CN111087385B - 选择性合成苄基三氟甲基硫醚的方法 - Google Patents

选择性合成苄基三氟甲基硫醚的方法 Download PDF

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CN111087385B
CN111087385B CN201911381050.8A CN201911381050A CN111087385B CN 111087385 B CN111087385 B CN 111087385B CN 201911381050 A CN201911381050 A CN 201911381050A CN 111087385 B CN111087385 B CN 111087385B
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谢劲
朱成建
徐文涛
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Abstract

一种选择性合成苄基三氟甲基硫醚的方法，它是以烷基芳烃ArCHR1R2为原料，在蓝光灯照射下，在溶液中，氩气气氛下，在少量碳酸钾存在下，以4CzIPN为光催化剂，与2‑((三氟甲基)硫基)异二氢吲哚‑1,3‑二酮
Figure DDA0002342254970000011
2a在室温下反应，得到得到苄基三氟甲基硫醚ArCR1R2SCF3(3)所述的光催化剂4CzIPN有如下结构：

Description

选择性合成苄基三氟甲基硫醚的方法
技术领域
本发明涉及一种选择性合成苄基三氟甲基硫醚的方法。
背景技术
三氟甲硫基官能团是一类重要的官能团[参见：Xu,X.H.；Matsuzaki,K.；Shibata,N.Chem.Rev.2015,115,731.]，同时也广泛存在于许多药物分子(tiflorex,toltrazuril,tiflorex，等)和生物活性分子结构中[参见：(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.]。直接通过C-H键活化来引入三氟甲硫基是最直接便捷的手段。目前只有一种铜催化的甲苯类似物的苄位三氟甲硫基化[Chen C.,Xu X.-H.,Yang B.,Qing F.-L.OrganicLetters 2014,16,3372.]，上述反应需要大大过量的原料，且需要强氧化剂激发，同时使用了金属试剂AgSCF3，底物兼容性差。因此，在无过渡金属条件下对苄基三氟甲基硫醚的高效选择性合成仍然是一大挑战。作为反应的原料，含苄基的烷基芳烃和杂环芳烃是非常易得的，并且在2018的畅销药物中，25％的药物分子均含有苄基C-H键[https://njardarson.lab.arizona.edu/sites/njardarson.lab.arizona.edu/files/2018Top200PharmaceuticalRetailSalesPosterLowResFinal_0.pdf]。本发明采用一种光催化激发，通过内部氢转移策略，直接高效定点实现一级、二级以及三级苄位C-H键的三氟甲硫基化，可以高效实现各类苄位三氟甲基硫醚的制备，该方法具有高选择性，广泛的兼容性，并且对于复杂分子以及药物均能实现三氟甲硫基化，该方法加速了先导化合物的优化，促进含氟药物的发展。
发明内容
本发明要解决的技术问题是提供一种选择性合成苄基三氟甲基硫醚以及其应用。
本发明的合成路线如下：
Figure BDA0002342254960000021
一种选择性合成苄基基三氟甲基硫醚的方法，它是以烷基芳烃或杂环芳烃ArCHR1R2为原料，在蓝光灯照射下，在无水乙腈中，氩气气氛下，在少量碳酸钾存在下，以光催化剂4CzIPN与沈试剂[2-((三氟甲基)硫基)异二氢吲哚-1,3-二酮)]
Figure BDA0002342254960000022
2a在室温下反应，得到三级烷基三氟甲基硫醚ArCR1R2SCF3(3a)；
所述的光催化剂4CzIPN有如下结构：
Figure BDA0002342254960000023
上述的制备方法，所述的ArCHR1R2中的Ar可以是芳环、或杂芳环，R1与R2基团可以是氢或烷基。
上述的制备方法，所述的ArCHR1R2 1与沈试剂2a的物质的量之比是1:1.3-1:2.5，优选的是1:1.3。
上述的制备方法，所述的光催化剂4CzIPN是烷基芳烃摩尔数的2％的摩尔量。
上述的制备方法，所述的碳酸钾是烷基芳烃1摩尔数的10-20％的摩尔量。
典型反应如下：
Figure BDA0002342254960000031
本发明的方法反应条件温和，不需要氧化剂以及高温条件，同时避免了过渡金属的残留，从稳定易得的烷基芳烃与三氟甲基硫试剂直接得到苄基三氟甲基硫醚。
原料合成：
原料N-三氟甲硫基邻苯二甲酰亚胺的合成
根据沈其龙老师的文献(Kang,K.；Xu,C.；Shen,Q.Organic ChemistryFrontiers2014,1,294.)，用AgSCF3(三氟甲硫醇银)和N-Bromophthalimide(N-溴邻苯二甲酰亚胺)在无水乙腈中，氩气条件下反应3h，然后通过旋转蒸发仪，蒸掉多余的乙腈，用15mL二氯甲烷溶解，过滤，取滤液，移除二氯甲烷，即可得到白色固体(N-三氟甲硫基邻苯二甲酰亚胺)。
Figure BDA0002342254960000032
2-((trifluoromethyl)thio)isoindoline-1,3-dione(N-三氟甲硫基邻苯二甲酰亚胺)2a,1H NMR(400MHz,CDCl3)δ8.03(dd,J＝5.4,3.1Hz,2H),7.89(dd,J＝5.4,3.1Hz,2H)；19F NMR(376MHz,CDCl3)δ-48.93；13C NMR(101MHz,CDCl3)δ165.7,135.4,131.4,127.9(q,J＝314.9Hz),124.7.
原料烷基芳烃的合成
通用步骤一：
Figure BDA0002342254960000033
根据文献(J.Am.Chem.Soc.,2015,137,14590)进行合成，具体操作如下，首先取一个100mL的Schlenk反应瓶，真空管线抽换气三次，氩气氛围下加入15mL无水四氢呋喃，和20mmol的芳烃，然后于-78℃下缓慢滴加正丁基锂(23mmol)，小心滴加完成后，然后缓慢恢复至室温，再置于45℃下反应2h，然后再冷却至-78℃，滴加溴代异戊烷(22mmol)的无水四氢呋喃(15mL)溶液，完成后置于室温过夜反应，然后用乙酸乙酯萃取，合并有机相，无水硫酸钠干燥，然后旋干拌样，柱色谱纯化，即可得到烷基芳烃。
Figure BDA0002342254960000041
2-isopentylbenzo[b]thiophene,1H NMR(500MHz,CDCl3)δ7.74(d,J＝7.9Hz,1H),7.64(d,J＝7.7Hz,1H),7.30–7.26(m,1H),7.22(td,J＝7.7,7.2,1.2Hz,1H),6.98(s,1H),2.92–2.87(m,2H),1.69–1.60(m,3H),0.95(d,J＝6.3Hz,6H)；13C NMR(126MHz,CDCl3)δ147.0,140.2,139.2,124.0,123.3,122.6,122.1,120.3,40.2,28.7,27.5,22.4.
Figure BDA0002342254960000042
-isopentylbenzofuran,1H NMR(400MHz,CDCl3)δ7.49–7.45(m,1H),7.40(dt,J＝7.7,1.1Hz,1H),7.22–7.13(m,2H),6.36(d,J＝1.0Hz,1H),2.81–2.73(m,2H),1.64(ddt,J＝9.8,5.3,3.1Hz,3H),0.95(d,J＝6.2Hz,6H)；13C NMR(101MHz,CDCl3)δ159.9,154.6,129.0,123.0,122.3,120.1,110.7,101.6,36.6,27.6,26.4,22.4.
通用步骤二：
Figure BDA0002342254960000043
具体操作如下，首先取一个100mL的圆底反应瓶，依次加入溶剂二氯甲烷、芳烃Ar2和无水三氯化铝，在冰浴下搅拌，滴加酰氯，完成后于0℃下反应3h，然后转移至室温下反应1h。结束后，水淬灭，乙酸乙酯萃取，合并有机相，无水硫酸钠干燥，然后旋干拌样，柱色谱纯化，即可得到烷基芳烃。(Suhana H.,Srinivasan P.C.Synthetic Communications,2003,33,3097.)
Figure BDA0002342254960000051
(4-ethylphenyl)(phenyl)methanone,1H NMR(400MHz,CDCl3)δ7.83–7.72(m,4H),7.61–7.54(m,1H),7.48(t,J＝7.5Hz,2H),7.31(d,J＝8.3Hz,2H),2.74(q,J＝7.6Hz,2H),1.29(t,J＝7.6Hz,3H)；13C NMR(101MHz,CDCl3)δ196.5,149.4,137.9,135.1,132.1,130.4,129.9,128.2,127.8,29.0,15.3.
Figure BDA0002342254960000052
(4-chlorophenyl)(4-ethylphenyl)methanone,1H NMR(400MHz,CDCl3)δ7.73(dd,J＝11.0,8.4Hz,4H),7.45(d,J＝8.5Hz,2H),7.31(d,J＝8.2Hz,2H),2.74(q,J＝7.6Hz,2H),1.28(t,J＝7.6Hz,3H)；13C NMR(101MHz,CDCl3)δ195.2,149.7,138.6,136.2,134.7,131.4,130.3,128.5,127.9,29.0,15.2.
Figure BDA0002342254960000053
(4-bromophenyl)(4-ethylphenyl)methanone,1H NMR(400MHz,CDCl3)δ7.72(d,J＝8.2Hz,2H),7.67(d,J＝8.6Hz,2H),7.62(d,J＝8.6Hz,2H),7.31(d,J＝8.2Hz,2H),2.74(q,J＝7.6Hz,2H),1.28(t,J＝7.6Hz,3H)；13C NMR(101MHz,CDCl3)δ195.4,149.8,136.7,134.7,131.5,131.5,130.3,127.9,127.2,29.0,15.3.
Figure BDA0002342254960000054
(4-ethylphenyl)(4-methoxyphenyl)methanone,1H NMR(400MHz,CDCl3)δ7.82(d,J＝8.9Hz,2H),7.70(d,J＝8.2Hz,2H),7.29(d,J＝8.2Hz,2H),6.95(d,J＝8.9Hz,2H),3.87(s,3H),2.73(q,J＝7.6Hz,2H),1.28(t,J＝7.6Hz,3H)；13C NMR(101MHz,CDCl3)δ195.3,163.0,148.8,135.7,132.4,130.4,130.0,127.6,113.4,55.4,28.9,15.3.
Figure BDA0002342254960000061
(2-chloro-4-fluorophenyl)(4-ethylphenyl)methanone,1H NMR(400MHz,CDCl3)δ7.72(d,J＝8.3Hz,2H),7.37(dd,J＝8.5,6.0Hz,1H),7.29(d,J＝8.4Hz,2H),7.21(dd,J＝8.6,2.4Hz,1H),7.08(td,J＝8.2,2.4Hz,1H),2.72(q,J＝7.6Hz,2H),1.27(t,J＝7.6Hz,3H)；19F NMR(376MHz,CDCl3)δ-108.21(td,J＝8.2,6.1Hz)；13C NMR(101MHz,CDCl3)δ193.9,163.1(d,J＝253.2Hz),151.0,135.0(d,J＝3.6Hz),134.1,132.8(d,J＝10.4Hz),130.7(d,J＝9.3Hz),130.3,128.2,117.5(d,J＝24.8Hz),114.1(d,J＝21.6Hz),29.0,15.1.
Figure BDA0002342254960000062
(4-ethylphenyl)(furan-2-yl)methanone,1H NMR(400MHz,CDCl3)δ7.91(d,J＝8.2Hz,2H),7.67(dd,J＝1.7,0.8Hz,1H),7.30(d,J＝8.1Hz,2H),7.21(dd,J＝3.6,0.8Hz,1H),6.56(dd,J＝3.6,1.7Hz,1H),2.70(q,J＝7.6Hz,2H),1.26(t,J＝7.6Hz,3H)；13C NMR(101MHz,CDCl3)δ182.0,152.2,149.3,146.7,134.6,129.3,127.7,120.0,111.9,28.7,15.0.
通用步骤三：
Figure BDA0002342254960000063
具体操作如下，首先取一个100mL的圆底反应瓶，依次加入溶剂羧酸或者酰胺或者醇，碱(碳酸钾或者碳酸铯)，N,N-二甲基甲酰胺，溴代烷烃，塞上塞子，于130℃下过夜反应，结束后，水淬灭，乙酸乙酯萃取，合并有机相，无水硫酸钠干燥，然后旋干拌样，柱色谱纯化，即可得到烷基芳烃。(W.Xu,J.Ma,X.A.Yuan,J.Dai,J.Xie,C.Zhu,Angew.Chem.Int.Ed.2018,57,10357.)
Figure BDA0002342254960000071
2,4-dichloro-1-(4-chloro-2-(4-phenylbutoxy)phenoxy)benzene,1H NMR(500MHz,CDCl3)δ7.33(d,J＝2.5Hz,1H),7.23(t,J＝7.5Hz,2H),7.13(t,J＝7.4Hz,1H),7.09–7.03(m,2H),6.99(dd,J＝8.8,2.5Hz,1H),6.94–6.84(m,3H),6.55(d,J＝8.8Hz,1H),3.82(t,J＝6.0Hz,2H),2.50(t,J＝7.6Hz,2H),1.59(dq,J＝12.2,6.1Hz,2H),1.49(dt,J＝14.8,7.1Hz,2H)；13C NMR(126MHz,CDCl3)δ152.5,150.9,142.6,141.8,130.5,129.9,128.2,128.2,127.4,127.3,125.6,124.0,122.3,120.7,117.3,114.5,68.6,35.2,28.4,27.3.
Figure BDA0002342254960000072
2-(4-phenylbutyl)benzo[d]isothiazol-3(2H)-one,1H NMR(400MHz,CDCl3)δ7.88(d,J＝8.0Hz,1H),7.71(d,J＝8.2Hz,1H),7.46(ddd,J＝8.1,6.9,1.2Hz,1H),7.33(t,J＝7.5Hz,1H),7.27(t,J＝7.5Hz,2H),7.22–7.13(m,3H),4.54(t,J＝6.3Hz,2H),2.70(t,J＝7.5Hz,2H),1.95–1.78(m,4H)；13C NMR(101MHz,CDCl3)δ163.1,151.5,142.1,128.5,128.4,128.3,125.7,125.4,124.2,123.0,120.0,68.5,35.5,28.6,27.8.
Figure BDA0002342254960000073
4-methylbenzyl 2-(4-(4-chlorobenzoyl)phenoxy)-2-methylpropanoate,1HNMR(500MHz,CDCl3)δ7.69(d,J＝8.5Hz,2H),7.63(d,J＝8.8Hz,2H),7.45(d,J＝8.4Hz,2H),7.14(d,J＝8.1Hz,2H),7.10(d,J＝7.8Hz,2H),6.76(d,J＝8.9Hz,2H),5.16(s,2H),2.30(s,3H),1.66(s,6H)；13C NMR(126MHz,CDCl3)δ194.2,173.4,159.5,138.4,138.3,136.4,132.1,131.9,131.1,130.2,129.2,128.6,128.5,117.2,79.4,67.3,25.4,21.2.
具体实施方式
利用下述实施例将有助于理解本发明，但并不限制本发明的内容。
实施例1
依次称取
Figure BDA0002342254960000081
(按上述方法合成，下同)(64.3mg,0.26mmol)，2-异戊基苯并[b]噻吩
Figure BDA0002342254960000082
(40.8mg,0.2mmol),4CzIPN(北京华威锐科化工有限公司提供，下同)(3.2mg,0.004mmol)，K2CO3(5.52mg,0.04mmol),加入反应管，通过真空管线抽换气三次，在氩气氛围下，加入4mL无水乙腈。然后置于两支45W蓝光灯(Kessil,A360NE/WE，下同。)照射下，室温反应12h。干法上样，柱层析(300-400目层析硅胶)得到产物44.4mg，
Figure BDA0002342254960000083
(洗脱液：正己烷)，产率73％，1H NMR(400MHz,CDCl3)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)；19F NMR(376MHz,CDCl3)δ-39.98；13C NMR(101MHz,CDCl3)δ145.5,139.6,139.1,130.3(q,J＝307.6Hz),124.6,124.5,123.6,122.5,122.4,46.0,44.0,25.8,22.6,21.5.HRMS(EI)calcd for C14H15F3S2(M+):304.0567,found 304.0569.
实施例2
先称取
Figure BDA0002342254960000084
(64.3mg,0.26mmol),4CzIPN(3.2mg,0.004mmol)，K2CO3(5.52mg,0.04mmol),加入反应管，通过真空管线抽换气三次，在氩气氛围下，加入4mL无水乙腈，然后小心加入
Figure BDA0002342254960000091
(37.7mg,0.2mmol)，然后置于两支45W蓝光灯照射下，室温反应12h。干法上样，柱层析(300-400目层析硅胶)得到产物44.2mg，
Figure BDA0002342254960000092
(洗脱液：正己烷)，产率76％，1H NMR(400MHz,CDCl3)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)；19F NMR(376MHz,CDCl3)δ-40.11；13C NMR(101MHz,CDCl3)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 C14H15F3OS(M+):288.0796,found 288.0792.
实施例3
先称取
Figure BDA0002342254960000093
(64.3mg,0.26mmol),4CzIPN(3.2mg,0.004mmol)，K2CO3(5.52mg,0.04mmol),加入反应管，通过真空管线抽换气三次，在氩气氛围下，加入4mL无水乙腈，然后小心加入
Figure BDA0002342254960000094
(40.3mg,0.2mmol)，然后置于两支45W蓝光灯照射下，室温反应12h。干法上样，柱层析(300-400目层析硅胶)得到产物34.2mg，
Figure BDA0002342254960000095
(洗脱液：体积比，石油醚60-90：乙酸乙酯＝20:1)，产率57％，1H NMR(400MHz,CDCl3)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)；19F NMR(376MHz,CDCl3)δ-39.74；13CNMR(101MHz,CDCl3)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 C14H14F3NNaOS+(M+Na)+324.0640；found:324.0635.
实施例4
先称取
Figure BDA0002342254960000101
(64.3mg,0.26mmol),4CzIPN(3.2mg,0.004mmol)，K2CO3(5.52mg,0.04mmol),加入反应管，通过真空管线抽换气三次，在氩气氛围下，加入4mL无水乙腈，然后小心加入
Figure BDA0002342254960000102
(50.5mg,0.2mmol)，然后置于两支45W蓝光灯照射下，室温反应12h。干法上样，柱层析(300-400目层析硅胶)得到产物54.6mg，
Figure BDA0002342254960000103
(洗脱液：正己烷)，产率77％，1H NMR(500MHz,CDCl3)δ7.30(dd,J＝5.0,3.0Hz,1H),7.15(dd,J＝2.9,1.1Hz,1H),7.05(dd,J＝5.0,1.4Hz,1H),4.42(dd,J＝8.5,6.6Hz,1H),2.03–1.89(m,2H),1.39–1.17(m,18H),0.88(t,J＝6.9Hz,3H)；19F NMR(471MHz,CDCl3)δ-39.89；13C NMR(126MHz,CDCl3)δ141.2,130.6(q,J＝307.4Hz),126.4,126.3,122.3,44.8(d,J＝1.7Hz),36.3,31.9,29.6,29.6,29.5,29.3,29.0,27.2,22.7,14.1.HRMS(EI)calcd for C17H27F3S2(M+):352.1506,found352.1515.
实施例5
先称取
Figure BDA0002342254960000104
(64.3mg,0.26mmol),4CzIPN(3.2mg,0.004mmol)，K2CO3(5.52mg,0.04mmol),加入反应管，通过真空管线抽换气三次，在氩气氛围下，加入4mL无水乙腈，然后小心加入
Figure BDA0002342254960000105
(24.1mg,0.2mmol)，然后置于两支45W蓝光灯照射下，室温反应12h。干法上样，柱层析(300-400目层析硅胶)得到产物22.5mg，
Figure BDA0002342254960000111
(洗脱液：正己烷)，产率51％，1H NMR(500MHz,CDCl3)δ7.24(d,J＝8.2Hz,2H),7.15(d,J＝7.9Hz,2H),4.50(q,J＝7.1Hz,1H),2.34(s,3H),1.71(d,J＝7.1Hz,3H)；19F NMR(471MHz,CDCl3)δ-40.16；13C NMR(126MHz,CDCl3)δ138.2,137.8,130.5(q,J＝307.9Hz),129.5,126.9,44.3(d,J＝1.8Hz),23.1,21.1.HRMS(EI)calcd for C10H11F3S(M+):220.0534,found 220.0530.
实施例6
先称取
Figure BDA0002342254960000112
(64.3mg,0.26mmol),4CzIPN(3.2mg,0.004mmol)，K2CO3(2.76mg,0.02mmol),加入反应管，通过真空管线抽换气三次，在氩气氛围下，加入4mL无水乙腈，然后小心加入
Figure BDA0002342254960000113
(38.5mg,0.2mmol)，然后置于两支45W蓝光灯照射下，室温反应12h。干法上样，柱层析(300-400目层析硅胶，下同)得到产物17.5mg，
Figure BDA0002342254960000114
(洗脱液：体积比,石油醚60-90:乙酸乙酯＝5:10)，产率51％，1H NMR(400MHz,CDCl3)δ7.25(s,4H),4.19(dd,J＝8.8,6.4Hz,1H),3.70(s,3H),3.62(s,2H),2.10–1.89(m,2H),0.92(t,J＝7.3Hz,3H)；19F NMR(376MHz,CDCl3)δ-39.79；13C NMR(101MHz,CDCl3)δ171.9,139.3,133.6,130.5(q,J＝308.05Hz),129.6,127.7,52.1,51.0(d,J＝1.7Hz),40.8,29.8,11.9.HRMS m/z(ESI)calcd for C13H15F3NaO2S+(M+Na)+315.0637；found:315.0636.
实施例7
先称取
Figure BDA0002342254960000121
(64.3mg,0.26mmol),4CzIPN(3.2mg,0.004mmol)，K2CO3(2.76mg,0.02mmol),加入反应管，通过真空管线抽换气三次，在氩气氛围下，加入4mL无水乙腈，然后小心加入
Figure BDA0002342254960000122
(38.5mg,0.2mmol)，然后置于两支45W蓝光灯照射下，室温反应12h。干法上样，柱层析(300-400目层析硅胶，下同)得到产物42.0mg，
Figure BDA0002342254960000123
(洗脱液:正己烷)，产率72％，1H NMR(400MHz,CDCl3)δ7.25(d,J＝8.7Hz,2H),6.86(d,J＝8.8Hz,2H),4.51(q,J＝7.0Hz,1H),3.97(t,J＝6.7Hz,2H),1.83(dp,J＝13.4,6.8Hz,1H),1.71(d,J＝7.0Hz,3H),1.67(q,J＝6.8Hz,2H),0.96(d,J＝6.6Hz,6H)；19F NMR(376MHz,CDCl3)δ-40.15；13C NMR(101MHz,CDCl3)δ158.8,132.8,130.5(q,J＝308.7Hz),128.2,114.7,66.4,44.2(d,J＝1.9Hz),38.0,25.1,23.1,22.6.HRMS(EI)calcd for C14H19F3OS(M+):292.1109,found 292.1115.
实施例8
先称取
Figure BDA0002342254960000124
(74.1mg,0.3mmol),4CzIPN(3.2mg,0.004mmol)，K2CO3(5.52mg,0.04mmol),加入反应管，通过真空管线抽换气三次，在氩气氛围下，加入4mL无水乙腈，然后小心加入
Figure BDA0002342254960000125
(购于南京化学试剂股份有限公司；33.7mg,0.2mmol)，然后置于两支45W蓝光灯照射下，室温反应12h。干法上样，柱层析(300-400目层析硅胶，下同)得到产物44.5mg，
Figure BDA0002342254960000126
(洗脱液:正己烷)，产率83％，1H NMR(400MHz,CDCl3)δ7.42–7.38(m,4H),7.37–7.32(m,4H),7.30–7.25(m,2H),5.69(s,1H)；19F NMR(376MHz,CDCl3)δ-40.81；13C NMR(101MHz,CDCl3)δ139.2,130.0(q,J＝309.7Hz),128.8,128.2,127.9,53.5.HRMS(EI)calcd for C14H11F3S(M+):268.0534,found268.0542.
实施例9
先称取
Figure BDA0002342254960000131
(64.3mg,0.26mmol),4CzIPN(3.2mg,0.004mmol)，K2CO3(4.14mg，0.03mmol)，加入反应管，通过真空管线抽换气三次，在氩气氛围下，加入4mL无水乙腈，然后小心加入
Figure BDA0002342254960000132
(购于萨恩化学技术(上海)有限公司；49.9mg,0.2mmol)，然后置于两支45W蓝光灯照射下，室温反应12h。干法上样，柱层析(300-400目层析硅胶，下同)得到产物34.7mg，
Figure BDA0002342254960000133
(洗脱液:体积比，石油醚60-90:乙酸乙酯＝50:1)，产率50％，1H NMR(400MHz,CDCl3)δ7.71(q,J＝8.0Hz,4H),7.57(d,J＝7.8Hz,2H),7.42(d,J＝7.8Hz,2H),4.33(t,J＝7.7Hz,1H),1.98(dq,J＝19.0,6.5,5.2Hz,2H),1.42–1.23(m,4H),0.88(t,J＝6.8Hz,3H)；19F NMR(376MHz,CDCl3)δ-39.72；13CNMR(101MHz,CDCl3)δ144.9,141.6,138.6,132.6,130.5(q,J＝308.4),128.2,127.6,127.5,118.9,111.1,49.2(d,J＝1.8Hz),36.1,29.4,22.1,13.8.HRMS m/z(ESI)calcd forC19H18F3NNaS+(M+Na)+372.1004；found:372.1016.
实施例10
先称取
Figure BDA0002342254960000134
(56.8mg,0.23mmol),4CzIPN(1.6mg,0.002mmol)，K2CO3(2.78mg,0.02mmol),加入反应管，通过真空管线抽换气三次，在氩气氛围下，加入2mL无水乙腈，然后小心加入
Figure BDA0002342254960000141
(购于萨恩化学技术(上海)有限公司；16.7mg,0.1mmol)，然后置于两支45W蓝光灯照射下，室温反应36h。干法上样，柱层析(300-400目层析硅胶，下同)得到产物17.7mg，
Figure BDA0002342254960000142
(洗脱液:正己烷)，产率48％，1H NMR(400MHz,CDCl3)δ7.77(dd,J＝15.2,7.6Hz,4H),7.49(td,J＝7.5,1.1Hz,2H),7.41(td,J＝7.6,1.2Hz,2H)；19FNMR(376MHz,CDCl3)δ-38.16；13C NMR(101MHz,CDCl3)δ142.9,138.6,130.5,128.3,128.2(q,J＝313.4Hz),125.7,120.8,63.2.IR(ATR):ν＝3064,2921,1451,1145,1110,1098,742cm-1.HRMS(EI)calcd for C15H8F6S2(M+):365.9972,found 365.9977.
实施例11
先称取
Figure BDA0002342254960000143
(123.5mg,0.5mmol),4CzIPN(3.2mg,0.004mmol)，K2CO3(5.52mg,0.04mmol),加入反应管，通过真空管线抽换气三次，在氩气氛围下，加入2mL无水乙腈，然后小心加入
Figure BDA0002342254960000144
(购于上海阿拉丁生化科技股份有限公司；26.9mg,0.1mmol)，然后置于两支45W蓝光灯照射下，室温反应36h。干法上样，柱层析(300-400目层析硅胶，下同)得到产物34.2mg，
Figure BDA0002342254960000145
(洗脱液:正己烷)，产率51％，1H NMR(500MHz,CDCl3)δ7.37(d,J＝1.5Hz,1H),7.33(d,J＝1.5Hz,3H),4.51(q,J＝7.1Hz,2H),1.72(d,J＝7.0Hz,6H)；19F NMR(471MHz,CDCl3)δ-40.16；13C NMR(126MHz,CDCl3)δ141.1,130.4(q,J＝307.4Hz),127.8,127.6,127.5,44.1(d,J＝0.8Hz),22.9.IR(ATR):ν＝22981,2359,1111,838,750cm-1.HRMS(EI)calcd for C12H12F6S2(M+):334.0285,found 334.0296.
实施例12
先称取
Figure BDA0002342254960000151
(37.1mg,0.15mmol),
Figure BDA0002342254960000152
(购于上海麦克林生化科技有限公司；18.5mg,0.1mmol)，4CzIPN(1.6mg,0.002mmol)，K2CO3(2.78mg,0.02mmol),加入反应管，通过真空管线抽换气三次，在氩气氛围下，加入2mL无水乙腈，然后置于两支45W蓝光灯照射下，室温反应24h。干法上样，柱层析(300-400目层析硅胶，下同)得到产物18.5mg，
Figure BDA0002342254960000153
(洗脱液:体积比，石油醚60-90:乙酸乙酯＝2:1)，产率51％，1HNMR(400MHz,CDCl3)δ7.50(dd,J＝8.3,6.6Hz,2H),7.47–7.39(m,2H),7.39–7.32(m,3H),6.69(d,J＝9.5Hz,1H),3.91(s,2H)；19F NMR(376MHz,CDCl3)δ-41.10；13C NMR(101MHz,CDCl3)δ161.6,140.5,137.2,134.3,130.4(q,J＝308.4Hz),129.5,128.7,126.5,122.5,113.1,31.2(q,J＝2.5Hz).HRMS m/z(ESI)calcd for C13H11F3NOS+(M+H)+286.0508；found:286.0506.
实施例13
先称取
Figure BDA0002342254960000154
(64.3mg,0.26mmol),4CzIPN(3.2mg,0.004mmol)，K2CO3(5.52mg,0.04mmol),加入反应管，通过真空管线抽换气三次，在氩气氛围下，加入4mL无水乙腈，然后小心加入
Figure BDA0002342254960000155
(56.7mg,0.2mmol)，然后置于45W蓝光灯照射下，室温反应12h。干法上样，柱层析(300-400目层析硅胶)得到产物52.5mg，
Figure BDA0002342254960000156
(洗脱液:体积比，石油醚60-90:乙酸乙酯＝100:1)，产率69％，1H NMR(400MHz,CDCl3)δ7.88(d,J＝8.0Hz,1H),7.76(d,J＝8.2Hz,1H),7.54–7.48(m,1H),7.41–7.27(m,6H),4.52(t,J＝6.3Hz,2H),4.40(dd,J＝9.1,6.4Hz,1H),2.32–2.11(m,2H),1.99–1.77(m,2H)19F NMR(376MHz,CDCl3)δ-39.73；13C NMR(101MHz,CDCl3)δ162.9,151.6,140.1,130.4(q,J＝308.4Hz),128.9,128.7,128.1,127.4,125.2,124.4,123.0,120.2,67.7,49.3,33.1,26.8.HRMS m/z(ESI)calcd for C18H17F3NOS2 +(M+H)+384.0698；found:384.0692.
实施例14
先称取
Figure BDA0002342254960000161
(64.3mg,0.26mmol),
Figure BDA0002342254960000162
(57.7mg,0.2mmol)，4CzIPN(3.2mg,0.004mmol)，K2CO3(5.52mg,0.04mmol),加入反应管，通过真空管线抽换气三次，在氩气氛围下，加入4mL无水乙腈，然后置于45W蓝光灯照射下，室温反应12h。干法上样，柱层析(300-400目层析硅胶)得到产物52.5mg，
Figure BDA0002342254960000163
(洗脱液:体积比，石油醚60-90:乙酸乙酯＝50:1)，产率53％，1H NMR(400MHz,CDCl3)δ8.03(d,J＝8.4Hz,2H),7.42(d,J＝8.3Hz,2H),4.93(td,J＝10.9,4.4Hz,1H),4.55(q,J＝7.1Hz,1H),2.11(ddt,J＝9.3,4.7,2.4Hz,1H),1.95(pd,J＝7.0,2.8Hz,1H),1.77–1.69(m,5H),1.59–1.50(m,2H),1.17–1.06(m,2H),0.92(dd,J＝6.8,4.2Hz,7H),0.79(d,J＝6.9Hz,3H)；19FNMR(376MHz,CDCl3)δ-40.12；13C NMR(101MHz,CDCl3)δ165.6,146.4(d,J＝2.5Hz),130.5,130.3(q,J＝308.4Hz),130.1,127.0,75.0,47.3,44.1(d,J＝1.8Hz),41.0,34.3,31.5,26.5,23.6,22.8,22.0,20.8,16.5.HRMS m/z(ESI)calcd for C20H27F3NaO2S+(M+Na)+411.1576；found:411.1581.
实施例15
先称取
Figure BDA0002342254960000171
(64.3mg,0.26mmol),
Figure BDA0002342254960000172
(购于上海毕得医药科技有限公司；48.9mg,0.2mmol)，4CzIPN(3.2mg,0.004mmol)，K2CO3(5.52mg,0.04mmol),加入反应管，通过真空管线抽换气三次，在氩气氛围下，加入4mL无水乙腈，然后置于45W蓝光灯照射下，室温反应12h。干法上样，柱层析(300-400目层析硅胶)得到产物42.8mg，
Figure BDA0002342254960000173
(洗脱液:体积比，石油醚60-90：乙酸乙酯＝50:1)，产率62％，1H NMR(400MHz,CDCl3)δ7.69(d,J＝1.8Hz,1H),7.36(d,J＝1.8Hz,1H),5.52(dd,J＝5.8,2.6Hz,1H),2.63(s,3H),2.48(d,J＝5.9Hz,2H),1.41(s,3H),1.37(s,9H),1.35(s,3H)；19F NMR(376MHz,CDCl3)δ-41.11；13C NMR(101MHz,CDCl3)δ199.5,154.8,153.1,134.9,134.5,130.8(q,J＝308.7Hz),125.8,123.5,49.1,46.4,43.2,35.0,31.4,31.1,29.6,28.4.HRMSm/z(ESI)calcd for C18H23F3NaOS+(M+Na)+367.1314；found:367.1311.
实施例16
先称取
Figure BDA0002342254960000174
(64.3mg,0.26mmol),4CzIPN(3.2mg,0.004mmol)，K2CO3(5.52mg,0.04mmol),加入反应管，通过真空管线抽换气三次，在氩气氛围下，加入4mL无水乙腈，再加入
Figure BDA0002342254960000175
(84.4mg，0.2mmol)，然后置于45W蓝光灯照射下，室温反应12h。干法上样，柱层析(300-400目层析硅胶)得到产物47.8mg，
Figure BDA0002342254960000181
(洗脱液:体积比，石油醚60-90：乙酸乙酯＝50:1)，产率46％，1H NMR(400MHz,CDCl3)δ7.40(s,1H),7.31(dt,J＝13.9,7.0Hz,3H),7.21(d,J＝7.5Hz,2H),7.06(d,J＝8.8Hz,1H),7.00–6.86(m,3H),6.58(d,J＝8.8Hz,1H),4.21(t,J＝7.8Hz,1H),3.86(t,J＝5.8Hz,2H),1.87(dt,J＝13.7,7.2Hz,2H),1.72–1.50(m,2H)；19F NMR(376MHz,CDCl3)δ-39.79；13C NMR(101MHz,CDCl3)δ152.5,150.7,142.7,140.1,130.7,130.4(q,J＝308.4Hz),130.3,128.8,128.0,127.8,127.6,127.3,124.1,122.4,121.3,117.3,114.7,68.1,49.2(d,J＝2.0Hz),32.8,26.9.HRMS m/z(ESI)calcd for C23H18Cl3F3NaO2S+(M+Na)+542.9937；found:542.9934.
实施例17
先称取
Figure BDA0002342254960000182
(37.1mg,0.15mmol),
Figure BDA0002342254960000183
(42.3mg,0.1mmol)，4CzIPN(1.6mg,0.002mmol)，K2CO3(5.52mg,0.02mmol),加入反应管，通过真空管线抽换气三次，在氩气氛围下，加入2mL无水乙腈，然后置于45W蓝光灯照射下，室温反应24h。干法上样，柱层析(300-400目层析硅胶)得到产物37.1mg，
Figure BDA0002342254960000184
(洗脱液:体积比，石油醚60-90：乙酸乙酯＝10:1)，产率71％，1H NMR(400MHz,CDCl3)δ8.01(d,J＝8.3Hz,2H),7.42(d,J＝8.3Hz,2H),4.94(tt,J＝11.3,4.9Hz,1H),4.55(q,J＝7.1Hz,1H),2.44(dd,J＝19.2,8.6Hz,1H),2.08(dt,J＝19.2,9.0Hz,1H),2.01–1.90(m,2H),1.85–1.45(m,12H),1.40–1.25(m,6H),1.17–0.98(m,2H),0.90(s,3H),0.87(s,3H),0.76(ddd,J＝11.9,10.2,3.9Hz,1H)；19F NMR(376MHz,CDCl3)δ-40.11；13C NMR(101MHz,CDCl3)δ221.2,165.6,146.4,130.5,130.2(q,J＝308.4Hz),130.1,127.0,74.3,54.3,51.4,47.8,44.7,44.1(d,J＝1.9Hz),36.7,35.9,35.7,35.1,34.0,31.5,30.8,28.3,27.5,22.8,21.8,20.5,13.8,12.3.HRMS m/z(ESI)calcd forC29H37F3NaO3S+(M+Na)+545.2308；found:545.2299.
实施例18
先称取
Figure BDA0002342254960000191
(37.1mg,0.15mmol),4CzIPN(1.6mg,0.002mmol)，K2CO3(2.78mg,0.02mmol),加入反应管，通过真空管线抽换气三次，在氩气氛围下，加入2mL无水乙腈，再加入
Figure BDA0002342254960000192
(44.5mg，0.1mmol)，然后置于45W蓝光灯照射下，室温反应24h。干法上样，柱层析(300-400目层析硅胶)得到产物16.9mg，
Figure BDA0002342254960000193
(洗脱液:体积比，石油醚60-90：乙酸乙酯＝50:1)，产率31％，1H NMR(400MHz,CDCl3)δ7.07(d,J＝2.8Hz,1H),6.79(d,J＝2.8Hz,1H),4.54(dd,J＝9.2,6.4Hz,1H),2.45(dd,J＝14.2,6.4Hz,1H),2.27(s,3H),2.21–2.16(m,1H),2.15(s,3H),1.51(dd,J＝12.3,6.0Hz,3H),1.41–1.19(m,15H),1.16–1.01(m,6H),0.85(dd,J＝11.0,6.6Hz,12H)；19F NMR(376MHz,CDCl3)δ-40.03；13C NMR(101MHz,CDCl3)δ170.0,149.9,142.9,131.0(q,J＝308.4Hz),128.4,123.8,119.3,118.1,76.9,41.0,39.4,38.4,37.9,37.4,37.3(d,J＝3.7Hz),37.2,32.8,32.6,28.0,25.6,24.8,24.4,22.7,22.6,21.1,21.0,19.7,19.6,16.3.HRMS m/z(ESI)calcd for C30H47F3NaO3S+(M+Na)+567.3090；found:567.3089.
实施例19
先称取
Figure BDA0002342254960000201
(64.3mg,0.26mmol),4CzIPN(3.2mg,0.004mmol)，K2CO3(5.52mg,0.04mmol),加入反应管，通过真空管线抽换气三次，在氩气氛围下，加入4mL无水乙腈，再加入
Figure BDA0002342254960000202
(44.1mg，0.2mmol)，然后置于45W蓝光灯照射下，室温反应12h。干法上样，柱层析(300-400目层析硅胶)得到产物52.5mg，
Figure BDA0002342254960000203
(洗脱液:体积比，石油醚60-90：乙酸乙酯＝50:1)，产率81％，1H NMR(500MHz,CDCl3)δ7.24(q,J＝8.4Hz,4H),4.07(d,J＝7.3Hz,1H),3.72(q,J＝7.2Hz,1H),3.67(s,3H),2.18–2.08(m,J＝6.7Hz,1H),1.49(d,J＝7.2Hz,3H),1.05(d,J＝6.7Hz,3H),0.90(d,J＝6.7Hz,3H)；19F NMR(471MHz,CDCl3)δ-39.90；13C NMR(126MHz,CDCl3)δ174.9(d,J＝1.2Hz),139.7(d,J＝1.7Hz),139.3,130.8(q,J＝307.0Hz),128.2,127.4,56.7(d,J＝0.6Hz),52.0,45.0,34.0,20.5,20.4,18.5.HRMS m/z(ESI)calcd for C15H19F3NaO2S+(M+Na)+343.0950；found:343.0952.
实施例20
先称取
Figure BDA0002342254960000204
(64.3mg,0.26mmol),4CzIPN(3.2mg,0.004mmol)，K2CO3(5.52mg,0.04mmol),加入反应管，通过真空管线抽换气三次，在氩气氛围下，加入4mL无水乙腈，再加入
Figure BDA0002342254960000205
(84.6，0.2mmol)，然后置于45W蓝光灯照射下，室温反应12h。干法上样，柱层析(300-400目层析硅胶)得到产物54.3mg，
Figure BDA0002342254960000206
(洗脱液:体积比，石油醚60-90：乙酸乙酯＝20:1)，产率52％，1H NMR(400MHz,CDCl3)δ7.67(dd,J＝20.6,8.7Hz,4H),7.44(d,J＝8.5Hz,2H),7.30–7.19(m,4H),6.78(d,J＝8.8Hz,2H),5.18(s,2H),4.07(s,2H),1.68(s,6H)；19F NMR(376MHz,CDCl3)δ-41.53；13C NMR(101MHz,CDCl3)δ194.1,173.4,159.4,138.4,136.3,135.5,134.9,131.9,131.1,130.5(q,J＝308.4Hz),130.3,129.0,128.9,128.5,117.2,79.4,66.8,33.8(q,J＝2.4Hz),25.4.HRMS m/z(ESI)calcd for C26H22ClF3NaO4S+(M+Na)+545.0772；found:545.0771.
实施例21
先称取
Figure BDA0002342254960000211
(64.3mg,0.26mmol),4CzIPN(3.2mg,0.004mmol)，K2CO3(5.52mg,0.04mmol),加入反应管，通过真空管线抽换气三次，在氩气氛围下，加入4mL无水乙腈，再加入
Figure BDA0002342254960000212
(52.9，0.2mmol)，然后置于45W蓝光灯照射下，室温反应12h。干法上样，柱层析(300-400目层析硅胶)得到产物38.2mg，
Figure BDA0002342254960000213
(洗脱液:体积比，石油醚60-90：乙酸乙酯＝50:1)，产率53％，1H NMR(400MHz,CDCl3)δ7.12(d,J＝7.6Hz,1H),6.71(d,J＝7.6Hz,1H),6.65(s,1H),4.08(s,2H),3.96(p,J＝2.6Hz,2H),3.67(s,3H),2.33(s,3H),1.74(d,J＝2.9Hz,4H),1.22(s,6H)；19F NMR(376MHz,CDCl3)δ-41.68；13C NMR(101MHz,CDCl3)δ178.3,156.6,139.7,131.2(q,J＝307.7Hz),130.1,121.1,120.8,112.3,68.0,51.7,42.1,37.1,29.1(q,J＝2.3Hz),25.2,25.0,21.6.HRMS m/z(ESI)calcd for C17H23F3NaO3S+(M+Na)+387.1212；found:387.1212.
实施例22
先称取
Figure BDA0002342254960000221
(64.3mg,0.26mmol),
Figure BDA0002342254960000222
(64.3mg,0.2mmol),4CzIPN(3.2mg,0.004mmol)，K2CO3(5.52mg,0.04mmol),加入反应管，通过真空管线抽换气三次，在氩气氛围下，加入4mL无水乙腈，然后置于45W蓝光灯照射下，室温反应12h。干法上样，柱层析(300-400目层析硅胶)得到产物53.2mg，
Figure BDA0002342254960000223
(洗脱液:体积比，石油醚60-90：乙酸乙酯＝10:1)，产率63％，1H NMR(400MHz,CDCl3)δ7.81(d,J＝8.3Hz,2H),7.39(d,J＝8.3Hz,2H),7.04(d,J＝7.5Hz,1H),4.82(td,J＝7.7,4.9Hz,1H),4.23(dd,J＝8.8,6.5Hz,1H),3.79(s,3H),3.66(s,3H),2.49(qt,J＝16.9,7.1Hz,2H),2.33(dtd,J＝14.3,7.1,4.9Hz,1H),2.18(tq,J＝14.6,7.3Hz,1H),2.08–1.89(m,2H),0.92(t,J＝7.3Hz,3H)；19F NMR(376MHz,CDCl3)δ-39.75；13C NMR(101MHz,CDCl3)δ173.8,172.4,166.6,144.8,133.1,130.3(q,J＝308.4Hz),127.8,127.6,52.7,52.3,52.0,50.8(d,J＝1.3Hz),30.2,29.6,27.1,11.9.HRMS m/z(ESI)calcd for C18H23F3NO5S+(M+H)+422.1244；found:422.1240.
实施例23
先称取
Figure BDA0002342254960000224
(64.3mg,0.26mmol),4CzIPN(3.2mg,0.004mmol)，K2CO3(5.52mg,0.04mmol),加入反应管，通过真空管线抽换气三次，在氩气氛围下，加入4mL无水乙腈，再加入
Figure BDA0002342254960000225
(42.1mg，0.2mmol)，然后置于45W蓝光灯照射下，室温反应12h。干法上样，柱层析(300-400目层析硅胶)得到产物42.8mg，
Figure BDA0002342254960000226
(洗脱液:体积比，石油醚60-90：乙酸乙酯＝50:1)，产率69％，1H NMR(400MHz,CDCl3)δ7.80(d,J＝7.9Hz,4H),7.62–7.57(m,1H),7.52–7.45(m,4H),4.58(q,J＝7.1Hz,1H),1.75(d,J＝7.1Hz,3H)；19F NMR(376MHz,CDCl3)δ-40.07；13C NMR(101MHz,CDCl3)δ196.0,146.1,137.4,137.2,132.5,130.6,130.3(q,J＝308.7Hz),130.0,128.3,127.0,44.1(d,J＝1.9Hz),22.8.HRMS m/z(ESI)calcd for C16H13F3NaOS+(M+Na)+333.0531；found:333.0527.
实施例24
先称取
Figure BDA0002342254960000231
(64.3mg,0.26mmol),4CzIPN(3.2mg,0.004mmol)，K2CO3(5.52mg,0.04mmol),加入反应管，通过真空管线抽换气三次，在氩气氛围下，加入4mL无水乙腈，再加入
Figure BDA0002342254960000232
(48.9mg，0.2mmol)，然后置于45W蓝光灯照射下，室温反应12h。干法上样，柱层析(300-400目层析硅胶)得到产物50.2mg，
Figure BDA0002342254960000233
洗脱液:体积比，石油醚60-90：乙酸乙酯＝50:1)，产率73％，1H NMR(400MHz,CDCl3)δ7.76(dd,J＝8.4,7.2Hz,4H),7.48(dd,J＝8.4,5.3Hz,4H),4.58(q,J＝7.1Hz,1H),1.75(d,J＝7.1Hz,3H)；19F NMR(376MHz,CDCl3)δ-40.07；13C NMR(101MHz,CDCl3)δ194.7,146.4,139.0,136.8,135.7,131.4,130.5,130.2(q,J＝308.4Hz),128.7,127.1,44.1,22.8.HRMS m/z(ESI)calcd for C16H12ClF3NaOS+(M+Na)+367.0142；found:367.0138.
实施例25
先称取
Figure BDA0002342254960000234
(64.3mg,0.26mmol),4CzIPN(3.2mg,0.004mmol)，K2CO3(5.52mg,0.04mmol),加入反应管，通过真空管线抽换气三次，在氩气氛围下，加入4mL无水乙腈，再加入
Figure BDA0002342254960000241
(57.9mg，0.2mmol)，然后置于45W蓝光灯照射下，室温反应12h。干法上样，柱层析(300-400目层析硅胶)得到产物49.8mg，
Figure BDA0002342254960000242
(洗脱液:体积比，石油醚60-90：乙酸乙酯＝50:1)，产率64％，1H NMR(400MHz,CDCl3)δ7.77(d,J＝8.3Hz,2H),7.69–7.61(m,4H),7.48(d,J＝8.3Hz,2H),4.58(q,J＝7.1Hz,1H),1.75(d,J＝7.0Hz,3H)；19F NMR(376MHz,CDCl3)δ-40.06；13C NMR(101MHz,CDCl3)δ194.9,146.4,136.7,136.1,131.7,131.5,130.5,130.2(q,J＝308.7Hz),127.7,127.1,44.1(q,J＝2.0Hz),22.8.HRMS m/z(ESI)calcd for C16H13BrF3OS+(M+H)+388.9817；found:388.9813.
实施例26
先称取
Figure BDA0002342254960000243
(64.3mg,0.26mmol),4CzIPN(3.2mg,0.004mmol)，K2CO3(5.52mg,0.04mmol),加入反应管，通过真空管线抽换气三次，在氩气氛围下，加入4mL无水乙腈，再加入
Figure BDA0002342254960000244
(48.1mg，0.2mmol)，然后置于45W蓝光灯照射下，室温反应12h。干法上样，柱层析(300-400目层析硅胶)得到产物43.4mg，
Figure BDA0002342254960000245
(洗脱液:体积比，石油醚60-90：乙酸乙酯＝50:1)，产率64％，1H NMR(400MHz,CDCl3)1H NMR(400MHz,CDCl3)δ7.82(d,J＝8.8Hz,2H),7.75(d,J＝8.3Hz,2H),7.46(d,J＝8.2Hz,2H),6.97(d,J＝8.9Hz,2H),4.58(q,J＝7.1Hz,1H),3.89(s,3H),1.75(d,J＝7.1Hz,3H)；19F NMR(376MHz,CDCl3)δ-40.07；13C NMR(101MHz,CDCl3)δ194.8,163.3,145.5,137.9,132.5,130.3,130.3(q,J＝308.7Hz),130.0,126.9,113.6,55.5,44.1,22.8.HRMS m/z(ESI)calcdfor C17H16F3O2S+(M+H)+341.0818；found:341.0818.
实施例27
先称取
Figure BDA0002342254960000251
(64.3mg,0.26mmol),4CzIPN(3.2mg,0.004mmol)，K2CO3(5.52mg,0.04mmol),加入反应管，通过真空管线抽换气三次，在氩气氛围下，加入4mL无水乙腈，再加入
Figure BDA0002342254960000252
(52.6mg，0.2mmol)，然后置于45W蓝光灯照射下，室温反应12h。干法上样，柱层析(300-400目层析硅胶)得到产物47.0mg，
Figure BDA0002342254960000253
(洗脱液:体积比，石油醚60-90：乙酸乙酯＝50:1)，产率65％，1H NMR(400MHz,CDCl3)δ7.78(d,J＝8.4Hz,2H),7.46(d,J＝8.3Hz,2H),7.40(dd,J＝8.5,5.9Hz,1H),7.22(dd,J＝8.5,2.4Hz,1H),7.10(td,J＝8.2,2.4Hz,1H),4.56(q,J＝7.1Hz,1H),1.73(d,J＝7.1Hz,3H)；19F NMR(376MHz,CDCl3)δ-40.08,-107.53(td,J＝8.2,6.0Hz)；13C NMR(101MHz,CDCl3)δ193.6,163.3(d,J＝254.2Hz),147.6,134.5(d,J＝3.8Hz),133.0(d,J＝10.6Hz),131.7,131.0(d,J＝9.3Hz),130.6,130.2(q,J＝308.7Hz),127.4,117.7(d,J＝24.9Hz),114.2(d,J＝21.5Hz),44.0(d,J＝2.1Hz),22.7.HRMS m/z(ESI)calcd for C16H12ClF4OS+(M+H)+363.0228；found:363.0227.
实施例28
先称取
Figure BDA0002342254960000254
(32.1mg,0.13mmol),4CzIPN(1.6mg,0.002mmol)，K2CO3(2.78mg,0.02mmol),加入反应管，通过真空管线抽换气三次，在氩气氛围下，加入2mL无水乙腈，再加入
Figure BDA0002342254960000261
(20.1mg，0.1mmol)，然后置于45W蓝光灯照射下，室温反应12h。干法上样，柱层析(300-400目层析硅胶)得到产物15.3mg，
Figure BDA0002342254960000262
(洗脱液:体积比，石油醚60-90：乙酸乙酯＝50:1)，产率51％，1H NMR(400MHz,CDCl3)δ7.98(d,J＝8.3Hz,2H),7.74–7.70(m,1H),7.49(d,J＝8.3Hz,2H),7.26(d,J＝3.4Hz,1H),6.61(dd,J＝3.6,1.7Hz,1H),4.58(q,J＝7.1Hz,1H),1.75(d,J＝7.0Hz,3H)；19F NMR(376MHz,CDCl3)δ-40.08；13C NMR(101MHz,CDCl3)δ181.7,152.3,147.1,146.3,136.8,130.3(q,J＝308.7Hz),129.9,127.1,120.6,112.3,44.1(d,J＝1.9Hz),22.8.IR(ATR):ν＝2978,2930,2350,1646,1608,1562,1464,1311,1292,1110,1015,853,766,757cm-1.HRMS m/z(ESI)calcd forC14H11F3NaO2S+(M+Na)+323.0324；found:323.0322。

Claims (5)

1.一种选择性合成ArCR1R2SCF3(3a)的方法，其特征是：它是以ArCHR1R2为原料，在蓝光灯照射下，在无水乙腈中，氩气气氛下，在碳酸钾存在下，以光催化剂4CzIPN与沈试剂
Figure FDA0003586502290000011
在室温下反应，得到ArCR1R2SCF3(3a)；所述的ArCHR1R2中的Ar是芳环或杂芳环，所述的R1与R2基团是氢或烷基；所述的光催化剂4CzIPN有如下结构：
Figure FDA0003586502290000012
2.根据权利要求1所述的制备方法，其特征是：所述的ArCHR1R2与沈试剂的物质的量之比是1:1.3-1:2.5。
3.根据权利要求1所述的制备方法，其特征是：所述的ArCHR1R2与沈试剂的物质的量之比是1:1.3。
4.根据权利要求1所述的制备方法，其特征是：所述的光催化剂4CzIPN是烷基芳烃摩尔数的2％的摩尔量。
5.根据权利要求1所述的制备方法，其特征是：所述的碳酸钾是烷基芳烃摩尔数的10-20％的摩尔量。
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