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CN103804348B - 一种亲电三氟甲硫基试剂、合成方法及其应用 - Google Patents

一种亲电三氟甲硫基试剂、合成方法及其应用 Download PDF

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CN103804348B
CN103804348B CN201210460539.6A CN201210460539A CN103804348B CN 103804348 B CN103804348 B CN 103804348B CN 201210460539 A CN201210460539 A CN 201210460539A CN 103804348 B CN103804348 B CN 103804348B
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沈其龙
吕龙
邵欣欣
王雪强
杨涛
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Shanghai Institute of Organic Chemistry of CAS
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Abstract

本发明涉及一种亲电三氟甲硫基化试剂、合成方法及其应用。该试剂具有如下的结构式：

Description

一种亲电三氟甲硫基试剂、合成方法及其应用
减少领域
本发明涉及一种亲电三氟甲硫基试剂、合成方法及其应用。可以用于亲电三氟甲硫基化试剂与一亲核试剂反应制备三氟甲硫基化的产物。
背景技术
三氟甲硫基（SCF3）具有很高的脂溶性(π＝1.44)[Okano,T.Eguchi,N.S.Syntlett.2001,1449-1451.]，有机小分子引入SCF3基团后可以明显地提高整个分子的脂溶性，直接增进了化合物的跨膜吸收。同时C-F键的键能远远大于C-H键的键能，而且三氟甲硫基是很强的吸电子基团，因而会降低小分子的电子云密度，使其在生物体内不易被代谢。这些因素的综合效应使得含三氟甲硫基的小分子的生物利用度大大提高，而不会降低相应的化合物活性，由此可以降低相应药物的给药剂量。此外，三氟甲硫基可以在双氧水等氧化条件下[14]很容易生成亚砜、砜类化合物这三类化合物由于独特的理化性质，其被广泛地引入药物或农药等生物活性分子中[Kolomeitsev,A.;Medebielle,M.;J.Chem.Soc.,Perkin Trans.2000,2183.]。
对于分子中引入三氟甲硫基的方法研究，前人进行了诸多探索与尝试。目前，现有的引入三氟甲硫基的方法主要是间接引入法和直接引入法。间接引入三氟甲硫基法即通过氟化反应等方式将具有特定反应活性的碳原子转变为三氟甲基或苯硫酚和二硫醚等化合物在适当的条件下直接与三氟甲基化试剂反应；而直接三氟甲硫基法则是通过一些已知的三氟甲硫基试剂反应，这里主要包括了亲核的三氟甲硫基试剂、亲电的三氟甲硫基试剂等将三氟甲硫基一步引入有机分子，涉及到三氟甲硫基中心硫和其他原子间的S-R键的形成[Boiko,V.N.Beilstein J.Org.Chem.2010,6,880-921.]。
亲核氟代法即通过高反应活性的氟源，如SbF3，HF等对具有特定反应活性的碳原子进行活化获得三氟甲基的方法。这种方法一般是三氯甲硫苯和过量的SbF3在无溶剂的条件下，通过加热进行氟氯交换，最后获得目标产物，收率为70-90%。但是该方式步骤较长，条件较苛刻。
Yagupolskii等人从1977年开始研究在紫外光照、液氨的存在下苯硫酚或二苯二硫醚等化合物和三氟碘甲烷的反应，收率一般中等到优秀(Yagupolskii,L.M.;Kondratenko,N.V.;Timofeeva,G.N.ZH.Org.Khim.1984,20,115-118.)。间接法的另外一个重要方式是通过现场生成的“CF3负离子”进攻苯硫基氯、硫氰酸盐和二硫醚等化合物，这主要是一个亲核取代的过程。但这类反应需要先合成苯硫酚或二苯二硫醚的衍生物。
亲电三氟甲基取代采取的策略主要是利用苯硫酚或者苯硫酚钠与亲电的三氟甲基化试剂反应，可以一步高效地向分子中引入SCF3基团。目前，使用这种方法的例子并不多，主要是由亲电三氟甲基化试剂的种类所限制。
总结间接引入法，不难发现它存在一下不足：1.亲核氟代法反应条件苛刻、底物耐受性低、试剂毒性高；2.单电子转移类型的方法一定程度上解决了试剂毒性的问题，然而必须借助于紫外光等自由基引发剂的帮助；3.硫酚或者二硫醚类化合物等的毒性和来源也是限制因素之一。
最近几年，通过过渡金属如铜、钯、镍等催化剂催化的交叉偶联反应，在温和条件下高效地向有机小分子直接引入三氟甲硫基已有许多报导，得到了很大的进展[Teverovskiy,G.;Surry,D.S.;Buchwald,S.L.Angew.Chem.,Int.Ed.2011,50,7312.;Zhang,C.-P.;Vicic.D.A.J.Am.Chem.Soc.2012,134,183-185.;Chen,C.Xie,Y.Chu,L.Wang,R.-W.Zhang,X.Qing,F.-L.Angew.Chem.Int.Ed.2012,51,2492-2495.;Zhang,C.-P.;Vicic.D.A.Chem.Asian.J.2012,7,1756-1758.;Chen,C.Chu,L.Qing,F.-L.J.Am.Chem.Soc.2012,134,12454-12457.]。这些反应克服了传统方法高温、高压、高毒性试剂等缺点。但是不难发现，过渡金属催化的亲核的三氟甲硫基化反应一般能高效地构建C(sp2)-SCF3和C(sp)-SCF3，将其应用于构建C(sp3)-SCF3的例子几乎没有。
构建C(sp3)-SCF3键的一个较简单的方法是利用亲电三氟甲硫基化试剂[Mirek,J.;Haas,A.J.Fluorine Chem.1981,19,67-70.；Croft,T.S.Phosphorus Sulfur Relat.Elem.1976,2,133-139.；Munavalli,S.;Rohrbaugh,D.K.;Rossman,D.I.Berg,F.J.;Wagner,G.E.W,Durst,H.D.Synthetic Communications.2000,31,2847-2854.；Gerdstemberger,M.R.C.;Haas,A.;Liebig,F.;J.Fluorime.Chem.1982,19,461-474.；Mendelson,W.L.;Liu,Jih..Hua.;Killmer,B.K.;Levinson,S.H;J.Org.Chem.1983,48,298-302.；Ferry,A.;Billard,T.;Langlois,E.R.;Bacque,E.;Angew.Chem.Int.Ed.2009,48,8551-8555.；Ferry,A.;Billard,T.;Langlois,E.R.;Bacque,E.;J.Fluorime.Chem.2012,134,160-163.;Ferry,A.;Billard,T.;Langlois,E.R..;Bacque,E.;Angew.Chem.Int.Ed.2012,51,10382-10385.;Yang,Y.;Jiang,X.-L.;Qing,F.–L.J.Org.Chem.2012,77，7538–7547.]。目前已知的亲电三氟甲硫基化试剂包括CF3SCl和PhNHSCF3。CF3SCl沸点较低而且毒性较大，不易操作。PhNHSCF3一般需要酸来活化氮硫键，参与构建C(sp3)-SCF3键目前例子不多。因此开发出易于合成和操作并且高效的亲电三氟甲硫基化试剂，十分迫切，而且有较大的发展潜力。
发明内容
本发明目的是提供一种发展了易合成而且高效的亲电三氟甲硫基化试剂；
本发明目的还提供一种上述亲电三氟甲硫基化试剂的简易和高效的合成方法；
本发明另一目的是提供一种上述亲电三氟甲硫基化试剂的应用，该亲电三氟甲硫基化试剂可以与一系列的亲核试剂反应，高产率地得到三氟甲硫基化的产物。
本发明的亲电三氟甲硫基化试剂具有如下的结构式：
本发明的亲电三氟甲硫基化试剂的可以由下述方法合成：在室温~60℃和有机溶剂中AgSCF3和P-152反应0.5~12小时；
所述的AgSCF3和P-152的摩尔比为1:0.5~3.0；所述的P-152是1-氯-1,3-二氢-3,3-二甲基-1,2-苯并碘氧杂戊环，化合物具体化学名称1-chloro-1,3-dihydro-3,3-dimethyl-1,2-Benziodoxole。上述的AgSCF3和P-152的摩尔比推荐为1:1。
所述的有机溶剂是乙醚、四氢呋喃、乙腈、丙酮、二氯甲烷、1，2-二氯乙烷、氯仿、四氯化碳、1，2-二甲氧基乙烷、1，2-二乙氧基乙烷、N，N-二甲基甲酰胺,苯、二乙二醇二甲醚、二乙二醇二乙醚等。
上述的反应推荐在惰性气体气氛中进行。
本发明的亲电三氟甲硫基化试剂的合成方法中，建议获得的产物经过过滤，浓缩，柱层析或蒸馏进一步进行纯化。
采用本发明的亲电三氟甲硫基化试剂的合成方法不仅方法简，而且该亲电三氟甲硫基化试剂能够用于和一亲核试剂反应制备三氟甲硫基化的产物，合成和操作简便并且高效。
本发明中涉及的化合物结构式和编号如下表所示：
具体实施方法
下述实施实例将对本发明做进一步详细描述，但本发明不限于这些具体实例。
实施例1亲电三氟甲硫基化试剂的合成
（1）向一个配有搅拌子经过烘箱干燥的100ml Schlenk管内在氩气气氛下依次加入0.208g(10mmol)AgSCF3和0.296g(10mmol)原料P-152，并加入50ml新鲜纯化的四氢呋喃。50℃预热后，反应在该温度下搅拌1小时，氟谱检测AgSCF3完全消失，硅藻土过滤，真空浓缩至最小体积。产物采用快速柱层析（湿法上样）过柱分离。洗脱剂：30-60℃石油醚，Rf：0.95。产率:30%。产物使用Kugelrohr蒸馏进一步纯化。
1H NMR(300MHz,CDCl3,293K,TMS)δ8.05(d,J=7.8Hz,1H),7.42-7.32(m,1H),6.97(t,J=7.2Hz,1H),1.86(s,6H)ppm;19F NMR(375MHz,CDCl3)δ-51.2(s,3F)ppm;IR(KBr):ν=3057,2976,2930,1583,1560,1464,1428,1384,1366,1262,1230,1174,1087,1048,1004,952,904,855,756,721,642,615,562,441cm-1.
（2）溶剂的筛选
向一个配有搅拌子经过烘箱干燥的20ml Schlenk管内在氩气气氛下依次加入0.0208g(0.1mmol)AgSCF3和0.0296g(0.1mmol)原料P-152，并加入0.5ml新鲜纯化的四氢呋喃。反应在室温下搅拌12小时，氟谱检测AgSCF3完全消失，加入13μL(0.1mmol)一氟萘为内标，氟谱检测得氟谱。
其中entry表示序号，solvent表示溶剂，yield表示产率，equiv表示当量，THf表示四氢呋喃，Aetone表示丙酮，DMF表示N，N－二甲基甲酰胺，Diglyme表示二乙二醇二甲醚，DME表示二乙二醇二甲醚。
（3）温度和当量的筛选
向一个配有搅拌子经过烘箱干燥的20ml Schlenk管内在氩气气氛下依次加入0.0208g(0.1mmol)AgSCF3和0.0296g(0.1mmol)原料P-152，并加入0.5ml新鲜纯化的四氢呋喃。反应在一定温度下搅拌一定时间，氟谱检测AgSCF3完全消失，加入13μL(0.1mmol)一氟萘为内标，氟谱检测得氟谱。
其中rt表示室温。
实施例2 亲电三氟甲硫基试剂的应用
所述的亲电三氟甲硫基试剂是S1。
对叔丁基苯基三氟甲硫醚
1-tert-Butyl-4-[(trifluoromethyl)thio]benzene 3-a
向一个配有搅拌子经过烘箱干燥的封管内在氩气气氛下依次加入0.0185g (0.05mmol)Cu(MeCN)4PF6,0.0160g(0.1mmol)2,2’-联吡啶，0.138g(1.0mmol)无水碳酸钾，0.3620g(0.5mmol)亲电三氟甲硫基试剂和0.1157g(0.65mmol)4-叔丁基苯基硼酸，并加入2.5ml新鲜纯化的二乙二醇二甲醚。反应在35℃下搅拌，氟谱检测直至亲电试剂完全消失，一般需要15小时。25ml蒸馏水，20ml无水乙醚加入反应体系萃取，有机相分离，水相采用20ml无水乙醚萃取3次，合并有机相后再用50ml蒸馏水萃取。使用无水硫酸钠干燥，真空浓缩。产物采用快速柱层析法过柱分离。洗脱剂：30-60℃石油醚，Rf：0.98。产率:90%。
1H NMR(300MHz,CDCl3,293K,TMS)δ7.59(d,J=8.1Hz,2H),7.45(d,J=8.1Hz,2H),1.34(s,9H)ppm;19F NMR(282MHz,CDCl3)δ-43.4(s,3F)ppm;IR(KBr):ν=2966,2908,2872,1596,1490,1464,1397,1366,1262,1160,1128,1104,1014,832,906,756,736,568cm-1.MS(EI):m/z(%)234,219(100),191.
对甲氧基苯基三氟甲硫醚
1-(Methoxy)-4-[(trifluoromethyl)thio]benzene 3-b
向一个配有搅拌子经过烘箱干燥的封管内在氩气气氛下依次加入0.0185g (0.05mmol)Cu(MeCN)4PF6，0.0160g(0.1mmol)2,2’-联吡啶，0.138g(1.0mmol)无水碳酸钾，0.3620g(0.5mmol)亲电三氟甲硫基试剂和0.0988g(0.65mmol)4-甲氧基苯基硼酸，并加入2.5ml新鲜纯化的二乙二醇二甲醚。反应在35℃下搅拌，氟谱检测直至亲电试剂完全消失，一般需要15小时。25ml蒸馏水，20ml无水乙醚加入反应体系萃取，有机相分离，水相采用20ml无水乙醚萃取3次，合并有机相后再用50ml蒸馏水萃取。使用无水硫酸钠干燥，真空浓缩。产物采用快速柱层析法过柱分离。洗脱剂：30-60℃石油醚/乙醚=50:1，Rf：0.50。产率:92%。
1H NMR(300MHz,CDCl3,293K,TMS)δ7.59(d,J=8.4Hz,2H),6.94(d,J=8.7Hz,2H),3.84(s,3H)ppm;19F NMR(282MHz,CDCl3)δ-44.4(s,3F)ppm;IR(KBr):ν=2945,1842,1593,1496,1464,1442,195,1255,1191,1089,1031,830,800,755,654,563,524cm-1.MS(EI):m/z(%)208(100),139,124,96.
对三氟甲硫基苯乙酮
1-(4-trifluoromethylsulfanyl-phenyl)-ethanone 3-c
向一个配有搅拌子经过烘箱干燥的封管内在氩气气氛下依次加入0.0185g (0.05mmol)Cu(MeCN)4PF6，0.0160g(0.1mmol)2,2’-联吡啶，0.138g(1.0mmol)无水碳酸钾，0.3620g(0.5mmol)亲电三氟甲硫基试剂和0.1066g(0.65mmol)4-乙酰基苯硼酸，并加入2.5ml新鲜纯化的二乙二醇二甲醚。反应在35℃下搅拌，氟谱检测直至亲电试剂完全消失，一般需要15小时。25ml蒸馏水，20ml无水乙醚加入反应体系萃取，有机相分离，水相采用20ml无水乙醚萃取3次，合并有机相后再用50ml蒸馏水萃取。使用无水硫酸钠干燥，真空浓缩。产物采用快速柱层析法过柱分离。洗脱剂：30-60℃石油醚/乙醚=20:1，Rf：0.50。产率:87%。
1H NMR(400MHz,CDCl3,293K,TMS)δ7.96(d,J=8.0Hz,2H),7.71(d,J=8.0Hz,2H),2.60(s,3H)ppm;19F NMR(375MHz,CDCl3)δ-42.3(s,3F)ppm;IR(KBr):v=2984,2936,2886,1600,1580,1493,1460,1413,1363,1205,1286,1254,1994,1113,1079,1065,932,898,873,850,814,755,690,619,522,474cm-1.MS(EI):m/z(%)220,205(100),177,136,108.
4－三氟甲硫基联苯
4-[(Trifluoromethyl)thio]biphenyl 3-d
向一个配有搅拌子经过烘箱干燥的封管内在氩气气氛下依次加入0.0185g (0.05mmol)Cu(MeCN)4PF6，0.0160g(0.1mmol)2,2’-联吡啶，0.138g(1.0mmol)无水碳酸钾，0.3620g(0.5mmol)亲电三氟甲硫基试剂和0.1287g(0.65mmol)4-联苯硼酸，并加入2.5ml新鲜纯化的二乙二醇二甲醚。反应在35℃下搅拌，氟谱检测直至亲电试剂完全消失，一般需要15小时。25ml蒸馏水，20ml无水乙醚加入反应体系萃取，有机相分离，水相采用20ml无水乙醚萃取3次，合并有机相后再用50ml蒸馏水萃取。使用无水硫酸钠干燥，真空浓缩。产物采用快速柱层析法过柱分离。洗脱剂：30-60℃石油醚，Rf：0.98。产率:92%。
1H NMR(400MHz,CDCl3,293K,TMS)δ7.76(d,J=8.4Hz,2H),7.67-7.62(m,4H),7.51-7.48(m,2H),7.44-7.45(m,1H)ppm;19F NMR(375MHz,CDCl3)δ-42.7(s,3F)ppm;IR(KBr):ν=3071,3032,1958,1920,1580,1557,1479,1396,1175,1109,1805,1015,1008,837,762,739,716,691,487cm-1.MS(EI):m/z(%)254(100),185,152,141,115.
对溴苯基三氟甲硫醚
Bromo-4-[(trifluoromethyl)thio]benzene 3-e
向一个配有搅拌子经过烘箱干燥的封管内在氩气气氛下依次加入0.0185g (0.05mmol)Cu(MeCN)4PF6，0.0160g(0.1mmol)2,2’-联吡啶，0.138g(1.0mmol)无水碳酸钾，0.3620g(0.5mmol)亲电三氟甲硫基试剂和0.1306g(0.65mmol)4-溴苯硼酸，并加入2.5ml新鲜纯化的二乙二醇二甲醚。反应在35℃下搅拌，氟谱检测直至亲电试剂完全消失，一般需要15小时。25ml蒸馏水，20ml无水乙醚加入反应体系萃取，有机相分离，水相采用20ml无水乙醚萃取3次，合并有机相后再用50ml蒸馏水萃取。使用无水硫酸钠干燥，真空浓缩。产物采用快速柱层析法过柱分离。洗脱剂：30-60℃石油醚，Rf：0.98。产率:95%。
1H NMR(300MHz,CDCl3,293K,TMS)δ7.47(d,J=8.1Hz,2H),7.43(d,J=8.7Hz,2H)ppm;19F NMR(282MHz,CDCl3)δ-43.2(s,3F)ppm;IR(KBr):ν=1474,1388,1212,1119,1084,1068,1011,819,756,732,508,498cm-1.MS(EI):m/z(%)257.9(100),188.9,158,108,69.
对乙烯基苯基三氟甲硫醚
Ethenyl-4-[(trifluoromethyl)thio]benzene 3-f
向一个配有搅拌子经过烘箱干燥的封管内在氩气气氛下依次加入0.0185g (0.05mmol)Cu(MeCN)4PF6，0.0160g(0.1mmol)2,2’－联吡啶，0.138g(1.0mmol)无水碳酸钾，0.3620g(0.5mmol)亲电三氟甲硫基试剂和0.0961g(0.65mmol)4-乙烯基苯硼酸，并加入2.5ml新鲜纯化的二乙二醇二甲醚。反应在35℃下搅拌，氟谱检测直至亲电试剂完全消失，一般需要15小时。25ml蒸馏水，20ml无水乙醚加入反应体系萃取，有机相分离，水相采用20ml无水乙醚萃取3次，合并有机相后再用50ml蒸馏水萃取。使用无水硫酸钠干燥，真空浓缩。产物采用快速柱层析法过柱分离。洗脱剂：30-60℃石油醚，Rf：0.98。产率:89%。
1H NMR(300MHz,CDCl3,293K,TMS)δ7.63(d,J=7.5Hz,2H),7.45(d,J=7.5Hz,2H),6.74(dd,J=17.4Hz,J=10.8Hz,1H),5.85(d,J=17.4Hz,1H),5.39(d,J=11.1Hz,1H)ppm;19F NMR(282MHz,CDCl3)δ-43.3(s,3F)ppm;IR(KBr):ν=2962,2917,2849,1733,1463,1261,1020,564,800,702cm-1.MS(EI):m/z(%)204(100),135,91.
2－甲氧基－6－萘基三氟甲硫醚
2-methoxy-6-[(trifluoromethyl)thio]naphthalene 3-g
向一个配有搅拌子经过烘箱干燥的封管内在氩气气氛下依次加入0.0185g (0.05mmol)Cu(MeCN)4PF6，0.0160g(0.1mmol)2,2’-联吡啶，0.138g(1.0mmol)无水碳酸钾，0.3620g(0.5mmol)亲电三氟甲硫基试剂和0.1404g(0.65mmol)6-甲氧基-2-萘硼酸，并加入2.5ml新鲜纯化的二乙二醇二甲醚。反应在35℃下搅拌，氟谱检测直至亲电试剂完全消失，一般需要15小时。25ml蒸馏水，20ml无水乙醚加入反应体系萃取，有机相分离，水相采用20ml无水乙醚萃取3次，合并有机相后再用50ml蒸馏水萃取。使用无水硫酸钠干燥，真空浓缩。产物采用快速柱层析法过柱分离。洗脱剂：30-60℃石油醚/乙醚＝20:1，Rf：0.50。产率:95%。
1HNMR(300MHz,CDCl3,293K,TMS)δ8.05(s,1H),7.66(d,J=8.7Hz,2H),7.15(d,J=8.7Hz,2H),7.05(s,1H),3.85(s,3H)ppm;19F NMR(282MHz,CDCl3)δ-42.9(s,3F)ppm;IR(KBr):ν=2018,2971,2943,2844,1629,1592,1498,1462,1473,1438,1409,1389,1266,1214,1138,1111,1208,912,852,814,799,752,733,658,548,470,403cm-1.MS(EI):m/z(%)258(100),189,145,102.
4-氰基苯基三氟甲硫醚
4-[(Trifluoromethyl)thio]benzonitrile 3-h
向一个配有搅拌子经过烘箱干燥的封管内在氩气气氛下依次加入0.0185g (0.05mmol)Cu(MeCN)4PF6，0.0160g(0.1mmol)2,2’-联吡啶，0.138g(1.0mmol)无水碳酸钾，0.3620g(0.5mmol)亲电三氟甲硫基试剂和0.0955g(0.65mmol)4-氰基苯硼酸，并加入2.5ml新鲜纯化的二乙二醇二甲醚。反应在35℃下搅拌，氟谱检测直至亲电试剂完全消失，一般需要15小时。25ml蒸馏水，20ml无水乙醚加入反应体系萃取，有机相分离，水相采用20ml无水乙醚萃取3次，合并有机相后再用50ml蒸馏水萃取。使用无水硫酸钠干燥，真空浓缩。产物采用快速柱层析法过柱分离。洗脱剂：30-60℃石油醚/乙醚＝10：1，Rf：0.50。产率:58%。
1H NMR(300MHz,CDCl3,293K,TMS)δ7.77(d,J=7.5Hz,2H),7.71(d,J=8.7Hz,2H)ppm;19F NMR(282MHz,CDCl3)δ-41.9(s,3F)ppm;IR(KBr):ν=3093,2234,1595,1488,1401,1274,1115,1082,1019,836,758,560,546cm-1.MS(EI):m/z(%)203,134(100),107,90,69.
3－硝基苯基三氟甲硫醚
3-[(Trifluoromethyl)thio]nitrobenzene 3-i
向一个配有搅拌子经过烘箱干燥的封管内在氩气气氛下依次加入0.0185g(0.05mmol)Cu(MeCN)4PF6，0.0160g(0.1mmol)2,2’-联吡啶，0.138g(1.0mmol)无水碳酸钾，0.3620g(0.5mmol)亲电三氟甲硫基试剂和0.1085g(0.65mmol)3-硝基苯硼酸，并加入2.5ml新鲜纯化的二乙二醇二甲醚。反应在35℃下搅拌，氟谱检测直至亲电试剂完全消失，一般需要15小时。25ml蒸馏水，20ml无水乙醚加入反应体系萃取，有机相分离，水相采用20ml无水乙醚萃取3次，合并有机相后再用50ml蒸馏水萃取。使用无水硫酸钠干燥，真空浓缩。产物采用快速柱层析法过柱分离。洗脱剂：30-60℃石油醚/乙醚＝10：1，Rf：0.50。产率:64%。
1H NMR(300MHz,CDCl3,293K,TMS)δ8.53(s,1H),8.37(d,J=8.1Hz,1H),8.00(d,J=7.8Hz,1H),7.66(t,J=8.1Hz,1H)ppm;19F NMR(282MHz,CDCl3)δ-42.5(s,3F)ppm;IR(KBr):ν=3091,1604,1538,1466,1351,1135,1104,1609,1000,876,753,733,707,675,657,509cm-1.MS(EI):m/z(%)223(100),204,177,127,108,95,69.
4-三氟甲硫基苯甲酸甲酯
Methyl 4-[(trifluoromethyl)thio]benzoate 3-j
向一个配有搅拌子经过烘箱干燥的封管内在氩气气氛下依次加入0.0185g (0.05mmol)Cu(MeCN)4PF6，0.0160g(0.1mmol)2,2’-联吡啶，0.138g(1.0mmol)无水碳酸钾，0.3620g(0.5mmol)亲电三氟甲硫基试剂和0.1170g(0.65mmol)4-甲氧羰基苯硼酸，并加入2.5ml新鲜纯化的二乙二醇二甲醚。反应在35℃下搅拌，氟谱检测直至亲电试剂完全消失，一般需要15小时。25ml蒸馏水，20ml无水乙醚加入反应体系萃取，有机相分离，水相采用20ml无水乙醚萃取3次，合并有机相后再用50ml蒸馏水萃取。使用无水硫酸钠干燥，真空浓缩。产物采用快速柱层析法过柱分离。洗脱剂：30-60℃石油醚/乙醚＝10：1，Rf：0.50。产率:58%。
1H NMR(400MHz,CDCl3,293K,TMS)δ8.08(d,J=8.4Hz,2H),7.72(d,J=7.8Hz,2H),3.95(s,3H)ppm;19F NMR(375MHz,CDCl3)δ-42.2(s,3F)ppm;IR(KBr):ν=2985,1725,1597,1466,1399,1368,1306,1274,1119,1083,1018,855,806,765,713,693cm-1.MS(EI):m/z(%)236,205(100),177,136,108.
3－三氟甲硫基喹啉
3-[(Trifluoromethyl)thio]quinoline 3-k
向一个配有搅拌子经过烘箱干燥的封管内在氩气气氛下依次加入0.0185g (0.05mmol)Cu(MeCN)4PF6，0.0160g(0.1mmol)2,2’-联吡啶，0.138g(1.0mmol)无水碳酸钾，0.3620g(0.5mmol)亲电三氟甲硫基试剂和0.1124g(0.65mzmol)3-喹啉硼酸，并加入2.5ml新鲜纯化的二乙二醇二甲醚。反应在35℃下搅拌，氟谱检测直至亲电试剂完全消失，一般需要15小时。25ml蒸馏水，20ml无水乙醚加入反应体系萃取，有机相分离，水相采用20ml无水乙醚萃取3次，合并有机相后再用50ml蒸馏水萃取。使用无水硫酸钠干燥，真空浓缩。产物采用快速柱层析法过柱分离。洗脱剂：30-60℃石油醚/乙醚＝50：1，Rf：0.50。产率:40%。
1H NMR(400MHz,CDCl3,293K,TMS)δ9.04(s,1H),8.54(s,1H),8.17(d,J=8.8Hz,1H),7.89-7.82(m,2H),7.65(t,J=7.2Hz,1H)ppm;19F NMR(375MHz,CDCl3)δ-42.3(s,3F)ppm;IR(KBr):ν=2961,2926,1619,1567,1489,1357,1260,1162,1108,108,1016,957,912,864,785,752,648,479cm-1.MS(EI):m/z(%)229(100),160,133,116,89.
2－甲氧基－3－三氟甲硫基吡啶
2-Methoxy-3-[(Trifluoromethyl)thio]pyridine 3-l
向一个配有搅拌子经过烘箱干燥的封管内在氩气气氛下依次加入0.0185g (0.05mmol)Cu(MeCN)4PF6，0.0160g(0.1mmol)2,2’-联吡啶，0.138g(1.0mmol)无水碳酸钾，0.3620g(0.5mmol)亲电三氟甲硫基试剂和0.9940g(0.65mmol)2-甲氧基-5-吡啶硼酸，并加入2.5ml新鲜纯化的二乙二醇二甲醚。反应在35℃下搅拌，氟谱检测直至亲电试剂完全消失，一般需要15小时。25ml蒸馏水，20ml无水乙醚加入反应体系萃取，有机相分离，水相采用20ml无水乙醚萃取3次，合并有机相后再用50ml蒸馏水萃取。使用无水硫酸钠干燥，真空浓缩。产物采用快速柱层析法过柱分离。洗脱剂：30-60℃石油醚/乙醚＝30：1，Rf：0.50。产率:65%。
1H NMR(400MHz,CDCl3,293K,TMS)δ8.39(d,J=2.4Hz,1H),7.79(dd,J=2.4Hz,J=2.4Hz,1H),7.78(d,J=8.4Hz,1H),3.96(s,3H)ppm;19F NMR(375MHz,CDCl3)δ-43.9(s,3F)ppm;IR(KBr):ν=2961,1590,1558,1481,1371,308,1288,1259,1163,1121,1101,1020,832,806,736,676,571,533,521cm-1.MS(EI):m/z(%)209(100),179,140,125,110,98,69.
（E)－4－甲氧基苯乙烯基三氟甲硫醚
(E)-1-methoxy-4-[2-(Trifluoromethyl)thioeth-1-en-1-yl]benzene 3-m
向一个配有搅拌子经过烘箱干燥的封管内在氩气气氛下依次加入0.0185g(0.05mmol)Cu(MeCN)4PF6，0.0160g(0.1mmol)2,2’-联吡啶，0.138g(1.0mmol)无水碳酸钾，0.3620g(0.5mmol)亲电三氟甲硫基试剂和0.1157g(0.65mmol)反式-2-(4-甲氧基苯基)乙烯基硼酸，并加入2.5ml新鲜纯化的二乙二醇二甲醚。反应在35℃下搅拌，氟谱检测直至亲电试剂完全消失，一般需要15小时。25ml蒸馏水，20ml无水乙醚加入反应体系萃取，有机相分离，水相采用20ml无水乙醚萃取3次，合并有机相后再用50ml蒸馏水萃取。使用无水硫酸钠干燥，真空浓缩。产物采用快速柱层析法过柱分离。洗脱剂：30-60℃石油醚/乙醚＝50：1，Rf：0.50。产率:75%。
1H NMR(400MHz,CDCl3,293K,TMS)δ7.35(d,J=8.8Hz,2H),6.99(d,J=15.2Hz,1H),6.89(d,J=8.8Hz,2H),6.57(d,J=15.2Hz,1H),3.83(s,3H)ppm;19FNMR(375MHz,CDCl3)δ-43.2(s,3F)ppm;IR(KBr):ν=3042,3006,260,2937,2840,1608,1572,1512,1466,1443,1420,1306,1259,1240,1203,1109,1035,960,838,862,770,755,545,523cm-1.MS(EI):m/z(%)234(100),207,165,150,134,121.
(E)-1-正辛烯基三氟甲硫醚
(E)-1-(Trifluoromethyl)thiooctylene 3-n
向一个配有搅拌子经过烘箱干燥的封管内在氩气气氛下依次加入0.0185g (0.05mmol)Cu(MeCN)4PF6，0.0160g(0.1mmol)2,2’-联吡啶，0.138g(1.0mmol)无水碳酸钾，0.3620g(0.5mmol)亲电三氟甲硫基试剂和0.1014g(0.65mmol)反-1-辛烯-1-基硼酸，并加入2.5ml新鲜纯化的二乙二醇二甲醚。反应在35℃下搅拌，氟谱检测直至亲电试剂完全消失，一般需要15小时。25ml蒸馏水，20ml无水乙醚加入反应体系萃取，有机相分离，水相采用20ml无水乙醚萃取3次，合并有机相后再用50ml蒸馏水萃取。使用无水硫酸钠干燥，真空浓缩。产物采用快速柱层析法过柱分离。洗脱剂：30-60℃石油醚/乙醚＝50：1，Rf：0.50。产率:75%。
1H NMR(400MHz,CDCl3,293K,TMS)δ6.28-6.22(m,1H),6.06(d,J=14.4Hz,1H),2.18(q,J=6.8Hz,2H),1.45-1.42(m,2H),1.42-1.29(m,6H),0.90(d,J=7.6Hz,3H)ppm;19F NMR(375MHz,CDCl3)δ-43.6(s,3F)ppm;IR(KBr):ν=2960,2931,2859,1468,1381,1261,1158,1190,954,909,807,756,737cm-1.MS(EI):m/z(%)212,141(100),128,115,87,69,55,43,28.
苯乙炔基三氟甲硫醚
(Phenylethynyl)(trifluoromethyl)sulfane 4-a
向一个配有搅拌子经过烘箱干燥的封管内在氩气气氛下依次加入0.0123g(0.06mmol)CuBr Me2S，0.0187g(0.12mmol)2,2’-联吡啶，0.0828g(0.6mmol)无水碳酸钾，0.1086g(0.3mmol)亲电三氟甲硫基试剂和0.0613g(0.6mmol)苯乙炔，并加入1.5ml新鲜纯化的1,2-二氯乙烷。反应在80℃下搅拌，氟谱检测直至亲电试剂完全消失，一般需要14小时。25ml蒸馏水，20ml二氯甲烷加入反应体系萃取，有机相分离，水相采用20ml二氯甲烷萃取3次，合并有机相。使用无水硫酸钠干燥，真空浓缩。产物采用快速柱层析法过柱分离。洗脱剂：30-60℃石油醚，Rf：0.98。产率:84%。
1H NMR(400MHz,CDCl3,293K,TMS)δ7.48(m,2H),7.44-7.36(m,3H)ppm;19FNMR(375MHz,CDCl3)δ-48.7(s,3F)ppm;IR(KBr):ν=2180,1488,1444,1384,1159,1104,1028,917,756,688,534cm-1.MS(EI):m/z(%)202(100),183,133,89,28,18.
4－叔丁基苯乙炔基三氟甲硫醚
((4-tert-Butylphenyl)ethynyl)(trifluoromethyl)sulfane 4-b
向一个配有搅拌子经过烘箱干燥的封管内在氩气气氛下依次加入0.0123g(0.06mmol)CuBr Me2S，0.0187g(0.12mmol)2,2’-联吡啶，0.0828g(0.6mmol)无水碳酸钾，0.1086g(0.3mmol)亲电三氟甲硫基试剂和0.0949g(0.6mmol)4-叔丁基苯乙炔，并加入1.5ml新鲜纯化的1,2-二氯乙烷。反应在80℃下搅拌，氟谱检测直至亲电试剂完全消失，一般需要14小时。25ml蒸馏水，20ml二氯甲烷加入反应体系萃取，有机相分离，水相采用20ml二氯甲烷萃取3次，合并有机相。使用无水硫酸钠干燥，真空浓缩。产物采用快速柱层析法过柱分离。洗脱剂：30-60℃石油醚，Rf：0.98。产率:88%。
1H NMR(300MHz,CDCl3,293K,TMS)δ7.48(d,J=7.5Hz,2H),7.40(d,J=8.7Hz,2H),1.34(s,9H)ppm;19F NMR(282MHz,CDCl3)δ-44.3(s,3F)ppm;IR(KBr):ν=3039，2967,2907,2870,2177,1605,1505,1464,1365,1269,1248,1159,1104,1018,835,758,563.MS(EI):m/z(%)258(100),243,174,146.
4－正戊基苯乙炔基三氟甲硫醚
((4-pentylphenyl)ethynyl)(trifluoromethyl)sulfane 4-c
向一个配有搅拌子经过烘箱干燥的封管内在氩气气氛下依次加入0.0123g (0.06mmol)CuBr Me2S，0.0187g(0.12mmol)2,2’-联吡啶，0.0828g(0.6mmol)无水碳酸钾，0.1086g(0.3mmol)亲电三氟甲硫基试剂和0.1034g(0.6mmol)4-正戊基苯乙炔，并加入1.5ml新鲜纯化的1,2-二氯乙烷。反应在80℃下搅拌，氟谱检测直至亲电试剂完全消失，一般需要14小时。25ml蒸馏水，20ml二氯甲烷加入反应体系萃取，有机相分离，水相采用20ml二氯甲烷萃取3次，合并有机相。使用无水硫酸钠干燥，真空浓缩。产物采用快速柱层析法过柱分离。洗脱剂：30-60℃石油醚，Rf：0.98。产率:91%。
1H NMR(300MHz,CDCl3,293K,TMS)δ7.44(d,J=7.8Hz,2H),7.18(d,J=8.1Hz,2H),2.64(t,J=7.5Hz,2H),1.66-1.61(m,2H),1.35-1.31(m,4H),0.92(t,J=6.6Hz,3H)ppm;19F NMR(282MHz,CDCl3)δ-44.3(s,3F)ppm;IR(KBr):ν=2959,2931,2859,2177,1607,1508,1467,1412,1379,1159,1105,1020,834,757cm-1.MS(EI):m/z(%)258(100),243,174,146.
6－甲氧基－2－萘乙炔基三氟甲硫醚
((6-Methoxynaphthalen-2-yl)ethynyl)(trifluoromethyl)sulfane 4-d
向一个配有搅拌子经过烘箱干燥的封管内在氩气气氛下依次加入0.0123g (0.06mmol)CuBr Me2S，0.0187g(0.12mmol)2,2’-联吡啶，0.0828g(0.6mmol)无水碳酸钾，0.1086g(0.3mmol)亲电三氟甲硫基试剂和0.1034g(0.6mmol)2-乙炔-6-甲氧基萘，并加入1.5ml新鲜纯化的1,2-二氯乙烷。反应在80℃下搅拌，氟谱检测直至亲电试剂完全消失，一般需要14小时。25ml蒸馏水，20ml二氯甲烷加入反应体系萃取，有机相分离，水相采用20ml二氯甲烷萃取3次，合并有机相。使用无水硫酸钠干燥，真空浓缩。产物采用快速柱层析法过柱分离。洗脱剂：30-60℃石油醚/乙醚=20:1，Rf：0.50。产率:84%。
1H NM R(400MHz,CDCl3,293K,TMS):δppm 7.97(s,1H),7.69(t,J=8.4Hz,2H),7.49(d,J=8.4Hz,1H),7.19(dd,J=9.2Hz,J=2.4Hz,1H),7.10(d,J=2.0Hz,1H),3.93(s,3H).19F NMR(282MHz,CDCl3)δ-46.3(s,3F)ppm;IR(KBr):ν=2967,2163,1621,1483,1456,1440,1413,1394,1272,1201,1161,1102,1030,870,849,814,777cm-1.MS(EI):m/z(%)282(100),213,198,170,126.HRMS:Calculated for 282(100),213,198,170,126.
4－溴苯乙炔基三氟甲硫醚
((4-Bromophenyl)ethynyl)(trifluoromethyl)sulfane 4-e
向一个配有搅拌子经过烘箱干燥的封管内在氩气气氛下依次加入0.0123g (0.06mmol)CuBr Me2S，0.0187g(0.12mmol)2,2’-联吡啶，0.0828g(0.6mmol)无水碳酸钾，0.1086g(0.3mmol)亲电三氟甲硫基试剂和0.1086g(0.6mmol)4-溴苯乙炔，并加入1.5ml新鲜纯化的1,2-二氯乙烷。反应在80℃下搅拌，氟谱检测直至亲电试剂完全消失，一般需要14小时。25ml蒸馏水，20ml二氯甲烷加入反应体系萃取，有机相分离，水相采用20ml二氯甲烷萃取3次，合并有机相。使用无水硫酸钠干燥，真空浓缩。产物采用快速柱层析法过柱分离。洗脱剂：30-60℃石油醚，Rf：0.98。产率:84%。
1H NMR(300MHz,CDCl3,293K,TMS)δ7.49(d,J=8.1Hz,2H),7.35(d,J=8.4Hz,2H)ppm;19F NMR(282MHz,CDCl3)δ-40.6(s,3F)ppm;IR(KBr):ν=2918,2179,1638,1585,1485,1158,1107,1071,1012,822,757,691,530cm-1.MS(EI):m/z(%)279.9(100),213,169,132.
4－三氟甲硫基乙炔基苯甲酸甲酯
Methyl 4-((trifluoromethylthio)ethynyl)benzoate 4-f
向一个配有搅拌子经过烘箱干燥的封管内在氩气气氛下依次加入0.0123g (0.06mmol)CuBr Me2S，0.0187g(0.12mmol)2,2’-联吡啶，0.0828g(0.6mmol)无水碳酸钾，0.1086g(0.3mmol)亲电三氟甲硫基试剂和0.1034g(0.6mmol)2-乙炔-6-甲氧基萘，并加入1.5ml新鲜纯化的1,2-二氯乙烷。反应在80℃下搅拌，氟谱检测直至亲电试剂完全消失，一般需要14小时。25ml蒸馏水，20ml二氯甲烷加入反应体系萃取，有机相分离，水相采用20ml二氯甲烷萃取3次，合并有机相。使用无水硫酸钠干燥，真空浓缩。产物采用快速柱层析法过柱分离。洗脱剂：30-60℃石油醚/乙醚=10:1，Rf：0.50。产率:85%。
1H NMR(400MHz,CDCl3,293K,TMS)δ8.01(d,J=8.0Hz,2H),7.53(d,J=8.0Hz,2H),3.92(s,3H)ppm;19F NMR(375MHz,CDCl3)δ-43.3(s,3F)ppm;IR(KBr):ν=2958,2850,2180,1732,1607,1437,1405,1308,1277,1162,1100,1019,858,820,768,758,759,694cm-1.MS(EI):m/z(%)260(100),229,191,160,132,93.
4－硝基苯乙炔基三氟甲硫醚
((4-Nitrophenyl)ethynyl)(trifluoromethyl)sulfane 4-g
向一个配有搅拌子经过烘箱干燥的封管内在氩气气氛下依次加入0.0123g(0.06mmol)CuBr Me2S，0.0187g(0.12mmol)2,2’-联吡啶，0.0828g(0.6mmol)无水碳酸钾，0.1086g(0.3mmol)亲电三氟甲硫基试剂和0.0883g(0.6mmol)4-硝基苯乙炔，并加入1.5ml新鲜纯化的1,2-二氯乙烷。反应在80℃下搅拌，氟谱检测直至亲电试剂完全消失，一般需要14小时。25ml蒸馏水，20ml二氯甲烷加入反应体系萃取，有机相分离，水相采用20ml二氯甲烷萃取3次，合并有机相。使用无水硫酸钠干燥，真空浓缩。产物采用快速柱层析法过柱分离。洗脱剂：30-60℃石油醚/乙醚=10:1，Rf：0.50。产率:82%。
1H NMR(300MHz,CDCl3,293K,TMS)δ8.23(d,J=9.0Hz,2H),7.63(d,J=9.0Hz,2H)ppm;19F NMR(282MHz,CDCl3)δ-44.3(s,3F)ppm;IR(KBr):ν=3107,2182,1593,1538,1353,1286,1169,1104,879,858,845,748,686cm-1.MS(EI):m/z(%)247(100),228,178,148,132,120,93.
4－三氟甲硫基乙炔基苯乙酮
((4-Acetylphenyl)ethynyl)(trifluoromethyl)sulfane 4-h
向一个配有搅拌子经过烘箱干燥的封管内在氩气气氛下依次加入0.0123g (0.06mmol)CuBr Me2S，0.0187g(0.12mmol)2,2’-联吡啶，0.0828g(0.6mmol)无水碳酸钾，0.1086g(0.3mmol)亲电三氟甲硫基试剂和0.0865g(0.6mmol)4-乙炔基苯乙酮，并加入1.5ml新鲜纯化的1,2-二氯乙烷。反应在80℃下搅拌，氟谱检测直至亲电试剂完全消失，一般需要14小时。25ml蒸馏水，20ml二氯甲烷加入反应体系萃取，有机相分离，水相采用20ml二氯甲烷萃取3次，合并有机相。使用无水硫酸钠干燥，真空浓缩。产物采用快速柱层析法过柱分离。洗脱剂：30-60℃石油醚/乙醚=20:1，Rf：0.50。产率:82%。
1H NMR(400MHz,CDCl3,293K,TMS)δ7.89(d,J=8.0Hz,2H),7.52(d,J=8.0Hz,2H),2.57(s,3H)ppm;19F NMR(375MHz,CDCl3)δ-43.3(s,3F)ppm;IR(KBr):ν=2179,1687,1601,1428,1404,1360,1265,1159,1101,1016,957,840,758,607cm-1.MS(EI):m/z(%)244(100),229,160,132.
4－氟苯乙炔基三氟甲硫醚
((3-Fluorophenyl)ethynyl)(trifluoromethyl)sulfane 4-i
向一个配有搅拌子经过烘箱干燥的封管内在氩气气氛下依次加入0.0123g (0.06mmol)CuBr Me2S，0.0187g(0.12mmol)2,2’-联吡啶，0.0828g(0.6mmol)无水碳酸钾，0.1086g(0.3mmol)亲电三氟甲硫基试剂和0.0721g(0.6mmol)3-苯乙炔，并加入1.5ml新鲜纯化的1,2-二氯乙烷。反应在80℃下搅拌，氟谱检测直至亲电试剂完全消失，一般需要14小时。25ml蒸馏水，20ml二氯甲烷加入反应体系萃取，有机相分离，水相采用20ml二氯甲烷萃取3次，合并有机相。使用无水硫酸钠干燥，真空浓缩。产物采用快速柱层析法过柱分离。洗脱剂：30-60℃石油醚，Rf：0.98。产率:73%。
1H NMR(400MHz,CDCl3,293K,TMS)δ7.34-7.26(m,2H),7.18(d,J=9.2Hz,1H),7.07-7.12(m,1H);19F NMR(375MHz,CDCl3)δ-46.0(s,3F),-114.8(m,1F)ppm;IR(KBr):ν=3077,2964,2177,1608,1583,1487,1435,1277,1264,1166,1104,1018,964,873,785,758,679,520,476cm-1.MS(EI):m/z(%)220(100),207,151,107.
1－三氟甲硫基乙炔基－3－噻吩
3-((Trifluoromethylthio)ethynyl)thiophene 4-j
向一个配有搅拌子经过烘箱干燥的封管内在氩气气氛下依次加入0.0123g (0.06mmol)CuBr Me2S，0.0187g(0.12mmol)2,2’-联吡啶，0.0828g(0.6mmol)无水碳酸钾，0.1086g(0.3mmol)亲电三氟甲硫基试剂和0.0649g(0.6mmol)3-乙炔基噻吩，并加入1.5ml新鲜纯化的1,2-二氯乙烷。反应在80℃下搅拌，氟谱检测直至亲电试剂完全消失，一般需要14小时。25ml蒸馏水，20ml二氯甲烷加入反应体系萃取，有机相分离，水相采用20ml二氯甲烷萃取3次，合并有机相。使用无水硫酸钠干燥，真空浓缩。产物采用快速柱层析法过柱分离。洗脱剂：30-60℃石油醚，Rf：0.98。产率:77%。
1H NMR(400MHz,CDCl3,293K,TMS)δ7.65-7.64(m,1H),7.32-7.30(m,1H),7.19-7.18(m,1H);19F NMR(375MHz,CDCl3)δ-46.5(s,3F)ppm;IR(KBr):ν=3111,2170,1359,1157,1103,960,875,840,793,757,625cm-1.MS(EI):m/z(%)208(100),189,139,95,69.
1－癸炔基三氟甲硫醚
Decy-nyl trifluoromethyl sulfane 4-k
向一个配有搅拌子经过烘箱干燥的封管内在氩气气氛下依次加入0.0123g (0.06mmol)CuBr Me2S，0.0187g(0.12mmol)2,2’-联吡啶，0.0828g(0.6mmol)无水碳酸钾，0.1086g(0.3mmol)亲电三氟甲硫基试剂和0.0830g(0.6mmol)1--癸炔，并加入1.5ml新鲜纯化的1,2-二氯乙烷。反应在80℃下搅拌，氟谱检测直至亲电试剂完全消失，一般需要14小时。25ml蒸馏水，20ml二氯甲烷加入反应体系萃取，有机相分离，水相采用20ml二氯甲烷萃取3次，合并有机相。使用无水硫酸钠干燥，真空浓缩。产物采用快速柱层析法过柱分离。洗脱剂：30-60℃石油醚，Rf：0.98。产率:61%。
1H NMR(400MHz,CDCl3,293K,TMS)δ2.39-2.36(m,2H),1.58-1.52(m,2H),1.40-1.28(m,10H),0.91-0.87(m,3H)ppm;19F NMR(375MHz,CDCl3)δ-44.6(s,3F)ppm;IR(KBr):ν=2930,2858,1458,1261,1158,1109,1019,806cm-1.MS(EI):m/z(%)238(100),169,139,93,81,71,55,41,29.
三氟甲硫基炔丙基苯基醚
(3-Phenoxyprop-1-ynyl)(trifluoromethyl)sulfane 4-l
向一个配有搅拌子经过烘箱干燥的封管内在氩气气氛下依次加入0.0123g (0.06mmol)CuBr Me2S，0.0187g(0.12mmol)2,2’-联吡啶，0.0828g(0.6mmol)无水碳酸钾，0.1086g(0.3mmol)亲电三氟甲硫基试剂和0.0793g(0.6mmol)苯基炔丙基醚，并加入1.5ml新鲜纯化的1,2-二氯乙烷。反应在80℃下搅拌，氟谱检测直至亲电试剂完全消失，一般需要14小时。25ml蒸馏水，20ml二氯甲烷加入反应体系萃取，有机相分离，水相采用20ml二氯甲烷萃取3次，合并有机相。使用无水硫酸钠干燥，真空浓缩。产物采用快速柱层析法过柱分离。洗脱剂：30-60℃石油醚/乙醚=20:1，Rf：0.50。产率:82%。
1H NMR(400MHz,CDCl3,293K,TMS)δ7.35-7.31(m,2H),7.05-7.03(m,2H),6.98-9.96(m,1H),4.87(s,2H)ppm;19F NMR(375MHz,CDCl3)δ-43.3(s,3F)ppm;IR(KBr):ν=3044,297,2854,1600,1590,1496,1373,1336,1304,1263,1162,1104,1066,1030,1010,993,884,778,753,690,503cm-1.MS(EI):m/z(%)232,207,163,139(100),103,69.9,28,18.
5－氟－1－茚酮－2－三氟甲硫基－2－羧酸－甲酯
Methyl-6-Fluoro-1-oxo-2-[(Trifluoromethyl)thio]-2,3-dihydro-1H-indene-2-carboxylate 5-a
向一个配有搅拌子经过烘箱干燥的100ml Schlenk管内在氩气气氛下依次加入0.362g(1.0mmol)亲电三氟甲硫基试剂、0.0672g(0.55mmol)4-二甲氨基吡啶和0.1041g(0.5mmol)5-氟-1-茚满酮-2-羧酸甲酯，并加入2.5ml新鲜纯化的二氯甲烷。反应在常温下搅拌过夜，氟谱检测亲电试剂完全消失，真空浓缩至最小体积。产物采用快速柱层析过柱分离。洗脱剂：30-60℃石油醚/乙醚=50/1，Rf：0.30。产率:96%。
1H NMR(400MHz,CDCl3,293K,TMS)δ7.52-7.48(m,1H),7.46-7.40(m,2H),4.14(d,J=17.6Hz,1H),3.79(s,3H),3.61(d,J=17.2Hz,1H)ppm;19F NMR(375MHz,CDCl3,293K,TMS)δ37.23(s,3F),112.33-112.34(m,1F)ppm;IR(KBr):ν=2960,1732,1615,1489,1437,1330,1290,1268,11125,1112,1028,937,867,830,764,527cm-1.MS(EI):m/z(%)308,280,249,207,179,175(100),152,107,59.
6－氟－1－茚酮－2－三氟甲硫基－2－羧酸－甲酯
Methyl-6-Fluoro-1-oxo-3-[(Trifluoromethyl)thio]-2,3-dihydro-1H-indene-2-carboxylate 5-b
向一个配有搅拌子经过烘箱干燥的100ml Schlenk管内在氩气气氛下依次加入0.362g(1.0mmol)亲电三氟甲硫基试剂、0.0672g(0.55mmol)4-二甲氨基吡啶和0.1041g(0.5mmol)6-氟-1-茚满酮-2-羧酸甲酯，并加入2.5ml新鲜纯化的二氯甲烷。反应在常温下搅拌过夜，氟谱检测亲电试剂完全消失，真空浓缩至最小体积。产物采用快速柱层析过柱分离。洗脱剂：30-60℃石油醚/乙醚=50/1，Rf：0.30。产率:95%。
1H NMR(400MHz,CDCl3,293K,TMS)δ7.82(dd,J=8.4Hz,J=5.2Hz,1H),7.19-7.12(m,2H),4.18(d,J=18.0Hz,1H),3.78(s,3H),3.64(d,J=17.2Hz,1H)ppm;19F NMR(375MHz,CDCl3,293K,TMS)δ37.3(s,3F),98.6-98.7(m,1F)ppm;IR(KBr):ν=3073,2960,2849,1728,1617,1596,1484,1435,1333,1295,1259,11109,1027,959,942,863,826,758,655,467cm-1.MS(EI):m/z(%)308,280,249,211,207(100),179,175,152,107,59.
5－氯－1－茚酮－2－三氟甲硫基－2－羧酸－甲酯
Methyl-5-Chloro-1-oxo-3-[(Trifluoromethyl)thio]-2,3-dihydro-1H-indene-2-carboxylate 5-c
向一个配有搅拌子经过烘箱干燥的100ml Schlenk管内在氩气气氛下依次加入0.362g(1.0mmol)亲电三氟甲硫基试剂、0.0672g(0.55mmol)4-二甲氨基吡啶和0.1123g(0.5mmol)l 5-氯-1-茚满酮-2-羧酸甲酯，并加入2.5ml新鲜纯化的二氯甲烷。反应在常温下搅拌过夜，氟谱检测亲电试剂完全消失，真空浓缩至最小体积。
产物采用快速柱层析过柱分离。洗脱剂：30-60℃石油醚/乙醚=50/1，Rf：0.30。产率:88%。
1H NMR(400MHz,CDCl3,293K,TMS)δ7.75(d,J=8.4Hz,1H),7.52(s,1H),7.44(d,J=8.4Hz,1H),4.17(d,J=18.0Hz,1H),3.80(s,3H),3.64(d,J=18.4Hz,1H)ppm;19F NMR(375MHz,CDCl3,293K,TMS)δ37.2(s,3F)ppm;IR(KBr):ν=2958,1730,1598,1458,1436,1328,1250,1159,1112,1027,997,959,822,780,758,726,685cm-1.MS(EI):m/z(%)324,296,265,223(100),195,191,168,89,59.
7-溴-3,4-二氢萘-1(2H)-酮－2－三氟甲硫基－2－羧酸－甲酯
Methyl 7-bromo-1-oxo-3-[(Trifluoromethyl)thio]-1,2,3,4-tetrahydronaphthalene-2-carboxylate 5-d
向一个配有搅拌子经过烘箱干燥的100ml Schlenk管内在氩气气氛下依次加入0.362g(1.0mmol)亲电三氟甲硫基试剂、0.0672g(0.55mmol)4-二甲氨基吡啶和0.142g(0.5mmol)7-溴-1-四氢萘酮-2-羧酸甲酯，并加入2.5ml新鲜纯化的二氯甲烷。反应在常温下搅拌过夜，氟谱检测亲电试剂完全消失，真空浓缩至最小体积。产物采用快速柱层析过柱分离。洗脱剂：30-60℃石油醚/乙醚=50/1，Rf：0.30。产率:86%。
1H NMR(400MHz,CDCl3,293K,TMS)δ8.12(s,1H),7.63(d,J=8.0Hz,1H),7.15(d,J=8.4Hz,1H),3.77(s,3H),3.21-3.00(m,3H),2.56-5.49(m,1H)ppm;19FNMR(375MHz,CDCl3,293K,TMS)δ36.1(s,3F)ppm;IR(KBr):ν=2960,2936,1746,1684,1589,1476,1244,1404,1359,1330,1276,1182,1104,1068,1026,974,962,905,834,80,767,636,614,486cm-1.MS(EI):m/z(%)166,121(100),91,77.(100).
4－溴－1－茚酮－2－三氟甲硫基－2－羧酸－甲酯
Methyl-4-Bromo-1-oxo-3-[(Trifluoromethyl)thio]-2,3-dihydro-1H-indene-2-carboxylate 5-e
向一个配有搅拌子经过烘箱干燥的100ml Schlenk管内在氩气气氛下依次加入0.362g(1.0mmol)亲电三氟甲硫基试剂、0.0672g(0.55mmol)4-二甲氨基吡啶和0.1345g(0.5mmol)4-溴-1-茚满酮-2-羧酸甲酯，并加入2.5ml新鲜纯化的二氯甲烷。反应在常温下搅拌过夜，氟谱检测亲电试剂完全消失，真空浓缩至最小体积。产物采用快速柱层析过柱分离。洗脱剂：30-60℃石油醚/乙醚=50/1，Rf：0.30。产率:84%。
1H NMR(400MHz,CDCl3,293K,TMS)δ7.88(d,J=0.8Hz,1H),7.78(d,J=7.6Hz,1H),7.37(t,J=7.6Hz,1H),4.10(d,J=18.0Hz,1H),3.80(s,3H),3.57(d,J=18.4Hz,1H)ppm;19F NMR(375MHz,CDCl3,293K,TMS)δ37.1(s,3F)ppm;IR(KBr):ν=2958,2857,1732,1560,1582,1466,1435,1319,1247,1208,1108,1072,1028,895,824,782,758,639,609,446,421cm-1.MS(EI):m/z(%)368,340,311,267,235(100),212,133,89,75,59.
6－溴－1－茚酮－2－三氟甲硫基－2－羧酸－甲酯
Methyl-6-Bromo-1-oxo-3-[(Trifluoromethyl)thio]-2,3-dihydro-1H-indene-2-carboxylate 5-f
向一个配有搅拌子经过烘箱干燥的100ml Schlenk管内在氩气气氛下依次加入0.362g(1.0mmol)亲电三氟甲硫基试剂、0.0672g(0.55mmol)4-二甲氨基吡啶和0.1345g(0.5mmol)6-溴-1-茚满酮-2-羧酸甲酯，并加入2.5ml新鲜纯化的二氯甲烷。反应在常温下搅拌过夜，氟谱检测亲电试剂完全消失，真空浓缩至最小体积。产物采用快速柱层析过柱分离。洗脱剂：30-60℃石油醚/乙醚=50/1，Rf：0.30。产率:95%。
1H NMR(300MHz,CDCl3,293K,TMS)δ7.94(s,1H),7.80(d,J=8.4Hz,1H),7.41(d,J=8.4Hz,1H),4.13(d,J=18.0Hz,1H),3.79(s,3H),3.60(d,J=18.0Hz,1H)ppm;19F NMR(282MHz,CDCl3,293K,TMS)δ37.5(s,3F)ppm;IR(KBr):ν=2957,2917,2848,1732,1599,1581,1472,1434,1416,1317,1245,1199,1159,1109,1028,964,898,865,822,757,704,683,60,583,498cm-1.MS(EI):m/z(%)368,340,311,267,235(100),212,133,89,75,59.
3,4-二氢萘-1(2H)-酮－2－三氟甲硫基－2－羧酸－甲酯
Methyl 1-oxo-3-[(Trifluoromethyl)thio]-1,2,3,4-tetrahydronaphthalene-2-carboxylte 5-g
向一个配有搅拌子经过烘箱干燥的100ml Schlenk管内在氩气气氛下依次加入0.362g(1.0mmol)亲电三氟甲硫基试剂、0.0672g(0.55mmol)4-二甲氨基吡啶和0.1021g(0.5mmol)1-四氢萘酮-2-羧酸甲酯，并加入2.5ml新鲜纯化的二氯甲烷。反应在常温下搅拌过夜，氟谱检测亲电试剂完全消失，真空浓缩至最小体积。产物采用快速柱层析过柱分离。洗脱剂：30-60℃石油醚/乙醚=50/1，Rf：0.30。产率:97%。
1H NMR(300MHz,CDCl3,293K,TMS)δ8.16(d,J=7.8Hz,1H),7.55(t,J=7.8Hz,1H),7.35(t,J=7.8Hz,1H),7.26(d,J=6.9Hz,1H),3.78(s,3H),3.34-3.23(m,1H),3.17-3.05(m,2H),2.61-2.51(m,1H)ppm;19F NMR(282MHz,CDCl3,293K,TMS)δ36.6(s,3F)ppm;IR(KBr):ν=2971,2937,1744,1686,1560,1485,1455,1437,1361,1299,1249,1227,1193,1111,1068,1039,976,888,872,841,775,761,742,631,484cm-1.MS(EI):m/z(%)368,340,311,267,235(100),212,133,89,75,59.
5,6－二甲氧基－1－茚酮－2－三氟甲硫基－2－羧酸－甲酯
Methyl-5,6-dimethoxy-1-oxo-3-[(Trifluoromethyl)thio]-2,3-dihydro-1H-indene-2-carboxyl ate 5-h
向一个配有搅拌子经过烘箱干燥的100ml Schlenk管内在氩气气氛下依次加入0.362g(1.0mmol)亲电三氟甲硫基试剂、0.0672g(0.55mmol)4-二甲氨基吡啶和0.5mmol 5,6-二甲氧基-1-茚满酮-2-羧酸甲酯，并加入2.5ml新鲜纯化的二氯甲烷。反应在常温下搅拌过夜，氟谱检测亲电试剂完全消失，真空浓缩至最小体积。产物采用快速柱层析过柱分离。洗脱剂：30-60℃石油醚/乙醚=20/1，Rf：0.30。产率:95%。
1H NMR(300MHz,CDCl3,293K,TMS)δ7.18(s,1H),6.91(s,1H),4.11(d,J=17.4Hz,1H),3.99(s,3H),3.90,3H),3.78(s,3H),3.57(d,J=17.4Hz,1H)ppm;19FNMR(282MHz,CDCl3,293K,TMS)δ37.8(s,3F)ppm;IR(KBr):ν=2958,2840,1723,1593,1506,1467,1456,1443,1425,1375,1316,1251,1224,1201,1162,1121,1021,1009,959,878,863,757,721,668,619,572,466cm-1.MS(EI):m/z(%)368,340,311,267,235(100),212,133,89,75,59.

Claims (7)

1.一种亲电三氟甲硫基化试剂，其具有如下的结构式：
2.一种如权利要求1所述的亲电三氟甲硫基化试剂的合成方法，其特征是采用下述方法获得：在室温～60℃和有机溶剂中，惰性气体气氛下，AgSCF3和1-氯-1,3-二氢-3,3-二甲基-1,2-苯并碘氧杂戊环反应0.5～12小时；所述的AgSCF3和1-氯-1,3-二氢-3,3-二甲基-1,2-苯并碘氧杂戊环的摩尔比为1:0.5～3.0。
3.如权利要求2所述的亲电三氟甲硫基化试剂的合成方法，其特征是所述的AgSCF3和1-氯-1,3-二氢-3,3-二甲基-1,2-苯并碘氧杂戊环的摩尔比为1:1。
4.如权利要求2所述的亲电三氟甲硫基化试剂的合成方法，其特征是所述的反应时在氩气气氛中进行。
5.如权利要求2所述的亲电三氟甲硫基化试剂的合成方法，其特征是所述的有机溶剂是乙醚、四氢呋喃、乙腈、丙酮、二氯甲烷、1，2－二氯乙烷、氯仿、四氯化碳、1，2－二甲氧基乙烷、1，2－二乙氧基乙烷、N，N－二甲基甲酰胺,苯、二乙二醇二甲醚或二乙二醇二乙醚。
6.如权利要求2所述的亲电三氟甲硫基化试剂的合成方法，其特征是所述的产物经过过滤，浓缩，柱层析或蒸馏纯化。
7.一种如权利要求1所述的亲电三氟甲硫基化试剂用于亲电三氟甲硫基化试剂与一亲核试剂反应制备三氟甲硫基化的产物。
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CN104945294B (zh) * 2014-03-31 2016-09-07 中国科学院上海有机化学研究所 含三氟甲硫基的化合物及其制备方法
CN105985266B (zh) * 2015-01-30 2018-02-16 中国科学院上海有机化学研究所 三氟甲硫基化试剂、制备方法及其应用
CN104974065A (zh) * 2015-06-15 2015-10-14 华东理工大学 一种制备α-三氟甲硫基化酮类化合物的方法
CN105669503B (zh) * 2016-01-12 2017-12-05 中山大学 三氟甲硫基试剂及其制备方法与在不对称三氟甲硫基化反应中的应用
CN105665011B (zh) * 2016-01-12 2018-03-16 中山大学 手性有机硒硫催化剂及其制备方法与在不对称反应中的应用
CN106256818B (zh) * 2016-07-08 2017-12-26 温州大学 一种带三氟甲硫基的茚酮和其衍生物及其制备方法
CN106187840B (zh) * 2016-07-08 2017-10-10 温州大学 一种带三氟甲硫基的茚酮类化合物及其制备方法
CN108299384A (zh) * 2018-02-26 2018-07-20 南开大学 三氟甲硫基转移试剂化合物及其合成方法
CN111718323B (zh) * 2020-07-10 2021-06-11 南宁师范大学 高价碘硫氰化试剂及其制备方法与应用
CN112608260B (zh) * 2020-12-24 2022-06-10 江南大学 一种脱硼酸合成芳乙烯基三氟甲硫醚类化合物的方法
CN114380743B (zh) * 2022-03-15 2023-08-11 四川大学 含氮化合物引入三氟甲硫基的方法
CN115583902B (zh) * 2022-08-22 2024-02-13 江苏医药职业学院 一种炔基硫醚类化合物的制备方法

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