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一種六氫吡啶-2,3-并吲哚-2-酮類化合物及其制備方法及應(yīng)用_2

文檔序號:9500627閱讀:來源:國知局
, 5H), 7.87-7.98 (m, IH); "C NMR (CDCI3,100 MHz)《:21. 4,28. 0,29. 6,32. 5,56. 1,66. 6,84. 7,112. 0 (d, /cf = 19. 4 Hz), 115.3 (d, /^^=18.0 Hz), 116.7 (d, =6. 2 Hz), 124.5, 128.3, 128.6, 129.7, 132.2, 135.5, 135.8, 138.4, 138.5, 149.1, 160.0 (d, 194.4 Hz), 172.1, 176. 0; HRMS巧SI-TCF) m/z: Calcd. for CsiHszFNNaOs [M+Na] + : 540. 2162;化und: 540. 2165. 本實施例制備中間體化合物3ka:Li曲t orange oil; Yield 87%;古NMR (CDCI3,400 MHz)1.56 (s, 9H), 1.86-1.99 (m, IH), 2. 11-2. 33 (m, 2H), 2.40-2. 51 (m, IH), 2.97 (d, /= 13.1 Hz, IH), 3.12 (d, /= 13.1 Hz, IH), 3.68 (s, 3H), 4.99 (m, 2H),6. 55-6.61 (m, 2H), 6.67-6. 74 (m, 2H), 7.07-7. 36 (m,8H), 7. 59 (d, / =8. OHz, IH); "cnMR (CDCI3,lOOMHz)《:27.9,29. 5,31.7,44.6,54. 3,55.0, 66.3, 84.0, 123.4, 124.1, 126.7, 128.2, 128.3, 128.5, 128.8, 130.8, 135.6, 139.8,148.6,158. 3,172. 3,177.6; HRMS巧SI-TCF) m/z: Calcd. for〔3化3順曰〇6[M+Na]+: 538.2205;化und: 538.2210. 本實施例制備中間體化合物J化.· Li曲t orange oil; Yield 93%;古NMR (CDCI3,400 MHz)《:1.56 (s, 9H), 1.84-1.94 (m, IH), 2.09-2. 19 (m, IH), 2. 23-2. 35 (m, IH), 2.41-2.51 (m, IH), 2.98-3.05 (m, IH), 3.14-3.22 (m, IH), 3.55 (s, 3H),6. 76-6.81(m, 2H),6.99-7. 29 (m,6H), 7. 56-7.61 (m, IH); "CNMR (CDCI3, 100 MHz)《:28.0,29.4,31.9,45.6,51.6,54. 3,84.0,114.9,123.4,124. 2, 126.8, 127.7, 128.4, 128.7, 129.9, 134.7, 139.9, 148.7, 173.0, 177.5; HRMS 巧SI-TCF) m/z: Calcd. for C24H27NNa〇5[M+Na] + : 432. 1786;化und: 432. 1789. 本實施例制備中間體化合物3mb: Li曲t orange oil; Yield 87%;古NMR (CDCI3,400 MHz)《:1.61 (s, 9H), 1.80-1.90 (m, IH), 2.07-2. 16 (m, IH), 2. 21-2. 31 (m, IH), 2.39-2.50 (m, IH), 3.06-3.12 (m, IH), 3.25-3.32 (m, IH), 3.51 (s, 3H), 3.54 (s, 3H), 6.57-6.61 (m, IH), 6.69-6.75 (m, IH), 6.92-6.97 (m, IH), 6.98-7. 11 (m, 3H), 7. 11-7. 20 (m, IH), 7.60-7.65 (m, IH); "CNMR (CDCI3,100 MHz)《:28.0,29.4,31.9,38. 2,51.5,53. 5,54. 5,83.9,109.8,114. 3,119. 7,123.4, 123.8, 124.1, 127.9, 128.2, 129.0, 131.3, 139.5, 149.0, 157.3, 173.0, 177. 9; HRMS巧SI-TOF) m/z: Calcd. for C25H29NNa〇6[M+Nar: 462. 1892;化und: 462. 1895. 本實施例制備中間體化合物:3nb: Li曲t orange oil; Yield 84%;古NMR (CDCI3,400 MHz)《:1.62 (s, 9H), 1.79-1.90 (m, IH), 2.07-2. 17 (m, IH), 2. 21-2. 32 (m, IH), 2.40-2.52 (m, IH), 3.11-3.16 (m, IH), 3.24-3.29 (m, IH), 3.54 (s, 3H), 3.67 (s, 3H), 3.74 (s, 3H), 6.48-6. 53 (m, IH), 6.66-6. 71 (m, IH), 6. 75-6.80 (m, IH), 7.00-7.09 (m, 2H), 7. 13-7. 29 (m, IH), 7.65-7.69 (m, IH); "C NMR (CDCI3,100 MHz)《:28. 0,29. 4,32. 6,37. 5,51. 5,53. 5,55. 7,60. 4, 84.0, 111.6, 114.5, 122.9, 124.0, 124.1, 128.1, 128.9, 129.2, 139.6, 147.7, 149.0,152. 3,173.0,178.0; HRMS巧SI-TCF) m/z: Calcd. forC26H3iNNa07[M+Na] + : 492.1998; Found: 492.1997. 本實施例制備中間體化合物3ob: Li曲t orange oil; Yield 88%;古NMR (CDCI3,400 MHz)《:1.55 (s, 9H), 1.88-1.97 (m, IH), 2. 10-2. 20 (m, IH), 2.23-2. 32 (m, IH), 2.40-2.49 (m, IH), 2.92-3.01 (m, IH), 3.10-3.17 (m, IH), 3.55 (s, 3H), 3.58 (s, 3H), 3.75 (s, 3H), 6.15-6.21 (m, IH), 6.37-6.44 (m, IH), 6.53-6.58 (m, IH), 7. 14-7. 30 (m, 3H), 7. 57-7.61 (m, IH) ; "c nMR (CDCI3,100 MHz)《: 28.0, 29.4, 32.0, 45.2, 51.5, 54.5, 55.5, 55.7, 84.0, 110.5, 112.8, 115.0, 122.1, 123.3, 124.0, 127.3, 128.4, 129.1, 140.1, 147.8, 148.0, 148.6, 172.8, 177. 4; HRMS巧SI-TOF) m/z: Calcd. for C2eH3iNNa〇7[M+Nar: 492. 1998;化und: 492. 1998. 本實施例制備中間體化合物化b:Li曲t orange oil; Yield 84%;古NMR (CDCI3,400 MHz)《:1.61 (s, 9H), 1.95-1.81 (m, IH), 2. 20-2.06 (m, IH), 2. :34-2. 21 (m, IH), 2.53-2.40 (m, IH), 3.11-3.03 (m, IH), 3.31-3.24 (m, IH), 3.48 (s, 3H), 3. 54 (s, 3H), 3.63 (s, 3H),6. 54-6.48 (m, 2H), 6.62-6. 58 (m, IH), 7.08-7.01 (m, 2H), 7. 29-7. 12 (m, IH), 7.67-7.60 (m, IH) ; "c nMR (CDCI3,100 MHz)《: 28.0, 29.4, 32.1, 38.1, 51.5, 53.6, 55.1, 55.5, 83.9, 110.8, 113.2, 114.3, 116.5, 123.5, 124.1, 124.6, 128.0, 129.0, 139.6, 149.0, 151.5, 152.7, 173.0, 177.8; HRMS巧SI-TOF) m/z: Calcd. for C2eH3iNNa07[M+Nar: 492. 1998;化und: 492. 1995. 本實施例制備中間體化合物3qb: Yellow oil; Yield 81%;電NMR (CDCI3,400 MHz)《:1.61 (s, 9H), 1.78-1.89 (m, IH), 2.06-2. 16 (m, IH), 2. 18-2. 29 (m, IH), 2. 37-2. 49 (m, IH), 2. 97-3. 05 (m, IH), 3. 16-3. 24 (m, IH), 3. 48 (s, 3H), 3.54 (s, 3H), 3.71 (s, 3H), 6.18-6.20 (m, IH), 6.24-6.28 (m, IH), 6.82-6.86 (m, IH),6.97-7. 07 (m, 2H), 7. 13-7. 20 (m, IH), 7. 61-7.69 (m, IH);口C NMR (CDCI3,100 MHz) δ : 28. 0,29. 4,31. 7,37. 8,51. 5,53. 7,54.6,55. 1,83.8, 97.8, 103.4, 114.4, 116.1, 123.4, 124.1, 127.9, 129.2, 131.7, 139.5, 149.0, 158. 3,159. 7,173.0,177.9; HRMS巧SI-TCF) m/z: Calcd. forC26H3iNNa07[M+Na] + : 492.1998;化und: 492. 1996. 本實施例制備中間體化合物:3rb:化Ilow oil; Yield 90%;電NMR (CDCI3,400 MHz)《:1.57 (s, 9H), 1.84-1.94 (m, IH), 2.07-2. 20 (m, 4H), 2. 22-2. 32 (m, IH), 2. 39-2. 52 (m, IH), 2. 92-3. 00 (m, IH), 3. 10-3. 16 (m, IH), 3. 55 (s, 3H), 6. 52-6. 65 (m, 2H),6. 85-6. 95 (m, 2H),7. 06-7. 29 (m, 3H),7. 55-7. 62 (m, IH); "CNMR (CDCI3,100MHz)《:21. 1,28.0,29.4,31.8,45.4,51.5,54. 2,83.9, 114.7, 123.4, 124.0, 126.8, 127.4, 127.4, 128.3, 128.8, 130.5, 134.6, 137.1, 139.9,148. 7,172. 9,177.4;HRMS巧SI-TCF)m/z:Calcd.forC25H29NNa〇5[M+Na] + : 446.1943;化und: 446. 1947. 本實施例制備中間體化合物3sb:Yellowoil;Yield85%;電NMR(CDCI3,400MHz)《:1.58 (s, 9H), 1.79-1.88 (m, IH), 1.97 (s, 3H), 2.06-2. 15 (m, IH), 2.28-2.37 (m, IH), 2.45-2.54 (m, IH), 3.06-3.10 (m, IH), 3.15-3.21 (m, IH), 3. 55 (s, 3H),6. 78-6. 82 (m,IH), 6.87-7. 11 (m, 5H), 7. 21-7. 27 (m,IH), 7.66-7. 71 (m, IH); "CNMR (CDCI3, 100MHz)《:19. 7,28.0,29.4,31.4,41.4, 51.5, 53.6, 84.0, 114.8, 123.7, 124.0, 125.2, 126.9, 128.5, 128.7, 130.3, 130. 5, 133. 3, 137. 2, 139.8, 148.8, 172.9, 177. 7; HRMS 巧SI-TCF)m/z: Calcd. forC25H29順a〇5[M+Na]+ : 446. 1943;Found: 446. 1945. 本實施例制備中間體化合物3憂.·Yellowoil;Yield89%;電NMR(CDCI3,400MHz)《:1.56 (s, 9H), 1.83-1.93 (m, IH), 2.08-2. 17 (m, IH), 2.20 (s, 3H), 2. 23-2. 31 (m,IH), 2. :34-2. 49 (m,IH), 2.95-3. 15 (m, 2H), 3.55 (s, 3H), 6.65-6. 78 (m, 2H), 6.82-6.89 (m, 2H), 7. 10-7. 17 (m, 2H), 7. 21-7. 24 (m, IH), 7. 59-7.61 (m, IH); "CNMR (CDCI3, 100MHz)《:20.9,27.9,29.4,31.8,45. 1, 51.5, 54.2, 83.9, 109.6, 114.8, 122.1, 123.4, 124.1, 128.0, 128.3, 128.8, 129. 7, 129.8, 131.6, 136. 2, 139.8, 148. 7, 173.0, 177.6;HRMS巧SI-TOF)m/z: Calcd.forC25H29NNa〇5[M+Na] + : 446. 1943;化und: 446. 1946. 本實施例制備中間體化合物3ub:化Ilowoil;Yield83%;電NMR(CDCI3,400MHz)《:1.12-1. 16 (m,6H), 1.56 (s, 9H), 1.83-1.92 (m, IH), 2.08-2. 17 (m, IH), 2.22-2.31 (m, IH), 2.41-2.50 (m, IH), 2.72-2.78 (m, IH), 2.97-3.15 (m, 2H), 3. 55 (s, 3H), 6.66-6. 74 (m, 2H), 6.86-6.93 (m, 2H), 7.09-7. 29 (m, 3H), 7. 57-7.61 (m, IH); "CNMR (CDCI3, 100MHz)《:23.8,23.9,28.0,29.4,31.7, 33.5, 45.2, 51.6, 54.2, 83.9, 114.8, 123.4, 124.1, 125.6, 128.3, 128.9, 129.8, 131.9, 139.8, 147. 3, 148.6, 173.0, 177. 5; HRMS 巧SI-TCF)m/z: Calcd. for〔2用33順日〇5[]?+胞]+ : 474. 2256;化und: 474. 2261. 本實施例制備中間體化合物3vb:Li曲tyellowoil;Yield88%;古NMR(CDCI3, 400MHz)δ:1.21 (s, 9H), 1.56 (s, 9H), 1.83-1.92 (m,IH), 2.09-2.19 (m,IH), 2. 22-2. 32 (m, IH), 2. 39-2. 50 (m, IH), 2. 97-3. 03 (m, IH), 3. 08-3. 14 (m,IH), 3. 55 (s, 3H),6.67-6. 74 (m, 2H),7.04-7. 29 (m, 5H),7. 57-7.63 (m, IH) ; "c NMR(CDCI3,100MHz)《:28.0,29. 5,31.2,31.7,34. 3,45. 1,51.6,54. 2,83.9, 114.8, 123.5, 124.1, 124.5, 128.3, 129.0, 129.6, 131.6, 139.9, 148.7, 149.6, 173. 0,177. 5;HRMS巧SI-TOF)m/z:Calcd.forC2sH35NNa〇5[M+化Γ: 488. 2412; 化und: 488. 2416. 本實施例制備中間體化合物3wb:Li曲tyellowoil;Yield80%;古NMR(CDCI3, 400MH
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