吡蚜酮衍生物及其制备方法和在杀虫方面的应用_3

文档序号:8916233阅读:来源:国知局
(m/z) :Calcd. for C17H17N6O4[M+H]+369. 1306 ;found 369. 1311.
[0068] (E)-4-(I-(6-(3-氨基苯氧基)吡啶-3-酰基)亚乙基氨基)-6-甲基-4, 5-二 氢-1,2,4-三嗪-3 (2H)-酮(1-10)的合成
[0069] 白色固体,收率 27%,熔点 187-188°C JH NMR(400MHz,DMS0-d6) : δ 9. 97(s,1H, NH),8.60(s,lH,Py-H),8.27(d,J = 8.8Hz,lH,Py-H),7.04(t,J = 7.2Hz,lH,Ar-H), 6. 96(d,J = 8. 8Hz,lH,Py-H),6. 42(d,J = 7. 2Hz,lH,Ar-H),6. 29(s,lH,Ar-H),6. 24(d,J = 7. 2Hz,1H,Ar-H),5. 27(s,2H,NH2),4. 15(s,2H,CH2),2. 19(s,3H,CH3),I. 94(s,3H,CH3) ;13C NMR(100MHz,DMS0-d6) δ 166. 6,164. 5,154. 4,150. 2,148. 6,146. 6,145. 2,138. 0,129. 7, 127. 5,110. 6,110. 3,107. 6,105. 9, 50. 7,19. 9,16. 8. ESI-HRMS (m/z) :Calcd. for C17H19N6O2 [M+H]+339. 1564 ;found339. 1569.
[0070] (E) -6-甲基-4- (I- (6- (4-乙基苯氧基)吡啶-3-酰基)亚乙基氨基)-4, 5-二 氢-1,2,4-三嗪-3 (2H)-酮(I-Il)的合成
[0071] 白色固体,收率 59%,熔点 131-132°C JH NMR(400MHz,DMS0-d6) : δ 9. 96(s,1H, NH),8.56(s,lH,Py-H),8.29(d,J = 8.8Hz,lH,Py-H),7.27(d,J = 7.2Hz,2H,Ar-H), 7.06(t,J = 7.2Hz,3H,Ar-H,Py-H),4.15(s,2H,CH2),2.63(q,J = 6.8Hz,2H,CH2CH3), 2.18(s,3H,CH3),1.94(s,3H,CH 3),1.21(t,J = 7.6Hz,3H,CH2CH3) ;13C 匪R(100MHz, DMS0-d6) δ 166. 8, 164. 6, 151. 3, 148. 8, 146. 6, 145. 4, 140. 4, 138. 3, 129. 0, 127. 8, 121. 2, HO. 9,50. 9,27. 6,20.1 , 17. 0, 15. 7. ESI-HRMS (m/z) :Calcd. for C 19H22N502 [M +H]+352. 1768 ;found 352. 1772.
[0072] (E)-6-甲基-4-(I-(6-(4-异丙基苯氧基)吡啶-3-酰基)亚乙基氨基)-4, 5-二 氢-1,2,4-三嗪-3 (2H)-酮(1-12)的合成
[0073] 白色固体,收率 53%,熔点 128-129°C JH NMR(400MHz,DMS0-d6) : δ 9. 96(s,1H, NH),8.57(s,lH,Py-H),8.29(d,J = 8.8Hz,lH,Py-H),7.30(d,J = 8.4Hz,2H,Ar-H), 7.07(t,J = 6.8Hz,3H,Ar-H,Py-H),4. 15(s,2H,CH2),2.89-2.96(m,lH,CH(CH3)2),2. 18(s, 3H,CH3),1.94(s,3H,CH3),1.22(d,J = 6.8Hz,6H,CH(CH3)2) ;13C NMR(100MHz,DMS0-d6) δ 166. 8,164. 6,151. 4, 148. 8,146. 6,145. 4,145. 0,138. 3,127. 8,127. 5,121. 2,110. 9, 50.9,32.9,24.0,20. 1,17. 0. ESI-HRMS (m/z) :Calcd. for C20H24N5O2 [M+H]+366. 1925 ;found 366. 1930.
[0074] (E)-6-甲基-4-(I-(6-(4-叔丁基苯氧基)吡啶-3-酰基)亚乙基氨基)-4, 5-二 氢-1,2,4-三嗪-3 (2H)-酮(1-13)的合成
[0075] 白色固体,收率 86 %,熔点 183-184 °C JH NMR(400MHz,DMS0-d6) : δ 9. 97 (s, lH,NH),8.57(s,lH,Py-H),8.30(d,J = 8.8Hz,lH,Py-H),7.45(d,J = 8·8Ηζ,2Η, Ar-H),7· 08(t,J = 6. 4Hz,3H,Ar-H,Py-H),4· 15(s,2H,CH2),2· 19(s,3H,CH3),I. 94(s, 3H,CH3),I. 31 (s,9H,C(CH3)3) ;13C NMR(100MHz,DMS0-d6) δ 166. 8,164. 6,151. 1,148. 8, 147. 2,146. 6,145. 4, 138. 3,127. 8,126. 5, 120. 8,110. 9,50. 9,34. 2,31. 3, 20. 1,17. 0, ESI-HRMS(m/z) :Calcd. for C21H26N5O2[M+H]+380. 2081 ;found 380.2089.
[0076] (E)-6-甲基-4-(I-(6-(4-溴苯氧基)吡啶-3-酰基)亚乙基氨基)-4, 5-二氢-I, 2.4- 三嗪-3 (2H)-酮(1-14)的合成
[0077] 白色固体,收率 50%,熔点 204_205°C JH NMR(400MHz,DMS0-d6) : δ 9. 98(s,1H, NH),8.58(s,lH,Py-H),8.32(d,J = 8.8Hz,lH,Py-H),7.62(d,J = 8.8Hz,2H,Ar-H), 7. 16(t,J = 8. 8Hz,3H,Ar-H,Py-H),4. 15(s,2H,CH2),2. 19(s,3H,CH3),I. 94(s,3H,CH3); 13C 匪R(100MHz,DMS0-d6) δ 166. 7, 164. 0,152. 8, 148. 8, 146. 5, 145. 4, 138. 5, 132. 6, 128. 3,123. 7,117. 0, 111. 3,50. 9,20. 1,17. 0. ESI-HRMS (m/z) :Calcd. for C17H17BrN5O2 [M +H]+402. 0560 ; found 402. 0566.
[0078] (E)-6-甲基-4-(I-(6-(4-碘苯氧基)吡啶-3-酰基)亚乙基氨基)-4, 5-二氢-I, 2.4- 三嗪-3 (2H)-酮(1-15)的合成
[0079] 白色固体,收率 46%,熔点 180-181°C JH NMR(400MHz,DMS0-d6) : δ 9. 97(s,1H, NH),8.57(s,lH,Py-H),8.31(d,J = 8.8Hz,lH,Py-H),7.77(d,J = 7.6Hz,2H,Ar-H), 7. 13(d,J = 8. 8Hz,1H,Py-H),7. 02(d,J = 7. 6Hz,2H,Ar-H),4. 15(s,2H,CH2),2. 19(s, 3H,CH3),I. 94(s,3H,CH3) ;13C NMR(100MHz,DMS0-d6) δ 166. 7,163. 9,153. 4,148. 7,146. 5, 145. 3,138. 4,128. 3,123. 9, 111. 3,89. 1,50. 9, 20. 1,17. 0· ESI-HRMS (m/z) :Calcd. for C17H 17IN502 [M+H]+450. 0421 ;found 450.0416.
[0080] (E)-6-甲基-4-(I-(6-(4-(苄氧基)苯氧基)吡啶-3-酰基)亚乙基氨基)-4, 5-二氢-1,2,4-三嗪-3 (2H)-酮(1-16)的合成
[0081] 白色固体,收率 50%,熔点 149-150°C JH NMR(400MHz,DMS0-d6) : δ 9. 96(s,1H, NH),8.55(s,lH,Py-H),8.27(d,J = 8.8Hz,lH,Py-H),7.47(d,J = 7.6Hz,2H,Ar-H), 7.41(t,J = 8.8Hz,2H,Ar-H),7.34(t,J = 7.2Hz,lH,Py-H),7.02-7.11(m,5H,Ar-H), 5.12(s,2H,OCH2),4.14 (s,2H,CH2),2.18 (s,3H,CH3),1.94 (s,3H,CH3) ;13C NMR (100MHz, DMS0-d6) δ 166. 8,164. 8,155. 4,148. 8,146. 8,146. 6,145. 3,138. 2,137. 1,128. 4,127. 8, 127. 7,122. 5,115. 6, HO. 6,69. 6,50. 9,20. 1,16. 9. ESI-HRMS (m/z) :Calcd. for C24H24IN5O3 [M+H]+430. 1874 ;found 430.1881.
[0082] (E)-6_甲基-4-(1-(6-(4-苯甲酰苯氧基)吡啶-3-酰基)亚乙基氨基)-4,5_二 氢-1,2,4-三嗪-3 (2H)-酮(1-17)的合成
[0083] 白色固体,收率 21%,熔点 173-174°C JH NMR(400MHz,DMS0-d6) : S9.97(s,lH, NH) ,8. 64(s, 1H, Py-H), 8. 37 (d, J = 8. 8Hz,lH, Py-H), 7. 84 (d, J = 8. 8Hz,2H, Ar-H), 7. 76(d, J = 7. 2Hz,2H, Ar-H), 7. 69 (t, J = 7. 6Hz,lH, Ar-H), 7. 58 (t, J = 7. 6Hz,lH, Ar-H) ,7. 35 (d, J = 8. 8Hz,2H, Ar-H), 7. 23 (d, J = 8. 8Hz,lH, Py-H), 4. 16 (s, 2H, CH2), 2.21(s,3H,CH3),1.95(s,3H,CH3) 03C NMR(100MHz,DMS0-d6) δ194·6,166·7,163·4,157·3, 146. 7,145. 4,138. 7,137. 2,133. 3,132. 5,131. 8,129. 5,128. 6,120. 9, 111. 9,50· 9,20· 1, 17. I. ESI-HRMS (m/z) :Calcd. for C24H22IN5O3[M+H]+428. 1717 ;found 428. 1720.
[0084] (E)-6-甲基-4-(I-(6-(4-异丙基-3-甲基苯氧基)吡啶-3-酰基)亚乙基氨 基)-4, 5-二氢-1,2,4-三嗪-3 (2H)-酮(1-18)的合成
[0085] 白色固体,收率 50%,熔点 164-165°C JH NMR(400MHz,DMS0-d6) : δ 9. 96(s,1H, NH),8.57(s,lH,Py-H),8.28(d,J = 8.8Hz,lH,Py-H),7.28(d,J = 8.0Hz,lH,Ar-H), 7.04(d,J = 8.4Hz,lH,Ar-H),6.95(d,J = 8.4Hz,2H,Ar-H,Py-H),4.15(s,2H,CH2), 3. 07-3. 13(m,1H,CH(CH3)2),2. 30(s,3H,CH3),2. 19(s,3H,CH3),I. 94(s,3H,CH3),I. 20(d, J = 6. 0Hz,6H,CH(CH3)2) ;13C NMR(100MHz,DMS0-d6) δ 166. 8,164. 7,150. 9,148. 8,146. 7, 145. 4,143. 0,138. 2,136. 4, 127. 7,125. 8,122. 6,118. 9, 110. 9,50· 9,28· 3,23· 2,20· 1, 18. 9,17. 0. ESI-HRMS (m/z) :Calcd. for C21H26IN5O2 [M+H]+380. 2081 ;found 380.2087.
[0086] (E)-6-甲基-4-(I-(6-(2-异丙基-5-甲基苯氧基)吡啶-3-酰基)亚乙基氨 基)-4, 5-二氢-1,2,4-三嗪-3 (2H)-酮(1-1
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