CN105504305A - 一种含3-(4-吡啶)吡唑-丙酸的配位聚合物及其制备方法、用途 - Google Patents
一种含3-(4-吡啶)吡唑-丙酸的配位聚合物及其制备方法、用途 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- ZPASEBVQANBCFC-UHFFFAOYSA-N propanoic acid;1h-pyrazole Chemical compound CCC(O)=O.C=1C=NNC=1 ZPASEBVQANBCFC-UHFFFAOYSA-N 0.000 title 1
- 239000010949 copper Substances 0.000 claims abstract description 25
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 24
- -1 biaryl compounds Chemical class 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 14
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- 238000000926 separation method Methods 0.000 claims description 8
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- 238000000034 method Methods 0.000 claims description 7
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- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
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- 125000004122 cyclic group Chemical group 0.000 abstract 1
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- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
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- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明属于无机/有机化学领域,具体涉及一种金属配位聚合物及其制备方法、用途。该配位聚合物的分子式为:[Cu(Hpypa)2(H2O)2)]n。将硝酸铜及Hpypa溶于水和N,N-二甲基甲酰胺的混合溶液中;将所得混合液转移到反应釜中加热至100-140℃保持20-30小时,降温,所得析出物即为目标配位聚合物。本发明配位聚合物作为催化剂催化合成联芳类化合物的用途。本发明采用铜离子及有机配体配位形成具有催化活性的配位聚合物,经过实验研究发现上述的配位聚合物催化剂实现了对联芳类化合物的高效制备并可循环利用。
Description
技术领域
本发明属于无机/有机化学领域,具体涉及一种金属配位聚合物及其制备方法、用途。
背景技术
联芳类化合物是许多天然有机物的重要组成部分,它在化工、医药、食品等领域的用途日益广泛。通过C-C键构筑联芳化合物在现代有机化学有机合成中具有重要地位,而Ullmann反应是通过构建C-C键合成对称联芳化合物的有效途径之一,并且可以广泛地拓展应用于芳基碳-氧、芳基碳-氮、芳基碳-硫等键的形成。传统的Ullmann偶联反应需要化学计量或者过量的铜试剂作为催化剂,反应温度通常在200℃以上,而且在反应中需要使用强碱,苛刻的反应条件严重影响了这一反应的推广,因此如何优化反应条件、降低反应温度及提高收率,使之能在较为温和的条件下进行一直是在这一领域进行研究的化学家们的主要目标。随着近年来的不断发展,在Ullmann反应催化剂的改良上取得了一定的进展,但是这些改进的方法仍然无法满足绿色化学的要求,比如使用了有毒的或昂贵的试剂及催化剂,需要预先合成格式试剂,条件严苛,催化剂无法实现回收循环利用等。
最近,配位聚合物(CPs)的设计和合成逐渐引起了化学家及材料学家的关注。配位聚合物是由金属离子和金属簇作为节点和有机配体相连接而自组装成的晶体材料。由于这种材料的结构富于变化,能表现出丰富多彩的拓扑结构,因此不仅具有结构的理论研究意义,同时可作为优良的功能材料,具有诱人的应用前景,目前对于这种材料的研究主要集中于光电磁性质的研究,而其在催化、气吸收及存储、荧光、传感和药物传输及金属离子吸附等方面同样具有潜在的应用价值。CPs不仅具有丰富的化学多样性和结构多样性,而且可以作为很多客体分子的主体,这些特征提供了多种多样的机会去创造需要的活性中心,决定了CPs可以作为优秀的催化材料。同时,CPs作为一种非均相催化剂具有固定的催化活性位点,以及易于从反应体系中分离,并且可循环利用等优点符合绿色化学的研究要求。
发明内容
本发明的目的在于提供一种含3-(4-吡啶)吡唑-丙酸的配位聚合物及其制备方法、用途。
为实现上述目的,本发明采取的技术方案如下:
一种含3-(4-吡啶)吡唑-丙酸的铜配位聚合物,其特征在于该铜配位聚合物的分子式为:[Cu(Hpypa)2(H2O)2)]n,n为任意正整数;其中,Hpypa即为3-(4-吡啶)吡唑-丙酸,Hpypa的结构式如下:
。
本发明铜配位聚合物的制备方法,步骤如下:
(1)将硝酸铜及Hpypa溶解在水和N,N-二甲基甲酰胺(DMF)的混合溶液中;
(2)将步骤(1)所得混合液转移到反应釜中加热至100-140℃保持20-30小时,降温,所得析出物即为目标产品。
较好地,硝酸铜和Hpypa的摩尔比为1:1-2:1;水和N,N-二甲基甲酰胺的总用量为每mmol硝酸铜添加70-90ml,水和N,N-二甲基甲酰胺的体积为2:1-1:2。
较好地,步骤(1)中,在40-60℃下加热溶解。
较好地,步骤(2)中,以5-10℃/h的速率降温。
本发明铜配位聚合物作为催化剂催化合成联芳类化合物的用途。
具体地,以卤代芳烃为反应底物、[Cu(Hpypa)2(H2O)2)]n为催化剂、镁屑为助催化剂、四氢呋喃为溶剂,50-70℃条件下加热4-6小时,过滤分离出催化剂和助催化剂,加入乙酸乙酯和水萃取,最后薄层层析分离纯化得到联芳类化合物。
较好地,乙酸乙酯和水的体积比为2:1-1:1。
较好地,[Cu(Hpypa)2(H2O)2)]n的物质的量是卤代芳烃物质的量的8-12%,镁屑的物质的量是卤代芳烃物质的量的1-1.2倍,四氢呋喃的用量为每mmol[Cu(Hpypa)2(H2O)2)]n添加30-50ml。
较好地,过滤后所得催化剂和助催化剂,再次依据前述方法循环利用。
本发明的有益效果:
本发明考虑到配位聚合物催化剂的优点,采用铜离子及有机配体配位形成具有催化活性的配位聚合物;本发明达到了在不用引入格式试剂的前提下,使用温和条件的简单方法高效合成联芳类化合物,并且催化过后的配位聚合物催化剂通过过滤分离出来,并再次投入进行催化合成实验,实现了催化剂的循环利用,这对将来合成联芳类化合物具有重要的指导意义。
附图说明
图1:实施例1产品的晶体结构图。
具体实施方式
下面结合实施例对本发明作详细的说明,实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
实施例1--含3-(4-吡啶)吡唑-丙酸的铜配位聚合物的合成
0.0108gHpypa(0.05mmol)和0.0243g硝酸铜(0.1mmol)分别溶于水(4mL)和DMF(4mL)中;将上述两种溶液混合搅拌加热至澄清,然后将混合液转移到反应釜中加热至130℃保持24小时后,以5℃/h的速率缓慢降至室温,过滤,得到蓝绿色的目标产物[Cu(Hpypa)2(H2O)2)]n,产率为78%(基于Hpypa计算)。产物经单晶X-射线衍射分析确定其晶体结构(图1),晶体学参数详见下表;元素分析:按C22H24CuN6O6(%)计算,理论值:C,49.62;H,4.51;N,15.79;实验值:C,49.86;H,4.36;N,15.61。
实施例2--催化合成联苯化合物
取0.05mmol(基于晶体结构单元的分子量来计算,即产品的物质的量=产品的质量/晶体结构单元Cu(Hpypa)2(H2O)2的分子量,下同,不再赘述)的实施例1产品[Cu(Hpypa)2(H2O)2)]n作为催化剂加入到0.5mmol溴代苯或碘代苯、0.6mmol打磨光亮的镁屑和2mlTHF混合物中,在70℃条件下加热6小时,过滤分离出催化剂和镁屑,加入10ml乙酸乙酯和10ml水萃取,用薄层层析分离纯化得到目标产品,产率:85%(溴代苯底物),90%(碘代苯底物);表征如下:1HNMR(400MHz,CDCl3):δ7.44-7.58(m,6H,CHar),7.78(d,4H,J=8.1Hz,CHar);13CNMR(100MHz,CDCl3):δ128.2,129.9,132.3,137.5。
实施例3--催化合成4,4-二甲基联苯化合物
取0.05mmol的实施例1产品[Cu(Hpypa)2(H2O)2)]n作为催化剂加入到0.5mmol的4-碘甲苯、0.6mmol打磨光亮的镁屑和2mlTHF混合物中,在70℃条件下加热6小时,过滤分离出催化剂和镁屑,加入10ml乙酸乙酯和10ml水萃取,用薄层层析分离纯化得到目标产品,产率:85%;表征如下:1HNMR(400MHz,CDCl3):δ2.35(s,6H,CH3),7.19(d,4H,J=7.8Hz,CHar),7.62(d,4H,J=7.8Hz,CHar);13CNMR(100MHz,CDCl3):δ21.5,128.8,130.1,135.1,142.8。
实施例4--催化合成4,4-二甲氧基联苯化合物
取0.05mmol的实施例1产品[Cu(Hpypa)2(H2O)2)]n作为催化剂加入到0.5mmol的4-碘苯甲醚或4-溴苯甲醚、0.6mmol打磨光亮的镁屑和2mlTHF混合物中,在70℃条件下加热6小时,过滤分离出催化剂和镁屑,加入10ml乙酸乙酯和10ml水萃取,用薄层层析分离纯化得到目标产品,产率:85%(4-碘苯甲醚底物),83%(4-溴苯甲醚底物);表征如下:1HNMR(400MHz,CDCl3):δ3.81(s,6H,OCH3),6.88(d,4H,J=8.5Hz,CHar),7.71(d,4H,J=8.5Hz,CHar);13CNMR(100MHz,CDCl3):δ55.4,113.4,130.7,132.1,162.7。
实施例5--催化合成4,4-二乙氧基联苯化合物
取0.05mmol的实施例1产品[Cu(Hpypa)2(H2O)2)]n作为催化剂加入到0.5mmol的4-碘苯乙醚、0.6mmol打磨光亮的镁屑和2mlTHF混合物中,在70℃条件下加热6小时,过滤分离出催化剂和镁屑,加入10ml乙酸乙酯和10ml水萃取,用薄层层析分离纯化得到目标产品,产率:80%;表征如下:1HNMR(400MHz,CDCl3):δ1.37(t,6H,J=7.0Hz,CH3),4.03(q,4H,J=7.0Hz,CH2),6.86(d,4H,J=8.5Hz,CHar),7.69(d,4H,J=8.5Hz,CHar);13CNMR(100MHz,CDCl3):δ14.6,63.7,113.9,130.6,132.1,162.2。
实施例2-5的反应式如下:
式中:R选自H、甲氧基、甲基、乙氧基其中一种;X选自:I、Br其中一种。
催化结果如下表:
实施例6--循环利用催化剂催化合成联苯化合物
将实施例2中过滤分离出的[Cu(Hpypa)2(H2O)2)]n和镁屑再次作为催化剂和助催化剂加入到0.5mmol溴代苯和2mlTHF的混合物中,在70℃条件下加热6小时,过滤分离出催化剂和镁屑,加入10ml乙酸乙酯和10ml水萃取,用薄层层析分离纯化得到目标产品。催化剂依上述方法循环利用五次,具体方法同上,产率依次为85%、81%、78%、79%、76%。
Claims (10)
1.一种含3-(4-吡啶)吡唑-丙酸的铜配位聚合物,其特征在于该铜配位聚合物的分子式为:[Cu(Hpypa)2(H2O)2)]n;其中,Hpypa即为3-(4-吡啶)吡唑-丙酸,Hpypa的结构式如下:
。
2.一种制备如权利要求1所述的铜配位聚合物的方法,其特征在于步骤如下:
(1)将硝酸铜及Hpypa溶解在水和N,N-二甲基甲酰胺的混合溶液中;
(2)将步骤(1)所得混合液转移到反应釜中加热至100-140℃保持20-30小时,降温,所得析出物即为目标产品。
3.如权利要求2所述的制备方法,其特征在于:硝酸铜和Hpypa的摩尔比为1:1-2:1;水和N,N-二甲基甲酰胺的总用量为每mmol硝酸铜添加70-90ml,水和N,N-二甲基甲酰胺的体积为2:1-1:2。
4.如权利要求2所述的制备方法,其特征在于:步骤(1)中,在40-60℃下加热溶解。
5.如权利要求2所述的制备方法,其特征在于:步骤(2)中,以5-10℃/h的速率降温。
6.如权利要求1所述的铜配位聚合物作为催化剂催化合成联芳类化合物的用途。
7.如权利要求6所述的用途,其特征在于:以卤代芳烃为反应底物、[Cu(Hpypa)2(H2O)2)]n为催化剂、镁屑为助催化剂、四氢呋喃为溶剂,50-70℃条件下加热4-6小时,过滤分离出催化剂和助催化剂,加入乙酸乙酯和水萃取,最后薄层层析分离纯化得到联芳类化合物。
8.如权利要求7所述的用途,其特征在于:乙酸乙酯和水的体积比为2:1-1:1。
9.如权利要求7所述的用途,其特征在于:[Cu(Hpypa)2(H2O)2)]n的物质的量是卤代芳烃物质的量的8-12%,镁屑的物质的量是卤代芳烃物质的量的1-1.2倍,四氢呋喃的用量为每mmol[Cu(Hpypa)2(H2O)2)]n添加30-50ml。
10.如权利要求7所述的用途,其特征在于:过滤后所得催化剂和助催化剂,再次依据前述方法循环利用。
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CN113201146A (zh) * | 2021-05-18 | 2021-08-03 | 郑州大学 | 一种含噻二唑/羧基的铜配位聚合物及其制备方法和应用 |
CN115286493A (zh) * | 2022-08-26 | 2022-11-04 | 北京格林凯默科技有限公司 | 4,4′-二乙氧基联苯的制备方法 |
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