[0022] 下面结合具体实施例进一步描述本发明,在不脱离本发明上述技术思想情况下,根据本领域普通技术知识和惯用手段做出的各种替换或变更,均包括在本发明的范围内。
[0023] 实施例1
[0024]
[0025] 室温下,在15mL反应管中依次加入N-(4-甲氧基苯基)-N-甲基-3-苯基丙炔酰胺33.1mg、对甲基苯硫酚31.2mg,光催化剂醇溶伊红0.8mg和乙腈2ml,混合均匀,然后在3w蓝色LED灯照射下搅拌反应12h,用TLC检测至反应完成后,经真空(0.08Mpa)减压浓缩至无溶剂,得到粗产物,然后用体积比为3:1的石油醚和乙酸乙酯的混合洗脱剂冲洗,硅胶柱快速柱层析,得到本实施例3-硫代螺环三烯酮产物,为黄色固体40.6mg,收率87%。
[0026] 1H NMR(CDCl3,500MHz,ppm):δ7.31-7.28(m,1H),7.25-7.20(m,2H),7.23-7.19(m,4H),6.99(d,J=8.0Hz,2H),6.51(d,J=10.2Hz,2H),6.45(d,J=10.3Hz,2H),2.88(s,3H),
2.26(s,3H);13C NMR(CDCl3,125MHz,ppm):δ184.0,167.8,151.7,145.3,137.8,133.1,
132.8,131.7,130.8,129.7,129.5,128.3,128.2,127.7,67.7,26.3,21.1;HRMS calc.for C23H19NO2SNa(M+Na)+,396.1034;found,396.1036.
[0027] 实施例2
[0028]
[0029] 室温下,在15mL反应管中依次加入N-(4-甲氧基苯基)-N-甲基-3-甲苯基丙炔酰胺34.9mg,对甲基苯硫酚31.2mg、醇溶伊红0.8mg,乙腈2ml,混合均匀,然后在3w蓝色LED灯照射下搅拌反应12h,用TLC检测至反应完成后,经真空(0.08Mpa)减压浓缩至无溶剂,得到粗产物,然后用体积比为3:1的石油醚和乙酸乙酯的混合洗脱剂冲洗,硅胶柱快速柱层析,得到本实施例3-硫代螺环三烯酮产物,为黄色固体33.4mg,收率69%。
[0030] 1H NMR(CDCl3,500MHz,ppm):δ7.21(d,J=7.9Hz,2H),7.15(d,J=7.9Hz,2H),7.07(d,J=7.9Hz,2H),7.00(d,J=7.9Hz,2H),6.51(d,J=10.1Hz,2H),6.46(d,J=10.1Hz,2H),2.86(s,3H),2.31(s,3H),2.27(s,3H);13C NMR(CDCl3,125MHz,ppm):δ184.1,167.8,
152.3,145.5,139.9,137.7,133.1,132.0,131.5,129.7,129.0,128.1,128.0,127.8,67.6,
26.2,21.3,21.1;HRMS calc.for C24H21NO2SNa(M+Na)+,410.1191;found,410.1195.[0031] 实施例3
[0032]
[0033] 室温下,在15mL反应管中依次加入N,3-二(4-甲氧基苯基)-N-甲基苯基丙炔酰胺36.9mg、对甲基苯硫酚31.2mg、醇溶伊红0.8mg,乙腈溶剂2ml,混合均匀,然后在3w蓝色LED灯照射下搅拌反应12h,用TLC检测至反应完成后,经真空(0.08Mpa)减压浓缩至无溶剂,得到粗产物,然后用体积比为2:1的石油醚和乙酸乙酯的混合洗脱剂冲洗,硅胶柱快速柱层析,得到本实施例3-硫代螺环三烯酮产物,为黄色油状固体32.8mg,产率65%。
[0034] 1H NMR(CDCl3,500MHz,ppm):δ7.28(t,J=8.6Hz,2H),7.21(d,J=7.9Hz,2H),7.02(d,J=7.8Hz,2H),6.78(d,J=8.6Hz,2H),6.51(d,J=10.2Hz,2H),6.48(d,J=10.2Hz,2H),3.78(s,3H),2.86(s,3H),2.28(s,3H);13C NMR(CDCl3,125MHz,ppm):δ184.1,167.9,
160.7,152.2,145.7,137.6,133.0,131.1,130.9,130.0,129.7,128.3,123.1,113.8,67.4,
55.3,26.1,21.1;HRMS calc.for C24H21NO3SNa(M+Na)+,426.1140;found,426.1143.[0035] 实施例4
[0036]
[0037] 室温下,在15mL反应管中依次加入3-(4-氟苯基)-N-(4-甲氧基苯基)-N-甲基苯基丙炔酰胺35.4mg、对甲基苯硫酚31.2mg、醇溶伊红0.8mg,乙腈溶剂2ml,混合均匀,然后在3w蓝色LED灯照射下搅拌反应12h,用TLC检测至反应完成后,经真空(0.08Mpa)减压浓缩至无溶剂,得到粗产物,然后用体积比为2:1的石油醚和乙酸乙酯的混合洗脱剂冲洗,硅胶柱快速柱层析,得到本实施例3-硫代螺环三烯酮产物,为黄色固体34.2mg,收率70%。
[0038] 1H NMR(CDCl3,500MHz,ppm):δ7.18(d,J=7.9Hz,4H),6.98(d,J=7.9Hz,2H),6.91(t,J=8.5Hz,2H),6.50(d,J=10.1Hz,2H),6.50(d,J=10.1Hz,2H),2.88(s,3H),2.27(s,3H);13C NMR(CDCl3,125MHz,ppm):δ183.8,167.7,163.1(d,J=249.4Hz),149.7,145.2,
138.1,133.3,133.2,131.9,130.2(d,J=33.5Hz),129.7,127.2,126.7(d,J=13.7Hz),
115.5(d,J=21.7Hz),67.7,26.3,21.1;HRMS calc.for C23H18FNO2SNa(M+Na)+,414.0940;
found,414.0937.
[0039] 实施例5
[0040]
[0041] 室温下,在15mL反应管中依次加入3-(4-氯苯基)-N-(4-甲氧基苯基)-N-甲基苯基丙炔酰胺37.4mg、对甲基苯硫酚31.2mg、醇溶伊红0.8mg,乙腈溶剂2ml,混合均匀,然后在3w蓝色LED灯照射下搅拌反应12h,用TLC检测至反应完成后,经真空(0.08Mpa)减压浓缩至无溶剂,得到粗产物,然后用体积比为2:1的石油醚和乙酸乙酯的混合洗脱剂冲洗,硅胶柱快速柱层析,得到本实施例3-硫代螺环三烯酮产物,为黄色油状固体29.0mg,收率57%。
[0042] 1H NMR(CDCl3,500MHz,ppm):δ7.10(d,J=7.6Hz,4H),7.01(d,J=8.3Hz,2H),6.90(d,J=7.9Hz,2H),6.42(d,J=10.0Hz,2H),6.38(d,J=10.1Hz,2H),2.81(s,3H),2.20(s,3H);13C NMR(CDCl3,125MHz,ppm):δ182.7,166.5,147.7,144.0,137.3,134.5,132.8,
132.2,131.2,128.7,128.5,128.0,127.5,125.7,66.6,25.3,20.1;HRMS calc.for C23H18ClNO2SNa(M+Na)+,430.0644;found,430.0649.
[0043] 实施例6
[0044]
[0045] 室温下,在15mL反应管中依次加入3-(4-溴苯基)-N-(4-甲氧基苯基)-N-甲基苯基丙炔酰胺42.9mg、对甲基苯硫酚31.2mg、醇溶伊红0.8mg,乙腈溶剂2ml,混合均匀,然后在3w蓝色LED灯照射下搅拌反应12h,用TLC检测至反应完成后,经真空(0.08Mpa)减压浓缩至无溶剂,得到粗产物,然后用体积比为2:1的石油醚和乙酸乙酯的混合洗脱剂冲洗,硅胶柱快速柱层析,得到本实施例3-硫代螺环三烯酮产物,为黄色油状固体29.9mg,收率53%。
[0046] 1H NMR(CDCl3,500MHz,ppm):δ7.32(d,J=8.4Hz,2H),7.16(d,J=8.0Hz,2H),7.00(d,J=8.4Hz,2H),6.96(d,J=7.9Hz,2H),6.48(d,J=10.2Hz,2H),6.45(d,J=10.2Hz,2H),2.88(s,3H),2.28(s,3H);13C NMR(CDCl3,125MHz,ppm):δ183.7,167.5,148.5,145.0,
138.4,133.9,133.3,132.3,131.4,129.8,129.7,129.5,126.6,123.8,67.6,26.3,21.2;
HRMS calc.for C23H18BrNO2SNa(M+Na)+,474.0139;found,474.0141.
[0047] 实施例7
[0048]
[0049] 室温下,在15mL反应管中依次加入N-(3-氯-4-甲氧基苯基)-N-甲基-3-苯基丙炔酰胺37.4mg、对甲基苯硫酚31.2mg、醇溶伊红0.8mg,乙腈溶剂2ml,混合均匀,然后在3w蓝色 LED灯照射下搅拌反应12h,用TLC检测至反应完成后,经真空(0.08Mpa)减压浓缩至无溶剂,得到粗产物,然后用体积比为3:1的石油醚和乙酸乙酯的混合洗脱剂冲洗,硅胶柱快速柱层析,得到本实施例3-硫代螺环三烯酮产物,为黄色固体36.1mg,收率71%。
[0050] 1H NMR(CDCl3,500MHz,ppm):δ7.30(t,J=7.1Hz,1H),7.24(d,J=7.3Hz,2H),7.19(d,J=8.0Hz,2H),7.13(d,J=7.5Hz,2H),6.97(d,J=7.8Hz,2H),6.72(d,J=2.2Hz,1H),6.55-6.49(m,2H),2.90(s,3H),2.26(s,3H);13C NMR(CDCl3,125MHz,ppm):δ177.2,167.4,
150.0,145.9,141.0,138.1,136.3,133.5,132.2,132.0,130.2,129.7,129.6,128.4,
128.2,127.1,69.5,26.5,21.1;HRMS calc.for C23H18ClNO2SNa(M+Na)+,430.0644;found,
430.0641.
[0051] 实施例8
[0052]
[0053] 室温下,在15mL反应管中依次加入N-(3,4-二甲氧基)-N-甲基-3-苯基丙炔酰胺36.9mg、对甲基苯硫酚31.2mg、醇溶伊红0.8mg,乙腈溶剂2ml,混合均匀然后在3w蓝色LED灯照射下搅拌反应12h,用TLC检测至反应完成后,经真空(0.08Mpa)减压浓缩至无溶剂,得到粗产物,然后用体积比为2:1的石油醚和乙酸乙酯的混合洗脱剂冲洗,硅胶柱快速柱层析,得到本实施例3-硫代螺环三烯酮产物,为白色油状固体29.2mg,收率58%。
[0054] 1H NMR(CDCl3,500MHz,ppm):δ7.29(t,J=7.2Hz,1H),7.25-7.21(m,4H),7.18(d,J=7.5Hz,2H),6.99(d,J=7.9Hz,2H),6.52-6.44(m,2H),5.35(d,J=2.1Hz,1H),3.66(s,3H),2.87(s,3H),2.27(s,3H);13C NMR(CDCl3,125MHz,ppm):δ179.5,167.5,153.8,152.9,
146.0,137.8,132.3,132.1,131.8,130.9,129.7,129.5,128.3,128.2,127.8,111.4,69.1,
55.5,26.0,21.1;HRMS calc.for C24H21NO3SNa(M+Na)+,426.1140;found,426.1147.[0055] 实施例9
[0056]
[0057] 室温下,在15mL反应管中依次加入N-(4-甲氧基-2-甲基苯基)-N-甲基-3-苯基丙炔酰胺34.9mg、对甲基苯硫酚31.2mg、醇溶伊红0.8mg,乙腈溶剂2ml,混合均匀,然后在3w蓝色LED灯照射下搅拌反应12h,用TLC检测至反应完成后,经真空(0.08Mpa)减压浓缩至无溶剂, 得到粗产物,然后用体积比为2:1的石油醚和乙酸乙酯的混合洗脱剂冲洗,硅胶柱快速柱层析,得到本实施例3-硫代螺环三烯酮产物,为黄色油状固体42.1mg,收率87%。
[0058] 1H NMR(CDCl3,500MHz,ppm):δ7.34-7.32(m,1H),7.29-7.25(m,4H),7.23(d,J=8.0Hz,2H),7.02(d,J=7.9Hz,2H),6.49(s,2H),6.37(s,1H),2.79(s,3H),2.29(s,3H),
13
1.78(s,3H);C NMR(CDCl3,125MHz,ppm):δ184.7,168.1,153.5,152.1,145.5,137.8,
133.0,132.6,132.0,131.5,130.6,129.8,128.4,128.1,127.9,69.7,25.8,21.1,17.9;
HRMS calc.for C24H21NO2SNa(M+Na)+,410.1191;found,410.1196.
[0059] 实施例10
[0060]
[0061] 室温下,在15mL反应管中依次加入N-(4-甲氧基苯基)-N-甲基-3-苯基丙炔酰胺33.1mg、苯硫酚26vL、醇溶伊红0.8mg,乙腈溶剂2ml,混合均匀,然后在3w蓝色LED灯照射下搅拌反应12h,用TLC检测至反应完成后,经真空(0.08Mpa)减压浓缩至无溶剂,得到粗产物,然后用体积比为2:1的石油醚和乙酸乙酯的混合洗脱剂冲洗,硅胶柱快速柱层析,得到本实施例3-硫代螺环三烯酮产物,为黄色油状物25.1mg,收率56%.
[0062] 1H NMR(CDCl3,500MHz,ppm):δ7.29-7.23(m,7H),7.20-7.17(m,3H),6.53(d,J=10.0Hz,2H),6.47(d,J=10.1Hz,2H),2.89(s,3H);13C NMR(CDCl3,125MHz,ppm):δ183.9,
167.7,152.8,145.1,133.2,132.2,131.7,131.0,130.7,129.7,128.9,128.3,128.1,
127.5,67.7,26.3;HRMS calc.for C22H17NO2SNa(M+Na)+,382.0878;found,382.0879.[0063] 实施例11
[0064]
[0065] 室温下,在15mL反应管中依次加入N-(4-甲氧基苯基)-N-甲基-3-苯基丙炔酰胺33.1mg、对甲氧基苯硫酚31vL、醇溶伊红0.8mg,乙腈2ml,混合均匀,然后在3w蓝色LED灯照射下搅拌反应12h,用TLC检测至反应完成后,经真空(0.08Mpa)减压浓缩至无溶剂,得到粗产物,然后用体积比为2:1的石油醚和乙酸乙酯的混合洗脱剂冲洗,硅胶柱快速柱层析,得到本实施例3-硫代螺环三烯酮产物,为黄色固体24.3mg,收率50%。
[0066] 1H NMR(CDCl3,500MHz,ppm):δ7.28-7.27(m,2H),7.24-7.22(m,3H),7.17-7.15(m,2H),6.69(d,J=8.9Hz,2H),6.49(d,J=10.3Hz,2H),6.43(d,J=10.2Hz,2H),3.74(s,3H),
2.87(s,3H); 13C NMR(CDCl3,125MHz,ppm):δ184.0,167.9,159.8,150.2,145.3,134.6,
133.5,133.1,130.7,129.4,128.3,128.2,121.1,114.5,67.7,55.3,26.3;HRMS calc.for C23H19NO3SNa(M+Na)+,412.0983;found,412.0985.
[0067] 实施例12
[0068]
[0069] 室温下,在15mL反应管中依次加入N-(4-甲氧基苯基)-N-甲基-3-苯基丙炔酰胺33.1mg、对氟苯硫酚27vL、醇溶伊红0.8mg,乙腈溶剂2ml,混合均匀,然后在3w蓝色LED灯照射下搅拌反应12h,用TLC检测至反应完成后,经真空(0.08Mpa)减压浓缩至无溶剂,得到粗产物,然后用体积比为3:1的石油醚和乙酸乙酯的混合洗脱剂冲洗,硅胶柱快速柱层析,得到本实施例3-硫代螺环三烯酮产物,为黄色固体29.2mg,收率62%。
[0070] 1H NMR(CDCl3,500MHz,ppm):δ7.31-7.30(m,3H),7.24(d,J=7.4Hz,2H),7.17(d,J=7.5Hz,2H),6.87(d,J=8.5Hz,2H),6.51(d,J=10.0Hz,2H),6.45(d,J=10.3Hz,2H),2.88(s,3H); 13C NMR(CDCl3,125MHz,ppm):δ183.9,167.6,162.5,151.6,145.0,134.2(d,J=8.3Hz),133.2,132.7,130.5,129.7,128.3,128.2,126.1(d,J=3.3Hz),116.1(d,J=+
22.0Hz),67.7,26.3;HRMS calc.for C22H16FNO2SNa(M+Na) ,400.0783;found,400.0788.[0071] 实施例13
[0072]
[0073] 室温下,在15mL反应管中依次加入N-(4-甲氧基苯基)-N-甲基-3-苯基丙炔酰胺33.1mg、对氯苯硫酚36.2mg、醇溶伊红0.8mg,乙腈溶剂2ml,混合均匀,然后在3w蓝色LED灯照射下搅拌反应12h,用TLC检测至反应完成后,经真空(0.08Mpa)减压浓缩至无溶剂,得到粗产物,然后用体积比为2:1的石油醚和乙酸乙酯的混合洗脱剂冲洗,硅胶柱快速柱层析,得到本实施例3-硫代螺环三烯酮产物,为黄色油状固体34.9mg,收率71%。
[0074] 1H NMR(CDCl3,500MHz,ppm):δ7.35-7.32(m,1H),7.29-7.26(m,2H),7.24-7.19(m,4H),7.15(d,J=8.7Hz,2H),6.52-6.46(m,4H),2.89(s,3H);13C NMR(CDCl3,125MHz,ppm):δ
183.8,167.5,152.9,144.9,133.9,133.3,132.7,132.0,130.5,130.0,129.9,129.1,
128.4,128.1, 67.8,26.3;HRMS calc.for C22H16ClNO2SNa(M+Na)+,416.0488;found,
416.0489.
[0075] 实施例14
[0076]
[0077] 室温下,在15mL反应管中依次加入N-(4-甲氧基苯基)-N-甲基-3-苯基丙炔酰胺33.1mg、间氯苯硫酚36.2mg、醇溶伊红0.8mg,乙腈溶剂2ml,混合均匀,然后在3w蓝色LED灯照射下搅拌反应12h,用TLC检测至反应完成后,经真空(0.08Mpa)减压浓缩至无溶剂,得到粗产物,然后用体积比为2:1的石油醚和乙酸乙酯的混合洗脱剂冲洗,硅胶柱快速柱层析,得到本实施例3-硫代螺环三烯酮产物,为黄色固体26.5mg,收率54%。
[0078] 1H NMR(CDCl3,500MHz,ppm):δ7.33-7.27(m,1H),7.28-7.25(m,2H),7.22-7.17(m,4H),7.13-7.11(m,2H),6.53(d,J=10.3Hz,2H),6.48(d,J=10.3Hz,2H),2.91(s,3H);13C NMR(CDCl3,125MHz,ppm):δ183.8,167.4,153.4,144.8,134.6,133.5,133.3,131.5,130.7,
130.4,129.9,129.0,128.4,128.0,127.7,67.9,26.4;HRMS calc.for C22H16ClNO2SNa(M+Na)+,416.0488;found,416.0486.
[0079] 实施例15
[0080]
[0081] 室温下,在15mL反应管中依次加入N-(4-甲氧基苯基)-N-甲基-3-苯基丙炔酰胺33.1mg、邻氯苯硫酚29vL、醇溶伊红0.8mg,乙腈溶剂2ml,混合均匀,然后在3w蓝色LED灯照射下搅拌反应12h,用TLC检测至反应完成后,经真空(0.08Mpa)减压浓缩至无溶剂,得到粗产物,然后用体积比为2:1的石油醚和乙酸乙酯的混合洗脱剂冲洗,硅胶柱快速柱层析,得到本实施例3-硫代螺环三烯酮产物,为白色油状固体26.0mg,收率53%。
[0082] 1H NMR(CDCl3,500MHz,ppm):δ7.32-7.30(m,1H),7.27-7.26(m,1H),7.25-7.21(m,5H),7.12-7.07(m,2H),6.53(d,J=10.2Hz,2H),6.46(d,J=10.2Hz,2H),2.90(s,3H);13C NMR(CDCl3,125MHz,ppm):δ184.0,167.4,152.0,145.1,135.8,133.2,131.1,130.5,130.2,
130.0,129.7,129.0,128.3,127.9,127.0,67.9,26.3;HRMS calc.for C22H16ClNO2SNa(M+Na)+,416.0488;found,416.0489.
[0083] 实施例16
[0084]
[0085] 室温下,在15mL反应管中依次加入N-(4-甲氧基苯基)-N-甲基-3-苯基丙炔酰胺33.1mg、2-萘硫醇29vL、醇溶伊红0.8mg,乙腈溶剂2ml,混合均匀,然后在3w蓝色LED灯照射下搅拌反应12h,用TLC检测至反应完成后,经真空(0.08Mpa)减压浓缩至无溶剂,得到粗产物,然后用体积比为2:1的石油醚和乙酸乙酯的混合洗脱剂冲洗,硅胶柱快速柱层析,得到本实施例3-硫代螺环三烯酮产物,为黄色油状固体30.7mg,收率60%。
[0086] 1H NMR(CDCl3,500MHz,ppm):δ7.79(d,J=1.5Hz,1H),7.74-7.72(m,1H),7.68-7.66(m,1H),7.63(d,J=8.6Hz,1H),7.45-7.43(m,2H),7.34-7.32(m,1H),7.23-7.16(m,
5H),6.54(d,J=10.2Hz,2H),6.46(d,J=10.2Hz,2H),2.89(s,3H);13C NMR(CDCl3,125MHz,ppm):δ183.9,167.8,152.5,145.1,133.4,133.2,132.5,132.4,130.7,130.6,130.0,
128.7,128.6,128.4,128.2,128.1,127.7,127.5,126.5,126.4,67.8,26.3;HRMS calc.for C26H19NO2SNa(M+Na)+,432.1034;found,432.1037.
[0087] 实施例17
[0088]
[0089] 室温下,在15mL反应管中依次加入N-(4-乙氧基苯基)-N-甲基-3-苯基丙炔酰胺34.9mg、对甲基苯硫酚31.2mg、醇溶伊红0.8mg,乙腈溶剂2ml,混合均匀,然后在3w蓝色LED灯照射下搅拌反应12h,用TLC检测至反应完成后,经真空(0.08Mpa)减压浓缩至无溶剂,得到粗产物,然后用体积比为2:1的石油醚和乙酸乙酯的混合洗脱剂冲洗,硅胶柱快速柱层析,得到本实施例3-硫代螺环三烯酮产物,为黄色固体29.8mg,收率64%。
[0090] 1H NMR(CDCl3,500MHz,ppm):δ7.31-7.28(m,1H),7.25-7.20(m,2H),7.23-7.19(m,4H),6.99(d,J=8.0Hz,2H),6.51(d,J=10.2Hz,2H),6.45(d,J=10.3Hz,2H),2.88(s,3H),
2.26(s,3H);13C NMR(CDCl3,125MHz,ppm):δ184.0,167.8,151.7,145.3,137.8,133.1,
132.8,131.7,130.8,129.7,129.5,128.3,128.2,127.7,67.7,26.3,21.1;HRMS calc.for +
C23H19NO2SNa(M+Na) ,396.1034;found,396.1039.
[0091] 实施例18
[0092]
[0093] 室温下,在15mL反应管中依次加入N-甲基-N,3-二苯基丙炔酰胺29.4mg、对甲基苯硫酚31.2mg、醇溶伊红0.8mg,乙腈溶剂2ml,混合均匀,然后在3w蓝色LED灯照射下搅拌反应12h,用TLC检测至反应完成后,经真空(0.08Mpa)减压浓缩至无溶剂,得到粗产物,然后用体积比为2:1的石油醚和乙酸乙酯的混合洗脱剂冲洗,硅胶柱快速柱层析,得到本实施例3-硫代螺环三烯酮产物,为黄色固体27.5mg,收率59%。
[0094] 1H NMR(CDCl3,500MHz,ppm):δ7.31-7.28(m,1H),7.25-7.20(m,2H),7.23-7.19(m,4H),6.99(d,J=8.0Hz,2H),6.51(d,J=10.2Hz,2H),6.45(d,J=10.3Hz,2H),2.88(s,3H),
2.26(s,3H);13C NMR(CDCl3,125MHz,ppm):δ184.0,167.8,151.7,145.3,137.8,133.1,
132.8,131.7,130.8,129.7,129.5,128.3,128.2,127.7,67.7,26.3,21.1;HRMS calc.for C23H19NO2SNa(M+Na)+,396.1034;found,396.1035.
[0095] 实施例19
[0096]
[0097] 室温下,在15mL反应管中依次加入N-(4-氟苯基)-N-甲基-3-苯基丙炔酰胺31.6mg、对甲基苯硫酚31.2mg、醇溶伊红0.8mg,乙腈溶剂2ml,混合均匀,然后在3w蓝色LED灯照射下搅拌反应12h,用TLC检测至反应完成后,经真空(0.08Mpa)减压浓缩至无溶剂,得到粗产物,然后用体积比为2:1的石油醚和乙酸乙酯的混合洗脱剂冲洗,硅胶柱快速柱层析,得到本实施例3-硫代螺环三烯酮产物,为黄色固体25.7mg,收率55%。
[0098] 1H NMR(CDCl3,500MHz,ppm):δ7.31-7.28(m,1H),7.25-7.20(m,2H),7.23-7.19(m,4H),6.99(d,J=8.0Hz,2H),6.51(d,J=10.2Hz,2H),6.45(d,J=10.3Hz,2H),2.88(s,3H),
2.26(s,3H);13C NMR(CDCl3,125MHz,ppm):δ184.0,167.8,151.7,145.3,137.8,133.1,
132.8,131.7,130.8,129.7,129.5,128.3,128.2,127.7,67.7,26.3,21.1;HRMS calc.for +
C23H19NO2SNa(M+Na) ,396.1034;found,396.1036.