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Synthesis method of trifluoromethyl thioester compound

A technology of trifluoromethyl thioester and synthesis method, applied in the direction of organic chemistry, etc., can solve the problems of limited practicability, difficulty in storage, high price, etc., and achieve the effect of reducing synthesis cost, cheap price, and beneficial to industrial production

Active Publication Date: 2021-02-12
SHANDONG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the practicality of these synthetic methods is limited due to the expensive price of these reagents or the need for pre-synthesis, toxicity, and difficulty in storage.

Method used

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  • Synthesis method of trifluoromethyl thioester compound
  • Synthesis method of trifluoromethyl thioester compound
  • Synthesis method of trifluoromethyl thioester compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Example 1: In this example, 4-phenylbenzoic acid trifluoromethylthio ester (S-(trifluoromethyl)[1,1'-biphenyl]- 4-carbothioate):

[0031] The reaction equation is:

[0032]

[0033]The synthesis steps and process are: add 4-phenylbenzoic acid (0.4mmol, 79.2mg), triphenylphosphine (2.0mmol, 524mg), tetrabutylammonium bromide ( 1.2mmol, 386mg), then added 4.0mL 1.2-dichloroethane; under inert gas protection, the reaction tube was fixed on a magnetic stirrer, and trifluoromethanesulfonic anhydride (2.0mmol, 564mg) was slowly added under an ice-water bath, After completion, react at 50°C for 12 hours, add appropriate amount of water to the reaction solution, extract with ethyl acetate, dry over anhydrous sodium sulfate, and finally use a rotary evaporator to remove the solvent, and the crude product is subjected to column chromatography (petroleum ether: ethyl acetate Esters=100:1) The target product (1a) was obtained by separation and purification with a yield of 57.7...

Embodiment 2

[0038] Example 2: In this example, 4-bromobenzoic acid trifluoromethylthioester (S-(trifluoromethyl)4-bromobenzothioate) was synthesized by using 4-bromobenzoic acid and trifluoromethanesulfonic anhydride:

[0039] The reaction equation is:

[0040]

[0041] The synthesis steps and process are: add p-bromobenzoic acid (0.4mmol, 80.4mg), triphenylphosphine (2.0mmol, 524mg), tetrabutylammonium iodide (1.2 mmol, 443mg), then add 2.0mL 1.2-dichloroethane; under the protection of inert gas, slowly add trifluoromethanesulfonic anhydride (2.0mmol, 564mg) under the ice-water bath and fix the reaction tube on the magnetic stirrer, room temperature React for 20 hours, add an appropriate amount of water to the reaction solution, extract with ethyl acetate, dry over anhydrous sodium sulfate, and finally use a rotary evaporator to remove the solvent, and the crude product is subjected to column chromatography (petroleum ether:ethyl acetate=500:1 ) separation and purification to obtain ...

Embodiment 3

[0046] Example 3: In this example, the product (S) was synthesized by reacting (S)-(+)-6-methoxy-α-methyl-2-naphthaleneacetic acid (naproxen) with trifluoromethanesulfonic anhydride -(+)-6-Methoxy-α-methyl-2-naphthaleneacetic acid trifluoromethylthio ester (S-(trifluoromethyl)(S)-2-(6-methoxynaphthalen-2-yl)propanethioate):

[0047] The reaction equation is:

[0048]

[0049] The synthesis steps and process are as follows: add (S)-(+)-6-methoxy-α-methyl-2-naphthaleneacetic acid (0.4mmol, 92mg), triphenyl phosphine (2.0mmol, 524mg), tetrabutylammonium iodide (1.2mmol, 442mg), then add 4.0mL 1.2-dichloroethane; slowly add trifluoromethanesulfonic anhydride (1.32 mmol, 372 mg), the reaction tube was fixed on a magnetic stirrer, reacted at room temperature for 48 hours, and was detected by TLC. After the reaction was complete, an appropriate amount of water was added to the reaction solution, extracted with ethyl acetate, dried over anhydrous sodium sulfate, and finally The s...

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Abstract

The invention belongs to the technical field of organic compound synthesis, and relates to a synthesis method of a trifluoromethyl thioester compound. The invention relates to the method for synthesizing a trifluoromethylthioester compound, which is used for synthesizing the trifluoromethylthioester compound by using trifluoromethanesulfonic anhydride as a trifluoromethylsulfur source. The methodcomprises the following steps: by taking a compound with carboxyl and trifluoromethanesulfonic anhydride as raw materials, constructing a carbon-sulfur bond under the activation of a trivalent phosphine reduction reagent, and separating and purifying to obtain the trifluoromethylthioester compound. According to the synthesis method of the trifluoromethyl thioester compound, the raw material sourceis wide, the price of a reaction reagent is low, the synthesis cost of the trifluoromethyl thioester compound is remarkably reduced, industrial production is facilitated, the synthesis conditions aremild and can also be carried out in a normal-pressure air atmosphere, the operation is simple and safe,metal participation is not needed, and environmental protection is achieved.

Description

technical field [0001] The invention belongs to the technical field of organic compound synthesis, and relates to a synthesis method of trifluoromethylthio ester compounds. Background technique [0002] Fluorine atoms play an important role in the design and synthesis of modern drugs (Liu X, Xu C, Wang M, et al. Trifluoromethyltrimethylsilane: nucleophilic trifluoromethylation and beyond[J]. Chem Rev, 2015, 115(2): 683-730. ), according to statistics, 15% to 20% of modern drugs contain fluorine-containing groups (Hui R, Zhang S, Tan Z, et al. Research Progress of Trifluoromethylation with Sodium Trifluoromethanesulfinate[J]. Chin J Org Chem (Organic Chemistry) , 2017, 37(12): 3060-3075). The presence of fluorine-containing groups helps to increase the lipophilicity and metabolic stability of drug molecules (Yang B, Xu XH, Qing FL. Copper-mediated radical 1,2-bis(trifluoromethylation) of alkenes with sodium trifluoromethanesulfinate[J].Org Lett,2015,17(8):1906-1909.), also ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C327/26C07C327/22
CPCC07C327/22C07C327/26
Inventor 史大永田阳刘瑞华李祥乾
Owner SHANDONG UNIV
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