CN111320550A - 一种五氯化铌与离子液体共催化制备酰胺类化合物的合成方法 - Google Patents
一种五氯化铌与离子液体共催化制备酰胺类化合物的合成方法 Download PDFInfo
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 65
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Abstract
本发明涉及一种五氯化铌与离子液体共催化制备酰胺类化合物的合成方法,其特征在于,包括以下步骤:称取有机羧酸、有机胺、五氯化铌和离子液体、分子筛,将上述物料加入到反应器中,加入有机溶剂,反应温度70‑110℃,反应时间6‑24小时,得到对应的酰胺产物。所述有机羧酸、有机胺、五氯化铌和离子液体,摩尔比为1:(1~3):(0.01~1):(0.05~1);所述有机羧酸和分子筛质量比为1:(0.2~1)。该方法扩大了底物范围,反应产率高(95%以上)、催化剂用量少、原子经济性高、而且催化剂便宜易得,可大大降低成产成本,适合工业化生产。
Description
技术领域
本发明属于有机合成技术领域,涉及一种酰胺类化合物的合成方法,具体涉及一种五氯化铌与离子液体共催化制备酰胺类化合物的合成方法。
背景技术
酰胺类化合物是天然生物活性分子和合成有机化合物中最常见的化合物之一。酰胺类化合物的合成在药物化学、生物化学和高分子合成等方面有着重要的应用。研究表明,目前超过四分之一的市场化药物是酰胺类化合物,比如,能够阻止胆固醇产生的阿伐他汀,血管紧张素受体抑制剂缬沙坦,治疗心绞痛和高血压的地尔硫卓等。这使得酰胺化反应成为制药领域里最常用的反应之一。另外,酰胺类化合物作为化工原料在润滑剂、清洁剂、工程塑料及除草剂领域也有着广泛的应用,参见[M.A.Fischbach,C.T.Walsh,Chem.Rev.,2006,106,3468-3496;L.U.H.Vogt,R.Madsen,J.AM.CHEM.SOC.,2008,130,17672-17673;X.Zhang,X.Chen,W.Zhao,Bioconjugate Chem,2017,28,109-2113;G.X.Wang,B.P.Sun,C.H.Peng,Org.Process Res.Dev.,2011,15,986-988.]。
目前,合成酰胺的经典方法主要包括:有机酸和胺在偶联试剂如三苯基膦等作用下生成酰胺,或通过酰卤、酸酐和活泼酯等与有机胺亲核加成制备得到。[参见H.Charville,D.A.Jackson,G.Hodges,Eur.J.Org.Chem,2011,2011,5981-5990.]虽然这些方法已被广泛用于合成酰胺类化合物,但是仍然存在明显的缺陷。例如:部分偶联试剂昂贵,使用的酰卤等价格较贵且较危险,反应产生卤化氢而导致酰胺化反应的原子经济性不高,且会腐蚀设备以及污染环境,产生废弃物多,后处理复杂等缺点。利用羧酸和胺在催化剂作用下直接缩合形成酰胺可以克服上述缺陷,是近年来高效、经济、绿色的合成酰胺的理想途径。
羧酸和胺直接酰胺化工艺目前主要围绕催化剂的开发及其反应条件的优化而进行,催化剂的正确选择能够有效地解决生产成本高,产品收率低,工业废弃物污染排放大等问题。
五氯化铌(NbCl5)具有优良的热稳定性和强的亲电性,同时地球资源丰富,也因作为一种强路易斯酸可以促进多种有机合成反应而引起了研究者们的重视,已有文献报道,可以利用五氯化铌催化制备酰胺,参见[Synthesis 2003,2,272–276;P hospho rus,Sulfur Silicon Relat Elem,2011,186,88-93]。然而,由于NbCl5在水中非常容易水解,所以制备酰胺时胺的用量(1:2.67)和NbCl5(1:0.33)的用量都很大,这也导致了反应原子经济性不高,后处理复杂,同时产率偏低的问题。
发明内容
本发明的目的在于提供一种五氯化铌与离子液体共催化制备酰胺类化合物的合成方法,以解决现有五氯化铌催化制备酰胺时,胺和NbCl5的用量大,反应原子经济性不高,后处理复杂,同时产率偏低的技术问题。
为实现上述目的,本发明具体是采用如下技术方案实现的:
一种五氯化铌与离子液体共催化制备酰胺类化合物的合成方法,包括以下步骤:称取有机羧酸、有机胺、五氯化铌和离子液体、分子筛,将上述物料加入到反应器中,加入有机溶剂,反应温度70-110℃,反应时间6-24小时,得到对应的酰胺产物。
作为本发明的优选,所述有机羧酸、有机胺、五氯化铌和离子液体,摩尔比为1:(1~3):(0.01~1):(0.05~1);所述有机羧酸和分子筛质量比为1:(0.2~1)。
作为本发明的优选,所述离子液体为咪唑类离子液体。
作为本发明的优选,所述有机溶剂为四氢呋喃、二氧六环、甲苯等。
作为本发明的优选,所述分子筛为3A分子筛、4A分子筛、5A分子筛。
作为本发明的进一步优选,所述有机羧酸、有机胺、五氯化铌和离子液体,摩尔比为1:1:0.08:0.05。
作为本发明的进一步优选,所述咪唑类离子液体选自以下化合物:
本发明具有以下优点和积极效果:
(1)本发明采用五氯化铌和离子液体在分子筛存在下促进有机羧酸和有机胺,直接合成酰胺,合成方法简单,反应条件更加温和,更加绿色环保,而且分子筛的加入能够降低水对NbCl5的分解,离子液体的加入有利于稳定NbCl5,从而增强其催化性能,该方法扩大了底物范围,反应产率高(95%以上)、催化剂用量少、原子经济性高、而且催化剂便宜易得,可大大降低成产成本,适合工业化生产。
(2)本发明在对离子液体进行选择时,意外的发现,咪唑类离子液体较吡啶类等其他类型的离子液体能够显著降低催化剂用量,同时提高产率。在本专利中加入(5%mmol)的NbCl5酰胺化产率已经可以达到85%,考虑是因为咪唑类化合物在阳离子脱氢时得到的卡宾(氮杂卡宾类离子液体)有仅利于稳定NbCl5(咪唑类离子液体可以和NbCl5形成络合物),从而增强其催化性能,同时氮杂卡宾可以活化有机羧酸的羰基,提高有机羧酸与胺的反应活性,通过双重作用实现催化剂低用量、高产率的效果。
附图说明
图1实施例1的核磁氢谱;
图2实施例2的核磁氢谱;
图3实施例3的核磁氢谱;
图4实施例4的核磁氢谱;
图5实施例5的核磁氢谱;
图6实施例6的核磁氢谱;
图7实施例7的核磁氢谱;
图8实施例8的核磁氢谱;
图9离子液体1的核磁氢谱;
图10离子液体2的核磁氢谱;
图11离子液体3的核磁氢谱;
图12离子液体4的核磁氢谱;
图13离子液体5的核磁氢谱。
具体实施方式
以下结合具体实施例对本发明作以进一步的阐述,以便本领域的技术人员更了解本发明所述的技术方案,但并不以此限制本发明。
本发明的化学方程式如下:
实施例1
将苯甲酸(244mg,2mmol),五氯化铌(11mg,0.08mmol),离子液体5(22mg,0.05mmol)和4A分子筛(122mg,50%,w/w%)加入圆底烧瓶中,后加入甲苯(4mL,2mL/mmol),室温搅拌30分钟后,后加入苄胺(214mg,2mmol),升温至回流,反应24小时。待反应完全后,经快速柱层析(石油醚→乙酸乙酯:三乙胺(200:1,v/v)过柱子,得到白色固体405mg,产率96%。1H NMR(400MHz,CDCl3)δ7.809(d,J=7.2Hz,2H),7.50(t,J=7.2Hz,1H),7.43(t,J=7.2Hz,2H),7.38–7.34(m,4H),7.33–7.27(m,1H),6.42(br.s,1H),4.65(d,J=5.6Hz,1H),核磁氢谱见图1。
离子液体5的合成
将N-甲基咪唑(4.6g,0.05mol)加入圆底烧瓶中预热至70℃,缓慢滴加溴代丁烷,继续加热回流4h。TLC检测反应完全后,冷却至室温,乙酸乙酯洗涤(3×15mL),旋转蒸发仪除去乙酸乙酯,并在60℃下真空干燥12h,得到甲基咪唑溴离子液体5。1H NMR(400MHz,CDCl3)δ10.31(s,1H),7.58(s,1H),7.46(s,1H),4.29(t,J=7.2Hz,2H),2.01–1.65(m,2H),1.43–1.26(m,2H),0.91(t,J=7.2Hz,3H).核磁氢谱见图13。
实施例2
将2-吡啶甲酸(246mg,2mmol),五氯化铌(11mg,0.08mmol),离子液体5(22mg,0.05mmol)和4A分子筛(122mg,50%,w/w%)加入圆底烧瓶中,后加入甲苯(4mL,2mL/mmol),室温搅拌30分钟后,后加入苄胺(214mg,2mmol),升温至回流,反应24小时。待反应完全后,经快速柱层析(石油醚→乙酸乙酯:三乙胺(200:1,v/v)过柱子,得到白色固体365mg,产率86%。1H NMR(400MHz,CDCl3)δ8.94(d,J=1.9Hz,1H),8.66(dd,J=4.8,1.2Hz,1H),8.12(d,J=8.0Hz,1H),7.42–7.22(m,6H),6.86(br.s,1H),4.63(d,J=5.7Hz,2H),核磁氢谱见图2。
实施例3
将3-噻吩甲酸(256mg,2mmol),五氯化铌(11mg,0.08mmol),离子液体5(22mg,0.05mmol)和4A分子筛(122mg,50%,w/w%)加入圆底烧瓶中,后加入甲苯(4mL,2mL/mmol),室温搅拌30分钟后,后加入苄胺(214mg,2mmol),升温至回流,反应24小时。待反应完全后,经快速柱层析(石油醚→乙酸乙酯:三乙胺(200:1,v/v)过柱子,得到白色固体386mg,产率89%。1H NMR(400MHz,CDCl3)δ7.90–7.83(m,1H),7.39(dd,J=4.8,0.8Hz,1H),7.35–7.25(m,6H),6.42(br.s,1H),4.59(d,J=6.0Hz,2H),核磁氢谱见图3。
实施例4
将4-甲氧基肉桂酸(356mg,2mmol),五氯化铌(11mg,0.08mmol),离子液体5(22mg,0.05mmol)和4A分子筛(122mg,50%,w/w%)加入圆底烧瓶中,后加入甲苯(4mL,2mL/mmol),室温搅拌30分钟后,后加入苄胺(214mg,2mmol),升温至回流,反应24小时。待反应完全后,经快速柱层析(石油醚→乙酸乙酯:三乙胺(200:1,v/v)过柱子,得到白色固体491mg,产率92%。1HNMR(400MHz,CDCl3)δ7.63(d,J=15.6Hz,1H),7.44(d,J=8.8Hz,2H),7.36–7.16(m,4H),7.24–7.16(m,1H),6.88(d,J=8.8Hz,2H),6.29(d,J=15.6Hz,1H),5.93(br.s,1H),4.56(d,J=5.6Hz,2H),3.82(s,3H),核磁氢谱见图4。
实施例5
将BOC-L-脯氨酸(430mg,2mmol),五氯化铌(11mg,0.08mmol),离子液体5(22mg,0.05mmol)和4A分子筛(122mg,50%,w/w%)加入圆底烧瓶中,后加入甲苯(4mL,2mL/mmol),室温搅拌30分钟后,后加入苄胺(214mg,2mmol),升温至回流,反应24小时。待反应完全后,经快速柱层析(石油醚→乙酸乙酯:三乙胺(200:1,v/v)过柱子,得到白色固体547mg,产率90%。1HNMR(400MHz,CDCl3)δ7.42–7.10(m,5H),6.35(br.s,1H),4.50–4.20(m,2H),3.42(s,2H),2.50–1.75(m,2H),1.41(s,9H),核磁氢谱见图5。
实施例6
将对硝基苯乙酸(362mg,2mmol),五氯化铌(11mg,0.08mmol),离子液体5(22mg,0.05mmol)和4A分子筛(122mg,50%,w/w%)加入圆底烧瓶中,后加入甲苯(4mL,2mL/mmol),室温搅拌30分钟后,后加入苄胺(214mg,2mmol),升温至回流,反应24小时。待反应完全后,经快速柱层析(石油醚→乙酸乙酯:三乙胺(200:1,v/v)过柱子,得到白色固体432mg,产率80%。1H NMR(400MHz,CDCl3)δ8.19(d,J=8.8Hz,1H),7.46(d,J=8.8Hz,1H),7.36–7.27(m,5H),5.86(br.s,1H),4.43(d,J=5.6Hz,1H),3.67(s,2H),核磁氢谱见图6。
实施例7
将苯甲酸(244mg,2mmol),五氯化铌(11mg,0.08mmol),离子液体5(22mg,0.05mmol)和4A分子筛(122mg,50%,w/w%)加入圆底烧瓶中,后加入甲苯(4mL,2mL/mmol),室温搅拌30分钟后,后加入环己胺(198mg,2mmol),升温至回流,反应24小时。待反应完全后,经快速柱层析(石油醚→乙酸乙酯:三乙胺(200:1,v/v)过柱子,得到白色固体320mg,产率79%。1H NMR(400MHz,CDCl3)δ7.75(d,J=7.6Hz,2H),7.54–7.38(m,3H),5.96(br.s,1H),4.10–3.90(m,1H),2.13–2.00(m,2H),1.84–1.72(m,2H),1.55–1.33(m,2H),1.35–1.15(m,2H),核磁氢谱见图7。
实施例8
将苯甲酸(244mg,2mmol),五氯化铌(11mg,0.08mmol),离子液体5(22mg,0.05mmol)和4A分子筛(122mg,50%,w/w%)加入圆底烧瓶中,后加入甲苯(4mL,2mL/mmol),室温搅拌30分钟后,后加入吗啡啉(174mg,2mmol),升温至回流,反应24小时。待反应完全后,经快速柱层析(石油醚→乙酸乙酯:三乙胺(200:1,v/v)过柱子,得到白色固体317mg,产率83%。1H NMR(400MHz,CDCl3)δ7.78(d,J=7.6Hz,2H),7.53–7.43(m,1H),7.44–7.36(m,2H),7.04(br.s,1H),3.78(t,J=5.2Hz,2H),3.65–3.52(m,4H),2.81(t,J=5.2Hz,2H),核磁氢谱见图8。
实施例9
与实施例1的区别在于:将NbCl5由0.08mmol变为0.1mmol,产率94%。
实施例10
与实施例9的区别在于:将离子液体5变为离子液体1,用量不变,仍然为0.05mmol,产率90。
离子液体1的合成
将N-甲基咪唑(4.6g,0.05mol)加入圆底烧瓶中预热至70℃,缓慢滴加1,3-二溴丙烷,继续加热回流4h。TLC检测反应完全后,冷却至室温,乙酸乙酯洗涤(3×15mL),旋转蒸发仪除去乙酸乙酯,并在60℃下真空干燥12h,得到甲基咪唑溴离子液体1。1H NMR(400MHz,D2O)δ8.85(s,1H),7.69–7.32(m,2H),4.55–4.23(m,4H),3.96(s,6H),2.65–2.51(m,2H),核磁氢谱见图9。
实施例11
与实施例10的区别在于:离子液体1为0.1mmol,产率89%。
实施例12
与实施例11的区别在于:离子液体1变为离子液体2,产率90%。
离子液体2的合成
将N-甲基咪唑(4.6g,0.05mol)加入圆底烧瓶中预热至70℃,缓慢滴加1,4-二溴丁烷,继续加热回流4h。TLC检测反应完全后,冷却至室温,乙酸乙酯洗涤(3×15mL),旋转蒸发仪除去乙酸乙酯,并在60℃下真空干燥12h,得到甲基咪唑溴离子液体2。1HNMR(400MHz,D2O)δ8.79(s,2H),7.79–7.24(m,4H),4.30(s,4H),3.94(s,6H),1.96(s,4H),核磁氢谱见图10。
实施例13
与实施例11的区别在于:离子液体1变为离子液体3,产率88%。
离子液体3的合成
将N-甲基咪唑(4.6g,0.05mol)加入圆底烧瓶中预热至70℃,缓慢滴加1,5-二溴戊烷,继续加热回流4h。TLC检测反应完全后,冷却至室温,乙酸乙酯洗涤(3×15mL),旋转蒸发仪除去乙酸乙酯,并在60℃下真空干燥12h,得到甲基咪唑溴离子液体3。1HNMR(400MHz,D2O)δ8.74(s,2H),7.48(d,J=14.6Hz,4H),4.30–4.12(m,4H),3.91(s,6H),2.10–1.81(m,4H),1.47–1.25(m,2H),核磁氢谱见图11。
实施例14
与实施例11的区别在于:离子液体1变为离子液体4,产率86%。
离子液体4的合成
将N-甲基咪唑(4.6g,0.05mol)加入圆底烧瓶中预热至70℃,缓慢滴加1,6-二溴己烷,继续加热回流4h。TLC检测反应完全后,冷却至室温,乙酸乙酯洗涤(3×15mL),旋转蒸发仪除去乙酸乙酯,并在60℃下真空干燥12h,得到甲基咪唑溴离子液体4。1H NMR(400MHz,D2O)δ8.73(s,2H),7.46(d,J=16.2Hz,4H),4.21(s,4H),3.90(s,6H),1.88(s,4H),1.36(s,4H),核磁氢谱见图12。
本发明在对苯甲酸和苄胺进行酰胺化时,还尝试如下反应,具体情况见下表:
通过上述实验可以看出,分子筛和离子液体的加入对于酰胺化反应有很大的促进作用,随着离子液体的加入催化性能显著提高,最后确定了反应的最优条件为:酸与胺的摩尔比为1:1,NbCl58%mmol,4A分子筛50%w/w,离子液体5%mmol,甲苯2mL/mmol,110℃,24h。
本发明提供的实施例和对比例只是部分具有代表性的案例,上述内容并不用于对本发明保护范围的限定,本发明保护范围以权利要求书记载的内容为准。
Claims (7)
1.一种五氯化铌与离子液体共催化制备酰胺类化合物的合成方法,其特征在于,包括以下步骤:称取有机羧酸、有机胺、五氯化铌和离子液体、分子筛,将上述物料加入到反应器中,加入有机溶剂,反应温度70-110℃,反应时间6-24小时,得到对应的酰胺产物。
2.根据权利要求1所述的一种五氯化铌与离子液体共催化制备酰胺类化合物的合成方法,其特征在于,所述有机羧酸、有机胺、五氯化铌和离子液体,摩尔比为1:(1~3):(0.01~1):(0.05~1);所述有机羧酸和分子筛质量比为1:(0.2~1)。
3.根据权利要求1所述的一种五氯化铌与离子液体共催化制备酰胺类化合物的合成方法,其特征在于,所述离子液体为咪唑类离子液体。
4.根据权利要求1所述的一种五氯化铌与离子液体共催化制备酰胺类化合物的合成方法,其特征在于,所述有机溶剂为四氢呋喃、二氧六环、甲苯。
5.根据权利要求1所述的一种五氯化铌与离子液体共催化制备酰胺类化合物的合成方法,其特征在于,所述分子筛为3A分子筛、4A分子筛、5A分子筛。
6.根据权利要求2所述的一种五氯化铌与离子液体共催化制备酰胺类化合物的合成方法,其特征在于,所述有机羧酸、有机胺、五氯化铌和离子液体,摩尔比为1:1:0.08:0.05。
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