CN108586345A - 氮杂环卡宾钯配合物及其制备方法与用途 - Google Patents

氮杂环卡宾钯配合物及其制备方法与用途 Download PDF

Info

Publication number
CN108586345A
CN108586345A CN201810110843.5A CN201810110843A CN108586345A CN 108586345 A CN108586345 A CN 108586345A CN 201810110843 A CN201810110843 A CN 201810110843A CN 108586345 A CN108586345 A CN 108586345A
Authority
CN
China
Prior art keywords
heterocyclic carbine
anthraquinone
bis
imidazoles
palladium complex
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201810110843.5A
Other languages
English (en)
Inventor
柳清湘
胡则亮
于少聪
赵志翔
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin University
Tianjin Normal University
Original Assignee
Tianjin Normal University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tianjin Normal University filed Critical Tianjin Normal University
Priority to CN201810110843.5A priority Critical patent/CN108586345A/zh
Publication of CN108586345A publication Critical patent/CN108586345A/zh
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/06—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2269—Heterocyclic carbenes
    • B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
    • C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/12—Polycyclic non-condensed hydrocarbons
    • C07C15/14—Polycyclic non-condensed hydrocarbons all phenyl groups being directly linked
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/20—Polycyclic condensed hydrocarbons
    • C07C15/24—Polycyclic condensed hydrocarbons containing two rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/06—Compounds containing nitro groups bound to a carbon skeleton having nitro groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/45—Monoamines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/18—Polycyclic aromatic halogenated hydrocarbons
    • C07C25/22—Polycyclic aromatic halogenated hydrocarbons with condensed rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/205—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/782—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic
    • C07C49/784—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic with all keto groups bound to a non-condensed ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/006—Palladium compounds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)

Abstract

本发明公开了1,8‑二[3‑(N‑乙基咪唑基)丙氧基]蒽醌六氟磷酸盐作为前体的氮杂环卡宾钯配合物及其制备方法，并使用合成的氮杂环卡宾钯配合物做催化剂，用于催化碳‑碳键交叉偶联反应。其中氮杂环卡宾钯配合物的制备方法：在氮气保护下，将1,8‑二[3‑(N‑乙基咪唑基)丙氧基]蒽醌六氟磷酸盐与钯化合物以摩尔比为2：1的比例加入到反应器皿内，加入有机溶剂，然后在0˚C～100˚C温度下反应12～24小时，过滤，乙醚扩散，得到氮杂环卡宾钯配合物。本发明制备得到的氮杂环卡宾钯配合物主要应用于催化剂技术领域。

Description

氮杂环卡宾钯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：21572159）和天津市自然科学基金（基金号：11JCZDJC22000）的资助下进行的。
技术领域
本发明属于有机合成和金属有机化学技术领域，涉及氮杂环卡宾金属配合物的合成。更具体的说是含1,8-二[3-(N-乙基咪唑基)丙氧基]蒽醌六氟磷酸盐作为前体的氮杂环卡宾钯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1991年，Aduengo第一次分离得到了游离的N-杂环卡宾，各种氮杂环卡宾金属配合物不断地被报道。近二十几年来，氮杂环卡宾逐渐成为金属有机化学的研究热点。氮杂环卡宾配体可以通过改变氮原子和卡宾骨架上的取代基而容易地得到，而且通过修饰取代基，易于调节空间位阻和电子性质。氮杂环卡宾通过与金属离子配位形成各种结构的金属配合物。与膦配体相比，氮杂环卡宾配体具有更高的热稳定性，耐水性，空气稳定性，较低的毒性等优点。在催化领域，其能够催化的反应种类广泛，催化效果也明显优于其它结构相似的膦配体形成的金属配合物，如高效催化烯烃的复分解反应，烯烃的氢硅化反应，呋喃的合成等等，所以氮杂环卡宾金属配合物在催化领域的研究极具价值。随著研究的深入，氮杂环卡宾金属配合物在其他领域会有更广泛的应用。
发明内容
本发明的目的在于提供蒽醌桥联的氮杂环双卡宾金属配合物，特别是1,8-二[3-(N-乙基咪唑基)丙氧基]蒽醌六氟磷酸盐作为前体的氮杂环卡宾钯配合物。
其结构式为：
本发明涉及了制备此类氮杂环卡宾钯配合物的方法。
本发明涉及此类氮杂环卡宾钯配合物的氢谱标定。
本发明所涉及的氮杂环卡宾钯配合物是通过扩散溶剂的方法得到的。
本发明更进一步涉及了1,8-二[3-(N-乙基咪唑基)丙氧基]蒽醌六氟磷酸盐作为前体的氮杂环卡宾钯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：
（1）用1,8-二(3-溴丙氧基)蒽醌和N-乙基-咪唑反应生成1,8-二[3-(N-乙基咪唑基)丙氧基]蒽醌卤化物，还可以通过六氟磷酸铵进行阴离子交换反应得到1,8-二[3-(N-乙基咪唑基)丙氧基]蒽醌六氟磷酸盐；其中1,8-二(3-溴丙氧基)蒽醌：N-乙基-咪唑的摩尔比为1：2；
（2）在惰性气体保护下，将1,8-二[3-(N-乙基咪唑基)丙氧基]蒽醌六氟磷酸盐与钯化合物以摩尔比为2：1mol的比例混合，加入有机溶剂，在0˚C～100˚C温度下反应12～24小时，过滤，乙醚扩散，得到氮杂环卡宾钯配合物。
本发明所述的N-乙基苯并咪唑还可以为甲基苯并咪唑、仲丁基苯并咪唑或苄基苯并咪唑；所述的金属化合物选自氧化银、醋酸银、醋酸鈀、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、1，2-二氯乙烷、丙酮、乙醚、乙腈、二甲基亚砜中的一种或几种的混合物。
本发明进一步公开了氮杂环卡宾钯配合物作为催化剂中的应用。主要是通过1,8-二[3-(N-乙基咪唑基)丙氧基]蒽醌六氟磷酸盐作为前体的氮杂环卡宾钯配合物应用于催化领域。特别是作为催化剂用于对溴代芳烃和苯硼酸的 Suzuki-Miyaura 偶联反应中。实验证明：氮杂环卡宾钯配合物在一定的条件下对反应有催化性能。如应用实例1在表1和表2中所示。本发明公开的氮杂环卡宾钯配合物及其制备方法与用途所具有的积极效果在于：在用于对溴代芳烃和苯硼酸的 Suzuki-Miyaura 偶联反应中，催化剂的制备容易。
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N-乙基-咪唑、蒽醌、1,3-二溴丙烷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50 mL 1,8-二羟基蒽醌(5.000 g, 20.8 mmol)、无水K2CO3 (15.000 g, 109.0mmol)、TBAB (0.134 g, 2.1 mmol)和1,3-二溴丙烷(8.404 g，41.6 mmol)的丙酮(50mL)溶液在回流下搅拌4天。旋干溶剂，向残余物中加入H2O (50 mL)，用二氯甲烷萃取悬浮液，合并有机相，用无水MgSO4干燥。旋干二氯甲烷，得到的黄色固体即1,8-双（3'-溴丙氧基）蒽醌，产率：5.100 g (50.8%)，熔点：120-122 ˚C。
将1,8-二(3-溴丙氧基)蒽醌7 (2.000 g, 4.1 mmol)和N-乙基咪唑(0.875 g,9.1 mmol)混合在100 mL丙酮中，回流搅拌5天，析出黄色油状液体，旋干溶剂，将得到的黄色油状液体溶在60 mL无水甲醇中，加入60 mL NH4PF6 (1.497 g, 9.1 mmol)的甲醇溶液。在室温下搅拌3天，析出黄色固体，抽滤，得到产物1,8-二[3-(N-乙基咪唑基)丙氧基]蒽醌六氟磷酸盐黄色固体。产率：3.026 g (91%)，熔点：144-146 ˚C。Anal. Calcd forC30H34N4O4P2F12: C, 44.78; H, 4.25; N, 6.96%. Found: C, 44.83; H, 4.18; N,6.78%. 1H NMR (400 MHZ, DMSO-d 6): δ1.36 (t, J = 7.2 Hz, 6H, CH 3), 2.37 (t, J =6 Hz, 4H, CH 2), 4.12-4.18 (m, 8H, CH 2), 4.51 (t, J = 6.6 Hz, 4H, CH 2), 7.57(t, J = 4 Hz, 2H, ArH), 7.71 (t, J = 8.4 Hz, 8H, ArH), 9.14 (s, 2H, 2-imiH);13C NMR (100 MHZ, DMSO-d 6): δ14.9 (CH3), 28.7 (CH2), 44.2 (CH2), 45.9 (CH2),65.1 (CH2), 118.7 (ArC), 120.2 (ArC), 122.1 (ArC), 122.5 (ArC), 123.3 (ArC),134.0 (ArC), 134.5 (ArC), 135.7 (ArC), 157.6 (ArC), 181.8 (2-imiC), 183.1(CO) (imi = imidazolium)。
在氮气保护下，将氧化银(0.086 g，0.3 mmol)加入到1,8-二[3-(N-乙基咪唑基)丙氧基]蒽醌六氟磷酸盐(0.200 g，0.2 mmol)的二甲基亚砜(5mL)和乙腈(25mL)溶液中，搅拌悬浮液加热回流24小时。过滤所得溶液，向滤液中加入二乙腈氯化钯(0.050 g，0.1mmol)，并在氮气保护下回流，连续搅拌24小时。 过滤所得溶液并浓缩至5 mL，加入乙醚(5mL) 过滤得到黄色粉末。1H NMR (400 MHZ, DMSO-d 6): δ1.39 (t, J = 4.4 Hz, 6H,CH 3), 2.39 (q, J = 7.2 Hz, 4H, CH 2), 4.18 (q, J = 7.2 Hz, 8H, CH 2), 4.53 (t, J= 7.2 Hz, 4H, CH 2), 7.56 (d, J = 4 Hz, 2H, ArH), 7.82 (m, 8H, ArH); 13C NMR(100 MHZ, DMSO-d 6): δ14.8 (CH3), 28.5 (CH2), 44.5 (CH2), 47.8 (CH2), 65.2(CH2), 117.1 (ArC), 118.4 (ArC), 121.1 (ArC), 121.6 (ArC), 122.5 (ArC), 132.6(ArC), 133.3 (ArC), 156.8 (ArC), 174.6 (2-bimiC), 182.1 (CO)。
实施例2
应用实例1
Suzuki-Miyaura 偶联反应的一般程序。在典型的反应之中，将卤代芳烃(0.5 mmol)，苯硼酸(0.6 mmol), 碱(1.2 mmol), 环状氮杂环双卡宾钯配合物(0.2 mol %)加入到混合溶剂(3mL，甲醇/水 = 3/1, V/V)中，这个反应体系在空气中以60 ˚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，然后将水(20 mL)加入到反应的混合体系中。加入二氯甲烷(10mL)，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，再将溶剂浓缩至5mL，通过GC分析或者色谱柱分离从而得到产物。
本发明提出的环状氮杂环双卡宾钯配合物是一种在标准状态下可以稳定存在的高级催化剂，具有结构稳定、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为实施例1中得到的氮杂环卡宾钯配合物在对溴甲苯和苯硼酸的 Suzuki-Miyaura 偶联反应中反应条件的筛选[1]
表1
[1] 反应条件：对溴甲苯0.50 mmol，苯硼酸0.60 mmol，碱1.2 mmol, 实施例2中制备的环状氮杂环双卡宾金属配合物0.2 mol %，溶剂5 mL, 60˚C。
[2] 反应过程中要点板跟踪。
[3] 用GC判定产物。
[4] 编号14中没有加实施例2中制备的环状氮杂环双卡宾金属配合物0.2 mol%，其他条件和[1]一样。
结论：本发明制备的催化剂在对溴甲苯和苯硼酸的 Suzuki-Miyaura 偶联反应中用乙醇/水(1:1)作为溶剂，K3PO4·3H2O作为碱，催化剂用量0.2 mol%，反应时间24小时是最佳的反应条件。
表2为实施例1中制备的氮杂环卡宾钯配合物催化剂卤代芳烃和苯硼酸的反应实例[1]
表2
[1] 反应条件：卤代芳烃0.50 mmol，苯硼酸0.60 mmol，K2CO3 1.0 mmol,实施例2中制备的氮杂环双卡宾金属配合物0.2 mol %，溶剂5 mL, TBAB (10 mol%)，60 ˚C。
[2] 反应过程中要点板跟踪。
[3] 用GC判定产物，分离产率。
结论：本发明制备的催化剂在乙醇/水(1:1)溶液中可以有效地催化大多数溴代芳烃和苯硼酸的Suzuki-Miyaura 偶联反应，对氯代芳烃也有一定的催化作用。
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 (5)

1.1,8-二[3-(N-乙基咪唑基)丙氧基]蒽醌六氟磷酸盐作为前体的氮杂环卡宾钯配合物，其特征在于它的结构式如下：
。
2.权利要求1所述的1,8-二[3-(N-乙基咪唑基)丙氧基]蒽醌六氟磷酸盐作为前体制备氮杂环卡宾钯配合物的方法，其特征在于：
（1）用1,8-二(3-溴丙氧基)蒽醌和N-乙基-咪唑反应生成1,8-二[3-(N-乙基咪唑基)丙氧基]蒽醌卤化物，还可以通过六氟磷酸铵进行阴离子交换反应得到1,8-二[3-(N-乙基咪唑基)丙氧基]蒽醌六氟磷酸盐；其中1,8-二(3-溴丙氧基)蒽醌：N-乙基-咪唑的摩尔比为1：2；
（2）在惰性气体保护下，将1,8-二[3-(N-乙基咪唑基)丙氧基]蒽醌六氟磷酸盐与钯化合物以摩尔比为2：1mol的比例混合，加入有机溶剂，在0˚C～100˚C温度下反应12～24小时，过滤，乙醚扩散，得到氮杂环卡宾钯配合物。
3.权利要求2所述的氮杂环卡宾钯配合物制备方法，其中所述的N-乙基苯并咪唑还可以为甲基苯并咪唑、仲丁基苯并咪唑或苄基苯并咪唑；所述的金属化合物选自氧化银、醋酸银、氯化钯、乙腈氯化钯的一种或几种的混合物。
4.权利要求2所述的氮杂环卡宾钯配合物制备方法，其中所述的有机溶剂选自四氢呋喃、二氯甲烷、1，2-二氯乙烷、丙酮、乙醚、乙腈、二甲基亚砜中的一种或几种的混合物。
5.权利要求1所述氮杂环卡宾钯配合物作为催化剂用于对溴甲苯和苯硼酸的 Suzuki-Miyaura 偶联反应中的应用。
CN201810110843.5A 2018-02-05 2018-02-05 氮杂环卡宾钯配合物及其制备方法与用途 Pending CN108586345A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810110843.5A CN108586345A (zh) 2018-02-05 2018-02-05 氮杂环卡宾钯配合物及其制备方法与用途

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810110843.5A CN108586345A (zh) 2018-02-05 2018-02-05 氮杂环卡宾钯配合物及其制备方法与用途

Publications (1)

Publication Number Publication Date
CN108586345A true CN108586345A (zh) 2018-09-28

Family

ID=63608866

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810110843.5A Pending CN108586345A (zh) 2018-02-05 2018-02-05 氮杂环卡宾钯配合物及其制备方法与用途

Country Status (1)

Country Link
CN (1) CN108586345A (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115260390A (zh) * 2022-07-26 2022-11-01 合肥工业大学 一种新型聚合氮杂环卡宾催化剂的制备及在糠酸合成工艺中的应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101219399A (zh) * 2008-01-24 2008-07-16 浙江大学 氮杂环卡宾金属钯催化剂的制备方法和用途
CN102276655A (zh) * 2011-06-20 2011-12-14 徐州师范大学 双氮杂环卡宾双钯配合物及其制备方法
CN104151364A (zh) * 2013-05-13 2014-11-19 南开大学 邻吡唑基苯基功能化的氮杂环卡宾钯配合物及其制备方法与应用

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101219399A (zh) * 2008-01-24 2008-07-16 浙江大学 氮杂环卡宾金属钯催化剂的制备方法和用途
CN102276655A (zh) * 2011-06-20 2011-12-14 徐州师范大学 双氮杂环卡宾双钯配合物及其制备方法
CN104151364A (zh) * 2013-05-13 2014-11-19 南开大学 邻吡唑基苯基功能化的氮杂环卡宾钯配合物及其制备方法与应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WEI TANG ET AL.: "N-Hetercocyclic carbene metallacrown ethers based on 1,8-dihydroxy-9,10-anthraquinone: Synthesis, structures and application in situ palladium-catalyzed Suzuki-Miyaura reaction", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115260390A (zh) * 2022-07-26 2022-11-01 合肥工业大学 一种新型聚合氮杂环卡宾催化剂的制备及在糠酸合成工艺中的应用

Similar Documents

Publication Publication Date Title
Fleckenstein et al. Aqueous cross-coupling: highly efficient Suzuki–Miyaura coupling of N-heteroaryl halides and N-heteroarylboronic acids
EP1064243B1 (en) Coupling reactions with palladium catalysts
CN103087105B (zh) 手性膦配体以及包含该配体的金属催化剂和它们的应用
CN103242300B (zh) 基于喹喔啉的氮杂环卡宾金属配合物及其制备方法与应用
Xu et al. Cyclometalated Pd (II) and Ir (III) 2-(4-bromophenyl) pyridine complexes with N-heterocyclic carbenes (NHCs) and acetylacetonate (acac): synthesis, structures, luminescent properties and application in one-pot oxidation/Suzuki coupling of aryl chlorides containing hydroxymethyl
CN101307065B (zh) 醚链连接的氮杂环双卡宾金属配合物及其制备方法与用途
CN107880079B (zh) 环状氮杂环双卡宾钯配合物及其制备方法与用途
CN104447700A (zh) 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
Pratihar et al. Azo-amide palladium (II) complexes: synthesis, characterization and application in C–C cross-coupling reactions
CN104844399A (zh) 一种合成2-氟代苯酚化合物的方法
CN102584864B (zh) 氮杂环卡宾金属冠醚及其在识别客体方面的应用
CN102321104B (zh) 烷基桥联的氮杂环双卡宾金属配合物及其制备方法与用途
CN110423217A (zh) 一种共轭烯炔化合物的制备方法
CN102229568B (zh) 苯基醚桥联的氮杂环卡宾金属配合物的制备与用途
CN108586345A (zh) 氮杂环卡宾钯配合物及其制备方法与用途
CN105728045B (zh) 新型线性α烯烃催化剂及其制备方法和应用
CN101445481B (zh) 硫代2,6-吡啶二甲酰胺骨架的钳形硫代酰胺配体及其络合物和用途
CN105418491B (zh) 一种1‑(4‑吡啶基)‑4‑(4＇‑吡啶基乙烯基)苯及其制备方法和用途
CN112778272B (zh) 一种2,2′-联氮杂芳环类双齿配体及其制备方法和应用
CN105294776B (zh) 一种含氮杂环芳香化合物的对称二聚体的制备方法
CN108276432B (zh) 芴桥联的环状氮杂环卡宾银配合物及其制备方法与应用
JP4413507B2 (ja) ピンサー型金属錯体及びその製造方法、並びにピンサー型金属錯体触媒
CN102671704B (zh) 一种Pd配合物催化剂及其制备方法及应用
CN102718714B (zh) 蒽桥联的四齿咪唑盐及其制备方法与应用
CN115232163B (zh) 一种硅中心手性分子化合物及其制备方法与应用

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20180928