CN103788137B - 二茂铁并哌啶酮类化合物及其制备方法 - Google Patents
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Abstract
一种二茂铁并哌啶酮类化合物,其化学结构通式为(I):(I)式中:R1、R2为脂肪族取代基、芳香族取代基、含有氧或卤素杂原子碳的脂肪族取代基或芳香族取代基,R1、R2可以相同,也可以不同;R3为脂肪族取代基、芳香族取代基、含酯基,甲氧基及各种卤素取代的苯环取代基;其制备方法,通过二茂铁甲酰胺与炔烃在醋酸钯条件下催化环化,形成相应的二茂铁并哌啶酮类化合物;该二茂铁并哌啶酮类化合物用于医药的制备。本方法的有益效果是:该二茂铁并哌啶酮类化合物的制备方法工艺简单、原料廉价易得、产率高、无需惰性气体保护、反应温度较温和,可制备多种二茂铁并哌啶酮类化合物以扩大在医药上的应用。
Description
技术领域
本发明涉及有机金属类化合物,特别是一种二茂铁并哌啶酮类化合物及其制备方法。
背景技术
有机金属类化合物已经证明具有有效的抗癌性,如顺铂,其中二茂铁类化合物也具有较好的生物活性,引起了化学家们的广泛关注,参阅:1)vanStaveren,D.R.;Metzler-Nolte,N.Chem.Rev.2004,104,5931;2)Fouda,M.F.R.;Abd-Elzaher,M.M.;Abdelsamaia,R.A.;Labib,A.A.Appl.Organometal.Chem.2007,21,613;3)Hartinger,C.G.;Dyson,P.J.Chem.Soc.Rev.2009,38,391;4)vanRijt,S.H.;Sadler,P.J.DrugDiscoveryToday2009,14,1089;5)Gasser,G.;Ott,I.;Metzler-Nolte,N.J.Med.Chem.2011,54,3;6)Ornelas,C.NewJ.Chem.2011,35,1973;7)Braga,S.S.;Silva,A.M.S.Organometallics2013,32,5626;8)Metzler-Nolte,N.;Salmain,M.inFerrocenes:Ligands,MaterialsandBiomolecules;P.Ed.;Wiley&SonsLtd:Chichester,England,2008,p499。
当二茂铁单元代替生物活性分子中的苯环,或简单地连接到其中,该分子的生物活性往往会有较显著的提高,目前,将二茂铁单元引入纯有机药品分子中成为提高药效的较先进策略,参阅:9)Top,S.;Tang,J.;Vessières,A.;Carrez,D.;Provot,C.;Jaouen,G.Chem.Commun.1996,955;10)Hillard,E.;Vessieres,A.;Thouin,L.;Jaouen,G.;Amatore,C.Angew.Chem.Int.Ed.2006,45,285;11)Hamels,D.;Dansette,P.M.;Hillard,E.A.;Top,S.;Vessières,A.;Herson,P.;Jaouen,G.;MansuyD.Angew.Chem.Int.Ed.2009,48,9124;12)Monserrat,J.-P.;Chabot,G.G.;Hamon,L.;Quentin,L.;Scherman,D.;Jaouen,G.;Hillard,E.A.Chem.Commun.2010,46,5145;13)Patra,M.;Ingram,K.;Pierroz,V.;Ferrari,S.;Spingler,B.;Keiser,J.;Gasser,G.J.Med.Chem.2012,55,8790;14)Navarro,M.;Castro,W.;Biot,C.Organometallics2012,31,5715;15)Kilpin,K.J.;Dyson,P.J.Chem.Sci.2013,4,1410;16)Jadhav,J.;Juvekar,A.;Kurane,R.;Khanapure,S.;Salunkhe,R.;Rashinkar,G.Eur.J.Med.Chem.2013,65,232。杂环化合物是在药物分子中广泛存在的结构单元,基于上述理由,很有必要发展一种从简单易得的原料高效合成二茂铁并杂环的方法。
在过去的二十年来,过渡金属催化C-H官能团化作为合成杂环的有效工具,取得了重要的发展,然而由于二茂铁的富电性,导致C-H活化过程中的过渡金属催化协同去质子化过程较为困难,仅仅有为数不多的过渡金属催化二茂铁的茂环C-H活化的例子;参见:17)Onitsuka,K;Yoshida,T.;Adachi,T.;Yoshida,T.;Sonogashira,K.Chem.Lett.1995,233;18)SiegelS.;Schmalz,H.-G.Angew.Chem.Int.Ed.1997,36,2456;19)Bringmann,G.;Hinrichs,J.;Peters,K.;Peters,E.-M.J.Org.Chem.2001,66,629;20)Datta,A.;A.;Plenio,H.Chem.Commun.2004,1508;21)Xia,J.-B.;You,S.-L.Organometallics.2007,26,4869;22)Piotrowicz,M.;Zakrzewski,J.;Makal,A.;J.;Malińska,M.;K.J.Organomet.Chem.2011,696,3499;23)Takebayashi,S.;Shizuno,T.;Otani,T.;Shibata,T.BeilsteinJ.Org.Chem.2012,8,1844;24)Zhang,H.;Cui,X.-L.;Yao,X.-N.;Wang,H.;Zhang,J.-Y;Wu,Y.-J.Org.Lett.2012,14,3012;25)Takebayashi,S.;Shibata,T.Organometallic.2012,31,4114;26)Singh,K.S.;Dixneuf,P.H.Organometallics2012,31,7320;27)Pi,C.;Li,Y.;Cui,X.;Zhang,H.;Han,Y.;Wu,Y.Chem.Sci.2013,4,2675;28)Gao,D.-W.;Shi,Y.-C.;Gu,Q.;Zhao,Z.-L.;You,S.-L.J.Am.Chem.Soc.2013,135,86;29)Piotrowicz,M.;Zakrzewski,J.Organometallics2013,32,5709.)。至今尚没有过渡金属催化二茂铁类化合物与炔烃环化形成杂环的报道,这大大限制了新型药物分子的开发和药效的研究。
因此,我们在这里公开制备一系列二茂铁并哌啶酮类化合物的研究成果。
发明内容
本发明的目的在于针对上述技术分析和存在问题,提供一种由二茂铁甲酰胺类化合物一步制备二茂铁并哌啶酮类化合物的方法,其制备方法工艺简单、原料廉价易得、产率高、无需惰性气体保护、反应温度较温和,可制备多种二茂铁并哌啶酮类化合物以扩大在医药上的应用。。
本发明的技术方案:
一种二茂铁并哌啶酮类化合物,其化学结构通式为(I):
式中:R1、R2为脂肪族取代基、芳香族取代基、含有氧或卤素杂原子碳的脂肪族取代基或芳香族取代基,R1、R2可以相同,也可以不同;R3为脂肪族取代基、芳香族取代基、含酯基,甲氧基及各种卤素取代的苯环取代基。
一种所述二茂铁并哌啶酮类化合物的制备方法,通过二茂铁甲酰胺与炔烃在醋酸钯条件下催化环化,形成相应的二茂铁并哌啶酮类化合物,步骤如下:
1)在预先烘干的装有磁子的反应管中,加入二茂铁甲酰胺、炔烃、醋酸钯、碳酸氢钠、四丁基溴化铵和一水合醋酸铜,混合均匀;
2)加入干燥的甲苯后,将反应管置于预热好的90-100℃油浴中,敞开口在空气中反应12-24小时;
3)加入二氯甲烷用旋转蒸发仪除去溶剂,过硅胶柱,即可制得棕红色固体状目标物。
所述二茂铁甲酰胺为不同氮取代基的酰胺类化合物,其取代基包括脂肪族取代基、芳香族取代基、含酯基、甲氧基及卤素取代的苯环取代基。
所述炔烃包括苯环上带有甲基、甲氧基、酯基、氟、氯或溴的芳香双取代对称炔烃以及苯基丙炔或苯基丙炔酸乙酯非对称炔烃。
所述二茂铁甲酰胺、炔烃、醋酸钯、碳酸氢钠、四丁基溴化铵和一水合醋酸铜的摩尔比为0.2:0.2:0.02:0.8:0.2:0.1。
所述甲苯与二茂铁甲酰胺的用量比为1.0mL:0.2mmol。
一种所述二茂铁并哌啶酮类化合物的应用,用于医药的制备。
本方法的有益效果是:该二茂铁并哌啶酮类化合物的制备方法工艺简单、原料廉价易得、产率高、无需惰性气体保护、反应温度较温和,可制备多种二茂铁并哌啶酮类化合物以扩大在医药上的应用。
附图说明
图1为二茂铁并哌啶酮类化合物的合成路线示意图。
图2为实施例合成的化合物1-24的结构式示意图。
具体实施方式
本发明的突出的实质性特点和显著效果,可以从下列实例中得以体现,但它们不对本发明作任何限制。
实施例:
一种二茂铁并哌啶酮类化合物,其化学结构通式为(I):
式中:R1、R2为脂肪族取代基、芳香族取代基、含有氧或卤素杂原子碳的脂肪族取代基或芳香族取代基,R1、R2可以相同,也可以不同;R3为脂肪族取代基、芳香族取代基、含酯基,甲氧基及各种卤素取代的苯环取代基。
一种所述二茂铁并哌啶酮类化合物1-24的制备方法,通过二茂铁甲酰胺与炔烃在醋酸钯条件下催化环化,形成相应的二茂铁并哌啶酮类化合物,步骤如下:
1)在预先烘干的装有磁子的25mLSchlenk反应管中,加入0.2mmol二茂铁甲酰胺、0.2mmol炔烃、0.02mmol醋酸钯、0.8mmol碳酸氢钠、0.2mmol四丁基溴化铵和0.1mmol一水合醋酸铜,混合均匀;
2)加入1.0mL干燥的甲苯后,将反应管置于预热好的90-100℃油浴中,敞开口在空气中反应12-24小时,其中化合物14、15是在100℃油浴中反应24小时,其他化合物是在90℃油浴中反应12小时;
3)加入二氯甲烷用旋转蒸发仪除去溶剂,过硅胶柱,即可制得棕红色固体状目标物。
图1为二茂铁并哌啶酮类化合物的合成路线示意图。
图2为实施例合成的化合物1-24的结构式示意图,其中,化合物1-16中为脂肪族取代基、芳香族取代基、含酯基,甲氧基及各种卤素取代的苯环取代基的二茂铁甲酰胺类化合物与二苯乙炔环化形成的不同R3取代的二茂铁并哌啶酮类化合物;化合物17-24为苯环上带甲基、甲氧基、酯基、氟、氯或溴的对称炔烃以及苯基丙炔或苯基丙炔酸乙酯非对称炔烃与N-苯基二茂铁甲酰胺环化形成的不同R1,R2取代的二茂铁并哌啶酮类化合物。
化合物1-24的核磁氢谱、核磁碳谱、高分辨质谱、熔点和产率见表1-3。
表1化合物1-24的1HNMR数据
表2化合物1-24的13CNMR数据
表3化合物1-24的分子式、产率、熔点和高分辨质谱
Claims (5)
1.一种二茂铁并哌啶酮类化合物的制备方法,所述二茂铁并哌啶酮类化合物的化学结构通式为(I):
式中:R1、R2为脂肪族取代基、芳香族取代基、含有氧或卤素杂原子碳的脂肪族取代基或芳香族取代基,R1、R2可以相同,也可以不同;R3为脂肪族取代基、芳香族取代基、含酯基,甲氧基及各种卤素取代的苯环取代基;
所述二茂铁并哌啶酮类化合物的制备方法,其特征在于:通过二茂铁甲酰胺与炔烃在醋酸钯条件下催化环化,形成相应的二茂铁并哌啶酮类化合物,步骤如下:
1)在预先烘干的装有磁子的反应管中,加入二茂铁甲酰胺、炔烃、醋酸钯、碳酸氢钠、四丁基溴化铵和一水合醋酸铜,混合均匀;
2)加入干燥的甲苯后,将反应管置于预热好的90-100℃油浴中,敞开口在空气中反应12-24小时;
3)加入二氯甲烷用旋转蒸发仪除去溶剂,过硅胶柱,即可制得棕红色固体状目标物。
2.根据权利要求1所述二茂铁并哌啶酮类化合物的制备方法,其特征在于:所述二茂铁甲酰胺为不同氮取代基的酰胺类化合物,其取代基为脂肪族取代基、芳香族取代基、含酯基、甲氧基及卤素取代的苯环取代基。
3.根据权利要求1所述二茂铁并哌啶酮类化合物的制备方法,其特征在于:所述炔烃为苯环上带有甲基、甲氧基、酯基、氟、氯或溴的芳香双取代对称炔烃以及苯基丙炔或苯基丙炔酸乙酯非对称炔烃。
4.根据权利要求1所述二茂铁并哌啶酮类化合物的制备方法,其特征在于:所述二茂铁甲酰胺、炔烃、醋酸钯、碳酸氢钠、四丁基溴化铵和一水合醋酸铜的摩尔比为0.2:0.2:0.02:0.8:0.2:0.1。
5.根据权利要求1所述二茂铁并哌啶酮类化合物的制备方法,其特征在于:所述甲苯与二茂铁甲酰胺的用量比为1.0mL:0.2mmol。
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WO2007036701A1 (en) * | 2005-09-27 | 2007-04-05 | The University Of Nottingham | Ferrocenyl phosphite ligands for asymmetric catalysis and a method for their production |
CN102746225A (zh) * | 2012-06-27 | 2012-10-24 | 天津大学 | 2-烷基-3,4-二取代异喹啉-1(2h)-酮类衍生物的制备方法 |
CN102746224A (zh) * | 2012-06-27 | 2012-10-24 | 天津大学 | 2-芳基-3,4-二取代异喹啉-1(2h)-酮类衍生物的制备方法 |
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