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Trifluoromethylthio reagent and its preparation method and application in asymmetric trifluoromethylthiolation reaction

A technology of trifluoromethylthio group and reagent, applied in the preparation of sulfonic acid amide, organic chemistry method, organic chemistry and other directions, can solve problems such as dose reduction, and achieve the effects of simple operation, high yield and high activity

Inactive Publication Date: 2017-12-05
SUN YAT SEN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

From a physiological point of view, compared with general drugs, fluorine-containing drugs have better biological penetration and better selectivity to target organs, which usually greatly reduces the dosage used.

Method used

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  • Trifluoromethylthio reagent and its preparation method and application in asymmetric trifluoromethylthiolation reaction
  • Trifluoromethylthio reagent and its preparation method and application in asymmetric trifluoromethylthiolation reaction
  • Trifluoromethylthio reagent and its preparation method and application in asymmetric trifluoromethylthiolation reaction

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] (1) In the glove box, put 7.5g of silver fluoride into the oven-dried reaction bottle, cap the bottle stopper and take it out of the glove box. Add 40mL redistilled acetonitrile and 12mL carbon disulfide in a nitrogen atmosphere, quickly install the reflux condenser and reflux overnight at 80°C. Then carbon disulfide was distilled off, and the remaining acetonitrile was spin-dried with a rotary evaporator to obtain a black solid. The black solid was then dissolved and washed with ethyl acetate and filtered through celite with multiple washes. The filtrate was spin-dried under dark conditions to obtain a viscous solid. After dissolving the viscous solid with 30 drops of acetonitrile, slowly add 90 mL of ether into the bottle along the bottle wall. After the mixture was allowed to stand at room temperature for 12 hours, it was placed at -20°C for 24 hours. Pour off the ether and continue to spin dry to obtain 4 g of off-white solid silver fluoride with metallic luster. ...

Embodiment 2

[0031](1) In the glove box, 15g of silver fluoride is packed into the oven-dried reaction bottle, and the bottle stopper is taken out of the glove box. Add 80mL redistilled acetonitrile and 25mL carbon disulfide in a nitrogen atmosphere, quickly install the reflux condenser and reflux overnight at 80°C. Then carbon disulfide was distilled off, and the remaining acetonitrile was spin-dried with a rotary evaporator to obtain a black solid. The black solid was then dissolved and washed with ethyl acetate and filtered through celite with multiple washes. The filtrate was spin-dried under dark conditions to obtain a viscous solid. After dissolving the viscous solid with 60 drops of acetonitrile, slowly add 180 mL of ether into the bottle along the bottle wall. After the mixture was allowed to stand at room temperature for 12 hours, it was placed at -20°C for 24 hours. Pour off the ether and continue to spin dry to obtain 8 g of off-white solid silver fluoride with metallic luster...

Embodiment 3

[0041] Embodiment 3: catalytic reaction example 1

[0042] Put 16.22mg (0.1mmol) of 4-phenyl-3-butenoic acid, 60mg of trifluoromethylthio reagent 1 and 8 mg of catalyst in a reaction flask, add 4mL of dichloromethane and 4.4mL of TfOH at 0°C and stir After 12 hours, the target product was obtained by flash column chromatography after spin-drying, with a yield of 84% and an ee value of 90%.

[0043]

[0044] 1 H NMR (400MHz, CDCl 3 )δ7.51–7.31(m,5H),5.39(d,J=6.4Hz,1H), 3.93(q,J=7.4Hz,1H),3.21(dd,J=18.2,8.4Hz,1H), 2.81(dd,J=18.2,7.4Hz,1H).

[0045] 13 C NMR (101MHz, CDCl 3 )δ172.89, 136.14, 134.45 (q, J=307.5Hz), 131.39, 129.67, 129.24, 128.34, 125.66, 125.62, 84.61, 45.83, 36.46.

[0046] 19 F NMR (377MHz, CDCl 3 )δ-39.63.

[0047] HR-ESI-MS m / z calcd.for C 11 h 9 f 3 NaO 2 S[M+Na] + :285.0168,found: 285.0173.

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Abstract

The invention discloses a trifluoromethylthiolation reagent and its preparation method and use in an asymmetric trifluoromethylthiolation reaction. The trifluoromethylthiolation reagent is prepared from commercial silver fluoride, dibenzenesulfonimide and t-butyl hypochlorite as basic raw materials through mixing. The preparation method has short reaction steps, operation easiness and high yield. The novel trifluoromethylthiolation reagent has stable chemical properties, is environmentally friendly and is convenient for storage. The trifluoromethylthiolation reagent has high activity in an asymmetric trifluoromethylthiolation reaction and has a wide application prospect in many organic reactions.

Description

Technical field: [0001] The invention relates to the field of organic fluorine chemistry, in particular to a trifluoromethylthio reagent, a preparation method thereof and its application in an asymmetric trifluoromethylthio esterification reaction. Background technique: [0002] Fluorine is the first element in the halogen group. Since the atomic radius and size of the fluorine atom and the hydrogen atom are similar, when the hydrogen atom in the molecule is replaced by the fluorine atom, it will not cause a significant change in the molecular configuration. However, due to the high electronegativity of fluorine atoms, when fluorine atoms replace hydrogen atoms, the electronic properties of the original molecule will often be greatly changed. From a molecular perspective, such changes usually lead to changes in the lipophilicity of molecules, changes in the electrostatic interaction of target structures, and inhibition of some metabolic pathways. From a physiological point ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C311/48C07C303/40C07D307/33
CPCC07B2200/07C07C303/40C07C311/48C07D307/33
Inventor 赵晓丹刘想
Owner SUN YAT SEN UNIV