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Method for selectively synthesizing benzyl trifluoromethyl sulfide

A selective, alkyl aromatic hydrocarbon technology, used in sulfide preparation, steroids, organic chemistry, etc., to solve problems such as excess and poor substrate compatibility

Active Publication Date: 2022-05-17
NANJING UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Currently there is only one copper-catalyzed benzylic trifluoromethylthiolation of toluene analogues [Chen C., Xu X.-H., Yang B., Qing F.-L.Organic Letters 2014,16,3372.], The above reaction requires a large excess of raw materials, and requires a strong oxidant to stimulate, while using the metal reagent AgSCF 3 , poor substrate compatibility
Therefore, the efficient and selective synthesis of benzyltrifluoromethyl sulfide under transition metal-free conditions remains a major challenge.

Method used

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  • Method for selectively synthesizing benzyl trifluoromethyl sulfide
  • Method for selectively synthesizing benzyl trifluoromethyl sulfide
  • Method for selectively synthesizing benzyl trifluoromethyl sulfide

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Experimental program
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Effect test

Embodiment 1

[0052] Weigh in turn (synthesized according to the above method, the same below) (64.3mg, 0.26mmol), 2-isoamylbenzo[b]thiophene (40.8mg, 0.2mmol), 4CzIPN (provided by Beijing Huawei Ruike Chemical Co., Ltd., the same below) (3.2mg, 0.004mmol), K 2 CO 3 (5.52mg, 0.04mmol), added to the reaction tube, pumped and purged three times through the vacuum line, and added 4mL of anhydrous acetonitrile under argon atmosphere. Then put it under the irradiation of two 45W blue light lamps (Kessil, A360NE / WE, the same below.), and react at room temperature for 12 hours. Dry loading, column chromatography (300-400 mesh chromatography silica gel) obtains 44.4 mg of product, (eluent: normal hexane), productive rate 73%, 1 H NMR (400MHz, CDCl 3)δ7.81–7.76(m,1H),7.70(dd,J=6.9,1.9Hz,1H),7.32(pd,J=7.1,1.4Hz,2H),7.22(s,1H),4.74(dd ,J=9.5,6.5Hz,1H),1.97(ddd,J=14.9,9.4,5.8Hz,1H),1.87(ddd,J=14.1,8.2,6.5Hz,1H),1.68(ddq,J=12.8 ,8.3,6.6Hz,1H),0.94(dd,J=6.6,5.6Hz,6H); 19 F NMR (376MHz, CDCl 3...

Embodiment 2

[0054] Weigh first (64.3mg, 0.26mmol), 4CzIPN (3.2mg, 0.004mmol), K 2 CO 3 (5.52mg, 0.04mmol), added to the reaction tube, pumped three times through the vacuum line, under argon atmosphere, added 4mL of anhydrous acetonitrile, and then carefully added (37.7mg, 0.2mmol), and then placed under the irradiation of two 45W blue light lamps, and reacted at room temperature for 12h. Dry loading, column chromatography (300-400 mesh chromatography silica gel) obtains 44.2 mg of product, (eluent: normal hexane), productive rate 76%, 1 H NMR (400MHz, CDCl 3 )δ7.52(dd, J=7.4,1.3Hz,1H),7.47(dd,J=8.2,0.9Hz,1H),7.28(td,J=8.3,7.8,1.5Hz,1H),7.22(td ,J=7.5,1.1Hz,1H),6.63(s,1H),4.54(dd,J=9.3,6.8Hz,1H),2.08(ddd,J=15.0,9.2,6.2Hz,1H),1.85( dt,J=14.0,7.4Hz,1H),1.65(dp,J=13.2,6.6Hz,1H),0.95(dd,J=6.6,5.4Hz,6H); 19 F NMR (376MHz, CDCl 3 )δ-40.11; 13 C NMR (101MHz, CDCl 3 )δ155.4, 154.9, 130.4 (q, J = 307.4Hz), 128.0, 124.5, 123.0, 121.0, 111.3, 104.5, 42.4, 41.1 (d, J = 1.9Hz), 25.8, 22.4...

Embodiment 3

[0056] Weigh first (64.3mg, 0.26mmol), 4CzIPN (3.2mg, 0.004mmol), K 2 CO 3 (5.52mg, 0.04mmol), added to the reaction tube, pumped three times through the vacuum line, under argon atmosphere, added 4mL of anhydrous acetonitrile, and then carefully added (40.3mg, 0.2mmol), and then placed under the irradiation of two 45W blue light lamps, and reacted at room temperature for 12h. Dry loading, column chromatography (300-400 mesh chromatography silica gel) obtains 34.2 mg of product, (eluent: volume ratio, petroleum ether 60-90: ethyl acetate=20:1), yield 57%, 1 H NMR (400MHz, CDCl 3 )δ8.40(d, J=8.6Hz, 1H), 7.49(d, J=1.8Hz, 1H), 7.43(d, J=3.8Hz, 1H), 7.29(dd, J=8.6, 1.9Hz, 1H), 6.62(dd, J=3.8, 0.8Hz, 1H), 4.31(dd, J=9.1, 6.2Hz, 1H), 2.63(s, 3H), 2.05(ddp, J=30.5, 14.8, 7.9, 7.3Hz, 2H), 0.91(t, J=7.3Hz, 3H); 19 F NMR (376MHz, CDCl 3 )δ-39.74; 13 CNMR (101MHz, CDCl 3 )δ168.5, 135.8, 135.0, 130.7, 130.6 (q, J=308.4Hz), 125.9, 124.6, 119.8, 116.8, 109.1, 51.5, 30.1, 23.9, ...

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Abstract

A kind of method of selective synthesis benzyl trifluoromethyl sulfide, it is based on alkyl aromatic hydrocarbon ArCHR 1 R 2 As a raw material, under the irradiation of a blue light, in a solution, under an argon atmosphere, in the presence of a small amount of potassium carbonate, with 4CzIPN as a photocatalyst, with 2-((trifluoromethyl)thio)isoindoline- 1,3-Diketone 2a reacted at room temperature to give the benzyl trifluoromethyl sulfide ArCR 1 R 2 SCF 3 (3) described photocatalyst 4CzIPN has following structure: the method reaction condition of the present invention is gentle, does not need oxidizing agent and high temperature condition, has avoided the residue of transition metal simultaneously, from stable and easy-to-get alkyl aromatic hydrocarbon and trifluoromethyl sulfide Reagent directly yields benzyl trifluoromethyl sulfide.

Description

technical field [0001] The invention relates to a method for selectively synthesizing benzyl trifluoromethyl sulfide. Background technique [0002] The trifluoromethylthio functional group is an important class of functional groups [see: Xu, X.H.; Matsuzaki, K.; Shibata, N. Chem. Rev. 2015, 115, 731.], and is also widely present in many drug molecules (tiflorex, toltrazuril , tiflorex, etc.) and bioactive molecular structures [see: (a) Counts, G.W.; Gregory, D.; Zeleznik, D.; Turck, M. Antimicrobial Agents and Chemotherapy 1977, 11, 708. (b) Houston, M.E.; Vander Jagt, D.L.; Honek, J.F. Bioorganic & Medicinal Chemistry Letters 1991, 1, 623.]. It is the most direct and convenient method to introduce trifluoromethylthio directly through C-H bond activation. Currently there is only one copper-catalyzed benzylic trifluoromethylthiolation of toluene analogues [Chen C., Xu X.-H., Yang B., Qing F.-L.Organic Letters 2014,16,3372.], The above reaction requires a large excess of ra...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D333/54C07D307/79C07D209/08C07D333/18C07C319/14C07C321/20C07C323/56C07C323/16C07C321/22C07D213/64C07C323/22C07D275/04C07J1/00C07D311/72C07D307/46
CPCC07D333/54C07D307/79C07D209/08C07D333/18C07C319/14C07D213/64C07D275/04C07J1/0011C07D311/72C07D307/46C07C2603/18C07C2601/14C07C2602/08C07C321/20C07C323/56C07C323/16C07C321/22C07C323/22
Inventor 谢劲朱成建徐文涛
Owner NANJING UNIV