CN115490614B - 一种含氰基取代的烯胺合成方法 - Google Patents
一种含氰基取代的烯胺合成方法 Download PDFInfo
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- 150000002081 enamines Chemical class 0.000 title claims abstract description 25
- 238000001308 synthesis method Methods 0.000 title claims abstract description 7
- 125000004093 cyano group Chemical group *C#N 0.000 title claims description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- -1 nickel bromide diethylene glycol dimethyl ether compound Chemical class 0.000 claims abstract description 18
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims abstract description 13
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- 239000003446 ligand Substances 0.000 claims abstract description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 3
- 239000002585 base Substances 0.000 claims description 2
- WHELTKFSBJNBMQ-UHFFFAOYSA-L dichlororuthenium;2-pyridin-2-ylpyridine;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ru+2].N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1 WHELTKFSBJNBMQ-UHFFFAOYSA-L 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 15
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 125000000524 functional group Chemical group 0.000 abstract description 5
- 239000003814 drug Substances 0.000 abstract description 4
- 229940079593 drug Drugs 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 3
- UHIPSWQNPNQBQY-UHFFFAOYSA-K 2-pyridin-2-ylpyridine trichlororuthenium hexahydrate Chemical compound O.O.O.O.O.O.Cl[Ru](Cl)Cl.N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1.N1=CC=CC=C1C1=CC=CC=N1 UHIPSWQNPNQBQY-UHFFFAOYSA-K 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 7
- 239000012973 diazabicyclooctane Substances 0.000 description 7
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- 239000003480 eluent Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012634 fragment Substances 0.000 description 2
- YDYCXDWUKJSHMI-UHFFFAOYSA-N n-cyclobutylidenehydroxylamine Chemical compound ON=C1CCC1 YDYCXDWUKJSHMI-UHFFFAOYSA-N 0.000 description 2
- 230000005418 spin wave Effects 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- RRSIMIHTHWYRRA-UHFFFAOYSA-L dibromonickel;1-methoxy-2-(2-methoxyethoxy)ethane Chemical compound Br[Ni]Br.COCCOCCOC RRSIMIHTHWYRRA-UHFFFAOYSA-L 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
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Abstract
本发明属于有机合成领域，涉及一种含氰基取代的烯胺的合成方法。以烯胺和环酮肟为原料，在氯化三(2，2‑联吡啶)钌六水合物和溴化镍二乙二醇二甲醚复合物双催化剂条件下，[4，4′‑双(1，1‑二甲基乙基)‑2，2′‑联吡啶]为配体，三乙烯二胺为碱，在可见光照射下，于N，N‑二甲基乙酰胺溶剂中进行反应，得到具有通式(I)的E‑构型氰基取代的烯胺类化合物。该方法第一次实现了以烯胺和环酮肟为原料，高效率、高选择性的合成了含氰基取代的烯胺类化合物反应实例。反应条件温和、官能团兼容性优越。在有机合成和药物合成中有着重要的应用价值。
Description
技术领域
本发明涉及化合物制备，属于有机合成领域。具体涉及含氰基取代的烯胺的合成方法。
背景技术
含氮有机化合物在许多药物分子中是起到药理活性的关键片段。烯胺类化合物在含氮有机化合物中是一类重要的结构片段和中间体。因其可以转化为重要的生物活性分子、药物分子和手性胺类化合物。并且很多生理活性分子中都含有烯胺片段。因此烯胺类化合物的合成在化学及医药科学中有着重要价值(式 1)。
式1.烯胺的重要性
基于烯胺的重要性，近来很多通过β-H官能化方法被报道。另一方面，氰基是重要的有机官能团和有机合成模块。在药物和生理活性分子中，氰基也是广泛存在的官能团。因此氰基的合成在有机合成中有着重要的价值。然而高效率、高选择性合成含末端氰基的烯胺类化合物还未被实现。因此，合成含末端氰基的烯胺化合物在有机合成化学和医药化学中有着重要的价值。
发明内容
针对目前还没有高效率、高选择性合成含氰基的烯胺化合物。本发明使用烯胺和环酮肟类衍生物，高效率的实现了含氰基烯胺的合成方法。为解决上述技术问题，本发明采用如下技术方案：一种含氰基取代的烯胺合成方法，其特征在于：以烯胺和环酮肟为原料，在氯化三(2，2-联吡啶)钌(II)六水合物[Ru(bpy)3Cl2·6H2O]和溴化镍二乙二醇二甲醚复合物(NiBr2·diglyme)双催化剂条件下，[4，4′-双(1，1-二甲基乙基)-2，2′-联吡啶](dtbpy)为配体，三乙烯二胺(DABCO) 为碱，在可见光照射下，于N，N-二甲基乙酰胺溶剂中，按下述反应式进行反应，得到具有通式(I)的E-构型氰基取代的烯胺类化合物：
优选地，所述Ru(bpy)3Cl2·6H2O的物质的量为烯胺的物质的量的5％。
所述NiBr2·diglyme的物质的量为烯胺的物质的量的8％。
所述dtbpy的物质的量为烯胺的物质的量的10％。
所述DABCO的物质的量为烯胺的物质的量的50％。
优选地，环酮肟的物质的量为烯胺的物质的量的2倍。
优选地，反应温度为室温，可见光波长为465nm，反应时间为12h。
该方法第一次实现了以烯胺和环酮肟为原料，高效率、高选择性的合成了含氰基取代的烯胺类化合物反应实例。反应条件温和、官能团兼容性优越。在有机合成和药物合成中有着重要的应用价值。
具体实施方式
下面通过具体实施方式对本发明的技术方案进行做进一步说明：
实施例1，该实施例的反应式如下所示：
(1)在空气下，Ru(bpy)3Cl2·6H2O(5mol％)、NiBr2·diglyme(8mol％)、 DABCO(50mol％)和环丁酮肟(0.4mmol)加入到一个带支管、含有磁子的密封反应管中，反应管抽冲氩气三次。向反应管中加入0.2mmol苯基烯胺和1mL DMAc，塞紧活塞于465nm光照下室温反应12小时。
(2)旋干步骤(1)中所得的有机相中的溶剂，得到粗产物，然后用硅胶柱纯化粗产物。洗脱剂为石油醚和乙酸乙酯混合物，分离收率为82％，产物纯度100％。
实施例2
该实施例的反应式如下所示：
(1)在空气下，Ru(bpy)3Cl2·6H2O(5mol％)、NiBr2·diglyme(8mol％)、 DABCO(50mol％)和环丁酮肟(0.4mmol)加入到一个带支管、含有磁子的密封反应管中，反应管抽冲氩气三次。向反应管中加入0.2mmol3-溴苯基取代的烯胺和1mL DMAc，塞紧活塞于465nm光照下室温反应12小时。
(2)旋干步骤(1)中所得的有机相中的溶剂，得到粗产物，然后用硅胶柱纯化粗产物。洗脱剂为石油醚和乙酸乙酯混合物，分离收率为77％，产物纯度100％。
实施例3
该实施例的反应式如下所示：
(1)在空气下，Ru(bpy)3Cl2·6H2O(5mol％)、NiBr2·diglyme(8mol％)、 DABCO(50mol％)和肟酯(0.4mmol)加入到一个带支管、含有磁子的密封反应管中，反应管抽冲氩气三次。向反应管中加入0.2mmol苯基取代的烯胺和 1mL DMAc，塞紧活塞于465nm光照下室温反应12小时。
(2)旋干步骤(1)中所得的有机相中的溶剂，得到粗产物，然后用硅胶柱纯化粗产物。洗脱剂为石油醚和乙酸乙酯混合物，分离收率为81％，产物纯度100％。
实施例4
该实施例的反应式如下所示：
(1)在空气下，Ru(bpy)3Cl2·6H2O(5mol％)、NiBr2·diglyme(8mol％)、 DABCO(50mol％)和肟酯(0.4mmol)加入到一个带支管、含有磁子的密封反应管中，反应管抽冲氩气三次。向反应管中加入0.2mmol苯基取代的烯胺和 1mL DMAc，塞紧活塞于465nm光照下室温反应12小时。
(2)旋干步骤(1)中所得的有机相中的溶剂，得到粗产物，然后用硅胶柱纯化粗产物。洗脱剂为石油醚和乙酸乙酯混合物，分离收率为80％，产物纯度100％。
实施例5
该实施例的反应式如下所示：
(1)在空气下，Ru(bpy)3Cl2·6H2O(5mol％)、NiBr2·diglyme(8mol％)、 DABCO(50mol％)和肟酯(0.4mmol)加入到一个带支管、含有磁子的密封反应管中，反应管抽冲氩气三次。向反应管中加入0.2mmol苯基取代的烯胺和 1mL DMAc，塞紧活塞于465nm光照下室温反应12小时。
(2)旋干步骤(1)中所得的有机相中的溶剂，得到粗产物，然后用硅胶柱纯化粗产物。洗脱剂为石油醚和乙酸乙酯混合物，分离收率为77％，产物纯度100％。
所用的各物质的量及反应条件同实施例进行实验拓展，以说明本发明的技术方案具有良好的官能团兼容性。
以上已将本发明做一详细说明，以上所述，仅为本发明之较佳实施例而已，当不能限定本申请实施范围，即凡依本申请范围所作均等变化与修饰，皆应仍属本发明涵盖范围。
附图说明
图1为本发明制备的产物3a的核磁共振氢谱；
图2为本发明制备的产物3a的核磁共振碳谱；图3为本发明制备的产物3i的核磁共振氢谱；图4为本发明制备的产物3i的核磁共振碳谱；图5为本发明制备的产物4a的核磁共振氢谱；图6为本发明制备的产物4a的核磁共振碳谱；图7为本发明制备的产物4e的核磁共振氢谱；图8为本发明制备的产物4e的核磁共振碳谱；图9为本发明制备的产物6a的核磁共振氢谱；图10为本发明制备的产物6a的核磁共振碳谱；图11为本发明制备的产物6b的核磁共振氢谱；图12为本发明制备的产物6b的核磁共振碳谱。
Claims (1)
1.一种含氰基取代的烯胺合成方法，其特征在于：以烯胺和环酮肟为原料，在氯化三(2，2-联吡啶)钌(II)六水合物和溴化镍二乙二醇二甲醚复合物双催化剂条件下，[4，4′-双(1，1-二甲基乙基)-2，2′-联吡啶]为配体，三乙烯二胺为碱，在可见光照射下，于N，N-二甲基乙酰胺溶剂中，按下述反应式进行反应，得到E-构型氰基取代的烯胺类化合物：
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