CN115304536B - 一种吲哚啉-2-酮化合物衍生物的制备及用途 - Google Patents

一种吲哚啉-2-酮化合物衍生物的制备及用途 Download PDF

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CN115304536B
CN115304536B CN202210885083.1A CN202210885083A CN115304536B CN 115304536 B CN115304536 B CN 115304536B CN 202210885083 A CN202210885083 A CN 202210885083A CN 115304536 B CN115304536 B CN 115304536B
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罗梅
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Abstract

一种由二苯甲酮腙、7‑氯靛红和一水合乙酸酮经一锅法反应在100ml无水甲醇溶剂中回流48小时后制备的的由以下化学式(Ⅰ)所示的化合物：该晶体(I)的合成方法，是称取二苯甲酮腙0.0235g及0.6914g7‑氯靛红和一水合乙酸酮配合物0.6720g，放入100.0mL烧瓶中，加入50mL无水甲醇做溶剂，室温搅拌48小时后，柱层析分离，用石油醚/二氯甲烷(1/1)洗脱，将收集的最后组分点自然挥发得7(E)‑氯‑3‑二苯基亚甲基吲哚啉‑2‑酮晶体；该晶体(I)的的用途，是作为催化剂在二苯甲酮亚胺与三甲基硅腈反应中显示了一定的催化效果，其转化率高达99％。

Description

一种吲哚啉-2-酮化合物衍生物的制备及用途
一、技术领域
本发明涉及一种化合物的用途，特别涉及一种吲哚啉-2-酮的制备及用途，确切地说是一种7(E)-氯-3-二苯基亚甲基吲哚啉-2-酮化合物的制备及用途。
二、背景技术
吲哚啉-2-酮化合物是重要的医药中间体，其用途极为广泛。其类似合成方法及应用已有文献报道【1】。
1.参考文献：
Synthesis and spectroscopic studies on the new Schiffbase derivedfrom the 1:1condensation of isatin with amines and its evaluating biologicalactivity,Khubeiz,Mohamad Jawad，International Journal of ChemTech Research(2016),9(7),516-522。
三、发明内容
本发明所称的化合物是由二苯甲酮腙、7-氯靛红和一水合乙酸酮一锅法在100ml无水甲醇溶剂中回流48小时后反应由以下化学式(I)所示的化合物：
其化学名称：7(E)-氯-3-二苯甲酮腙2-吲哚酮
俗名：二苯甲酮-7-氯靛红吖嗪
本化合物(I)的合成方法是称取二苯甲酮腙0.0235g及0.6914g7-氯靛红和一水合乙酸酮配合物0.6720g，放入100.0mL烧瓶中，加入50mL无水甲醇做溶剂，室温搅拌48小时后，柱层析分离，用石油醚/二氯甲烷(1/1)洗脱，将收集的最后组分点自然挥发得7(E)-氯-3-二苯基亚甲基吲哚啉-2-酮晶体。
该反应的反应机理可推测如下：二苯甲酮腙在铜盐作用下，首先，发生二聚形成二苯甲酮腙二聚体中间体二苯甲酮吖嗪,再与7-氯靛红反应，一步行成目标产物。
该目标产物在二苯甲酮亚胺的腈硅化反应中显示了较好的催化性能，其转化率达99％。
四、附图说明
图1目标产物二苯甲酮-7-氯靛红吖嗪的单晶衍射图。
五、具体实施方式
1.(E)-氯-3-二苯基亚甲基吲哚啉-2-酮的制备
在100mL两口瓶中,无水无氧条件下,称取二苯甲酮腙0.0235g及1.0g7-氯靛红和一水合乙酸酮配合物0.6720g，放入5.0mL烧瓶中，加入50mL无水甲醇做溶剂，室温搅拌48小时后，柱层析分离，用石油醚/二氯甲烷(1/1)洗脱，将收集的最后组分点自然挥发得7(E)-氯-3-二苯基亚甲基吲哚啉-2-酮晶体；产率82％；红棕色晶体,熔点>200℃；1H NMR(500MHz,298K,CDCl3)δppm 10.9(s,1H)7.76-7.78(m,2H,ArH),7.62(d,J＝7.5Hz,ArH),7.41-7.54(m,7H),7.41(d,J＝8.2Hz,1H),7.19(d,J＝7.3Hz,1H),13C{1H}NMR(125MHz,298K,CDCl3)164.6,158.5,146.2,142.0,138.1,136.5,134.0,132.8,130.8,129.9,129.2(x2),129.0(x2),128.6(x2),128.2(x2),125.9,123.5,118.5,115.9；HRMS(EI)m/z(％)calcd for C21H14N3OCl360.0896；found：359.8130；νmax(cm-1)3084,1725，1615，1583，1475，1442，1432，1400，1317，1328，1317，1299，1222，1170，1137，1072，1031，1072，1009，1000，948，931，910，836，796，796，766，757，732，664，652，593，558；
氮化合物晶体数据如下：
Table 2晶体典型的键长数据：
Table 4Bond Lengths for lm-12-yellow_autored.
Table 4Bond Lengths for lm-12-yellow_autored.
Table 3晶体典型的键长数据
Table 5Bond Angles for lm-12-yellow_autored.
Table 5Bond Angles for lm-12-yellow_autored.
目标化合物I在二苯甲酮亚胺的腈硅化反应应用；
称取0.1mmol配合物，置于25mL小烧瓶中，加入2mL无水甲醇，再向溶液中加入1.0mmol二苯甲酮亚胺和0.3mL三甲基硅腈，常温下搅拌15h，进行1HNMR检测。催化转化率:75％；
1H NMR(600MHz,CDCl3,27℃)δ7.23–7.59(m,10H),4.10(s,2H)。

Claims (4)

1.一种由二苯甲酮腙、7-氯靛红和一水合乙酸酮经一锅法反应在100mL无水甲醇溶剂中回流48小时后制备的的由以下化学式(Ⅰ)所示的化合物：
2.权利要求1所述的化合物，在293K温度下，在牛津X-射线单晶衍射仪上，用经石墨单色器单色化的CuKα射线单斜晶系,12/a：晶胞参数：/>α＝90°；β＝99.926°；/>γ＝90°。
3.权利要求1所述的化合物的合成方法，本化合物(I)的合成方法是称取二苯甲酮腙0.0235g及0.6914g7-氯靛红和一水合乙酸酮配合物0.6720g，放入100.0mL烧瓶中，加入50mL无水甲醇做溶剂，室温搅拌48小时后，柱层析分离，用石油醚/二氯甲烷按体积比1：1洗脱，将收集的最后组分点自然挥发得7(E)-氯-3-二苯基亚甲基吲哚啉-2-酮晶体。
4.权利要求1所述的化合物的用途，其特征在于，作为催化剂在二苯甲酮亚胺与三甲基硅腈反应中显示了一定的催化效果，其转化率高达75％。
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JPWO2007072841A1 (ja) * 2005-12-20 2009-05-28 宇部興産株式会社 ２−オキシインドール化合物の製法
CN102933577A (zh) * 2010-05-20 2013-02-13 纳幕尔杜邦公司 杀真菌的肟和腙
CN109912491A (zh) * 2019-04-08 2019-06-21 齐鲁工业大学 4-羟基二苯甲酮腙-靛红席夫碱的制备和用途

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JP4054035B2 (ja) * 2005-09-08 2008-02-27 日本電信電話株式会社 データベース構築装置、データベース構築方法、データベース構築プログラムおよび記録媒体
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US5164404A (en) * 1991-03-15 1992-11-17 Neurosearch A/S Hydrazone derivatives and their use
JPWO2007072841A1 (ja) * 2005-12-20 2009-05-28 宇部興産株式会社 ２−オキシインドール化合物の製法
CN102933577A (zh) * 2010-05-20 2013-02-13 纳幕尔杜邦公司 杀真菌的肟和腙
CN109912491A (zh) * 2019-04-08 2019-06-21 齐鲁工业大学 4-羟基二苯甲酮腙-靛红席夫碱的制备和用途

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