[0024] 为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解,下面结合具体实施例,进一步阐明本发明,但下述实施例仅为本发明的优选实施例,并非全部。基于实施方式中的实施例,本领域技术人员在没有做出创造性劳动的前提下所获得其它实施例,都属于本发明的保护范围。
[0025] 下述实施例中,若无特殊说明,所用的操作方法均为常规操作方法,所用设备均为常规设备。
[0026] 下述实施例中,苯磺酸(TsOH)购自探索公司,货号为98‑11‑3;三氟甲基亚磺酸钠(Na2SO2CF3)购自探索公司,货号为2926‑29‑6。
[0027] 实施例1
[0028] 如下式所示,将784.4mg(4mmol)芳基脒、520.2mg(4mmol)炔醛底物和水(0.3mL)加入25ml带有搅拌子的试管中,于室温加入5mL甲苯,再加入688.1mg(4mmol)苯磺酸、623.8mg(4mmol)三氟甲基亚磺酸钠,在80℃下搅拌4小时,水洗后用硅胶层析分离得到目标产物,88%产率。
[0029]
[0030] 1H NMR(400MHz,CDCl3)δ7.57(d,J=7.6Hz,2H),7.40‑7.32(m,8H),7.30‑7.28(m,1H),7.25‑7.20(m,2H),7.16‑7.12(m,2H),6.67(s,1H),5.97(s,1H),3.34(s,1H).[0031] 13C NMR(100MHz,CDCl3)δ146.4,145.2,142.2,138.1,129.6,129.4,129.4,128.7,
128.7,128.6,128.3,128.3,128.3,128.2,128.2,127.6,126.7,126.7,125.8,125.8,
119.8,70.3.
[0032] HR‑MALDI‑MS m/z calcd.for C22H18N2O[M+H]+:327.1492,found:327.1490.[0033] 实施例2
[0034] 如下式所示,将45.3mg(0.2mmol)芳基脒、26.0mg(0.2mmol)炔醛底物和水(0.1mL)加入25mL带有搅拌子的试管中,于室温加入2mL甲苯,再加入31.7mg(0.2mmol)苯磺酸、31.2mg(0.2mmol)三氟甲基亚磺酸钠,在80℃下搅拌4小时,水洗后用硅胶层析分离得到目标产物,80%产率。
[0035]
[0036] 1H NMR(400MHz,CDCl3)δ7.57(d,J=7.2Hz,2H),7.39‑7.35(m,4H),7.31‑7.29(m,1H),7.25‑7.19(m,3H),7.08‑7.05(m,2H),6.86‑6.82(m,2H),6.62(s,1H),5.96(s,1H),
4.20(s,1H),3.80(s,3H).
[0037] 13C NMR(100MHz,CDCl3)δ159.1,146.5,145.1,142.5,131.2,130.0,128.6,128.6,128.4,128.2,128.2,128.1,128.1,127.5,127.0,127.0,126.7,126.7,120.1,114.4,
114.4,70.3,55.5.
[0038] HR‑MALDI‑MS m/z calcd.for C23H21N2O2[M+H]+:357.1598,found:357.1615.[0039] 实施例3
[0040] 如下式所示,将57.8mg(0.2mmol)芳基脒、26.0mg(0.2mmol)炔醛底物和水(0.1mL)加入25mL带有搅拌子的试管中,于室温加入2mL甲苯,再加入31.7mg(0.2mmol)苯磺酸、31.2mg(0.2mmol)三氟甲基亚磺酸钠,在80℃下搅拌4小时,水洗后用硅胶层析分离得到目标产物,68%产率。
[0041]
[0042] 1H NMR(400MHz,CDCl3)δ7.56(d,J=7.1Hz,2H),7.48–7.45(m,2H),7.40‑7.35(m,3H),7.33‑7.30(m,1H),7.11‑7.10(m,2H),7.04‑7.00(m,2H),6.98‑6.94(m,1H),6.64(s,
1H),5.95(s,1H),3.82(s,1H),2.28(s,3H).
[0043] 13C NMR(100MHz,CDCl3)δ146.7,145.5,142.1,138.3,137.2,132.5,132.5,129.7,129.5,129.3,128.3,128.3,128.1,127.6,127.2,127.2,126.7,126.7,125.7,121.7,
119.4,70.3,21.3.
[0044] HR‑MALDI‑MS m/z calcd.for C23H20BrN2O[M+H]+:419.0754,found:419.0754.[0045] 实施例4
[0046] 如下式所示,将39.2mg(0.2mmol)芳基脒、31.6mg(0.2mmol)炔醛底物和水(0.1mL)加入25mL带有搅拌子的试管中,于室温加入2mL甲苯,再加入31.7mg(0.2mmol)苯磺酸、31.2mg(0.2mmol)三氟甲基亚磺酸钠,在80℃下搅拌4小时,水洗后用硅胶层析分离得到目标产物,81%产率。
[0047]
[0048] 1H NMR(400MHz,CDCl3)δ7.38‑7.33(m,7H),7.30‑7.27(m,1H),7.26‑7.22(m,2H),7.17‑7.12(m,3H),6.72(s,1H),5.88(s,1H),3.69(s,1H),2.27(d,J=5.4Hz,6H).[0049] 13C NMR(100MHz,CDCl3)δ146.4,145.5,139.8,138.3,136.4,135.8,130.0,129.5,
129.3,129.3,128.7,128.7,128.4,128.1,128.1,128.0,127.9,125.8,125.8,124.1,
119.7,70.4,19.8,19.5.
[0050] HR‑MALDI‑MS m/z calcd.for C24H23N2O[M+H]+:355.1805,found:355.1803.[0051] 实施例5
[0052] 如下式所示,将39.2mg(0.2mmol)芳基脒、24.8mg(0.2mmol)炔醛底物和水(0.1mL)加入25mL带有搅拌子的试管中,于室温加入2mL甲苯,再加入31.7mg(0.2mmol)苯磺酸、31.2mg(0.2mmol)三氟甲基亚磺酸钠,在80℃下搅拌4小时,水洗后用硅胶层析分离得到目标产物,88%产率。
[0053]
[0054] 1H NMR(400MHz,CDCl3)δ7.39‑7.33(m,5H),7.26‑7.13(m,5H),7.04(s,1H),4.77(dd,J=7.6,5.6Hz,1H),3.39(s,1H),1.98‑1.84(m,2H),1.59‑1.41(m,2H),1.37‑1.30(m,4H),0.89(t,J=7.0Hz,3H).
[0055] 13C NMR(100MHz,CDCl3)δ146.1,145.5,138.3,130.0,129.3,129.3,128.7,128.7,128.3,128.1,128.1,128.0,125.7,125.7,118.3,68.4,36.8,31.7,25.6,22.6,14.0.[0056] HR‑MALDI‑MS m/z calcd.for C21H25N2O[M+H]+:321.1961,found:321.1963.[0057] 实施例6
[0058] 与实施例1不同的是,反应底物为3mmol芳基脒和1mmol炔醛底物。其余皆与实施例1相同,65%产率。
[0059] 1H NMR(400MHz,CDCl3)δ7.57(d,J=7.6Hz,2H),7.40‑7.32(m,8H),7.30‑7.28(m,1H),7.25‑7.20(m,2H),7.16‑7.12(m,2H),6.67(s,1H),5.97(s,1H),3.34(s,1H).[0060] 13C NMR(100MHz,CDCl3)δ146.4,145.2,142.2,138.1,129.6,129.4,129.4,128.7,
128.7,128.6,128.3,128.3,128.3,128.2,128.2,127.6,126.7,126.7,125.8,125.8,
119.8,70.3.
[0061] HR‑MALDI‑MS m/z calcd.for C22H18N2O[M+H]+:327.1492,found:327.1490.[0062] 实施例7
[0063] 与实施例1不同的是,添加剂为2mmol苯磺酸、6mmol三氟甲基亚磺酸钠。其余皆与实施例1相同,60%产率。
[0064] 1H NMR(400MHz,CDCl3)δ7.57(d,J=7.6Hz,2H),7.40‑7.32(m,8H),7.30‑7.28(m,1H),7.25‑7.20(m,2H),7.16‑7.12(m,2H),6.67(s,1H),5.97(s,1H),3.34(s,1H).[0065] 13C NMR(100MHz,CDCl3)δ146.4,145.2,142.2,138.1,129.6,129.4,129.4,128.7,
128.7,128.6,128.3,128.3,128.3,128.2,128.2,127.6,126.7,126.7,125.8,125.8,
119.8,70.3.
[0066] HR‑MALDI‑MS m/z calcd.for C22H18N2O[M+H]+:327.1492,found:327.1490.[0067] 实施例8
[0068] 与实施例1不同的是,质子酸替换为相同用量的乙酸。其余皆与实施例1相同,83%产率。
[0069] 1H NMR(400MHz,CDCl3)δ7.57(d,J=7.6Hz,2H),7.40‑7.32(m,8H),7.30‑7.28(m,1H),7.25‑7.20(m,2H),7.16‑7.12(m,2H),6.67(s,1H),5.97(s,1H),3.34(s,1H).[0070] 13C NMR(100MHz,CDCl3)δ146.4,145.2,142.2,138.1,129.6,129.4,129.4,128.7,
128.7,128.6,128.3,128.3,128.3,128.2,128.2,127.6,126.7,126.7,125.8,125.8,
119.8,70.3.
[0071] HR‑MALDI‑MS m/z calcd.for C22H18N2O[M+H]+:327.1492,found:327.1490.[0072] 对比例1
[0073] 与实施例1不同的是,添加剂为1mmol苯磺酸、7mmol三氟甲基亚磺酸钠,其余皆相同。未得到目标产物。
[0074] 上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。