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6-hydroxyl quinine quaternary ammonium salt asymmetric phase transfer catalyst, preparation method and application of 6-hydroxyl quinine quaternary ammonium salt asymmetry phase transfer catalyst

A technology of phase transfer catalyst and chinatine, which is applied in the directions of catalytic reaction, chemical instrument and method, preparation of organic compounds, etc., can solve the problems such as application that has not been publicly reported, low enantioselectivity, etc., and achieves mild reaction conditions, The effect of high reaction efficiency

Inactive Publication Date: 2016-04-06
DALIAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] In 2001, DuPont used cinchonine to asymmetrically hydroxylate 5-chloro-1-indanone-2-carboxylic acid methyl ester (Pest.Manages.Sci.2001,57,153–164) to obtain the S-configuration product, enantiomeric selection 50% ee, and used in industrial production, but the enantioselectivity is low
[0010] From the perspective of the type of catalyst, 6-hydroxyl cinchona base quaternary ammonium salt catalysts are rarely reported, and its application in the hydroxylation catalysis of β-dicarbonyl compounds has not yet been publicly reported.

Method used

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  • 6-hydroxyl quinine quaternary ammonium salt asymmetric phase transfer catalyst, preparation method and application of 6-hydroxyl quinine quaternary ammonium salt asymmetry phase transfer catalyst
  • 6-hydroxyl quinine quaternary ammonium salt asymmetric phase transfer catalyst, preparation method and application of 6-hydroxyl quinine quaternary ammonium salt asymmetry phase transfer catalyst
  • 6-hydroxyl quinine quaternary ammonium salt asymmetric phase transfer catalyst, preparation method and application of 6-hydroxyl quinine quaternary ammonium salt asymmetry phase transfer catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] Embodiment 1: Preparation of 6-hydroxyl-N-(4-fluoro-2 trifluoromethylbenzyl) quinine quaternary ammonium bromide

[0040]Add 0.5 g (1.6 mmol) of 6-hydroxy-quinine and 0.49 g (1.9 mmol) of p-fluoro-o-trifluoromethylbenzyl bromide into a 50 ml three-necked flask, and add 20 ml of anhydrous THF. The system was heated to 75°C, and the reaction was tracked by TLC. After 6 hours of reflux reaction, the system was cooled, and 30 ml of diethyl ether was added, and the system had obvious solid precipitation. It was filtered, washed three times with ether to obtain a brown solid, and dried to obtain 0.68 g of the product, with a yield of 75%.

[0041] 1 HNMR (500MHz, Chloroform-d) δ8.63 (d, J = 4.5Hz, 1H), 8.45 (dd, J = 10.1, 4.4Hz, 1H), 7.91 (s, 1H), 7.67–7.60 (m, 2H ),7.30(m,1H),7.22(s,1H),6.86(m,1H),6.36(s,1H),5.71(s,1H),5.60–5.51(m,1H),5.48(m, 1H), 5.42(d, J=17.5Hz, 1H), 5.00(dd, J=10.3, 1.8Hz, 1H), 4.57(d, J=9.8Hz, 1H), 4.36(s, 2H), 3.04( dd,J=12.4,10.4Hz,1H),2.86(t,J=1...

Embodiment 2

[0042] Embodiment 2: Preparation of 6-hydroxyl-N-(2-trifluoromethylbenzyl) quinine quaternary ammonium bromide

[0043] 0.5 g (1.6 mmol) of 6-hydroxy-quinine and 0.45 g (1.9 mmol) of m-trifluoromethylbenzyl bromide were added to a 50 ml three-necked flask, and 20 ml of anhydrous dichloromethane was added. The system was heated to 75°C, and the reaction was tracked by TLC. After reflux for 6 hours, cool down, add 20ml of diethyl ether, filter, wash with diethyl ether 3 times to obtain a brown solid, and dry to obtain 0.85g of the product, with a yield of 82%.

[0044] 1 HNMR (500MHz, Chloroform-d) δ8.76(s, 1H), 8.66(d, J=4.6Hz, 1H), 7.99(s, 1H), 7.74(d, J=4.9Hz, 2H), 7.68( s,1H),7.53(d,J=9.1Hz,1H),7.39(d,J=7.8Hz,1H),7.24(s,1H),6.71(d,J=9.1Hz,1H),6.29( s,1H),6.09(d,J=12.1Hz,1H),5.67(s,1H),5.51–5.44(m,1H),5.41(dd,J=10.0,5.1Hz,1H),5.36(d ,J=17.4Hz,1H),5.00(m,1H),4.60(d,J=10.0Hz,1H),4.20(s,1H),3.96(d,J=12.8Hz,1H),3.01(t ,J=11.6Hz,1H),2.89(t,J=11.8Hz,1H),2.51(s,1H),2.09(t,J=12....

Embodiment 3

[0045] Example 3: Preparation of 6-hydroxy-N-(1,2,3,4,5-pentafluoro-benzyl) quinine quaternary ammonium bromide

[0046] Add 0.5 g (1.6 mmol) of 6-hydroxy-quinine and 0.52 g (1.9 mmol) of 1,2,3,4,5-pentafluoro-benzyl bromide into a 50 ml three-necked flask, and add 20 ml of anhydrous THF. The system was heated to 75°C, and the reaction was tracked by TLC. After reflux for 6 hours, cool down, add 20 ml of diethyl ether, filter, wash with diethyl ether three times to obtain a brown solid, and dry to obtain 0.62 g of the product, with a yield of 76%.

[0047] 1 HNMR (500MHz, DMSO-d 6 )δ10.15(s,1H),8.73(d,J=4.5Hz,1H),7.95(d,J=9.1Hz,1H),7.67(d,J=4.4Hz,1H),7.57–7.33( m,2H),6.75–6.54(m,1H),6.37(t,J=2.6Hz,1H),5.77(s,1H),5.42(d,J=13.5Hz,1H),5.14(dt,J =17.2,1.3Hz,1H),5.03(dt,J=10.4,1.2Hz,1H),4.91(d,J=13.4Hz,1H),4.17(d,J=7.5Hz,2H),4.08(q ,J=5.2Hz,2H),3.66–3.58(m,4H),2.68–2.57(m,1H),2.18(t,J=10.5Hz,2H),2.01(q,J=3.2Hz,1H) ,1.76(dq,J=6.5,3.1Hz,4H),1.53–1.27(m,1H).

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Abstract

The invention discloses a 6-hydroxyl quinine quaternary ammonium salt asymmetric phase transfer catalyst, a preparation method and application of the 6-hydroxyl quinine quaternary ammonium salt asymmetry phase transfer catalyst and belongs to the field of organic synthesis. In a two-phase system of an oxidizing agent, an alkaline solution and an inert solvent, the 6-hydroxyl quinine quaternary ammonium salt asymmetric phase transfer catalyst converts a beta-dicarbonyl compound into a chiral alpha-hydroxyl-beta-dicarbonyl compound; the usage quantity of the chiral 6-hydroxyl quinine quaternary ammonium salt asymmetric phase transfer catalyst is 0.5-50 mol% of the beta-dicarbonyl compound, and under the mild condition that reaction temperature is -15 DEG C-65 DEG C, the yield of the chiral alpha-hydroxyl-beta-dicarbonyl compound is larger than or equal to 90%, and the enantioselectivity is higher than or equal to 70% ee. The method is mild in reaction condition, environmentally friendly, high in reaction efficiency and suitable for large-scale production and preparation.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and relates to a method for preparing chiral α-hydroxyl-β-dicarbonyl compounds by catalyzing an asymmetric phase transfer catalyst of 6-hydroxycinchoaline quaternary ammonium salt. Background technique [0002] The optically active α-hydroxy-β-dicarbonyl structure is ubiquitous in the molecular structures of natural products and some drugs and pesticides; this structure is also a synthon for the synthesis of other important functional molecular structure intermediates, such as chiral diol compounds. The most ideal way to synthesize chiral α-hydroxy-β-dicarbonyl compounds is chiral catalytic oxidation of β-dicarbonyl compounds. [0003] In recent years, a series of documents or patents have reported the preparation methods of chiral α-hydroxy-β-dicarbonyl compounds. [0004] In 2001, DuPont used cinchonine to carry out asymmetric hydroxylation of 5-chloro-1-indanone-2-carboxylic acid methyl ester...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/02C07C69/757C07C67/31
CPCB01J31/0244B01J2231/70C07C67/31
Inventor 孟庆伟卿海王亚坤尹航郑泽浩杨帆陈帅
Owner DALIAN UNIV OF TECH
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