实施例
除非特殊限定,普遍反应条件如下:
氮气保护下,将氮杂环卡宾-钯络合物(6.5mg,2.0mol%),叔丁醇钠(144mg,3.0equiv),四氢呋喃(0.5mL),咪唑并[1,2-a]吡啶(52μL,0.5mmol)和氯苯(76μL,0.75mmol)依次加入封管中。将混合物120℃下加热反应12小时。停止反应,将混合物自然冷却至室温,旋转蒸发仪除去溶剂,残留物用快速柱层析分离得到纯净产物,所有产率为分离纯化后产物的产率。
表格1.反应条件优化
a所有反应均以1a(0.5mmol),2a(0.75mmol),4(2.0mol%),碱(3.0当量),溶剂(0.5mL)在120℃下反应12小时。b分离收率。
表格2.氮杂环卡宾-钯络合物4催化1a与2的反应。
a除非特别说明,所有反应均以1a(0.5mmol),2(0.75mmol),4(2.0mol%),NaOtBu(3.0当量)在四氢呋喃(0.5mL)中反应。b分离收率。c4(4.0mol%)。
表格3.氮杂环卡宾-钯络合物4催化1与2的反应。
a除非特别说明,所有反应均以1(0.5mmol),2(0.75mmol),4(2.0mol%),NaOtBu(3.0当量),四氢呋喃(0.5mL)在120℃反应12小时。b分离收率。c130℃.
对比例
将2-甲基咪唑并[1,2-a]吡啶2i(66mg,0.5mmol),氯苯2a(78.4mg,0.7mmol),醋酸钯(2.5mol%),丁基二金刚烷基膦(10mol%),碳酸铯(1.5mmol)和N-甲基吡咯烷酮(2mL)在油浴120℃中加热反应24小时。反应结束后,加入8毫升水。水溶液用乙醚萃取(3×8mL),有机相合并后用无水硫酸镁干燥。溶剂浓缩后用柱层析分离得到产物。
从上述文献报导结果可知,与本发明实施例相比,此反应底物局限性大,即咪唑并[1,2-a]吡啶2-位上必须有甲基取代基;所用配体合成步骤复杂,且对空气和水汽敏感,导致操作不易;反应所使用的溶剂毒性较大,对环境危害严重;反应后处理复杂,需结合萃取、干燥等步骤。
附:本发明实施例所合成产物的表征数据
化合物3a:黄色固体。1H NMR(500MHz,CDCl3,TMS)δ8.31(d,J=7.0Hz,1H),7.69(s,1H),7.66(d,J=9.0Hz,1H),7.55-7.53(m,2H),7.49(t,J=8.0Hz,2H),7.41-7.38(m,1H),7.19-7.15(m,1H),6.77(td,J=7.0,1.0Hz,1H).13C NMR(125MHz,CDCl3)δ146.0,132.3,129.13,129.08,128.0,127.8,125.6,124.1,123.2,118.1,112.4.
化合物3b:棕色液体。1H NMR(500MHz,CDCl3,TMS)δ7.83(dt,J=6.5,1.0Hz,1H),7.66(t,J=4.5Hz,2H),7.47-7.41(m,2H),7.18(ddd,J=9.0,6.5,1.0Hz,1H),7.08(td,J=7.5,1.0Hz,1H),7.05(d,J=8.0Hz,1H),6.75(td,J=7.0,1.0Hz,1H),3.80(s,3H).13C NMR(125MHz,CDCl3)δ157.1,145.9,133.1,131.8,130.2,125.2,123.8,123.0,121.0,118.0,117.7,111.5,111.2,55.4.
化合物3c:白色固体。1H NMR(500MHz,CDCl3,TMS)δ8.35(d,J=6.5Hz,1H),7.70(s,1H),7.66(d,J=9.0Hz,1H),7.41(t,J=8.0Hz,1H),7.18(t,J=8.0Hz,1H),7.13(d,J=7.5Hz,1H),7.08(s,1H),6.94(dd,J=8.0,2.5Hz,1H),6.79(t,J=6.5Hz,1H),3.85(s,3H).13C NMR(125MHz,CDCl3)δ160.0,146.0,132.4,130.4,130.1,125.4,124.1,123.3,120.0,118.0,113.5,113.3,112.4,55.2.
化合物3d:白色固体。1H NMR(500MHz,CDCl3,TMS)δ8.24(d,J=7.0Hz,1H),7.65(d,J=9.5Hz,1H),7.62(s,1H),7.45(d,J=8.5Hz,2H),7.16(t,J=8.0Hz,1H),7.04(d,J=8.5Hz,2H),6.77(t,J=7.0Hz,1H),3.86(s,3H).13C NMR(125MHz,CDCl3)δ159.4,145.6,131.8,129.5,125.4,123.8,123.1,121.3,117.9,114.5,112.2,55.2.
化合物3e:棕色液体。1H NMR(500MHz,CDCl3,TMS)δ7.76(d,J=7.0Hz,1H),7.69(d,J=9.0Hz,1H),7.62(s,1H),7.41-7.30(m,4H),7.20(ddd,J=9.0,6.5,1.0Hz,1H),6.77(t,J=6.5Hz,1H),2.17(s,3H).13C NMR(125MHz,CDCl3)δ145.4,138.2,132.8,131.1,130.6,129.1,128.2,126.2,124.6,123.9,123.6,118.0,112.2,19.7.
化合物3f:棕色液体。1H NMR(500MHz,CDCl3,TMS)δ8.32(d,J=7.0Hz,1H),7.67(s,1H),7.65(d,J=9.0Hz,1H),7.40-7.33(m,3H),7.21(d,J=7.5Hz,1H),7.18-7.15(m,1H),6.77(td,J=7.0,1.0Hz,1H),2.42(s,3H).13C NMR(125MHz,CDCl3)δ145.9,138.9,132.3,129.1,129.0,128.8,128.6,125.7,124.9,124.0,123.3,118.0,112.3,21.3.
化合物3g:黄色固体。1H NMR(500MHz,CDCl3,TMS)δ8.31(d,J=7.0Hz,1H),7.68-7.66(m,2H),7.45(d,J=8.0Hz,2H),7.33(d,J=8.0Hz,2H),7.20-7.17(m,1H),6.80(t,J=6.5Hz,1H),2.44(s,3H).13C NMR(125MHz,CDCl3)δ145.9,138.2,132.1,129.9,128.0,126.2,125.7,124.1,123.3,118.1,112.4,21.3.
化合物3h:棕色液体。1H NMR(500MHz,CDCl3,TMS)δ8.01-7.99(m,1H),7.74(s,1H),7.68(d,J=9.0Hz,1H),7.49(t,J=7.5Hz,1H),7.42(dd,J=13.5,7.5Hz,1H),7.31-7.19(m,3H),6.81(t,J=7.5Hz,1H).13C NMR(125MHz,CDCl3)δ159.7(d,JC-F=247.375Hz),146.2,133.7(d,JC-F=0.75Hz),131.1(d,JC-F=3.125Hz),130.2(d,JC-F=8.125Hz),124.7(d,JC-F=3.5Hz),124.3,124.2(d,JC-F=4.625Hz),119.9,117.8,116.9(d,JC-F=15.0Hz),116.1(d,JC-F=21.375Hz),112.3.MS(ESI):213[M+H]+;HRMS(ESI)calcd for C13H10FN2[M+H]+:213.0823;found:213.0840;IR(neat)ν1635,1542,1497,1483,1469,1450,1351,1301,1270,1256,1216,1177,1146,1118,1090,1008,970,897,865,814,779,753,737cm-1.
化合物3i:棕色液体。1H NMR(500MHz,CDCl3,TMS)δ8.33(d,J=7.0Hz,1H),7.72(s,1H),7.67(d,J=9.0Hz,1H),7.47(td,J=8.0,6.0Hz,1H),7.34(dt,J=7.5,1.0Hz,1H),7.26(dt,J=9.5,2.0Hz,1H),7.21(ddd,J=9.0,6.5,1.0Hz,1H),7.10(tdd,J=8.5,2.5,1.0Hz,1H),6.83(td,J=7.0,1.0Hz,1H).13C NMR(125MHz,CDCl3)δ163.0(d,JC-F=245.875Hz),146.3,132.9,131.2(d,JC-F=8.375Hz),130.8(d,JC-F=8.625Hz),124.4,123.3(d,JC-F=3.0Hz),123.1,118.2,114.9(d,JC-F=21.0Hz),114.5(d,JC-F=22.125Hz),112.7.MS(ESI):213[M+H]+;HRMS(ESI)calcd for C13H10FN2[M+H]+:213.0823;found:213.0840;IR(neat)ν1610,1582,1495,1469,1436,1354,1295,1264,1208,1157,1129,1115,848,791,750,734cm-1.
化合物3j:棕色液体。1H NMR(500MHz,CDCl3,TMS)δ8.24(d,J=7.0Hz,1H),7.68(d,J=10.0Hz,2H),7.55-7.51(m,2H),7.25-7.19(m,3H),6.82(td,J=7.0,1.0Hz,1H).13C NMR(125MHz,CDCl3)δ162.4(d,JC-F=247.0Hz),145.9,132.4,129.9(d,JC-F=8.125Hz),125.2(d,JC-F=3.125Hz),124.5,124.1,123.0,118.2,116.2(d,JC-F=21.625Hz),112.5.
化合物3k:棕色液体。1H NMR(500MHz,CDCl3,TMS)δ8.35(d,J=7.0Hz,1H),7.71(s,1H),7.68(d,J=9.0Hz,1H),7.56(d,J=8.5Hz,2H),7.53(d,J=8.5Hz,2H),7.21(t,J=8.0Hz,1H),6.83(d,J=7.0Hz,1H),6.78(dd,J=17.5,11.0Hz,1H),5.83(d,J=17.5Hz,1H),5.33(d,J=11.0Hz,1H).13C NMR(125MHz,CDCl3)δ146.1,137.3,136.0,132.5,128.5,127.8,126.9,125.4,124.2,123.3,118.1,114.5,112.5.MS(ESI):221[M+H]+;HRMS(ESI)calcd for C15H13N2[M+H]+:221.1073;found:221.1091;IR(neat)ν1627,1604,1540,1483,1407,1351,1301,1273,1253,1163,1149,1129,1115,1008,989,962,910,903,893,858,848,843,754,738,736cm-1.
化合物3l:白色固体。熔点:80-81℃。1H NMR(500MHz,CDCl3,TMS)δ9.93(d,J=7.0Hz,1H),8.64(d,J=5.0Hz,1H),8.13(s,1H),7.72-7.68(m,3H),7.2t(t,J=8.0Hz,1H),7.16-7.11(m,1H),6.92(t,J=7.0Hz,1H).13C NMR(125MHz,CDCl3)δ150.5,148.6,147.4,136.4,134.5,128.0,125.4,123.5,120.8,120.3,117.4,112.8.MS(ESI):196[M+H]+;HRMS(ESI)calcd for C12H10N3[M+H]+:196.0869;found:196.0879;IR(neat)ν1587,1531,1495,1444,1438,1360,1348,1320,1306,1273,1261,1185,1171,1126,1093,1014,992,968,888,851,837,782,751,736,716cm-1.
化合物3m:棕色液体。1H NMR(500MHz,CDCl3,TMS)δ8.20(d,J=7.0Hz,1H),7.61(s,1H),7.53-7.47(m,4H),7.41-7.36(m,2H),6.61(d,J=7.5Hz,1H),2.39(s,3H).13C NMR(125MHz,CDCl3)δ146.5,135.0,132.0,129.4,129.0,127.8,127.7,125.1,122.4,116.4,115.0,21.1.
化合物3n:棕色液体。1H NMR(500MHz,CDCl3,TMS)δ8.22(d,J=7.0Hz,1H),7.62(s,1H),7.40-7.31(m,2H),7.11(d,J=7.5Hz,1H),7.06(s,1H),6.92(dd,J=8.0,1.5Hz,1H),6.61(d,J=7.0Hz,1H),3.84(s,3H),2.38(s,3H).13C NMR(125MHz,CDCl3)δ159.9,146.4,135.0,132.0,130.5,130.0,124.8,122.5,119.8,116.3,115.0,113.3,113.0,55.1,21.0.MS(ESI):239[M+H]+;HRMS(ESI)calcd for C15H15N2O[M+H]+:239.1179;found:239.1200;IR(neat)ν1646,1599,1573,1542,1492,1464,1433,1340,1298,1292,1287,1233,1185,1166,1141,1110,1042,989,845,776,746,698cm-1.
化合物3o:棕色液体。1H NMR(500MHz,CDCl3,TMS)δ8.22(d,J=7.0Hz,1H),7.60(s,1H),7.41-7.33(m,4H),7.20(d,J=7.0Hz,1H),6.62(dd,J=7.0,1.5Hz,1H),2.43(s,3H),2.40(s,3H).13C NMR(125MHz,CDCl3)δ146.5,138.9,134.9,132.1,129.4,129.0,128.6,128.5,125.2,124.8,122.6,116.4,115.0,21.4,21.1.MS(ESI):223[M+H]+;HRMS(ESI)calcd for C15H15N2[M+H]+:223.1230;found:223.1247;IR(neat)ν1647,1608,1544,1497,1463,1346,1332,1301,1268,1184,1167,1134,1114,1033,905,884,858,842,789,779,742,703cm-1.
化合物3p:黄色固体。熔点:99-100℃。1H NMR(500MHz,CDCl3,TMS)δ7.89(dd,J=7.0,3.0Hz,1H),7.66(s,1H),7.49(td,J=7.5,1.5Hz,1H),7.44-7.39(m,2H),7.29-7.21(m,2H),6.67-6.64(m,1H),2.41(s,3H).13C NMR(125MHz,CDCl3)δ159.6(d,JC-F=247.125Hz),146.7,135.4,133.4,131.0(d,JC-F=3.25Hz),130.0(d,JC-F=8.125Hz),124.7(d,JC-F=3.5Hz),123.5(d,JC-F=4.75Hz),119.5,117.2(d,JC-F=15.0Hz),116.2(d,JC-F=1.875Hz),116.1,114.9,21.1.MS(ESI):227[M+H]+;HRMS(ESI)calcd for C14H12FN2[M+H]+:227.0979;found:227.0998;IR(neat)ν1647,1545,1496,1449,1340,1300,1275,1213,1186,1139,1117,1092,975,867,848,825,810,787,758,748cm-1.
化合物3q:黄色固体。1H NMR(500MHz,CDCl3,TMS)δ8.12(d,J=7.0Hz,1H),7.58(s,1H),7.49(dd,J=8.5,6.0Hz,2H),7.41(s,1H),7.20(t,J=8.5Hz,2H),6.64(d,J=7.0Hz,1H),2.41(s,3H).13C NMR(125MHz,CDCl3)δ162.3(d,JC-F=246.75Hz),146.5,135.1,132.1,129.7(d,JC-F=8.125Hz),125.5(d,JC-F=3.375Hz),124.1,122.2,116.5,116.2(d,JC-F=21.625Hz),115.2,21.1.
化合物3r:棕色液体。1H NMR(500MHz,CDCl3,TMS)δ8.10(d,J=1.0Hz,1H),7.63(s,1H),7.57-7.49(m,5H),7.40(tt,J=7.0,1.5Hz,1H),7.03(dd,J=9.0,1.5Hz,1H),2.29(s,3H).13C NMR(125MHz,CDCl3)δ145.1,132.3,129.4,129.1,127.9,127.3,125.3,122.0,120.8,117.4,18.2.
化合物3s:黄色液体。1H NMR(500MHz,CDCl3,TMS)δ8.13(s,1H),7.64(s,1H),7.56(d,J=9.0Hz,1H),7.42(t,J=8.0Hz,1H),7.13(d,J=7.5Hz,1H),7.08(s,1H),7.03(d,J=9.0Hz,1H),6.94(dd,J=8.5,2.5Hz,1H),3.86(s,3H),2.29(s,3H).13C NMR(125MHz,CDCl3)δ160.0,145.1,132.2,130.6,130.1,127.3,125.1,122.0,120.9,120.1,117.3,113.7,113.1,55.2,18.2.MS(ESI):239[M+H]+;HRMS(ESI)calcd for C15H15N2O[M+H]+:239.1179;found:239.1200;IR(neat)ν1607,1576,1540,1526,1500,1472,1427,1357,1332,1298,1278,1239,1211,1157,1132,1042,978,844,799,781,753,696cm-1.
化合物3t:棕色液体。1H NMR(500MHz,CDCl3,TMS)δ8.09(s,1H),7.62(s,1H),7.55(d,J=9.5Hz,1H),7.39(t,J=7.5Hz,1H),7.34(d,J=7.5Hz,2H),7.21(d,J=7.5Hz,1H),7.02(dd,J=9.5,1.5Hz,1H),2.43(s,3H),2.29(s,3H).13C NMR(125MHz,CDCl3)δ145.1,138.9,132.2,129.3,128.9,128.7,128.6,127.1,125.4,124.9,121.9,120.9,117.3,21.4,18.2.MS(ESI):223[M+H]+;HRMS(ESI)calcd for C15H15N2[M+H]+:223.1230;found:223.1250;IR(neat)ν1606,1583,1541,1505,1460,1357,1340,1299,1265,1232,1153,1134,1092,1042,856,845,786,753,703cm-1.
化合物3u:黄色固体。熔点:80-81℃。1H NMR(500MHz,CDCl3,TMS)δ7.78(s,1H),7.68(s,1H),7.58(d,J=9.5Hz,1H),7.49(td,J=7.5,1.5Hz,1H),7.45-7.40(m,1H),7.29-7.22(m,2H),7.07(dd,J=9.0,1.0Hz,1H),2.30(s,3H).13C NMR(125MHz,CDCl3)δ159.7(d,JC-F=247.25Hz),145.3,133.6,131.1(d,JC-F=3.25Hz),130.1(d,JC-F=8.125Hz),127.5,124.6(d,JC-F=3.5Hz),121.9(d,JC-F=6.375Hz),119.6,117.3,117.1,116.2(d,JC-F=21.5Hz),18.2.MS(ESI):227[M+H]+;HRMS(ESI)calcd for C14H12FN2[M+H]+:227.0979;found:227.0998;IR(neat)ν1548,1528,1503,1469,1458,1436,1354,1334,1301,1264,1230,1208,1152,1138,1118,1084,1037,965,930,861,830,809,795,768,753cm-1.
化合物3v:棕色液体。1H NMR(500MHz,CDCl3,TMS)δ8.11(d,J=0.5Hz,1H),7.66(s,1H),7.57(d,J=9.5Hz,1H),7.47(td,J=8.0,6.0Hz,1H),7.34(dt,J=8.0,1.5Hz,1H),7.26(ddd,J=9.5,2.0,1.5Hz,1H),7.11-7.06(m,2H),2.32(s,3H).13C NMR(125MHz,CDCl3)δ163.1(d,JC-F=245.625Hz),145.4,132.8,131.5(d,JC-F=8.25Hz),130.7(d,JC-F=8.625Hz),127.6,124.1,123.4(d,JC-F=2.875Hz),122.4,120.7,117.5,114.7(d,JC-F=21.125Hz),114.5(d,JC-F=22.0Hz),18.3.
化合物3w:棕色液体。1H NMR(500MHz,CDCl3,TMS)δ8.01(s,1H),7.60(s,1H),7.57(d,J=9.0Hz,1H),7.52(dd,J=8.5,5.5Hz,2H),7.22(t,J=8.5Hz,2H),7.06(dd,J=9.0,1.0Hz,1H),2.32(s,3H).13C NMR(125MHz,CDCl3)δ162.5(d,JC-F=246.75Hz),145.2,132.3,130.1(d,JC-F=8.125Hz),127.4,125.6(d,JC-F=3.375Hz),124.3,122.3,120.7,117.6,116.3(d,JC-F=21.625Hz),18.3.MS(ESI):227[M+H]+;HRMS(ESI)calcd for C14H12FN2[M+H]+:227.0979;found:227.0985;IR(neat)ν1551,1531,1506,1490,1358,1338,1305,1229,1151,1134,1095,962,931,840,835,811,798,759,744,735cm-1.
化合物3x:黄色固体。熔点:105-106℃。1H NMR(500MHz,CDCl3,TMS)δ8.13(d,J=8.0Hz,1H),7.53(s,1H),7.52-7.46(m,4H),7.38-7.35(m,1H),6.91(d,J=2.5Hz,1H),6.51(dd,J=7.5,2.5Hz,1H),3.86(s,3H).13C NMR(125MHz,CDCl3)δ157.4,147.5,131.7,129.3,129.0,127.7,127.6,124.7,123.8,107.4,95.1,55.3.MS(ESI):225[M+H]+;HRMS(ESI)calcd for C14H13N2O[M+H]+:225.1022;found:225.1038;IR(neat)ν1646,1601,1548,1507,1475,1434,1301,1233,1162,1180,1139,1109,1028,972,947,907,864,841,831,776,766,750,738,699cm-1.
化合物3y:黄色固体。熔点:134-135℃。1H NMR(500MHz,CDCl3,TMS)δ8.16(d,J=7.5Hz,1H),7.52(s,1H),7.38(t,J=7.5Hz,1H),7.33(d,J=8.5Hz,2H),7.20(d,J=7.0Hz,1H),6.91(d,J=2.5Hz,1H),6.53(dd,J=7.5,2.5Hz,1H),3.88(s,3H),2.43(s,3H).13C NMR(125MHz,CDCl3)δ157.5,147.6,139.0,131.8,129.4,129.0,128.7,128.5,125.0,124.8,124.0,107.4,95.3,55.5,21.5.MS(ESI):239[M+H]+;HRMS(ESI)calcd for C15H15N2O[M+H]+:239.1179;found:239.1203;IR(neat)ν1652,1604,1537,1509,1478,1430,1348,1295,1233,1183,1163,1042,951,866,860,840,809,774,743,702cm-1.
化合物3z:棕色液体。1H NMR(500MHz,CDCl3,TMS)δ7.83(dd,J=7.5,3.0Hz,1H),7.58(s,1H),7.49(td,J=7.5,1.5Hz,1H),7.43-7.38(m,1H),7.28-7.21(m,2H),6.94(d,J=2.0Hz,1H),6.55(dd,J=7.5,2.5Hz,1H),3.88(s,3H).13C NMR(125MHz,CDCl3)δ159.6(d,JC-F=246.875Hz),157.8,147.8,133.2,131.1(d,JC-F=3.25Hz),130.0(d,JC-F=8.125Hz),124.9(d,JC-F=4.875Hz),124.7(d,JC-F=3.5Hz),119.1,117.2(d,JC-F=15.0Hz),116.2(d,JC-F=21.5Hz),107.3,95.0,55.4.MS(ESI):243[M+H]+;HRMS(ESI)calcd for C14H12FN2O[M+H]+:243.0928;found:243.0929;IR(neat)ν1647,1617,1575,1547,1494,1449,1338,1304,1276,1212,1187,1145,1092,1036,975,946,937,869,849,825,809,789,761,747cm-1.
化合物3aa:黄色固体。熔点:132-133℃。1H NMR(500MHz,CDCl3,TMS)δ8.15(d,J=7.5Hz,1H),7.56(s,1H),7.45(td,J=7.5,6.0Hz,1H),7.31-7.29(m,1H),7.22(dt,J=10.0,2.0Hz,1H),7.09-7.05(m,1H),6.92(d,J=2.5Hz,1H),6.55(dd,J=7.5,2.5Hz,1H),3.88(s,3H).13C NMR(125MHz,CDCl3)δ163.1(d,JC-F=245.625Hz),157.7,147.9,132.4,131.5(d,JC-F=8.25Hz),130.7(d,JC-F=8.625Hz),123.7,123.1(d,JC-F=2.875Hz),114.6,114.3(d,JC-F=22.125Hz),107.8,95.3,55.4.MS(ESI):243[M+H]+;HRMS(ESI)calcd forC14H12FN2O[M+H]+:243.0928;found:243.0963;IR(neat)ν1652,1610,1582,1542,1534,1506,1483,1467,1436,1346,1337,1298,1236,1202,1180,1163,1143,1104,1022,951,871,859,843,775,760,743cm-1.
化合物3ab:黄色固体。熔点:135-136℃。1H NMR(500MHz,CDCl3,TMS)δ8.05(d,J=7.5Hz,1H),7.50-7.47(m,3H),7.19(t,J=9.0Hz,2H),6.92(d,J=2.5Hz,1H),6.53(dd,J=7.5,2.0Hz,1H),3.88(s,3H).13C NMR(125MHz,CDCl3)δ162.3(d,JC-F=246.625Hz),157.6,147.5,131.8,129.7(d,JC-F=8.0Hz),125.5(d,JC-F=3.375Hz),123.7(d,JC-F=20.0Hz),116.2(d,JC-F=21.625Hz),107.6,95.2,55.5.MS(ESI):243[M+H]+;HRMS(ESI)calcd forC14H12FN2O[M+H]+:243.0928;found:243.0963;IR(neat)ν1649,1557,1545,1506,1491,1475,1431,1345,1295,1219,1180,1156,1139,1106,1020,944,851,837,821,810,789,775,736cm-1.
化合物3ac:棕色液体。1H NMR(500MHz,CDCl3,TMS)δ8.26(dd,J=4.0,2.0Hz,1H),7.74(s,1H),7.65(dd,J=10.0,5.5Hz,1H),7.56-7.52(m,4H),7.47-7.43(m,1H),7.15-7.11(m,1H).13C NMR(125MHz,CDCl3)δ153.6(d,JC-F=235.25Hz),143.8,133.7(d,JC-F=1.875Hz),129.3,128.8,128.5,127.8,127.0,118.6(d,JC-F=9.125Hz),116.3(d,JC-F=25.625Hz),110.0(d,JC-F=41.375Hz).
化合物3ad:黄色固体。熔点:86-87℃。1H NMR(500MHz,CDCl3,TMS)δ8.29(d,J=1.5Hz,1H),7.74(s,1H),7.65(dd,J=10.0,5.5Hz,1H),7.45(t,J=8.0Hz,1H),7.14-7.11(m,2H),7.06(s,1H),6.98(dd,J=8.5,2.0Hz,1H),3.87(s,3H).13C NMR(125MHz,CDCl3)δ160.2,153.5(d,JC-F=235.375Hz),143.8,133.7,130.4,130.0,126.9,119.9,118.6(d,JC-F=9.125Hz),116.3(d,JC-F=25.625Hz),113.7(d,JC-F=27.75Hz),110.3,110.0,55.3.MS(ESI):243[M+H]+;HRMS(ESI)calcd for C14H12FN2O[M+H]+:243.0928;found:243.0963;IR(neat)ν1652,1599,1585,1540,1503,1483,1461,1441,1329,1304,1259,1239,1219,1146,1121,1039,954,859,831,817,800,789,762,703cm-1.
化合物3ae:棕色液体。1H NMR(500MHz,CDCl3,TMS)δ8.27(s,1H),7.72(s,1H),7.65(dd,J=10.0,5.5Hz,1H),7.42(t,J=7.5Hz,1H),7.35(d,J=7.5Hz,2H),7.25(s,1H),7.12(t,J=9.5Hz,1H),2.45(s,3H).13C NMR(125MHz,CDCl3)δ153.5(d,JC-F=235.125Hz),143.7,139.2,133.6(d,JC-F=1.875Hz),129.3(d,JC-F=11.625Hz),128.7,128.5,127.2,124.8,118.6(d,JC-F=9.125Hz),116.2(d,JC-F=25.625Hz),110.1(d,JC-F=41.375Hz),21.5.MS(ESI):227[M+H]+;HRMS(ESI)calcd for C14H12FN2[M+H]+:227.0979;found:227.0997;IR(neat)ν1652,1604,1594,1503,1326,1306,1292,1253,1225,1197,1146,1118,1101,948,852,816,788,757,699cm-1.
化合物3af:棕色液体。1H NMR(500MHz,CDCl3,TMS)δ7.95-7.93(m,1H),7.77(s,1H),7.66(dd,J=9.5,5.0Hz,1H),7.51-7.43(m,2H),7.31-7.24(m,2H),7.18-7.13(m,1H).13C NMR(125MHz,CDCl3)δ159.6(d,JC-F=247.5Hz),153.3(d,JC-F=235.25Hz),143.9,134.9,130.9(d,JC-F=3.125Hz),130.6(d,JC-F=8.125Hz),124.8(d,JC-F=3.625Hz),121.4,118.3(d,JC-F=9.125Hz),116.5(d,JC-F=15.0Hz),116.34(d,JC-F=25.625Hz),116.27(d,JC-F=21.25Hz),111.2(d,JC-F=4.75Hz),110.9(d,JC-F=4.875Hz).MS(ESI):231[M+H]+;HRMS(ESI)calcd for C13H9F2N2[M+H]+:231.0728;found:231.0736;IR(neat)ν1652,1545,1529,1506,1467,1336,1299,1266,1229,1199,1159,1129,1084,950,867,842,814,794,755cm-1.