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Fluorine-containing three-membered ring compound, preparation method of fluorine-containing three-membered ring compound and preparation method of fluoroalkyl sulfonium salt

A compound and three-membered ring technology, applied in the field of fluorine-containing three-membered ring compounds, can solve the problems of complicated preparation method steps, difficult to obtain raw materials, complicated operation steps and the like

Inactive Publication Date: 2016-04-27
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] The technical problem to be solved in the present invention is to overcome the tedious operation steps of the preparation method of fluoroalkyl sulfonium salt in the prior art, the raw materials are not easy to get, and the cumbersome steps of the preparation method of the three-membered ring compound substituted by fluoroalkyl in the prior art, Due to the defects of high risk factor of raw materials, a fluorine-containing three-membered ring compound, its preparation method and a preparation method of fluoroalkylsulfonium salt are provided

Method used

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  • Fluorine-containing three-membered ring compound, preparation method of fluorine-containing three-membered ring compound and preparation method of fluoroalkyl sulfonium salt
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  • Fluorine-containing three-membered ring compound, preparation method of fluorine-containing three-membered ring compound and preparation method of fluoroalkyl sulfonium salt

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Experimental program
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Effect test

Embodiment 1-1-1

[0173]

[0174] Add paraformaldehyde (7.5g, 250 / nmmol), TAMA (nitromethylaniline trifluoroacetic acid 11.05g, 50mmol) into the 250mL three-necked flask, stirrer, add THF (50mL) under nitrogen protection after pumping, as The aryl ethyl ketone substrate represented by Formula 5 (50 mmol) was heated to reflux. After reacting for 10 hours, the stirring was stopped, the solution was returned to room temperature, the solvent was evaporated under reduced pressure, and the obtained paste was dissolved in 150 mL of ethyl acetate. After washing with water (100 mL×2) in a separatory funnel to remove a large amount of TAMA salt, the amine contained in the solution was removed with 1M HCl. Wash once more with 100 mL of water, then wash with saturated sodium bicarbonate solution until the solution becomes neutral, wash with saturated brine, and dry over anhydrous sodium sulfate. Petroleum ether: ethyl acetate (50:1) column chromatography to obtain the compound shown in formula 4.

[0...

Embodiment 1-1-2

[0204]

[0205] A substituted arylaldehyde (20mmol, 1.0equiv), p-toluenesulfonamide (20mmol, 3.424g, 1.0equiv) and tetraethylorthosilicate (80mmol, 16.82g, 4.0equiv) as shown in Formula 6 were mixed In a 100mL round bottom flask. Install a water separator and a condenser, and evaporate most of the ethanol produced in the reaction at 160°C. Situation 1: If crystals are precipitated in the system, stop heating and stirring, wait to cool to room temperature, wash with a small amount of mixed solvent (the volume ratio of ethyl acetate to petroleum ether is about 1:10), filter with suction, and wash with ethanol The cake was dried two to three times, and the obtained solid was weighed to calculate the yield after vacuum drying. Situation 2: There is still no solid precipitation after a large amount of ethanol is evaporated, and if there is crystal precipitation after cooling, it should be treated as situation 1. Situation 3: If there is still no solid precipitation after cooli...

Embodiment 1-1 3

[0238] The synthesis of embodiment 1-1 trifluoroethyl diphenylsulfonium salt

[0239]

[0240] Mix trifluoroethyl trifluoromethanesulfonate (9.28g, 40mmol) and diphenyl sulfide (37.2g, 0.2mol) in a 100mL sealed tube, heat in an oil bath at 150°C for 24h, stop heating, and cool naturally The sealed tube was opened, and a solid precipitated out. The solid was washed with ether, filtered with suction to obtain a white product, recrystallized with tetrahydrofuran, and dried to obtain 26.78 g of white crystals, with a yield of 80% and a purity of 99.9% by HPLC.

[0241]

[0242] 1 HNMR (400MHz, acetone-d 6 )δ8.36(d, J=7.7Hz, 4H), 7.93(t, J=7.7Hz, 2H), 7.84(t, J=7.7Hz, 4H), 5.75(q, J=8.8Hz, 2H) ; 19 FNMR (376MHz, acetone-d 6 )δ-60.80(t,J=8.8Hz,3F),-78.50(s,3F).

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Abstract

The invention discloses a fluorine-containing three-membered ring compound shown in the formula V-a, V-b or V-c and a preparation method thereof. The preparation method comprises that in an organic solvent, fluoroalkyl sulfur ylide shown in the formula III' and a double-bond compound shown in the formula IV-a, IV-b or IV-c undergo an annulation reaction to produce the fluorine-containing three-membered ring compound shown in the formula V-a, V-b or V-c. The invention also discloses a preparation method of a fluoroalkyl sulfonium salt shown in the formula III or IV. The preparation method comprises that sulfur ether shown in the formula I and fluoroalkyl sulfonate shown in the formula II or a compound shown in the formula II' undergo a nucleophilic substitution reaction in a solvent or without a solvent. The preparation method has simple processes, utilizes easily available raw materials, has short reaction time, a high product yield, high product purity, mild conditions and simple and convenient post-treatment processes and can be industrialized easily.

Description

technical field [0001] The invention specifically relates to a fluorine-containing three-membered ring compound, a preparation method thereof and a preparation method of a fluoroalkylsulfonium salt. Background technique [0002] Due to the characteristics of strong electronegativity, low polarizability, and small atomic radius of fluorine atoms, fluorine-containing compounds often exhibit special physical and chemical properties, so they are widely used in many fields such as biomedicine and materials. In the field of biomedicine, studies have shown that the introduction of fluorine atoms into drug molecules can often greatly improve their lipid solubility and metabolic stability, thereby achieving the purpose of improving drug activity. In the past few decades, the design of drug molecules basically involved the introduction of fluorine atoms (Qiu, X.-L.; Yue, X.; Qing, F.-L. InInChiralDrugs: Chemistry and Biological Action; Lin, G.-Q. ; You, Q.-D.; Cheng, J.-F. Ed.; John ...

Claims

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Application Information

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IPC IPC(8): C07B37/10C07C45/68C07C49/813C07C201/12C07C205/45C07C49/84C07D307/46C07D301/02C07D303/46C07D303/08C07D303/34C07D405/04C07D203/02C07D203/24C07C381/12
Inventor 肖吉昌段亚亚周斌林锦鸿
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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