CN113797976B - 一种用于催化制备取代酮类化合物的铱催化剂 - Google Patents
一种用于催化制备取代酮类化合物的铱催化剂 Download PDFInfo
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Abstract
本发明公开了一种用于催化制备取代酮类化合物的铱催化剂,属于化学材料领域。本发明首先以(2H‑1,2,3‑三氮唑‑1‑基)乙酸作为配体,与铱合成得到了铱催化剂TriaIrX2(其中X为Cl、Br或I),该铱催化剂在温和条件下具有优异的催化活性,与传统催化剂相比,具有更高效的催化性能,能够提高反应的立体选择性,能够用于苯甲醇类化合物和苯乙酮类化合物制备取代酮类化合物的反应和双酚F的合成反应,催化剂的应用场景广阔。
Description
本发明为申请号为202011286680.X、申请日为2020年11月17日、发明名称为“一种用于催化炔丙基酯重排制备取代酮类化合物的铱催化剂”的分案。
技术领域
本发明涉及一种用于催化制备取代酮类化合物的铱催化剂,属于化学材料与药物领域。
背景技术
α,β-不饱和羰基化合物及其衍生物是一类常见的取代酮类化合物,它存在于许多具有生物活性天然产物以及药物分子中。同时,α,β-不饱和羰基化合物还是药物合成和天然产物合成中重要的中间体,其还原产物饱和羰基化合物和烯丙醇类化合物是医药、激素、食品添加剂、农药等的重要中间体。
α,β-不饱和羰基化合物的合成方法具有多种,例如:加热条件下的羟醛缩合、Claisen-Schmidt反应、Perkin反应、Knoevenagel缩合、Meyer-Schuster重排等途径都是合成此类化合物的常用方法。此外,利用过渡金属催化的反应来合成α,β-不饱和羰基化合物的方法近些年也有诸多报导,但通常需要在强酸或者金属催化剂及加热的条件下进行,传统催化剂往往存在着活性低、选择性差等缺点,亟需发展一种温和的催化体系合成α,β-不饱和羰基化合物。
发明内容
为了解决现有技术存在的问题,本发明提供了一种用于多种反应环境的铱催化剂及其制备方法,本发明首先以(2H-1,2,3-三氮唑-1-基)乙酸配体,与铱合成得到了铱催化剂TriaIrCl2,能够用于催化苯甲醇与2-溴苯乙酮反应合成取代酮类化合物的反应,产率为93%,酮类化合物的选择性>98%。用途多样且催化性能优异,具有良好的应用场景。同时,该催化剂还可以用于双酚F的合成中,可以得到80%的产率和大于90%的化学选择性。
本发明的第一个目的是提供一种用于铱催化剂TriaIrX2的制备方法,所述方法包括如下过程:
将(2H-1,2,3-三氮唑-1-基)乙酸(Tria)、醋酸钠和铱源分散在溶剂中,在20-80℃下进行反应,反应结束后,冷却,固液分离、收集清液,浓缩干燥,制得铱催化剂(TriaIrX2)。
在本发明的一种实施方式中,所述溶剂为乙醇、甲醇、四氢呋喃、N,N-二甲基甲酰胺。
在本发明的一种实施方式中,所述铱源为IrX3;X为氯、溴、碘。
在本发明的一种实施方式中,所述(2H-1,2,3-三氮唑-1-基)乙酸相对溶剂的浓度为0.1~1mmol/mL。
在本发明的一种实施方式中,所述(2H-1,2,3-三氮唑-1-基)乙酸与醋酸钠的摩尔比为1:1。
在本发明的一种实施方式中,所述(2H-1,2,3-三氮唑-1-基)乙酸与铱源的摩尔用量比为1:1~1:2。
在本发明的一种实施方式中,所述反应是在120-480r/min转速下进行的。
在本发明的一种实施方式中,所述方法中还包括:固液分离、收集固体后,将固体在溶解在二氯甲烷中,并用石油醇或者正己烷进行重结晶,固液分离、收集固体,干燥。
在本发明的一种实施方式中,所述方法具体包括如下步骤:
(1)将(2H-1,2,3-三氮唑-1-基)乙酸和乙醇混合均匀,然后再加入与(2H-1,2,3-***-1-基)乙酸摩尔比为1:1的醋酸钠,搅拌反应30-60min;
(2)向步骤(1)得到的反应溶液中加入IrX3,在20-80℃下搅拌反应12-24h,反应结束后冷却、过滤,将过滤得到的上清液通过真空浓缩得到粗产品;
(3)将步骤(2)所得的粗产品溶解在二氯甲烷中,并用石油醚进行重结晶,固液分离、干燥即可得到铱催化剂TriaIrX2。
在本发明的一种实施方式中,步骤(1)中(2H-1,2,3-***-1-基)乙酸和乙醇的比例为1mmol:1~10mL。
在本发明的一种实施方式中,步骤(1)中所述搅拌的速度为120-480r/min;步骤(2)中所述搅拌的速度为200-800r/min。
在本发明的一种实施方式中,步骤(2)中所述过滤优选为通过硅藻土进行过滤。
在本发明的一种实施方式中,步骤(3)中所述固液分离为过滤或离心分离。
在本发明的一种实施方式中,步骤(3)中所述干燥优选为真空干燥,优选温度为30℃,时间为24h。
本发明的第二个目的是利用上述方法制备得到一种铱催化剂。
本发明的第三个目的是提供上述铱催化剂应用在催化合成双酚F中。
本发明的第四个目的是提供一种合成双酚F的方法,所述方法以上述的铱催化剂TriaIrCl2为催化剂。
在本发明的一种实施方式中,所述催化合成双酚F的反应路线为:
在本发明的一种实施方式中,所述方法具体包括:在反应容器中加入苯酚、上述制备得到的铱催化剂TriaIrCl2和甲醛,在35-60℃下反应1-8h,用碳酸氢钠调pH为5-6,分离有机相,随后溶解于NaOH溶液中,用浓盐酸调pH约为2-5,即得到产品双酚F。
在本发明的一种实施方式中,所述苯酚、铱催化剂、甲醛的摩尔比为10:3:5。
本发明的第五个目的是提供一种催化苯甲醇类化合物和苯乙酮类化合物制备取代酮类化合物的方法,所述方法是利用上述的铱催化剂TriaIrCl2为催化剂。
在本发明的一种实施方式中,所述催化苯甲醇类化合物和苯乙酮类化合物制备取代酮类化合物的反应路线为:
其中,R3、R4分别独立地选自:氢、卤素、C1-8烷基、烷氧基、卤代烷基。
与现有技术相比,本发明具有以下优势:
(1)本发明的催化剂无需用到贵金属,大大降低了催化剂的成本,可工业化生产。
(2)本发明制备得到的铱催化剂可以用于双酚F的合成中,可以得到80%的产率和大于90%的化学选择性。
(3)本发明制备得到的铱催化剂能够用于合成双酚F的反应,用途多样且催化性能优异,具有更广泛的应用场景。
具体实施方式
收率的计算公式:收率=(实际产物质量/理论产物质量)×100%;
本发明涉及的配体(2H-1,2,3-三氮唑-1-基)乙酸的来源:原料2H-1,2,3-三氮唑-4-羧酸甲酯由购买获得,参照Design and Synthesis of Alanine Triazole Ligands andApplication in Promotion of Hydration,Allene Synthesis and Borrowing HydrogenReactions(Advanced Synthesis&Catalysis,358(9),1433-1439;2016)中方法,在THF/MeOH(1:1)和LiOH水溶液的混合溶液中添加2H-1,2,3-三氮唑-4-羧酸甲酯,在室温下搅拌1-2小时后,加入HCl水溶液,酸化至pH至2~3,旋蒸除去溶剂,抽滤得到(2H-1,2,3-三氮唑-1-基)乙酸。
实施例1铱催化剂的制备
将(2H-1,2,3-三氮唑-1-基)乙酸(1.0mmol),加入圆底烧瓶中,加入10mL无水乙醇,搅拌均匀,然后再加入NaOAc(1.0mmol),室温下搅拌反应45min。然后向上述溶液中加入IrCl3,反应混合物在25℃下搅拌反应12h,待反应结束冷却至室温。反应结束后,将浑浊液通过硅藻土进行过滤,澄清溶液通过真空减压除去溶剂得到粗产品。将所得粗产品进一步溶解在DCM(10mL)中,并用正己烷(50mL)进行重结晶,再次抽滤,真空干燥得到TriaIrCl2。
实施例2铱催化剂的制备
将(2H-1,2,3-三氮唑-1-基)乙酸(1.0mmol),EtOH(10mL)加入圆底烧瓶中,搅拌均匀,然后再加入NaOAc(1.0mmol),室温下搅拌反应45min。然后向上述溶液中加入IrCl3,反应混合物在25℃下搅拌反应12h,待反应结束冷却至室温。反应结束后,将浑浊液通过硅藻土进行过滤,澄清溶液通过真空减压除去溶剂得到粗产品。将所得粗产品进一步溶解在DCM(10mL)中,并用石油醚(50mL)进行重结晶,再次抽滤,真空干燥得到TriaIrCl2。
实施例3铱催化剂的制备
将(2H-1,2,3-三氮唑-1-基)乙酸(1.0mmol),EtOH(10mL)加入圆底烧瓶中,搅拌均匀,然后再加入NaOAc(1.0mmol),室温下搅拌反应60min。然后向上述溶液中加入IrCl3,反应混合物在60℃下搅拌反应12h,待反应结束冷却至室温。反应结束后,将浑浊液通过硅藻土进行过滤,澄清溶液通过真空减压除去溶剂得到粗产品。将所得粗产品进一步溶解在DCM(10mL)中,并用石油醚(50mL)进行重结晶,再次抽滤,真空干燥得到TriaIrCl2。
实施例4催化合成双酚F
在100mL烧瓶中加入5mmol苯酚,加热至完全融化,加入实施例1制备得到的TriaIrCl2催化剂1.5mmol),再滴加入2.5mmol的甲醛溶液,在50℃下反应4h,加入适量碳酸氢钠调pH约为5-6,分离有机相,减压蒸馏,将粗产品溶解于适量NaOH溶液中,用浓盐酸调pH约为6,即得到产品双酚F,产率80%,产物的化学选择性为92%。
双酚F的表征数据:
1H NMR(400MHz,acetone-d6,δppm):3.8(s,2H),6.75(m,4H),7.03(m,4H),8.1(s,2H).
实施例5:催化苯甲醇与2-溴苯乙酮反应合成取代酮类化合物
将2mmol苯甲醇与2.4mmol 2-溴苯乙酮投入25mL反应瓶中,随后加入0.1mmol实施例1制备得到的TriaIrCl2催化剂以及1mmol NaOH,以甲苯作为反应的溶剂,并放在110℃油浴锅中磁力搅拌24h,待反应结束并冷却至室温后加入蒸馏水,并用乙酸乙酯萃取3次(3x20mL),分液收集有机相,将有机相通过旋转蒸发仪旋转蒸发,最后利用柱层析分离得到产品1-(2-溴苯基)-3-苯基丙烷-1-酮,产率为93%,酮类化合物的选择性>98%。
1-(2-溴苯基)-3-苯基丙烷-1-酮的表征数据:
1H NMR(400MHz,CDCl3,δppm):7.50(d,J=8.0Hz,2H),7.29-7.22(m,7H),3.15(t,J=7.2Hz,2H),2.97(t,J=7.2Hz,2H).13C NMR(100MHz,CDCl3,δppm):203.3,141.7,140.7,133.6,131.6,128.2,128.4,128.4,127.4,126.2,118.6,44.2,30.1。
Claims (7)
1.一种制备铱催化剂的方法,其特征在于,所述方法包括如下过程:
将(2H-1,2,3-三氮唑-1-基)乙酸、醋酸钠和铱源分散在溶剂中,在20-80℃下进行反应,反应结束后,冷却,固液分离、收集清液,浓缩干燥,制得铱催化剂;
所述铱源为IrX3;X为氯、溴、碘。
2.根据权利要求1所述的方法,其特征在于,所述(2H-1,2,3-三氮唑-1-基)乙酸相对溶剂的浓度为0.1~1mmol/mL。
3.根据权利要求1所述的方法,其特征在于,所述(2H-1,2,3-三氮唑-1-基)乙酸与铱源的摩尔用量比为1:1~1:2。
4.根据权利要求1-3任一项所述的方法,其特征在于,所述溶剂为乙醇、甲醇、四氢呋喃、N,N-二甲基甲酰胺。
5.权利要求1-4任一项所述方法制备得到的一种铱催化剂。
6.一种合成双酚F的方法,其特征在于,所述方法是利用权利要求5所述的铱催化剂作为催化剂。
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---|
Effect of Ligand Chelation and Sacrificial Oxidant on the Integrity of Triazole-Based Carbene Iridium Water Oxidation Catalysts;Mazloomi Z et al;《INORGANIC CHEMISTRY》;20200908;第59卷(第17期);全文 * |
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