[0041] 下面结合具体实施例对本发明做进一步的描述。
[0042] 实施例1~15
[0043] 按照表1的原料配比在35mL的Schlenk管中加入单质碘、过氧化叔丁醇(TBHP,70%的水溶液)、腙(II)、脂肪胺(III)和有机溶剂1mL,混合搅拌均匀,按照表2的反应条件反应完成后,过滤,硅胶拌样,经过柱层析纯化得到相应的1,3,5-三取代的1,2,4-三氮唑化合物(Ⅰ),反应过程如下式所示:
[0044]
[0045] 表1实施例1~11的原料加入量
[0046]
[0047]
[0048] 表2
[0049]
[0050] 表1和表2中,T为反应温度,t为反应时间,Ph为苯基,OMe为甲氧基,n-Bu为正丁基。
[0051] 部分化合物的结构确认数据:
[0052] 由实施例1制备得到的1,2,4-三氮唑化合物(I-1)的核磁共振(1H NMR和13C NMR)检测数据为:
[0053]
[0054] 1H NMR(CDCl3,400MHz)δ8.19(d,2H,J=8.0Hz),7.56(d,2H,J=8.0Hz),7.33-7.4213
(m,8H),7.00(d,2H,J=8.78Hz),3.86(s,3H). C NMR(CDCl3,100MHz)δ161.7,160.6,
154.5,138.2,129.9,129.3,128.9,128.7,128.5,128.0,128.0,125.3,123.4,113.9,
55.2.HRMS(EI-TOF)calcd for C21H18N3O(M+H+):328.1450found:328.1455。
[0055] 由实施例2制备得到的1,2,4-三氮唑化合物(I-2)的核磁共振(1H NMR和13C NMR)检测数据为:
[0056]
[0057] 1H NMR(CDCl3,400MHz)δ7.48(d,2H,J=7.2Hz),7.32-7.40(m,8H),2.74(s,2H),13
1.09(s,9H). C NMR(CDCl3,100MHz)δ158.9,154.6,138.3,129.7,129.3,128.9,128.5,
128.5,128.1,125.3,41.9,31.4,29.6.HRMS(EI-TOF)calcd for C19H22N3(M+H+):292.1814,found:292.1833.
[0058] 由实施例3制备得到的1,2,4-三氮唑化合物(I-3)的核磁共振(1H NMR和13C NMR)检测数据为:
[0059]
[0060] 1H NMR(CDCl3,400MHz)δ8.18(d,2H,J=6.8Hz),7.51(d,2H,J=7.6Hz),7.28-7.41(m,6H),7.23(d,2H,J=8.0Hz),7.16(d,2H,J=8.4Hz).13C NMR(CDCl3,100MHz)δ161.7,154.6,138.9,135.8,130.7,129.9,129.9,129.3,128.9,128.5,128.5,128.0,126.5,+
125.2,21.1.HRMS(EI-TOF)calcd for C21H18N3(M+H):312.1501,found:312.1503.[0061] 由实施例4制备得到的1,2,4-三氮唑化合物(I-4)的核磁共振(1H NMR和13C NMR)检测数据为:
[0062]
[0063] 1H NMR(CDCl3,400MHz)δ8.24(dd,2H,J=8.0Hz,1.6Hz),7.43-7.47(m,10H),7.16(d,2H,J=8.0Hz),2.37(s,3H).13C NMR(CDCl3,100MHz)δ161.8,154.8,140.3,138.4,130.7,129.4,129.3,129.0,128.9,128.8,128.5,126.6,125.5,125.0,21.4.HRMS(EI-TOF)calcd for C21H18N3(M+H+):312.1501,found:312.1518.
[0064] 由实施例5制备得到的1,2,4-三氮唑化合物(I-5)的核磁共振(1H NMR和13C NMR)检测数据为:
[0065]
[0066] 1H NMR(CDCl3,400MHz)δ8.11(d,2H,J=8.0Hz),7.31-7.46(m,8H),2.75(t,2H,J=8.0Hz),1.66-1.72(m,2H),1.26-1.32(m,2H),0.81(t,3H,J=7.4Hz).13C NMR(CDCl3,
100MHz)δ161.3,157.0,137.5,130.9,129.3,129.1,128.8,128.4,126.3,125.1,30.0,
26.2,22.2,13.5.HRMS(EI-TOF)calcd for C18H20N3(M+H+):278.1657,found:278.1660。