Method for selectively synthesizing benzyl trifluoromethyl sulfide

A technology of benzyl trifluoromethyl sulfide and selectivity, which is applied in the field of selective synthesis of benzyl trifluoromethyl sulfide, can solve problems such as excess and poor substrate compatibility, and achieves avoiding residues and mild reaction conditions. Effect

Active Publication Date: 2020-05-01
NANJING UNIV
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  • 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

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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

Examples

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-isopentylbenzo[b]thiophene (40.8mg, 0.2mmol), 4CzIPN (provided by Beijing Warwick Chemical Co., Ltd., the same below) (3.2mg, 0.004mmol), K 2 CO 3 (5.52mg, 0.04mmol) was added to the reaction tube, evacuated three times through the vacuum line, and under an argon atmosphere, 4mL of anhydrous acetonitrile was added. Then put it under the irradiation of two 45W blue lights (Kessil, A360NE / WE, the same below), and react at room temperature for 12h. Dry loading, column chromatography (300-400 mesh chromatography silica gel) to obtain 44.4 mg of product, (Eluent: n-hexane), the yield is 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 )δ-39.98; 13 C NMR(101M...

Embodiment 2

[0054] Weigh first (64.3mg, 0.26mmol), 4CzIPN (3.2mg, 0.004mmol), K 2 CO 3 (5.52mg, 0.04mmol), add to the reaction tube, ventilate three times through the vacuum line, under argon atmosphere, add 4mL anhydrous acetonitrile, and then carefully add (37.7mg, 0.2mmol), then placed under the irradiation of two 45W blue light, and react at room temperature for 12h. Dry loading, column chromatography (300-400 mesh chromatography silica gel) to obtain 44.2mg of product, (Eluent: n-hexane), the yield is 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, 7.4 Hz, 1H), 1.65 (dp, J = 13.2, 6.6 Hz, 1H), 0.95 (dd, J = 6.6, 5.4 Hz, 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),25.8,22.4,21.7.HRMS(EI)calcd for C 14 H 15 F 3 ...

Embodiment 3

[0056] Weigh first (64.3mg, 0.26mmol), 4CzIPN (3.2mg, 0.004mmol), K 2 CO 3 (5.52mg, 0.04mmol), add to the reaction tube, ventilate three times through the vacuum line, under argon atmosphere, add 4mL anhydrous acetonitrile, and then carefully add (40.3mg, 0.2mmol), then placed under two 45W blue lights, and reacted at room temperature for 12h. Dry loading, column chromatography (300-400 mesh chromatography silica gel) to obtain 34.2mg of product, (Eluent: volume ratio, petroleum ether 60-90: ethyl acetate = 20:1), the yield is 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, 0.8 Hz, 1H), 4.31 (dd, J = 9.1, 6.2 Hz, 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),125.9,124.6,119.8,116.8,109.1,51.5,30.1,23.9,12.0.HRMS m / z(ESI)calcdfor C 14 H 14 F 3 NNaOS + (M...

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Abstract

The invention discloses a method for selectively synthesizing benzyl trifluoromethyl sulfide. The method comprises the following steps: taking alkyl aromatic hydrocarbon ArCHR1R2 as a raw material; and under irradiation by a blue light lamp, in a solution, under the argon atmosphere and under presence of a small amount of potassium carbonate, taking 4CzIPN as a photocatalyst to react with 2-((trifluoromethyl) sulfenyl)isoindoline-1, 2, 3, 4-thiadiazole to obtain photocatalyst 4CzIPN shown in the benzyl trifluoromethyl sulfide ArCR1R2SCF3 (3), wherein the photocatalyst 4CzIPN has the followingstructure shown in the specification. According to the method, the reaction conditions are mild, no oxidizing agent or high-temperature condition is needed, residues of transition metal are avoided, and benzyl trifluoromethyl sulfide is directly obtained from alkyl arene and trifluoromethyl sulfide reagents which are stable and easy to obtain.

Description

Technical field [0001] The invention relates to a method for selectively synthesizing benzyl trifluoromethyl sulfide. Background technique [0002] Trifluoromethylthio functional group is an important type of functional group [see: Xu, XH; Matsuzaki, K.; Shibata, N. Chem. Rev. 2015, 115, 731.], and it is also widely present in many drug molecules (tiflorex, toltrazuril , tiflorex, etc.) and biologically active molecular structures [see: (a) Counts, GW; Gregory, D.; Zeleznik, D.; Turck, M. Antimicrobial Agents and Chemotherapy 1977, 11,708. (b) Houston, ME; Vander Jagt, DL; Honek, JF Bioorganic & Medicinal Chemistry Letters 1991, 1, 623.]. The introduction of trifluoromethylthio group directly through C-H bond activation is the most direct and convenient method. At present, there is only one copper-catalyzed trifluoromethylthio of toluene analogues at the benzyl position [Chen C.,Xu X.-H.,Yang B.,Qing F.-L.Organic Letters 2014,16,3372.], The above reaction requires a large exce...

Claims

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Application Information

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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
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