CN109400564B - 一种含三氟甲基的苯并二氢吡喃-4-酮类化合物及其制备方法 - Google Patents
一种含三氟甲基的苯并二氢吡喃-4-酮类化合物及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种以烯丙基水杨醛(I)类化合物为作为反应的起始原料、三氟甲基亚磺酸钠(II)为三氟甲基源以及过硫酸盐为氧化剂,通过三氟甲基与烯丙基水杨醛发生自由基加成、自由基环化以及氧化反应而得到含三氟甲基的苯并二氢吡喃‑4‑酮类目标化合物(III)及其制备方法。此方法涉及的反应条件温和、操作简单,产物多样性、可以实现克级规模的生产。
Description
技术领域
本发明涉及化学合成领域,具体为一种含三氟甲基的苯并二氢吡喃-4-酮类化合物及其制备方法。
背景技术
苯并二氢吡喃-4-酮类化合物是一类重要的有机化工原料,在诸多领域如有机合成、高分子、合成药物、农药等展示了广泛的应用前景。而含三氟甲基的化合物则具有独特的生物以及化学活性。因此,含三氟甲基的苯并二氢吡喃-4-酮类化合物将同时具备苯并二氢吡喃-4-酮化合物和含三氟甲基化合物的性质和特点。迄今为止,所报道的苯并二氢吡喃-4-酮类化合物的合成方法主要通过迈克尔加成(参考文献:J.Chem.Soc.1935,866;Org.Biomol.Chem.2011,9,6930;Org.Lett.2011,13,4526;Chem.Commun.2012,48,11796;Angew.Chem.Int.Ed.2015,54,13302;ChemCatChem.2017,9,465)以及分子内的脱水缩合(参考文献:J.Org.Chem.1961,26,4941;Eur.J.Org.Chem.2003,4575;Org.Lett.2012,14,2710;Molecules2015,20,43;Tetrahedron Lett.2016,57,3841)获得,而对于三氟甲基化的苯并二氢吡喃-4-酮类化合物的合成,目前还未见报道。
发明内容
为了克服上述现有技术中的不足,本发明提供了一种以烯丙基水杨醛(I)类化合物为作为反应的起始原料、三氟甲基亚磺酸钠(II)为三氟甲基源以及过硫酸盐为氧化剂,通过单电子转移历程过硫酸盐可氧化三氟甲基亚磺酸钠为三氟甲基自由基,从而与烯丙基水杨醛发生自由基加成、自由基环化以及氧化反应而得到含三氟甲基的苯并二氢吡喃-4-酮类目标化合物(III)。该方法底物范围非常广阔,可以构建各种各样的含三氟甲基的苯并二氢吡喃-4-酮类化合物。此方法涉及的反应条件温和、操作简单,产物多样性、可以实现克级规模的生产。
本发明的目的是这样实现的:
将结构(I)的醛类化合物、结构(II)的三氟甲基试剂以及氧化剂分散在溶剂中,通过加热搅拌即可得到具有结构(III)的三氟甲基化苯并二氢吡喃-4-酮类化合物:
III的具体结构为:
所述的氧化剂为过硫酸钾、过硫酸钠或过硫酸铵;
所述的溶剂为乙腈、乙醇、异丙醇、N,N-二甲基甲酰胺、丙酮、1,4-二氧六环、二甲亚砜、乙酸乙酯或二氯甲烷与水的混合物;
所述的醛类化合物与三氟甲基试剂的摩尔比为1:1—1:1.6;
所述的醛类化合物与氧化剂的摩尔比为1:1—1:3;
所述的反应温度为50℃—100℃;
所述的反应时间为8—12h。
有益效果:与现有化学合成领域相关技术相比,本发明第一次实现了无过渡金属催化剂条件下碳碳双键的三氟甲基化和酰基化的双官能团化反应。通过自由基历程过硫酸盐引发三氟甲基自由基的生成,继而与烯丙基水杨醛来直接构建含三氟甲基的苯并二氢吡喃-4-酮类化合物。该反应条件温和、操作简单,可以制备各种取代的目标化合物。
附图说明
图1a、1b和1c分别为根据本发明实施例1制备含三氟甲基的苯并二氢吡喃-4-酮类化合物2a的核磁共振氢谱、氟谱和碳谱;
图2a、2b和2c分别为根据本发明实施例2制备含三氟甲基的苯并二氢吡喃-4-酮类化合物2b的核磁共振氢谱、氟谱和碳谱;
图3a、3b和3c分别为根据本发明实施例3制备含三氟甲基的苯并二氢吡喃-4-酮类化合物2c的核磁共振氢谱、氟谱和碳谱;
图4a、4b和4c分别为根据本发明实施例4制备含三氟甲基的苯并二氢吡喃-4-酮类化合物2d的核磁共振氢谱、氟谱和碳谱。
具体实施方式
下面结合附图及实施例,对本发明做进一步的说明:
所述的一种含三氟甲基的苯并二氢吡喃-4-酮类化合物及其制备方法,包括以下步骤:
将结构(I)的醛类化合物、结构(II)的三氟甲基试剂以及氧化剂分散在溶剂中,通过加热搅拌即可得到具有结构(III)的三氟甲基化苯并二氢吡喃-4-酮类化合物:
III的具体结构为:
所述的氧化剂为过硫酸钾、过硫酸钠或过硫酸铵;
所述的溶剂为乙腈、乙醇、异丙醇、N,N-二甲基甲酰胺、丙酮、1,4-二氧六环、二甲亚砜、乙酸乙酯或二氯甲烷与水的混合物;
所述的醛类化合物与三氟甲基试剂的摩尔比为1:1—1:1.6;
所述的醛类化合物与氧化剂的摩尔比为1:1—1:3;
所述的反应温度为50℃—100℃;
所述的反应时间为8—12h。
实施例1
在一个洁净干燥的20mL Schlenk耐压反应管中依次加入1mmol烯丙基水杨醛、1.5mmol三氟甲基亚磺酸钠、3mmol过硫酸钾,再加入1.5mL乙腈和2.5mL水作溶剂,将反应管密封置于70℃的油浴锅中加热反应8小时。反应结束后,加入乙酸乙酯萃取反应混合物,将有机相通过旋转蒸发仪旋干,再将所得的残余物以石油醚和乙酸乙酯作为洗脱剂,通过硅胶柱分离,得到的目标产物为无色油状液体,产率为62%。
本实施例制备的产物核磁共振氢谱如图1a所示,核磁共振氟谱如图1b所示,核磁共振碳谱如图1c所示。从图谱中可以确认,获得的产物为目标化合物2a。
实施例2
在一个洁净干燥的20mL Schlenk耐压反应管中依次加入1mmol 4-甲氧基烯丙基水杨醛、1.5mmol三氟甲基亚磺酸钠、2.5mmol过硫酸钾,再加入1.5mL乙腈和2.5mL水作溶剂,将反应管密封置于80℃的油浴锅中加热反应8小时。反应结束后,加入乙酸乙酯萃取反应混合物,将有机相通过旋转蒸发仪旋干,再将所得的残余物以石油醚和乙酸乙酯作为洗脱剂,通过硅胶柱分离,得到的目标产物为白色固体,产率为38%。
本实施例制备的产物核磁共振氢谱如图2a所示,核磁共振氟谱如图2b所示,核磁共振碳谱如图2c所示。从图谱中可以确认,获得的产物为目标化合物2b。
实施例3
在一个洁净干燥的20mL Schlenk耐压反应管中依次加入1mmol 4-甲基烯丙基水杨醛、1.4mmol三氟甲基亚磺酸钠、3.0mmol过硫酸钠,再加入1.5mL二甲亚砜和2.5mL水作溶剂,将反应管密封置于100℃的油浴锅中加热反应8小时。反应结束后,加入乙酸乙酯萃取反应混合物,将有机相通过旋转蒸发仪旋干,再将所得的残余物以石油醚和乙酸乙酯作为洗脱剂,通过硅胶柱分离,得到的目标产物为白色固体,产率为58%。
本实施例制备的产物核磁共振氢谱如图3a所示,核磁共振氟谱如图3b所示,核磁共振碳谱如图3c所示。从图谱中可以确认,获得的产物为目标化合物2c。
实施例4
在一个洁净干燥的20mL Schlenk耐压反应管中依次加入1mmol 5-甲基烯丙基水杨醛、1.4mmol三氟甲基亚磺酸钠、2.5mmol过硫酸钠,再加入1.5mL乙腈和2.5mL水作溶剂,将反应管密封置于100℃的油浴锅中加热反应12小时。反应结束后,加入乙酸乙酯萃取反应混合物,将有机相通过旋转蒸发仪旋干,再将所得的残余物以石油醚和乙酸乙酯作为洗脱剂,通过硅胶柱分离,得到的目标产物为无色油状固体,产率为62%。
本实施例制备的产物核磁共振氢谱如图4a所示,核磁共振氟谱如图4b所示,核磁共振碳谱如图4c所示。从图谱中可以确认,获得的产物为目标化合物2d。
在一个实施方案中,本发明提供的一种含三氟甲基的苯并二氢吡喃-4-酮类化合物及其制备方法,在无需任何的过渡金属催化作用下,可以由过硫酸盐引发三氟甲基亚磺酸钠生成三氟甲基自由基而直接与烯丙基水杨醛类化合物发生自由基加成、环化、氧化机理来构建含三氟甲基的苯并二氢吡喃-4-酮类化合物。
在本发明中,所述的三氟甲基亚磺酸钠在氧化剂过硫酸盐的单电子氧化作用下可生成三氟甲基自由基,生成的三氟甲基自由基与烯丙基水杨醛类化合物发生自由基加成而构建中间体碳自由基A,继而发生环化反应,得到中间体氧自由基B,然后在过硫酸盐的氧化下,发生一个协同的氢原子转移过程而得到目标化合物含三氟甲基的苯并二氢吡喃-4-酮。本发明提供了一种制备含三氟甲基的苯并二氢吡喃-4-酮的新方法,以2a为例,具体机理如下图所示:
上述是对本发明优选的实施例的说明,以使本领域技术人员能够实现或使用本发明,对这些实施例的一些修改对本领域专业人员来说是显而易见的,本文中所定义的一般原理可以在不脱离本发明的范围或精神情况下,在其他实施例中实现。因此,本发明范围不受上述具体实施例的限制。
Claims (5)
2.根据权利要求1所述的一种含三氟甲基的苯并二氢吡喃-4-酮类化合物制备方法,其特征在于:所述的醛类化合物与三氟甲基试剂的摩尔比为1:1—1:1.6。
3.根据权利要求1所述的一种含三氟甲基的苯并二氢吡喃-4-酮类化合物制备方法,其特征在于:所述的醛类化合物与氧化剂的摩尔比为1:1—1:3。
4.根据权利要求1所述的一种含三氟甲基的苯并二氢吡喃-4-酮类化合物制备方法,其特征在于:所述的反应温度为50℃—100℃。
5.根据权利要求1所述的一种含三氟甲基的苯并二氢吡喃-4-酮类化合物制备方法,其特征在于:所述的反应时间为8—12h。
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