1H-1,2,4-三唑脒类化合物及其制备方法和应用转让专利
申请号 : CN201610608404.8
文献号 : CN106349236B
文献日 : 2018-11-16
发明人 : 覃兆海 , 贾长青 , 马永强 , 杨冬燕 , 车传亮 , 刘雪莲
申请人 : 中国农业大学
摘要 :
权利要求 :
1.1H-1,2,4-三唑脒类化合物,其特征在于,所述化合物的结构通式为 其
中,R1为氢、C1~C10饱和或不饱和脂肪烃基、取代或未取代的苯基、取代或未取代的吡啶基、取代或未取代的噻唑基、取代或未取代的呋喃基、取代或未取代的萘基;其中,所述取代苯基中的取代基为卤素、羟基、氨基、C1~C5烷基、C1~C5烷氧基、C1~C5氟代烷基或C1~C5氟代烷氧基、芳基、芳氧基;所述取代吡啶基中的取代基为卤素、C1~C5烷基、C1~C5烷氧基、C1~C5氟代烷基或C1~C5氟代烷氧基、芳氧基;所述取代呋喃基中的取代基为卤素、三氟甲基;所述取代萘基中的取代基为C1~C5烷基、羟基、硝基、卤素、氨基;
R2为氢、C1~C10饱和或不饱和脂肪烃基、C1~C10饱和或不饱和脂肪烃基、取代或未取代的苄基、取代或未取代的吡啶甲基、取代或未取代的噻唑甲基、取代或未取代的吡唑甲基、取代或未取代的恶唑甲基、取代或未取代的异恶唑甲基、或四氢呋喃甲基;其中,所述取代苄基、取代吡啶甲基、取代噻唑甲基、取代吡唑甲基、取代恶唑甲基和取代异恶唑甲基中的取代基可独立地选自下述基团中的任意一种或几种:卤素、氨基、羟基、C1~C5烷基、C1~C5烷氧基、C1~C5氟代烷基和C1~C5氟代烷氧基;
R3为氢、C1~C10饱和或不饱和脂肪烃基、取代或未取代的苯基、取代或未取代的吡啶基、取代或未取代的呋喃基、取代或未取代的萘基;其中,所述取代苯基中的取代基可为卤素、羟基、氨基、C1~C5烷基、C1~C5烷氧基、C1~C5氟代烷基或C1~C5氟代烷氧基、芳基、芳氧基;
所述的1H-1,2,4-三唑脒类化合物用作杀虫剂。
2.根据权利要求1所述的1H-1,2,4-三唑脒类化合物,其特征在于,R1为乙烯基、乙炔基、氯代吡啶基、氯代噻唑基、四氢呋喃-3-基;R2为C1~C10不饱和脂肪烃基、卤代吡啶甲基、卤代噻唑甲基、四氢呋喃甲基。
3.根据权利要求1所述的1H-1,2,4-三唑脒类化合物,其特征在于,R1为氢、卤代苯基、C3~C7饱和或不饱和脂肪烃基;R2为氢、取代苯基、C1~C7饱和或不饱和脂肪烃基;R3为甲基、乙基、苄基、取代苯基、取代或未取代的吡啶基。
4.权利要求1-3任一项所述的1H-1,2,4-三唑脒类化合物的制备方法,其特征在于,具体步骤为:
将化合物I溶于溶剂,搅拌下使之完全溶解,加入化合物III,室温下搅拌3~6h,反应液浓缩后纯化,得到所述1H-1,2,4-三唑脒类化合物。
5.根据权利要求4所述的制备方法,其特征在于,溶解化合物I的溶剂包括乙腈、N,N-二甲基乙酰胺、氯苯、四氢呋喃中的一种。
6.根据权利要求1所述的1H-1,2,4-三唑脒类化合物,其特征在于,所述1H-1,2,4-三唑脒类化合物用于杀灭蚜虫。
说明书 :
1H-1,2,4-三唑脒类化合物及其制备方法和应用
技术领域
背景技术
发明内容
具体实施方式
0.02mol,0.24g)加入完毕后,室温下搅拌3h,TLC检测反应完全后,停止搅拌,反应液减压浓缩后,用V乙酸乙酯:V石油醚=1:4快速柱层析,得淡黄色油状物0.50g,产率91%。1H NMR(CDCl3,
300MHz)δ8.49(s,1H,CH),8.07~8.03(m,2H,Ph),7.41~7.28(m,3H,Ph),4.17(d,J=
7.2Hz,2H,CH2),3.02(s,3H,CH3),3.01(s,3H,CH3),1.89~1.79(m,2H,CH2),1.42~1.25(m,
2H,CH2),0.94(t,J=7.50Hz,3H,CH3);13C NMR(CDCl3,75MHz)δ158.8,158.3,156.6,132.1,
128.1,128.1,125.7,45.6,40.2,34.1,31.4,19.5,13.4;HRMS calcd for C15H21N5(M+H)+
272.1870,found 272.1870.
22.8,11.1;HRMS calcd for C14H18N6O2(M+H)+303.1564,found 303.1560.
139.7,136.2,42.0,40.5,34.5,28.6,21.5.HRMS(ESI)m/z calcd for C12H17ClN6S(M+H)+
313.0997,found 313.1000。化合物II-3.收率85%,1H NMR(300MHz,CDCl3)δ:8.44(s,1H,CH),7.68~7.05(m,4H,Ph),4.08~4.01(m,2H,CH2),3.77(s,3H,OCH3),3.11(s,3H,CH3),
3.01(s,3H,CH3),1.30(t,J=7.20Hz,3H,CH3).13C NMR(75MHz,CDCl3)δ:157.5,157.1,
156.9,156.2,130.3,129.5,121.8,120.0,112.1,55.6,40.1,34.1,14.7.HRMS(ESI)m/z calcd for C14H19N5O(M+H)+274.1662,found 274.1664.
157.3,156.9,133.1,130.7,129.6,121.8,120.3,117.3,112.4,55.9,48.7,40.3,
34.3.HRMS(ESI)m/z calcd for C15H19N5O(M+H)+286.1662,found 286.1665.[0029] 化合物II-5.收率86%,1H NMR(300MHz,CDCl3)δ:8.51(s,1H,CH),7.78~7.26(m,
4H,Ph),4.22~4.15(m,2H,CH2),3.09(s,3H,CH3),3.08(s,3H,CH3),1.44(t,J=7.20Hz,3H,
13
CH3). C NMR(75MHz,CDCl3)δ:157.9,157.1,132.8,131.4,130.3,129.4,126.4,41.3,
40.5,34.3,31.8,22.6,14.7,14.0.HRMS(ESI)m/z calcd for C13H16ClN5(M+H)+278.1167,found 278.1169.
157.0,156.8,132.6,131.4,131.1,130.1,129.2,126.3,45.7,40.3,34.2,31.4,19.5,
13.5.HRMS(ESI)m/z calcd for C15H20ClN5(M+H)+306.1480,found 306.1478.[0031] 化合物II-7.收率83%,1H NMR(300MHz,CDCl3)δ:8.46(s,2H,CH),7.82~7.37(m,
4H,Ph),6.02~5.91(m,1H,=CH),5.20~5.06(m,2H,CH2=),4.70~4.68(m,2H,CH2),3.12(s,2H,CH3),3.01(s,3H,CH3).13C NMR(75MHz,CDCl3)δ:158.5,157.4,156.5,133.6,131.5,
131.1,130.4,129.9,126.9,117.2,48.0,40.3,34.2.HRMS(ESI)m/z calcd for C14H16ClN5(M+H)+290.1167,found 290.1168.
156.8,154.5,149.1,131.2,130.1,128.7,125.9,123.1,45.7,40.3,34.1,31.2,19.4,
13.3.HRMS(ESI)m/z calcd for C15H20N6O2(M+H)+317.1721,found 317.1724.[0033] 化合物II-9.收率87%,1H NMR(300MHz,DMSO)δ:8.37(s,1H,CH),7.93~7.57(m,
4H,Ph),6.00~5.88(m,1H,=CH),5.18~5.02(m,2H,CH2=),4.67~4.65(m,2H,CH2),3.11(s,3H,CH3),3.01(s,3H,CH3).13C NMR(75MHz,DMSO)δ:159.1,157.4,154.2,148.9,133.3,
131.9,129.8,124.9,123.5,117.2,48.1,40.3,34.3.HRMS(ESI)m/z calcd for C14H16N6O2+
(M+H) 301.1408,found 301.1411.
14.7.HRMS(ESI)m/z calcd for C13H16ClN5(M+H)+278.1167,found 278.1168.[0035] 化合物II-11.收率82%,1H NMR(300MHz,CDCl3)δ:8.48(s,1H,CH),7.95~7.45(m,
4H,Ph),3.99(t,J=6.9Hz,2H,CH2),3.12(s,3H,CH3),3.01(s,3H,CH3),1.80~1.73(m,2H,CH2),0.84(t,J=7.20Hz,3H,CH3).13C NMR(75MHz,CDCl3)δ:159.2,157.2,156.5,133.0,
131.1,128.6,127.1,47.2,34.1,22.5,11.1.HRMS(ESI)m/z calcd for C14H18ClN5(M+H)+
292.1323,found 292.1326.
157.6,156.8,134.1,130.8,128.4,127.2,45.8,40.5,34.3,31.5,19.7,13.5.HRMS(ESI)m/z calcd for C15H20ClN5(M+H)+306.1480,found 306.1479.
13
(s,3H,CH3),3.07(s,3H,CH3). C NMR(75MHz,CDCl3)δ:159.0,158.0,156.9,134.2,132.8,
130.6,128.4,127.2,117.4,48.6,40.5,34.4.HRMS(ESI)m/z calcd for C14H16ClN5(M+H)+
290.1167,found 290.1169.
7.20Hz,3H,CH3).13C NMR(75MHz,CDCl3)δ:159.0,156.9,156.5,147.5,138.4,126.3,
123.7,41.5,40.6,34.4,14.6.HRMS(ESI)m/z calcd for C13H16N6O2(M+H)+289.1408,found
289.1404.
156.9,156.5,147.5,138.4,126.3,123.7,46.1,40.6,34.4,31.5,19.7,13.5.HRMS(ESI)m/z calcd for C15H20N6O2(M+H)+317.1721,found 317.1721.
132.6,126.4,123.6,117.4,48.8,40.6,34.4.HRMS(ESI)m/z calcd for C14H16N6O2(M+H)+
301.1408,found 301.1411.
156.7,128.5,128.4,127.7,127.6,115.3,115.0,41.2,40.5,34.3,14.7.HRMS(ESI)m/z +
calcd for C13H16FN5(M+H) 262.1463,found 262.1461.
161.4,159.0,157.7,156.7,128.5,128.4,127.7,127.6,115.3,115.0,47.8,40.5,34.3,
22.9,11.1.HRMS(ESI)m/z calcd for C14H18FN5(M+H)+276.1619,found 276.1618.[0043] 化合物II-20.收率87%,1H NMR(300MHz,CDCl3)δ:8.50(s,1H,CH),8.04~7.99(m,
2H,Ph),7.10~7.04(m,2H,Ph),4.10(t,J=6.90Hz,2H,CH2),3.11(s,3H,CH3),3.07(s,3H,CH3),1.88~1.78(m,2H,CH2),1.39~1.29(m,2H,CH2),0.94(t,J=7.20Hz,3H,CH3);13C NMR(75MHz,CDCl3)δ:164.6,161.4,158.9,157.8,156.7,128.5,128.5,127.7,127.6,115.3,
115.0,45.8,40.5,34.3,31.5,19.7,13.5.HRMS(ESI)m/z calcd for C15H20FN5(M+H)+
290.1776,found 290.1774.
161.4,159.0,158.0,156.8,132.9,128.3,128.3,127.7,127.6,117.3,115.2,114.9,48.5,
40.5,34.3.HRMS(ESI)m/zcalcd for C14H16FN5(M+H)+274.1463,found 274.1464.[0045] 化合物II-22.收率83%,1H NMR(300MHz,CDCl3)δ:8.51(s,1H,CH),7.98~7.96(m,
2H,Ph),6.93~6.90(m,2H,Ph),4.15(q,J=7.20Hz,2H,CH2),3.11(s,3H,CH3),3.08(s,3H,CH3),1.42(t,J=7.20Hz,3H,CH3);13C NMR(75MHz,CDCl3)δ:159.9,158.5,158.3,156.7,
127.2,125.0,113.7,55.2,41.8,40.5,34.3,14.7.HRMS(ESI)m/z calcd for C14H19N5O(M++
H) 274.1662,found 274.1664.
158.8,158.4,156.6,127.2,125.0,113.6,55.1,47.7,40.4,34.2,22.9,11.1.HRMS(ESI)m/z calcd for C15H21N5O(M+H)+288.1819,found 288.1820.
31.5,19.6,13.5.HRMS(ESI)m/z calcd for C16H23N5O(M+H) 302.1975,found 302.1973.[0048] 化合物II-25.收率83%,1H NMR(300MHz,CDCl3)δ:8.51(s,1H,CH),8.00~7.95(m,
2H,Ph),6.94~6.90(m,2H,Ph),6.06~5.97(m,1H,=CH),5.23~5.17(m,CH2=),4.75~
4.72(m,2H,CH2),3.10(s,3H,CH3),3.07(s,3H,CH3);13C NMR(75MHz,CDCl3)δ:159.9,158.8,
158.7,156.8,133.0,127.3,124.9,117.2,113.6,55.1,48.5,40.5,34.3.HRMS(ESI)m/z calcd for C15H19N5O(M+H)+286.1662,found 286.1661.
13
CH2),1.40(t,3H,CH3),1.24(s,3H,CH3);C NMR(75MHz,CDCl3)δ:162.8,160.3 155.7,
153.6,129.1,128.4,116.0,48.8,42.5,38.8,15.0,12.8.HRMS(ESI)m/z calcd for C14H18FN5(M+H)+276.1619,found 276.1615.
160.1,153.4,153.2,136.4,129.1,128.5,128.1,127.9,127.0,116.0,49.0,57.3,38.4,
23.3,11.2.HRMS(ESI)m/z calcd for C20H22FN5(M+H)+352.1932,found 352.1927.[0051] 化合物II-28.收率81%,1H NMR(300MHz,CDCl3)δ:8.52(s,1H,CH),8.12(d,2H,Ph),7.55(d,2H,Ph),7.37~6.96(m,4H,Ph),4.26(s,2H,CH2),3.97(t,2H,CH2),3.04(s,3H,CH3),1.38(t,3H,CH3);13C NMR(75MHz,CDCl3)δ:160.1,153.4,153.2,134.5,134.3,132.6,
130.6,130.3,129.3,128.9,128.6,42.8,38.4,15.0.HRMS(ESI)m/z calcd for C19H19Cl2N5(M+H)+388.1090,found 388.1089.
23.3,11.2.HRMS(ESI)m/z calcd for C19H20Cl2N6(M+H) 403.1199,found 403.1196.[0053] 实施例3:II系列化合物的杀虫活性测定