本发明涉及化合物的合成，具体涉及一种氮杂β-取代morita-baylis-hillman型化合物及其合成方法。
背景技术：
氮杂morita-baylis-hillman(mbh)型化合物是一种高官能团化的β-氨基羰基化合物，能够进行水解、烷基化、氢化、双羟化、偶联、环加成、环氧化等多种类型的反应，在有机合成、药物合成及天然产物合成中应用广泛。
目前，氮杂mbh型化合物一般是通过氮杂mbh反应来获得，即采用α,β-不饱和化合物与亚胺在催化剂作用下合成。但是，经典的mbh反应存在两个局限：一是反应速率很慢，一般需要数天甚至数周才能完成反应；二是这类反应只适用于β位无取代的α,β-不饱和化合物，无法合成β-取代的氮杂mbh型化合物。因此，有必要发明一种反应时间短、底物适用范围广，可以合成氮杂β-取代的mbh型化合物的新方法。
溴代巴豆酸酯类化合物在金属的作用下是一类良好的亲核试剂，例如在镁的作用下可以与亚胺发生grignard反应；在锌的作用下可以与亚胺发生reformatsky反应等。但现有文献并未记载使用溴代巴豆酸酯类化合物与亚胺反应得到氮杂β-取代的mbh型化合物的方法。
技术实现要素：
针对现有技术中存在的不足，本发明提供了一种使用溴代巴豆酸酯类化合物与亚胺快速反应得到氮杂β-取代mbh型化合物的新方法。
一种氮杂β-取代morita-baylis-hillman型化合物及其合成方法，包括：
s1：于有机溶剂中，在回流搅拌和金属试剂存在的条件下使下式1所示化合物与下式2所示化合物反应一段时间；
其中，r1为苯基，2-甲基苯基，3-甲基苯基，4-甲基苯基，2-溴苯基，3-溴苯基，4-溴苯基，4-氟苯基，4-三氟甲基苯基，4-甲氧基苯基，3，4-二甲氧基苯基，3，4-二氧亚甲基苯基，4-苯基苯基，呋喃基，噻吩基，萘基，蒽基，苯乙基，苯乙烯基，环己基或丙基；
r2为乙基或甲基；
s2：将反应温度降至室温，将dbu加入反应混合物中，一段时间后，萃取，干燥，减压蒸除溶剂，通过硅胶柱色谱法纯化残余物，得氮杂β-取代mbh型化合物。
进一步的，所述金属试剂为锌。
进一步的，所述化合物1与化合物2的摩尔比为1:1.1。
进一步的，所述有机溶剂为四氢呋喃。
进一步的，所述反应温度为有机溶剂回流温度。
本发明还提供了由上述合成方法制备的氮杂β-取代morita-baylis-hillman型化合物，其结构式如下式3所示：
其中，r1为苯基，2-甲基苯基，3-甲基苯基，4-甲基苯基，2-溴苯基，3-溴苯基，4-溴苯基，4-氟苯基，4-三氟甲基苯基，4-甲氧基苯基，3，4-二甲氧基苯基，3，4-二氧亚甲基苯基，4-苯基苯基，呋喃基，噻吩基，萘基，蒽基，苯乙基，苯乙烯基，环己基或丙基；
r2为乙基或甲基。
与现有技术相比，本发明的有益效果：
本发明的合成方法提供了一种通过使用溴代巴豆酸酯类化合物与亚胺快速反应得到氮杂β-取代mbh型化合物的新方法，与传统合成方法相比具有反应时间短，底物范围广，操作简单等优点，且具有广泛的适用性，能够用于多种氮杂β-取代morita-baylis-hillman型化合物的合成。
具体实施方式：
实施例1
向取代n-亚苄基-4-甲基苯磺酰胺1(0.50mmol)和4-溴巴豆酸酯2(0.55mmol)的无水thf(2ml)混合物中加入锌粉(0.75mmol)。回流搅拌反应1小时，然后将反应温度降至室温，将dbu(150μl，1.00mmol)加入反应混合物中，3小时后，将混合物用乙酸乙酯(3×10ml)萃取，干燥，减压蒸除溶剂，并通过硅胶柱色谱法(石油醚:乙酸乙酯＝4:1-2:1)纯化残余物，得氮杂β-取代mbh型化合物3，所得各氮杂β-取代mbh型化合物的化学式及表征如下：
2-(((4-甲基苯基)磺酰氨基)(苯基)甲基)丁-2-烯酸乙酯(3aa).
收率88％；mp110-112℃.e:z＝77:23；1hnmr(400mhz,cdcl3)majorisomerδ7.68(d,j＝8.0hz,2h),7.26-7.20(m,7h),6.86(q,j＝7.2hz,1h),6.34(d,j＝10.4hz,1h),5.60(d,j＝10.4hz,1h),4.08-3.94(m,2h),2.40(s,3h),1.83(d,j＝7.2hz,3h),1.13(t,j＝7.2hz,3h)；minorisomerδ7.68(d,j＝8.0hz,2h),7.26-7.20(m,7h),6.09(q,j＝7.2hz,1h),5.78(d,j＝9.6hz,1h),5.15(d,j＝9.6hz,1h),4.08-3.94(m,2h),2.40(s,3h),1.83(d,j＝7.2hz,3h),1.08(t,j＝7.2hz,3h).13cnmr(100mhz,cdcl3)majorisomerδ165.9,143.1,140.6,139.1,138.3,131.2,129.3,128.4,127.3,127.0,125.8,60.8,53.2,21.5,14.3,14.0.hrms(esi)m/zcalcdforc20h23nnao4s[m+na]+396.1245；found396.1251.
2-((2-溴苯基)((4-甲基苯基)磺酰氨基)甲基)丁-2-烯酸乙酯(3ba).
收率78％；mp161-163℃.e:z＝90:10；1hnmr(400mhz,cdcl3)majorisomerδ7.63(d,j＝8.0hz,2h),7.44(t,j＝8.0hz,2h),7.15(d,j＝8.4hz,2h),7.11(t,j＝8.0hz,1h),7.02(t,j＝8.0hz,1h),6.81(q,j＝7.2hz,1h),6.36(d,j＝10.0hz,1h),5.82(d,j＝10.0hz,1h),4.09-4.00(m,2h),2.35(s,3h),1.92(d,j＝7.2hz,3h),1.18(t,j＝7.2hz,3h)；minorisomerδ7.63(d,j＝8.0hz,2h),7.44(t,j＝8.0hz,1h),7.29(d,j＝8.0hz,1h),7.19-7.00(m,4h),6.16(q,j＝7.2hz,1h),5.75(d,j＝8.8hz,1h),5.59(d,j＝8.8hz,1h),4.09-3.96(m,2h),2.36(s,3h),1.86(d,j＝7.2hz,3h),1.17(t,j＝7.2hz,3h).13cnmr(100mhz,cdcl3)majorisomerδ166.8,143.1,137.9,137.6,132.8,130.3,129.8,129.2,128.8,127.1,127.0,122.9,60.9,53.7,21.4,15.4,14.0.hrms(esi)m/zcalcdforc20h22brnnao4s[m+na]+474.0351；found474.0378.
2-((3-溴苯基)((4-甲基苯基)磺酰氨基)甲基)丁-2-烯酸乙酯(3ca).
收率79％；mp91-93℃.e:z>95:5；1hnmr(400mhz,cdcl3)majorisomerδ7.66(d,j＝8.0hz,2h),7.33(s,1h),7.32(s,1h),7.22(d,j＝8.0hz,2h),7.19(d,j＝8.0hz,1h),7.12(d,j＝8.0hz,1h),6.88(q,j＝7.2hz,1h),6.34(d,j＝10.4hz,1h),5.55(d,j＝10.4hz,1h),4.10-3.96(m,2h),2.40(s,3h),1.83(d,j＝7.2hz,3h),1.15(t,j＝7.2hz,3h).13cnmr(100mhz,cdcl3)majorisomerδ165.7,143.4,141.5,141.2,138.0,130.7,130.4,129.9,129.4,129.0,126.9,124.6,122.6,60.9,52.8,21.5,14.4,14.0.hrms(esi)m/zcalcdforc20h22brnnao4s[m+na]+474.0351；found474.0380.
2-((4-溴苯基)((4-甲基苯基)磺酰氨基)甲基)丁-2-烯酸乙酯(3da)
收率75％；mp85-87℃.e:z＝65:35；1hnmr(400mhz,cdcl3)majorisomerδ7.66(d,j＝8.0hz,2h),7.37(d,j＝8.4hz,2h),7.22(d,j＝8.4hz,2h),7.13(d,j＝8.4hz,2h),6.86(q,j＝7.2hz,1h),6.33(d,j＝10.4hz,1h),5.52(d,j＝10.0hz),4.10-3.95(m,2h),2.41(s,3h),1.82(d,j＝7.2hz,3h),1.15(t,j＝7.2hz,3h)；minorisomer1hnmr(400mhz,cdcl3)δ7.66(d,j＝8.0hz,2h),7.36(d,j＝7.6hz,2h),7.24(d,j＝8.4hz,2h),7.09(d,j＝8.4hz,2h),6.07(q,j＝7.2hz,1h),5.86(d,j＝9.6hz,1h),5.08(d,j＝9.6hz,1h),4.10-3.95(m,2h),2.41(s,3h),1.82(d,j＝7.6hz,3h),1.11(t,j＝7.2hz,3h).13cnmr(100mhz,cdcl3)majorisomerδ165.8,143.3,140.9,138.3,138.1,131.5,130.9,129.4,127.7,126.9,121.3,60.9,52.9,21.5,14.3,14.0.hrms(esi)m/zcalcdforc20h22brnnao4s[m+na]+474.0351；found474.0377.
2-((4-氟苯基)((4-甲基苯基)磺酰氨基)甲基)丁-2-烯酸乙酯(3ea)
收率72％；mp123-125℃.e:z>95:5；1hnmr(400mhz,cdcl3)majorisomerδ7.66(d,j＝8.0hz,2h),7.24-7.21(m,4h),6.94(t,j＝8.8hz,2h),6.85(q,j＝7.2hz,1h),6.34(d,j＝10.0hz,1h),5.55(d,j＝10.4hz,1h),4.09-3.96(m,2h),2.41(s,3h),1.81(d,j＝7.2hz,2h),1.15(t,j＝7.2hz,3h).13cnmr(100mhz,cdcl3)δ165.9,162.0(j＝244.3hz),143.3,140.8,138.1,134.8(j＝3.0hz),131.0,129.4,127.6(j＝8.0hz),126.9,115.3(j＝21.2hz),60.8,52.8,21.5,14.3,14.0.hrms(esi)m/zcalcdforc20h22fnnao4s[m+na]+414.1151；found414.1151.
2-(((4-甲基苯基)磺酰氨基)(4-(三氟甲基)苯基)甲基)丁-2-烯酸乙酯(3fa).
收率86％；e:z＝86:14；1hnmr(400mhz,cdcl3)majorisomerδ7.66(d,j＝8.0hz,2h),7.50(d,j＝8.0hz,2h),7.38(d,j＝8.0hz,2h),7.22(d,j＝8.0hz,2h),6.91(q,j＝7.2hz,1h),6.42(d,j＝10.4hz,1h),5.62(d,j＝10.4hz,1h),4.09-3.95(m,2h),2.40(s,3h),1.84(d,j＝7.2hz,3h),1.14(t,j＝7.2hz,3h)；minorisomerδ7.66(d,j＝8.0hz,2h),7.48(d,j＝8.0hz,2h),7.35(d,j＝8.0hz,2h),7.23(d,j＝8.0hz,2h),6.11(q,j＝7.2hz,1h),6.02(d,j＝9.6hz,1h),5.18(d,j＝9.6hz,1h),4.10-3.95(m,2h),2.40(s,3h),1.84(d,j＝7.2hz,3h),1.10(t,j＝7.2hz,3h).13cnmr(100mhz,cdcl3)δ165.8,143,5141.3,138.0,130.7,129.4,126.9,125.4(q,j＝3.8hz),61.0,53.1,21.5,14.4,14.0.hrms(esi)m/zcalcdforc21h22f3nnao4s[m+na]+464.1119；found464.1110.
2-(((4-甲基苯基)磺酰氨基)(邻甲苯基)甲基)丁-2-烯酸乙酯(3ga)
收率81％；mp120-122℃.e:z＝91:9；1hnmr(400mhz,cdcl3)majorisomerδ7.62(d,j＝8.4hz,2h),7.20(d,j＝8.8hz,2h),7.17-7.01(m,4h),6.75(q,j＝7.2hz,1h),6.25(d,j＝10.0hz,1h),5.70(d,j＝10.0hz,1h),4.05-3.91(m,2h),2.39(s,3h),2.38(s,3h),1.78(d,j＝7.2hz,3h),1.15(t,j＝7.2hz,3h)；minorisomerδ7.62(d,j＝8.4hz,2h),7.19(d,j＝8.8hz,2h),7.17-7.01(m,4h),6.05(q,j＝7.2hz,1h),5.51(d,j＝8.4hz,1h),5.28(d,j＝8.0hz,1h),4.05-3.91(m,2h),2.39(s,3h),2.20(s,3h),1.83(d,j＝7.2hz,3h),1.13(t,j＝7.2hz,3h).13cnmr(100mhz,cdcl3)majorisomerδ166.7,143.0,140.4,138.1,136.5,136.4,130.7,129.2,127.6,127.2,127.1,125.8,60.8,51.7,21.5,19.8,14.4,14.0.hrms(esi)m/zcalcdforc21h25nnao4s[m+na]+410.1402；found410.1396.
2-(((4-甲基苯基)磺酰氨基)(间甲苯基)甲基)丁-2-烯酸乙酯(3ha).
收率87％；mp91-93℃.e:z>95:5；1hnmr(400mhz,cdcl3)majorisomerδ7.67(d,j＝8.0hz,2h),7.21(d,j＝8.0hz,2h),7.13(t,j＝7.6hz,1h),7.09(s,1h),7.01(d,j＝7.6hz,2h),6.84(q,j＝7.2hz,1h),6.35(d,j＝10.4hz,1h),5.56(d,j＝10.4hz,1h),4.08-3.94(m,2h),2.39(s,3h),2.27(s,3h),1.82(d,j＝7.2hz,3h),1.13(t,j＝7.2hz,3h)；minorisomerδ7.67(d,j＝8.0hz,2h),7.21(d,j＝8.0hz,2h),7.13(t,j＝7.6hz,1h),7.09(s,1h),7.01(d,j＝7.6hz,2h),6.09(q,j＝7.2hz,1h),5.79(d,j＝9.6hz,1h),5.12(d,j＝9.6hz,1h),4.08-3.94(m,2h),2.39(s,3h),2.24(s,3h),1.82(d,j＝7.2hz,3h),1.08(t,j＝7.2hz,3h).13cnmr(100mhz,cdcl3)majorisomerδ166.0,143.1,140.5,139.0,138.3,138.0,131.2,129.3,128.3,128.0,127.0,126.6,122.8,60.7,53.2,21.5,21.5,14.3,14.0.hrms(esi)m/zcalcdforc21h25nnao4s[m+na]+410.1402；found410.1404.
2-(((4-甲基苯基)磺酰氨基)(对甲苯基)甲基)丁-2-烯酸乙酯(3ia)
收率83％；mp92-94℃.e:z＝78:22；1hnmr(400mhz,cdcl3)majorisomerδ7.67(d,j＝8.0hz,2h),7.21(d,j＝8.0hz,2h),7.14(d,j＝8.0hz,2h),7.06(d,j＝8.0hz,2h),6.83(q,j＝7.2hz,1h),6.33(d,j＝10.4hz,1h),5.56(d,j＝10.4hz,1h),4.07-3.94(m,2h),2.40(s,3h),2.29(s,3h),1.81(d,j＝7.2hz,3h),1.14(t,j＝7.2hz,3h)；minorisomerδ7.67(d,j＝8.0hz,2h),7.23(d,j＝8.0hz,2h),7.08-7.02(m,4h),6.09(q,j＝7.2hz,1h),5.76(d,j＝9.2hz,1h),5.12(d,j＝9.6hz,1h),4.07-3.94(m,2h),2.40(s,3h),2.29(s,3h),1.81(d,j＝7.2hz,3h),1.09(t,j＝7.2hz,3h).13cnmr(100mhz,cdcl3)majorisomerδ166.0,143.1,140.4,138.3,136.9,136.1,131.3,129.3,129.1,127.0,125.8,60.7,53.1,21.5,21.0,14.3,14.0.hrms(esi)m/zcalcdforc21h25nnao4s[m+na]+410.1402；found410.1395.
2-((4-甲氧基苯基)((4-甲基苯基)磺酰氨基)甲基)丁-2-烯酸乙酯(3ja).
收率85％；mp105-107℃.e:z>95:5；1hnmr(400mhz,cdcl3)majorisomerδ7.66(d,j＝8.4hz,2h),7.21(d,j＝8.0hz,2h),7.17(d,j＝8.8hz,2h),6.82(q,j＝7.2hz,1h),6.78(d,j＝8.8hz,2h),6.34(d,j＝10.4hz,1h),5.54(d,j＝10.4hz,1h),4.07-4.00(m,2h),3.76(s,3h),2.40(s,3h),1.80(d,j＝7.2hz,3h),1.15(t,j＝7.2hz,3h).13cnmr(100mhz,cdcl3)majorisomerδ166.0,158.8,143.1,140.4,138.2,131.2,131.1,129.3,127.1,127.0,113.8,60.7,55.2,52.8,21.5,14.2,14.0.hrms(esi)m/zcalcdforc21h25nnao5s[m+na]+426.1351；found426.1352.
2-((3,4-二甲氧基苯基)((4-甲基苯基)磺酰氨基)甲基)丁-2-烯酸乙酯(3ka).
收率87％；mp80-82℃.e:z＝80:20；1hnmr(400mhz,cdcl3)majorisomerδ7.67(d,j＝8.4hz,2h),7.22(d,j＝8.0hz,2h),6.86(s,1h),6.85(q,j＝7.2hz,1h),6.73-6.66(m,2h),6.36(d,j＝10.4hz,1h),5.54(d,j＝10.0hz,1h),4.10-3.97(m,2h),3.83(s,3h),3.79(s,3h),2.40(s,3h),1.82(d,j＝7.2hz,3h),1.16(t,j＝7.2hz,3h)；minorisomerδ7.67(d,j＝8.4hz,2h),7.22(d,j＝8.0hz,2h),6.86(s,1h),6.73-6.66(m,2h),6.08(q,j＝7.2hz,1h),5.73(d,j＝9.2hz,1h),5.11(d,j＝9.2hz,1h),4.11-3.97(m,2h),3.83(s,3h),3.76(s,3h),2.40(s,3h),1.82(d,j＝7.2hz,3h),1.12(t,j＝7.2hz,3h).13cnmr(100mhz,cdcl3)majorisomerδ166.1,149.0,148.3,143.1,140.5,138.3,131.6,129.3,127.0,117.9,110.8,109.4,60.8,55.9,55.8,53.1,21.5,14.2,14.1.hrms(esi)m/zcalcdforc22h27nnao6s[m+na]+456.1457；found456.1444.
2-(苯并[d][1,3]二氧杂环戊烯-5-基((4-甲基苯基)磺酰氨基)甲基)丁-2-烯酸乙酯(3la).
收率79％；mp130-132℃.e:z＝78:22；1hnmr(400mhz,cdcl3)majorisomerδ7.66(d,j＝8.0hz,2h),7.22(d,j＝8.0hz,2h),6.83(q,j＝7.2hz,1h),6.77(s,1h),6.73-6.66(m,2h),6.34(d,j＝10.4hz,1h),5.91(s,2h),5.49(d,j＝10.4hz,1h),4.10-3.97(m,2h),2.40(s,3h),1.80(d,j＝7.2hz,3h),1.17(t,j＝7.2hz,3h)；minorisomerδ7.66(d,j＝8.0hz,2h),7.25(d,j＝8.4hz,2h),6.72(s,1h),6.66(d,j＝7.6hz,2h),6.06(q,j＝7.2hz,1h),5.91(s,2h),5.74(d,j＝9.6hz,1h),5.05(d,j＝9.2hz,1h),4.10-3.97(m,2h),2.41(s,3h),1.81(d,j＝7.2hz,3h),1.13(t,j＝7.2hz,3h).13cnmr(100mhz,cdcl3)majorisomerδ166.0,147.9,146.8,143.2,140.5138.2,133.0,131.2,129.3,127.0,119.2,108.0,106.8,101.1,60.8,53.1,21.5,14.2,14.0.hrms(esi)m/zcalcdforc21h23nnao6s[m+na]+440.1144；found440.1155.
2-([1,1'-联苯基]-4-基((4-甲基苯基)磺酰氨基)甲基)丁-2-烯酸乙酯(3ma)
收率85％；mp124-126℃.e:z＝75:25；1hnmr(400mhz,cdcl3)majorisomerδ7.69(d,j＝8.0hz,2h),7.53(d,j＝8.0hz,2h),7.47(d,j＝8.0hz,2h),7.41(t,j＝7.6hz,2h),7.34-7.31(m,2h),7.25(s,1h),7.20(d,j＝8.4hz,2h),6.89(q,j＝7.2hz,1h),6.39(d,j＝10.4hz,1h),5.64(d,j＝10.4hz,1h),4.08-4.00(m,2h),2.39(s,3h),1.85(d,j＝7.2hz,3h),1.15(t,j＝7.2hz,3h)；minorisomerδ7.69(d,j＝8.0hz,2h),7.53(d,j＝8.0hz,2h),7.46(d,j＝8.0hz,2h),7.41(t,j＝7.6hz,2h),7.34-7.31(m,2h),7.24(d,j＝8.4hz,2h),6.13(q,j＝7.2hz,1h),5.85(d,j＝9.6hz,1h),5.20(d,j＝9.2hz,1h),4.08-4.00(m,2h),2.39(s,3h),1.85(d,j＝7.2hz,3h),1.11(t,j＝7.2hz,3h).13cnmr(100mhz,cdcl3)majorisomerδ166.0,143.2,140.7,140.6,140.2,138.2,138.1,131.1,129.3,128.7,127.3,127.1,127.0,127.0,126.3,60.8,53.1,21.5,14.4,14.0.hrms(esi)m/zcalcdforc26h27nnao4s[m+na]+472.1558；found472.1546.
2-(((4-甲基苯基)磺酰氨基)(萘-2-基)甲基)丁-2-烯酸乙酯(3na).
收率86％；mp76-78℃.e:z＝67:33；1hnmr(400mhz,cdcl3)majorisomerδ7.78-7.67(m,5h),7.65(s,1h),7.45-7.41(m,2h),7.37(d,j＝7.6hz,1h),7.18(d,j＝8.0hz,2h),6.91(q,j＝7.2hz,1h),6.49(d,j＝10.0hz,1h),5.75(d,j＝9.6hz,1h),4.07-3.94(m,2h),2.35(s,3h),1.88(d,j＝7.6hz,3h),1.12(t,j＝7.2hz,3h)；minorisomerδ7.78-7.67(m,5h),7.61(s,1h),7.45-7.41(m,2h),7.29(d,j＝8.4hz,1h),7.18(d,j＝8.0hz,2h),6.91(q,j＝7.2hz,1h),5.92(d,j＝9.2hz,1h),5.32(d,j＝9.6hz,1h),4.07-3.94(m,2h),2.35(s,3h),1.86(d,j＝7.6hz,3h),1.06(t,j＝7.2hz,3h).13cnmr(100mhz,cdcl3)majorisomerδ166.0,143.2,140.8,138.2,136.4,133.1,132.6,131.1,129.3,128.2,128.0,127.5,127.0,126.1,125.9,124.7,124.1,60.8,53.5,21.5,14.4,14.0.hrms(esi)m/zcalcdforc24h25nnao4s[m+na]+446.1402；found446.1391.
2-(蒽-9-基((4-甲基苯基)磺酰氨基)甲基)丁-2-烯酸乙酯(3oa).
收率42％；mp80-82℃.e:z＝87:13；1hnmr(400mhz,cdcl3)majorisomerδ8.23(s,1h),8.06(d,j＝8.0hz,2h),7.87(d,j＝8.0hz,2h),7.44-7.38(m,4h),6.89(d,j＝8.0hz,2h),6.73(d,j＝8.8hz,1h),6.47(d,j＝8.0hz,2h),6.21(q,j＝7.2hz,1h),5.58(d,j＝8.0hz,1h),4.11-3.92(m,2h),2.11(s,3h),1.91(d,j＝7.2hz,3h),0.98(t,j＝7.2hz,3h)；minorisomerδ8.32(d,j＝8.4hz,2h),8.26(d,j＝8.4hz,2h),7.88-7.85(m,2h),7.44-7.38(m,4h),7.08(d,j＝8.0hz,2h),6.93(d,j＝8.8hz,1h),6.86-6.79(m,1h),6.63-6.60(m,3h),4.11-3.92(m,2h)2.16(s,3h),1.56(d,j＝7.6hz,3h),1.05(t,j＝7.2hz,3h).13cnmr(100mhz,cdcl3)majorisomerδ166.9,142.3,136.2,134.7,133.9,131.3,129.3,128.6,128.5,128.4,126.5,126.2,124.8,123.8,60.7,54.2,21.2,15.2,13.8.hrms(esi)m/zcalcdforc28h27nnao4s[m+na]+496.1558；found496.1556.
2-(呋喃-2-基((4-甲基苯基)磺酰氨基)乙基)丁-2-烯酸甲酯(3pa).
收率67％；mp75-77℃.e:z＝63:37；1hnmr(400mhz,cdcl3)majorisomerδ7.68(d,j＝8.0hz,2h),7.25-7.21(m,3h),6.86(q,j＝7.2hz,1h),6.35(d,j＝10.4hz,1h),6.23-6.20(m,1h),6.10(dd,j＝12.4,hz,j＝3.2hz,1h),5.61(d,j＝10.0hz,1h),4.17-4.01(m,2h),2.40(s,3h),1.86(d,j＝7.2hz,3h),1.19(t,j＝7.2hz,3h)；minorisomerδ7.68(d,j＝8.0hz,2h),7.25-7.21(m,3h),6.23-6.21(m,1h),6.17(q,j＝7.2hz,1h),6.07(dd,j＝12.4,hz,j＝3.2hz,1h),5.80(d,j＝9.6hz,1h),5.20(d,j＝9.6hz,1h),4.17-4.10(m,2h),2.40(s,3h),1.86(d,j＝7.2hz,3h),1.18(t,j＝7.2hz,3h).13cnmr(100mhz,cdcl3)majorisomerδ165.8,152.0,143.2,141.8,141.3,138.1,129.4,129.3,127.0,110.5,106.6,60.8,48.9,21.5,14.2,14.0.hrms(esi)m/zcalcdforc18h21nnao5s[m+na]+386.1038；found386.1013.
2-(((4-甲基苯基)磺酰氨基)(噻吩-2-基)甲基)丁-2-烯酸甲酯(3qa).
收率76％；mp76-78℃.e:z＝71:29；1hnmr(400mhz,cdcl3)majorisomerδ7.69(d,j＝8.0hz,2h),7.22(d,j＝8.0hz,2h),7.14(d,j＝4.8hz,1h),6.88-6.82(m,2h),6.76(s,1h),6.49(d,j＝10.4hz,1h),5.73(d,j＝10.4hz,1h),4.15-4.00(m,2h),2.40(s,3h),1.86(d,j＝7.2hz,3h),1.17(t,j＝7.2hz,3h)；minorisomerδ7.70(d,j＝8.0hz,2h),7.25(d,j＝8.0hz,2h),7.14(d,j＝4.8hz,1h),6.88-6.82(m,1h),6.77(s,1h),6.17(q,j＝7.2hz,1h),6.02(d,j＝9.6hz,1h),5.29(d,j＝10.0hz,1h),4.15-4.00(m,2h),2.40(s,3h),1.86(d,j＝7.2hz,3h),1.14(t,j＝7.2hz,3h).13cnmr(100mhz,cdcl3)majorisomerδ165.8,143.8,143.3,140.7,138.0,131.0,129.4,127.1,126.9,125.0,124.1,60.9,50.7,21.5,14.1,14.0.hrms(esi)m/zcalcdforc18h21nnao4s2[m+na]+402.0810；found402.0797.
(4e)-2-亚乙基-3-((4-甲基苯基)磺酰氨基)-5-苯基戊-4-烯酸乙酯(3ra).
收率83％；mp77-79℃.e:z>95:5；1hnmr(400mhz,cdcl3)majorisomerδ7.68(d,j＝8.0hz,2h),7.27-7.18(m,7h),6.79(q,j＝7.2hz,1h),6.31(d,j＝16.0hz,1h),6.09-6.00(m,2h),5.10(dd,j＝10.0hz,j＝6.4hz,1h),4.14-4.04(m,2h),2.33(s,3h),1.85(d,j＝7.2hz,3h),1.23(t,j＝7.2hz,3h).13cnmr(100mhz,cdcl3)majorisomerδ166.0,143.2,140.0,138.3,136.2,131.3,130.8,129.4,128.4,127.8,127.1,127.1,126.5,60.8,52.9,21.4,14.1.hrms(esi)m/zcalcdforc22h25nnao4s[m+na]+422.1402；found422.1389.
2-亚乙基-3-((4-甲基苯基)磺酰氨基)-5-苯基戊酸乙酯(3sa).
收率42％；mp61-63℃.e:z>95:5；1hnmr(400mhz,cdcl3)majorisomerδ7.62(d,j＝8.0hz,2h),7.28-7.24(m,2h),7.21-7.17(m,3h),7.13(d,j＝7.2hz,2h),6.57(q,j＝7.2hz,1h),5.90(d,j＝10.4hz,1h),4.34-4.28(m,1h),4.05(q,j＝7.2hz,1h),2.73-2.66(m,1h),2.62-2.55(m,1h),2.40(s,3h),2.18-2.09(m,1h),1.83-1.72(m,1h),1.53(d,j＝7.2hz,3h),1.20(t,j＝7.2hz,3h).13cnmr(100mhz,cdcl3)majorisomerδ166.0,143.0,141.0,139.9,138.3,131.2,129.2,128.5,128.4,127.0,126.0,60.5,50.5,36.6,32.2,21.5,14.1,13.8.hrms(esi)m/zcalcdforc22h27nnao4s[m+na]+424.1558；found424.1550.
2-(环己基((4-甲基苯基)磺酰氨基)甲基)丁-2-烯酸乙酯(3ta).
收率43％；mp94-96℃.e:z>95:5；1hnmr(400mhz,cdcl3)majorisomerδ7.60(d,j＝8.0hz,2h),7.19(d,j＝8.0hz,2h),6.64(q,j＝7.2hz,1h),5.84(d,j＝10.0hz,1h),4.10-4.02(m,2h),3.96(t,j＝10.0hz,1h),2.39(s,3h),2.17(d,j＝9.2hz,1h),1.77-1.73(m,1h),1.67(d,j＝7.2hz,3h),1.63-1.59(m,2h),1.44-1.41(m,1h),1.24(t,j＝7.2hz,3h),0.96-0.86(m,1h),0.79-0.69(m,1h).13cnmr(100mhz,cdcl3)majorisomerδ166.4,142.8,140.7,138.6,130.2,129.1,126.9,60.5,56.3,41.0,30.5,29.9,26.2,26.0,25.8,21.5,14.5,14.1.hrms(esi)m/zcalcdforc20h29nnao4s[m+na]+402.1715；found402.1717.
2-亚乙基-4-甲基-3-((4-甲基苯基)磺酰氨基)戊酸乙酯(3ua).
收率39％；mp79-81℃.e:z>95:5；1hnmr(400mhz,cdcl3)majorisomerδ7.61(d,j＝8.0hz,2h),7.19(d,j＝8.0hz,2h),6.64(q,j＝7.2hz,1h),5.84(d,j＝10.0hz,1h),4.06(q,j＝7.2hz,1h),3.88(t,j＝10.0hz,1h),2.39(s,3h),2.00-1.90(m,1h),1.69(d,j＝7.2hz,3h),1.21(t,j＝7.2hz,3h),1.05(d,j＝6.8hz,3h),0.73(d,j＝6.8hz,3h).13cnmr(100mhz,cdcl3)majorisomerδ166.3,142.8,140.6,138.5,130.5,129.1,126.9,60.5,57.5,32.1,21.5,20.1,19.5,14.4,14.1.hrms(esi)m/zcalcdforc17h25nnao4s[m+na]+362.1402；found362.1401.
2-(((4-甲基苯基)磺酰氨基)(苯基)甲基)丁-2-烯酸甲酯(3bb).
收率85％；mp99-101℃.e:z＝92:8；1hnmr(400mhz,cdcl3)majorisomerδ7.67(d,j＝8.0hz,2h),7.28-7.21(m,7h),6.86(q,j＝7.2hz,1h),6.32(d,j＝10.4hz,1h),5.60(d,j＝10.4hz,1h),3.57(s,3h),2.40(s,3h),1.83(d,j＝7.2hz,3h)；minorisomerδ7.67(d,j＝8.0hz,2h),7.28-7.21(m,7h),6.12(q,j＝7.2hz,1h),5.76(d,j＝9.6hz,1h),5.16(d,j＝9.6hz,1h),3.55(s,3h),2.40(s,3h),1.83(d,j＝7.2hz,3h).13cnmr(100mhz,cdcl3)majorisomerδ166.4,143.2,140.9,139.0,138.2,131.1,129.3,128.4,127.3,127.0,125.8,53.2,51.8,21.5,14.3.hrms(esi)m/zcalcdforc19h21nnao4s[m+na]+382.1089；found382.1117.
2-((4-溴苯基)((4-甲基苯基)磺酰氨基)甲基)丁-2-烯酸甲酯(3cb).
收率85％；mp114-116℃.e:z＝86:14；1hnmr(400mhz,cdcl3)majorisomerδ7.66(d,j＝8.4hz,2h),7.37(d,j＝8.4hz,2h),7.22(d,j＝8.0hz,2h),7.12(d,j＝8.0hz,2h),6.87(q,j＝7.2hz,1h),6.31(d,j＝10.4hz,1h),5.53(d,j＝10.4hz,1h),3.58(s,3h),2.41(s,3h),1.82(d,3h)；minorisomerδ7.66(d,j＝8.4hz,2h),7.37(d,j＝8.4hz,2h),7.25(d,j＝8.0hz,2h),7.08(d,j＝8.4hz,2h),6.10(q,j＝7.2hz,1h),5.84(d,j＝9.6hz,1h),5.09(d,j＝9.6hz,1h),3.57(s,3h),2.41(s,3h),1.82(d,3h).13cnmr(100mhz,cdcl3)majorisomerδ166.2,143.4,141.3,138.1,138.0,131.5,130.7,129.4,127.7,126.9,121.4,52.8,51.9,21.5,14.4.hrms(esi)m/zcalcdforc19h20brnnao4s[m+na]+460.0194；found460.0186.
2-((4-氟苯基)((4-甲基苯基)磺酰氨基)甲基)丁-2-烯酸甲酯(3db)
收率82％；mp106-108℃.e:z＝85:15；1hnmr(400mhz,cdcl3)majorisomerδ7.66(d,j＝8.0hz,2h),7.23-7.20(m,4h),5.96-5.91(m,2h),6.87(q,j＝7.2hz,1h),6.32(d,j＝10.0hz,1h),5.56(d,j＝10.0hz,1h),3.58(s,3h),2.41(s,3h),1.82(d,j＝7.2hz,3h)；minorisomerδ7.66(d,j＝8.0hz,2h),7.37(d,j＝8.4hz,1h),7.20-7.16(m,2h),7.12(d,j＝8.0hz,1h),6.96-6.91(m,2h),6.09(q,j＝7.2hz,1h),5.80(d,j＝9.2hz,1h),5.12(d,j＝9.6hz,1h),3.57(s,3h),2.41(s,3h),1.82(d,j＝7.2hz,3h).13cnmr(100mhz,cdcl3)majorisomerδ166.4,162.3(j＝244.3hz),143.3,141.0,138.1,134.8(j＝3.6hz),130.9,129.4,127.7(j＝8.0hz),127.0,115.2(j＝21.9hz),52.7,51.9,21.5,14.3.hrms(esi)m/zcalcdforc19h20fnnao4s[m+na]+400.0995；found400.0973.
2-(((4-甲基苯基)磺酰氨基)(对甲苯基)甲基)丁-2-烯酸甲酯(3eb).
收率81％；mp133-135℃.e:z＝85:15；1hnmr(400mhz,cdcl3)majorisomerδ7.67(d,j＝8.4hz,2h),7.21(d,j＝8.0hz,2h),7.13(d,j＝8.0hz,2h),7.06(d,j＝8.4hz,2h),6.84(q,j＝7.2hz,1h),6.29(d,j＝10.4hz,1h),5.56(d,j＝10.4hz,1h),3.57(s,3h),2.40(s,3h),2.29(s,3h),1.82(d,j＝7.2hz,3h)；minorisomerδ7.67(d,j＝8.4hz,2h),7.24(d,j＝8.0hz,2h),7.13(d,j＝8.0hz,2h),7.06(d,j＝8.0hz,2h),6.12(q,j＝7.2hz,1h),5.70(d,j＝9.2hz,1h),5.16(d,j＝9.2hz,1h),3.57(s,3h),2.40(s,3h),2.29(s,3h),1.82(d,j＝7.2hz,3h).13cnmr(100mhz,cdcl3)majorisomerδ166.4,143.1,140.7,138.3,137.0,136.0,131.2,129.3,129.2,127.0,125.8,53.0,51.8,21.5,21.0,14.3.hrms(esi)m/zcalcdforc20h23nnao4s[m+na]+396.1245；found396.1228.
2-((4-甲氧基苯基)((4-甲基苯基)磺酰氨基)甲基)丁-2-烯酸甲酯(3fb)
收率89％；mp124-126℃.e:z>95:5；1hnmr(400mhz,cdcl3)majorisomerδ7.66(d,j＝8.0hz,2h),7.21(d,j＝8.0hz,2h),7.16(d,j＝8.4hz,2h),6.83(q,j＝7.2hz,1h),6.78(d,j＝8.8hz,2h),6.30(d,j＝10.4hz,1h),5.54(d,j＝10.4hz,1h),3.76(s,3h),3.57(s,3h),2.40(s,3h),1.81(d,j＝7.2hz,3h).13cnmr(100mhz,cdcl3)majorisomerδ166.5,158.8,143.1,140.6,138.2,131.1,131.0,129.3,127.1,127.0,113.8,55.3,52.8,51.8,21.5,14.3.hrms(esi)m/zcalcdforc20h23nnao5s[m+na]+412.1195；found412.1203.
2-((3,4-二甲氧基苯基)((4-甲基苯基)磺酰氨基)甲基)丁-2-烯酸甲酯(3gb).
收率93％；mp103-105℃.e:z＝86:14；1hnmr(400mhz,cdcl3)majorisomerδ7.67(d,j＝8.0hz,2h),7.22(d,j＝8.0hz,2h),6.85(q,j＝7.2hz,1h),6.85(s,1h),6.72(d,j＝8.4hz,1h),6.67(d,j＝8.4hz,1h),6.34(d,j＝10.0hz,1h),5.55(d,j＝10.4hz,1h),3.83(s,3h),3.79(s,3h),3.59(s,3h),2.40(s,3h),1.82(d,j＝7.2hz,3h)；minorisomerδ7.67(d,j＝8.0hz,2h),7.24(d,j＝8.0hz,2h),6.73-6.65(m,3h),6.11(q,j＝7.2hz,1h),5.72(d,j＝9.2hz,1h),5.12(d,j＝9.2hz,1h),3.83(s,3h),3.76(s,3h),3.59(s,3h),2.40(s,3h),1.82(d,j＝7.2hz,3h).13cnmr(100mhz,cdcl3)δ166.6,149.0,148.3,143.2,140.8,138.2,131.5,131.0,129.3,127.0,117.8,110.8,109.4,55.9,55.8,53.0,51.8,21.5,14.3.hrms(esi)m/zcalcdforc21h25nnao6s[m+na]+442.1300；found442.1300.
2-([1,1'-联苯基]-4-基((4-甲基苯基)磺酰氨基)甲基)丁-2-烯酸甲酯(3hb).
收率88％；mp152-154℃.e:z＝87:13；1hnmr(400mhz,cdcl3)majorisomerδ7.69(d,j＝8.0hz,2h),7.53(d,j＝7.6hz,2h),7.48(d,j＝8.4hz,2h),7.42(t,j＝7.6hz,2h),7.35-7.26(m,3h),7.22(d,j＝8.0hz,2h),6.89(q,j＝7.2hz,1h),6.37(d,j＝9.6hz,1h),5.64(d,j＝10.0hz,1h),3.59(s,3h),2.40(s,3h),1.86(d,j＝7.2hz,3h)；minorisomerδ7.69(d,j＝8.0hz,2h),7.53(d,j＝7.6hz,2h),7.46(d,j＝8.4hz,2h),7.42(t,j＝7.6hz,2h),7.35-7.26(m,3h),7.23(d,j＝8.0hz,2h),6.16(q,j＝7.2hz,1h),5.82(d,j＝9.2hz,1h),5.20(d,j＝9.6hz,1h),3.60(s,3h),2.40(s,3h),1.85(d,j＝6.8hz,3h).13cnmr(100mhz,cdcl3)majorisomerδ166.4,143.2,141.0,140.6,140.3,138.2,138.0,131.0,129.3,128.7,127.3,127.3,127.0,127.0,126.3,53.1,51.9,21.5,14.4.hrms(esi)m/zcalcdforc25h25nnao4s[m+na]+458.1402；found458.1393.