CN106905098B - 一种邻碘代α-酰氧基羰基化合物的合成方法 - Google Patents

一种邻碘代α-酰氧基羰基化合物的合成方法 Download PDF

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CN106905098B
CN106905098B CN201710107418.6A CN201710107418A CN106905098B CN 106905098 B CN106905098 B CN 106905098B CN 201710107418 A CN201710107418 A CN 201710107418A CN 106905098 B CN106905098 B CN 106905098B
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李毅
王亚洲
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Abstract

本发明提供了一种邻碘代α‑酰氧基羰基化合物的合成方法，其是以EBX试剂为原料，有机溶剂与水的混合液为溶剂，在Ｎ‑杂环卡宾前体盐的催化下合成的。与现有方法相比，本发明方法可适用底物范围广，反应条件温和，操作简便，而且反应效率高。

Description

一种邻碘代α-酰氧基羰基化合物的合成方法
技术领域
本发明属于化学合成技术领域，具体涉及一种由Ｎ-杂环卡宾催化EBX试剂合成邻碘代α-酰氧基羰基化合物的方法。
背景技术
邻碘代α-酰氧基羰基化合物在有机合成化学中是重要的结构单元，广泛存在于具有生物活性的天然产物中，是常见的合成药物结构单元。上个世纪七十年代以来，关于邻碘代α-酰氧基羰基化合物的合成与研究获得了化学界的广泛关注。早前是以α-卤代羰基化合物或者α-重氮基酮与碱性羧酸盐和酮在重金属氧化剂作用下通过偶联反应来制备邻碘代α-酰氧基羰基化合物。随后发现，超值碘化合物可作为有效的氧化剂以促进酰氧基化反应。近年来，EBX试剂由于具有性能温和、对环境友好等优点慢慢引起了人们的兴趣，并发现可使用N-芳基亚胺和EBX试剂在钯催化剂作用下制备邻碘代α-酰氧基羰基化合物。但是，大多数已报道的反应存在某些缺点，例如需要使用过量的酮、过量的具潜在危险的过氧化物氧化剂、有毒金属催化剂，及反应条件苛刻、低产率。因而发展一种步骤简单、操作方便、条件温和、底物适用范围广而且效率高的合成邻碘代α-酰氧基羰基化合物的新方法仍是目前研究的重点和难点。本发明提供了一种以EBX试剂为原料，以N-杂环卡宾作为催化剂，合成邻碘代α-酰氧基羰基化合物的简便实用的方法。
发明内容
本发明的目的在于提供一种邻碘代α-酰氧基羰基化合物的合成方法，其具有适用底物范围广、反应条件温和、操作简便、反应效率高等特点。
为实现上述目的，本发明采用如下技术方案：
一种邻碘代α-酰氧基羰基化合物的合成方法，其是以EBX试剂为原料，Ｎ-杂环卡宾前体盐作为催化剂，有机溶剂与水的混合液为溶剂，在碱存在的条件下，于0-120℃反应14-18 h小时后，经分离纯化制得；其合成工艺如下：
；
其中，R1、R2任意独立选自H，C1-C16的烷基，C3-C16的环烷基，C4-C10的芳基，取代芳基，含N、O或S的杂环基或杂芳基；所述芳基为苯基或萘基；所述取代芳基包括C1-C4的烷基取代、C1-C4的烷氧基取代、C1-C4的全氟烷基取代或卤素取代。
EBX试剂、碱与Ｎ-杂环卡宾盐的摩尔比为1:0.2-1.1:0.01-0.05。所述碱包括碳酸盐、醋酸盐、磷酸盐、胺中的任意一种，如碳酸铯、碳酸钾、碳酸钠、乙酸钠、乙酸钾、叔丁醇钾、磷酸钾、N,N-二异丙基乙胺、DBU、三乙胺、4-二甲氨基吡啶；所述Ｎ-杂环卡宾前体盐包括咪唑盐、烯基咪唑盐、噻唑盐、三氮唑盐中的任意一种。
有机溶剂与水混合的体积比为100:2.5；所述有机溶剂为1，4-二氧六环、丙酮、甲苯、苯、乙腈、二氯甲烷、四氢呋喃、二甲基亚砜、N，N-二甲基甲酰胺、1，2-二氯乙烷、甲醇、二甲苯、乙醚、三氯甲烷、环己烷、正己烷、正庚烷、四氯化碳或石油醚中的任意一种。
反应温度优选0-50℃。
分离纯化的方法包括重结晶、薄层层析、柱层析、减压蒸馏。如用重结晶的方法，推荐溶剂为极性溶剂与非极性溶剂的混合溶剂，推荐溶剂可为二氯甲烷-正己烷、异丙醇-石油醚、乙酸乙酯-石油醚、乙酸乙酯-正己烷或异丙醇-乙酸乙酯-石油醚等混合溶剂。用薄层层析和柱层析方法，所用的展开剂为极性溶剂与非极性溶剂的混合溶剂，推荐溶剂可为异丙醇-石油醚、乙酸乙酯-石油醚、乙酸乙酯-正己烷或异丙醇-乙酸乙酯-石油醚等混合溶剂，其体积比可以分别是：极性溶剂：非极性溶剂＝1：0.1-500，例如乙酸乙酯：石油醚＝1：0.1-50，异丙醇：石油醚＝1：0.1-500。
本发明的显著优点在于：本发明提供了一种由EBX试剂为原料，N-杂环卡宾前体盐作为催化剂，在碱存在条件下，高效一步合成邻碘代α-酰氧基羰基化合物的方法。与现有方法相比，该方法可适用于多种不同类型的EBX试剂，且其原料廉价易得，反应条件温和，操作简便，产率好。
附图说明
图1为化合物A1的1H NMR图（a）与13C NMR图（b）。
图2为化合物A2的1H NMR图（a）与13C NMR图（b）。
图3为化合物A3的1H NMR图（a）与13C NMR图（b）。
图4为化合物A4的1H NMR图（a）与13C NMR图（b）。
图5为化合物A5的1H NMR图（a）与13C NMR图（b）。
图6为化合物A6的1H NMR图（a）与13C NMR图（b）。
图7为化合物A7的1H NMR图（a）与13C NMR图（b）。
图8为化合物A10的1H NMR图（a）与13C NMR图（b）。
图9为化合物A13的1H NMR图（a）与13C NMR图（b）。
图10为化合物A18的1H NMR图（a）与13C NMR图（b）。
具体实施方式
在氮气保护下，向一干燥反应管中依次加入EBX试剂（0.2 mmol）、N-卡宾催化剂前体盐（0.02 mmol）、乙酸钠（0.04mmol），并向体系中加入2 mL 1, 4-二氧六环，最后加入50μL的水，20℃下反应约16 h后，停止搅拌，减压除去溶剂，柱层析分离纯化，淋洗剂为乙酸乙酯和石油醚，收集组分，得相应产物A；其反应方程如下：
，
其中，R1、R2任意独立选自H，C1-C16的烷基，C3-C16的环烷基，C4-C10的芳基，取代芳基、含N、O或S的杂环基或杂芳基；所述芳基为苯基或萘基；所述取代芳基包括C1-C4的烷基取代、C1-C4的烷氧基取代、C1-C4的全氟烷基取代或卤素取代。
实施例1 化合物A1
乙酸乙酯/石油醚=1, 11, v/v; 白色固体, 产率: 90%；1H NMR (400 MHz,Chloroform-d) δ: 8.11-8.00 (m, 2H), 7.97 (d, J = 7.4 Hz, 2H), 7.63 (t, J =7.4 Hz, 1H), 7.51 (t, J = 7.7 Hz, 2H), 7.45 (t, J=7.6 Hz, 1H), 7.19 (td, J =7.8, 1.6 Hz, 1H), 5.60 (s, 2H). 13C NMR (101 MHz, Chloroform-d) δ: 191.7,165.8, 141.4, 134.2, 134.1, 134.0, 133.1, 131.7, 128.9, 128.0, 127.83, 94.5,66.7。
实施例2 化合物A2
乙酸乙酯/石油醚=1: 15, v/v; 白色固体, 产率; 86%; 1H NMR (400 MHz,Chloroform-d) δ: 8.04 (ddd, J = 15.3, 7.9, 1.3 Hz, 2H), 7.86 (d, J = 8.2 Hz,2H), 7.45 (td, J = 7.6, 1.0 Hz, 1H), 7.30 (d, J = 8.0 Hz, 2H), 7.19 (td, J =7.7, 1.7 Hz, 1H), 5.57 (s, 2H), 2.43 (s, 3H). 13C NMR (101 MHz, CDCl3) δ:191.3, 165.8, 145.0, 141.4, 134.2, 133.0, 131.7, 131.7, 129.6, 128.0, 127.9,94.4, 66.7, 21.8. HRMS (ESI) exact mass calculated for C16H13IO3 [M+Na]+:402.9802, found: 402.9804; IR (neat): νmax (cm-1) = 3063, 2988, 1729, 1693,1103, 1016, 742, 699。
实施例3 化合物A3
乙酸乙酯/石油醚=1: 11, v/v; 白色固体, 产率: 81%; 1H NMR (400 MHz,Chloroform-d) δ: 7.96 (d, J = 7.9 Hz, 2H), 7.87 (s, 2H), 7.61 (d, J = 7.1 Hz,1H), 7.50 (t, J = 6.9 Hz, 2H), 7.01 (d, J = 7.9 Hz, 1H), 5.59 (s, 2H), 2.35(s, 3H). 13C NMR (101 MHz, CDCl3) δ: 191.8, 165.9, 141.1, 138.2, 134.2, 134.1,134.0, 133.8, 132.4, 128.9, 127.8, 90.4, 66.7, 20.9. HRMS (ESI) exact masscalculated for C16H13IO3 [M+Na]+: 402.9802, found: 402.9805; IR (neat): νmax(cm-1) = 3053, 2990, 1718, 1687, 1301, 1273, 1114, 700。
实施例4 化合物A4
乙酸乙酯/石油醚=1: 20, v/v; 白色固体, 产率: 76%; 1H NMR (400 MHz,Chloroform-d) δ: 8.18 (d, J = 2.4 Hz, 1H), 8.00-7.93 (m, 2H), 7.87 (d, J =8.4 Hz, 1H), 7.67-7.60 (m, 1H), 7.52 (dd, J = 8.4, 7.1 Hz, 2H), 7.32 (dd, J =8.4, 2.4 Hz, 1H), 5.60 (s, 2H). 13C NMR (101 MHz, CDCl3) δ: 191.3, 164.53,142.7, 136.1, 135.6, 134.5, 134.1, 134.0, 129.0, 127.8, 122.4, 92.5, 76.7,67.0. HRMS (ESI) exact mass calculated for C15H10BrIO3 [M+Na]+: 466.8751,found: 466.8747; IR (neat): νmax (cm-1) = 2989, 1708, 1692, 1319, 1276, 969,718。
实施例5 化合物A5
乙酸乙酯/石油醚=1: 10, v/v; 浅黄色固体, 产率: 69%; 1H NMR (400 MHz,Chloroform-d) δ : 8.14-8.01 (m, 4H), 7.89-7.80 (m, 2H), 7.48 (td, J = 7.7,1.1 Hz, 1H), 7.24 (td, J = 7.7, 1.7 Hz, 1H), 5.59 (s, 2H). 13C NMR (101 MHz,CDCl3) δ 190.8, 165.6, 141.6, 137.1, 133.6, 133.3, 132.8, 131.7, 128.3,128.1, 117.6, 117.3, 94.6, 66.7. HRMS (ESI) exact mass calculated forC16H10INO3 [M+ Na]+: 413.9598, found: 413.9594; IR (neat): νmax (cm-1) = 3067,2915, 1694, 1603, 1361,1268, 1227, 1116。
实施例6 化合物A6
乙酸乙酯/石油醚=1: 4, v/v; 白色固体, 产率: 66%;1H NMR (400 MHz,Chloroform-d) δ: 8.13-8.01 (m, 6H), 7.48 (td, J = 7.6, 1.2 Hz, 1H), 7.22 (td,J = 7.7, 1.7 Hz, 1H), 5.62 (s, 2H), 2.68 (s, 3H). 13C NMR (101 MHz, CDCl3) δ197.2, 191.4, 165.7, 141.5, 140.8, 137.3, 133.8, 133.2, 131.7, 128.7, 128.1,128.0, 94.5, 66.8, 26.9. HRMS (ESI) exact mass calculated for C17H13IO4 [M+ Na]+:430.9752, found: 430.9749; IR (neat): νmax (cm-1) = 2955, 1724, 1690, 1274,1243, 1123, 911, 700。
实施例7 化合物A7
乙酸乙酯/石油醚=1: 12, v/v; 无色液体, 产率: 65%；1H NMR (400 MHz,Chloroform-d) δ : 8.03 (dd, J = 8.0, 1.2 Hz, 1H), 7.98 (dd, J = 7.8, 1.7 Hz,1H), 7.45 (td, J = 7.6, 1.2 Hz, 1H), 7.20 (td, J = 7.6, 1.8 Hz, 1H), 4.92 (s,2H), 2.53 (t, J = 7.4 Hz, 2H), 1.66 (p, J = 7.4 Hz, 2H), 1.38 (h, J = 7.4 Hz,2H), 0.94 (t, J = 7.3 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 203.5, 165.7, 141.5,134.0, 133.1, 131.5, 128.0, 94.4, 68.6, 38.7, 25.3, 22.3, 13.8. νmax (cm-1) =3062, 2988, 2936, 1738, 1699, 1597, 1451, 1229,1161, 699。
实施例8 化合物A8
乙酸乙酯/石油醚=1: 8，v/v; 白色固体, 产率: 60%; 1H NMR (400 MHz,Chloroform-d) δ: 8.20 (d, J = 8.5 Hz, 2H), 8.10-8.01 (m, 4H), 7.48 (td, J =7.6, 1.2 Hz, 1H), 7.23 (td, J = 7.7, 1.7 Hz, 1H), 5.62 (s, 2H), 4.45 (q, J =7.1 Hz, 2H), 1.45 (t, J = 7.1 Hz, 3H). 13C NMR (101 MHz, CDCl3) δ 191.5,165.7, 165.5, 141.5, 137.2, 135.1, 133.9, 133.2, 131.7, 130.1, 128.0, 127.8,94.5, 66.8, 61.6, 14.3; HRMS (ESI) exact mass calculated for C18H15IO5 [M+ Na]+:460.9857, found:460.9859; IR (neat): νmax (cm-1) = 3062, 2988, 2936, 1738,1699, 1597, 1451, 1229,1161, 699。
实施例9 化合物A9
乙酸乙酯/石油醚=1: 14，v/v; 白色固体, 产率: 58%; NMR (400 MHz,Chloroform-d) δ: 8.34 (d, J = 2.1 Hz, 1H), 7.96 (d, J = 7.6 Hz, 2H), 7.72 (d,J = 8.3 Hz, 1H), 7.63 (d, J = 7.4 Hz, 1H), 7.57-7.46 (m, 3H), 5.60 (s, 2H).13C NMR (101 MHz, CDCl3) δ 191.4, 164.4, 142.8, 142.0, 140.2, 135.8, 134.1,134.1, 129.0, 127.8, 93.8, 93.2, 66.9. HRMS (ESI) exact mass calculated forC15H15I2O3 [M+ Na]+: 514.8612, found: 514.8615; IR (neat): νmax (cm-1) = 3067,2915, 1694, 1603, 1361, 1268, 1227, 1116。
实施例10 化合物A10
乙酸乙酯/石油醚=1:10, v/v；浅黄色固体，产率：55%; 1H NMR (400 MHz,Chloroform-d) δ: 8.11-7.96 (m, 2H), 7.91 (d, J = 8.4 Hz, 2H), 7.54-7.36 (m,3H), 7.20 (t, J = 7.4 Hz, 1H), 5.55 (s, 2H). 13C NMR (101 MHz, CDCl3) δ 190.7,165.7, 141.5, 140.5, 133.9, 133.2, 132.5, 131.7, 129.3, 129.2, 128.0, 94.5,66.6. HRMS (ESI) exact mass calculated for C15H10ClIO3 [M+ Na]+: 422.9256,found: 422.9253; IR (neat): νmax (cm-1) = 3066, 1710, 1695, 1635, 1324, 1191,1178.699。
实施例11 化合物A11
乙酸乙酯/石油醚=1:10, v/v；白色固体，产率：63%；1H NMR (400 MHz,Chloroform-d) δ 8.10 (s, 1H), 8.03 (ddd, J = 8.0, 2.9, 1.4 Hz, 2H), 7.88 (d,J = 7.8 Hz, 1H), 7.75 (d, J = 8.0 Hz, 1H), 7.42 (dt, J = 23.8, 7.8 Hz, 2H),7.20 (td, J = 7.6, 1.5 Hz, 1H), 5.54 (s, 2H). 13C NMR (101 MHz, CDCl3) δ190.6, 165.7, 141.5, 136.9, 135.9, 133.9, 133.2, 131.7, 130.9, 130.5, 128.0,126.3, 123.3, 94.5, 66.6. HRMS (ESI) exact mass calculated for C15H10I2O3 [M+Na]+: 514.8612, found: 514.8615; IR (neat): νmax (cm-1) = 3067, 2915, 1694,1603, 1361,1268, 1227, 1116。
实施例12 化合物A12
乙酸乙酯/石油醚=1:5, v/v；白色固体，产率：50%；1H NMR (400 MHz,Chloroform-d) δ: 8.35 (d, J = 8.8 Hz, 2H), 8.13 (d, J = 8.8 Hz, 2H), 8.03(ddd, J = 7.7, 4.8, 1.4 Hz, 2H), 7.46 (t, J = 7.6 Hz, 1H), 7.21 (td, J = 7.8,1.5 Hz, 1H), 5.60 (s, 2H). 13C NMR (101 MHz, CDCl3) δ 190.7, 165.6, 150.8,141.6, 138.6, 133.5, 133.4, 131.7, 129.0, 128.1, 124.2, 94.6, 66.8. HRMS(ESI) exact mass calculated for C15H10INO5 [M+ Na]+: 433.9497, found: 433.9495;IR (neat): νmax (cm-1) = 3072, 1711, 1692, 1517, 1347, 1334, 1196, 1178, 1008,850, 702。
实施例13 化合物A13
乙酸乙酯/石油醚=1:8, v/v；浅黄色固体，产率：50%；1H NMR (400 MHz,Chloroform-d) δ: 8.11-8.01 (m, 4H), 7.78-7.71 (m, 2H), 7.68-7.61 (m, 2H),7.55-7.38 (m, 4H), 7.20 (td, J = 7.7, 1.7 Hz, 1H), 5.63 (s, 2H). 13C NMR (101MHz, CDCl3) δ 191.3, 165.8, 146.7, 141.4, 139.6, 134.1, 133.1, 132.9, 131.7,129.0, 128.5, 128.4, 128.0, 127.6, 127.3, 94.5, 66.7. HRMS (ESI) exact masscalculated for C21H15IO3 [M+ Na]+: 464.9959, found: 464.9956; IR (neat): νmax(cm-1) = 3054, 3025, 1714, 1698, 1636, 1449, 1324, 1223, 1009, 770,685。
实施例14 化合物A14
乙酸乙酯/石油醚=1:10, v/v；白色固体，产率：46%；1H NMR (400 MHz,Chloroform-d) δ: 8.04 (ddd, J = 7.6, 5.7, 1.4 Hz, 2H), 7.81 (dd, J = 3.9, 1.1Hz, 1H), 7.73 (dd, J = 5.0, 1.1 Hz, 1H), 7.45 (td, J = 7.6, 1.2 Hz, 1H),7.23-7.15 (m, 2H), 5.48 (s, 2H). 13C NMR (101 MHz, CDCl3) δ 184.9, 165.7,141.5, 140.3, 134.5, 133.9, 133.1, 132.1, 131.7, 128.4, 128.0, 94.5, 66.4.HRMS (ESI) exact mass calculated for C13H9IO3S [M+ Na]+: 394.9210, found:394.9213; IR (neat): νmax (cm-1) =3087, 1707, 1692, 1624, 1207, 1171, 702。
实施例15 化合物A15
乙酸乙酯/石油醚=1:15, v/v；浅黄色固体，产率：80%；1H NMR (400 MHz,Chloroform-d) δ: 8.03 (dt, J = 16.2, 7.8 Hz, 3H), 7.60 (q, J = 7.0 Hz,1H),7.45 (t, J = 7.6 Hz, 1H), 7.34-7.24 (m,1H), 7.19 (t, J = 7.4 Hz, 2H), 5.49(d, J = 3.8 Hz, 2H). 13C NMR (101 MHz, CDCl3) δ 190.0(d, J = 4.9 Hz), 165.7,162.4(d, J = 255.0 Hz), 141.4, 135.8(d, J = 9.1 Hz), 134.1, 133.0, 131.7,130.9(d, J =3.0 Hz), 128.0, 124.9(d, J = 3.1 Hz), 122.4, 122.28, 116.6(d, J =23.5 Hz), 94.5, 69.8(d, J = 14.1 Hz). 19F NMR (376 MHz, None) δ -108.26. HRMS(ESI) exact mass calculated for C15H10 FIO3 [M+ Na]+: 406.9552, found:406.9555; IR (neat): νmax (cm-1) = 3067, 2991, 1735, 1699, 1625, 1470, 1264,1116, 1013, 699。
实施例16 化合物A16
乙酸乙酯/石油醚=1:11, v/v；白色固体，产率：75%；1H NMR (400 MHz,Chloroform-d) δ: 8.07-7.88 (m, 3H), 7.83 (dt, J = 9.1, 2.5 Hz, 1H), 7.71-7.60(m, 1H), 7.55 (ddd, J = 8.6, 5.1, 1.9 Hz, 2H), 7.00 (ddt, J = 8.9, 6.4, 1.9Hz, 1H), 5.63 (s, 2H). 13C NMR (101 MHz, CDCl3) δ 191.3, 164.7, 164.6, 163.7,161.2, 142.8(d, J = 7.3 Hz), 135.6(d, J = 7.3 Hz), 134.1(d, J = 3.3 Hz),129.0, 127.81, 120.7(d, J = 21.6 Hz), 119.2 (d, J = 24.3 Hz), 87.5(d, J =3.5), 66.9. 19F NMR (376 MHz, None) δ -113.74. HRMS (ESI) exact masscalculated for C15H10 FIO3 [M+ Na]+: 406.9552, found: 406.9553; IR (neat): νmax(cm-1) = 3055, 2997, 1715, 1684, 1600, 1280, 1239, 1120, 966, 714。
实施例17 化合物A17
乙酸乙酯/石油醚=1:20 , v/v；白色固体，产率：62%；1H NMR (400 MHz,Chloroform-d) δ: 8.02 (ddd, J = 14.1, 8.9, 6.6 Hz, 4H), 7.46 (t, J = 7.6 Hz,1H), 7.24-7.11 (m, 3H), 5.56 (s, 2H). 19F NMR (376 MHz, CDCl3) δ -103.07. 13CNMR (101 MHz, CDCl3) δ 190.2, 166.2(d, J = 257 Hz) 165.7, 141.5, 133.9,133.2, 131.1(d, J = 108.6 Hz), 130.6, 130.5, 128.0, 116.2(d, J = 22.1 Hz),94.5, 66.5. HRMS (ESI) exact mass calculated for C15H10 FIO3 [M+ Na]+:406.9552, found: 406.9556; IR (neat): νmax (cm-1) = 3067, 2915, 1694, 1603,1361,1268, 1227, 1116。
实施例18 化合物A18
乙酸乙酯/石油醚=1：20，v/v；白色固体，产率：60%；1H NMR (400 MHz,Chloroform-d) δ: 8.05 (ddd, J = 16.1, 7.9, 1.4 Hz, 2H), 7.83-7.73 (m, 2H),7.51-7.35 (m, 3H), 7.20 (td, J = 7.7, 1.7 Hz, 1H), 5.60 (s, 2H), 2.44 (s,3H). 13C NMR (101 MHz, CDCl3) δ 191.9, 165.8, 141.4, 138.8, 134.8, 134.2,134.2, 133.1, 131.7, 128.8, 128.4, 128.0,125.0, 94.5, 66.8, 21.4. HRMS (ESI)exact mass calculated for C16H13 IO3 [M+ Na]+: 402.9802, found: 402.9805; IR(neat): νmax (cm-1) = 3064, 2987, 1720, 1698, 1257, 1228, 1076, 968, 739。
实施例19 化合物A19
乙酸乙酯/石油醚=1：10，v/v；白色固体，产率：55%；1H NMR (400 MHz,Chloroform-d) δ: 8.15-7.99 (m, 4H), 7.78 (d, J = 8.3 Hz, 2H), 7.46 (td, J =8.5, 7.7, 0.9 Hz, 1H), 7.21 (td, J = 7.7, 1.6 Hz, 1H), 5.59 (s, 2H). 13C NMR(101 MHz, CDCl3) δ 191.1, 165.7 141.53, 136.8, 135.2(q, J = 98.9 Hz), 133.8,133.2, 131.7, 128.3, 128.1, 126.0(q, J = 11.2 Hz), 123.4(q, J = 823.8 Hz),94.5, 66.7. 19F NMR (376 MHz, CDCl3) δ -63.25. HRMS (ESI) exact masscalculated for C16H10 F3IO3 [M+ Na]+: 456.9520, found: 456.9521; IR (neat): νmax(cm-1) = 2955, 1724, 1690, 1274, 1243, 1123, 1126, 699。
实施例20 化合物A20
乙酸乙酯/石油醚=1：12，v/v；白色固体，产率：48%；1H NMR (400 MHz,Chloroform-d) δ: 8.13-7.97 (m, 2H), 7.83 (d, J = 8.5 Hz, 2H), 7.66 (d, J =8.5 Hz, 2H), 7.45 (td, J = 7.7, 1.3 Hz, 1H), 7.20 (td, J = 7.7, 1.7 Hz, 1H),5.54 (s, 2H). 13C NMR (101 MHz, CDCl3) δ190.9, 165.7, 141.5, 133.8, 133.2,132.9, 132.3, 131.7, 129.3, 128.1,128.1, 94.5, 66.5。
实施例21 化合物A21
乙酸乙酯/石油醚=1：10，v/v；白色固体，产率：73%；1H NMR (400 MHz,Chloroform-d) δ: 8.12-7.96 (m, 2H), 7.74 (d, J = 7.7 Hz, 1H), 7.66 (d, J =9.0 Hz, 1H), 7.55-7.42 (m, 2H), 7.34 (td, J = 8.2, 2.3 Hz, 1H), 7.20 (td, J =7.7, 1.7 Hz, 1H), 5.56 (s, 2H). 13C NMR (101 MHz, CDCl3) δ 190.7(d, J =2.0Hz), 165.7, 162.9(d, J = 250.0 Hz), 141.5, 136.1(d, J = 6.4Hz), 133.9, 133.2,131.7, 130.7(d, J = 7.8 Hz), 128.0, 123.5(d, J = 3.1 Hz), 121.1(d, J = 21.6Hz), 114.7(d, J = 22.6 Hz), 94.5, 66.7. 19F NMR (376 MHz, None) δ -111.70.HRMS (ESI) exact mass calculated for C15H10 FIO3 [M+ Na]+: 406.9552, found:406.9554; IR (neat): νmax (cm-1) = 2983, 1719, 1702, 1306, 1126, 966, 744,694。
实施例22 化合物A22
乙酸乙酯/石油醚=1：10，v/v；白色固体，产率：40%；1H NMR (400 MHz,Chloroform-d) δ: 8.05-7.94 (m, 2H), 7.43 (td, J = 7.6, 1.2 Hz, 1H), 7.17 (td,J = 7.7, 1.6 Hz, 1H), 5.15 (s, 2H), 1.26 (s, 9H). 13C NMR (101 MHz, CDCl3) δ207.4, 165.9, 141.3, 134.3, 132.9, 131.6, 128.0, 94.2, 65.2, 42.9, 26.3. HRMS(ESI) exact mass calculated for C13H15 IO3 [M+ Na]+: 368.9959, found: 368.9956;IR (neat): νmax (cm-1) = 2975, 2936, 1731, 1699, 1450, 1280, 1229, 1158, 970,700。
实施例23 化合物A23
乙酸乙酯/石油醚=1：12，v/v；浅黄色油状物，产率：55%；1H NMR (400 MHz,Chloroform-d) δ: 8.12 (dt, J = 16.2, 7.8 Hz, 1H), 8.05 (q, J = 7.0 Hz, 2H),7.77 (t, J = 7.6 Hz, 2H), 747(m, 1H), 7.55 (t, J = 7.4 Hz, 1H), 5.70 (s, J =3.8 Hz, 2H). 13C NMR (101 MHz, CDCl3) δ: 198.3, 165.9, 141.3, 139.4, 134.5,133.8, 132.9, 132.1, 132.1, 130.5, 129.5, 127.5, 115.8, 111.5, 94.1, 67. HRMS(ESI) exact mass calculated for C16H10INO3 [M+Na]+: 413.9598, found:413.9595;IR (neat): νmax (cm-1) = 3053, 2991, 1735, 1699, 1625, 1470, 1264, 1200, 1013,702。
实施例24 化合物A24
乙酸乙酯/石油醚=1：10，v/v；浅黄色油状物，产率：50%；1H NMR (400 MHz,Chloroform-d) δ: 8.89-7.93 (ddd, J = 16.1, 7.9, 1.4 Hz, 2H), 7.75(m, 2H),7.55-7.49 (m, 3H), 7.18 (td, J = 7.7, 1.7 Hz, 1H), 5.70 (s, 2H), 3.83 (s,3H). 13C NMR (101 MHz, CDCl3) δ: 191.9, 165.8, 141.4, 138.8, 134.8, 134.2,134.2, 133.1, 131.7, 128.8, 128.4, 128.0, 125.0, 94.5, 67.5, 55.8. HRMS (ESI)exact mass calculated for C16H13 IO4 [M+Na]+: 418.9752, found: 418.9754; IR(neat): νmax (cm-1) = 306, 2987, 1720, 1698, 1257, 1228, 1076, 1112, 699。
实施例25 化合物A25
乙酸乙酯/石油醚=1：11，v/v；浅黄色油状物，产率：58%；1H NMR (400 MHz,Chloroform-d) δ: 7.98 (dt, J = 8.5, 1.5 Hz, 2H), 7.71-7.67 (m, 1H), 7.63 (t,J = 6.9, 1.2 Hz, 1H), 7.52 (t, J = 7.7 Hz, 2H), 7.18-7.11 (m, 2H), 5.61 (s,2H). 13C NMR (101 MHz, CDCl3) δ 191.0, 164.4, 160.7, 158.2, 135.4(d, J = 3.54Hz), 134.2, 134.0, 132.8(d, J = 8.7 Hz), 128.4(d, J =100.1 Hz), 115.9(d, J =21.5 Hz), 92.9, 67.3, 29.7. 19F NMR (376 MHz, CDCl3) δ -109.09.HRMS (ESI)exact mass calculated for C15H10 FIO3 [M+Na]+: 406.9552, found: 406.9550; IR(neat): νmax (cm-1) = 3055, 2997, 1715, 1684, 1600, 1280, 1239, 1120, 966, 714。
实施例26 化合物A26
乙酸乙酯/石油醚=1：10，v/v；浅黄色油状物，产率：54%；1H NMR (400 MHz,Chloroform-d) δ: 8.18 (d, J = 2.4 Hz, 1H), 8.00-7.93 (m, 2H), 7.87 (d, J =8.4 Hz, 1H), 7.67-7.60 (m, 1H), 7.52 (dd, J = 8.4, 7.1 Hz, 2H), 7.32 (dd, J =8.4, 2.4 Hz, 1H), 5.60 (s, 2H). 13C NMR (101 MHz, CDCl3) δ 190.7, 165.6,150.8, 141.6, 138.6, 133.5, 133.4, 131.7, 129.0, 128.1, 124.2, 94.6, 66.8.HRMS (ESI) exact mass calculated for C15H10INO5 [M+ Na]+: 433.9497, found:433.9494; IR (neat): νmax (cm-1) = 3072, 1711, 1692, 1517, 1347, 1334, 1196,1178, 1008, 850, 699。
实施例27 化合物A27
乙酸乙酯/石油醚=1：15，v/v；浅黄色油状物，产率：52%；1H NMR (400 MHz,Chloroform-d) δ: 8.13 (s, 1H), 8.03 (ddd, J = 8.0, 2.9, 1.4 Hz, 2H), 7.82(d,J = 7.8 Hz, 1H), 7.79 (d, J = 8.0 Hz, 1H), 7.55 (dt, J = 23.8, 7.8 Hz, 2H),7.45 (td, J = 7.6, 1.5 Hz, 1H), 5.70 (s, 2H). 13C NMR (101 MHz, CDCl3) δ190.6, 165.7, 141.5, 136.9, 135.9, 133.9, 133.2, 131.7, 130.9, 130.5, 128.0,126.3, 123.3, 94.5, 66.6. HRMS (ESI) exact mass calculated for C15H10BrIO3 [M+Na]+: 466.8751, found: 466.8747; IR (neat): νmax (cm-1) = 3067, 2915, 1694,1603, 1361,1268, 1227, 1116。
实施例28 化合物A28
乙酸乙酯/石油醚=1：15，v/v；浅黄色油状物，产率：50%；1H NMR (400 MHz,Chloroform-d) δ: 8.04 (ddd, J = 7.6, 5.7, 1.4 Hz, 2H), 7.81 (dd, J = 3.9, 1.1Hz, 1H), 7.55 (dd, J = 5.0, 1.1 Hz, 1H), 5.41 (s, 2H),1.98 (m, 2H) ,0.89 (m,2H),0.64 (m, 2H); 13C NMR (101 MHz, CDCl3) δ210.2, 165.9, 141.3, 134.5, 132.1,130.5, 127.5,94.1, 69.6, 19.7, 9.8, 9.8; HRMS (ESI) exact mass calculated forC13H9IO3S [M+Na]+: 352.9646, found: 352.9643; IR (neat): νmax (cm-1) = 3087,1707, 1692, 1624, 1207, 1171, 702。
实施例29 化合物A29
乙酸乙酯/石油醚=1：8，v/v；浅黄色油状物，产率：65%；1H NMR (400 MHz,Chloroform-d) δ: 8.04 (ddd, J = 15.3, 7.9, 1.3 Hz, 2H), 7.86 (d, J = 8.2 Hz,2H), 7.82 (td, J = 7.6, 1.0 Hz, 1H), 7.55 (d, J = 8.0 Hz, 2H), 7.10 (td, J =7.7, 1.7 Hz, 1H), 5.70 (s, 2H), 3.83 (s, 3H). 13C NMR (101 MHz, CDCl3) δ191.3, 165.8, 145.0, 141.4, 134.2, 133.0, 131.7, 131.7, 129.6, 128.0, 127.9,94.4, 66.7, 55.8. HRMS (ESI) exact mass calculated for C16H13 IO4 [M+Na]+:418.9752, found: 418.9754; IR (neat): νmax (cm-1) = 3063,2988, 1729, 1693,1103, 1016, 742,720。
实施例30 化合物A30
乙酸乙酯/石油醚=1：10，v/v；浅黄色油状物，产率:5%；1H NMR (400 MHz,Chloroform-d) δ: 9.15 (s, 1H), 8.82 (m, J = 7.4 Hz, 1H), 8.34 (t, J = 7.4 Hz,1H), 7.89-7.93 (t, J = 7.7 Hz, 2H), 7.82 (m, J = 7.6 Hz, 1H), 7.64 (m, J =7.8, 1.6 Hz, 1H), 7.55 (t, J = 7.8, 1.6 Hz, 1H), 5.55(s, 2H). 13C NMR (101MHz, Chloroform-d) δ 198.3 , 165.9 , 150.1 , 149.6 , 141.3 , 136.2, 134.5 ,132.3 ,132.1 , 130.5 , 127.5, 123.7, 94.1, 67.2. HRMS (ESI) exact masscalculated forC14H10INO3[M+Na]+: 389.9598, found: 389.9595; IR (neat): νmax (cm-1) = 3035, 2851, 1750, 1714, 1596, 1459, 1374,1112, 700。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。

Claims (3)

1. 一种邻碘代α-酰氧基羰基化合物的合成方法，其特征在于：以EBX试剂为原料，Ｎ-杂环卡宾前体盐作为催化剂，有机溶剂与水的混合液为溶剂，在碱存在的条件下，于0-120℃反应14-18 h小时后，经分离纯化制得所述邻碘代α-酰氧基羰基化合物；其结构式为：
；
其中，R1、R2任意独立选自H，C1-C16的烷基，C3-C16的环烷基，C4-C10的芳基，取代芳基，含N、O或S的杂环基或杂芳基；所述芳基为苯基或萘基；所述取代芳基包括C1-C4的烷基取代、C1-C4的烷氧基取代、C1-C4的全氟烷基取代或卤素取代；
其中，EBX试剂、碱与Ｎ-杂环卡宾前体盐的摩尔比为1:0.2-1.1:0.01-0.05；
所述EBX试剂的结构式为：；
所述碱包括碳酸盐、醋酸盐、磷酸盐、胺中的任意一种；
所述Ｎ-杂环卡宾前体盐包括咪唑盐、烯基咪唑盐、噻唑盐、三氮唑盐中的任意一种。
2.根据权利要求1所述邻碘代α-酰氧基羰基化合物的合成方法，其特征在于：有机溶剂与水混合的体积比为100:2.5；
所述有机溶剂为1，4-二氧六环、丙酮、甲苯、苯、乙腈、二氯甲烷、四氢呋喃、二甲基亚砜、N，N-二甲基甲酰胺、1，2-二氯乙烷、甲醇、二甲苯、乙醚、三氯甲烷、环己烷、正己烷、正庚烷、四氯化碳或石油醚中的任意一种。
3.根据权利要求1所述邻碘代α-酰氧基羰基化合物的合成方法，其特征在于：分离纯化的方法包括重结晶、薄层层析、柱层析、减压蒸馏。
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