本发明属于有机合成技术领域，具体涉及一种分子间n–n成键的合成方法及对应合成的化合物。
背景技术：
氮元素无疑是构建有用杂环的最重要的元素。氮原子特殊的位阻和电性特征使其在有机合成中非常有用，因此在大部分具有生物活性的分子中均有氮原子的身影。除了n–c键以外，多种n-杂原子键存在于自然分子和合成化合物中，其中n–n键是非常常见的。通过前期的文献调研发现，目前构建四取代肼类化合物的方法中，不管是通过化学合成方式或者生物合成方式，均无法通过对n–n键直接偶联的方式来构筑。现有的方法主要是利用已含有n–n单键或者n＝n双键前体化合物进行改造(例如可以对肼类化合物进行取代反应或者对偶氮类化合物进行加成反应，通过构筑c–n键，从而实现四取代肼类化合物的合成)，但该类前体化合物种类较少，使该策略无法实现肼类化合物的多样可调性合成。目前虽然有一些例子报道了分子间n–n偶联反应，但均无法使用n–n偶联策略构筑四取代肼类化合物。
技术实现要素：
本发明的目的是提供一种分子间n–n成键的合成方法。本发明完成了氮宾对n–h键的直接插入反应，开发了一类全新的n–n偶联反应的方法。该反应使用3-取代-1,4,2-二噁唑-5-酮化合物作为氮宾前体，在催化剂的作用下，可以实现与胺类化合物的分子间直接n–n偶联反应，一步构建四取代肼类化合物。
为实现上述目的，本发明采用如下技术方案：
一种分子间n–n成键的合成方法，包括以下步骤：
式i化合物和式ii化合物在催化剂的作用下反应生成式iii化合物；
所述式ⅰ化合物的结构式为其中，r为一级烷基(-ch3)、二级烷基(-ch2-r1)、三级烷烃(-ch-r2r3)或苯环；通过与金属催化剂配位结合，脱除二氧化碳，形成氮宾。现有技术中ⅰ化合物主要用于形成氮宾，发生后续的curtius重排反应或者分子内/分子间的c-h键胺化反应。基于上述反应需求，本发明中的r为一级烷基(-ch3)、二级烷基(-ch2-r1),三级烷基(-ch-r2r3)或苯环与环状结构直接相连的碳上至少有一个氢原子可满足反应要求，而四级烷烃的位阻太大，形成的金属氮宾极易发生curtius重排反应，从而无法得到n–n偶联的产物。
所述式ⅱ化合物的结构式为其中，r`为一级烷基(-ch3)、二级烷基(-ch2-r1)、三级烷基(-ch-r2r3)或苯环；r`不能为氢原子，主要原因是由于ar-nh2的配位性太强，可以与金属催化剂形成稳定的配合物，进而毒化催化剂，无法催化反应。而本专利所述的r’需要是含有碳的取代基团，主要是降低式ii化合物的配位性，同时又保持该化合物的亲核性，式ii化合物中保留的n–h键主要是是为了与金属催化剂中的卤素原子形成氢键，从而辅助亲核进攻，得到相应的目标产物。式ⅱ化合物的作用作为亲核试剂，进攻形成的金属氮宾中间体，从而实现n–n键的构筑。ar是芳环。
现有技术中一般采用一级芳胺作为亲核试剂，由于一级芳胺(即r`＝h)与金属催化剂的配位性和亲核性太强，从而与金属氮宾作用只能得到脲类副产物，而无法实现n–n偶联反应。本技术中采用的二级芳胺(n-烷基芳胺或者二芳胺)通过增加芳胺的位阻，降低亲核能力和与金属氮宾的配位能力，同时n–h键存在可以与金属催化剂中的卤原子形成分子间的氢键作用，辅助芳胺对氮宾的进攻，从而实现n–n偶联反应。
所述式ⅲ化合物的结构式为
所述催化剂为含卤素的金属催化剂，具体可为含卤素的铱催化剂、铁催化剂或钌催化剂。现有技术中的金属催化剂的作用主要是只能与式ⅰ化合物结合，通过脱除二氧化碳，从而得到金属氮宾中间体，随后发生发生后续的curtius重排反应或者分子内/分子间的c–h键胺化反应。而其中并未报道卤素的氢键辅助作用。本技术中，通过计算化学辅助，发现了催化剂中的卤素还可以与式ⅱ化合物中的n–h形成分子间氢键作用。
优选的，本发明中式ⅰ化合物和式ⅱ化合物没有特定反应比例的要求，但从经济效率和产率的角度综合考虑，优选式ⅰ化合物和式ⅱ化合物的摩尔比为1-1.5:1。
优选的，所述催化剂为含卤素的铱催化剂、铁催化剂或钌催化剂；所述含卤素的铱催化剂与式ⅱ化合物的摩尔比为0.5％-5％:1；所述含卤素的铁催化剂与式ⅱ化合物的摩尔比为5％-10％:1；所述含卤素的钌催化剂与式ⅱ化合物的摩尔比为5％-10％:1。
优选的，所述铱催化剂为含卤素三价铱催化剂(卤素为氯或者溴)，三价铱催化剂参与的反应过程或作用。相对于铁催化剂和钌催化剂来所，铱催化剂催化效率更高，条件更加温和。
优选的，所述铁催化剂为卤化铁或卤化亚铁催化剂(卤素为氯或者溴)；所述钌催化剂为含卤素二价钌催化剂(卤素为氯)。
优选的，该反应可以在无溶剂下进行或者在含氯烷烃有机溶剂(二氯甲烷/三氯甲烷/二氯乙烷等)中进行。含氯烷烃有机溶剂的作用主要是为了稀释反应，降低反应速率，从而抑制副反应。
优选的，该反应在氯烷烃有机溶剂中进行时，式ⅱ化合物在氯烷烃有机溶剂中的摩尔浓度为0.2-4mol/l。
优选的，反应体系在空气或惰性气体中均可反应。
优选的，所述r具体为甲基、丁基、戊基、甲基环丙基、甲基环丁基、甲基环戊基、甲基环己基、环戊基、环己基、n-boc环己基、苯基取代的环丁基或苯基。
所述ar具体为苯基、2-甲基苯基、2-氟苯基、8-萘基、4-甲基苯基、4-氟苯基、4-氯苯基、4-三氟甲基苯基、4-硝基苯基、4-氰基苯基、3-氯苯基或3-三氟甲基苯基。
优选的，所述r`具体为甲基、环丙基、n-芳基取代的氨基酸、丙氰基、n-boc环己基、四氢喹啉基以及取代的四氢喹啉基。
一种分子间n–n成键合成合成方法对应合成的化合物具体如下：
有益效果
1.本发明首次实现了氮宾对n–h键的插入反应，实现对四取代肼类化合物的一步合成,为药物或材料分子合成提供了新的合成途径。
2、该反应在无溶剂条件、常温下及空气中均能实现上述反应，具有操作简单，条件温和的优点。
3、本反应相对于现有技术具有合成多样性更强的特点。
具体实施方式
实施例1-38
实施例1采用上述反应方程式中的标准条件，即化合物1和化合物2，在chcl3的溶剂中，常温氮气保护下，以[cp*ircl2]2为催化剂，反应12小时，得到目标化合物3以及可能的副产物，即化合物4-7；其中，化合物1和化合物2的摩尔比为1.5:1，[cp*ircl2]2和化合物2的摩尔比为1％:1，此时化合物2的摩尔浓度为4.0m。
实施例2-40与实施例1采用的反应条件基本相同，不同之处如下表1所示，同时各实施例的反应结果也如表1所示。
其中％(a)指的是核磁收率，％(b)指的是核磁收率
实施例1-40主要是反应条件的筛选，从上表中可以看出，含卤素的铱催化剂、铁催化剂或钌催化剂；尤其是含卤素三价铱催化剂(卤素为氯或者溴)，三价铱催化剂参与的反应过程或作用。相对于铁催化剂和钌催化剂来所，铱催化剂催化效率更高，条件更加温和。
本发明的反应中由于化合物1和化合物2混合后是液态，故无溶剂条件下也均可实现反应，由于篇幅限制，本发明未一一列举。
本发明的反应在空气条件和氮气条件下均可进行，但是氮气条件下的反应收率相对更高一些，由于篇幅限制，本发明未一一列举。
本发明的反应中，加入上述列举的催化剂即可实现上述反应，且随着催化剂加入量的增多，反应收率呈逐渐增加的趋势，从经济和实际试验操作便于称量的角度等考虑，选择优选的催化剂用量为铱催化剂与式2化合物的摩尔比为0.5％-5％:1；铁催化剂与式2化合物的摩尔比为5％-10％:1；钌催化剂与式ⅱ化合物的摩尔比为5％-10％:1，由于篇幅限制，本发明的催化剂用量未一一列举。
实施例41-
实施例41-采用与实施例1(即下述方程式中的a条件)或实施例37(即下述方程式中的b条件)基本相同的反应条件，区别仅在于式ⅰ化合物和/或式ⅱ化合物的不同。
其中，实施例41-46中，式ⅰ化合物r为甲基，式ⅱ化合物为选用不同r`取代基的化合物，其中ar为苯环，具体反应结果如下：
[a]指的是反应条件a，[b]指的是反应条件b；
实施例47-56中，其中，式ⅰ化合物r为甲基，式ⅱ化合物为选用不同ar取代基的化合物，r`为甲基，具体反应结果如下：
其中，实施例57-69中，式ⅰ化合物r为甲基，式ⅱ化合物为选用不同ar和r`取代基的化合物，具体反应结果如下：r`具体为甲基、环丙基(化合物17)、n-芳基取代的氨基酸【n-苯基甘氨酸乙酯，n-苯基丙氨酸甲酯，n-苯基苯丙氨酸甲酯，n-苯基甘氨酸-脯氨酸甲酯】(化合物25-28)、丙氰基(化合物15)、n-boc环己基(化合物16)、四氢喹啉基(化合物19)以及取代的四氢喹啉基(化合物20-23)。
其中，实施例70-82中，式ⅰi化合物r`为甲基，ar为苯基，式化合物为选用不同r取代基的化合物。r具体为甲基、丁基(化合物29a)、戊基(化合物29b)、甲基环丙基(化合物30a)、甲基环丁基(化合物30b)、甲基环戊基(化合物30c)、甲基环己基(化合物30d)、环戊基(化合物33)、环己基(化合物34)、n-boc环己基(化合物35)、苯基取代的环丁基(化合物31)、苯基(化合物32)，溴代己基(化合物38)，n-phth保护的beta氨基酸(化合物36)。
其中，实施例83-100中，式ⅰi化合物为四氢哌啶、苯并吗啉、苯并氮呯、n-苯基取代的氨基酸甲酯或n-芳基取代多肽类化合物，式i化合物为选用不同r取代基的化合物(包括氯代戊基(化合物45)、吲哚丁酸(化合物47)、二苄基丙基(化合物48)、n-phth保护的gama氨基酸(化合物52和53)和n-phth保护的beta氨基酸(化合物54)。
上述化合物对应的测试数据如下：
淡黄色油状液体(rf＝0.37,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.64(s,0.5h),7.32–7.09(m,7h),6.96–6.88(m,1h),6.84–6.79(m,1.5h),6.78–6.70(m,1h),3.09and3.05(2×s,3h),2.71–2.56(m,2h),2.42–2.33(m,1h),2.21–2.12(m,1h),2.05–1.86(m,2h).碳谱数据(101mhz,cdcl3)δ178.01,171.90,149.55,149.35,141.65,141.41,129.42,129.14,128.56,128.52,128.49,128.44,128.42,128.37,126.09,125.92,120.68,119.66,113.41,113.04,112.99,42.38,40.71,35.30,35.27,33.54,30.50,26.98,25.94.高分辨质谱(esi)m/zcalcdforc17h21n2o+[m+h]+:269.1648,found:269.1641.
白色固体(rf＝0.33,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ8.87(s,1h),7.36(d,j＝6.4hz,3h),7.26(t,j＝7.3hz,4h),7.16(d,j＝7.5hz,3h),3.34(s,3h),2.65(t,j＝7.5hz,2h),2.19(t,j＝7.4hz,2h),1.98(p,j＝8.8,7.9hz,2h).碳谱数据(101mhz,cdcl3)δ172.06,154.84,141.35,129.30,128.63,128.55,128.51,127.21,126.11,35.02,31.92,26.49.高分辨质谱(esi)m/zcalcdforc18h21n2o3+[m+h]+:313.1547,found:313.1548.
白色固体(rf＝0.41,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.41(t,j＝7.8hz,2h),7.33–7.27(m,1h),7.26–7.19(m,5h),7.17–7.06(m,3h),4.31(s,1h),3.26(s,3h),3.24–3.16(m,3h),2.56(t,j＝7.8hz,3h),1.74(q,j＝7.4hz,2h).碳谱数据(101mhz,cdcl3)δ157.36,143.66,141.76,130.13,128.47,128.40,127.48,127.36,125.95,40.47,37.23,33.28,31.98.高分辨质谱(esi)m/zcalcdforc17h21n2o+[m+h]+:269.1648,found:269.1645.
白色固体(rf＝0.18,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.99(s,0.5h),7.33–7.18(m,2.5h),6.95–6.89(m,0.5h),6.86–6.72(m,2.5h),3.11and3.09(2×s,3h),2.03and1.96(2×s,3h)碳谱数据(101mhz,cdcl3)δ176.12,169.33,149.44,149.33,129.43,129.12,120.66,119.69,113.35,113.04,42.10,40.69,20.97,19.14.
白色固体(rf＝0.22,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.53(s,0.4h),7.37–7.13(m,2.6h),7.00–6.77(m,3h),3.59–3.45(m,2h),2.06and2.04(2×s,3h),1.24–1.15(m,3h).碳谱数据(101mhz,cdcl3)δ176.62,169.52,148.73,148.40,129.56,129.29,120.79,119.80,114.06,114.03,113.39,48.73,46.46,21.05,19.35,11.33,10.71,10.66.
白色固体(rf＝0.26,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.64(s,0.4h),7.36–7.18(m,8h),7.13(s,0.6h),6.99–6.92(m,1.6h),6.89–6.80(m,1.4h),4.70and4.57(2×s,2h),1.89and1.84(2×s,3h).碳谱数据(101mhz,cdcl3)δ176.14,169.43,149.12,148.64,137.15,135.45,129.58,129.29,128.83,128.75,128.70,128.03,127.99,127.55,121.17,119.70,114.37,112.94,59.07,56.32,20.92,19.36.
白色固体(rf＝0.30,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.34–7.20(m,2h),7.00(brs,1h),6.96–6.80(m,3h),4.29–4.11(m,1h),2.13and2.02(2×s,1h),1.29,1.17and1.01(3×d,j＝6.6hz,6h),.碳谱数据(101mhz,cdcl3)δ177.21,170.25,149.02,147.80,129.58,129.39,121.14,119.95,115.17,114.01,52.70,50.51,21.00,20.25,19.25,15.45.
白色固体(rf＝0.26,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.67–7.46(m,0.4h),7.33–7.19(m,2.2h),7.18–7.05(m,0.6h),6.98–6.77(m,2.8h),5.97–5.78(m,1h),5.33–5.19(m,2h),4.26–3.87(m,2h),2.04and2.02(2×s,3h).碳谱数据(101mhz,cdcl3)δ176.16,169.38,148.61,148.31,132.67,130.91,129.54,129.24,120.94,120.37,119.89,118.75,114.02,113.35,57.37,55.33,20.98,19.51.高分辨质谱(esi)m/zcalcdforc11h15n2o+[m+h]+:191.1179,found:191.1178.
白色固体(rf＝0.25,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ8.08and7.79(2×s,1h),7.36–7.20(m,4h),7.14–6.96(m,6h),2.07and2.03(2×s,3h).碳谱数据(101mhz,cdcl3)δ176.37,169.32,146.06,145.98,129.58,129.29,123.76,123.12,119.57,119.39,21.01,19.69.
淡黄色油状液体(rf＝0.22,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.59(s,0.3h),7.14–6.99(m,2h),6.96(s,0.7h),6.80–6.69(m,2h),3.12and3.10(2×s,3h),2.28and2.14(2×s,3h),2.06and2.01(2×s,3h).碳谱数据(101mhz,cdcl3)δ175.99,169.08,147.37,147.26,130.28,129.98,129.73,129.39,113.64,113.52,42.50,41.18,21.19,20.46,20.44,19.23.高分辨质谱(esi)m/zcalcdforc10h15n2o+[m+h]+:179.1179,found:179.1175.
白色固体(rf＝0.17,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ8.23–7.94(m,0.5h),7.40–7.28(m,0.5h),7.01–6.82(m,2h),6.81–6.61(m,2h),3.14–2.96(m,3h),2.03and1.95(2×s,3h).碳谱数据(101mhz,cdcl3)δ176.00,169.28,167.84,158.84,158.30,156.46,155.94,145.92,145.90,145.79,115.97,115.74,115.62,115.39,115.37,114.91,114.83,114.45,114.37,42.75,41.12,21.03,19.18.19fnmr(376mhz,cdcl3)δ-125.48,-125.51,-126.99.
白色固体(rf＝0.20,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.48(s,0.5h),7.28–7.15(m,2h),7.00(s,0.5h),6.81–6.69(m,1h),3.17and3.16(2×s,3h),2.05and2.04(2×s,3h).
碳谱数据(101mhz,cdcl3)δ175.94,169.23,148.09,147.98,129.36,129.04,125.85,124.68,114.61,114.20,42.31,40.87,21.08,19.21.
白色固体(rf＝0.19,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.72–7.64(m,0.6h),7.56–7.41(m,2h),7.21(s,0.4h),6.91–6.75(m,2h),3.24and3.21(2×s,3h),2.05and2.02(2×s,3h).碳谱数据(101mhz,cdcl3)δ175.93,169.16,151.65,151.55,126.97,126.94,126.90,126.86,126.69,126.65,126.61,126.58,126.13,125.92,123.44,123.23,122.18,121.33,121.00,112.50,111.95,41.86,40.60,21.05,19.19.19fnmr(376mhz,cdcl3)δ-62.64,-62.86.高分辨质谱(esi)m/zcalcdforc10h12f3n2o+[m+h]+:233.0896,found:233.0891.
浅黄色固体.(rf＝0.08,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ8.23–8.08(m,2h),7.62(s,0.7h),7.16(s,0.3h),6.90–6.71(m,2h),3.36and3.33(2×s,3h),2.11and2.02(2×s,3h).碳谱数据(101mhz,cdcl3)δ175.34,168.97,153.93,153.74,140.68,139.71,126.16,126.01,111.71,111.16,41.81,40.64,20.98,19.18.高分辨质谱(esi)m/zcalcdforc9h13n3o3+[m+h]+:210.0873,found:210.0868.
黄色固体.(rf＝0.10,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ8.50(s,0.8h),7.60(s,0.2h),7.51–7.31(m,2h),6.85–6.57(m,2h),3.21and3.12(2×s,3h),1.98and1.95(2×s,3h).碳谱数据(101mhz,cdcl3)δ175.69,169.51,152.16,133.77,133.44,120.08,119.57,112.54,111.97,102.17,100.51,41.42,40.07,20.80,19.12.高分辨质谱(esi)m/zcalcdforc10h12n3o+[m+h]+:190.0975,found:190.0974.
白色固体(rf＝0.20,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ8.17and7.33(2×brs,1h),7.22–7.06(m,1h),6.91–6.52(m,3h),3.12and3.06(2×s,3h),2.00and1.95(2×s,3h).碳谱数据(101mhz,cdcl3)δ176.05,169.51,150.52,150.41,135.38,135.00,130.51,130.19,120.51,119.34,113.33,112.79,111.36,110.91,77.48,77.16,76.84,42.02,40.53,20.94,19.16.高分辨质谱(esi)m/zcalcdforc9h12cln2o+[m+h]+:199.0633,found:199.0629.
白色固体(rf＝0.20,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.93(s,0.57h),7.39(t,j＝8.0hz,0.45h),7.34–7.25(m,1h),7.17(d,j＝7.7hz,0.41h),7.08–7.03(m,0.96h),7.03–6.99(m,0.44h),6.95(s,0.57h),6.89(dd,j＝8.4,2.5hz,0.6h),3.18(2×s,3h),2.02(2×s,3h).碳谱数据(101mhz,cdcl3)δ176.04,169.42,149.73,149.53,132.11,131.79,131.69,131.48,131.38,131.06,130.13,130.10,129.75,125.68,125.49,122.98,122.79,117.24,117.21,117.17,117.13,116.30,116.08,116.04,116.01,115.97,115.72,109.71,109.67,109.63,109.59,109.19,109.15,109.11,109.07,42.13,40.60,20.99,19.20.19fnmr(377mhz,cdcl3)δ-62.68,-62.71.高分辨质谱(esi)m/zcalcdforc10h12f3n2o+[m+h]+:233.0896,found:233.0893.
白色固体(rf＝0.43,hexane/acetone＝3:1).氢谱数据(400mhz,meod)δ7.40(d,j＝8.0hz,2h),7.30–7.18(m,2h),7.01(t,j＝7.4hz,1h),1.95(s,3h).碳谱数据(101mhz,meod)δ169.18,152.62,137.91,128.58,123.37,118.64,17.90.高分辨质谱(esi)m/zcalcdforc9h11n2o3+[m+h]+:195.0764,found:195.0763.
淡黄色油状液体(rf＝0.24,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.92(s,0.6h),7.26(s,0.4h),7.21–7.10(m,3h),7.09–6.96(m,1h),3.07and2.89(2×s,3h),2.36and2.26(2×s,3h),2.11and1.91(2×s,3h).碳谱数据(101mhz,cdcl3)δ174.86,167.86,149.92,148.20,132.40,131.59,131.46,131.00,127.07,126.30,125.10,124.23,118.85,117.63,46.69,42.23,21.19,19.90,18.66,18.19.
白色固体(rf＝0.23,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.90–7.31(m,1h),7.15–6.84(m,4h),3.22and3.10(2×s,3h),2.14and1.94(2×s,3h).碳谱数据(101mhz,cdcl3)δ169.09,155.76,124.76,124.68,124.62,124.59,124.28,124.24,123.12,119.10,119.07,118.66,116.99,116.78,116.54,116.33,45.35,42.08,21.18,19.51.19fnmr(376mhz,cdcl3)δ-124.05,-124.09,-125.45.
白色固体(rf＝0.19,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ8.30–8.19(m,1h),8.16–7.95(m,0.5h),7.92–7.75(m,1h),7.69–7.05(m,5.5h),3.21and3.10(2×s,3h),2.16and1.89(2×s,3h).碳谱数据(101mhz,cdcl3)δ174.99,168.03,148.14,146.15,134.67,128.78,128.53,128.17,127.57,126.38,126.31,126.26,126.22,125.88,125.57,125.48,125.16,123.99,122.93,115.20,114.41,48.50,43.00,21.44,20.15.高分辨质谱(esi)m/zcalcdforc13h15n2o+[m+h]+:215.1179,found:215.1174.
棕色油状物.(rf＝0.13,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ8.44and7.92(2×s,3h),7.37–7.18(m,2h),7.07–6.65(m,3h),3.75–3.60(m,2h),2.70–2.47(m,2h),2.02and1.89(2×s,3h).碳谱数据(101mhz,cdcl3)δ176.64,170.27,147.78,147.12,129.77,129.48,122.22,120.41,118.76,118.17,114.77,112.86,51.24,48.07,20.88,19.44,16.08,15.20.高分辨质谱(esi)m/zcalcdforc11h14n3o+[m+h]+:204.1131,found:204.1126.
白色固体(rf＝0.21,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.33–7.19(m,2h),7.16–6.98(m,1h),6.98–6.75(m,3h),4.21(s,2h),3.97–3.72(m,1h),2.90–2.60(m,2h),2.08and1.99(2×s,3h),1.91–1.60(m,4h),1.56–1.33(m,9h).碳谱数据(101mhz,cdcl3)δ176.93,170.32,154.81,154.59,148.31,147.10,129.75,129.54,121.75,120.25,115.45,113.85,80.03,59.87,57.44,29.93,28.53,21.00,19.39.
高分辨质谱(esi)m/zcalcdforc18h27n3nao3+[m+na]+:356.1945,found:356.1941.
白色固体(rf＝0.33,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.69(s,0.48h),7.36–7.19(m,2h),7.16–6.92(m,3h),6.89–6.84(m,0.48h),2.91–2.79(m,0.47h),2.68-2.56(m,0.47h),2.01and1.95(2×s,3h),1.08–0.67(m,4h).碳谱数据(101mhz,cdcl3)δ176.04,169.34,149.42,149.25,129.35,129.02,35.45,33.85,21.15,19.09.高分辨质谱(esi)m/zcalcdforc11h14n2ona+[m+na]+:213.0998,found:213.0998.
淡黄色油状液体(rf＝0.15,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ9.94(s,1h),7.43–7.15(m,5h),4.52(d,j＝24.4hz,2h),2.92(d,j＝20.8hz,2h),2.01(d,j＝3.2hz,3h).碳谱数据(101mhz,cdcl3)δ168.79,155.86,155.35,136.01,128.71,127.74,127.68,53.35,52.41,34.74,33.60,19.39.高分辨质谱(esi)m/zcalcdforc11h15n2o3+[m+h]+:223.1077,found:223.1075.
白色固体(rf＝0.22,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.50(s,0.3h),7.14–6.92(m,2.7h),6.86–6.67(m,2h),3.48–3.20(m,2h),2.91–2.70(m,2h),2.24–1.99(m,5h).碳谱数据(101mhz,cdcl3)δ176.19,145.57,129.54,129.33,127.33,127.07,123.78,123.27,120.51,119.49,112.91,112.58,53.10,51.64,27.05,26.84,22.52,22.24,21.22,19.05.高分辨质谱(esi)m/zcalcdforc11h15n2o+[m+h]+:191.1179,found:191.1175.
浅黄色固体.(rf＝0.20,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.84–7.44(m,0.25h),7.34(s,0.26h),7.18–6.56(m,4.5h),3.74–3.15(m,1h),2.98–2.59(m,2h),2.33–1.75(m,5h),1.33–1.08(m,3h).碳谱数据(101mhz,cdcl3)δ177.10,176.66,169.53,146.43,143.97,129.45,129.29,129.06,127.41,127.19,127.03,124.77,122.54,120.88,119.67,114.12,112.19,57.04,55.10,30.79,28.17,26.52,22.65,21.05,20.18,19.36,19.06,14.29.高分辨质谱(esi)m/zcalcdforc12h17n2o+[m+h]+:205.1335,found:205.1331.
白色固体(rf＝0.13,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.51(s,0.6h),7.40–7.18(m,2h),7.06(s,0.4h),6.85–6.63(m,1h),3.65–3.39(m,2h),2.88–2.68(m,2h),2.23–1.99(m,4h).碳谱数据(101mhz,cdcl3)δ175.73,169.10,148.68,132.99,132.70,131.87,131.60,123.60,122.72,120.39,119.79,111.83,111.18,101.98,100.11,52.58,50.97,26.81,26.60,21.71,21.41,21.01,19.01.高分辨质谱(esi)m/zcalcdforc12h14n3o+[m+h]+:216.1331,found:216.1127.
白色固体(rf＝0.1,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ8.54–8.33(m,0.7h),7.97–7.87(m,0.3h),7.85–7.61(m,1h),7.54–7.31(m,1h),7.05–6.71(m,2h),3.85–3.42(m,2h),3.05–2.63(m,2h),2.15and2.05(2×s,3h).碳谱数据(101mhz,cdcl3)δ192.97,192.26,175.76,169.30,151.93,151.75,135.90,135.55,128.25,127.94,121.27,120.76,119.96,119.84,113.85,113.58,53.41,51.56,38.60,38.34,21.07,19.34.高分辨质谱(esi)m/zcalcdforc11h13n2o2+[m+h]+:205.0972,found:205.0966.
白色固体(rf＝0.16,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.52(s,0.4h),6.96–6.68(m,4.6h),4.53–4.26(m,2h),3.57–3.32(m,2h),2.10and2.03(2×s,3h).碳谱数据(101mhz,cdcl3)δ175.77,169.14,145.04,144.80,134.86,122.52,121.68,121.51,121.39,116.97,116.84,114.41,114.15,65.14,64.96,51.19,49.92,21.22,19.28.高分辨质谱(esi)m/zcalcdforc10h13n2o2+[m+h]+:193.0972,found:193.0966.
白色固体(rf＝0.32,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ8.40and7.93(2×s,1h),7.20–7.03(m,3h),7.01–6.85(m,1h),3.53–3.35(m,1h),3.11–2.70(m,3h),2.09and2.04(2×s,3h),1.95–1.56(m,3h),1.26(s,1h).碳谱数据(101mhz,cdcl3)δ175.14,168.94,150.49,149.61,133.17,132.68,130.51,130.34,127.07,126.66,123.35,122.49,116.83,115.90,60.48,58.92,35.05,34.76,29.35,25.49,25.23,21.34,19.80.高分辨质谱(esi)m/zcalcdforc12h17n2o+[m+h]+:205.1335,found:205.1331.
白色固体(rf＝0.29,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ8.32–8.16(m,0.49h),7.68–7.60(m,0.46h),7.35–7.18(m,2h),7.00–6.70(m,3h),4.56–4.41(m,0.48h),4.30(s,1h),4.24–4.07(m,2h),4.05–3.92(m,0.49h),2.06and2.04(2×s,3h),1.33–1.13(m,3h).碳谱数据(101mhz,cdcl3)δ170.73,169.51,148.08,147.49,129.62,129.34,121.38,120.67,113.42,113.09,61.59,61.48,55.04,53.38,21.07,19.48,14.23,14.19.高分辨质谱(esi)m/zcalcdforc12h17n2o3+[m+h]+:237.1234,found:237.1231.
白色固体(rf＝0.29,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.82and7.48(2×s,1h),7.36–7.18(m,2h),7.02–6.86(m,2h),6.81(d,j＝8.0hz,1h),4.74–4.62(m,1h),3.70and3.64(2×s,3h),2.13and2.03(2×s,3h),1.58(t,j＝8.0hz,3h).碳谱数据(101mhz,cdcl3)δ176.23,174.59,173.28,170.28,148.93,148.04,129.57,129.31,121.90,121.17,114.61,114.04,58.92,57.36,52.22,52.21,20.85,19.21,15.87,15.77.高分辨质谱(esi)m/zcalcdforc12h17n2o3+[m+h]+:237.1234,found:237.1230.
白色固体(rf＝0.37,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.93and7.60(2×s,1h),7.33–7.06(m,7h),7.02–6.68(m,3h),4.99–4.55(m,1h),3.50and3.45(2×s,3h),3.36–2.98(m,2h),2.09and1.43(2×s,3h).碳谱数据(101mhz,cdcl3)δ173.88,172.78,169.88,149.15,148.00,136.79,136.38,129.68,129.63,129.43,129.25,128.92,128.88,128.68,128.66,127.23,127.08,122.45,121.66,115.43,114.62,65.10,64.58,52.24,51.92,36.86,35.92,21.15,18.96.高分辨质谱(esi)m/zcalcdforc18h21n2o3+[m+h]+:313.1547,found:313.1543.
白色固体(rf＝0.1,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ8.35,8.30,7.90and7.79(4×s,1h),7.32–7.17(m,2h),6.95–6.73(m,3h),4.67–3.74(m,4h),3.73–3.60(m,3h),3.59–3.47(m,1h),2.36–1.80(m,7h).碳谱数据(101mhz,cdcl3)δ175.45,172.31,169.47,168.34,148.12,129.50,129.20,121.10,120.52,113.49,58.95,58.75,53.78,53.43,52.94,52.40,46.71,46.38,46.26,31.57,28.96,28.86,24.94,22.23,21.13,19.61.高分辨质谱(esi)m/zcalcdforc16h22n3o4+[m+h]+:320.1605,found:320.1603.
淡黄色油状液体(rf＝0.36,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.40–7.17(m,3h),6.99–6.91(m,0.6h),6.91–6.76(m,2.4h),3.18and3.16(2×s,3h),2.38(q,j＝7.3hz,1h),2.24(t,j＝7.6hz,1h),1.77–1.52(m,2h),1.47–1.21(m,2h),0.95and0.89(2×t,j＝7.3hz,3h).碳谱数据(101mhz,cdcl3)δ178.57,172.14,149.69,149.40,129.51,129.26,120.75,119.90,113.47,113.09,77.48,77.16,76.84,42.55,40.97,34.39,30.93,27.76,26.64,22.62,22.60,13.97,13.92.高分辨质谱(esi)m/zcalcdforc12h19n2o+[m+h]+:207.1492,found:207.1491.
淡黄色油状液体(rf＝0.43,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.33–7.16(m,2.7h),6.89–6.72(m,3.3h),3.16and3.13(2×s,3h),2.41–2.26(m,1h),2.26–2.12(m,1h),1.78–1.55(m,2h),1.39–1.16(m,4h),0.96–0.77(m,3h).碳谱数据(101mhz,cdcl3)δ178.48,172.16,149.68,149.43,129.49,129.22,120.72,119.80,113.44,113.07,42.52,40.90,34.56,31.65,31.61,31.17,25.36,24.21,22.51,22.48,14.06,14.01.高分辨质谱(esi)m/zcalcdforc13h21n2o+[m+h]+:221.1648,found:221.1643.
白色固体(rf＝0.57,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.44–7.14(m,2.6h),6.96–6.76(m,3.4h),3.17and3.15(2×s,3h),2.40–2.32(m,1h),2.26–2.17(m,1h),1.74–1.58(m,2h),1.37–1.19(m,28h),0.88(t,j＝6.7hz,3h).碳谱数据(101mhz,cdcl3)δ178.49,172.13,149.74,149.47,129.55,129.29,120.78,119.90,113.49,113.12,77.48,77.16,76.84,42.59,40.99,34.70,32.09,31.26,29.86,29.83,29.78,29.67,29.64,29.52,29.49,25.74,24.58,22.86,14.28.高分辨质谱(esi)m/zcalcdforc25h45n2o+[m+h]+:389.3526,found:389.3522.
无色油状液体.(rf＝0.40,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.57–7.43(m,0.5h),7.37–7.15(m,2h),6.98–6.91(m,0.5h),6.89–6.72(m,3h),3.15and3.13(2×s,3h),2.83–2.63(m,1h),2.55–2.41(m,1h),2.36–2.27(m,1h),2.23–2.06(m,2h),2.01–1.55(m,4h).碳谱数据(101mhz,cdcl3)δ177.34,170.89,149.76,149.37,129.55,129.28,120.80,119.91,113.48,113.09,42.64,41.93,41.04,38.24,32.91,31.84,28.68,28.64,18.81,18.65.高分辨质谱(esi)m/zcalcdforc13h19n2o+[m+h]+:219.1492,found:219.1485.
白色固体(rf＝0.40,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.56(s,0.6h),7.39–7.21(m,2h),7.01–6.93(m,0.4h),6.91–6.79(m,3h),3.16and3.17(2×s,3h),2.51–2.15(m,3h),1.97–1.78(m,2h),1.74–1.49(m,4h),1.30–1.03(m,2h).碳谱数据(101mhz,cdcl3)δ178.00,171.75,149.69,149.42,129.47,129.19,120.70,119.74,113.44,113.08,42.54,40.85,40.75,37.17,37.06,35.85,32.81,32.72,25.09,25.03.高分辨质谱(esi)m/zcalcdforc14h21n2o+[m+h]+:233.1648,found:233.1642.
白色固体(rf＝0.44,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.52(s,0.6h),7.34–7.18(m,2h),6.97–6.90(m,0.4h),6.88–6.76(m,3h),3.14and3.12(2×s,3h),2.33–2.18(m,1h),2.09–2.01(m,1h),1.94–1.82(m,1h),1.81–1.57(m,4h),1.34–1.18(m,3h),1.18–1.05(m,1h),1.03–0.80(m,2h).碳谱数据(101mhz,cdcl3)δ177.73,171.42,149.68,149.43,129.45,129.19,120.69,119.74,113.47,113.09,42.56,42.41,40.91,38.49,35.25,34.08,33.41,33.34,33.27,26.30,26.26,26.20,26.17,26.13.高分辨质谱(esi)m/zcalcdforc15h23n2o+[m+h]+:247.1805,found:247.1798.
白色固体(rf＝0.47,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.39–7.21(m,2.6h),7.00–6.73(m,3.4h),3.19and3.16(2×s,3h),2.40–2.24(m,1h),2.18–2.05(m,2h),1.86–1.39(m,10h),1.34–1.10(m,2h).碳谱数据(101mhz,cdcl3)δ177.83,171.48,149.70,149.43,129.49,129.24,120.73,119.85,113.49,113.13,43.03,42.63,40.99,39.20,36.91,35.67,34.90,34.73,28.35,26.38,26.31.高分辨质谱(esi)m/zcalcdforc16h25n2o+[m+h]+:261.1961,found:261.1955.
淡黄色油状液体(rf＝0.32,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.59(s,0.5h),7.31–7.09(m,6.5h),6.98–6.87(m,0.8h),6.82–6.71(m,1.2h),6.58–6.49(m,1h),3.01–2.88(m,5h),2.72–2.61(m,1h),2.51–2.41(m,1h).碳谱数据(101mhz,cdcl3)δ177.36,171.16,149.50,149.14,141.07,140.53,129.39,129.07,128.65,128.52,128.50,126.43,126.21,120.72,119.61,113.46,112.97,77.47,77.16,76.84,42.28,40.61,36.14,32.88,31.50,30.56.高分辨质谱(esi)m/zcalcdforc16h19n2o+[m+h]+:255.1492,found:255.1484.
白色固体(rf＝0.34,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ8.10–7.98(m,1h),7.89–7.70(m,2h),7.61–7.20(m,5h),7.04–6.84(m,3h),3.30and3.06(2×s,3h).碳谱数据(101mhz,cdcl3)δ166.53,149.46,132.88,132.25,129.33,128.91,127.31,120.01,113.21,40.96.
氢谱数据(400mhz,cdcl3)δ7.65–7.52(m,0.6h),7.32–7.17(m,2h),6.97–6.89(m,0.4h),6.89–6.72(m,3h),3.13(s,3h),3.09–2.98(m,0.4h),2.61–2.49(m,0.6h),1.96–1.43(m,8h).碳谱数据(101mhz,cdcl3)δ181.61,175.25,149.94,149.53,129.40,129.16,120.66,119.52,113.55,112.87,43.43,42.90,40.78,39.65,30.44,30.37,30.17,26.26,26.11.高分辨质谱(esi)m/zcalcdforc13h19n2o+[m+h]+:219.1492,found:219.1486.
淡黄色油状液体(rf＝0.43,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.50–7.35(m,0.7h),7.32–7.19(m,2h),6.98–6.75(m,3h),6.70–6.63(m,0.3h),3.19–3.08(m,3h),2.78–2.63(m,0.3h),2.20–2.07(m,0.7h),1.93–1.61(m,5h),1.59–1.44(m,2h),1.34–1.13(m,4h),0.92–0.76(m,1h).碳谱数据(101mhz,cdcl3)δ181.27,174.87,150.06,149.53,129.46,129.20,120.83,119.63,113.72,112.96,43.63,43.16,40.88,39.07,29.55,29.28,28.97,25.79,25.74,25.71,25.58.高分辨质谱(esi)m/zcalcdforc14h21n2o+[m+h]+:233.1648,found:233.1641.
淡黄色油状液体(rf＝0.29,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ8.43–8.34(m,0.7h),7.32–7.29(m,0.5h),7.23–7.16(m,1.5h),7.00–6.65(m,3.3h),4.24–3.91(m,2h),3.16–3.01(m,3h),2.88–2.54(m,2h),2.28–2.02(m,1h),1.74–1.52(m,4h),1.46and1.44(2×s,9h).碳谱数据(101mhz,cdcl3)δ179.36,173.76,154.64,149.92,149.34,129.45,129.08,121.09,119.50,113.77,112.81,79.67,79.59,77.36,43.32,40.91,40.57,37.18,28.46,28.27,28.03,27.90.高分辨质谱(esi)m/zcalcdforc18h27n3o3na+[m+na]+:356.1945,found:356.1941
淡黄色固体(rf＝0.25,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.85–7.77(m,1.90h),7.73–7.66(m,3h),7.33–7.25(m,2h),6.96–6.82(m,2h),6.64(brs,0.24h),4.23–4.06(m,1h),3.27and3.15(2×s,3h),2.94(brs,0.28h),2.85–2.48(m,2.93h),2.38–2.28(m,1.57h),2.22–1.98(m,0.68h),1.79–1.64(m,4h).碳谱数据(101mhz,cdcl3)δ172.42,168.32,149.65,133.96,133.85,132.22,132.13,129.53,129.32,123.22,123.14,120.99,119.67,113.80,113.16,50.69,50.19,43.51,40.93,37.56,27.42,27.35,26.42,26.15.高分辨质谱(esi)m/zcalcdforc22h24n3o3+[m+h]+:378.1812,found:378.1809.
白色固体(rf＝0.42,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ8.36(s,0.5h),7.31–7.08(m,5.5h),7.07–6.87(m,2.5h),6.86–6.68(m,2.5h),3.10and3.00(2×s,3h),2.60–2.26(m,1.7h),1.82–1.47(m,1.8h),1.22–1.11(m,0.9h).碳谱数据(101mhz,cdcl3)δ171.57,149.81,149.67,149.48,140.73,140.58,140.19,130.19,129.43,129.36,129.17,128.56,128.43,128.37,127.33,126.88,126.54,126.47,126.43,126.29,126.21,126.15,120.77,120.67,119.58,113.91,113.66,113.05,42.29,40.69,29.81,26.46,26.05,25.12,24.24,20.93,20.26,16.76,16.43,16.36.高分辨质谱(esi)m/zcalcdforc17h19n2o+[m+h]+:267.1492,found:267.1489.
淡黄色油状液体(rf＝0.33,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ8.17(s,0.5h),7.32–7.24(m,1h),7.24–7.15(m,1h),7.13–7.05(m,0.5h),6.98–6.88(m,0.5h),6.85–6.78(m,1.5h),6.77–6.69(m,1h),3.52–3.29(m,2h),3.09and3.05(2×s,3h),2.42–2.31(m,0.8h),2.17–2.08(m,0.8h),1.86–1.73(m,2h),1.68–1.51(m,2h),1.48–1.35(m,2h).碳谱数据(101mhz,cdcl3)δ177.97,172.06,149.49,149.32,129.38,129.06,120.65,119.50,113.35,112.89,42.39,40.62,33.86,33.79,33.70,32.43,32.35,30.84,27.83,27.73,24.55,23.47.高分辨质谱(esi)m/zcalcdforc13h20brn2o+[m+h]+:299.0754,found:299.0747.无色油状液体(rf＝0.35,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.73–7.60(s,0.5h),7.39–7.22(m,2h),7.00–6.94(m,0.5h),6.92–6.80(m,3h),5.96–5.77(m,1h),5.20–4.96(m,2h),3.13and3.12(2×s,3h),2.59–2.31(m,4h).碳谱数据(101mhz,cdcl3)δ177.45,171.24,149.61,149.31,137.34,136.81,129.54,129.25,120.86,119.95,116.26,115.51,113.51,113.15,42.60,41.00,33.87,29.55,28.43.高分辨质谱(esi)m/zcalcdforc12h17n2o+[m+h]+:205.1335,found:205.1335.
白色固体(rf＝0.50,dcm/meoh＝20:1)氢谱数据(400mhz,cdcl3)δ7.30–7.18(m,2h),6.82–6.68(m,3h),5.93(s,1h),4.09–3.97(m,1h),3.42–3.26(m,2h),2.98(s,3h),2.49–2.18(m,3h),1.84–1.72(m,1h).碳谱数据(101mhz,cdcl3)δ177.97,149.42,129.47,129.45,117.57,112.82,59.07,53.06,39.57,29.95,29.82,24.71.
淡黄色油状液体(rf＝0.57,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.34–7.20(m,2.5h),6.94(t,j＝7.3hz,0.5h),6.88–6.77(m,3h),5.40–5.29(m,2h),3.18and3.15(2×s,3h),2.41–2.31(m,1h),2.22(t,j＝7.6hz,1h),2.07–1.96(m,4h),1.75–1.56(m,2h),1.38–1.20(m,28h),0.88(t,j＝6.6hz,3h).碳谱数据(101mhz,cdcl3)δ178.45,172.09,149.67,149.41,130.05,130.02,129.50,129.25,120.74,119.87,113.44,113.09,42.54,40.96,34.66,32.04,31.22,29.91,29.83,29.75,29.70,29.65,29.61,29.52,29.49,29.45,27.34,25.71,24.54,22.82,14.26.高分辨质谱(esi)m/zcalcdforc29h51n2o+[m+h]+:443.3996,found:443.3989.
棕色油状液滴.(rf＝0.30,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.65(s,0.5h),7.36–7.17(m,2h),6.96–6.90(m,1h),6.88–6.73(m,2.5h),3.14and3.13(2×s,3h),2.39(q,j＝7.8hz,1h),2.27–2.12(m,3h),2.00–1.86(m,1h),1.86–1.65(m,2h),1.67–1.45(m,2h).碳谱数据(101mhz,cdcl3)δ177.91,171.72,149.61,149.38,129.50,129.22,120.78,119.79,113.44,113.04,84.16,84.11,77.48,77.16,76.84,68.85,68.62,42.53,40.86,30.66,28.15,28.03,24.67,23.55,18.29,18.26.高分辨质谱(esi)m/zcalcdforc14h19n2o+[m+h]+:231.1492,found:231.1486.
淡黄色油状液体(rf＝0.33,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.38(s,0.5h),7.32–7.19(m,2h),6.94–6.88(m,0.5h),6.87–6.76(m,3h),3.15and3.14(2×s,3h),2.58–2.40(m,1h),2.33(t,j＝7.4hz,1h),2.26–2.12(m,2h),1.89–1.81(m,1h),1.80–1.74(m,2h),1.70–1.65(m,2h).碳谱数据(101mhz,cdcl3)δ177.74,171.53,149.61,149.39,129.50,129.27,120.74,119.90,113.46,113.08,42.40,40.94,33.15,29.93,24.60,23.67,18.39,18.30,3.62,3.52.高分辨质谱(esi)m/zcalcdforc14h19n2o+[m+h]+:231.1492,found:231.1487.
淡黄色油状液体(rf＝0.19,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.88–7.79(m,2h),7.75–7.66(m,2h),7.34–7.22(m,2.4h),6.96–6.90(m,0.6h),6.88–6.74(m,3h),3.75–3.61(m,2h),3.18and3.16(2×s,3h),2.44–2.20(m,2h),1.83–1.62(m,4h),1.49–1.32(m,2h).碳谱数据(101mhz,cdcl3)δ177.97,168.63,168.56,149.64,149.38,134.08,134.00,132.28,132.23,129.56,129.29,123.36,123.31,120.81,119.93,113.46,113.09,42.59,40.99,37.98,37.80,34.35,31.02,29.84,28.55,28.37,26.80,26.56,25.03,24.06.高分辨质谱(esi)m/zcalcdforc21h24n3o3+[m+h]+:366.1812,found:366.1811.
棕色油状液体.(rf＝0.29,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.58–7.49(m,0.5h),7.32–7.26(m,1h),7.24–7.19(m,1h),7.10–7.04(m,1h),7.04–6.99(m,1h),6.96–6.90(m,1h),6.86–6.81(m,1h),6.80–6.75(m,1h),6.65–6.52(m,2h),3.72–3.54(m,8h),3.12and3.09(2×s,3h),2.64–2.49(m,2h),2.43–2.34(m,1h),2.25–2.16(m,1h),2.02–1.84(m,2h).碳谱数据(101mhz,cdcl3)δ178.08,171.92,149.56,149.34,144.40,144.24,130.81,130.45,129.75,129.68,129.41,129.15,120.64,119.68,113.39,112.97,112.18,112.13,53.58,42.42,40.77,40.59,34.15,33.65,30.48,27.30,26.20.高分辨质谱(esi)m/zcalcdforc21h28cl2n3o+[m+h]+:408.1604,found:408.1596.
淡黄色油状液体(rf＝0.34,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ8.00–7.82(m,0.4h),7.13–6.90(m,2.5h),6.81(t,j＝7.4hz,0.6h),6.77–6.61(m,1.5h),3.54–3.46(m,2h),3.44–3.14(m,2h),2.92–2.65(m,2h),2.40(t,j＝6.6hz,1h),2.26–1.96(m,3h),1.86–1.66(m,3h).碳谱数据(101mhz,cdcl3)δ177.79,171.58,145.61,145.38,129.51,129.24,127.22,126.97,123.87,123.10,120.53,119.25,112.81,112.36,53.17,51.43,44.65,44.60,33.34,32.13,31.96,30.19,27.02,26.73,22.83,22.45,22.20,21.78.高分辨质谱(esi)m/zcalcdforc14h20cln2o+[m+h]+:267.1259,found:267.1251.
棕色油状液体(rf＝0.38,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.71–7.49(2×s,0.5h),7.29–7.09(m,5h),7.09–6.86(m,2.5h),6.82–6.58(m,2h),5.54–5.20(m,2h),3.45–3.07(m,2h),2.87–2.53(m,4h),2.44–2.22(m,3h),2.18–1.91(m,5h),1.72–1.54(m,2h).碳谱数据(101mhz,cdcl3)δ178.25,171.88,145.64,145.38,141.95,141.92,130.52,130.31,129.99,129.94,129.76,129.57,129.50,129.40,129.14,128.54,128.50,128.41,128.26,128.21,127.15,126.90,125.79,125.74,125.69,123.71,123.68,122.97,120.36,119.11,112.86,112.35,53.06,51.36,51.33,36.01,35.87,35.84,34.40,34.11,33.62,33.36,32.05,31.86,30.50,30.25,29.20,29.14,27.01,26.80,26.71,26.69,25.26,25.11,24.33,24.19,22.40,22.16.高分辨质谱(esi)m/zcalcdforc23h29n2o+[m+h]+:349.2274,found:349.2272.
淡黄色油状液体(rf＝0.14,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ8.13and8.05(m,1h),7.58and7.53(2×d,j＝7.8hz,1h),7.33–7.27(m,1h),7.21–6.54(m,8h),4.37–4.05(m,2h),3.49–3.07(m,2h),2.93–2.68(m,2h),2.52–2.37(m,1h),2.29–2.18(m,1h),2.13–1.99(m,2h).碳谱数据(101mhz,cdcl3)δ178.15,172.14,145.05,144.77,136.48,134.95,134.88,127.52,122.42,122.08,122.00,121.82,121.65,121.62,121.54,121.30,119.34,119.27,118.94,118.90,116.88,116.84,115.62,115.28,114.31,114.05,111.37,111.25,65.02,64.92,51.17,49.86,33.97,30.95,25.92,25.01,24.74,24.63.高分辨质谱(esi)m/zcalcdforc20h22n3o2+[m+h]+:336.1707,found:336.1704.
浅黄色固体.(rf＝0.21,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.75and7.38(brs×2,1h),7.31–6.80(m,14h),3.38–3.21(m,1h),3.00–2.76(m,1h),2.73–2.34(m,8h),2.14–1.52(m,4h),1.24(s,1h).碳谱数据(101mhz,cdcl3)δ176.38,171.03,150.73,149.66,140.49,140.21,133.28,132.88,130.54,129.45,128.50,128.28,127.13,126.76,126.25,125.98,123.47,122.62,116.92,115.81,61.02,59.00,40.20,40.09,39.88,39.10,38.14,37.66,35.64,35.01,34.87,29.81,29.33,25.55,25.27.高分辨质谱(esi)m/zcalcdforc27h31n2o+[m+h]+:399.2431,found:399.2428.
白色固体(rf＝0.24,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.86(s,0.53h),7.82–7.62(m,4h),7.35–7.28(m,0.51h),7.21–7.12(m,0.46h),7.06–6.92(m,2h),6.90–6.81(m,0.72h),6.80–6.68(m,1h),6.66–6.60(m,1h),5.06–4.73(m,1h),3.25–2.91(m,4h),2.84–2.65(m,0.8h),1.97(s,0.34h),1.49and1.43(2×d,j1＝j2＝8.0hz,3h).碳谱数据(101mhz,cdcl3)δ175.22,169.02,168.36,149.12,134.12,133.92,132.02,129.51,128.97,123.31,123.17,120.87,119.62,113.59,112.97,44.34,42.74,42.39,40.54,38.02,35.14,19.10,19.00.高分辨质谱(esi)m/zcalcdforc19h20n3o3+[m+h]+:338.1499,found:338.1498.
白色固体(rf＝0.19,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ8.29(s,0.6h),7.87–7.55(m,4h),7.21–6.99(m,2.4h),6.89–6.66(m,3h),3.79–3.44(m,2h),3.15–2.93(m,3h),2.54–2.04(m,3h),1.84–1.58(m,1h),1.31–1.09(m,2h),0.99–0.74(m,6h).碳谱数据(101mhz,cdcl3)δ170.69,168.88,168.68,149.48,149.35,134.04,133.82,131.93,131.90,131.81,129.19,128.93,123.22,123.07,123.04,120.38,119.33,113.50,113.25,112.96,42.46,42.11,41.98,41.90,41.76,41.44,40.49,37.45,33.29,31.75,25.20,25.17,22.84,22.81,22.67,22.47,22.31.高分辨质谱(esi)m/zcalcdforc23h28n3o3+[m+h]+:394.2125,found:394.2125.
白色固体(rf＝0.20,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.94(s,0.64h),7.87–7.77(m,2h),7.74–7.66(m,2h),7.49(s,0.40h),7.28–7.19(m,2h),6.97–6.79(m,3h),4.66(q,j＝8.0hz,1h),3.81(t,j＝4.0hz,1h),3.74–3.66(m,3h),3.62(s,1h),2.54–2.29(m,2h),2.19–1.87(m,2h),1.60–1.55(m,3h).碳谱数据(101mhz,cdcl3)δ177.09,174.44,171.97,168.54,148.12,134.07,133.90,132.04,132.01,129.55,129.29,123.31,123.16,121.97,121.07,114.81,114.15,59.21,57.50,52.19,37.48,37.42,31.58,28.43,24.90,23.33,15.90,15.74.高分辨质谱(esi)m/zcalcdforc22h24n3o5+[m+h]+:410.1710,found:410.1709.
浅黄色固体.(rf＝0.14,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ8.28(s,0.62h),7.92–7.66(m,4h),7.65–7.31(m,0.67h),7.25–7.14(m,1.56h),6.93–6.71(m,2.46h),4.71–4.09(m,3h),3.93–3.39(m,7h),2.67–1.64(m,7h),1.39–1.07(m,3h),1.03–0.79(m,6h).碳谱数据(101mhz,cdcl3)δ175.95,172.33,172.28,170.92,169.02,168.89,168.69,168.25,149.03,148.25,134.17,133.97,132.12,129.40,129.17,129.12,123.33,123.28,120.37,113.78,113.60,113.44,58.92,58.81,58.74,53.43,52.83,52.35,46.35,46.25,42.36,41.89,41.73,37.78,33.48,33.42,31.59,31.40,28.97,28.92,25.43,25.34,24.96,23.04,22.96,22.59,22.53,22.45,22.23.高分辨质谱(esi)m/zcalcdforc30h37n4o6+[m+h]+:549.2708,found:549.2703.
白色固体(rf＝0.1,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ8.58and8.11(2×s,0.71h),7.88–7.55(m,6.52h),7.07–6.88(m,1.35h),6.72(t,j＝8.0hz,0.56h),6.59(d,j＝4.0hz,1h),5.30(t,j＝4.0hz,1h),5.01–4.74(m,1h),4.63(q,j＝8.0hz,0.48h),4.47–4.26(m,1.52h),3.79–3.66(m,1h),3.63–3.51(m,3h),3.45–3.34(m,1.48h),3.25–3.13(m,0.57h),2.84–1.89(m,4h),1.52and1.47(2×d,j1＝j2＝8.0hz,3h),1.40and1.34(2×d,j1＝j2＝8.0hz,3h).碳谱数据(101mhz,cdcl3)δ174.84,172.87,172.52,172.42,170.23,168.59,168.28,168.11,158.13,149.23,147.85,133.91,133.76,129.36,128.88,123.20,122.98,121.76,120.65,115.23,114.04,58.93,57.44,56.24,52.32,52.05,47.75,46.81,46.71,44.09,42.98,42.80,37.63,34.59,29.65,28.81,24.89,18.97,18.87,15.85,14.86,14.60.高分辨质谱(esi)m/zcalcdforc27h31n4o6+[m+h]+:507.2238,found:507.2237.
(74.5mg,0.41mmol)aspaleyellowoilin92％yield.氢谱数据(400mhz,cdcl3)δ7.26(d,j＝8.0hz,1h),7.19(td,j＝7.7,1.6hz,1h),7.08(dd,j＝7.4,1.5hz,1h),6.89(td,j＝7.3,1.3hz,1h),3.65(br,2h),3.18–3.10(m,2h),2.81–2.73(m,2h),1.83(p,j＝5.8hz,2h),
1.61–1.51(m,2h).碳谱数据(101mhz,cdcl3)δ153.56,133.53,130.05,126.78,121.95,115.48,63.13,35.08,29.61,25.47.
白色固体(rf＝0.40,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.12(d,j＝7.5hz,1h),7.04(dd,j＝7.3,1.2hz,1h),6.96(t,j＝7.5hz,1h),5.71(t,j＝7.0hz,1h),4.17(qt,j＝6.8,3.5hz,2h),3.41(d,j＝11.6hz,1h),2.97–2.85(m,2h),2.80–2.73(m,2h),2.64(dd,j＝14.9,8.2hz,1h),2.25(s,3h),2.07–1.95(m,3h),1.31–1.20(m,4h).碳谱数据(101mhz,cdcl3)δ172.91,170.14,149.54,130.78,129.24,128.93,124.15,121.12,60.89,60.85,58.25,43.39,34.33,29.94,26.74,21.17,14.31.高分辨质谱(esi)m/zcalcdforc17h23n2o3+[m+h]+:303.1703,found:303.1702.
淡黄色油状液体(rf＝0.50,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.55(dd,j＝8.0,1.0hz,1h),7.18–7.13(m,1h),7.06(dd,j＝8.1,7.0hz,1h),4.43–4.36(m,2h),4.18(q,j＝7.2hz,2h),3.99(s,2h),3.17–3.11(m,2h),2.21–2.12(m,2h),2.07–1.97(m,2h),1.29–1.23(m,3h).碳谱数据(101mhz,cdcl3)δ170.51,138.91,126.59,125.60,124.67,120.62,117.95,61.26,54.32,35.87,33.75,29.84,28.56,27.56,14.33.高分辨质谱(esi)m/zcalcdforc15h19n2o2+[m+h]+:259.1441,found:259.1442.
浅黄色固体(rf＝0.86,hexane/acetone＝3:1)氢谱数据(400mhz,cdcl3)δ7.33(d,j＝7.7hz,1h),6.99(t,j＝7.4hz,1h),6.92(d,j＝7.1hz,1h),4.02–3.94(m,2h),3.17–3.08(m,2h),2.78–2.65(m,4h),2.18–2.10(m,2h),2.09–2.01(m,2h),2.01–1.92(m,2h),1.91–1.83(m,2h).碳谱数据(101mhz,cdcl3)δ137.21,136.61,128.85,126.43,121.70,119.00,115.42,110.54,46.07,34.81,29.55,27.80,23.63,23.25,22.85,21.30.高分辨质谱(esi)m/zcalcdforc16h20n+[m+h]+:226.1590,found:226.1589.
白色固体(rf＝0.15,hexane/acetone＝3:1).氢谱数据(400mhz,cdcl3)δ8.95(s,1h),7.46–7.20(m,5h),3.37(s,3h),2.01(s,3h).碳谱数据(101mhz,cdcl3)δ169.03,154.81,129.27,127.19,125.92,19.59高分辨质谱(esi)m/zcalcdforc10h13n2o3+[m+h]+:209.0921,found:209.0918.
以上仅是本发明的优选实施方式，应当指出的是，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的发明内容。