CN108579809B - 一种含氮杂环卡宾钯化合物的纳米颗粒催化剂及其制备方法 - Google Patents
一种含氮杂环卡宾钯化合物的纳米颗粒催化剂及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种含氮杂环卡宾钯化合物的纳米颗粒催化剂及其制备方法,将氮杂环卡宾钯化合物和两亲性聚合物DSPE‑PEG2000,在少量二甲基亚砜溶液中溶解,然后在超声的条件下,将该二甲基亚砜溶液缓慢的滴加到去离子水中,通过两亲性聚合物的自组装,形成包裹氮杂环卡宾钯化合物的纳米颗粒催化剂。本发明合成的纳米颗粒催化剂,由于含有氮杂环卡宾钯化合物,具有催化交叉偶联反应的效果,并且由于纳米颗粒的水溶性,使得该催化剂可以在水溶液中使用,环境友好;催化反应结束后,反应产物不溶于水,而纳米颗粒催化剂溶于水,可以非常方便的回收利用催化剂,循环使用;因此该类型催化剂在精细化工等行业中具有广泛的应用前景。
Description
技术领域
本发明涉及属于催化剂制备技术领域,具体地说是涉及一种含氮杂环卡宾钯化合物的纳米颗粒催化剂及其制备方法。
背景技术
在绿色和可持续的化学中,以水作为反应介质具有非常重要的意义。水的价格便宜,不易燃,对环境友好,而且水溶性低的有机产物可以很容易地通过过滤从含水反应混合物中分离出来。迄今为止,已有许多反应在水中完成如:氢转移反应,1,3-偶极环加成反应,交叉偶联反应等。因此,开发适用于水溶液反应的催化剂就显得特别重要,特别是在催化领域应用广泛的钯催化剂。
目前应用于水相催化的钯催化剂主要有溶于水的均相催化剂和不溶于水的非均相催化剂两大类。水溶性的钯催化剂由于在水介质中具有较高的催化效率,而且也能应用于生物体系,因此受到了更多的研究。通常,在钯化合物的配体上引入亲水基团可以实现催化剂的水溶性。但是亲水配体合成复杂,而且在空气中也容易潮解,限制了它们的应用。
发明内容
为了克服现有水溶性钯催化剂的不足,本发明提供了一种含氮杂环卡宾钯化合物的纳米颗粒催化剂及其制备方法。将两亲性聚合物DSPE-PEG2000(二硬脂酰基磷脂酰乙醇胺-聚乙二醇2000)和疏水的氮杂环卡宾钯化合物在水溶液中通过自组装,形成水溶性的纳米颗粒;在水中,两亲性聚合物DSPE-PEG2000形成的纳米颗粒外层亲水,内层疏水,从而将疏水的氮杂环卡宾包含其中,形成水溶性的钯催化剂。
一种含氮杂环卡宾钯化合物的纳米颗粒催化剂,在纳米颗粒中包含氮杂环卡宾钯化合物,所述纳米颗粒为两亲性聚合物DSPE-PEG2000,所述氮杂环卡宾钯化合物的阳离子结构通式为[PdL(CH3CN)Cl]+,其中L为氮杂环卡宾配体,其分子式为:
X为C或N,R为苄基或2,4,6-三甲基苯基。
作为优选,所述氮杂环卡宾钯化合物的阴离子为PF6 -。
作为优选,所述氮杂环卡宾配体为吡啶官能团化的氮杂环卡宾配体,其分子式为:
作为优选,所述氮杂环卡宾配体为嘧啶官能团化的氮杂环卡宾配体,其分子式为:
一种含氮杂环卡宾钯化合物的纳米颗粒催化剂的制备方法,包括下述步骤:
(1)氮杂环卡宾钯化合物的制备:以2-溴吡啶或2-氯嘧啶与取代咪唑反应得到官能化的咪唑盐配体,然后在乙腈溶剂中与氧化银避光反应,再加入金属钯盐反应,过滤,滤液浓缩,重结晶得到氮杂环卡宾钯化合物;
(2)纳米颗粒催化剂的制备:在二甲基亚砜溶剂中加入两亲性聚合物DSPE-PEG2000和氮杂环卡宾钯化合物,溶解;然后将该二甲基亚砜溶液缓慢滴加到去离子水中,在水溶液中两亲性聚合物通过自组装形成包含氮杂环卡宾钯化合物的纳米颗粒催化剂。
两亲性聚合物DSPE-PEG2000分子式为:
作为优选,步骤(1)中,氧化银的用量为官能化的咪唑盐配体的二分之一当量,避光反应的时间为4~6小时。
作为优选,金属钯的用量为官能化的咪唑盐配体的当量,与金属钯盐反应的温度为室温,反应时间为2~4小时。
作为优选,重结晶使用的溶剂为乙醚。
作为优选,步骤(2)中,所述DSPE-PEG2000、氮杂环卡宾钯化合物、二甲基亚砜的重量比为1:0.5~12.5:10~100。
作为优选,步骤(2)具体为:在100~200微升二甲基亚砜溶剂中加入2~10毫克两亲性聚合物DSPE-PEG2000和5~25毫克氮杂环卡宾钯化合物,在超声条件下溶解;然后将该二甲基亚砜溶液在超声条件下缓慢滴加到20~50毫升去离子水中,在水溶液中两亲性聚合物通过自组装形成包含氮杂环卡宾钯化合物的纳米颗粒催化剂。
本发明由于纳米颗粒的双层结构和水溶性,可以将疏水的氮杂环卡宾钯化合物带入水中,形成水溶性的钯催化剂,从而克服了传统水溶性催化剂配体合成复杂,在空气中也容易潮解的问题;本发明为水溶性催化剂,环境友好,催化反应结束后,反应产物不溶于水,而纳米颗粒催化剂溶于水,可以非常方便的回收利用催化剂,循环使用;该类型催化剂在精细化工等行业中具有广泛的应用前景。
附图说明
图1是纳米颗粒催化剂形成过程图;
图2是纳米颗粒1b@DSPE-PEG2000、2b@DSPE-PEG2000、和3b@DSPE-PEG2000的丁达尔现象图;
图3是纳米颗粒1b@DSPE-PEG2000的透射电镜图;
图4是纳米颗粒2b@DSPE-PEG2000的透射电镜图;
图5是纳米颗粒3b@DSPE-PEG2000的透射电镜图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步说明,但本发明所要保护的范围并不限于此。
实施例1
氮杂环卡宾钯化合物1b的合成
在室温下,加入配体1a(381mg,1mmol),乙腈20mL,氧化银(116mg,0.5mmol),反应5小时,加入[Pd(CH3CN)2]Cl2(260mg,1mmol),室温继续反应2小时,然后过滤,滤液浓缩,加入乙醚析出黄色固体,将黄色固体依次用乙醚洗涤2次,再用乙腈溶解,缓慢加入乙醚,结晶得到439mg氮杂环卡宾钯化合物1b,产率78%。1H NMR(CD3CN):8.57(s,pyridine CH,1H),8.34(t,J=7.6Hz,pyridine CH,1H),7.90(s,imidazole CH,1H),7.84(d,J=7.6Hz,pyridineCH,1H),7.58(t,J=6.4Hz,pyridine CH,1H),7.42(m,phenyl,5H),7.27(s,imidazole CH,1H),5.97(s,CH2,2H),2.19(s,CH3CN,3H).13C NMR(CD3CN):151.5(Pd–C),150.5,144.6,136.1,129.4,129.0,128.3,125.4,124.7,118.5,113.4,53.6。
实施例2
氮杂环卡宾钯化合物2b的合成
在室温下,加入配体2a(431mg,1mmol),乙腈20mL,氧化银(116mg,0.5mmol),反应5小时,加入[Pd(CH3CN)2]Cl2(260mg,1mmol),室温继续反应2小时,然后过滤,滤液浓缩,加入乙醚析出黄色固体,将黄色固体依次用乙醚洗涤2次,再用乙腈溶解,缓慢加入乙醚,结晶得到472mg氮杂环卡宾钯化合物2b,产率77%。1H NMR(dmso-d6):8.59-8.55(m,2H),8.47-8.43(m,2H),7.73-7.69(m,2H),7.61(t,J=7.6Hz,1H),7.56-7.48(m,3H),7.38-7.29(m,3H),6.34(s,CH2,2H).13C NMR(dmso-d6):151.7(Pd–C),146.7,144.3,135.1,133.8,129.7,129.0,128.3,127.6,126.9,126.4,123.3,118.5,114.0,113.9,113.6,50.7,1.51。
实施例3
氮杂环卡宾钯化合物3b的合成
在室温下,加入配体3a(410mg,1mmol),乙腈20mL,氧化银(116mg,0.5mmol),反应5小时,加入[Pd(CH3CN)2]Cl2(260mg,1mmol),室温继续反应2小时,然后过滤,滤液浓缩,加入乙醚析出黄色固体,将黄色固体依次用乙醚洗涤2次,再用乙腈溶解,缓慢加入乙醚,结晶得到387mg氮杂环卡宾钯化合物3b,产率65%。1H NMR(dmso-d6):9.18(s,pyrimidine CH,1H),8.73(s,pyrimidine CH,1H),8.46(s,imidazole CH,1H),7.79(t,J=5.2Hz,pyrimidineCH,1H),7.69(s,imidazole CH,1H),7.01(s,Mes CH,2H),2.31(s,Mes CH3,3H),2.06(s,CH3CN,3H),2.05(s,Mes CH3,6H),13C NMR(dmso-d6):162.3,156.2,156.2(Pd–C),149.1,139.3,134.8,134.5,128.9,126.5,120.9,119.1,118.5,21.1,17.8,1.54。
实施例4
纳米颗粒催化剂形成过程参照图1,在二甲基亚砜溶剂中加入两亲性聚合物DSPE-PEG2000和氮杂环卡宾钯化合物,溶解;然后将该二甲基亚砜溶液缓慢滴加到去离子水中,在水溶液中两亲性聚合物通过自组装形成包含氮杂环卡宾钯化合物的纳米颗粒催化剂。
具体的,含氮杂环卡宾钯化合物1b的纳米颗粒催化剂1b@DSPE-PEG2000的制备
在室温下,加入DSPE-PEG20002mg,氮杂环卡宾钯化合物1b 5mg,二甲基亚砜200μL,超声助溶。然后在超声条件下,将该二甲基亚砜溶液缓慢的滴加到10mL去离子水溶液中,形成纳米颗粒1b@DSPE-PEG2000的水溶液。
实施例5
含氮杂环卡宾钯化合物2b的纳米颗粒催化剂2b@DSPE-PEG2000的制备
在室温下,加入DSPE-PEG20002mg,氮杂环卡宾钯化合物2b 6mg,二甲基亚砜200μL,超声助溶。然后在超声条件下,将该二甲基亚砜溶液缓慢的滴加到10mL去离子水溶液中,形成纳米颗粒2b@DSPE-PEG2000的水溶液。
实施例6
含氮杂环卡宾钯化合物3b的纳米颗粒催化剂3b@DSPE-PEG2000的制备
在室温下,加入DSPE-PEG20002mg,氮杂环卡宾钯化合物1b 6mg,二甲基亚砜200μL,超声助溶。然后在超声条件下,将该二甲基亚砜溶液缓慢的滴加到10mL去离子水溶液中,形成纳米颗粒3b@DSPE-PEG2000的水溶液。
实施例7
含氮杂环卡宾钯化合物的纳米颗粒催化剂的表征:利用丁达尔现象,透射电镜、粒径仪对合成的纳米颗粒1b@DSPE-PEG2000、2b@DSPE-PEG2000、和3b@DSPE-PEG2000进行表征。
图2从左到右分别是纳米颗粒1b@DSPE-PEG2000、2b@DSPE-PEG2000、和3b@DSPE-PEG2000的水溶液。根据丁达尔现象,激光照射后溶胶(纳米颗粒)溶液会形成一个通路。如图2所示,三者的水溶液在激光照射后都形成了清晰的光路,说明三者都形成了纳米颗粒水溶液。
图3~5分别是纳米颗粒1b@DSPE-PEG2000、2b@DSPE-PEG2000、和3b@DSPE-PEG2000的透射电镜图,标尺为100nm。从上图可以看出,氮杂环卡宾金属化合物和两亲性聚合物DSPE-PEG2000通过自组装后形成了近圆形的纳米颗粒,粒径在100纳米以下。通过粒径仪检测,1b@DSPE-PEG2000、2b@DSPE-PEG2000和3b@DSPE-PEG2000的粒径大小分别为38.7±2.2nm、64.1±3.5nm、和42.7±2.6nm。
实施例8
在反应瓶中加入三(4-溴苯基)胺(145mg,0.3mmol),对甲氧基苯硼酸(180mg,1.2mmol),碳酸钾(207mg,1.5mmol),四丁基溴化铵(TBAB)(322mg,1.0mmol),5mL含0.1mol%3b@DSPE-PEG2000纳米颗粒的水溶液,60℃反应3小时。反应结束,冷却到室温,离心,去掉清液,固体部分溶于二氯甲烷,用无水硫酸钠干燥,再浓缩,过硅胶柱分离,得到产物,产率:90%。1H NMR(400MHz,CDCl3):δ7.52(d,J=8.8Hz,6H),7.47(d,J=8.8Hz,6H),7.20(d,J=8.8Hz,6H),6.97(d,J=8.8Hz,6H),3.85(s,9H).13C NMR(100MHz,CDCl3):δ158.9,146.4,135.2,133.3,127.7,127.4,124.4,114.2,55.4。
实施例9
在反应瓶中加入三(4-溴苯基)胺(145mg,0.3mmol),间甲氧基苯硼酸(180mg,1.2mmol),碳酸钾(207mg,1.5mmol),四丁基溴化铵(TBAB)(322mg,1.0mmol),5mL含0.1mol%3b@DSPE-PEG2000纳米颗粒的水溶液,60℃反应3小时。反应结束,冷却到室温,离心,去掉清液,固体部分溶于二氯甲烷,用无水硫酸钠干燥,再浓缩,过硅胶柱分离,得到产物,产率:92%。1H NMR(400MHz,CDCl3):δ7.52(d,J=8.8Hz,6H),7.34(t,J=8.0Hz,3H),7.22(d,J=8.8Hz,6H),7.18(d,J=8.0Hz,3H),7.12(s,3H),6.87(d,J=8.0Hz,3H),3.86(s,9H).13C NMR(100MHz,CDCl3):δ160.0,146.9,142.1,135.5,129.8,128.0,124.4,119.3,112.5,112.3,55.3。
实施例10
在反应瓶中加入三(4-溴苯基)胺(145mg,0.3mmol),邻甲氧基苯硼酸(180mg,1.2mmol),碳酸钾(207mg,1.5mmol),四丁基溴化铵(TBAB)(322mg,1.0mmol),5mL含0.1mol%3b@DSPE-PEG2000纳米颗粒的水溶液,60℃反应3小时。反应结束,冷却到室温,离心,去掉清液,固体部分溶于二氯甲烷,用无水硫酸钠干燥,再浓缩,过硅胶柱分离,得到产物,产率:91%。1H NMR(400MHz,CDCl3):δ7.48(s,3H),7.45(s,3H),7.35(d,J=7.6Hz,3H),7.28(t,J=7.6Hz,3H),7.23(s,3H),7.21(s,3H),7.02(t,J=7.6Hz,3H),6.97(d,J=7.6Hz,3H),3.83(s,9H).13C NMR(100MHz,CDCl3):δ156.5,146.5,132.7,130.7,130.3,128.3,123.7,120.9,111.2,56.5。
实施例11
在反应瓶中加入三(4-溴苯基)胺(145mg,0.3mmol),对叔丁基苯硼酸(214mg,1.2mmol),碳酸钾(207mg,1.5mmol),四丁基溴化铵(TBAB)(322mg,1.0mmol),5mL含0.1mol%3b@DSPE-PEG2000纳米颗粒的水溶液,60℃反应3小时。反应结束,冷却到室温,离心,去掉清液,固体部分溶于二氯甲烷,用无水硫酸钠干燥,再浓缩,过硅胶柱分离,得到产物,产率:92%。1H NMR(400MHz,CDCl3):δ7.52(t,J=8.8Hz,12H),7.45(d,J=8.8Hz,6H),7.22(d,J=8.8Hz,6H),1.36(s,27H).13C NMR(100MHz,CDCl3):δ149.8,146.7,137.8,135.4,127.7,126.4,125.7,124.4,34.5,31.4。
实施例12
在反应瓶中加入三(4-溴苯基)胺(145mg,0.3mmol),对乙酰基苯硼酸(197mg,1.2mmol),碳酸钾(207mg,1.5mmol),四丁基溴化铵(TBAB)(322mg,1.0mmol),5mL含0.1mol%3b@DSPE-PEG2000纳米颗粒的水溶液,60℃反应3小时。反应结束,冷却到室温,离心,去掉清液,固体部分溶于二氯甲烷,用无水硫酸钠干燥,再浓缩,过硅胶柱分离,得到产物,产率:91%。1H NMR(400MHz,CDCl3):δ8.03(d,J=8.4Hz,6H),7.69(d,J=8.4Hz,6H),7.59(d,J=8.4Hz,6H),7.27(d,J=8.4Hz,6H),2.64(s,9H).13C NMR(100MHz,CDCl3):δ197.7,147.3,145.0,135.6,134.6,129.0,128.2,126.7,124.6,26.7。
实施例13
在反应瓶中加入三(4-溴苯基)胺(145mg,0.3mmol),对醛基苯硼酸(180mg,1.2mmol),碳酸钾(207mg,1.5mmol),四丁基溴化铵(TBAB)(322mg,1.0mmol),5mL含0.1mol%3b@DSPE-PEG2000纳米颗粒的水溶液,60℃反应3小时。反应结束,冷却到室温,离心,去掉清液,固体部分溶于二氯甲烷,用无水硫酸钠干燥,再浓缩,过硅胶柱分离,得到产物,产率:88%。1H NMR(400MHz,CDCl3):δ10.05(s,3H),7.95(d,J=8.0Hz,6H),7.76(d,J=8.0Hz,6H),7.61(d,J=8.4Hz,6H),7.28(d,J=8.8Hz,6H).13C NMR(100MHz,CDCl3):δ191.8,147.5,146.3,135.0,134.5,130.4,1287.4,127.1,124.7。
实施例14
在反应瓶中加入三(4-溴苯基)胺(145mg,0.3mmol),对甲酸甲酯基苯硼酸(215mg,1.2mmol),碳酸钾(207mg,1.5mmol),四丁基溴化铵(TBAB)(322mg,1.0mmol),5mL含0.1mol%3b@DSPE-PEG2000纳米颗粒的水溶液,60℃反应3小时。反应结束,冷却到室温,离心,去掉清液,固体部分溶于二氯甲烷,用无水硫酸钠干燥,再浓缩,过硅胶柱分离,得到产物,产率:85%。1H NMR(400MHz,CDCl3):δ8.10(d,J=8.4Hz,6H),7.66(d,J=8.4Hz,6H),7.57(d,J=8.4Hz,6H),7.25(d,J=8.4Hz,6H),3.94(s,9H).13C NMR(100MHz,CDCl3):δ167.0,147.3,144.8,134.6,130.2,128.6,128.2,126.5,124.6,52.1。
实施例15
在反应瓶中加入三(4-溴苯基)胺(145mg,0.3mmol),对氰基苯硼酸(177mg,1.2mmol),碳酸钾(207mg,1.5mmol),四丁基溴化铵(TBAB)(322mg,1.0mmol),5mL含0.1mol%3b@DSPE-PEG2000纳米颗粒的水溶液,60℃反应3小时。反应结束,冷却到室温,离心,去掉清液,固体部分溶于二氯甲烷,用无水硫酸钠干燥,再浓缩,过硅胶柱分离,得到产物,产率:80%。1H NMR(400MHz,CDCl3):δ7.70(q,J=8.8Hz,12H),7.55(d,J=8.8Hz,6H),7.26(d,J=8.8Hz,6H).13C NMR(100MHz,CDCl3):δ147.5,144.7,134.0,132.7,128.3,127.2,124.7,119.0,110.6。
实施例16
在反应瓶中加入三(4-溴苯基)胺(145mg,0.3mmol),对氯苯硼酸(187mg,1.2mmol),碳酸钾(207mg,1.5mmol),四丁基溴化铵(TBAB)(322mg,1.0mmol),5mL含0.1mol%3b@DSPE-PEG2000纳米颗粒的水溶液,60℃反应3小时。反应结束,冷却到室温,离心,去掉清液,固体部分溶于二氯甲烷,用无水硫酸钠干燥,再浓缩,过硅胶柱分离,得到产物,产率:86%。1H NMR(400MHz,CDCl3):δ7.51(d,J=8.4Hz,6H),7.48(d,J=8.4Hz,6H),7.39(d,J=8.4Hz,6H),7.22(d,J=8.4Hz,6H).13C NMR(100MHz,CDCl3):δ146.7,139.0,134.6,133.0,128.9,127.9,127.8,124.5。
实施例17
在反应瓶中加入三(4-溴苯基)胺(145mg,0.3mmol),对甲氧基苯硼酸(178mg,1.2mmol),碳酸钾(207mg,1.5mmol),四丁基溴化铵(TBAB)(322mg,1.0mmol),5mL含0.1mol%3b@DSPE-PEG2000纳米颗粒的水溶液,60℃反应3小时。反应结束,冷却到室温,离心,去掉清液,固体部分溶于二氯甲烷,用无水硫酸钠干燥,再浓缩,过硅胶柱分离,得到产物,产率:91%。1H NMR(400MHz,CDCl3):δ7.57(d,J=8.4Hz,6H),7.54(d,J=8.4Hz,6H),7.48(d,J=8.4Hz,6H),7.24(d,J=8.4Hz,6H),5.80(d,J=17.6Hz,3H),5.27(d,J=10.8Hz,3H).13C NMR(100MHz,CDCl3):δ146.8,140.0,136.5,136.3,135.2,127.7,126.7,124.5,113.7。
Claims (9)
2.根据权利要求1所述的含氮杂环卡宾钯化合物的纳米颗粒催化剂,其特征在于:所述氮杂环卡宾钯化合物的阴离子为PF6 -。
5.权利要求1所述含氮杂环卡宾钯化合物的纳米颗粒催化剂的制备方法,其特征在于包括下述步骤:
(1)氮杂环卡宾钯化合物的制备:以2-溴吡啶或2-氯嘧啶与取代咪唑反应得到官能化的咪唑盐配体,然后在乙腈溶剂中与氧化银避光反应,再加入金属钯盐反应,过滤,滤液浓缩,重结晶得到氮杂环卡宾钯化合物;
(2)纳米颗粒催化剂的制备:在二甲基亚砜溶剂中加入两亲性聚合物DSPE-PEG2000和氮杂环卡宾钯化合物,溶解;然后将该二甲基亚砜溶液缓慢滴加到去离子水中,在水溶液中两亲性聚合物通过自组装形成包含氮杂环卡宾钯化合物的纳米颗粒催化剂。
6.根据权利要求5所述含氮杂环卡宾钯化合物的纳米颗粒催化剂的制备方法,其特征在于:步骤(1)中,氧化银与官能化的咪唑盐配体的摩尔比为0.5:1,避光反应的时间为4~6小时。
7.根据权利要求6所述含氮杂环卡宾钯化合物的纳米颗粒催化剂的制备方法,其特征在于:金属钯盐与官能化的咪唑盐配体的摩尔比为1:1,与金属钯盐反应的温度为室温,反应时间为2~4小时。
8.根据权利要求7所述含氮杂环卡宾钯化合物的纳米颗粒催化剂的制备方法,其特征在于:重结晶使用的溶剂为乙醚。
9.根据权利要求5所述含氮杂环卡宾钯化合物的纳米颗粒催化剂的制备方法,其特征在于步骤(2)具体为:在100~200微升二甲基亚砜溶剂中加入2~10毫克两亲性聚合物DSPE-PEG2000和5~25毫克氮杂环卡宾钯化合物,在超声条件下溶解;然后将该二甲基亚砜溶液在超声条件下缓慢滴加到20~50毫升去离子水中,在水溶液中两亲性聚合物通过自组装形成包含氮杂环卡宾钯化合物的纳米颗粒催化剂。
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