CN104447700A - 联二萘酚桥联的氮杂环双卡宾金属配合物及其制备方法与用途 - Google Patents

联二萘酚桥联的氮杂环双卡宾金属配合物及其制备方法与用途 Download PDF

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CN104447700A
CN104447700A CN201410683262.2A CN201410683262A CN104447700A CN 104447700 A CN104447700 A CN 104447700A CN 201410683262 A CN201410683262 A CN 201410683262A CN 104447700 A CN104447700 A CN 104447700A
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binaphthol
metal complex
benzoglyoxaline
pyridine
heterocyclic ring
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柳清湘
赵丽轩
王红
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Tianjin Normal University
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Abstract

本发明公开了通过(S)-2,2’-二[2’’-(N-吡啶苯并咪唑)乙氧基]-1,1’-联二萘酚六氟磷酸盐作为前体的氮杂环双卡宾金属配合物及其制备方法，并使用合成的氮杂环双卡宾金属配合物做催化剂，用于催化多种类型碳-碳键的交叉偶联反应。其中氮杂环双卡宾金属配合物的制备方法：在氮气保护下，将(S)-2,2’-二[2’’-(N-吡啶苯并咪唑)乙氧基]-1,1’-联二萘酚六氟磷酸盐与金属化合物以摩尔比为1：1的比例加入到反应器皿内，加入有机溶剂，然后在60?C温度下反应24小时，过滤，乙醚扩散，得到氮杂环双卡宾金属配合物。本发明制备的通过(S)-2,2’-二[2’’-(N-吡啶苯并咪唑)乙氧基]-1,1’-联二萘酚六氟磷酸盐作为前体的氮杂环双卡宾金属配合物主要应用于催化剂技术领域。

Description

联二萘酚桥联的氮杂环双卡宾金属配合物及其制备方法与用途
关于资助研究或开发的声明 
本发明是在国家自然科学基金（基金号为21172172），天津市自然科学基金（基金号为11JCZDJC22000），天津市高等学校创新团队培养计划（基金号为TD12-5038 ）和天津师范大学应用开发研究基金(基金号：52XK1202) 资助下进行的。
技术领域
  本发明属于有机合成和金属有机化学技术领域，涉及联二萘酚桥联的氮杂环双卡宾金属配合物的合成。更具体的说是含(S)-2,2’-二[2’’-(N-吡啶苯并咪唑)乙氧基]-1,1’-联二萘酚六氟磷酸盐作为前体的氮杂环双卡宾金属配合物的制备方法以及其在催化领域中的应用。 
背景技术
自从稳定的游离N-杂环卡宾(NHC)被分离出来以后，引起了许多研究者的兴趣，越来越多的人把目光投向这一研究领域。N-杂环卡宾由于易制备、结构多样化、与中心金属的配位能力强等特点而成为人们研究的热点。N-杂环卡宾不但拥有独特的反应活性和分子结构，而且具有广泛的应用范围，其在均相催化、新型发光材料、液晶材料及抗菌药物等方面均有较好的应用。N-杂环卡宾被看作是有机膦配体的代替和扩展，它可形成稳定的金属-卡宾σ键，不易解离，在催化反应中无需加入过量的配体，并且它们的配合物拥有对水，热和空气良好的稳定性等优点。N-杂环卡宾配合物的催化性能在许多反应中优于膦配体金属配合物，是一类有潜在应用价值的催化剂。N-杂环卡宾金属配合物能够催化的反应主要包括：如碳-碳偶联反应、芳胺化反应、烯烃复分解反应等。N-杂环卡宾不仅作为金属有机化学的研究对象，还能用作反应底物参与到有机反应中，如N-杂环卡宾参与的亲核Wanzlick型反应，使用咪唑类化合物合成两性离子，对二氧化碳进行固定而发生的羧化反应以及强亲核N-杂环卡宾为底物的多组分反应等。随着研究的深入和研究范围的拓展，N-杂环卡宾化学会在更多的领域显示出更广泛的应用价值和前景。 
发明内容
本发明的目的在于提供联二萘酚桥联的氮杂环双卡宾金属配合物，特别是(S)-2,2’-二[2’’-(N-吡啶苯并咪唑)乙氧基]-1,1’-联二萘酚六氟磷酸盐作为前体的氮杂环双卡宾金属配合物。 
本发明也涉及制备此类氮杂环双卡宾金属配合物前体的方法。 
本发明同时又涉及了制备此类氮杂环双卡宾金属配合物的方法，并对其进行晶体学表征。 
本发明涉及此类氮杂环双卡宾金属配合物的氢谱标定。 
本发明涉及此类氮杂环双卡宾金属配合物的晶体的养成方法，测量数据和数据的研究。 
本发明所涉及的氮杂环双卡宾金属配合物均是通过扩散或挥发的方法培养得到的。 
本发明中的氮杂环双卡宾金属配合物均通过X-射线衍射仪进行测定和数据表征。 
本发明更进一步涉及了通过(S)-2,2’-二[2’’-(N-吡啶苯并咪唑)乙氧基]-1,1’-联二萘酚六氟磷酸盐作为前体的氮杂环双卡宾金属配合物主要应用于催化领域。 
为完成上述各项发明目的，本发明技术方案如下： 
具有通式（Ⅰ）的氮杂环双卡宾金属配合物，其中的(S)-2,2’-二[2’’-(N-吡啶苯并咪唑)乙氧基]-1,1’-联二萘酚六氟磷酸盐具有如（Ⅱ）所示的结构式：
  
所述的金属化合物选自氧化银、醋酸银、碳酸银、醋酸钯、氯化钯、乙腈氯化钯的一种或几种的混合物。
本发明所述(S)-2,2’-二[2’’-(N-吡啶苯并咪唑)乙氧基]-1,1’-联二萘酚六氟磷酸盐作为前体的氮杂环双卡宾金属配合物的方法，其特征在于： 
（1）用(S)-联二萘酚和2-氯乙醇反应生成(S)-2,2’-二(2’’-羟乙氧基)-1,1’-联二萘酚，再将上述化合物与二氯亚砜和吡啶在三氯甲烷为溶液的体系下合成(S)-2,2’-二(2’’-氯乙氧基)-1,1’-联二萘酚，接着与苯并咪唑吡啶反应生成(S)-2,2’-二[2’’-(N-吡啶苯并咪唑)乙氧基]-1,1’-联二萘酚氯化物。再通过六氟磷酸铵进行阴离子交换反应得到(S)-2,2’-二[2’’-(N-吡啶苯并咪唑)乙氧基]-1,1’-联二萘酚六氟磷酸盐；
（2）在惰性气体保护下，将(S)-2,2’-二[2’’-(N-吡啶苯并咪唑)乙氧基]-1,1’-联二萘酚六氟磷酸盐与金属化合物以摩尔比为1：1mol的比例混合，加入有机溶剂，在60?C温度下反应24小时，过滤，乙醚扩散，得到双卡宾金属配合物。
本发明所述的1-取代基苯并咪唑为乙基苯并咪唑、正丁基苯并咪唑、正丙基苯并咪唑、仲丁基苯并咪唑、苄基苯并咪唑或1-吡啶甲基苯并咪唑；所述的金属化合物选自氧化银、醋酸银、碳酸银、醋酸钯、氯化钯、乙腈氯化钯的一种或几种的混合物。 
本发明所述的有机溶剂选自四氢呋喃、二氯甲烷、三氯甲烷、1，2-二氯乙烷、丙酮、乙醚、乙腈、N，N-二甲基甲酰胺、二甲基亚砜中的一种或几种的混合物。 
本发明所述的氮杂环双卡宾金属配合物，其中典型的氮杂环双卡宾钯配合物的晶体结构参数如下： 
 
 
晶体数据和结构精修参数包含在支持性信息中。在Bruker SMART 1000 CCD衍射仪上进行，实验温度为293(2)K, 在50kV 和20mA下，用Mo-Kα 辐射(0.71073?)操作，用SMART和SAINT软件进行数据收集和还原，θ的范围是 1.8o < θ< 25o。应用SADABS 程序进行经验吸收矫正。晶体结构由直接方法解出，用SHELXTL包对全部非氢原子坐标各向异性热参数进行全矩阵最小二乘法修正。
本发明中公开的氮杂环双卡宾金属配合物是并列的关系，无优先主次之分。 
本发明进一步公开了氮杂环双卡宾金属配合物在制备作为催化剂的应用。主要是通过(S)-2,2’-二[2’’-(N-吡啶苯并咪唑)乙氧基]-1,1’-联二萘酚六氟磷酸盐作为前体的氮杂环双卡宾金属配合物主要应用于催化领域。 
实验证明：氮杂环双卡宾金属配合物在一定的条件下对反应有催化性能。如应用实例2在表1和表2中所示。 
附图说明： 
图1为含氮杂环双卡宾钯配合物（实施例2）的黄色晶体结构图。
具体实施方式
以下结合较佳实施例，对本发明做进一步的描述，特别加以说明的是，制备本发明化合物的起始物质(S)-联二萘酚、1-吡啶苯并咪唑、2-氯乙醇、二氯亚砜、吡啶等均可以从市场上买到或容易地通过已知的方法制得。 
制备本发明化合物所用到的试剂全部来源于天津市元立化工有限公司，级别为分析纯。 
另外需要加以说明的是：所有的实验操作运用Schlenk技术，溶剂经过标准流程纯化。所有用于合成和分析的试剂都是分析纯，并没有经过进一步的处理。熔点通过Boetius区截机测定。1H NMR谱通过汞变量Vx400分光光度计记录，测量区间：400 MHz。化学位移，δ，参考国际标准的TMS测定。 
实施例1 
将(S)-联二萘酚(5.000 g,17.4 mmol)溶于DMF（100 mL）中，然后在室温下加入K2CO3(9.646 g, 69.9 mmol), N2保护下在50 ?C条件下搅拌1h，然后向其中缓慢滴下2-氯乙醇(5.628 g, 69.9 mmol), 当滴加完成后，将反应温度升温至110?C反应24h。反应完全后将反应体系迅速放入冰水浴中搅拌0.5h。有大量白色絮状物析出。即为产物(S)-2,2’-二(2’-羟乙氧基)-1,1’-联二萘酚。产率：6.008 g (92%)。M.p.: 112-114 ?C。1H NMR (400 MHz,CDCl3): δ 8.02 (d, J = 8.8 Hz, 2H, ArH), 7.93 (d, J = 8.0 Hz, 2H, ArH), 7.48 (d, J = 9.2 Hz, 2H, ArH), 7.41 (t, J = 7.4 Hz, 2H, ArH), 7.30 (t, J = 7.4 Hz, 2H, ArH),7.17 (d, J = 8.4 Hz, 2H, ArH), 4.28 (m, 2H, CH 2 ), 4.08 (m, 2H, CH 2 ), 3.66 (m, 4H, CH 2),2.31 (m, 2H, OH). 13C NMR (100 MHz, CDCl3): δ153.5 (PhC), 133.8 (PhC), 129.8 (PhC), 129.6 (PhC), 128.1 (PhC), 126.7 (PhC), 125.2 (PhC), 124.2 (PhC), 120.3 (PhC), 115.9 (PhC), 71.7 (OCH2 CH2), 61.2 (OCH2 CH2). 
将(S)-2,2’-二(2’’-羟乙氧基)-1,1’-联二萘酚(5.000 g, 13.4 mmol)和吡啶(5.288 g, 66.8 mmol)溶解在100mL三氯甲烷中，再将二氯亚砜(7.947 g, 66.8 mmol)溶解在10mL三氯甲烷中并装入恒压滴液漏斗，反应体系温度控制室温，向反应瓶中滴加二氯亚砜的三氯甲烷溶液，当滴加完成后，将反应温度升温至70?C反应24h。待反应完全后冷却至室温，加入水(3 × 100 mL)水洗，有机层用无水硫酸镁干燥，旋干溶剂，将所得的油状物用石油醚重结晶得到淡黄色固体即为产物。产率：3.571 g (65%)。M.p.: 101-103 ?。1H NMR (400 MHz,CDCl3): δ7.97 (d, J = 8.8 Hz, 2H, ArH), 7.88 (d, J = 8.4 Hz, 2H, ArH), 7.43 (d, J = 8.8 Hz, 2H, ArH), 7.37 (t, J = 7.4 Hz, 2H, ArH), 7.25 (t, J = 7.6 Hz, 2H, ArH), 7.13 (d, J = 8.4 Hz, 2H, ArH), 4.21(m, 4H, CH 2 ), 3.40 (m, 4H, CH 2). 13C NMR (100 MHz, CDCl3): δ153.6 (PhC), 147.9 (PhC), 134.0 (PhC), 129.6 (PhC), 127.9 (PhC), 126.5 (PhC), 125.4 (PhC), 124.1 (PhC),121.0 (PhC), 116.3 (PhC), 70.1 (OCH2CH2), 41.7 (OCH2 CH2). 
将(1.274 g, 6.1 mmol)1-吡啶苯并咪唑与(1.000 g, 2.4 mmol)(S)-2,2’-二(2’’-氯乙氧基)-1,1’-联二萘酚溶于100mL甲苯中，在回流的条件下搅拌3天，析出油状物质，得到了(S)-2,2’-二[2’’-(N-吡啶苯并咪唑)乙氧基]-1,1’-联二萘酚氯化物，再将此氯化物溶于100mL甲醇,再向反应体系中加入(1.439 g, 8.8 mmol)的六氟磷酸铵，在室温条件下搅拌反应3天，析出白色粉末。抽滤，便得到了(S)-2,2’-二[2’’-(N-吡啶苯并咪唑)乙氧基]-1,1’-联二萘酚六氟磷酸盐的白色粉末。产量：1.734 g，产率：68.0%，熔点：148-150 ?C。1H NMR (400 MHz, DMSO-d6): δ9.43 (s, 2H, 2-bimiH), 8.43 (d, J = 4.4 Hz, 2H, ArH), 7.98 (d, J = 8.8 Hz, 2H, ArH), 7.90 (q, J = 2.6 Hz, 4H, ArH), 7.77 (d, J = 8.4 Hz, 2H, ArH), 7.63 (d, J = 8.0 Hz, 2H, ArH), 7.50 (t, J = 7.8 Hz, 2H, ArH), 7.43 (d, J = 9.6 Hz, 2H, ArH), 7.37 (q, J = 4.0 Hz, 2H, ArH), 7.28 (t, J = 8.4 Hz, 4H, ArH), 7.21 (t, J = 7.8 Hz, 2H, ArH), 6.99 (m, J = 5.0 Hz, 2H, ArH), 6.58 (d, J = 8.4 Hz, 2H, ArH), 5.68 (m, 3H, CH 2), 4,63 (t, J = 4.6 Hz, 3H, CH 2), 4.38 (t, J = 4.4 Hz, 3H, CH 2), 4.15 (q, J = 5.2 Hz, 3H, CH 2). 13C NMR (100 MHz, DMSO-d6): δ153.1 (ArC), 149.9 (ArC), 142.9(ArC), 138.0 (bimi-NCN), 132.9 (ArC), 131.1 (ArC),130.9 (ArC), 130.0 (ArC), 129.3(ArC), 128.4 (ArC), 126.8 (ArC), 126.7 (ArC), 126.6 (ArC), 126.4 (ArC), 125.5(ArC), 125.0(ArC), 124.2 (ArC), 123.2 (ArC), 119,6 (ArC), 116.3 (ArC), 114.0 (ArC), 113.0 (ArC), 67.8 (OCH2CH2), 51.2 (OCH2 CH2), 49.0 (CH2), 47.2 (CH2) (bimi = benzimidazole).
其实验流程如下式所示：
 
实施例2
在氮气保护下，以除水1,2-二氯乙烷和DMSO(30 mL, v:v=2:1)为溶剂,加入苯并咪唑盐配体(S)-2,2’-二[2’’-(N-吡啶咪唑)乙氧基]-1,1’-联二萘酚六氟磷酸盐 (0.209g, 0.2mmol) 和(0.042 g, 0.2mmol) Pd(OAc)2以及 (0.179g, 1.3mmol) K2CO3在55℃的条件下反应24小时，过滤，滤掉滤渣，旋干溶剂，用水洗涤后再用二氯甲烷萃取，分液，经干燥后旋干加入混合有机溶剂后放入试管中在惰性溶剂中扩散令其缓慢结晶得到白色晶体配合物，此金属配合物在空气和潮湿的条件下是稳定的。产率：0.057 g (25%)，M.p.: 280-282?C. 1H NMR (400 MHz, DMSO-d6): δ 8.24 (m, 7H, PhH), 7.98(m, 4H, PhH), 7.80 (d, J = 8.4 Hz, 2H, PhH), 7.65 (t, J = 6.6 Hz, 2H, PhH), 7.44 (m, 7H, PhH), 4.90 (m, 2H, CH 2), 4.52 (m, 2H, CH 2),4.24 (m, 2H, CH 2), 2.89 (s, 3H, CH 2 ), 2.73 (s, 3H, CH 2) (bimi = benimidazole).
其实验流程如下式所示：
  
晶体结构见说明书附图1。
实施例2制备的氮杂环双卡宾钯配合物晶体结构参数 
 
晶体数据和结构精修参数包含在支持性信息中。
衍射仪：Bruker SMART 1000 CCD衍射仪； 
实验温度：293(2)K, 在50kV 和20mA下，用Mo-Kα 辐射(0.71073?)操作；
θ的范围是 1.8o < θ< 25o；
数据收集和还原：用SMART和SAINT软件；
吸收矫正：SADABS 程序进行经验。
应用实例1 
Heck-Mizoroki 偶联反应的一般程序。卤代芳烃(0.50 mmol)，苯乙烯(0.6 mmol)，K2CO3 (1.0 mmol), 实施例1中制备的氮杂环双卡宾金属配合物(0.1 mol %)加入到有机溶剂(3.0 mL)中, 这个反应体系在空气中以100 ?C的温度搅拌反应。在预期的反应时间结束之后，将反应停止，然后将(20 mL)水加入到反应的混合体系中。加入(15 mL)乙醚，混合物开始分层。然后用水将有机层洗三次（每次用10mL），用无水硫酸镁进行干燥，溶液滤出，再将溶剂除去，粗产物提纯是通过色谱柱进行分离，用正己烷和二氯甲烷(10:1)的混合溶液做洗脱液。
本发明提出的氮杂环双卡宾金属配合物是一种在标准状态下可以稳定存在的高级催化剂，具有结构可调整、制备简洁、催化效果明显的优点，有望在催化剂领域得到应用。 
表1.实施例2中得到的氮杂环双卡宾金属配合物在]溴苯和苯乙烯为模式反应底物最优反应条件的筛选 [a]
 
 [1] 反应条件：卤代芳烃(0.50 mmol)，苯乙烯(0.6 mmol)，碱(1.2 mmol), ,实施例2中制备的氮杂环双卡宾金属配合物(0.1 mol%), PEG-400 (10 mol%), TBAB (10% mol), 溶剂(6 mL),, 100 ?C。 
[2] 反应过程中要点板跟踪。 
[3] 分离产率。 
表2. 实施例2中制备的氮杂环双卡宾金属配合物在卤代芳烃和苯乙烯的Heck-Mizoroki偶联反应中的反应实例[1]
 
 
 [1] 反应条件：卤代芳烃(0.50 mmol)，苯乙烯(0.6 mmol)，K2CO3 (1.0 mmol), ,实施例2中制备的氮杂环双卡宾金属配合物0.1 mol %, PEG-400 (10 mol%),1,4-dioxane (6 mL),, 100 ?C。 
[2] 反应过程中要点板跟踪。 
[3] 分离产率。 
  
综上所述，本发明的内容并不局限在实例中，相同领域内的有识之士可以在本发明的技术指导思想之内可以轻易提出其他的实例，但这种实例都包括在本发明的范围之内。

Claims (6)

1.具有通式（Ⅰ）的氮杂环双卡宾金属配合物，其中的(S)-2,2’-二[2’’-(N-吡啶苯并咪唑)乙氧基]-1,1’-联二萘酚六氟磷酸盐（Ⅱ）所示的结构式：
                                                 
所述的金属化合物选自氧化银、醋酸银、碳酸银、醋酸钯、氯化钯、乙腈氯化钯的一种或几种的混合物。
2.权利要求1所述的氮杂环双卡宾金属配合物，其中所述(S)-2,2’-二[2’’-(N-吡啶苯并咪唑)乙氧基]-1,1’-联二萘酚六氟磷酸盐作为前体的氮杂环双卡宾金属配合物的制备方法，其特征在于：
（1）用(S)-联二萘酚和2-氯乙醇反应生成(S)-2,2’-二(2’’-羟乙氧基)-1,1’-联二萘酚，再将上述化合物与二氯亚砜和吡啶在三氯甲烷为溶液的体系下合成(S)-2,2’-二(2’’-氯乙氧基)-1,1’-联二萘酚，接着与苯并咪唑吡啶反应生成(S)-2,2’-二[2’’-(N-吡啶苯并咪唑)乙氧基]-1,1’-联二萘酚氯化物；
再通过六氟磷酸铵进行阴离子交换反应得到(S)-2,2’-二[2’’-(N-吡啶苯并咪唑)乙氧基]-1,1’-联二萘酚六氟磷酸盐；
（2）在惰性气体保护下，将(S)-2,2’-二[2’’-(N-吡啶苯并咪唑)乙氧基]-1,1’-联二萘酚六氟磷酸盐与金属化合物以摩尔比为1：1mol的比例混合，加入有机溶剂，在60?C温度下反应24小时，过滤，乙醚扩散，得到双卡宾金属配合物。
3.权利要求2所述的制备方法，其中所述的1-取代基苯并咪唑为乙基苯并咪唑、正丁基苯并咪唑、正丙基苯并咪唑、仲丁基苯并咪唑、苄基苯并咪唑或1-吡啶甲基苯并咪唑；所述的金属化合物选自氧化银、醋酸银、碳酸银、醋酸鈀、氯化钯、乙腈氯化钯的一种或几种的混合物。
4.权利要求2所述的制备方法，其中所述的有机溶剂选自四氢呋喃、二氯甲烷、三氯甲烷、1，2-二氯乙烷、丙酮、乙醚、乙腈、N，N-二甲基甲酰胺、二甲基亚砜中的一种或几种的混合物。
5.权利要求1所述氮杂环双卡宾金属配合物，其中氮杂环双卡宾钯配合物的晶体结构参数如下：
 
。
6.权利要求1所述氮杂环双卡宾金属配合物在制备作为催化剂中的应用。
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