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一種合成3-鹵亞甲基-2,3-二氫苯并呋喃類化合物的方法_2

文檔序號:9318586閱讀:來源:國知局
薄 膜):vnax(cm 3 = 3061,1649, 1500, 1460, 1235, 1089, 744, 730 ;HRMS(EI)calcdfor(M+)C9H 6C120:199. 9800,Found:199. 9799.
[0043] 反式-A3:iH匪R(400MHz,CDC13)S8. 00(d,J= 2. 4Hz,1H),7. 20(dd,J= 8. 6, 2. 4Hz, 1H), 6. 79 (d,J= 8. 6Hz, 1H), 6. 07(t,J= 2. 4Hz, 1H), 5. 12 (d,J= 2. 4Hz, 2H); 13C匪R(101MHz,CDC13)S163. 0, 135. 9, 131. 0, 125. 7, 125. 6, 125. 5, 111. 3, 107. 5, 74. 9;11?(薄膜)^_(〇111)= 3061,1500,1460,1235,1089,980,744,730;11冊3伍1)。&1。(1 for(M+)C9H6C120:199. 9800,Found: 199. 9802.
[0044] A4:
[0045]
[0046] 石油醚淋洗;無色油狀物,順式:反式=2. 5:1,總產(chǎn)率:79 % ;
[0047] 順式-A4:蟲NMR(400MHz,CDC13)S7. 13 (s, 1H),7. 02 (d,J= 8. 4Hz, 1H),6. 77 (d,J =8. 4Hz, 1H), 6. 33(t,J= 3. 2Hz, 1H), 5. 13 (d,J= 3. 2Hz, 2H), 2. 30 (s, 3H). 13C 匪R(101MHz,CDC13)S162. 0, 139. 4, 131. 5, 130. 4, 123. 3, 120. 7, 110. 5, 105. 3, 74. 4, 20. 8 ;IR(薄膜):vnax(cm 3 = 3060, 1649, 1500, 1450, 1375, 1230, 1089, 744;HRMS(El)calcd for(M+)C10H9C10:180. 0342,Found: 180. 0344.
[0048] 反式-A4:蟲NMR(400MHz,CDC13)S7. 85 (s, 1H),7. 06 (d,J= 8. 2Hz, 1H),6. 76 (d,J =8. 2Hz,1H),6. 00(d,J= 1. 2Hz,1H),5. 08(s,2H),2. 33(s,3H).13CNMR(101MHz,CDC13)S1 62. 6, 137. 1,131. 9, 130. 2, 126. 0, 124. 0, 109. 9, 105. 6, 74. 4, 21. 0;IR(薄膜):vnax(cm工) =3060, 1500, 1450, 1375, 1230, 1089, 980, 744;HRMS(El)calcdfor(M+)C10H9C10:180. 0335 ,Found:180. 0338.
[0049] A5:
[0050]
[0051] 石油醚淋洗;無色油狀物,順式:反式=1. 6:1,總產(chǎn)率:76% ;
[0052] 順式-A5:4NMR(400MHz,CDC13)S7. 36(dd,J= 7. 8, 1. 2Hz1H),7. 25(dd,J= 7. 8, 1. 2Hz, 1H), 6. 78(t,J=7. 8Hz, 1H), 6. 40(t,J=3. 2Hz, 1H), 5. 22(d,J=3. 2Hz, 2H); 13CNMR(101MHz,CDC13)S160. 7, 138. 7, 133. 4, 124. 9, 122. 4, 119. 5, 107. 5, 103. 9, 74. 7 ; IR(薄膜):vnax (cm1) = 3061,1649, 1500, 1460, 1230, 1089,740,668;HRMS(El)calcd for(M+)C9H6BrC10:243. 9295,Found: 243. 9296.
[0053]反式-A5:4NMR(400MHz,CDC13)S7. 98 (dd,J= 7. 8, 1. 0Hz, 1H),7. 41 (dd,J= 7. 8, 1. 0Hz, 1H), 6. 84(t,J=7. 8Hz, 1H), 6. 07(t,J=2. 8Hz, 1H), 5. 19 (d,J=2. 8Hz, 2H); 13C匪R(101MHz,CDC13)S161. 3, 136. 5, 133. 9, 125. 5, 124. 7, 122. 3, 107. 7, 103. 4, 74. 7;11?(薄膜)^_(〇111)= 3061,1500,1460,1230,1089,980,740,668;11冊3伍1)。&1。(1 for(M+)C9H6BrC10:243. 9291,Found: 243. 9288.
[0054] A6:
[0055]
[0056] 石油醚淋洗;無色油狀物,順式:反式=2:1,總產(chǎn)率:93% ;
[0057]順式-A6:H匪R(400MHz,CDC13)S7. 44(d,J= 2. 0Hz, 1H), 7. 32(dd,J= 2. 0, 8. 4Hz, 1H), 6. 78 (d,J= 8. 4Hz, 1H), 6. 41 (t,J= 3. 6Hz, 1H), 5. 19 (d,J= 3. 2Hz, 2H); 13CNMR(101MHz,CDC13)S162. 8, 138. 0, 133. 3, 125. 6, 123. 5, 113. 1,112. 5, 107. 3, 74. 9 ; IR(薄膜):vnax (cm1) = 3061,1649, 1500, 1460, 1230, 1089,740,669;HRMS(El)calcd for(M+)C9H6BrC10:243. 9291,Found: 243. 9293.
[0058]反式-A6:蟲NMR(400MHz,CDC13)S8. 14 (s, 1H),7. 33 (d,J=8. 8Hz, 1H),6. 73 (d,J =8.8Hz,lH),6.06(t,J= 2.4Hz,1H),5.ll(d,J= 2.4Hz,2H);13CNMR(101MHz,CDC13)S1 63. 5, 135. 7, 133. 8, 128. 4, 126. 2, 112. 9, 111. 9, 107. 6, 74. 8 ;IR(薄膜):vnax(cm 3 = 30 61, 1500, 1460, 1250, 1089, 980, 740, 668;HRMS(El)calcdfor(M+)C9H6BrC10:243. 9291,Fou nd:243. 9289.
[0059] A7:
[0060]
[0061] 乙酸乙酯/石油醚=1/50,v/v;無色油狀物,順式:反式=2:1,總產(chǎn)率:88% ;
[0062]順式-A7:巾NMR(400MHz,CDC13)S7. 96(s,1H),7. 87(d,J= 8. 8Hz,1H),6. 89(d,J =8. 8Hz, 1H), 6. 51(t,J=3. 2Hz, 1H), 5. 23(d,J=3. 2Hz, 2H), 2. 56(s,3H);13C NMR(101MHz,CDC13)S196. 3, 167. 3, 137. 6, 132. 2, 130. 9, 124. 1,121. 2, 110. 6, 107. 8, 75. 4, 26;IR(薄膜):vnax(cm 3 =3068, 1720, 1649, 1500, 1460, 1230, 1089, 744 ;HRMS(ESI) calcdfor(MH+)CnH10C102:209 . 0 3 64,Found:209. 0363.
[0063]反式-A7:巾NMR(400MHz,CDC13)S8. 63 (s, 1H),7. 93 (d,J=8. 4Hz, 1H),6. 88 (d,J =8.4Hz,lH),6.12(s,lH),5.19(d,J= 2.4Hz,2H),2.58(s,3H);13CNMR(101MHz,CDC13) S196. 4, 168. 0, 135. 3, 132. 6, 130. 9, 126. 6, 124. 5, 110. 3, 107. 8, 75. 4, 26. 5 ;IR(薄 膜):Vnax(cm3 = 3068, 1720, 1500, 1460, 1230, 1089, 980, 744;HRMS(ESI)calcdfor(MH+)CnH10C102:209 . 0 361,Found: 209. 0359.
[0064] A8:
[0065]
[0066] 乙酸乙酯/石油醚=1/100,v/v;無色油狀物,順式:反式=2:1,總產(chǎn)率:92%;
[0067] 順式-A8:蟲NMR(400MHz,CDC13)S8. 02 (s,1H),7. 95 (d,J= 8. 0Hz,1H),6. 89 (d,J =8.0Hz,1H),6.50 (t,J= 4.0Hz,1H),5.23 (d,J= 4.0Hz,2H),3.91 (s,3H);13C NMR(101MHz,CDC13)S167. 2, 166. 4, 137. 7, 132. 9, 123. 9, 123. 3, 122. 5, 110. 6, 107. 5, 75. 4 ,52. 1 ;IR(薄膜):vnax(cm 3 = 3058, 1735, 1649, 1590, 1500, 1230, 1083, 744;HRMS(ESI) calcdfor(MH+)CnH10C103:2 2 5 . 03 1 3,Found: 225. 0308.
[0068] 反式-A8:蟲NMR(400MHz,CDC13)S8. 70 (s, 1H),8. 00 (d,J= 8. 5Hz, 1H),6. 88 (d,J =8. 5Hz, 1H), 6. 11 (d,J= 0. 6Hz, 1H), 5. 19(d,J= 1. 4Hz, 2H), 3. 91 (s, 3H) ;13C NMR(101MHz,CDC13)S167. 9, 166. 6, 135. 4, 133. 7, 127. 6, 124. 4, 123. 2, 110. 2, 107. 8, 75. 3, 52. 1 ;IR(薄膜):vnax(cm 3 = 3058, 1735, 1590, 1500, 1230, 1083, 980, 744;HRMS(ESI) calcdfor(MH+)CnH10C103:2 2 5 . 03 1 3,Found: 225. 0308.
[0069] A9:
[0070]
[0071] 石油醚淋洗;無色油狀物,順式:反式=1. 5:1,總產(chǎn)率:76% ;
[0072] 順式-A9:iHNMR(400MHz,CDC13)S7. 74(d,J= 8. 0Hz,1H),7. 71 (d,J= 8. 2Hz ,2H), 7. 29-7. 21(m, 4H), 7. 00(t,J= 7. 6Hz, 1H), 6. 37 (t,J= 3. 2Hz, 1H), 4. 58 (d,J= 3.2Hz,2H),2.37(s,3H);13CNMR(101MHz,CDCl3)Sl44.5(d,J= 2.8Hz),135.7,133.8,130. 4, 129. 9, 127. 2, 127. 1,123. 8, 120. 5, 115. 2, 108. 3, 53. 9, 21. 6 ;IR(薄膜):vnax(cm 3 = 30 61, 1735, 1649, 1590, 1500, 1230, 1089, 744;HRMS(ESI)calcdfor(M+Na)C16H14ClNNa02S+: 342 .0326,Found: 342. 0328.
[0073] 反式-A9:泊NMR(400MHz,CDC13)S8. 09 (d,J= 7. 6Hz,1H),7. 77 (d,J =8. 0Hz, 1H), 7. 70 (d,J= 8. 0Hz, 2H), 7. 34 (t,J= 7.
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