CN114149451B - 一种CuII双核配合物及其制备方法和在机械力下催化C-S耦合反应中的应用 - Google Patents
一种CuII双核配合物及其制备方法和在机械力下催化C-S耦合反应中的应用 Download PDFInfo
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- CN114149451B CN114149451B CN202111368468.2A CN202111368468A CN114149451B CN 114149451 B CN114149451 B CN 114149451B CN 202111368468 A CN202111368468 A CN 202111368468A CN 114149451 B CN114149451 B CN 114149451B
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- 238000005859 coupling reaction Methods 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- 229910052802 copper Inorganic materials 0.000 title claims abstract description 7
- 239000000956 alloy Substances 0.000 title claims description 6
- 229910045601 alloy Inorganic materials 0.000 title claims description 6
- 238000000227 grinding Methods 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- -1 1, 3-bis (2-pyridylmethyl) benzimidazole chlorate Chemical compound 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
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- 239000003054 catalyst Substances 0.000 claims abstract description 12
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- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 7
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims abstract description 5
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
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- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- PSWDQTMAUUQILQ-UHFFFAOYSA-N 2-[(6-methoxy-4-methylquinazolin-2-yl)amino]-5,6-dimethyl-1h-pyrimidin-4-one Chemical compound N1=C(C)C2=CC(OC)=CC=C2N=C1NC1=NC(=O)C(C)=C(C)N1 PSWDQTMAUUQILQ-UHFFFAOYSA-N 0.000 description 1
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- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- KGPGFQWBCSZGEL-ZDUSSCGKSA-N GSK690693 Chemical compound C=12N(CC)C(C=3C(=NON=3)N)=NC2=C(C#CC(C)(C)O)N=CC=1OC[C@H]1CCCNC1 KGPGFQWBCSZGEL-ZDUSSCGKSA-N 0.000 description 1
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- OSVHLUXLWQLPIY-KBAYOESNSA-N butyl 2-[(6aR,9R,10aR)-1-hydroxy-9-(hydroxymethyl)-6,6-dimethyl-6a,7,8,9,10,10a-hexahydrobenzo[c]chromen-3-yl]-2-methylpropanoate Chemical compound C(CCC)OC(C(C)(C)C1=CC(=C2[C@H]3[C@H](C(OC2=C1)(C)C)CC[C@H](C3)CO)O)=O OSVHLUXLWQLPIY-KBAYOESNSA-N 0.000 description 1
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- MUTCAPXLKRYEPR-ITWZMISCSA-N methyl (e,3r,5s)-7-[4-bromo-2,3-bis(4-fluorophenyl)-5-propan-2-ylpyrrol-1-yl]-3,5-dihydroxyhept-6-enoate Chemical compound COC(=O)C[C@H](O)C[C@H](O)\C=C\N1C(C(C)C)=C(Br)C(C=2C=CC(F)=CC=2)=C1C1=CC=C(F)C=C1 MUTCAPXLKRYEPR-ITWZMISCSA-N 0.000 description 1
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- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
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- C07D277/62—Benzothiazoles
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Abstract
本发明公开一种CuII双核配合物及其制备方法和在机械力下催化C‑S耦合反应中的应用。采用的技术方案是:以苯并咪唑和2‑氯甲基吡啶盐酸盐为原料,在常温无溶剂条件下,用球磨法制备1,3‑双(2‑吡啶基甲基)苯并咪唑氯酸盐(L)。并以L和氯化铜为原料进一步研磨合成双核铜配合物[Cu2(L)2Cl6]。以巯基苯并噻唑和溴苯乙酮为原料,以双核铜配合物为催化剂,采用微量液体辅助研磨的方式进行C‑S耦合反应,快速获得高产率耦合产物。本发明采用机械力法一锅两步快速简易的制得新型双核铜催化剂,同时将该催化剂在微量液体辅助研磨条件下催化C‑S耦合反应,操作及处理简单,反应条件温和且快速有效,20分钟即可完成反应。
Description
技术领域
本发明涉及一种新型双核配合物的绿色合成和应用。涉及一种绿色高效、操作简便的CuII双核配合物的制备方法以及一种无惰性气体保护、微量液体辅助下机械研磨催化C-S耦合反应的新方法,属于新材料的催化领域。
背景技术
近二十年来,人们对氮杂环卡宾及其金属配合物有着很大的兴趣,已合成和研究了许多单齿、双齿和三齿卡宾配体的金属配合物。其中,以吡啶为单元的螯合卡宾配体的过渡金属配合物因其在金属有机化学以及均相催化中的潜在应用而受到广泛关注。但绝大多数配体的制备需要较为苛刻的反应条件,如长时间的高温回流、惰性气体的保护或高压等,因此使用能够提高效率、减少污染的绿色化学合成方法是十分有必要的。
机械研磨作为一种新型、绿色的反应方式,在有机合成反应中得到越来越广泛的应用。机械催化是机械化学中一个新兴的方向,它是在机械力条件下进行的催化反应,反应进行的能量来自于手工研磨或球磨所产生的机械能而非传统的热能。因此,这项技术不仅避免了有毒有害溶剂的过度使用,还极大的简化了实验过程,在提高反应速率、大幅缩短反应时间的同时,还能在一定程度上提高反应收率。
含硫有机化合物广泛存在于化工、医药、材料、农用化学品及天然产品中,其中,C-S键在生物和药学活性分子及有机材料的制备中起着至关重要的作用。在C-S交叉偶联中,Reddy等人采用ZnO作为催化剂通过机械化学实现了C-S偶联,即在无溶剂条件下研磨4-5分钟快速得到了多种硫化物的衍生物(Eur.J.Org.Chem.2017,8,1207-1214)。Browne等人开发了一种由Pd-PEPPSI催化的C-S偶联,并且在球磨条件下实现了多种芳基卤化物和硫醇衍生物的有效应用(Org.Lett.2020,22,7433-7438)。但是双核配合物在C-S偶联中的催化性能研究却极少,尤其是在机械催化领域中。
发明内容
本发明的目的之一是利用CuII作为金属节点,选取1,3-双(2-吡啶基甲基)苯并咪唑氯酸盐作为有机配体,以机械研磨的方式得到具有双核CuII结构的配合物。
本发明的目的之二是以双核CuII结构的配合物作为催化剂,在少量溶剂辅助研磨下高效快速的催化C-S偶联反应。
本发明采用的技术方案为:一种CuII双核配合物,是以CuII作为金属节点,选取1,3-双(2-吡啶基甲基)苯并咪唑氯酸盐(L)作为有机配体,通过机械研磨的方式获得的[Cu2(L)2Cl6]。
一种CuII双核配合物的制备方法,包括如下步骤:将1,3-双(2-吡啶基甲基)苯并咪唑氯酸盐(L)与氯化铜置于研钵中,取微量溶剂,研磨2-3分钟,所得产物重结晶,得目标产物CuII双核配合物[Cu2(L)2Cl6]。
优选的,所述1,3-双(2-吡啶基甲基)苯并咪唑氯酸盐的合成方法,包括以下步骤:以苯并咪唑、2-氯甲基吡啶盐酸盐和碳酸氢钠为原料,在无溶剂的条件下,利用行星式球磨机研磨,得到棕红色粘稠物质,提纯后得到目标产物1,3-双(2-吡啶基甲基)苯并咪唑氯酸盐。
优选的,上述1,3-双(2-吡啶基甲基)苯并咪唑氯酸盐的合成方法,按摩尔比,苯并咪唑:2-氯甲基吡啶盐酸盐:碳酸氢钠=1:2:4。
优选的,上述CuII双核配合物的制备方法,按摩尔比,1,3-双(2-吡啶基甲基)苯并咪唑氯酸盐:氯化铜=1:1。
优选的,上述CuII双核配合物的制备方法,所述溶剂为甲醇。
优选的,上述CuII双核配合物的制备方法,为获得目标催化剂的三维结构,获取单晶衍射所需要的适合单晶,所述重结晶是,将研磨所得产物置于甲醇中,室温静置4-8小时,得到绿色的块状晶体。
本发明提供的CuII双核配合物作为催化剂在机械力下催化C-S耦合反应中的应用。
优选的,方法如下:以巯基苯并噻唑衍生物(1)和溴苯乙酮衍生物(2)为原料、CuII双核配合物[Cu2(L)2Cl6]为催化剂,采用微量有机溶剂辅助机械研磨的方法,于常温下反应,以研杵研磨至完全反应,反应完成后将反应混合物分离纯化,得到C-S耦合产物(3);反应式如下:
其中,R1为-H或-CH3;R1'为-H或-Br;R2为-H、-CH3、-OCH3、-Ph或卤素。
优选的,按物质的量之比,巯基苯并噻唑衍生物:溴苯乙酮衍生物:[Cu2(L)2Cl6]=1:1:0.01。
优选的,所述有机溶剂为乙腈、乙醇、环己烷或四氢呋喃。
更优选的,所述有机溶剂为乙腈。
优选的,所述分离纯化的方法为:反应完全后,将反应混合物溶于二氯甲烷中,过滤,将所得滤液用水萃取2-3次后合并有机相,采用体积比为50:1的石油醚和乙酸乙酯混合溶液作为洗脱剂,进行硅胶柱层析分离纯化。研磨方法中,研磨至完全反应的时间为20分钟。
本发明的有益效果是:
1、本发明提供了一种反应时间短、对环境友好、操作简单的含吡啶的螯合卡宾配体:1,3-双(2-吡啶基甲基)苯并咪唑氯酸盐(L)的制备方法。
2、本发明将1,3-双(2-吡啶基甲基)苯并咪唑氯酸盐(L)与氯化铜,通过固态研磨得到具有双核CuII结构的配合物([Cu2(L)2Cl6]),产率高达100%,纯度高、反应迅速、操作简单且易于实现工业化生产。
3、本发明使用廉价易得且稳定的二价铜盐代替了贵金属盐。
4、本发明使用机械催化制备C-S耦合产物,绿色温和,在大大缩短反应时间的同时,明显提高了反应的收率。
5、本发明所有反应均在常规条件下进行,无需高温高压或惰性气体保护,简化了实验步骤。
6、本发明反应仅使用微量液体辅助研磨,杜绝了大量有机溶剂的使用,降低了反应成本的同时,尽可能的降低了对环境的危害。
附图说明
图1是实施例1制备的1,3-双(2-吡啶基甲基)苯并咪唑氯酸盐(L)的1H NMR图。
图2是实施例1制备的1,3-双(2-吡啶基甲基)苯并咪唑氯酸盐(L)的FT-IR图。
图3是实施例1制备的目标产物研磨粉末与重结晶晶体的粉末衍射图对比。
图4是实施例1制备的CuII双核配合物([Cu2(L)2Cl6])单晶结构图。
图5是实施例2中3a的1H NMR图。
图6是实施例2中3a的13C NMR图。
具体实施方式
为了更好的理解本发明,下面结合具体实施例对本发明进行进一步的描述
实施例1CuII双核配合物([Cu2(L)2Cl6])
(一)机械研磨法制备1,3-双(2-吡啶基甲基)苯并咪唑氯酸盐(L)
在常温条件下,将苯并咪唑(0.74g,6.25mmol),2-氯甲基吡啶盐酸盐(2.034g,12.5mmol),NaHCO3(2.1g,25mmol)置于100mL研磨钢罐中,加入直径为9mm、重量为4g的钢球5个,直径为6mm、重量为0.9g的钢球6个。封闭钢罐后,将其放入行星式球磨机内,以450r/min的转速研磨4h,然后将所得棕红色粘稠物质溶于2×10mL乙醇中,过滤,减压蒸馏除去乙醇后,所得产物溶于二氯甲烷并用无水MgSO4干燥,再用四氢呋喃萃冷,干燥后得棕色粉末,即为1,3-双(2-吡啶基甲基)苯并咪唑氯酸盐(0.74g,35%),记为L。
制备的1,3-双(2-吡啶基甲基)苯并咪唑氯酸盐(L)的1H NMR图如图1,FT-IR图如图2,结构表征如下:
M.P.:169.2-170.8℃
1H NMR(300MHz,CDCl3)δ=11.74(s,1H),8.50(d,J=4.7Hz,2H),7.91–7.67(m,6H),7.52(dd,J=6.3,3.1Hz,2H),7.31–7.21(m,2H),6.04(s,4H).
IR(KBr):ν=1594.09cm-1(C=N),753.13cm-1(Cl-)
(二)机械研磨制备CuII双核配合物
将L(0.0337g,0.10mmol)和CuCl2·2H2O(0.0171g,0.10mmol)置于玛瑙研钵中,加入2滴甲醇(60μL)作为辅助研磨剂,研磨约2-3min,至研钵中物质变为绿色,且呈干粉状态时停止研磨,即可得到L的CuII双核配合物(0.0508g,100%)。
重结晶:将得到的CuII双核配合物绿色粉末转移至50mL锥形瓶中,加入5mL甲醇,静置4-8小时后,得到绿色透明块状晶体,产率为72%。
图3是制备的目标产物研磨粉末与重结晶晶体的粉末衍射图对比。图4是制备的CuII双核配合物([Cu2(L)2Cl6])单晶结构图。结构表征如下:
M.P.:139.4-140.6℃
IR(KBr):ν=1601.98cm-1(C=N),774.90cm-1(Cl-).
采用Bruker D8-Advance X-射线粉末衍射仪和Bruker D8-Quest单晶衍射仪对上述研磨产物和晶体分别进行粉末和单晶衍射实验。通过粉末衍射对比,表明机械力研磨制得的双核配合物与重结晶得到的单晶为同一种物质(图3)。晶体三维结构表明其结构式为[Cu2(L)2Cl6],如图4所示。晶体学数据如表1。
表1CuII双核配合物[Cu2(L)2Cl6]的单晶数据表
实施例2CuII双核配合物作为催化剂在机械力下催化C-S耦合反应中的应用
方法如下:以巯基苯并噻唑衍生物(1)和溴苯乙酮衍生物(2)为原料、CuII双核配合物[Cu2(L)2Cl6]为催化剂,采用微量有机溶剂辅助机械研磨的方法,于常温下反应,反应完成后将反应混合物分离纯化,得到C-S耦合产物(3)。反应式如下:
其中,R1为-H或-CH3;R1'为-H或-Br;R2为-H、-CH3、-OCH3、-Ph或卤素。
优选的,巯基苯并噻唑衍生物(1):溴苯乙酮衍生物(2):[Cu2(L)2Cl6]的物质的量之比为1:1:0.01。
优选的,有机溶剂为乙腈、乙醇、环己烷或四氢呋喃。
更优选的,有机溶剂为乙腈。
优选的,分离纯化的方法为:反应完全后,将反应混合物溶于二氯甲烷中,过滤,将所得滤液用水萃取2-3次后合并有机相,采用体积比为50:1的石油醚和乙酸乙酯混合溶液作为洗脱剂,进行硅胶柱层析分离纯化。
(一)化合物3a的制备
反应式如下:
在常温条件下,将2-巯基苯并噻唑1a(0.167g,1.0mmol),2-溴苯乙酮2a(0.199g,1.0mmol)与催化剂[Cu2(L)2Cl6](0.00958g,0.01mmol)置于玛瑙研钵中,滴加2滴乙腈后,室温研磨20分钟。
反应结束后,将全部反应物溶于二氯甲烷中,并用3×10mL水萃取,合并有机相后用无水MgSO4干燥,加入少量硅胶后减压蒸馏除去溶剂,所得固态物质采用体积比为50:1的石油醚和乙酸乙酯混合溶液作为洗脱剂,进行硅胶柱层析分离,收集含目标组分的洗脱剂并旋蒸除去溶剂,得到白色固体3a(0.2829g,99.1%)。
图5为化合物3a的1H NMR图。图6为化合物3a的13C NMR图。化合物3a的表征如下:
1H NMR(300MHz,CDCl3)δ=8.09(d,J=7.5Hz,2H),7.81(d,J=8.1Hz,1H),7.75(d,J=7.4Hz,1H),7.62(d,J=7.5Hz,1H),7.52(t,J=7.7Hz,2H),7.40(s,1H),7.29(t,J=7.6Hz,1H),4.98(s,2H).
13C NMR(75MHz,CDCl3)δ=192.75(s),165.10(s),152.69(s),135.31(d,J=4.6Hz),133.69(s),128.53(d,J=18.2Hz),125.89(s),124.25(s),121.33(s),120.94(s),40.92(s).
IR(KBr):ν=1597.43cm-1(C=O).
(二)化合物3b-3i的制备
方法如下:同(一),如表2,从不同取代基的化合物1和不同取代基的化合物2出发,在[Cu2(L)2Cl6]的催化下得到各种C-S耦合产物化合物3b-3i,其结果如表2所示:
表2
1、化合物3b表征:
白色固体,1H NMR(300MHz,CDCl3):δ=8.17–8.08(m,2H),7.80(d,J=8.1Hz,1H),7.75(d,J=7.9Hz,1H),7.40(t,J=7.7Hz,1H),7.30(t,J=7.6Hz,1H),7.18(t,J=8.6Hz,2H),4.93(s,2H).13C NMR(75MHz,CDCl3)δ=191.35(s),167.68(s),164.97(s),164.28(s),152.63(s),135.37(s),131.77(d,J=3.0Hz),131.20(d,J=9.5Hz),125.95(s),124.34(s),121.33(s),121.00(s),115.99(s),115.70(s),40.59(s).IR(KBr):ν=1597.33cm-1(C=O).
2、化合物3c表征:
白色固体,1H NMR(300MHz,DMSO):δ=8.11(d,J=8.6Hz,2H),8.01(d,J=7.2Hz,1H),7.75(d,J=7.9Hz,1H),7.67(d,J=8.6Hz,2H),7.47–7.40(m,1H),7.36(t,J=7.6Hz,1H),5.16(s,2H).13C NMR(75MHz,DMSO)δ=192.21(s),165.79(s),152.51(s),138.83(s),134.86(s),134.21(s),130.49(s),129.09(s),126.46(s),124.61(s),121.95(s),121.14(s),40.93(s).IR(KBr):ν=1598.16cm-1(C=O).
3、化合物3d表征:
白色固体,1H NMR(300MHz,DMSO):δ=8.11(d,J=8.6Hz,2H),8.01(d,J=7.2Hz,1H),7.75(d,J=7.5Hz,1H),7.67(d,J=8.6Hz,2H),7.44(t,J=8.3Hz,1H),7.36(t,J=7.6Hz,1H),5.16(s,2H).13C NMR(75MHz,DMSO)δ=192.16(s),164.88(s),152.69(s),135.49(s),134.20(s),132.11(s),130.07(s),129.12(s),126.06(s),124.46(s),121.44(s),121.10(s),40.49(s).IR(KBr):ν=1598.25cm-1(C=O).
4、化合物3e表征:
浅黄色固体,1H NMR(300MHz,CDCl3):δ=7.97(d,J=8.2Hz,2H),7.82(d,J=8.0Hz,1H),7.74(d,J=8.0Hz,1H),7.39(t,J=7.7Hz,1H),7.29(t,J=7.5Hz,3H),4.95(s,2H),2.43(s,3H).13C NMR(75MHz,CDCl3)δ=192.34(s),165.26(s),152.72(s),144.69(s),135.31(s),132.73(s),129.32(s),128.52(s),125.86(s),124.21(s),121.30(s),120.91(s),40.94(s),21.62(s).IR(KBr):ν=1599.15cm-1(C=O).
5、化合物3f表征:
白色固体,1H NMR(300MHz,DMSO):δ=8.07(d,J=8.9Hz,2H),8.00(d,J=7.9Hz,1H),7.78(d,J=8.0Hz,1H),7.44(t,J=7.1Hz,1H),7.35(t,J=7.5Hz,1H),7.11(d,J=8.8Hz,2H),5.12(s,2H),3.88(s,3H).13C NMR(75MHz,DMSO)δ=191.20(s),166.12(s),163.72(s),152.61(s),134.83(s),130.98(s),128.27(s),126.42(s),124.53(s),121.88(s),121.13(s),114.17(s),55.73(s),40.83(s).3IR(KBr):ν=1595.30cm-1(C=O).
6、化合物3g表征:
白色固体,1H NMR(300MHz,CDCl3):δ=8.15(d,J=8.4Hz,2H),7.83(d,J=7.8Hz,1H),7.74(t,J=7.6Hz,3H),7.64(d,J=6.9Hz,2H),7.53–7.37(m,4H),7.30(t,J=8.2Hz,1H),5.00(s,2H).13C NMR(75MHz,CDCl3)δ=192.50(s),165.30(s),152.75(s),146.50(s),139.59(s),135.45(s),134.08(s),129.09(d,J=16.3Hz),128.41(s),127.33(d,J=9.1Hz),126.04(s),124.41(s),121.45(s),121.07(s),40.98(s).IR(KBr):ν=1600.00cm-1(C=O).
7、化合物3h表征:
白色固体,1H NMR(300MHz,DMSO):δ=8.11(d,J=7.2Hz,2H),7.82–7.76(m,1H),7.71(t,J=7.4Hz,1H),7.59(t,J=7.5Hz,2H),7.26–7.18(m,2H),5.09(s,2H),2.36(s,3H).13C NMR(75MHz,DMSO)δ=193.33(s),164.48(s),151.65(s),135.82(s),134.70(s),133.78(s),130.61(s),128.91(s),128.49(s),126.82(s),124.52(s),119.24(s),17.65(s).IR(KBr):ν=1595.42cm-1(C=O).
8、化合物3i表征:
白色固体,1H NMR(300MHz,DMSO):δ=8.30(d,J=2.0Hz,1H),8.09(d,J=7.2Hz,2H),7.71(dd,J=13.3,8.1Hz,2H),7.60(t,J=7.6Hz,3H),5.19(s,2H).13C NMR(75MHz,DMSO)δ=192.79(s),167.44(s),151.64(s),136.85(s),135.40(s),133.95(s),129.51(s),128.97(s),128.55(s),124.45(s),122.52(s),116.99(s),41.21(s).IR(KBr):ν=1598.19cm-1(C=O)。
Claims (11)
1.一种CuII双核配合物,其特征在于,所述CuII双核配合物,是以CuII作为金属节点,选取1,3-双(2-吡啶基甲基)苯并咪唑氯酸盐(L)作为有机配体,通过机械研磨方式获得的[Cu2(L)2Cl6]。
2.一种CuII双核配合物的制备方法,其特征在于,制备方法包括如下步骤:将1,3-双(2-吡啶基甲基)苯并咪唑氯酸盐(L)与氯化铜置于研钵中,加入微量溶剂,研磨2-3分钟,所得产物重结晶,得目标产物CuII双核配合物[Cu2(L)2Cl6]。
3.根据权利要求2所述的制备方法,其特征在于,所述1,3-双(2-吡啶基甲基)苯并咪唑氯酸盐(L)的合成方法,包括如下步骤:以苯并咪唑、2-氯甲基吡啶盐酸盐和碳酸氢钠为原料,在无溶剂的条件下,利用行星式球磨机研磨,得到棕红色粘稠物质,提纯后得到目标产物1,3-双(2-吡啶基甲基)苯并咪唑氯酸盐(L)。
4.根据权利要求3所述的制备方法,其特征在于,按摩尔比,苯并咪唑:2-氯甲基吡啶盐酸盐:碳酸氢钠=1:2:4。
5.根据权利要求2所述的制备方法,其特征在于,按摩尔比,1,3-双(2-吡啶基甲基)苯并咪唑氯酸盐:氯化铜=1:1。
6.根据权利要求2所述的制备方法,其特征在于,所述溶剂为甲醇;所述重结晶是,将产物置于甲醇中,室温静置4-8小时。
7.权利要求1所述的CuII双核配合物作为催化剂在机械力下催化C-S耦合反应中的应用。
9.根据权利要求8所述的应用,其特征在于,按物质的量之比,巯基苯并噻唑衍生物:溴苯乙酮衍生物:[Cu2(L)2Cl6]=1:1:0.01;所述有机溶剂为乙腈、乙醇、环己烷或四氢呋喃。
10.根据权利要求9所述的应用,其特征在于,所述有机溶剂为乙腈。
11.根据权利要求8所述的应用,其特征在于,所述分离纯化的方法为:反应完全后,将反应混合物溶于二氯甲烷中,过滤,将所得滤液用水萃取2-3次后合并有机相,采用体积比为50:1的石油醚和乙酸乙酯混合溶液作为洗脱剂,进行硅胶柱层析分离纯化。
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