CN108530329B - 一种制备三级烷基三氟甲基硫醚的方法 - Google Patents
一种制备三级烷基三氟甲基硫醚的方法 Download PDFInfo
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Abstract
Description
技术领域
本发明涉及一种制备三级烷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(Adenosine analogue,cefazaflur,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.]。尽管有少数几类通过三氟甲硫基金属试剂来构建一级或二级烷基三氟甲基硫醚,但是在无过渡金属条件下对三级烷基三氟甲基硫醚的定点合成仍然是一大挑战。反应的原料是三级烷氧醚(OCH2OCH3,-MOM),非常容易大规模制备[参见:Han,J.H.;Kwon,Y.E.;Sohn,J.-H.; Ryu,D.H.Tetrahedron 2010,66,1673.]。采用一种光催化与有机协同催化的,三级烷基 -MOM醚的直接定点三氟甲硫基化可以高效实现各类三级烷基三氟甲基硫醚的制备,在精细化工、材料科学和制药领域都有较好应用。
发明内容
本发明要解决的技术问题是提供一种制备三级烷基三氟甲基硫醚以及其应用。
本发明的合成路线如下:
一种制备三级烷基三氟甲基硫醚的方法,它是以三级烷氧醚(OCH2OCH3,-MOM)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,以光催化剂4CzIPN和有机硫醇催化剂4-巯基萘并[2,1-d:1′,2′-f][1,3,2]二氧代环庚烯-4-氧化物(4-mercaptodinaphtho[2,1-d:1′,2′-f][1,3,2]dioxaphosphepine 4-oxide)协同催化,与2-((trifluoromethyl)thio)isoindoline-1,3-dione(2-[(三氟甲基)硫基]异二氢吲哚-1,3- 二酮)在室温下反应,得到三级烷基三氟甲基硫醚
所述的光催化剂4CzIPN与有机硫醇催化剂有如下结构:
上述的制备方法,所述的三级烷基三氟甲基硫醚中的R1基团可以是各种取代的芳基、杂芳基或烷基等,R2基团可以是甲基、乙基或CH2TMS等。
上述的制备方法,所述的在溶液中是在二氯甲烷(dichloromethane)中。
上述的制备方法,所述的三级烷氧醚1与沈试剂2a的物质的量之比是1∶1-1∶2,优选的是1∶1.5。
上述的制备方法,所述的光催化剂4CzIPN与硫醇催化剂的用量是三级烷氧醚1摩尔数的2%的摩尔量。
上述的制备方法,所述的碳酸钾是三级烷氧醚1摩尔数的10%的摩尔量。
典型反应如下:
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,从稳定易制备的各种三级烷氧醚与三氟甲基硫试剂直接得到三级烷基三氟甲基硫醚。
具体实施方式
光催化剂4CzIPN由北京华威锐科化工有限公司提供。
有机硫醇催化剂合成:
根据文献(Kato,S.;Saga,Y.;Kojima,M.;Fuse,H.;Matsunaga,S.;Fukatsu,A.;Kondo,M.; Masaoka,S.;Kanai,M.J.Am.Chem.Soc.2017,139,2204.)进行合成,具体操作如下:取联萘酚2.9g(10mmol)加入到60mL吡啶中,于室温在搅拌状态下滴加PSCl34.3mL(42mmol),然后与85℃下反应3h,冷却至室温,然后加入15mL水,再与90℃反应2h,反应结束后冷却至室温,以饱和碳酸氢钠溶液淬灭,用乙酸乙酯萃取,合并有机相,以无水硫酸钠干燥,干法拌样,柱色谱纯化,得到白色固体粉末。
1H NMR(400MHz,CDCl3)δ8.02(d,J=8.7Hz,1H),7.91(d,J=8.1Hz,1H),7.79(s,2H), 7.62(t,J=8.8Hz,2H),7.40(t,J=7.3Hz,1H),7.24(dq,J=20.4,11.6,10.1Hz,4H),7.15- 7.08(m,1H),6.48(s,1H);31P NMR(162MHz,CDCl3)δ67.40.
原料合成:
原料N-三氟甲硫基邻苯二甲酰亚胺的合成
根据文献(Kang,K.;Xu,C.;Shen,Q.Organic Chemistry Frontiers 2014,7,294.),用 AgSCF3(三氟甲硫醇银)和N-溴邻苯二甲酰亚胺(N-Bromophthalimide)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,去滤液,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)。N-溴邻苯二甲酰亚胺2a,1H NMR(400MHz,CDC13)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.
原料烷基醚的合成
通用步骤:
根据文献(Han,J.H.;Kwon,Y.E.;Sohn,J.-H.;Ryu,D.H.Tetrahedron 2010,66,1673)进行合成,具体操作如下,首先取一个100mL的圆底烧瓶,称取10mmol的烷基三级醇,然后加入20mL二氯甲烷溶解,搅拌均匀,再加入约4mL的二异丙基乙胺(4.4mmol),然后置于冰浴中,搅拌条件下,小心加入氯甲基甲醚(MOMCl)约1.2mL,约5min后,置于60摄氏度的加热搅拌器中反应,过夜,待反应结束后,在冰浴条件下,加入饱和氯化铵溶液,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,即可得到相应的烷基醚。
(2-(methoxymethoxy)-2-methylpropyl)benzene,1H NMR(400MHz, CDCl3)δ7.23-7.17(m,2H),7.16-7.11(m,3H),4.68(s,2H),3.26(s,3H),2.74(s,2H),1.14(s,6H);13C NMR(101MHz,CDCl3)δ138.1,130.6,127.8,126.1,91.0,76.6,55.0,48.5, 26.0.
1H NMR(400MHz,CDCl3)δ4.75(s,2H),3.40(s,3H),2.21(d,J=10.9Hz,2H),1.90-1.76(m,6H),1.76-1.65(m,4H),1.49(d,J=12.4Hz,2H),1.35(s,3H);13C NMR(101 MHz,CDCl3)δ90.1,79.1,55.5,38.5,36.8,34.7,32.8,27.6,27.1,22.8.
1-chloro-4-(2-(methoxymethoxy)-2-methylpropyl)benzene,1H NMR (400MHz,Chloroform-d)δ7.23(d,J=8.4Hz,2H),7.14(d,J=8.4Hz,2H),4.72(s,2H), 3.32(s,3H),2.76(s,2H),1.19(s,6H);13C NMR(101MHz,CDCl3)δ136.6,132.0,131.9, 127.9,91.0,76.3,55.0,47.9,25.9.
1-methoxy-4-(2-(methoxymethoxy)-2-methylpropyl)benzene,1H NMR(400MHz,CDCl3)δ7.04(d,J=8.6Hz,2H),6.74(d,J=8.7Hz,2H),4.67(s,2H), 3.71(s,3H),3.26(s,3H),2.67(s,2H),1.12(s,6H);13C NMR(101 MHz,CDCl3)δ158.0,131.5,130.2,113.2,91.0,76.7,55.1,55.0,47.5,25.9.
1-bromo-2-(2-(methoxymethoxy)-2-methylpropyl)benzene,1g,10mmol scale,colorless oil,(1.51g,55%),Rf=0.8(petroleum ether/ethylacetate 20∶1);1H NMR(400 MHz,CDCl3)δ7.53(dd,J=8,0.8Hz,1H),7.38(dd,J=7.7,1.6Hz,1H),7.21(dt,J=7.6, 1.2Hz,1H),7.05(td,J=7.7,1.6Hz,1H),4.74(s,2H),3.33(s,3H),3.05(s,2H),1.27(s, 6H);13C NMR(101 MHz,CDCl3)δ137.7,132.6,132.6,127.6,126.5,90.8,77.0,54.9,46.5, 25.8.
1H NMR(500MHz,CDCl3)δ7.31(t,J=7.5Hz,2H),7.25-7.18(m,3H),4.80-4.74(m,2H),3.43(s,3H),2.75-2.68(m,2H),1.92-1.84(m,2H),1.35(s,3H),1.23-1.08(m,2H),0.12(s,9H);13C NMR(126MHz,CDCl3)δ142.8,128.3,128.3,125.6,90.8,78.9,55.4,44.1,30.5,29.4,27.0,0.6.
1H NMR(500MHz,CDCl3)δ4.70(s,2H),3.36(s,3H),1.51-1.46(m,2H),1.34-1.24(m,14H),1.21(s,6H),0.88(t,J=6.9Hz,3H);13C NMR(126MHz,CDCl3)δ91.0,76.3,55.0,41.9,31.9,30.2,29.7,29.6,29.3,26.3,24.0,22.7,14.1.
1H NMR(500MHz,CDCl3)δ4.70(s,2H),3.53(t,J=6.8Hz,2H),3.36(s,3H),1.81-1.73 (m,2H),1.52-1.41(m,4H),1.40-1.28(m,4H),1.23(s,6H);13C NMR(126MHz,CDCl3) δ90.9,76.2,55.0,45.1,41.8,32.6,29.4,26.9,26.3,23.8.
6-(methoxymethoxy)-6-methylundecane
1H NMR(500MHz,CDCl3)δ4.68(s,2H),3.37(s,3H),1.50-1.44(m,4H),1.35-1.24(m, 12H),1.17(s,3H),0.89(t,J=7.1Hz,6H);13C NMR(126MHz,CDCl3)δ90.7,78.5,55.3,39.1,32.5,23.9,23.4,22.7,14.1.
1H NMR(400MHz,CDCl3)δ4.71(s,2H),3.36(s,3H),1.63(td,J=13.3,11.5,4.4Hz,2H), 1.49-1.23(m,20H),1.18(s,3H);13C NMR(101MHz,CDCl3)δ90.5,79.2,55.1,34.0,26.5, 26.1,25.1,22.6,22.1,19.7.
1H NMR(500MHz,CDCl3)δ7.58(d,J=8.5Hz,2H),7.50(d,J=8.1Hz,2H),7.41(t,J= 7.7Hz,2H),7.31(t,J=7.4Hz,1H),7.27(d,J=8.1Hz,2H),4.76(s,2H),3.34(s,3H),2.84 (s,2H),1.24(s,6H);13C NMR(126MHz,CDCl3)δ141.0,139.0,137.2,131.0,128.7,127.0, 126.9,126.5,91.0,76.6,55.0,48.1,26.0.
2-fluoro-4′-(3-(methoxymethoxy)-3-methylbutan-2-y1)-1,1′-biphenyl
1H NMR(400MHz,CDCl3)δ7.55(d,J=8.1Hz,2H),7.42(t,J=7.6Hz,2H),7.36-7.29(m,2H),7.12-7.06(m,2H),4.76-4.69(m,2H),3.34(s,3H),2.83(q,J=7.1Hz,1H),1.35(d,J=7.1Hz,3H),1.23(s,3H),1.17(s,3H);13C NMR(101 MHz,CDCl3)δ160.4,158.0,145.8(d,J=7.4Hz),135.8(d,J=1.1Hz),129.6(d,J=4.0Hz),128.9(d,J=2.9Hz),128.3, 127.4,126.6(d,J=13.5Hz),125.4(d,J=3.1Hz),116.8,116.6,91.0,77.9,55.1,49.9,24.7, 24.2.15.8.
1H NMR(400MHz,CDCl3)δ7.15(d,J=8.1Hz,2H),7.03(d,J=8.1Hz,2H),4.73-4.67(m,2H),3.31(s,3H),2.81(q,J=7.2Hz,1H),2.43(d,J=7.2Hz,2H),1.83(dq,J=13.6,6.8Hz,1H),1.33(d,J=7.2Hz,3H),1.16(s,3H),1.14(s,3H),0.89(d,J=6.6Hz,6H);13CNMR(101MHz,CDCl3)δ139.4,128.9,128.3,90.9,78.3,55.0,49.6,45.0,30.2,24.9,23.6,22.4.15.7.
1H NMR(400MHz,CDCl3)δ7.64(dd,J=8.2,1.4Hz,2H),7.58(dd,J=8.2,1.4Hz,2H), 7.38-7.26(m,6H),4.74(s,2H),3.39(s,3H),2.99-2.94(m,2H),2.12-2.06(m,2H),1.31 (s,6H);13C NMR(101MHz,CDCl3)δ163.7,145.0,135.0,132.6,129.1,128.5,128.5,128.2, 127.9,127.9,126.3,91.0,75.2,55.2,38.8,26.1,23.1.
1H NMR(400MHz,CDCl3)δ7.08(dd,J=5.1,1.2Hz,1H),6.86(dd,J=5.1,3.4Hz,1H), 6.77-6.73(m,1H),4.70(s,2H),3.31(s,3H),2.94(s,2H),1.19(s,6H);13C NMR(101MHz,CDCl3)δ139.8,126.8,126.2,124.3,91.2,76.0,55.3,42.8,25.9.
7-(methoxymethoxy)-7-methyloctyl furan-2-carboxylate
1H NMR(500MHz,CDCl3)δ7.58(s,1H),7.18(s,1H),6.51(s,1H),4.70(s,2H),4.30(t,J =6.7Hz,2H),3.36(s,3H),1.75(p,J=6.9Hz,2H),1.53-1.47(m,2H),1.46-1.40(m,2H), 1.38-1.31(m,4H),1.21(s,6H);13C NMR(126MHz,CDCl3)δ158.8,146.2,144.8,117.7,111.8,91.0,76.2,65.0,55.1,41.8,29.8,28.7,26.3,25.9,23.9.
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
先称取(37.1mg,0.15mmol),4CzIPN(北京华威锐科化工有限公司提供,下同)(1.6mg,0.002mmol),K2CO3(1.38mg,0.01mmol),有机硫醇催化剂(自己合成,下同)(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL二氯甲烷,然后小心加入(2-(甲氧基甲氧基)-2-甲基丙基)苯(19.4mg,0.1mmol),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17.4mg(正己烷),产率74%,1H NMR(400MHz,CDCl3)δ7.34-7.27(m,3H),7.22-7.17(m,2H), 3.01(s,2H),1.45(s,6H);19F NMR(376MHz,CDCl3)δ-35.12;13C NMR(101MHz,CDCl3) δ136.2,131.1(q,J=308.05),130.9,128.0,127.0,51.9,49.2,28.8.MS(EI)m/z 234(M)+
实施例2
先称取(37.1mg,0.15mmol),4CzIPN(1.6mg,0.002mmol),K2CO3(1.38mg,0.01mmol),有机硫醇催化剂(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL二氯甲烷,然后小心加入 (22.9mg,0.1mmol),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22.8mg(正己烷),产率 76%,1H NMR(400MHz,CDCl3)δ7.28(d,J=8.4Hz,2H),7.13(d,J=8.4Hz,2H),2.98(s, 2H),1.43(s,6H);19F NMR(376MHz,CDCl3)δ-35.15;13C NMR(101 MHz,CDCl3)δ 134.6,133.0,132.2,131.0(q,J=309.06Hz),128.2,51.6,48.4,28.8.MS(EI)m/z 268(M+).
实施例3
先称取(37.1mg,0.15mmol),4CzIPN(1.6mg,0.002mmol),K2CO3(1.38mg,0.01mmol),有机硫醇催化剂(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL二氯甲烷,然后小心加入22.5mg,0.1mmol),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22.8mg(正己烷),产率76%,1H NMR(400MHz,CDCl3)δ7.11(d, J=8.6Hz,2H),6.84(d,J=8.7Hz,2H),3.80(s,3H),2.95(s,2H),1.43(s,6H);19F NMR (376MHz,CDCl3)δ-35.08;13C NMR(101MHz,CDCl3)δ158.6,131.9,131.2(q,J=307.5 Hz),128.2,113.4,55.2,52.2,48.3,28.8.MS(EI)m/z264(M+).
实施例4
先称取(27.1mg.0.1mmol),(37.1mg,0.15 mmol),4CzIPN(1.6mg,0.002mmol),K2CO3(1.38mg,0.01mmol),有机硫醇催化剂(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL 二氯甲烷,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18.9mg(正己烷),产率61%,1H NMR (500MHz,CDCl3)δ7.59(d,J=7.8Hz,2H),7.54(dd,J=8.1,1.6Hz,2H),7.46-7.40(m, 2H),7.36-7.31(m,1H),7.28-7.25(m,2H),3.05(s,2H),1.48(s,6H).19F NMR(471MHz, CDCl3)δ-35.05.13C NMR(126MHz,CDCl3)δ140.7,139.8,135.2,131.3,131.1(q,J= 308.3),128.8,127.3,127.0,126.7,52.0,48.8,28.9.MS(EI)m/z310(M+).
实施例5
先称取(37.1mg,0.15mmol),4CzIPN(1.6mg,0.002mmol),K2CO3(1.38mg,0.01mmol),有机硫醇催化剂(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL二氯甲烷,然后小心加入 (27.1mg,0.1mmol),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18.8mg(正己烷),产率60%,1H NMR(400MHz,CDCl3)δ7.58(dd,J=8.0,1.1Hz,1H),7.35(dd,J=7.7,1.7Hz,1H),7.27(td,J=7.5,1.2Hz,1H),7.12(td,J=7.8,1.7Hz,1H),3.30(s,2H),1.51(s,6H);19F NMR(376MHz,CDCl3)δ-35.19;13CNMR(101MHz,CDCl3)δ136.1,133.3,132.8,131.0 (q,J=309.06Hz),128.7,127.0,126.2,52.9,47.0,28.8.MS(EI)m/z233[(M-Br)+].
实施例6
先称取(37.1mg,0.15mmol),4CzIPN(1.6mg,0.002mmol),K2CO3(1.38mg,0.01mmol),有机硫醇催化剂(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL二氯甲烷,然后小心加入(27.1mg,0.1mmol),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(石油醚60-90:乙酸乙酯=100∶1),产率51%,1H NMR (400MHz,CDCl3)δ7.58-7.52(m,2H),7.44(t,J=7.5Hz,2H),7.40-7.33(m,2H),7.10- 7.01(m,2H),3.13(q,J=7.1Hz,1H),1.48(dd,J=10.5,3.3Hz,9H);19F NMR(376MHz, CDCl3)δ-34.73;13C NMR(101 MHz,CDCl3)δ159.2(d,J=247.9Hz),143.2(d,J=7.2 Hz),135.5(d,J=1.2Hz),131.1(q,J=307.7Hz),130.0(d,J=4.0Hz),128.9(d,J=2.9 Hz),128.5,127.7,127.5,125.5(d,J=3.2Hz),116.8(d,J=23.2Hz),55.5,49.2,28.9,25.8, 16.5.MS(EI)m/z342(M+).
实施例7
先称取(49.4mg,0.2mmol),4CzIPN(1.6mg,0.002mmol),K2CO3(1.38 mg,0.01mmol),有机硫醇催化剂(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL二氯甲烷,然后小心加入(26.5mg,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,下同)得到产物18.0mg(正己烷),产率59%,1H NMR(400MHz,CDCl3)δ7.12(d,J=8.2Hz,2H),7.06(d,J=8.2Hz,2H), 3.04(q,J=7.2Hz,1H),2.45(d,J=7.2Hz,2H),1.85(dp,J=13.6,6.8Hz,1H),1.46-1.40 (m,9H),0.90(d,J=6.6Hz,6H);19F NMR(376MHz,CDCl3)δ-34.76;13C NMR(101MHz, CDCl3)δ140.4,138.7,129.0,128.6,128.0(q,J=191.9Hz),56.0,49.2(d,J=1.2Hz),45.0, 30.2,29.0(d,J=0.9Hz),25.7(d,J=1.3Hz),22.4(d,J=2.4Hz),16.5.MS(EI)m/z 304 (M+).
实施例8
先称取(37.1mg,0.15mmol),4CzIPN(1.6mg,0.002mmol),K2CO3(1.38mg,0.01mmol),有机硫醇催化剂(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL二氯甲烷,然后小心加入(35.2mg,0.1mmol),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 16.4mg(石油醚60-90:乙酸乙酯=10:1),产率42%,1H NMR(500MHz,CDCl3)δ7.63 (d,J=8.2Hz,2H),7.58(d,J=8.2Hz,2H),7.39-7.32(m,6H),3.09-3.00(m,2H),2.33- 2.25(m,2H),1.54(s,6H);19F NMR(471MHz,CDCl3)δ-35.70;13C NMR(101MHz, CDCl3)δ162.5,145.4,135.2,132.5,130.8(q,J=309.06Hz),129.0,128.7,128.6,128.4, 128.1,128.0,126.4,51.3,39.8,29.3,24.1.MS(EI)m/z 391(M+).
实施例9
先称取(37.1mg,0.15mmol),4CzIPN(1.6mg,0.002mmol),K2CO3(1.38mg,0.01mmol),硫醇(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL二氯甲烷,然后小心加入((2-(甲氧基甲氧基)-2-甲基-4-苯基丁基)三甲基硅烷)(28.1mg,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,下同)得到产物17.0mg(正己烷),产率53%,1H NMR(400MHz,CDCl3)δ7.29 (t,J=7.4Hz,2H),7.19(t,J=6.9Hz,3H),2.86(td,J=12.8,5.0Hz,1H),2.74(td,J=12.9, 5.7Hz,1H),2.10-1.94(m,2H),1.61(s,3H),1.26(s,2H),0.14(s,9H);19F NMR(376MHz,CDCl3)δ-35.89;13C NMR(101MHz,CDCl3)δ141.6,130.9(q,J=308.4Hz),128.5,128.4, 126.0,56.8,45.5,31.5,31.3(d,J=0.1Hz),30.5(d,J=0.2Hz),0.9.MS(EI)m/z320(M+).
实施例10
先称取(37.1mg,0.15mmol),4CzIPN(1.6mg,0.002mmol),K2CO3(1.38mg,0.01mmol),有机硫醇催化剂(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL二氯甲烷,然后小心加入(23.1mg,0.1mmol),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18.9mg(正己烷),产率70%,1HNMR(400MHz,CDCl3) δ1.67-1.60(m,2H),1.45(s,6H),1.41(dd,J=10.1,5.1Hz,2H),1.27(s,12H),0.88(t,J= 6.8Hz,3H);19F NMR(376MHz,CDCl3)δ-35.63;13C NMR(101 MHz,CDCl3)δ130.4(q, J=308.6Hz),52.2,43.3,31.9,29.8,29.6,29.5,29.4(d,J=1.4Hz),29.3,24.6,22.7,14.1. MS(EI)m/z 270(M+).
实施例11
先称取(37.1mg,0.15mmol),4CzIPN(1.6mg,0.002mmol),K2CO3(1.38mg,0.01mmol),有机硫醇催化剂(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL二氯甲烷,然后小心加入(26.8mg,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 17.9mg(正己烷),产率70%,1H NMR(400MHz,CDCl3)δ3.54(t,J=6.7Hz,2H),1.83 -1.73(m,2H),1.68-1.62(m,2H),1.51-1.39(m,10H),1.33(ddd,J=15.5,6.4,1.6Hz, 2H);19F NMR(376MHz,CDCl3)δ-35.65;13C NMR(101 MHz,CDCl3)δ131.1(q,J= 308.6Hz),52.1,45.1,43.1,32.5,29.4,29.4,29.0,26.7,24.5;MS(EI)m/z 306(M+).
实施例12
先称取(37.1mg,0.15mmol),4CzIPN(1.6mg,0.002mmol),K2CO3(1.38mg,0.01mmol),硫醇(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL二氯甲烷,然后小心加入(23.1 mg,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20.3mg(正己烷),产率75%,1HNMR (400MHz,CDCl3)δ1.67-1.58(m,4H),1.42-1.24(m,15H),0.90(t,J=7.1Hz,6H);19F NMR(376MHz,CDCl3)δ-35.19;13C NMR(101MHz,CDCl3)δ131.2(q,J=307.5Hz), 56.3,40.6(d,J=1.1Hz),32.03,26.8(d,J=0.8Hz),23.8,22.5,14.0.MS(EI)m/z270(M+).
实施例13
先称取(37.1mg,0.15mmol),4CzIPN(1.6mg,0.002mmol),K2CO3(1.38mg,0.01mmol),硫醇(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL二氯甲烷,然后小心加入(21.1mg,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20.0mg(正己烷),产率80%,1H NMR(400MHz,CDCl3)δ2.46-2.38(m,2H),2.18-2.09(m,2H),2.00-1.83(m,4H),1.79(s,3H),1.75-1.63(m, 6H);19F NMR(376MHz,CDCl3)δ-34.25;13C NMR(101MHz,CDCl3)δ131.5(q,J= 307.8Hz),61.5,39.0,37.4,33.8,33.2,27.2,27.1,26.9.MS(EI)m/z250(M+).
实施例14
先称取(37.1mg,0.15mmol),4CzIPN(1.6mg,0.002mmol),K2CO3(1.38mg,0.01mmol),硫醇(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL二氯甲烷,然后小心加入(24.3mg,0.1 mmol),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27.0mg(正己烷),产率48%,1H NMR(400MHz, CDCl3)δ1.68-1.59(m,2H),1.51(s,3H),1.35(s,18H),0.88(q,J=8.3,6.7Hz,2H);19F NMR(376MHz,CDCl3)δ-34.84;13CNMR(101 MHz,CDCl3)δ131.2(q,J=308.9Hz), 56.0,35.1,28.4,26.3,26.0,22.7,22.2,19.8.MS(EI)m/z 282(M+).
实施例14
先称取(49.4mg,0.2mmol),4CzIPN(1.6mg,0.002mmol),K2CO3(1.38 mg,0.01mmol),硫醇(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL二氯甲烷,然后小心加入(20.3mg,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13.0mg(正己烷),产率54%,1H NMR(500MHz,CDCl3) δ7.21(dd,J=5.2,1.1Hz,1H),6.97(dd,J=5.1,3.5Hz,1H),6.88(d,J=3.0Hz,1H),3.23 (s,2H),1.50(s,6H);19F NMR(471 MHz,CDCl3)δ-35.28;13C NMR(126MHz,CDCl3)δ 137.8,131.0(q,J=307.0Hz),128.1,126.7,124.8,51.5,43.2,28.9.MS(EI)m/z240(M+).
实施例16
先称取(49.4mg,0.2mmol),4CzIPN(1.6mg,0.002mmol),K2CO3(1.38 mg,0.01mmol),硫醇(0.8mg,0.002mmol),加入反应管,通过真空管线抽换气三次,在氩气氛围下,加入1mL二氯甲烷,然后小心加入(30.0 mg,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,下同)得到产物21.2mg(石油醚60-90:乙酸乙酯=20∶1-10∶1),产率63%,1H NMR(400MHz,CDCl3)δ7.58(dd,J=1.7,0.8Hz,1H), 7.18(dd,J=3.5,0.7Hz,1H),6.51(dd,J=3.5,1.7Hz,1H),4.30(t,J=6.7Hz,2H),1.76(p, J=6.7Hz,2H),1.65(dd,J=10.5,5.6Hz,2H),1.50-1.40(m,10H),1.37(td,J=9.2,8.5, 3.0Hz,2H);19FNMR(376MHz,CDCl3)δ-35.65;13C NMR(101 MHz,CDCl3)δ158.8, 146.2,144.9,131.1(q,J=308.8Hz),117.7,111.8,64.9,52.1,43.1,29.4,28.6,25.8,24.5. MS(ESI)calcd forC15H22F3O3S+[M+H]+339.12,found 339.15。
Claims (6)
2.根据权利要求1所述的制备方法,其特征是:所述的在溶液中是在二氯甲烷中。
5.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与有机硫醇催化剂的用量是三级烷氧醚摩尔数的2%的摩尔量。
6.根据权利要求1所述的制备方法,其特征是:所述的碳酸钾是三级烷氧醚摩尔数的10%的摩尔量。
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