CN104030994A - 1,2,3—三唑类化合物的合成方法 - Google Patents

1,2,3—三唑类化合物的合成方法 Download PDF

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CN104030994A
CN104030994A CN201410131047.1A CN201410131047A CN104030994A CN 104030994 A CN104030994 A CN 104030994A CN 201410131047 A CN201410131047 A CN 201410131047A CN 104030994 A CN104030994 A CN 104030994A
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孙绍发
高涛
石文娟
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Hubei University of Science and Technology
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    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
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    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
    • C07D249/06—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles with aryl radicals directly attached to ring atoms
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
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    • C07—ORGANIC CHEMISTRY
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    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
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Abstract

本发明公开了一种1,2,3—三唑类化合物的合成方法，以水为反应溶剂，以酮类化合物和叠氮类化合物作为原料，在胺类化合物催化作用下，反应得到1,2,3—三唑类化合物，本发明反应条件温和，环境友好，操作简便，产率高，具有良好工业应用前景。

Description

1,2,3—三唑类化合物的合成方法
技术领域
本发明涉及1,2,3—三唑类化合物的合成方法,属于有机化合物工艺应用技术领域。
背景技术
1，2, 3-三唑又称连三唑,作为重要的三氮芳杂环,易形成氢键、配位键等,可发挥多种非共价键相互作用,因而1, 2,3-三唑环作为一种核心骨架可用于构筑材料、催化剂、药物及其超分子药物等多种类型的功能分子,显示出1, 2, 3-三唑类化合物在药学、化学、生物学、材料学等领域有着广泛的应用前景。尤其在医药领域, 1, 2, 3-三唑类化合物在抗细菌、抗真菌、抗结核、抗病毒、抗癌等方面不断取得新的研究进展。迄今已有多种1, 2, 3-三唑类化合物进入临床实验或用于临床,其在制药领域发挥越来越重要的作用。
1, 2, 3-三唑类化合物的合成方法很多，但是这些合成方法大多使用有机化合物作为反应溶剂，部分方法还需使用贵金属作为催化剂，反应条件苛刻，污染大，成本高,本发明避免了以上合成方法中的种种不足及缺陷，提供了一种有效制备1, 2, 3-三唑类化合物的新方法，该方法使用有机小分子化合物作为催化剂，使用水作为反应溶剂，通过1,3—偶极环加成反应，一步合成目标产物。该合成方法使用的催化剂毒性小，反应条件温和，操作简便，产率高，成本低廉，反应过程绿色环保，适用于工业化生产。
发明内容
1、一种1,2,3—三唑类化合物的合成方法，以水为反应溶剂，以酮类化合物和叠氮类化合物作为原料，在胺类化合物催化作用下，反应得到1,2,3—三唑类化合物,反应过程如式（I ）所示：
1 2 3
式（I )
其中，R1为芳香烃类基团；R2为烷基、芳香基；R3为烷基、酯基；其中2还可以为环己酮、环庚酮、环辛酮类化合物。本发明中，R1、R2、R3包括但不仅仅局限于上述基团。
2、 如权利要求1所述1,2,3—三唑类化合物的合成方法，其特征在于，所述催化剂为胺类化合物，包括如以下10种化合物。
3、如权利要求1所述1,2,3—三唑类化合物的合成方法，其特征在于，所述催化剂用量为叠氮类化合物的0.2当量。
4、如权利要求 1 所述1,2,3—三唑类化合物的合成方法，其特征在于，所述溶剂为水。
5、如权利要求 1 所述1,2,3—三唑类化合物的合成方法，其特征在于，所述叠氮类化合物的用量为1当量，所述酮类化合物的用量为2当量。
6、如权利要求 1 所述1,2,3—三唑类化合物的合成方法，其特征在于，所述反应温度为80℃。
7、如权利要求 1 所述1,2,3—三唑类化合物的合成方法，其特征在于，所述反应时间为48小时以上。
本发明的优点包括：本发明所使用催化剂为有机小分子催化剂，不含过度金属、容易制备、价格低廉、反应条件温和、稳定性强、对环境友好。其次，此合成方法简单、操作容易、产物收率高，实用性尤其显著；本发明具有成本低、效率高、工艺简、污染少的特色，可以进行工业化生产。
具体实施方式
结合以下具体实施例，对本发明作进一步的详细说明，本发明的保护内容不局限于以下实施例。在不背离发明构思的精神和范围下，本领域技术人员能够想到的变化和优点都被包括在本发明中，并且以所附的权利要求书为保护范围。实施本发明的过程、条件、试剂、实验方法等，除以下专门提及的内容之外，均为本领域的普遍知识和公知常识，本发明没有特别限制内容。以下实施例所给出的数据包括具体操作和反应条件及产物。产物纯度通过核磁鉴定。
实施例1
将叠氮苯 1a (0.25 mmol), 环己酮 2a (0.5 mmol)和催化剂 XI (0.05 mmol) 加入到 0.5 mL 水中。在80oC的条件下搅拌反应48小时。 反应混合物用二氯甲烷多次萃取，用旋转蒸发仪回收溶剂，粗产物经快速硅胶柱层析纯化，用正己烷/乙酸乙酯 (比例10:1 → 4:1) 洗脱得到所需的产品3aa，产率81% ; 1H NMR (300 MHz, CDCl3): δ = 7.56−7.43 (m, 5H), 2.91−2.73 (m, 4H), 1.96−1.85 (m, 4H). 13C NMR (75 MHz, CDCl3): δ = 143.71, 136.67, 131.81, 129.21, 129.17, 122.81, 22.51, 22.22, 21.72, 21.58. HRMS (ESI): calcd for C12H14N3 [M + H]+ 200.1182, found 200.1190。
实施例2
操作步骤同实施例1，产率92% ; 1H NMR (300 MHz, CDCl3):δ= 7.53−7.45 (m, 2H), 7.20 − 7.13 (m, 2H), 2.79 − 2.67 (m, 4H), 1.92−1.80 (m, 4H). 13C NMR (75 MHz, CDCl3): δ = 163.90, 160.60, 143.92, 132.02, 125.00, 116.48, 22.58, 22.31, 21.80, 21.53. HRMS (ESI): calcd for C12H13FN3 [M + H]+ 218.1088, found 218.1091。
实施例3
操作步骤同实施例1，产率90%;1H NMR (300 MHz, CDCl3):δ= 7.52−7.40 (m, 4H), 2.84 − 2.66 (m, 4H), 1.88–1.80 (m, 4H). 13C NMR (75 MHz, CDCl3):δ= 144.14, 135.34, 134.34, 131.92, 129.57, 124.09, 22.61, 22.29, 21.81, 21.74. HRMS (ESI): calcd for C12H13ClN3 [M + H]+ 234.0793, found 234.0801。
实施例4
操作步骤同实施例1，产率83% ;1H NMR (300 MHz, CDCl3): δ = 7.61 (dd, J = 6.8 Hz, 1.9 Hz, 2H), 7.42 (dd, J = 6.8 Hz, 1.8Hz, 2H), 2.81 − 2.70 (m, 4H), 1.93−1.78 (m, 4H). 13C NMR (75 MHz, CDCl3): δ = 144.19, 135.83, 132.56, 131.90, 124.34, 122.28, 22.62, 22.28, 21.81, 21.76. HRMS (ESI): calcd for C12H13BrN3 [M + H]+ 278.0287, found 278.0297。
实施例5
操作步骤同实施例1，产率80%;1H NMR (300 MHz, CDCl3) δ = 7.57 (d, J = 1.5, 1H), 7.44 − 7.35 (m, 3H), 2.80 − 2.71 (m, 4H), 1.87 − 1.81 (m, 4H). 13C NMR (75 MHz, CDCl3): δ = 144.18, 137.78, 135.10, 131.95, 130.42, 128.53, 123.08, 120.86, 22.59, 22.26, 21.79. HRMS (ESI): calcd for C12H13ClN3 [M + H]+ 234.0793, found 234.0799。
实施例6
操作步骤同实施例1，产率79% ; 1H NMR (300 MHz, CDCl3): δ = 7.70 (s, 1H), 7.52 − 7.41 (m, 2H), 7.33 (t, J = 8.1 Hz, 1H), 2.80 − 2.69 (m, 4H), 1.89 − 1.77 (m, 4H). 13C NMR (75 MHz, CDCl3): δ = 144.08, 137.74, 131.90, 131.38, 130.60, 125.82, 122.76, 121.21, 22.50, 22.16, 21.69. HRMS (ESI): calcd for C12H13BrN3 [M + H]+ 278.0287, found 278.0283。
实施例7
操作步骤同实施例1，产率72% yield; 1H NMR (300 MHz, CDCl3): δ = 7.53 (dd, J = 7.1 Hz, 1.5 Hz, 1H), 7.47 − 7.37 (m, 3H), 2.80 (t, J = 4.9 Hz, 2H), 2.47 (t, J = 5.0, 2H), 1.96 − 1.79 (m, 4H). 13C NMR (75 MHz, CDCl3): δ = 142.85, 134.27, 131.06, 130.34, 128.88, 127.62, 22.48, 22.28, 21.71, 20.21. HRMS (ESI): calcd for C12H13ClN3 [M + H]+ 234.0793, found 234.0793。
实施例8
操作步骤同实施例1，产率68% yield; 1H NMR (300 MHz, CDCl3): δ = 7.58 (d, J = 2.1 Hz, 1H), 7.41 (dd, J = 8.4 Hz, 2.0 Hz, 1H), 7.34 (d, J = 8.4 Hz, 1H), 2.82 (t, J = 4.5 Hz, 2H), 2.48 (t, J = 4.4 Hz, 2H), 1.90 − 1.81 (m, 4H). 13C NMR (75 MHz, CDCl3): δ = 143.15, 136.63, 134.35, 133.40, 133.00, 132.03, 130.32, 129.73, 128.06, 22.50, 22.33, 21.75, 20.29. HRMS (ESI): calcd for C12H12Cl2N3 [M + H]+ 268.0403, found 268.0402。
实施例9
操作步骤同实施例1，产率81% ; 1H NMR (300 MHz, CDCl3): δ = 7.76 (d, J = 8.6 Hz, 2H), 7.70 (d, J = 8.7 Hz, 2H), 2.82 − 2.76 (m, 4H), 1.89 − 1.82 (m, 4H). 13C NMR (75 MHz, CDCl3): δ = 144.51, 139.61, 132.02, 126.69, 122.78, 86.28, 22.62, 22.21, 21.99, 21.80. HRMS (ESI): calcd for C13H13F3N3 [M + H]+ 268.1056, found 268.1060。
实施例10
操作步骤同实施例1，产率75% ; 1H NMR (300 MHz, CDCl3): δ = 7.91 (d, J = 1.8Hz, 1H), 7.70 − 7.61 (m, 2H), 2.79 − 2.71 (m, 4H), 1.90 − 1.81 (m, 4H). 13C NMR (75 MHz, CDCl3): δ = 144.57, 135.46, 132.61, 131.98, 126.51, 121.83, 121.75, 22.51, 22.11, 21.73. HRMS (ESI): calcd for C13H12ClF3N3 [M + H]+ 302.0666, found 302.0667。
实施例11
操作步骤同实施例1，产率69% ; 1H NMR (300 MHz, CDCl3): δ = 8.02 − 7.98 (m, 1H), 7.65 − 7.52 (m, 2H), 7.39 − 7.28 (m, 1H), 4.08 (q, J = 7.1 Hz, 2H), 2.80 (t, J = 5.2 Hz, 2H), 2.42 (t, J = 5.1 Hz, 2H), 1.85 − 1.79 (m, 4H), 1.05 (t, J = 7.0 Hz, 3H). 13C NMR (75 MHz, CDCl3): δ = 165.03, 142.53, 135.39, 134.04, 132.57, 131.33, 129.78, 128.71, 127.67, 61.41, 22.55, 22.35, 21.71, 20.20, 13.70. HRMS (ESI): calcd for C15H18N3O2 [M + H]+ 272.1394, found 272.1393。
实施例12
操作步骤同实施例1，产率76% ; 1H NMR (300 MHz, CDCl3): δ = 7.49 − 7.44 (m, 1H), 7.40 − 7.33 (m, 2H), 7.18 − 7.03 (m, 5H), 2.84−2.79 (m, 2H), 2.72 − 2.67 (m, 2H), 1.89 − 1.81 (m, 4H). 13C NMR (75 MHz, CDCl3): δ = 157.68, 156.25, 143.78, 131.99, 131.78, 129.90, 124.68, 124.01, 119.37, 118.91, 22.64, 22.39, 21.86, 21.57. HRMS (ESI): calcd for C18H18N3O[M + H]+ 292.1444, found 292.1447。
实施例13
操作步骤同实施例1，产率73% yield; 1H NMR (300 MHz, CDCl3): δ = 7.45 (d, J = 8.4, 2H), 7.32 (d, J = 8.5Hz, 2H), 2.89 − 2.82 (m, 2H), 2.78 − 2.65 (m, 4H), 1.92 − 1.84 (m, 4H), 1.69 − 1.63 (m, 2H), 1.42 − 1.26 (m, 8H), 0.90 (t, J = 6.8 Hz, 3H). 13C NMR (75 MHz, CDCl3): δ = 143.71, 143.58, 134.53, 131.88, 129.23, 122.91, 35.44, 31.69, 31.21, 29.08, 29.03, 22.68, 22.54, 22.43, 21.89, 21.68, 13.97. HRMS (ESI): calcd for C19H28N3 [M + H]+ 298.2278, found 298.2280。
实施例14
操作步骤同实施例1，产率86% ; 1H NMR (300 MHz, CDCl3): δ = 7.43 (d, J = 8.3 Hz, 2H), 7.33 (d, J = 8.4 Hz, 2H), 3.00 − 2.90 (m, 1H), 2.81 − 2.69 (m, 4H), 1.87 − 1.81 (m, 4H), 1.26 (d, J = 6.9 Hz, 6H). 13C NMR (75 MHz, CDCl3): δ = 149.42, 143.69, 134.58, 131.89, 127.29, 122.98, 33.74, 23.78, 22.66, 22.41, 21.87, 21.66. HRMS (ESI): calcd for C15H20N3 [M + H]+ 242.1652, found 242.1656。
实施例15
操作步骤同实施例1，产率77% ; 1H NMR (300 MHz, CDCl3): δ = 7.50 (d, J = 8.7 Hz, 2H), 7.44 (d, J = 8.7 Hz, 2H), 2.82 − 2.71 (m, 4H), 1.87 − 1.79 (m, 4H), 1.34 (s, 9H). 13C NMR (75 MHz, CDCl3): δ = 151.73, 143.73, 134.32, 131.91, 126.26, 122.65, 34.68, 31.20, 22.69, 22.44, 21.91, 21.72. HRMS (ESI): calcd for C16H22N3 [M + H]+ 256,1808, found 256.1816。
实施例16
操作步骤同实施例1，产率83% yield; 1H NMR (300 MHz, CDCl3): δ = 7.12 (s, 2H), 7.05 (s, 1H), 2.82 − 2.69 (m, 4H), 2.36 (s, 6H), 1.86 − 1.80 (m, 4H). 13C NMR (75 MHz, CDCl3): δ = 143.68, 139.22, 136.67, 131.87, 130.11, 120.81, 22.68, 22.44, 21.88, 21.75, 21.16. HRMS (ESI): calcd for C14H18N3 [M + H]+ 228.1495, found 228.1502。
实施例17
操作步骤同实施例1，产率74% yield;1H NMR (300 MHz, CDCl3): δ = 7.52 − 7.45 (m, 2H), 7.33 − 7.28 (m, 1H), 2.84 − 2.72 (m, 4H), 2.45 (s, 3H), 1.91 − 1.86 (m, 4H). 13C NMR (75 MHz, CDCl3): δ = 144.01, 137.64, 135.21, 134.47, 131.90, 129.80, 125.32, 121.34, 22.63, 22.32, 21.83, 21.72, 20.10. HRMS (ESI): calcd for C13H14ClN3 [M + H]+ 248.0949, found 248.0952。
实施例18
操作步骤同实施例1，产率72% ;1H NMR (300 MHz, CDCl3): δ = 8.01 − 7.90 (m, 2H), 7.59 − 7.33 (m, 5H), 2.90 (t, J = 6.0, 2H), 2.39 (t, J = 6.1, 2H), 1.89 − 1.75 (m, 4H). 13C NMR (75 MHz, CDCl3): δ = 143.00, 134.45, 134.07, 132.75, 130.16, 129.28, 128.13, 127.59, 126.84, 124.95, 124.32, 122.50, 22.63, 22.39, 21.88, 20.38. HRMS (ESI): calcd for C16H16N3 [M + H]+ 250.1339, found 250.1343。
实施例19
操作步骤同实施例1，产率81% ; 1H NMR (300 MHz, CDCl3): δ = 7.55 − 7.39 (m, 5H), 2.96 (dd, J = 15.9 Hz, 5.1 Hz, 1H), 2.76 − 2.70 (m, 2H), 2.36 (dd, J = 15.9 Hz, 9.6 Hz 1H), 1.96 − 1.90 (m, 2H), 1.51 − 1.42 (m, 1H), 1.12 (d, J = 6.6 Hz, 1H). 13C NMR (75 MHz, CDCl3): δ = 144.21, 136.90, 131.74, 129.36, 128.47, 122.94, 30.84, 30.04, 29.11, 21.05, 21.01. HRMS (ESI): calcd for C13H16N3 [M + H]+ 241.1339, found 214.1340。
实施例20
操作步骤同实施例1，产率82% ; 1H NMR (300 MHz, CDCl3 ): δ = 7.54 − 7.38 (m, 5H), 2.99 (dd, J = 15.8 Hz, 5.0 Hz, 1H), 2.75 − 2 .69 (m, 2H), 2.35 (dd, J = 15.8 Hz, 9.8 Hz, 1H), 2.01 − 1.96 (m, 1H), 1.78 − 1.65 (m, 1H), 1.50 − 1.38 (m, 3H), 0.98 (t, J = 7.3 Hz, 3H). 13C NMR (75 MHz, CDCl3): δ = 144.22, 136.88, 131.93, 129.34, 128.42, 122.86, 35.90, 28.72, 28.22, 27.79, 21.10, 11.50. HRMS (ESI): calcd for C14H18N3 [M + H]+ 228.1495, found 228.1504。
实施例21
操作步骤同实施例1，产率71% ; 1H NMR (300 MHz, CDCl3): δ = 7.55 − 7.33 (m, 5H), 2.92 (dd, J = 15.7 Hz, 4.8 Hz, 1H), 2.80 − 2.66 (m, 2H), 2.50 − 2.41 (m, 1H), 2.16 − 2.11 (m, 1H), 2.04 − 1.98 (m, 1H), 1.72 − 1.61 (m, 1H), 1.52 − 1.66 (m, 1H), 0.97 (dd, J = 6.6 Hz, 2.4 Hz, 3H). 13C NMR (75 MHz, CDCl3): δ = 144.60, 136.86, 131.96, 129.35, 128.41, 122.80, 40.76, 31.68, 26.47, 24.99, 21.61, 20.04, 19.42. HRMS (ESI): calcd for C15H20N3 [M + H]+ 228.1495, found 228.1504。
实施例22
操作步骤同实施例1，产率74% ; 1H NMR (300 MHz, CDCl3): δ = 7.57 − 7.36 (m, 5H), 2.72 (t, J = 6.3 Hz, 2H), 2.59 (s, 2H), 1.61 (t, J = 6.4 Hz, 2H), 1.04 (s, 6H). 13C NMR (75 MHz, CDCl3): δ = 144.06, 136.94, 130.80, 129.37, 128.47, 122.86, 35.64, 35.56, 30.43, 27.66, 18.95. HRMS (ESI): calcd for C14H18N3 [M + H]+ 228.1495, found 228.1497。
实施例23
操作步骤同实施例1，产率71% yield;1H NMR (300 MHz, CDCl3): δ = 7.51 − 7.39 (m, 5H), 2.81 (t, J = 6.3 Hz, 2H), 2.48 (s, 2H), 1.63 (t, J = 6.5, 2H), 0.99 (s, 6H). 13C NMR (75 MHz, CDCl3): δ = 142.73, 136.77, 131.90, 129.34, 128.48, 123.06, 35.49, 35.28, 31.06, 27.66, 19.03. HRMS (ESI): calcd for C14H18N3 [M + H]+ 228.1495, found 228.1499。
实施例24
操作步骤同实施例1，产率69% ; 1H NMR (300 MHz, CDCl3): δ = 7.55 − 7.46 (m, 1H), 4.19 (q, J = 7.1 Hz, 2H), 3.18 (dd, J = 16.0 Hz, 5.6 Hz, 1H), 3.03 (dd, J = 18.3 Hz, 6.8 Hz, 1H), 2.91 − 2.77 (m, 3H), 2.32 − 2.24 (m, 1H), 1.98 − 1.92 (m, 1H), 1.28 (t, J = 7.2 Hz, 3H). 13C NMR (75 MHz, CDCl3): δ = 173.94, 142.39, 136.52, 131.15, 129.35, 128.58, 122.82, 60.65, 39.28, 25.25, 24.44, 20.40, 14.01. HRMS (ESI): calcd for C15H18N3O2 [M + H]+ 272.1394, found 272.1400。
实施例25
操作步骤同实施例1，产率73% ; 1H NMR (300 MHz, CDCl3): δ = 7.56 − 7.42 (m, 5H), 4.08 − 4.00 (m, 4H), 3.05 (s, 2H), 2.88 (t, J = 6.5 Hz, 2H), 2.01 (t, J = 6.5 Hz, 2H). 13C NMR (75 MHz, CDCl3): δ = 142.72, 136.71, 130.88, 129.43, 128.68, 123.02, 108.24, 64.73, 33.11, 31.67, 19.09. HRMS (ESI): calcd for C14H16N3O2 [M + H]+ 258.1237, found 258.1236。
实施例26
操作步骤同实施例1，产率77% ; 1H NMR (300 MHz, CDCl3): δ = 7.56 − 7.46 (m, 5H), 3.92 (s, 2H), 3.02 − 2.97 (m, 2H), 2.92 − 2.86 (m, 2H). 13C NMR (75 MHz, CDCl3): δ = 139.89, 136.25, 131.85, 129.54, 129.14, 123.80, 25.57, 24.48, 23.41. HRMS (ESI): calcd for C11H12N3S[M + H]+ 218.0746, found 218.0746。
实施例27
操作步骤同实施例1，产率93% ; 1H NMR (300 MHz, CDCl3): δ = 7.49 − 7.36 (m, 5H), 2.94 − 2.89 (m, 2H), 2.72 − 2.68 (m, 2H), 1.75 − 1.73 (m, 2H), 1.71 − 1.64 (m, 4H). 13C NMR (75 MHz, CDCl3): δ = 147.14, 136.38, 135.47, 129.17, 129.00, 125.14, 30.71, 27.03, 26.90, 26.86, 24.56. HRMS (ESI): calcd for C13H16N3 [M + H]+ 214.1339, found 214.1343。
实施例28
操作步骤同实施例1，产率86% yield; 1H NMR (300 MHz, CDCl3): δ = 7.48 − 7.33 (m, 5H), 2.93 − 2.88 (m, 2H), 2.71 − 2.65 (m, 2H), 1.77 − 1.68 (m, 4H), 1.48 − 1.45 (m, 4H). 13C NMR (75 MHz, CDCl3): δ = 144.80, 136.48, 133.77, 129.17, 129.05, 125.04, 27.97, 27.24, 25.37, 25.07, 24.26, 21.81. HRMS (ESI): calcd for C14H18N3 [M + H]+ 228.1495, found 228.1501。
实施例29
操作步骤同实施例1，产率88% ; 1H NMR (300 MHz, CDCl3): δ = 8.34 (d, J = 7.3 Hz, 2H), 7.60 (d, J = 7.3 Hz, 1H), 7.52 (t, J = 7.4 Hz, 2H), 7.44 − 7.34 (m, 10H). 13C NMR (75 MHz, CDCl3): δ = 186.48, 143.37, 140.98, 136.99, 135.65, 132.93, 130.51, 130.03, 129.65, 129.32, 129.16, 128.28, 128.07, 125.84, 125.07. HRMS (ESI): calcd for C21H16N3O[M + H]+ 326.1288, found 326.1277。
实施例30
操作步骤同实施例1，产率85%; 1H NMR (300 MHz, CDCl3): δ = 7.57 − 7.41 (m, 5H), 4.44 (q, J = 7.1 Hz, 2H), 2.56 (s, 3H), 1.42 (t, J = 7.1 Hz, 3H). 13C NMR (75 MHz, CDCl3): δ = 161.56, 138.67, 136.55, 135.30, 129.89, 129.50, 125.18, 14.19, 9.79. HRMS (ESI): calcd for C21H16N3O2 [M + H]+ 232.1081, found 232.1075。
实施例31
操作步骤同实施例1，产率85%; 1H NMR (300 MHz, CDCl3): δ = 7.32 − 7.14 (m, 10H), 4.41 (q, J = 7.2 Hz, 2H), 1.22 (t, J = 7.1, 3H). 13C NMR (75 MHz, CDCl3): δ = 160.47, 140.40, 136.48, 135.33, 129.84, 129.46, 129.08, 128.88, 127.88, 125.31, 124.78, 60.66, 13.69. HRMS (ESI): calcd for C17H16N3O2 [M + H]+ 294.1237, found 294.1242。

Claims (8)

1.一种1,2,3—三唑类化合物的合成方法，以水为反应溶剂，以酮类化合物和叠氮类化合物作为原料，在胺类化合物催化作用下，反应得到1,2,3—三唑类化合物,反应过程如式（I ）所示：
1 2 3
式（I )
其中，R1为芳香烃类基团；R2为烷基、芳香基；R3为烷基、酯基；其中2还可以为环己酮、环庚酮、环辛酮类化合物。
2.本发明中，R1、R2、R3包括但不仅仅局限于上述基团。
3.如权利要求1所述1,2,3—三唑类化合物的合成方法，其特征在于，所述催化剂为胺类，如以下10种化合物。
4.如权利要求1所述1,2,3—三唑类化合物的合成方法，其特征在于，所述催化剂用量为叠氮类化合物的0.2当量。
5.如权利要求 1 所述1,2,3—三唑类化合物的合成方法，其特征在于，所述溶剂为水。
6.如权利要求 1 所述1,2,3—三唑类化合物的合成方法，其特征在于，所述叠氮类化合物的用量为1当量，所述酮类化合物的用量为2当量。
7.如权利要求 1 所述1,2,3—三唑类化合物的合成方法，其特征在于，所述反应温度为80℃。
8.如权利要求 1 所述1,2,3—三唑类化合物的合成方法，其特征在于，所述反应时间为48小时以上。
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CN105622532A (zh) * 2016-03-01 2016-06-01 青岛大学 多取代-1,2,3-三氮唑螺环类化合物的合成方法
CN105732526A (zh) * 2016-04-12 2016-07-06 青岛大学 1,4,5-三取代-1,2,3-三氮唑衍生物及其制备方法

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CN105439967A (zh) * 2015-12-12 2016-03-30 青岛大学 1,4,5-三取代-1,2,3-三氮唑类化合物的合成方法
CN105622532A (zh) * 2016-03-01 2016-06-01 青岛大学 多取代-1,2,3-三氮唑螺环类化合物的合成方法
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