloroform-d) δ7.73(d, J=8.2Hz, 1H), 7.50(dd, J=1.7, 0.8Hz, 1H), 7.44–7.36(m, 1H), 4.19(s, 1H), 3.79–3.65(m, 4H), 3.24(dt, J=17.5, 1.0Hz, 1H). 13 C NMR (101MHz, CDCl 3 )δ 199.51, 171.56, 153.61, 142.82, 132.00, 129.04, 126.77, 126.40, 80.45, 53.59, ...

Embodiment 51

[0058] Preparation of 2-Hydroxy-1-indanone-2-carboxylic acid-N-phenyl-carboxamide Ib-1

[0059]

[0060] Weigh 0.1mmol 1-indanone-2-formic acid-N-phenylcarboxamide IIb-1, add 5mol% tetrabutylammonium bromide, 0.2mol cumyl hydroperoxide (mass fraction is 85%), Put it into a 10mL single-port reaction tube, add 2mL of pure water, and stir the reaction at 60°C. After reacting for 12 hours, the mixture was extracted twice with ethyl acetate, washed once with water, dried over anhydrous sodium sulfate, filtered, and spin-dried. The crude product was separated by column chromatography (petroleum ether: ethyl acetate = 25:1, v / v) to obtain the hydroxylated product 2-hydroxy-1-indanone-2-carboxylic acid methyl ester Ib-1 (18mg, yield 67% ); 1 H NMR (400MHz, Chloroform-d)δ8.74(s,1H),7.88–7.62(m,2H),7.57–7.39(m,4H),7.30(dd,J=8.6,7.4Hz,2H), 7.11(td, J=7.3, 1.2Hz, 1H), 4.01–3.78(m, 2H), 3.19(d, J=16.7Hz, 1H). 13 C NMR (101MHz, CDCl 3 ) δ 203.10, 168.27, 153.03, 136.90, 136.54, 133....

Embodiment 96

[0095] Gram-level Preparation of Methyl 2-Hydroxy-1-indanone-2-carboxylate Ia-1

[0096]

[0097] Weigh 10mmol 1-indanone-2-formic acid methyl ester IIa-1, add 5mol% tetrabutylammonium bromide, 20mol cumyl hydroperoxide (mass fraction is 85%), put into 250mL single-port reaction flask, 200 mL of pure water was added, and the reaction was stirred at 60°C. After reacting for 12 hours, the mixture was extracted twice with ethyl acetate and concentrated. The hydroxylated product was directly precipitated in ethyl acetate, and the hydroxylated product 2-hydroxy-1-indanone-2-carboxylic acid methyl ester Ia-1 (2.05 g, yield 90%) was obtained by filtration.

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Abstract

The invention discloses a method for synthesizing α-hydroxy-β-dicarbonyl compounds by using water as a solvent, belonging to the technical field of organic synthesis. The effectiveness of the invention is mainly reflected in the fact that by using green water as a solvent, adding cheap and easy-to-obtain surfactants, and using the free radical oxidative coupling strategy generated by peroxides, it has successfully realized the addition of no organic solvents, no acids and no bases. The aqueous phase α-hydroxylation of green β-dicarbonyl compounds provides a novel and efficient way for the preparation of α-oxo-β-dicarbonyl compounds with great application value. In addition, the post-treatment of the reaction is simple, and it can still maintain a good reaction effect when it is scaled up to the gram level, and has broad production and application prospects.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a method for synthesizing α-hydroxyl-β-dicarbonyl compounds by using water as a solvent. Background technique [0002] As we all know, water is the source of life. Many complex biosynthesis and life processes take place in water. For chemists, water has many advantages compared with other organic solvents, it can reduce the reaction cost, simplify the process flow, and be environmentally friendly, which meets the requirements of green chemical development (Chem.Soc.Rev., 2012,41,1415 –1427). But for most chemical reactions, the presence of water usually has a bad effect on the reaction, such as the reduction of yield and poor selectivity. Most fine chemical synthesis uses petroleum-derived solvents, which generate a large amount of toxic waste, causing great environmental pollution and high production costs. Therefore, no matter in industry or academia, ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C67/31C07C69/757C07C231/12C07C235/82
CPCC07C67/31C07C231/12C07C2602/08C07C2602/10C07C69/757C07C235/82
Inventor 王亚坤高庆贺刘兴霞张涛王帅飞李洛豪智浩宇
Owner XINXIANG MEDICAL UNIV
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