一种异噁唑啉的简单制备方法

本发明涉及一种制备异噁唑啉的方法，属于有机合成技术领域。

背景技术：

异噁唑啉是广泛存在于天然产物、药物分子、生物活性分子、农药以及功能材料的核心骨架。另外，它也被用作过渡金属催化的配体。化学家们发展了一系列制备异噁唑啉的方法，但均有明显的缺点，比如：需要大过量的氧化剂或脱水剂；原料昂贵或制备繁琐；反应条件苛刻；需要昂贵有害的过渡金属等。例如：（1）从炔烃和硝酸铜出发原位生成腈氧化物中间体再进一步与烯烃偶极环加成制备异噁唑啉的工作，但是反应必须在氮气氛下才能有着更高的产率，与此同时，该方法不可避免需要使用当量的过渡金属硝酸铜（价格昂贵且有毒有害），不适合药物分子的合成（参见：angew.chem.,int.ed.2015,54,8795）；（2）亚硝酸叔丁酯引发的重氮化合物与烯烃三组分制备异噁唑啉的反应。但反应中需要用到制备繁琐而且危险的重氮化合物，限制了其在制备生物活性分子中的应用（参见：chem.sci.,2021,12,774）。综上，很有必要开发一种原料来源丰富、成本低廉、安全、操作简便的方法来高效率的合成异噁唑啉类化合物。

技术实现要素：

本发明的目的是提供一种制备异噁唑啉的方法，该方法具有原料来源丰富、反应底物普适性广，操作简便，反应条件温和等优点。

为达到上述发明目的，本发明采用的技术方案是：

一种异噁唑啉的简单制备方法，以醛、对甲苯磺酰肼、烯烃和亚硝酸酯为反应底物，在碱与铜催化剂存在下，在有机溶剂中反应得到异噁唑啉。

本发明得到的产物为异噁唑啉，其化学结构式为：

。

本发明中，所述醛的化学结构通式为：；所述烯烃的化学结构通式为：；所述亚硝酸酯的化学结构通式为：。

上述结构式中，r¹选自芳基、取代芳基、杂芳香基、萘基或者烯基，比如芳基或者取代芳基为：，r²、r³独立的选自氢、烷基、氟、氯、溴、羧酸、酰胺、硫醚、氨基、烷氧基、三氟甲基、硝基、氰基、酯基、羟基或者砜基；r⁴、r⁵独立的选自氢、烷基、芳基、酯基、醚、酰胺基、羰基、硅基、羟基、缩醛、氰基、卤素、炔基、羧基、磷酸酯基；r⁶选自叔丁基、正丁基、异丁基、异丙基。

上述技术方案中，将醛、对甲苯磺酰肼在醇溶剂中混合后，再加入烯烃、亚硝酸酯、有机溶剂、铜催化剂、碱，反应得到异噁唑啉；优选的，将醛、对甲苯磺酰肼在甲醇中，60℃下搅拌30分钟后，除去甲醇，再加入烯烃、亚硝酸酯、有机溶剂、铜催化剂、碱，反应得到异噁唑啉。

上述技术方案中，所述铜催化剂为氯化铜、氯化亚铜、溴化亚铜或者碘化亚铜；优选的，所述铜催化剂为氯化铜。

上述技术方案中，所述铜催化剂用量为烯烃摩尔量的5～20%；优选的铜催化剂用量为烯烃摩尔量的10%。

本发明还公开了一种无金属催化剂制备异噁唑啉的方法，将苯甲醛化合物、对甲苯磺酰肼在甲醇溶剂中混合后，再加入烯烃、亚硝酸酯、有机溶剂、碱，反应得到异噁唑啉；

其中，所述苯甲醛化合物的化学结构通式如下：

所述烯烃的化学结构通式为r2-ch2ch2；

所述亚硝酸酯的化学结构通式为o=n-or⁶；

所述异噁唑啉的化学结构通式如下：

式中，r1选自氢、烷基、氟、氯、溴、羧酸、酰胺、硫醚、氨基、烷氧基、三氟甲基、硝基、氰基、酯基、羟基或者砜基；r2选自烷基、芳基、酯基、羰基、醚、酰胺基、硅基、羟基、缩苯甲醛化合物、氰基、卤素、炔基、羧基或者磷酸酯基；r⁶选自叔丁基、正丁基、异丁基或者异丙基。优选的，r1选自氢、烷基、氟、氯、溴；r2选自芳基、酯基，比如苯基、-cooet、取代苯基。

上述技术方案中，将苯甲醛化合物、对甲苯磺酰肼在醇溶剂中，60℃下搅拌30分钟后，除去甲醇溶剂，再加入烯烃、亚硝酸酯、有机溶剂、碱，反应得到异噁唑啉。

本发明中，所述反应的反应温度为25～80℃；反应时间为12～24小时；优选的反应温度为65℃；反应时间为24小时。

本发明中，所述反应在碱存在下进行，所使用的碱为tmeda、dabco、碳酸钠；所述有机溶剂为乙酸乙酯、四氢呋喃、乙腈、丙酮、氯仿、n,n-二甲基甲酰胺。优选的，碱优选有机胺，比如为tmeda，有机溶剂为四氢呋喃。

本发明中，所述醛化合物用量为烯烃摩尔量的1～1.5倍；对甲苯磺酰肼用量为烯烃摩尔量的1～1.5倍，亚硝酸酯用量为烯烃摩尔量的3～5倍；碱的用量为烯烃摩尔量的1～1.8倍；优选的，所述醛化合物用量为烯烃摩尔量的1.3倍；对甲苯磺酰肼用量为烯烃摩尔量的1.4倍，亚硝酸酯用量为烯烃摩尔量的4倍，碱的用量为烯烃摩尔量的1.5倍。

本发明的反应在空气中进行。反应结束后，用饱和氯化钠溶液淬灭，再用乙酸乙酯萃取后，利用旋转蒸发仪除去溶剂、硅胶吸附，最后用乙酸乙酯和石油醚的混合溶剂进行柱层析即可得产物异噁唑啉。

本发明的制备方法示意如下：

本发明还公开了根据上述方法制备得到的异噁唑啉。

由于上述技术方案的运用，本发明与现有技术相比具有下列优点:

本发明使用cucl2为催化剂实现了醛、对甲苯磺酰肼、烯烃和亚硝酸叔丁酯的多组分反应来制备异噁唑啉，与现有技术中的原料预制备难、原料用量大和条件苛刻相比，反应更经济、底物普适性更广、原料易得、后期官能团化更易。本发明公开的方法反应条件温和，催化剂廉价而且用量少，克级规模反应良好，后处理简便，有利于在药物分子合成和大规模工业化中的应用。本发明使用的反应物、添加剂、碱、催化剂等原料廉价易得，反应组成合理，无需配体，反应步骤少，仅需一步反应即可得到官能团化的异噁唑啉，符合绿色化学和药物化学的要求和方向。尤其是，本发明公开了无催化剂制备异噁唑啉的方法，避免了过渡金属的使用，有利于进一步用于药物分子与生物活性分子的合成中。

具体实施方式

下面结合实施例对本发明作进一步描述：

本发明的醛、烯烃、对甲苯磺酰肼、碱、亚硝酸酯、催化剂和溶剂皆为市场化商品，可直接购买。实验具体操作方法以及测试方法为本领域常规方法，反应在常规环境中进行。

实施例一

空气中，向具有磁力搅拌子的试管中，添加对溴苯甲醛（0.65mmol），对甲苯磺酰肼（0.7mmol）和meoh（1ml），将混合物在60℃下搅拌30分钟。真空除去溶剂后，依次加入cucl2（0.05mmol），thf（2.0ml），丙烯酸乙酯（0.5mmol），tmeda（0.75mmol），tbn（2.0mmol）和thf（2.0ml）。将试管用封口膜密封，并在65℃下搅拌24h，用饱和氯化钠溶液淬灭，再用乙酸乙酯萃取后，利用旋转蒸发仪除去溶剂、硅胶吸附，最后用乙酸乙酯和石油醚的混合溶剂进行柱层析即可得产物异噁唑啉3aa。产率：88%;mp:66-68^oc;¹hnmr(400mhz,cdcl3)δ7.51(s,4h),5.15(dd,j=10.5,7.9hz,1h),4.24(q,j=7.1hz,2h),3.592(d,j=7.9hz,1h),3.586(d,j=10.5hz,1h),1.30(t,j=7.1hz,3h);¹³cnmr(100mhz,cdcl3)δ169.9,155.1,131.9,128.2,127.4,124.7,78.2,62.0,38.5,14.0;hrms(esi-tof):anal.calcd.forc12h12⁷⁹brnnao3⁺:319.9893,c12h12⁸¹brnnao3⁺:321.9872,found:319.9881,321.9890;ir(neat,cm^-1):υ2972,2933,1738,1195,1160,1008,890,821。丙烯酸乙酯反应放大到20mmol规模，同样的条件，产率为85%。

实施例二

在实施例一的基础上，反应条件做单因素变化：

将第二次加入的thf（2.0ml）更换为丙酮（2.0ml），产率：84%。

将第二次加入的thf（2.0ml）更换为乙腈（2.0ml），产率：54%。

将亚硝酸叔丁酯tbn更换为亚硝酸异丙酯（2.0mmol），产率：79%。

将亚硝酸叔丁酯tbn更换为亚硝酸正丁酯（2.0mmol），产率：68%。

将cucl2（0.05mmol）更换为cucl（0.05mmol），产率：77%。

将cucl2（0.05mmol）更换为cubr（0.05mmol），产率：83%。

将cucl2（0.05mmol）更换为cui（0.05mmol），产率：56%。

将cucl2（0.05mmol）更换为cu(oac)2（0.05mmol），产率：58%。

将四甲基乙二胺tmeda更换为n,n-二甲基乙醇胺dabco（0.75mmol），产率：68%。

将四甲基乙二胺tmeda更换为碳酸钠（0.75mmol），产率：16%。

将四甲基乙二胺tmeda更换为碳酸钾（0.75mmol），产率<1%。

将四甲基乙二胺tmeda更换为氢氧化钠（0.75mmol），产率<1%。

省略tmeda，产率<1%。

实施例三在实施例一的基础上，省略铜催化剂

空气中，向具有磁力搅拌子的试管中，添加对溴苯甲醛（0.65mmol），对甲苯磺酰肼（0.7mmol）和meoh（1ml），将混合物在60℃下搅拌30分钟。真空除去溶剂后，依次加入丙烯酸乙酯（0.5mmol），tmeda（0.75mmol），tbn（2.0mmol）和thf（2.0ml）。将试管用封口膜密封，并在65℃下搅拌24h，用饱和氯化钠溶液淬灭，再用乙酸乙酯萃取后，利用旋转蒸发仪除去溶剂、硅胶吸附，最后用乙酸乙酯和石油醚的混合溶剂进行柱层析即可得产物异噁唑啉3aa。产率：61%。

实施例四

以化合物1为苯甲醛为例，即r¹为苯基。空气中，向具有磁力搅拌子的试管中，添加苯甲醛（0.65mmol），对甲苯磺酰肼（0.7mmol）和meoh（1ml），将混合物在60℃下搅拌30分钟。真空除去溶剂meoh后，依次加入cucl2（0.05mmol），thf（2.0ml），丙烯酸乙酯（0.5mmol），tmeda（0.75mmol），tbn（2.0mmol）和thf（2.0ml）。将试管用封口膜密封，并在65℃下搅拌24h。用饱和氯化钠溶液淬灭，再用乙酸乙酯萃取后，利用旋转蒸发仪除去溶剂、硅胶吸附，最后用乙酸乙酯和石油醚的混合溶剂进行柱层析即可得产物异噁唑啉4。产率：93%；¹hnmr(400mhz,cdcl3)δ7.69–7.63(m,2h),7.43–7.35(m,3h),5.14(dd,j=10.4,7.9hz,1h),4.24(q,j=7.1hz,2h),3.623(d,j=7.9hz,1h),3.617(d,j=10.4hz,1h),1.30(t,j=7.1hz,3h);¹³cnmr(100mhz,cdcl3)δ170.0,155.9,130.3,128.6,128.4,126.8,78.0,61.8,38.7,14.0;anal.calcd.forc12h13nnao3⁺:242.0788,found:242.0778;ir(neat,cm^-1):υ2976,2936,2906,1750,1209,1182,1035,901,762,695。上述产物化合物4的结构式如下：

保持反应条件不变，仅仅更换化合物1，得到的产物以及表征如下：

产率：87%yield;¹hnmr(400mhz,cdcl3)δ7.56(d,j=8.0hz,2h),7.20(d,j=8.0hz,2h),5.13(dd,j=10.5,7.8hz,1h),4.25(q,j=7.1hz,2h),3.615(d,j=7.8hz,1h),3.608(d,j=10.5hz,1h),2.37(s,3h),1.31(t,j=7.1hz,3h);¹³cnmr(100mhz,cdcl3)δ170.2,155.8,140.7,129.4,126.8,125.7,77.9,61.9,38.9,21.4,14.0;hrms(esi-tof):anal.calcd.forc13h15nnao3⁺:256.0944,found:256.0956;ir(neat,cm^-1):υ2978,2960,2927,1752,1204,1183,1030,901,819.

产率：91%;¹hnmr(400mhz,cdcl3)δ7.60(d,j=8.2hz,2h),7.41(d,j=8.2hz,2h),5.12(dd,j=10.2,8.0hz,1h),4.23(q,j=7.1hz,2h),3.64–3.59(m,2h),1.32-1.26(m,12h);¹³cnmr(100mhz,cdcl3)δ170.1,155.7,153.7,126.6,125.6,125.5,77.8,61.7,38.8,34.7,31.0,13.9;hrms(esi-tof):anal.calcd.forc16h21nnao3⁺:298.1414,found:298.1427;ir(neat,cm^-1):υ2983,2938,1735,1513,1203,1158,893,836.

产率：85%;¹hnmr(400mhz,cdcl3)δ7.59(d,j=8.9hz,2h),6.89(d,j=8.9hz,2h),5.11(dd,j=10.3,8.0hz,1h),4.24(q,j=7.1hz,2h),3.81(s,3h),3.593(d,j=8.0hz,1h),3.587(d,j=10.3hz,1h),1.30(t,j=7.1hz,3h);¹³cnmr(100mhz,cdcl3)δ170.3,161.2,155.4,128.4,121.0,114.1,77.8,61.8,55.3,39.0,14.0;hrms(esi-tof):anal.calcd.forc13h15nnao4⁺:272.0893,found:272.0890;ir(neat,cm^-1):υ2980,2938,2840,1735,1608,1516,1252,1202,1177,1019,888,832.

产率：84%;mp:63-65^oc;¹hnmr(400mhz,cdcl3)δ7.54(d,j=8.6hz,2h),7.20(d,j=8.6hz,2h),5.12(dd,j=10.3,8.1hz,1h),4.23(q,j=7.1hz,2h),3.67–3.48(m,2h),2.46(s,3h),1.29(t,j=7.1hz,3h);¹³cnmr(100mhz,cdcl3)δ170.0,155.4,141.9,127.0,125.6,124.7,77.9,61.8,38.6,14.9,14.0;hrms(esi-tof):anal.calcd.forc13h15nnao3s⁺:288.0665,found:288.0675;ir(neat,cm^-1):υ2989,2921,1748,1199,1032,1022,894,817.

产率：87%;mp:45-47^oc;¹hnmr(400mhz,cdcl3)δ7.72–7.60(m,2h),7.12–7.03(m,2h),5.14(dd,j=10.4,8.0hz,1h),4.24(q,j=7.1hz,2h),3.69–3.47(m,2h),1.30(t,j=7.1hz,3h);¹³cnmr(100mhz,cdcl3)δ170.0,163.8(d,j=251.3hz),154.9,128.8(d,j=8.6hz),124.8(d,j=3.4hz),115.8(d,j=22.0hz),78.1,61.9,38.7,14.0;¹⁹fnmr(376mhz,cdcl3)δ-109.3;hrms(esi-tof):anal.calcd.forc12h12fnnao3⁺:260.0693,found:260.0683;ir(neat,cm^-1):υ2983,2938,1735,1603,1513,1203,1158,894,836.

产率：84%;mp:57-58^oc;¹hnmr(400mhz,cdcl3)δ7.58(d,j=8.6hz,2h),7.35(d,j=8.6hz,2h),5.15(dd,j=10.5,7.9hz,1h),4.24(q,j=7.1hz,2h),3.60(d,j=7.9hz,1h),3.59(d,j=10.5hz,1h),1.30(t,j=7.1hz,3h);¹³cnmr(100mhz,cdcl3)δ169.9,155.0,136.3,128.9,128.0,127.0,78.2,62.0,38.5,14.0;hrms(esi-tof):anal.calcd.forc12h12³⁵clnnao3⁺:276.0398,found:276.0393;ir(neat,cm^-1):υ2987,2963,2906,1749,1340,1215,1203,1032,908,839,827.

产率：60%;¹hnmr(400mhz,cdcl3)δ7.78(d,j=8.2hz,2h),7.66(d,j=8.2hz,2h),5.21(dd,j=11.0,7.5hz,1h),4.27(q,j=7.2hz,2h),3.65(d,j=7.5hz,1h),3.64(d,j=11.0hz,1h),1.32(t,j=7.2hz,3h);¹³cnmr(100mhz,cdcl3)δ169.8,155.0,132.1(q,j=32.7hz),132.0,127.1,125.7(q,j=3.7hz),123.7(q,j=272.2hz),78.5,62.1,38.4,14.0;¹⁹fnmr(376mhz,cdcl3)δ-63.0;hrms(esi-tof):anal.calcd.forc13h12f3nnao3⁺:310.0661,found:310.0674;ir(neat,cm^-1):υ2977,2939,1739,1321,1161,1120,1066,886,840.

产率：85%;¹hnmr(400mhz,cdcl3)δ7.50(d,j=8.7hz,2h),7.31–7.23(m,4h),7.15–6.99(m,8h),5.12(dd,j=10.5,7.5hz,1h),4.26(q,j=7.1hz,2h),3.59(d,j=7.5hz,1h),3.58(d,j=10.5hz,1h),1.32(t,j=7.1hz,3h);¹³cnmr(100mhz,cdcl3)δ170.3,155.5,149.8,146.9,129.4,127.9,125.2,123.9,121.7,121.3,77.8,61.8,39.0,14.1;hrms(esi-tof):anal.calcd.forc24h23n2o3⁺:387.1703,found:387.1706;ir(neat,cm^-1):υ2952,2939,1736,1589,1487,1272,1028,754,696.

产率：60%;¹hnmr(400mhz,cdcl3)δ7.91(d,j=8.5hz,2h),7.81(d,j=8.5hz,2h),5.19(t,j=9.3hz,1h),4.23(q,j=7.1hz,2h),3.63(d,j=9.3hz,2h),3.03(s,3h),1.28(t,j=7.1hz,3h);¹³cnmr(100mhz,cdcl3)δ169.5,154.7,141.6,133.6,127.7,127.5,78.6,62.0,44.2,38.1,13.9;hrms(esi-tof):anal.calcd.forc13h15nnao5s⁺:320.0563,found:320.0565;ir(neat,cm^-1):υ3026,3007,2927,1731,1308,1225,1150,892,846,777.

产率：54%;¹hnmr(400mhz,cdcl3)δ7.77(d,j=8.1hz,2h),7.69(d,j=8.1hz,2h),5.21(dd,j=11.0,7.6hz,1h),4.26(q,j=7.2hz,2h),3.71–3.57(m,2h),1.31(t,j=7.2hz,3h);¹³cnmr(100mhz,cdcl3)δ169.5,154.7,132.8,132.5,127.3,118.1,113.7,78.7,62.2,38.0,14.0;hrms(esi-tof):anal.calcd.forc13h12n2nao3⁺:267.0740,found:267.0751;ir(neat,cm^-1):υ2985,2936,2226,1721,1284,1018,889,868,849,832.

产率：41%;¹hnmr(400mhz,cdcl3)δ8.25(d,j=8.8hz,2h),7.84(d,j=8.8hz,2h),5.24(dd,j=11.0,7.6hz,1h),4.27(q,j=7.1hz,2h),3.68(d,j=7.6hz,1h),3.66(d,j=11.0hz,1h),1.32(t,j=7.1hz,3h);¹³cnmr(100mhz,cdcl3)δ169.5,154.5,148.6,134.5,127.6,124.0,78.9,62.2,38.1,14.0;hrms(esi-tof):anal.calcd.forc12h12n2nao5⁺:287.0638,found:287.0649;ir(neat,cm^-1):υ3115,2988,2965,1728,1513,1342,1256,910,848.

产率：72%;¹hnmr(400mhz,dmso-d6)δ8.00(d,j=8.1hz,2h),7.81(d,j=8.1hz,2h),5.31(dd,j=11.8,6.8hz,1h),4.17(q,j=7.1hz,2h),3.81(dd,j=17.4,11.8hz,1h),3.66(dd,j=17.4,6.8hz,1h),1.23(t,j=7.1hz,3h);¹³cnmr(100mhz,dmso-d6)δ169.9,166.8,156.0,132.4,132.3,129.8,127.1,78.1,61.4,38.3,14.0;hrms(esi-tof):anal.calcd.forc13h13nnao5⁺:286.0686,found:286.0673;ir(neat,cm^-1):υ3071,2980,2921,2673,2553,1754,1681,1288,1197,1025,862,771.

产率：53%;¹hnmr(400mhz,dmso-d6)δ10.15(s,1h),7.68(d,j=8.6hz,2h),7.62(d,j=8.6hz,2h),5.22(dd,j=11.6,6.6hz,1h),4.16(q,j=7.1hz,2h),3.72(dd,j=17.2,11.6hz,1h),3.58(dd,j=17.2,6.6hz,1h),2.07(s,3h),1.22(t,j=7.1hz,3h);¹³cnmr(100mhz,dmso-d6)δ170.2,168.8,155.8,141.3,127.7,122.9,118.9,77.5,61.3,38.7,24.2,14.0;hrms(esi-tof):anal.calcd.forc14h16n2nao4⁺:299.1002,found:299.1001;ir(neat,cm^-1):υ3305,3039,2994,2947,1749,1668,1522,1201,1022,896,829.

产率：75%;¹hnmr(400mhz,cdcl3)δ7.27–7.19(m,3h),7.09(d,j=8.0hz,1h),6.94(dd,j=8.0,2.5hz,1h),5.15(dd,j=10.0,8.4hz,1h),4.25(q,j=7.1hz,2h),3.65–3.57(m,2h),1.29(t,j=7.1hz,3h);¹³cnmr(100mhz,cdcl3)δ170.5,156.4,156.3,130.0,129.2,119.1,118.2,113.5,77.9,62.2,39.0,14.0;hrms(esi-tof):anal.calcd.forc12h13nnao4⁺:258.0737,found:258.0724;ir(neat,cm^-1):υ3451,2987,2960,1737,1450,1191,1160,1024,837,789,685.

产率：49%;¹hnmr(400mhz,cdcl3)δ8.43–8.41(m,1h),8.28–8.24(m,1h),8.08–8.04(m,1h),7.63–7.58(m,1h),5.24(dd,j=10.8,7.7hz,1h),4.27(q,j=7.1hz,2h),3.69(d,j=7.7hz,1h),3.68(d,j=10.8hz,1h),1.32(t,j=7.1hz,3h);¹³cnmr(100mhz,cdcl3)δ169.5,154.4,148.3,132.4,130.4,129.9,124.9,121.6,78.7,62.2,38.2,14.0;hrms(esi-tof):anal.calcd.forc12h12n2nao5⁺:287.0638,found:287.0627;ir(neat,cm^-1):υ3089,2974,2924,1745,1528,1352,1337,1205,891,739,679.

产率：73%;¹hnmr(400mhz,cdcl3)δ7.89(s,1h),7.86(d,j=7.8hz,1h),7.66(d,j=7.8hz,1h),7.53(t,j=7.8hz,1h),5.20(dd,j=10.5,7.9hz,1h),4.26(q,j=7.1hz,2h),3.65(d,j=7.9hz,1h),3.65(d,j=10.5hz,1h),1.31(t,j=7.1hz,3h);¹³cnmr(100mhz,cdcl3)δ169.7,154.9,131.2(q,j=32.7hz),129.9,129.4,129.3,126.9(q,j=3.7hz),123.6(q,j=272.3hz),123.6(q,j=3.8hz),78.4,62.1,38.4,14.0;¹⁹fnmr(376mhz,cdcl3)δ-62.9;hrms(esi-tof):anal.calcd.forc13h12f3nnao3⁺:310.0661,found:310.0648;ir(neat,cm^-1):υ2979,2938,2907,1738,1311,1165,1122,1098,900,803,693.

产率：71%;¹hnmr(400mhz,cdcl3)δ7.87–7.82(m,1h),7.43–7.35(m,1h),7.18–7.13(m,1h),7.12–7.06(m,1h),5.14(dd,j=10.0,8.6hz,1h),4.25(q,j=7.1hz,2h),3.72–3.68(m,2h),1.30(t,j=7.2hz,3h);¹³cnmr(100mhz,cdcl3)δ170.0,160.3(d,j=252.7hz),152.7(d,j=3.0hz),132.1(d,j=8.6hz),129.1(d,j=3.0hz),124.4(d,j=3.4hz),116.6(d,j=11.5hz),116.3(d,j=22.0hz),78.1(d,j=2.3hz),61.8,40.4(d,j=7.7hz),14.0;¹⁹fnmr(376mhz,cdcl3)δ-112.5;hrms(esi-tof):anal.calcd.forc12h12fnnao3⁺:260.0693,found:260.0684;ir(neat,cm^-1):υ2983,2929,2854,1736,1454,1203,1027,898,758.

产率：83%;¹hnmr(400mhz,cdcl3)δ7.62(dd,j=7.6,1.3hz,1h),7.53(dd,j=7.6,1.8hz,1h),7.38–7.33(m,1h),7.31–7.26(m,1h),5.20(dd,j=11.0,7.0hz,1h),4.28(q,j=7.1hz,2h),3.83(dd,j=17.3,11.0hz,1h),3.76(dd,j=17.3,7.0hz,1h),1.33(t,j=7.1hz,3h);¹³cnmr(100mhz,cdcl3)δ169.9,156.9,133.6,131.2,130.9,130.1,127.5,121.7,78.4,61.8,41.2,14.0;hrms(esi-tof):anal.calcd.forc12h12⁷⁹brnnao3⁺:319.9893,c12h12⁸¹brnnao3⁺:321.9872,found:319.9874,321.9912;ir(neat,cm^-1):υ2982,2938,1736,1341,1200,1026,1016,852,756.

产率：87%;¹hnmr(400mhz,cdcl3)δ7.35–7.20(m,4h),5.10(t,j=9.0hz,1h),4.26(q,j=7.1hz,2h),3.67(d,j=9.0hz,2h),2.55(s,3h),1.31(t,j=7.1hz,3h);¹³cnmr(100mhz,cdcl3)δ170.2,156.7,138.1,131.5,129.6,128.8,127.6,125.7,77.0,61.8,41.3,22.8,14.0;hrms(esi-tof):anal.calcd.forc13h15nnao3⁺:256.0944,found:256.0940;ir(neat,cm^-1):υ2981,2928,1735,1336,1200,1030,889,852,758.

产率：67%;¹hnmr(400mhz,cdcl3)δ7.74(dd,j=7.7,1.8hz,1h),7.36(ddd,j=8.3,7.4,1.8hz,1h),6.99–6.88(m,2h),5.08(dd,j=11.3,7.2hz,1h),4.24(q,j=7.1hz,2h),3.83(s,3h),3.74(d,j=11.3hz,1h),3.70(d,j=7.2hz,1h),1.30(t,j=7.1hz,3h);¹³cnmr(100mhz,cdcl3)δ170.5,157.4,155.4,131.6,129.4,120.7,117.6,111.3,77.9,61.6,55.4,41.4,14.0;hrms(esi-tof):anal.calcd.forc13h15nnao4⁺:272.0893,found:272.0891;ir(neat,cm^-1):υ2981,2940,2840,1735,1600,1462,1248,1199,1026,891,853,754.

产率：69%;¹hnmr(400mhz,cdcl3)δ7.77(dd,j=7.8,1.7hz,1h),7.38–7.33(m,1h),6.98–6.88(m,2h),5.10(dd,j=11.0,7.2hz,1h),4.26(q,j=7.1hz,2h),4.07(q,j=7.0hz,2h),3.86–3.68(m,2h),1.43(t,j=7.0hz,3h),1.31(t,j=7.1hz,3h);¹³cnmr(100mhz,cdcl3)δ170.6,156.8,155.6,131.5,129.4,120.6,117.6,112.0,78.0,63.9,61.6,41.5,14.6,14.0;hrms(esi-tof):anal.calcd.forc14h17nnao4⁺:286.1050,found:286.1063;ir(neat,cm^-1):υ2983,2950,2939,2890,1730,1453,1282,1255,1030,888,760.

产率：51%;¹hnmr(400mhz,cdcl3)δ9.54(s,1h),7.37–7.30(m,1h),7.19(d,j=7.8hz,1h),7.03(d,j=8.1hz,1h),6.95–6.89(m,1h),5.13(dd,j=10.8,7.4hz,1h),4.27(q,j=7.2hz,2h),3.79–3.68(m,2h),1.32(t,j=7.2hz,3h);¹³cnmr(100mhz,cdcl3)δ169.6,157.8,157.3,132.1,128.5,119.6,117.1,113.0,76.7,62.2,39.0,14.0;hrms(esi-tof):anal.calcd.forc12h13nnao4⁺:258.0737,found:258.0730;ir(neat,cm^-1):υ3211,3057,2984,2939,1737,1494,1258,1201,1157,754,655.

产率：77%;¹hnmr(400mhz,cdcl3)δ7.55(d,j=8.8hz,2h),6.88(d,j=8.8hz,2h),5.09(dd,j=9.8,8.5hz,1h),4.22(q,j=7.1hz,2h),4.09–4.04(m,2h),3.94(t,j=4.5hz,2h),3.67–3.45(m,2h),2.65(s,1h),1.28(t,j=7.1hz,3h);¹³cnmr(100mhz,cdcl3)δ170.2,160.3,155.4,128.4,121.2,114.6,77.7,69.2,61.8,61.0,38.9,14.0;hrms(esi-tof):anal.calcd.forc14h17nnao5⁺:302.0999,found:302.0989;ir(neat,cm^-1):υ3412,2993,2944,1742,1257,1210,1169,1076,1026,890,837,818.

产率：74%;¹hnmr(400mhz,cdcl3)δ7.76–7.71(m,1h),7.33–7.26(m,2h),5.15(t,j=9.3hz,1h),4.25(q,j=7.1hz,2h),3.68(d,j=9.3hz,1h),3.67(d,j=9.3hz,1h),1.30(t,j=7.1hz,3h);¹³cnmr(100mhz,cdcl3)δ169.8,159.8(d,j=257.1hz),152.0(d,j=3.3hz),130.0(d,j=3.6hz),128.0(d,j=3.4hz),124.9(d,j=9.8hz),120.0(d,j=25.4hz),115.8(d,j=11.7hz),78.3(d,j=2.5hz),61.9,40.1(d,j=7.7hz),14.0;¹⁹fnmr(376mhz,cdcl3)δ-100.3;hrms(esi-tof):anal.calcd.forc12h11⁷⁹brfnnao3⁺:337.9799,c12h11⁸¹brfnnao3⁺:339.9778,found:337.9795,339.9771;ir(neat,cm^-1):υ3072,2985,2929,2855,1726,1594,1203,1170,908,878,869,823.

产率：62%;¹hnmr(400mhz,cdcl3)δ9.55(s,1h),7.28(d,j=8.9hz,1h),7.16(s,1h),6.98(d,j=8.9hz,1h),5.16(dd,j=11.0,7.2hz,1h),4.29(q,j=7.1hz,2h),3.81–3.61(m,2h),1.34(t,j=7.1hz,3h);¹³cnmr(100mhz,cdcl3)δ169.3,156.9,155.9,131.9,127.7,124.3,118.6,114.3,77.0,62.4,38.8,14.1;hrms(esi-tof):anal.calcd.forc12h12³⁵clnnao4⁺:292.0347,found:292.0329;ir(neat,cm^-1):υ3072,2996,2967,2930,2911,1751,1384,1204,1193,1170,812,667.

产率：76%;¹hnmr(400mhz,cdcl3)δ8.99(d,j=8.6hz,1h),7.91–7.85(m,2h),7.62–7.57(m,1h),7.56–7.50(m,2h),7.45(dd,j=8.1,7.3hz,1h),5.17(dd,j=9.8,8.2hz,1h),4.29(q,j=7.1hz,2h),3.85–3.78(m,2h),1.33(t,j=7.1hz,3h);¹³cnmr(100mhz,cdcl3)δ170.1,156.4,133.8,131.1,130.4,128.4,127.8,127.5,126.9,126.3,125.4,124.6,77.0,61.9,41.6,14.0;hrms(esi-tof):anal.calcd.forc16h15nnao3⁺:292.0944,found:292.0934;ir(neat,cm^-1):υ3050,2982,2938,1735,1318,1202,1024,891,801,773.

产率：77%;¹hnmr(400mhz,cdcl3)δ7.31(s,1h),6.45(s,1h),5.02(dd,j=11.2,7.1hz,1h),4.20(q,j=7.1hz,2h),3.86(s,3h),3.79(s,3h),3.78(s,3h),3.75–3.63(m,2h),1.26(t,j=7.1hz,3h);¹³cnmr(100mhz,cdcl3)δ170.6,154.9,152.5,151.7,143.0,111.1,108.6,96.9,77.8,61.5,56.14,56.11,55.8,41.4,13.9;hrms(esi-tof):anal.calcd.forc15h19nnao6⁺:332.1105,found:332.1104;ir(neat,cm^-1):υ3003,2978,2939,2839,1715,1462,1271,1207,1162,1025,797.

产率：69%;¹hnmr(400mhz,cdcl3)δ7.83–7.74(m,2h),7.42–7.32(m,3h),5.20(dd,j=11.2,7.2hz,1h),4.28(q,j=7.0hz,2h),3.80–3.62(m,2h),1.33(t,j=7.0hz,3h);¹³cnmr(100mhz,cdcl3)δ169.7,152.3,140.5,138.8,131.0,126.14,126.12,124.7,124.2,122.4,78.6,62.1,39.0,14.0;hrms(ei-tof):anal.calcd.forc14h13no3s:275.0616,found:275.0614;ir(neat,cm^-1):υ2983,2961,2922,1747,1193,1163,1153,898,832,749,727.

产率：69%;¹hnmr(400mhz,cdcl3)δ7.94(dd,j=8.7,1.8hz,1h),7.88(s,1h),7.85–7.78(m,3h),7.54–7.46(m,2h),5.20(dd,j=11.3,7.1hz,1h),4.27(q,j=7.1hz,2h),3.76(dd,j=16.8,7.1hz,1h),3.69(dd,j=16.8,11.3hz,1h),1.32(t,j=7.1hz,3h);¹³cnmr(100mhz,cdcl3)δ170.1,156.0,134.0,132.7,128.4,128.3,127.7,127.2,127.1,126.6,126.0,123.4,78.1,61.9,38.6,14.0;hrms(esi-tof):anal.calcd.forc16h15nnao3⁺:292.0944,found:292.0940;ir(neat,cm^-1):υ3062,2983,2955,1743,1200,1191,1162,898,821,749.

产率：75%;¹hnmr(400mhz,cdcl3)δ8.46(s,1h),8.16(dd,j=8.1,1.7hz,1h),7.67(ddd,j=8.7,7.1,1.7hz,1h),7.48–7.37(m,2h),5.10(dd,j=11.8,6.9hz,1h),4.22(q,j=7.1hz,2h),3.90(dd,j=18.1,11.8hz,1h),3.75(dd,j=18.1,6.9hz,1h),1.27(t,j=7.1hz,3h);¹³cnmr(100mhz,cdcl3)δ175.0,170.0,155.8,154.9,151.7,134.2,125.9,125.8,123.9,118.2,114.4,77.9,61.7,40.4,14.0;hrms(esi-tof):anal.calcd.forc15h13nnao5⁺:310.0686,found:310.0690;ir(neat,cm^-1):υ2977,2924,1754,1650,1615,1465,1189,1034,813,759.

产率：58%;¹hnmr(400mhz,cdcl3)δ7.49–7.42(m,2h),7.39–7.29(m,3h),7.06(d,j=16.5hz,1h),6.77(d,j=16.5hz,1h),5.10(dd,j=10.8,7.5hz,1h),4.26(q,j=7.1hz,2h),3.49(d,j=7.5hz,1h),3.48(d,j=10.8hz,1h),1.32(t,j=7.1hz,3h);¹³cnmr(100mhz,cdcl3)δ170.0,156.9,137.4,135.4,129.1,128.8,127.0,116.8,78.0,61.9,37.4,14.0;hrms(esi-tof):anal.calcd.forc14h15nnao3⁺:268.0944,found:268.0936;ir(neat,cm^-1):υ3069,2978,2924,1737,1589,1362,1340,1162,1073,894,882,785,691.

产率：87%;¹hnmr(400mhz,cdcl3)δ7.48–7.42(m,2h),7.36–7.27(m,3h),4.96(dd,j=10.5,7.6hz,1h),4.19(q,j=7.1hz,2h),3.85–3.76(m,2h),3.23(s,3h),2.56(s,3h),1.25(t,j=7.1hz,3h);¹³cnmr(100mhz,cdcl3)δ170.6,163.6,153.4,151.3,134.1,129.3,127.7,125.3,97.0,76.2,61.5,40.7,34.5,14.0,13.1;hrms(esi-tof):anal.calcd.forc17h20n3o4⁺:330.1448,found:330.1468;ir(neat,cm^-1):υ2988,2918,2852,1738,1650,1548,1310,1281,1089,1032,976,854,751.

产率：73%;¹hnmr(400mhz,cdcl3)δ5.02(dd,j=10.7,7.5hz,1h),4.21(q,j=7.1hz,2h),3.75(s,3h),3.65(d,j=7.5hz,1h),3.64(d,j=10.7hz,1h),2.36(s,3h),1.27(t,j=7.1hz,3h);¹³cnmr(100mhz,cdcl3)δ170.1,149.5,148.3,127.1,106.3,76.9,61.8,40.0,36.1,15.1,14.0;hrms(esi-tof):anal.calcd.forc11h14³⁵cln3nao3⁺:294.0616,c11h14³⁷cln3nao3⁺:296.0586,found:294.0625,296.0592;ir(neat,cm^-1):υ2996,2937,2851,1729,1529,1367,1275,1028,892,808.

实施例五

以丙烯酸丁酯为例，向具有磁力搅拌子的试管中，添加对溴苯甲醛（0.65mmol），对甲苯磺酰肼（0.7mmol）和meoh（1ml），将混合物在60℃下搅拌30分钟。真空除去溶剂后，依次加入cucl2（0.05mmol），thf（2.0ml），丙烯酸丁酯（0.5mmol），tmeda（0.75mmol），tbn（2.0mmol）和thf（2.0ml）。将试管用封口膜密封，并在65℃下搅拌24h。用饱和氯化钠溶液淬灭，再用乙酸乙酯萃取后，利用旋转蒸发仪除去溶剂、硅胶吸附，最后用乙酸乙酯和石油醚的混合溶剂进行柱层析即可得产物异噁唑啉4aj。产率：88%;¹hnmr(400mhz,cdcl3)δ7.52(s,4h),5.16(dd,j=10.4,8.0hz,1h),4.19(t,j=6.7hz,2h),3.63–3.56(m,2h),1.70–1.61(m,2h),1.43–1.32(m,2h),0.92(t,j=7.4hz,3h);¹³cnmr(100mhz,cdcl3)δ169.9,155.1,131.9,128.2,127.5,124.7,78.2,65.8,38.5,30.4,18.9,13.6;¹hrms(esi-tof):anal.calcd.forc14h16⁷⁹brnnao3⁺:348.0206,c14h16⁸¹brnnao3⁺:350.0185,found:348.0188,350.0204;ir(neat,cm^-1):υ2958,2931,2872,1738,1210,1058,1006,888,861,819.产物4aj如下：

保持反应条件不变，仅仅更换烯烃化合物2，得到的产物以及表征如下：

产率：80%;¹hnmr(400mhz,cdcl3)δ7.50(s,4h),5.03(t,j=9.4hz,1h),3.53(d,j=9.4hz,2h),1.48(s,9h);¹³cnmr(100mhz,cdcl3)δ168.8,154.9,131.8,128.2,127.6,124.5,82.7,78.9,38.3,27.8;¹hrms(esi-tof):anal.calcd.forc14h16⁷⁹brnnao3⁺:348.0206,c14h16⁸¹brnnao3⁺:350.0185,found:348.0195,350.0200;ir(neat,cm^-1):υ2976,2935,1733,1590,1346,1149,1007,894,866,834,820.

产率：83%;¹hnmr(400mhz,cdcl3)δ7.51(s,4h),7.39–7.32(m,5h),5.24–5.17(m,3h),3.59(d,j=7.7hz,1h),3.58(d,j=10.7hz,1h);¹³cnmr(100mhz,cdcl3)δ169.6,155.1,134.8,131.8,128.5,128.4,128.2,127.3,124.7,78.1,67.4,38.4;¹hrms(esi-tof):anal.calcd.forc17h14⁷⁹brnnao3⁺:382.0049,c17h14⁸¹brnnao3⁺:384.0029,found:382.0042,384.0030;ir(neat,cm^-1):υ3068,3037,2955,1755,1174,1162,881,825,734,693.

产率：67%;¹hnmr(400mhz,cdcl3)δ7.59–7.50(m,4h),7.43–7.33(m,2h),7.28–7.21(m,1h),7.16–7.10(m,2h),5.41(dd,j=11.3,7.0hz,1h),3.77(dd,j=17.0,7.0hz,1h),3.70(dd,j=17.0,11.3hz,1h);¹³cnmr(100mhz,cdcl3)δ168.3,155.2,150.1,131.9,129.4,128.3,126.2,124.8,121.0,78.1,38.5;¹hrms(esi-tof):anal.calcd.forc16h12⁷⁹brnnao3⁺:367.9893,c16h12⁸¹brnnao3⁺:369.9872,found:367.9881,369.9859;ir(neat,cm^-1):υ3070,3043,2976,2927,1773,1589,1489,1193,1162,1069,818,748.

产率：60%;¹hnmr(400mhz,cdcl3)δ7.58–7.52(m,4h),5.28(dd,j=11.1,7.0hz,1h),4.65(dq,j=12.6,8.3hz,1h),4.53(dq,j=12.6,8.3hz,1h),3.76–3.56(m,2h);¹³cnmr(100mhz,cdcl3)δ168.4,155.1,132.1,128.4,127.1,125.1,122.5(q,j=277.2hz),77.5,61.2(q,j=37.1hz),38.7;¹⁹fnmr(376mhz,cdcl3)δ-73.7;hrms(esi-tof):anal.calcd.forc12h9⁷⁹brf3nnao3⁺:373.9610,c12h9⁸¹brf3nnao3⁺:375.9590,found:373.9605,375.9593;ir(neat,cm^-1):υ2991,2977,2923,1772,1274,1176,1161,1054,971,894,824.

产率：60%;¹hnmr(400mhz,cdcl3)δ7.51(s,4h),5.21(t,j=9.2hz,1h),4.81(dd,j=15.5,2.5hz,1h),4.75(dd,j=15.5,2.5hz,1h),3.62(d,j=9.2hz,2h),2.52(t,j=2.5hz,1h);¹³cnmr(100mhz,cdcl3)δ169.1,155.1,132.0,128.3,127.2,124.8,77.8,76.6,75.8,53.2,38.5;hrms(esi-tof):anal.calcd.forc13h10⁷⁹brnnao3⁺:329.9736,c13h10⁸¹brnnao3⁺:331.9716,found:329.9721,331.9710;ir(neat,cm^-1):υ3277,2977,2945,1742,1219,1204,1069,1021,895,884,821,638.

产率：81%;¹hnmr(400mhz,dmso-d6)δ7.67(d,j=8.6hz,2h),7.64(d,j=8.6hz,2h),5.60(dd,j=11.3,7.2hz,1h),3.78(dd,j=17.0,7.2hz,1h),3.54(dd,j=17.0,11.3hz,1h),3.11(s,3h),2.88(s,3h);¹³cnmr(100mhz,dmso-d6)δ167.4,156.1,131.9,128.7,128.1,123.7,77.4,36.72,36.70,35.4;hrms(esi-tof):anal.calcd.forc12h13⁷⁹brn2nao2⁺:319.0053,c12h13⁸¹brn2nao2⁺:321.0032,found:319.0041,321.0030;ir(neat,cm^-1):υ2925,2860,1649,1396,1151,1003,897,824.

产率：85%yield(137.9mg);mp:114-116^oc;¹hnmr(400mhz,benzene-d6)δ7.22(d,j=8.4hz,2h),7.14(d,j=8.4hz,2h),4.78(dd,j=11.2,7.7hz,1h),4.11(dd,j=16.6,7.7hz,1h),3.18–3.07(m,3h),3.00(dq,j=14.4,7.1hz,1h),2.63(dd,j=16.6,11.2hz,1h),0.93(t,j=7.1hz,3h),0.88(t,j=7.1hz,3h);¹³cnmr(100mhz,benzene-d6)δ166.3,156.3,132.0,128.7,128.6,124.3,78.8,41.8,40.7,36.7,14.4,12.8;hrms(esi-tof):anal.calcd.forc14h17⁷⁹brn2nao2⁺:347.0366,c14h17⁸¹brn2nao2⁺:349.0345,found:347.0332,349.0329;ir(neat,cm^-1):υ2968,2930,2871,1633,1261,1068,1005,895,830.

产率：45%;¹hnmr(400mhz,dmso-d6)δ8.14(t,j=5.7hz,1h),7.68–7.60(m,4h),5.12(dd,j=11.6,7.0hz,1h),4.71(t,j=5.5hz,1h),3.68(dd,j=17.2,11.6hz,1h),3.54(dd,j=17.2,7.0hz,1h),3.45–3.40(m,2h),3.26–3.10(m,2h);¹³cnmr(100mhz,dmso-d6)δ169.7,156.0,131.9,128.8,128.0,123.8,79.4,59.6,41.6,38.5;hrms(esi-tof):anal.calcd.forc12h13⁷⁹brn2nao3⁺:335.0002,c12h13⁸¹brn2nao3⁺:336.9981,found:334.9983,336.9962;ir(neat,cm^-1):υ3240,2950,2924,2887,1641,1535,1204,1058,1038,902,825.

产率：75%;¹hnmr(400mhz,dmso-d6)δ7.73–7.59(m,4h),5.62(dd,j=11.4,7.2hz,1h),3.83(dd,j=17.0,7.2hz,1h),3.73–3.43(m,9h);¹³cnmr(100mhz,dmso-d6)δ166.2,156.2,131.9,128.8,128.0,123.8,77.2,66.2,66.1,45.8,42.3,36.6;hrms(esi-tof):anal.calcd.forc14h15⁷⁹brn2nao3⁺:361.0158,c14h15⁸¹brn2nao3⁺:363.0138,found:361.0139,363.0139;ir(neat,cm^-1):υ2969,2930,2860,1637,1422,1234,1113,1024,891,826.

产率：53%;¹hnmr(400mhz,dmso-d6)δ7.71–7.58(s,5h),7.44(s,1h),5.07(dd,j=11.6,7.0hz,1h),3.66(dd,j=17.3,11.7hz,1h),3.53(dd,j=17.3,7.0hz,1h);¹³cnmr(100mhz,dmso-d6)δ171.9,155.8,131.9,128.8,128.0,123.8,79.3,38.3;hrms(esi-tof):anal.calcd.forc10h9⁷⁹brn2nao2⁺:290.9740,c10h9⁸¹brn2nao2⁺:292.9719,found:290.9724,292.9711;ir(neat,cm^-1):υ3410,3185,2969,2928,1650,1591,1401,1010,896,820.

产率：56%;¹hnmr(400mhz,cdcl3)δ7.58–7.51(m,4h),7.41–7.30(m,5h),5.75(dd,j=11.0,8.3hz,1h),3.75(dd,j=16.6,11.0hz,1h),3.31(dd,j=16.6,8.3hz,1h);¹³cnmr(100mhz,cdcl3)δ155.3,140.6,131.9,128.8,128.4,128.3,128.1,125.8,124.4,82.8,42.9;hrms(esi-tof):anal.calcd.forc15h12⁷⁹brnnao⁺:323.9994,c15h12⁸¹brnnao⁺:325.9974,found:323.9984,325.9967;ir(neat,cm^-1):υ3068,3041,2968,2921,2851,1587,1335,1159,1007,901,830,757,697,671.

产率：52%;¹hnmr(400mhz,cdcl3)δ7.55(s,4h),7.40–7.32(m,2h),7.10–7.02(m,2h),5.73(dd,j=11.0,8.3hz,1h),3.74(dd,j=16.6,11.0hz,1h),3.27(dd,j=16.6,8.3hz,1h);¹³cnmr(100mhz,cdcl3)δ162.6(d,j=247.0hz),155.3,136.4(d,j=3.2hz),132.0,128.3,128.1,127.7(d,j=8.2hz),124.5,115.7(d,j=21.6hz),82.2,42.9;¹⁹fnmr(376mhz,cdcl3)δ-113.6;hrms(esi-tof):anal.calcd.forc15h11⁷⁹brfnnao⁺:341.9900,c15h11⁸¹brfnnao⁺:343.9880,found:341.9896,343.9894;ir(neat,cm^-1):υ2975,2927,1591,1347,1193,1161,1009,889,820.

产率：46%;¹hnmr(400mhz,cdcl3)δ7.53(s,4h),7.37–7.28(m,4h),5.71(dd,j=11.0,8.2hz,1h),3.74(dd,j=16.6,11.0hz,1h),3.25(dd,j=16.6,8.2hz,1h);¹³cnmr(100mhz,cdcl3)δ155.2,139.1,134.1,131.9,128.9,128.1,127.2,124.5,82.0,42.9;hrms(esi-tof):anal.calcd.forc15h12⁷⁹brclno⁺:335.9785,c15h12⁸¹brclno⁺:337.9765,found:335.9819,337.9777;ir(neat,cm^-1):υ3068,2959,2922,1589,1488,1348,1093,1009,908,837,823.

产率：50%;¹hnmr(400mhz,cdcl3)δ7.52(s,4h),7.48(d,j=8.4hz,2h),7.24(d,j=8.4hz,2h),5.68(dd,j=11.0,8.1hz,1h),3.74(dd,j=16.7,11.0hz,1h),3.24(dd,j=16.7,8.1hz,1h);¹³cnmr(100mhz,cdcl3)δ155.2,139.6,131.9,131.8,128.09,128.07,127.5,124.5,122.2,82.0,42.8;hrms(esi-tof):anal.calcd.forc15h12⁷⁹br⁷⁹brno⁺:379.9280,c15h12⁷⁹br⁸¹brno⁺:381.9260,c15h12⁸¹br⁸¹brno⁺:383.9239,found:379.9261,381.9252,383.9222;ir(neat,cm^-1):υ3062,2969,2917,1589,1488,1348,1071,1008,909,837,820.

产率：55%;¹hnmr(400mhz,cdcl3)δ7.60–7.48(m,4h),7.26(d,j=8.0hz,2h),7.18(d,j=8.0hz,2h),5.70(dd,j=11.0,8.5hz,1h),3.70(dd,j=16.7,11.0hz,1h),3.28(dd,j=16.7,8.5hz,1h),2.34(s,3h);¹³cnmr(100mhz,cdcl3)δ155.3,138.1,137.5,131.9,129.4,128.5,128.1,125.8,124.3,82.9,42.7,21.1;hrms(esi-tof):anal.calcd.forc16h14⁷⁹brnnao⁺:338.0151,c16h14⁸¹brnnao⁺:340.0131,found:338.0157,340.0122;ir(neat,cm^-1):υ2977,2917,2860,1587,1397,1344,1070,1006,905,831,813.

产率：57%;¹hnmr(400mhz,cdcl3)δ7.54(s,4h),7.37–7.31(m,1h),7.18–7.07(m,2h),7.04–6.98(m,1h),5.74(dd,j=11.1,8.0hz,1h),3.77(dd,j=16.6,11.1hz,1h),3.28(dd,j=16.6,8.0hz,1h);¹³cnmr(100mhz,cdcl3)δ163.0(d,j=246.7hz),155.2,143.3(d,j=6.9hz),132.0,130.4(d,j=8.1hz),128.14,128.10,124.5,121.3(d,j=3.0hz),115.2(d,j=21.2hz),112.8(d,j=22.4hz),81.9(d,j=1.8hz),42.9;¹⁹fnmr(376mhz,cdcl3)δ-112.0;hrms(esi-tof):anal.calcd.forc15h11⁷⁹brfnnao⁺:341.9900,c15h11⁸¹brfnnao⁺:343.9880,found:341.9906,343.9900;ir(neat,cm^-1):υ2974,2925,2891,1588,1485,1454,1251,1143,1071,1053,897,873,830,784,692.

产率：57%;¹hnmr(400mhz,cdcl3)δ7.53(s,5h),7.46–7.42(m,1h),7.32–7.28(m,1h),7.26–7.21(m,1h),5.70(dd,j=11.1,8.0hz,1h),3.75(dd,j=16.7,11.1hz,1h),3.27(dd,j=16.7,8.0hz,1h);¹³cnmr(100mhz,cdcl3)δ155.2,143.0,131.9,131.3,130.3,128.8,128.1,128.0,124.5,124.3,122.8,81.8,42.9;hrms(esi-tof):anal.calcd.forc15h12⁷⁹br⁷⁹brno⁺:379.9280,c15h12⁷⁹br⁸¹brno⁺:381.9260,c15h12⁸¹br⁸¹brno⁺:383.9239,found:379.9266,381.9236,383.9210;ir(neat,cm^-1):υ3093,3071,2974,2919,1589,1569,1340,1161,1072,894,881,830,818,785,691,661.

产率：56%;¹hnmr(400mhz,cdcl3)δ7.65(s,1h),7.60–7.47(m,7h),5.80(dd,j=11.1,8.1hz,1h),3.81(dd,j=16.7,11.1hz,1h),3.30(dd,j=16.7,8.1hz,1h);¹³cnmr(100mhz,cdcl3)δ155.2,141.7,132.0,131.1(q,j=32.5hz),129.3,129.1,128.1,128.0,125.1(q,j=3.7hz),124.6,122.6(q,j=4.0hz),81.9,43.0;¹⁹fnmr(376mhz,cdcl3)δ-62.6;hrms(esi-tof):anal.calcd.forc16h11⁷⁹brf3nnao⁺:391.9868,c16h11⁸¹brf3nnao⁺:393.9848,found:391.9885,393.9844;ir(neat,cm^-1):υ3062,3006,2949,1324,1171,1117,1072,905,895,837,802,701,661.

产率：60%;¹hnmr(400mhz,cdcl3)δ7.55(s,4h),6.03(dd,j=12.0,8.5hz,1h),3.78(dd,j=16.8,12.0hz,1h),3.50(dd,j=16.8,8.5hz,1h);¹³cnmr(100mhz,cdcl3)δ154.9,132.0,128.2,127.6,124.8,72.4,40.6;¹⁹fnmr(376mhz,cdcl3)δ-141.35–-142.79(m,2f),-152.46–-152.70(m,1f),-160.98–-161.22(m,2f);hrms(esi-tof):anal.calcd.forc15h7⁷⁹brf5nnao⁺:413.9523,c15h7⁸¹brf5nnao⁺:415.9503,found:413.9508,415.9506;ir(neat,cm^-1):υ3061,2977,2930,1523,1503,1130,1012,964,894,840,824.

产率：44%;¹hnmr(400mhz,cdcl3)δ7.53(s,4h),6.63(dd,j=9.9,3.5hz,1h),3.51(dd,j=17.6,9.9hz,1h),3.35–3.27(m,1h),3.20–3.14(m,1h),3.11(dd,j=17.6,3.5hz,1h),2.42–2.36(m,2h),2.08–1.92(m,2h);¹³cnmr(100mhz,cdcl3)δ175.3,154.6,132.0,128.1,127.5,124.8,82.2,41.5,36.8,30.9,17.6;hrms(esi-tof):anal.calcd.forc13h13⁷⁹brn2nao2⁺:331.0053,c13h13⁸¹brn2nao2⁺:333.0032,found:331.0036,333.0051;ir(neat,cm^-1):υ2980,2921,2890,1683,1397,1283,1261,1238,886,816,790.

产率：77%;¹hnmr(400mhz,cdcl3)δ7.65–7.60(m,2h),7.55–7.48(m,4h),7.46–7.36(m,3h),4.32(dd,j=15.6,11.3hz,1h),3.39(dd,j=15.6,11.3hz,1h),3.09(t,j=15.6hz,1h),0.49(s,3h),0.47(s,3h);¹³cnmr(100mhz,cdcl3)δ155.7,135.2,133.9,131.7,129.7,128.5,128.2,128.0,123.9,74.2,37.7,-5.1,-5.7;hrms(esi-tof):anal.calcd.forc17h18⁷⁹brnnaosi⁺:382.0233,c17h18⁸¹brnnaosi⁺:384.0213,found:382.0235,384.0212;ir(neat,cm^-1):υ3052,2956,2902,1588,1251,1115,896,821,779,736,697.

产率：37%;¹hnmr(400mhz,cdcl3)δ7.51(s,4h),4.90–4.82(m,1h),3.87(dd,j=12.3,3.2hz,1h),3.67(dd,j=12.3,4.4hz,1h),3.34(dd,j=16.6,10.7hz,1h),3.26(dd,j=16.6,8.0hz,1h),2.41(s,1h);¹³cnmr(100mhz,cdcl3)δ156.2,131.9,128.2,128.1,124.4,81.5,63.5,36.0;hrms(esi-tof):anal.calcd.forc10h11⁷⁹brno⁺:255.9968,c10h11⁸¹brno⁺:257.9947,found:255.9970,257.9933;ir(neat,cm^-1):υ3375,2936,2922,2852,1592,1399,1007,927,907,827,820,805.

产率：53%;¹hnmr(400mhz,cdcl3)δ7.99(d,j=7.5hz,2h),7.71–7.65(m,1h),7.61–7.50(m,4h),7.46(d,j=8.5hz,2h),5.56(dd,j=10.9,4.5hz,1h),4.02(dd,j=18.3,4.5hz,1h),3.77(dd,j=18.3,10.9hz,1h);¹³cnmr(100mhz,cdcl3)δ156.1,135.1,134.6,132.1,129.7,129.2,128.4,126.2,125.5,93.3,36.5;hrms(esi-tof):anal.calcd.forc15h12⁷⁹brnnao3s⁺:387.9613,c15h12⁸¹brnnao3s⁺:389.9593,found:387.9625,389.9600;ir(neat,cm^-1):υ3006,2940,2895,1592,1310,1089,1010,612.

产率：38%;¹hnmr(400mhz,cdcl3)δ7.55(s,4h),6.82(dd,j=6.9,1.4hz,1h),3.58(dd,j=17.8,6.9hz,1h),3.31(dd,j=17.8,1.4hz,1h),2.07(s,3h);¹³cnmr(100mhz,cdcl3)δ169.6,156.1,132.1,128.4,127.2,125.2,95.9,41.0,21.0;hrms(esi-tof):anal.calcd.forc11h10⁷⁹brnnao3⁺:305.9736,c11h10⁸¹brnnao3⁺:307.9716,found:305.9746,307.9719;ir(neat,cm^-1):υ2956,2919,2851,1750,1363,1218,1172,1063,1029,949,845,818.

产率：54%;¹hnmr(400mhz,cdcl3)δ7.59–7.49(m,4h),5.67(dd,j=6.7,1.7hz,1h),3.85(dt,j=9.4,6.6hz,1h),3.53(dt,j=9.4,6.7hz,1h),3.36(dd,j=17.3,6.7hz,1h),3.16(dd,j=17.3,1.7hz,1h),1.60–1.51(m,2h),1.41–1.30(m,2h),0.91(t,j=7.3hz,3h);¹³cnmr(100mhz,cdcl3)δ156.1,131.9,128.22,128.16,124.5,103.4,68.2,41.2,31.5,19.1,13.8;hrms(esi-tof):anal.calcd.forc13h17⁷⁹brno2⁺:298.0437,c13h17⁸¹brno2⁺:300.0417,found:298.0426,300.0415;ir(neat,cm^-1):υ2957,2930,2871,1591,1350,1189,1093,1071,1009,886,841.

产率：39%;¹hnmr(400mhz,cdcl3)δ7.54(s,4h),5.05(dd,j=11.9,6.3hz,1h),3.63(dd,j=17.0,6.3hz,1h),3.45(dd,j=17.0,11.9hz,1h),2.71(t,j=7.4hz,2h),1.66–1.55(m,2h),1.36–1.24(m,4h),0.88(t,j=6.8hz,3h);¹³cnmr(100mhz,cdcl3)δ209.2,155.8,132.0,128.3,124.9,84.4,38.9,36.9,31.3,22.7,22.4,13.9;hrms(esi-tof):anal.calcd.forc15h18⁷⁹brnnao2⁺:346.0413,c15h18⁸¹brnnao2⁺:348.0393,found:346.0391,348.0421;ir(neat,cm^-1):υ2949,2924,2867,2855,1707,1591,896,888,823.

产率：96%;¹hnmr(400mhz,cdcl3)δ7.59–7.48(m,4h),4.10(dd,j=15.6,11.4hz,1h),3.41(dd,j=15.6,11.4hz,1h),3.06(t,j=15.6hz,1h),0.16(s,9h);¹³cnmr(100mhz,cdcl3)δ155.6,131.8,128.8,128.2,124.0,74.7,37.5,-3.9;hrms(esi-tof):anal.calcd.forc12h16⁷⁹brnnaosi⁺:320.0077,c12h16⁸¹brnnaosi⁺:322.0056,found:320.0066,322.0051;ir(neat,cm^-1):υ2958,2924,1399,1247,1195,1071,1008,889,863,823.

产率：49%;¹hnmr(400mhz,cdcl3)δ7.56–7.47(m,4h),7.44–7.38(m,2h),7.34–7.28(m,2h),7.27–7.20(m,1h),4.88(dddd,j=11.0,8.7,6.7,4.5hz,1h),3.45–3.33(m,2h),3.22(dd,j=16.8,6.7hz,1h),2.99(dd,j=13.6,8.7hz,1h);¹³cnmr(100mhz,cdcl3)δ155.4,134.6,131.9,130.1,129.1,128.3,128.1,126.8,124.4,79.8,39.2,37.7;hrms(esi-tof):anal.calcd.forc16h14⁷⁹brnnaos⁺:369.9872,c16h14⁸¹brnnaos⁺:371.9851,found:369.9858,371.9852;ir(neat,cm^-1):υ3058,3020,2924,1583,1436,1071,1006,895,822,735,689.

产率：66%;mp:65-67^oc;¹hnmr(400mhz,cdcl3)δ7.51(s,4h),4.89–4.82(m,1h),4.27–4.15(m,4h),3.68–3.52(m,2h),1.33(t,j=5.8hz,3h),1.30(t,j=7.0hz,3h);¹³cnmr(100mhz,cdcl3)δ155.4(d,j=6.3hz),131.9,128.2,127.4,124.8,76.1,74.5,63.5(d,j=7.0hz),63.1(d,j=6.8hz),37.4,16.4(d,j=5.6hz);hrms(esi-tof):anal.calcd.forc13h17⁷⁹brnnao4p⁺:383.9971,c13h17⁸¹brnnao4p⁺:385.9950,found:383.9956,385.9958;ir(neat,cm^-1):υ2949,2917,1617,1540,1372,1311,1124,1031,911,802,694.

4bn产率：34%;¹hnmr(400mhz,cdcl3)δ7.52(s,4h),4.76(ddd,j=11.1,7.1,4.4hz,1h),4.54(d,j=4.4hz,1h),3.82–3.69(m,2h),3.69–3.56(m,2h),3.39(dd,j=16.9,7.1hz,1h),3.28(dd,j=16.9,11.1hz,1h),1.25(t,j=7.0hz,3h),1.16(t,j=7.0hz,3h);¹³cnmr(100mhz,cdcl3)δ155.9,131.8,128.4,128.1,124.2,102.1,81.6,64.5,63.6,35.5,15.3,15.2;hrms(esi-tof):anal.calcd.forc14h18⁷⁹brnnao3⁺:350.0362,c14h18⁸¹brnnao3⁺:352.0342,found:350.0352,352.0329;ir(neat,cm^-1):υ2976,2929,2882,1592,1399,1349,1120,1061,1009,899,823.

4bo产率：47%;¹hnmr(400mhz,cdcl3)δ7.95(d,j=8.4hz,2h),7.63–7.56(m,4h),7.43(d,j=8.4hz,2h),7.08(d,j=6.8hz,1h),3.70(dd,j=17.7,6.8hz,1h),3.47(d,j=17.7hz,1h),1.32(s,9h);¹³cnmr(100mhz,cdcl3)δ165.2,157.5,156.2,132.2,129.8,128.5,127.3,126.2,125.4,125.2,96.7,41.4,35.1,31.0;hrms(ei-tof):anal.calcd.forc20h20⁷⁹brno3:401.0627,c20h20⁸¹brno3:403.0606,found:401.0621,403.0600;ir(neat,cm^-1):υ2964,2924,2871,1723,1265,1087,1073,1009,948,845,821,773,706.

4bp产率：41%;¹hnmr(400mhz,cdcl3)δ7.50(s,4h),4.98(s,1h),4.89–4.80(m,1h),3.50–3.26(m,3h),3.11(dd,j=16.9,7.5hz,1h),1.38(s,9h);¹³cnmr(100mhz,cdcl3)δ156.2,156.1,131.9,128.2,128.1,124.4,80.4,79.7,43.5,37.1,28.2;hrms(esi-tof):anal.calcd.forc15h19⁷⁹brn2nao3⁺:377.0471,c15h19⁸¹brn2nao3⁺:379.0451,found:377.0466,379.0445;ir(neat,cm^-1):υ3374,2978,2941,2872,1708,1512,1492,1245,1157,1009,917,885,819.

4bq产率：36%;¹hnmr(400mhz,cdcl3)δ7.51(s,4h),4.97–4.88(m,1h),3.84(t,j=5.9hz,2h),3.43(dd,j=16.5,10.4hz,1h),3.03(dd,j=16.5,8.0hz,1h),2.22(s,1h),2.08–1.85(m,2h);¹³cnmr(100mhz,cdcl3)δ156.0,131.9,128.4,128.0,124.3,79.6,59.6,40.2,37.7;hrms(esi-tof):anal.calcd.forc11h12⁷⁹brnnao2⁺:291.9944,c11h12⁸¹brnnao2⁺:293.9923,found:291.9949,293.9922;ir(neat,cm^-1):υ3293,2937,2880,1591,1399,1348,1041,1033,899,824,795.

4br产率：44%;¹hnmr(400mhz,dmso-d6)δ8.32(d,j=7.6hz,1h),8.12(d,j=7.5hz,1h),8.09–8.04(m,1h),8.03–7.97(m,1h),7.65(d,j=8.6hz,2h),7.60(d,j=8.6hz,2h),5.16–5.06(m,1h),4.01(dd,j=15.2,7.4hz,1h),3.88(dd,j=15.2,4.8hz,1h),3.60(dd,j=17.2,10.6hz,1h),3.39–3,31(m,1h);¹³cnmr(100mhz,dmso-d6)δ159.0,156.2,136.7,136.0,135.4,131.9,128.7,128.4,126.2,125.3,123.6,121.7,77.8,41.7,37.9;hrms(esi-tof):anal.calcd.forc17h13⁷⁹brn2nao4s⁺:442.9672,c17h13⁸¹brn2nao4s⁺:444.9651,found:442.9660,444.9621;ir(neat,cm^-1):υ3088,3027,1732,1326,1265,1179,1160,906,869,816,754,676.

4bs产率：40%;¹hnmr(400mhz,cdcl3)δ7.84–7.79(m,2h),7.73–7.66(m,2h),7.48(s,4h),4.83–4.74(m,1h),3.93–3.77(m,2h),3.45(dd,j=16.6,10.5hz,1h),3.01(dd,j=16.6,8.1hz,1h),2.24–2.13(m,1h),2.04–1.95(m,1h);¹³cnmr(100mhz,cdcl3)δ168.1,155.4,133.9,131.9,131.8,128.4,128.0,124.2,123.2,79.4,39.9,34.7,33.9;hrms(esi-tof):anal.calcd.forc19h15⁷⁹brn2nao3⁺:421.0158,c19h15⁸¹brn2nao3⁺:423.0138,found:421.0133,423.0146;ir(neat,cm^-1):υ3066,2930,2847,1703,1395,1007,906,814,716,706.

4bt产率：33%;¹hnmr(400mhz,cdcl3)δ7.54–7.41(m,12h),5.20–5.06(m,3h),4.23–4.09(m,6h),3.66–3.47(m,6h),1.51(q,j=7.3hz,2h),0.87(t,j=7.3hz,3h);¹³cnmr(100mhz,cdcl3)δ169.4,155.3,131.9,128.2,127.2,124.8,78.0,64.9,41.1,38.3,23.1,7.2;ir(neat,cm^-1):υ2965,2926,1740,1591,1347,1193,1161,1008,891,864,820.

4bu产率：70%;¹hnmr(400mhz,cdcl3)δ7.56(d,j=8.4hz,2h),7.49(d,j=8.4hz,2h),4.62(d,j=8.3hz,1h),3.43(d,j=8.3hz,1h),2.62–2.58(m,1h),2.50–2.43(m,1h),1.62–1.51(m,2h),1.50–1.44(m,1h),1.39–1.29(m,1h),1.23–1.11(m,2h);¹³cnmr(100mhz,cdcl3)δ156.0,131.8,128.3,128.2,123.8,88.1,56.7,42.9,39.1,32.2,27.3,22.6;hrms(esi-tof):anal.calcd.forc14h14⁷⁹brnnao⁺:314.0151,c14h14⁸¹brnnao⁺:316.0131,found:314.0153,316.0113;ir(neat,cm^-1):υ2960,2948,2872,1588,1399,1068,1007,881,814.

4bv产率：85%;¹hnmr(400mhz,dmso-d6)δ7.68(d,j=8.3hz,2h),7.62(d,j=8.3hz,2h),4.41(t,j=6.8hz,2h),3.76(d,j=17.6hz,1h),3.70(d,j=17.6hz,1h),2.66–2.53(m,2h);¹³cnmr(100mhz,dmso-d6)δ174.5,156.0,132.0,128.8,127.6,124.1,85.1,66.1,41.6,33.9;hrms(esi-tof):anal.calcd.forc12h10⁷⁹brnnao3⁺:317.9736,c12h10⁸¹brnnao3⁺:319.9716,found:317.9756,319.9706;ir(neat,cm^-1):υ2942,2927,1741,1592,1350,1199,1008,892,821.

4bw产率：40%;¹hnmr(400mhz,cdcl3)δ7.54(d,j=8.7hz,2h),7.51(d,j=8.7hz,2h),3.54(s,2h),3.23–3.12(m,1h),2.99(dd,j=13.3,9.8hz,2h),2.67(dd,j=13.3,5.1hz,2h);¹³cnmr(100mhz,cdcl3)δ156.0,132.0,128.0,127.9,124.7,122.1,84.5,45.8,40.8,15.2;hrms(esi-tof):anal.calcd.forc13h11⁷⁹brn2nao⁺:312.9947,c13h11⁸¹brn2nao⁺:314.9927,found:312.9927,314.9941;ir(neat,cm^-1):υ2976,2923,2875,2852,2239,1699,1400,1363,1160,1084,1008,894,819.

4bx产率：42%;¹hnmr(400mhz,cdcl3)δ7.54–7.47(m,4h),3.74(d,j=12.0hz,1h),3.57(d,j=12.0hz,1h),3.47(d,j=16.6hz,1h),2.97(d,j=16.6hz,1h),2.36(s,1h),1.42(s,3h);¹³cnmr(100mhz,cdcl3)δ156.1,131.8,128.7,128.0,124.2,87.9,67.2,41.7,22.6;hrms(esi-tof):anal.calcd.forc11h12⁷⁹brnnao2⁺:291.9944,c11h12⁸¹brnnao2⁺:293.9923,found:291.9952,293.9929;ir(neat,cm^-1):υ3396,2975,2928,2869,1591,1490,1399,1354,1055,1009,909,821,795.

实施例六

在实施例四的基础上，更换化合物1与化合物2，其余不变，得到如下产物：

4by产率：60%;¹hnmr(400mhz,dmso-d6)δ8.32(d,j=7.6hz,1h),8.16–7.95(m,3h),7.60(d,j=8.8hz,2h),7.00(d,j=8.8hz,2h),5.10–5.01(m,1h),3.97(dd,j=15.1,7.4hz,1h),3.89–3.76(m,4h),3.56(dd,j=17.1,10.5hz,1h),3.37–3.29(m,1h);¹³cnmr(100mhz,dmso-d6)δ160.8,159.0,156.2,136.8,136.0,135.4,128.3,126.3,125.3,121.7,121.6,114.3,77.1,55.4,41.7,38.3;hrms(esi-tof):anal.calcd.forc18h17n2o5s⁺:373.0853,found:373.0859;ir(neat,cm^-1):υ3069,2963,2920,2848,1739,1321,1300,1248,1178,1162,1018,839,747,671.

4bz产率：36%;¹hnmr(400mhz,cdcl3)δ7.57–7.45(m,1h),7.34–7.28(m,1h),7.21–7.13(m,1h),6.14(s,1h),4.91–4.83(m,1h),3.63–3.46(m,2h),3.34(dd,j=16.9,10.7hz,1h),3.07(dd,j=16.9,7.5hz,1h),1.97(s,3h);¹³cnmr(100mhz,cdcl3)δ170.8,155.4,151.5(dd,j=253.5,12.6hz),150.3(dd,j=249.8,13.2hz),126.2(dd,j=6.3,4.0hz),123.2(dd,j=6.7,3.7hz),117.7(d,j=17.9hz),115.6(d,j=18.8hz),80.3,42.2,37.3,23.1;¹⁹fnmr(376mhz,cdcl3)δ-134.0(d,j=22.0hz,1f),-136.2(d,j=22.0hz,1f);hrms(esi-tof):anal.calcd.forc12h12f2n2nao2⁺:277.0759,found:277.0756;ir(neat,cm^-1):υ3294,2988,2942,2926,1738,1651,1225,1192,1026,1009,822.

4ca产率：52%;¹hnmr(400mhz,cdcl3)δ7.60(d,j=8.8hz,2h),7.45(d,j=8.8hz,1h),6.89(d,j=8.8hz,2h),6.84(dd,j=8.8,2.5hz,1h),6.76(d,j=2.5hz,1h),6.08(s,1h),5.12–5.04(m,1h),4.17(dd,j=10.0,5.3hz,1h),4.11(dd,j=10.0,4.9hz,1h),3.81(s,3h),3.50(dd,j=16.7,10.7hz,1h),3.32(dd,j=16.7,7.0hz,1h),2.35(s,3h);¹³cnmr(100mhz,cdcl3)δ161.2,161.1,161.0,155.9,154.9,152.4,128.2,125.5,121.5,114.0,113.9,112.3,112.1,101.6,78.1,69.0,55.3,37.6,18.5;hrms(esi-tof):anal.calcd.forc21h20no5⁺:366.1336,found:366.1354;ir(neat,cm^-1):υ2961,2932,1731,1607,1251,1155,1071,891,827.

4cb产率：46%yield(110.6mg);mp:113-115^oc;¹hnmr(400mhz,cdcl3)δ7.81–7.71(m,3h),7.54–7.42(m,3h),7.40–7.31(m,2h),7.25–7.19(m,1h),7.18–7.13(m,1h),4.75–4.61(m,1h),4.43–4.23(m,2h),4.01–3.85(m,4h),3.14–3.03(m,1h),2.84–2.73(m,1h),2.19–2.05(m,1h),2.03–1.89(m,1h),1.68–1.62(m,3h);¹³cnmr(100mhz,cdcl3)δ174.4,174.3,157.61,157.59,155.66,155.64,135.54,135.49,133.6,131.7,129.13,129.12,128.78,128.77,128.31,128.28,127.84,127.83,127.15,127.12,126.1,126.0,125.9,125.8,124.07,124.06,119.06,119.04,105.54,105.50,78.9,78.6,61.3,61.2,55.20,55.19,45.4,45.3,39.53,39.50,33.89,33.87,18.5,18.3;hrms(ei-tof):anal.calcd.forc25h24⁷⁹brno4:481.0889,c25h24⁸¹brno4:483.0868,found:481.0893,483.0891;ir(neat,cm^-1):υ2960,2937,1728,1604,1176,1159,1026,858,823,813.

4cc产率：45%;¹hnmr(400mhz,cdcl3)δ7.63(d,j=8.3hz,2h),7.49(d,j=8.3hz,2h),7.46–7.41(m,4h),6.96(d,j=2.4hz,1h),6.87(d,j=9.0hz,1h),6.66(dd,j=9.0,2.4hz,1h),4.76–4.67(m,1h),4.34–4.22(m,2h),3.81(s,3h),3.67(s,2h),3.26(dd,j=16.5,10.4hz,1h),2.88(dd,j=16.5,8.0hz,1h),2.37(s,3h),2.14–2.01(m,1h),2.01–1.88(m,1h);¹³cnmr(100mhz,cdcl3)δ170.6,168.1,155.9,155.6,139.2,135.8,133.7,131.8,131.0,130.7,130.5,129.0,128.3,127.9,124.2,114.9,112.3,111.4,101.2,78.4,61.5,55.6,39.7,34.1,30.2,13.3;hrms(ei-tof):anal.calcd.forc30h26⁷⁹brcln2o5:608.0714,c30h26⁸¹brcln2o5:610.0693,found:608.0717,610.0674;ir(neat,cm^-1):υ2978,2957,2929,2832,1733,1679,1591,1477,1355,1315,1219,1068,826,751.

4cd产率：71%;¹hnmr(400mhz,cdcl3)δ7.57–7.50(m,4h),7.28(s,1h),6.95–6.81(m,2h),5.39(dd,j=11.2,7.2hz,1h),3.83–3.63(m,2h),2.92–2.84(m,2h),2.54–2.45(m,1h),2.41–2.34(m,1h),2.29–2.20(m,1h),2.17–1.94(m,4h),1.66–1.42(m,6h),0.89(s,3h);¹³cnmr(100mhz,cdcl3)δ220.5,168.5,155.1,147.9,138.0,137.8,131.8,128.2,127.2,126.3,124.7,120.9,118.1,78.1,50.1,47.7,43.9,38.5,37.7,35.6,31.3,29.1,26.0,25.5,21.4,13.6;hrms(esi-tof):anal.calcd.forc28h29⁷⁹brno4⁺:522.1274,c28h29⁸¹brno4⁺:524.1254,found:522.1256,524.1250;ir(neat,cm^-1):υ2930,2876,2854,2820,1766,1744,1220,1189,1176,1002,886,817.

4ce产率：46%;¹hnmr(400mhz,cdcl3)δ7.54(s,4h),7.32(d,j=8.3hz,2h),7.27–7.24(m,2h),7.21–7.12(m,4h),7.00–6.94(m,2h),6.93–6.87(m,2h),5.39(dd,j=10.9,7.3hz,1h),4.68(t,j=6.0hz,1h),4.62(d,j=2.3hz,1h),3.80–3.67(m,2h),3.14–2.93(m,2h),1.99–1.84(m,4h);¹³cnmr(100mhz,cdcl3)δ168.2,167.2,162.0(d,j=245.5hz),158.9(d,j=243.6hz),155.3,150.2,139.9(d,j=3.1hz),135.6,133.5(d,j=2.8hz),132.0,128.3,127.3(d,j=8.0hz),127.1,127.0,125.0,122.0,118.3(d,j=7.8hz),115.8(d,j=22.7hz),115.2(d,j=21.3hz),78.1,72.9,60.6,60.2,38.6,36.4,24.9;¹⁹fnmr(376mhz,cdcl3)δ-114.9,-117.5;ir(neat,cm^-1):υ3418,3063,2926,2855,1740,1507,1216,1198,1169,1154,831,729.

4cf产率：62%;¹hnmr(400mhz,cdcl3)δ7.48(s,4h),5.35–5.30(m,1h),5.10(t,j=9.3hz,1h),4.71–4.60(m,1h),3.56(d,j=9.3hz,2h),2.48(t,j=8.7hz,1h),2.36–2.29(m,2h),2.25–1.84(m,8h),1.68–1.51(m,5h),1.46–1.38(m,3h),1.20–1.08(m,3h),1.00–0.92(m,4h),0.57(s,3h);¹³cnmr(100mhz,cdcl3)δ209.2,169.1,155.0,139.0,131.8,128.2,127.4,124.5,122.5,78.2,75.5,63.4,56.6,49.6,43.7,38.5,38.4,37.64,37.60,36.7,36.4,31.6,31.3,27.3,24.3,22.6,20.8,19.1,13.0;ir(neat,cm^-1):υ2943,2931,2853,1733,1702,1508,1214,1169,1155,1010,904,832。