CN109810147B - Pyrene-labeled benzimidazole nitrogen heterocyclic carbene palladium metal complex, and preparation and application thereof - Google Patents
Pyrene-labeled benzimidazole nitrogen heterocyclic carbene palladium metal complex, and preparation and application thereof Download PDFInfo
- Publication number
- CN109810147B CN109810147B CN201910139773.0A CN201910139773A CN109810147B CN 109810147 B CN109810147 B CN 109810147B CN 201910139773 A CN201910139773 A CN 201910139773A CN 109810147 B CN109810147 B CN 109810147B
- Authority
- CN
- China
- Prior art keywords
- benzimidazole
- pyrene
- metal complex
- reaction
- heterocyclic carbene
- 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.)
- Active
Links
Images
Abstract
The invention relates to a pyrene-labeled benzimidazole nitrogen heterocyclic carbene palladium metal complex, which is a pyrene-labeled benzimidazole nitrogen heterocyclic carbene palladium metal complex prepared by using benzimidazole as a framework and pyridine as an axial ligand, and has the structural formula as follows:
Description
Technical Field
The invention relates to the technical field of catalysis, in particular to a pyrene-labeled benzimidazole nitrogen heterocyclic carbene-palladium metal complex, and preparation and application thereof.
Background
The complex catalyst is a complex formed by taking transition metal as a center, and a transition metal atom positioned at the center has electronic unsaturation of a d orbital and acts with different orbitals of a ligand to form a metal-ligand chemical bond. N-heterocyclic carbenes (NHCs) are novel ligands with strong electron donating capability, and compared with the traditional phosphine ligand, the coordination mode of the N-heterocyclic carbenes (NHCs) and the metal is very similar to that of an organic phosphine ligand. However, the azacyclo-carbene ligand has the characteristics of simple synthesis, low toxicity, strong electron supply capability, strong coordination capability with central metal, and especially good stability to water, heat and air, and is incomparable with phosphine ligands.
In recent years, research on N-heterocyclic carbene metal complexes has become one of the research hotspots in the fields of coordination chemistry, organic chemistry, catalytic chemistry and the like, and particularly has been very successful in the fields of N-heterocyclic palladium-carbene metal complex catalyzed C-C, C-O, C-N coupling reaction and N-heterocyclic ruthenium metal complex catalyzed olefin metathesis reaction and the like (chem. Rev. 2009,109, 3612-3176; Acc. chem. Res. 2008, 41, 1440-1449; Angew. chem., int. Ed. 2008, 47, 3122-3172; Coor. chem. Rev 2007, 251, 610-641; Angew. chem., Int. Ed. 2007, 46, 2768-2813).
Because the N-heterocyclic carbene metal complexes with different frameworks have respective special structures and reaction properties, in order to understand and explore the potential applications and future application prospects of the N-heterocyclic carbene metal complexes from multiple aspects and multiple levels, the development of the N-heterocyclic carbene metal complexes with novel structures has very important significance in the fields of organic synthetic chemistry, catalytic chemistry, metal organic chemistry and the like. At present, basic structural units of the N-heterocyclic carbene metal complex developed at home and abroad are mainly based on five-membered ring structures such as imidazole or dihydroimidazole, and the benzimidazole N-heterocyclic carbene metal complex as one of representative frameworks is less researched and is still in the beginning stage. For example: huynh et al adopts 1, 3-diisopropylbenzimidazole bromide, acetic acid and sodium bromide to react in dimethyl sulfoxide solvent to generate carbene dimer, then uses acetonitrile to depolymerize to obtain a benzimidazole nitrogen heterocyclic carbene palladium metal complex with a novel structure, and applies the benzimidazole nitrogen heterocyclic palladium metal complex in catalytic Suzuki coupling reaction (Organometallics, 2006,25, 3267-doped 3274.).
Alpha, beta-unsaturated alkynone as a carbonyl compound is an important fine chemical and medical intermediate, and is widely applied to synthesis of natural products, bioactive molecules, polyfunctional compounds, heterocyclic compounds, derivatives thereof and the like. Under the catalytic action of a transition metal complex, cheap and easily available organic halogenated aromatic hydrocarbon, alkyne and CO are used as raw materials, and the synthesis of the alpha, beta-unsaturated alkynone compound through the Sonogashira carbonylation reaction is a simple and efficient route, and has the advantages of atom economy, environmental friendliness, simplicity and convenience in operation and the like. Palladium-phosphine metal complexes containing phosphine ligands are high-efficiency catalyst systems for catalyzing Sonogashira carbonylation reaction, however, a large amount of toxic phosphine ligands are required to be added to stabilize Pd (0) catalytic active centers in the catalyst systems, and a plurality of disadvantages exist (chem. Soc. Rev, 2011, 4986-. So far, no report on the related application of the benzimidazolyl N-heterocyclic carbene metal complex in the Sonogashira carbonylation reaction exists.
Disclosure of Invention
The invention aims to solve the technical problem of providing a pyrene-labeled benzimidazole nitrogen heterocyclic carbene palladium metal complex.
The invention aims to solve another technical problem of providing a preparation method of the pyrene-labeled benzimidazole nitrogen heterocyclic carbene palladium metal complex.
The third technical problem to be solved by the invention is to provide the application of the pyrene-labeled benzimidazole n-heterocyclic carbene palladium metal complex.
In order to solve the problems, the pyrene-labeled benzimidazole nitrogen heterocyclic carbene palladium metal complex is characterized in that: by benzimidazoleThe pyrene-labeled benzimidazole nitrogen heterocyclic carbene palladium metal complex prepared by using oxazole as a framework and pyridine as an axial ligand has a structural formula as follows:
。
the preparation method of the pyrene-labeled benzimidazole nitrogen heterocyclic carbene palladium metal complex comprises the following steps:
synthesizing 1- (2-bromoethoxy) pyrene:
taking acetone as a solvent, and mixing 1-hydroxypyrene, cesium carbonate and 1, 2-dibromoethane according to a molar ratio of 1: 1.5-2.5: 3.5-4.5, heating at 60-80 ℃, reacting under reflux for 4-15 hours, and separating and purifying the product after the reaction is finished to obtain 1- (2-bromoethoxy) pyrene;
synthesizing 1- (ethoxy) pyrenyl benzimidazole:
taking acetonitrile as a reaction solvent, and mixing the 1- (2-bromoethoxy) pyrene, benzimidazole and potassium hydroxide according to a molar ratio of 1: 1.3-2.0: 1.1-1.5, heating at 80-100 ℃, reacting under reflux for 20-30 hours, and separating and purifying the product after the reaction is finished to obtain 1- (ethoxy) pyrenyl benzimidazole;
the synthesis of the 1- (ethoxy) pyrene-3-benzyl benzimidazole bromide salt:
taking acetonitrile as a reaction solvent, and reacting the 1- (ethoxy) pyrenyl benzimidazole and benzyl bromide according to a molar ratio of 1: 1.0 to 1.5, and heating and reacting at 80 to 100 ℃ for reflux for 20 to 30 hours. Separating and purifying the product after the reaction is finished to obtain 1- (ethoxy) pyrene-3-benzyl benzimidazole bromine salt;
step four, synthesizing a pyrene-marked benzimidazole nitrogen heterocyclic carbene palladium metal complex:
taking pyridine as a reaction solvent, and reacting palladium chloride, the 1- (ethoxy) pyrene-3-benzyl benzimidazole bromide, potassium carbonate and potassium bromide according to a molar ratio of 1: 1.0-1.5: 3-10: 8-20, heating and refluxing for 20-30 hours at 80-100 ℃, and separating and purifying the product after the reaction is finished to obtain the pyrene-labeled benzimidazole nitrogen heterocyclic carbene palladium metal complex.
The synthesis process is as follows:
the application of the pyrene-labeled benzimidazole nitrogen heterocyclic carbene palladium metal complex is characterized in that: the pyrene-labeled benzimidazole nitrogen heterocyclic carbene palladium metal complex is used as a catalyst to synthesize an intermediate alpha, beta-unsaturated alkynone in a one-step mode in a Sonogashira carbonylation reaction of three components, namely iodo-aromatic hydrocarbon, carbon monoxide (CO) and terminal alkyne; the addition amount of the benzimidazole nitrogen heterocyclic carbene palladium metal complex is 0.5-3 mol%, preferably 0.1-0.25 mol% of the molar amount of the iodo-aromatic hydrocarbon.
The reaction formula for synthesizing the alpha, beta-unsaturated alkynone by the Sonogashira carbonylation reaction is as follows:
wherein: the carbon monoxide pressure is 0.5-3.0 MPa, preferably 1.0-2.0 MPa; it is preferable to use high purity carbon monoxide, and a mixed gas such as hydrogen gas or an inert gas may be added as long as it does not affect the reaction.
The reaction temperature is 60-140 ℃, and preferably 80-100 ℃; the reaction time is 6-30 h.
The structural formula of the iodo aromatic hydrocarbon is
(ii) a In the formula R1Refers to one of methyl, methoxy, amino, fluorine, chlorine, trifluoromethyl, formate and naphthyl.
The terminal alkyne structural formula is:
(ii) a In the formula R2Is one of phenyl, 4-fluorophenyl, 4-bromophenyl, 4-methylphenyl, 4-ethylphenyl, 4-butylphenyl, 4-tert-butylphenyl, 4-methoxyphenyl and 4-pentyloxyphenyl.
The reaction solvent is one of toluene, tetrahydrofuran, dioxane, acetonitrile and anisole.
The base used in the reaction is one of triethylamine, potassium carbonate, cesium carbonate and sodium acetate.
Compared with the prior art, the invention has the following advantages:
1. the method has the advantages of mild reaction conditions, simple and convenient process, convenient operation, easy realization of equipment requirements and reaction conditions, and suitability for large-scale production.
2. The preparation method is simple, the catalyst consumption is small, and the catalytic efficiency is high.
3. In the application of the Sonogashira carbonylation reaction, the application range of the substrate is wider, and the high-purity alpha, beta-unsaturated alkynone can be obtained with high yield by simple column separation of the reaction mixture.
4. Experimental results prove that the selectivity and the conversion rate of the Sonogashira carbonylation reaction are high by adopting the benzimidazole nitrogen heterocyclic carbene palladium metal complex as a catalyst.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a single crystal spectrum of the catalyst of the present invention.
FIG. 2 is a hydrogen nuclear magnetic spectrum of the catalyst of the present invention.
FIG. 3 is a carbon nuclear magnetic hydrogen spectrum of the catalyst of the present invention.
FIG. 4 is a UV-visible spectrum (concentration 1.26X 10) of the catalyst of the present invention-5mol/L）。
FIG. 5 is a fluorescence spectrum of the catalyst of the present invention (concentration: 1.26X 10)-5mol/L, excitation wavelength 386 nm).
Detailed Description
The pyrene-labeled benzimidazole nitrogen heterocyclic carbene palladium metal complex is a pyrene-labeled benzimidazole nitrogen heterocyclic carbene palladium metal complex prepared by using benzimidazole as a framework and pyridine as an axial ligand, and has the structural formula:
。
embodiment 1 a preparation method of pyrene-labeled benzimidazole n-heterocyclic carbene palladium metal complex includes the following steps:
synthesizing 1- (2-bromoethoxy) pyrene:
in a 100mL dry round-bottom flask, 35mL of acetone, 1-hydroxypyrene (2.18 g, 10 mmol), and Cs were added in this order2CO3(6.5 g, 19.9 mmol) and 1, 2-dibromoethane (7.48 g, 39.8 mmol), and the reaction was heated at 60 ℃ for 6 hours. After the reaction solution was cooled to room temperature, dichloromethane and water were added to conduct extraction for a plurality of times. Adding anhydrous MgSO into organic phase4Drying, filtering and rotary steaming. The product was finally isolated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 4: 1) to give 1- (2-bromoethoxy) pyrene (2.282 g, yield 70%) as a yellow solid.
1H NMR (400 MHz, CDCl3，298k)：δ 8.49 (d, J = 9.2 Hz, 1H), 8.10 (m, 4H), 7.97 (m, 2H), 7.91 (d, J = 9.0 Hz, 1H), 7.51 (d, J = 8.4 Hz, 1H), 4.64 (t, J= 6.2 Hz, 2H), 3.85 (t, J = 6.2 Hz, 2H).
13C NMR (101 MHz, CDCl3)： δ 152.01 (s), 131.64 (d, J = 2.7 Hz), 127.16 (s), 126.76 (s), 126.24 (s), 125.92 (s), 125.90 (d, J = 3.7 Hz), 125.46 (s), 125.41 (d, J = 9.0 Hz), 124.84 (s), 124.47 (d, J = 8.8 Hz), 124.43 (s), 121.11 (s), 120.77 (s), 109.65 (s), 68.99 (s), 29.44 (s).
HRMS (ESI) calculated for C18H15BrO [M]: 326.0306 found 326.0375。
Synthesizing 1- (ethoxy) pyrenyl benzimidazole:
a250 mL dry round bottom flask was refluxed with 0.376 g of benzimidazole and 100mL of acetonitrile for 1 hour, refluxed with 0.14 g of potassium hydroxide for 30 minutes, refluxed with 0.652 g of 1- (2-bromoethoxy) pyrene, and refluxed at 90 ℃ for 24 hours. After the reaction solution was cooled to room temperature, 10 mL of n-pentane was added, filtered, washed three times with 20mL of n-pentane, and dried in vacuo to give 1- (ethoxy) pyrenyl benzimidazole (0.617 g, 85% yield) as a pale yellow solid.
1H NMR (400 MHz, DMSO) δ 8.53 (s, 1H), 8.19 (m, 4H), 8.01 (ddd, J = 26.1, 18.6, 9.2 Hz, 4H), 7.86 (d, J = 8.1 Hz, 1H), 7.70 (dd, J = 21.8, 8.3 Hz, 2H), 7.33 (t, J = 7.2 Hz, 1H), 7.23 (m, 1H), 4.93 (t, J = 4.9 Hz, 2H), 4.71 (t, J = 5.0 Hz, 2H).
13C NMR (101 MHz, DMSO) δ 144.68 (s), 143.41 (s), 133.99 (s), 131.03 (d, J = 17.3 Hz), 127.20 (s), 126.40 (d, J = 7.2 Hz), 125.88 (s), 124.87 (s), 124.45 (s), 124.24 (s), 123.95 (s), 122.29 (s), 121.52 (s), 120.67 (s), 119.43 (s), 110.66 (s), 109.71 (s), 67.25 (s), 43.87 (s), 39.90 (s), 39.69 (s), 39.49 (s), 39.28 (s), 39.07 (s).
HRMS (ESI) calculated for C25H19N2O [M]: 363.1497; found 363.1508。
The synthesis of the 1- (ethoxy) pyrene-3-benzyl benzimidazole bromide salt:
in a 25 mL Schlenk reaction tube, 0.724 g of 1- (ethoxy) pyrenyl benzimidazole was dissolved in 2 mL of acetonitrile under nitrogen, 2.2 mmol of benzyl bromide was added, and the mixture was refluxed at 90 ℃ for 24 hours. The reaction was cooled to room temperature, 6 mL of n-pentane was added, filtered, washed three times with 20mL of n-pentane, and dried under vacuum to give 1- (ethoxy) pyrene-3-benzylbenzimidazole bromide as a white gray solid (1.010 g, 95% yield).
1H NMR (400 MHz, DMSO) δ 10.47 (s, 1H), 8.39 (d, J = 8.3 Hz, 1H), 8.23 (m, 4H), 8.04 (ddd, J = 25.5, 13.4, 6.6 Hz, 5H), 7.73 (m, 3H), 7.56 (m, 2H), 7.29 (m, 3H), 5.90 (s, 2H), 5.29 (t, J = 4.2 Hz, 2H), 4.90 (t, J = 4.3 Hz, 2H).
13C NMR (101 MHz, DMSO) δ 152.02 (s), 143.62 (s), 134.37 (s), 131.98 (s), 131.43 (m), 129.27 (d, J = 19.6 Hz), 128.84 (s), 127.68 (s), 127.28 (s), 127.00 (s), 126.33 (s), 125.54 (s), 125.35 (m), 125.18 (d, J = 21.4 Hz), 124.85 (s), 124.42 (s), 121.18 (s), 119.67 (s), 114.77 (s), 114.48 (s), 110.33 (s), 66.73 (s), 50.39 (s), 47.25 (s).
HRMS (ESI) calculated for C32H24N2O+ [M-Br] 452.1883 found: 452.1899。
Step four, synthesizing a pyrene-marked benzimidazole nitrogen heterocyclic carbene palladium metal complex:
in a 25 mL Schlenk reaction tube, 1- (ethoxy) pyrene-3-benzylbenzimidazole bromide (0.55 mmol), potassium carbonate (5 mmol), potassium bromide (10 mmol) and palladium (II) chloride (0.5 mmol) were added in this order under nitrogen protection, pyridine (3 mL) was added, the reaction mixture was stirred at 90 ℃ for 24 hours, after completion of the reaction, the solution was cooled to room temperature, filtered through a short-layer celite, washed with 20mL of dichloromethane and the filtrate was concentrated. The solution was slowly added to 40 mL of hexane and stirred for 3h, during which time a yellow material formed, which was then filtered to give a pale yellow solid pyrene-labeled benzimidazole N-heterocyclic carbene palladium metal complex (0.410 g, 88% yield).
A single crystal of the pyrene-labeled benzimidazole nitrogen heterocyclic carbene palladium metal complex is cultured by a solvent diffusion method, and the fine structure of the pyrene-labeled benzimidazole nitrogen heterocyclic carbene palladium metal complex is determined by X-ray single crystal diffraction, hydrogen nuclear magnetism, carbon nuclear magnetism and high-resolution mass spectrum (see figures 1-3). Further ultraviolet-visible spectrum and fluorescence spectrum prove that the side chain of the catalyst contains pyrene group (see fig. 4-5).
1H NMR (400 MHz, DMSO) δ 8.96 (d, J = 4.8 Hz, 1H), 8.19 (m, 4H), 8.01 (m, 6H), 7.84 (d, J = 8.6 Hz, 1H), 7.58 (m, 5H), 7.23 (ddd, J = 68.1, 25.4, 12.3 Hz, 6H), 6.13 (d, J = 57.3 Hz, 2H), 5.57 (s, 2H), 5.21 (d, J = 86.1 Hz, 2H).
13C NMR (101 MHz, DMSO) δ 152.65 (s), 136.06 (d, J = 1.2 Hz), 131.63 (s), 131.40 (s), 129.00 (s), 128.58 (d, J = 21.1 Hz), 127.70 (s), 127.10 (m), 126.93 (s), 126.53 (d, J = 21.8 Hz), 125.43 (dd, J = 14.0, 11.9 Hz),124.95 (s), 124.69 (s), 124.47 (s), 123.81 (s), 121.37 (d, J = 1.8 Hz), 119.70 (s), 112.48 (s), 112.03 (s), 110.26 (s), 52.80 (s), 47.92 (s).
HRMS (ESI) calcd. for C37H29N3OPd[M-2Br]: 637.1345 found: 637.1399。
Embodiment 2 a preparation method of pyrene-labeled benzimidazole n-heterocyclic carbene palladium metal complex, comprising the following steps:
synthesizing 1- (2-bromoethoxy) pyrene:
in a 100mL dry round-bottom flask, 50mL of acetone, 1-hydroxypyrene (2.18 g, 10 mmol), and Cs were added in this order2CO3(4.884 g, 15.0 mmol) and 1, 2-dibromoethane (6.573 g, 35.0 mmol), the reaction was heated at 70 ℃ under reflux for 4 hours. After the reaction solution was cooled to room temperature, dichloromethane and water were added to conduct extraction for a plurality of times. Adding anhydrous MgSO into organic phase4Drying, filtering and rotary steaming. Finally, the product was isolated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 4: 1) to finally obtain 1- (2-bromoethoxy) pyrene (1.98 g, yield 60%) as a yellow solid.
Synthesizing 1- (ethoxy) pyrenyl benzimidazole:
in a 250mL dry round bottom flask, 1.3 mmol of benzimidazole and 120mL of acetonitrile solution were refluxed for 1 hour, 1.1 mmol of potassium hydroxide was further refluxed for 30 minutes, 0.326g of 1- (2-bromoethoxy) pyrene was added, and the reaction was refluxed at 80 ℃ for 20 hours. After the reaction solution was cooled to room temperature, 15mL of n-pentane was added, filtered, washed three times with 30mL of n-pentane, and dried in vacuo to give 1- (ethoxy) pyrenyl benzimidazole (0.254 g, 70% yield) as a pale yellow solid.
The synthesis of the 1- (ethoxy) pyrene-3-benzyl benzimidazole bromide salt:
in a 25 mL Schlenk reaction tube, 0.363 g of 1- (ethoxy) pyrenyl benzimidazole was dissolved in 2 mL of acetonitrile under nitrogen protection, 1.0 mmol of benzyl bromide was added, and the reaction was refluxed at 80 ℃ for 20 hours. The reaction was cooled to room temperature, 4 mL of n-pentane was added, filtered, washed three times with 25 mL of n-pentane and dried under vacuum to give 1- (ethoxy) pyrene-3-benzylbenzimidazole bromide as a white gray solid (0.425 g, 80% yield).
Step four, synthesizing a pyrene-marked benzimidazole nitrogen heterocyclic carbene palladium metal complex:
in a 25 mL Schlenk reaction tube, 1- (ethoxy) pyrene-3-benzylbenzimidazole bromide (1.0 mmol), potassium carbonate (3 mmol), potassium bromide (8 mmol), palladium (II) chloride (1 mmol) were added in this order under nitrogen protection, pyridine (6 mL) was added, the reaction mixture was stirred at 80 ℃ for 20 hours, after the reaction was completed, the solution was cooled to room temperature, filtered through a short layer of celite, washed by adding 30mL of dichloromethane, and the filtrate was concentrated. The solution was slowly added to 50mL of hexane and stirred for 3h, during which time a yellow material formed, which was then filtered to give a pale yellow solid pyrene-labeled benzimidazole N-heterocyclic carbene palladium metal complex (0.635 g, 79% yield).
Embodiment 3 a preparation method of pyrene-labeled benzimidazole n-heterocyclic carbene palladium metal complex, comprising the following steps:
synthesizing 1- (2-bromoethoxy) pyrene:
in a 100mL dry round-bottom flask, 60mL of acetone, 1-hydroxypyrene (2.18 g, 10 mmol), and Cs were added in this order2CO3(8.145 g, 25.0 mmol) and 1, 2-dibromoethane (8.451 g, 45.0 mmol) were reacted by heating at 80 ℃ for 15 hours. After the reaction solution was cooled to room temperature, dichloromethane and water were added to conduct extraction for a plurality of times. Adding anhydrous MgSO into organic phase4Drying, filtering and rotary steaming. The product was finally isolated and purified by column chromatography (eluent: petroleum ether: dichloromethane = 4: 1) to give 1- (2-bromoethoxy) pyrene (1.5 g, yield 46%) as a yellow solid.
Synthesizing 1- (ethoxy) pyrenyl benzimidazole:
in a 250mL dry round bottom flask, 2.0 mmol of benzimidazole and 150mL of acetonitrile solution are added for refluxing for 1 hour, 1.5 mmol of potassium hydroxide is added for refluxing for 30min, 1.0 mmol of 1- (2-bromoethoxy) pyrene is added, and the reaction is carried out for 30 hours at 100 ℃ under refluxing. After the reaction solution was cooled to room temperature, 20mL of n-pentane was added, filtered, washed three times with 60mL of n-pentane, and dried in vacuo to give 1- (ethoxy) pyrenyl benzimidazole (0.261 g, 72% yield) as a pale yellow solid.
The synthesis of the 1- (ethoxy) pyrene-3-benzyl benzimidazole bromide salt:
in a 25 mL Schlenk reaction tube, under nitrogen protection, 1.0 mmol of 1- (ethoxy) pyrenyl benzimidazole was dissolved in 4 mL of acetonitrile, 1.5 mmol of benzyl bromide was added, and the reaction was refluxed at 100 ℃ for 30 hours. The reaction was cooled to room temperature, 10 mL of n-pentane was added, filtered, washed three times with 40 mL of n-pentane, and dried under vacuum to give 1- (ethoxy) pyrene-3-benzylbenzimidazole bromide as a white gray solid (0.399 g, 75% yield).
Step four, synthesizing a pyrene-marked benzimidazole nitrogen heterocyclic carbene palladium metal complex:
in a 25 mL Schlenk reaction tube, 1- (ethoxy) pyrene-3-benzylbenzimidazole bromide (1.5 mmol), potassium carbonate (6 mmol), potassium bromide (12 mmol), palladium (II) chloride (1.0 mmol) were added in this order under nitrogen protection, pyridine (3 mL) was added, the reaction mixture was stirred at 100 ℃ for 30 hours, after completion of the reaction, the solution was cooled to room temperature, filtered through a short-layer celite, washed with 10 mL of dichloromethane, and the filtrate was concentrated. The solution was slowly added to 10 mL of hexane and stirred for 3h, during which time a yellow material formed, which was then filtered to give a pale yellow solid pyrene-labeled benzimidazole N-heterocyclic carbene palladium metal complex (0.502 g, 63% yield).
The pyrene-labeled benzimidazole nitrogen heterocyclic carbene palladium metal complex obtained in the above embodiments 1 to 3 is used as a catalyst to be applied to a Sonogashira carbonylation reaction of three components, namely iodo-aromatic hydrocarbon, carbon monoxide (CO) and terminal alkyne.
Example 4
A50 mL autoclave was charged with 5mL of toluene, 1 mmol of iodobenzene, 1.2 mmol of phenylacetylene, 2.0 mmol of triethylamine, and 0.5 mol% of benzimidazole N-heterocyclic carbene palladium metal complex (relative to the iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 18 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1, 3-diphenyl-2-propyne-1-ketone is more than 99 percent, and the separation yield is 98 percent.
1H NMR (400 MHz, CDCl3) δ 8.15 (m, 2H), 7.57 (m, 3H), 7.39 (m, 5H)。
13C NMR (100MHz, CDCl3) δ 178.05 (s), 136.91 (s), 134.16 (s), 133.10 (s), 130.84 (s), 129.61 (s), 128.69 (d, J = 6.2 Hz), 120.15 (s), 93.15 (s), 86.92 (s)。
HRMS (ESI) calcd. for C15H11O [M+H]: 207.0804, found: 207.0804。
IR (KBr, cm−1) 2203, 1644, 1254, 1002, 755。
Example 5
A50 mL autoclave was charged with 5mL of toluene, 1 mmol of iodobenzene, 1.2 mmol of phenylacetylene, 2.0 mmol of potassium carbonate, and 0.5 mol% of benzimidazole N-heterocyclic carbene palladium metal complex (relative to the iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 18 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1, 3-diphenyl-2-propyne-1-ketone is more than 99 percent, and the separation yield is 15 percent.
Example 6
A50 mL autoclave was charged with 5mL of toluene, 1 mmol of iodobenzene, 1.2 mmol of phenylacetylene, 2.0 mmol of sodium carbonate, and 0.5 mol% of benzimidazole N-heterocyclic carbene palladium metal complex (relative to the iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 18 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1, 3-diphenyl-2-propyne-1-ketone is more than 99 percent, and the separation yield is 10 percent.
Example 7
A50 mL autoclave was charged with 5mL of toluene, 1 mmol of iodobenzene, 1.2 mmol of phenylacetylene, 2.0 mmol of sodium acetate, and 0.5 mol% of benzimidazole N-heterocyclic carbene palladium metal complex (relative to the iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 18 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1, 3-diphenyl-2-propyne-1-ketone is more than 99 percent, and the separation yield is 25 percent.
Example 8
A50 mL autoclave was charged with 5mL tetrahydrofuran, 1 mmol iodobenzene, 1.2 mmol phenylacetylene, 2.0 mmol triethylamine, 0.5 mol% benzimidazole N-heterocyclic carbene palladium metal complex (relative to iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 18 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1, 3-diphenyl-2-propyne-1-ketone is more than 99 percent, and the separation yield is 90 percent.
Example 9
A50 mL autoclave was charged with 5mL dioxane, 1 mmol iodobenzene, 1.2 mmol phenylacetylene, 2.0 mmol triethylamine, 0.5 mol% benzimidazole N-heterocyclic carbene palladium metal complex (relative to iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 18 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1, 3-diphenyl-2-propyne-1-ketone is more than 99 percent, and the separation yield is 88 percent.
Example 10
A50 mL autoclave was charged with 5mL acetonitrile, 1 mmol iodobenzene, 1.2 mmol phenylacetylene, 2.0 mmol triethylamine, and 0.5 mol% benzimidazole N-heterocyclic carbene palladium metal complex (relative to iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 18 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1, 3-diphenyl-2-propyne-1-ketone is more than 99 percent, and the separation yield is 82 percent.
Example 11
A50 mL autoclave was charged with 5mL anisole, 1 mmol iodobenzene, 1.2 mmol phenylacetylene, 2.0 mmol triethylamine, 0.5 mol% benzimidazole N-heterocyclic carbene palladium metal complex (relative to iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 18 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1, 3-diphenyl-2-propyne-1-ketone is more than 99 percent, and the separation yield is 67 percent.
Example 12
A50 mL autoclave was charged with 5mL of toluene, 1 mmol of iodobenzene, 1.2 mmol of phenylacetylene, 2.0 mmol of triethylamine, and 0.5 mol% of benzimidazole N-heterocyclic carbene palladium metal complex (relative to the iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 80 ℃ by using a temperature controller, reacting for 18 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1, 3-diphenyl-2-propyne-1-ketone is more than 99 percent, and the separation yield is 83 percent.
Example 13
A50 mL autoclave was charged with 5mL of toluene, 1 mmol of iodobenzene, 1.2 mmol of phenylacetylene, 2.0 mmol of triethylamine, and 0.5 mol% of benzimidazole N-heterocyclic carbene palladium metal complex (relative to iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 1.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 18 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1, 3-diphenyl-2-propyne-1-ketone is more than 99 percent, and the separation yield is 82 percent.
Example 14
A50 mL autoclave was charged with 5mL of toluene, 1 mmol of iodobenzene, 1.2 mmol of phenylacetylene, 2.0 mmol of triethylamine, and 0.25mol% of benzimidazole N-heterocyclic carbene palladium metal complex (relative to the iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 18 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1, 3-diphenyl-2-propyne-1-ketone is more than 99 percent, and the separation yield is 92 percent.
Example 15
A50 mL autoclave was charged with 5mL of toluene, 1 mmol of iodobenzene, 1.2 mmol of phenylacetylene, 2.0 mmol of triethylamine, and 0.5 mol% of benzimidazole N-heterocyclic carbene palladium metal complex (relative to the iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 4 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1, 3-diphenyl-2-propyne-1-ketone is more than 99 percent, and the separation yield is 55 percent.
Example 16
A50 mL autoclave was charged with 5mL of toluene, 1 mmol of iodobenzene, 1.2 mmol of phenylacetylene, 2.0 mmol of triethylamine, and 0.5 mol% of benzimidazole N-heterocyclic carbene palladium metal complex (relative to the iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 6 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1, 3-diphenyl-2-propyne-1-ketone is more than 99 percent, and the separation yield is 85 percent.
Example 17
A50 mL autoclave was charged with 5mL of toluene, 1 mmol of iodobenzene, 1.2 mmol of phenylacetylene, 2.0 mmol of triethylamine, and 0.5 mol% of benzimidazole N-heterocyclic carbene palladium metal complex (relative to the iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 12 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1, 3-diphenyl-2-propyne-1-ketone is more than 99 percent, and the separation yield is 95 percent.
Example 18
A50 mL autoclave was charged with 5mL of toluene, 1 mmol of 2-methyl iodobenzene, 1.2 mmol of phenylacetylene, 2.0 mmol of triethylamine, and 0.5 mol% of benzimidazole N-heterocyclic carbene palladium metal complex (relative to iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 18 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1- (2-tolyl) -3-phenyl-2-propyne-1-one is more than 99 percent, and the separation yield is 75 percent.
1H NMR (400 MHz, CDCl3) δ 8.23 (dd, J = 7.8, 1.2 Hz, 1H), 7.59 (m, 2H), 7.35 (m, 5H), 7.20 (m, 1H), 2.61 (s, 3H)。
13C NMR (100 MHz, CDCl3) δ 179.80 (s), 140.51 (s), 135.76 (s), 133.19 (s), 132.94 (s), 132.19 (s), 130.60 (s), 128.66 (s), 125.90 (s), 120.38 (s), 91.82 (s), 88.40 (s), 21.96 (s)。
HRMS (ESI) calcd. for C16H13O [M+H]: 221.0961, found: 221.0961。
IR (KBr, cm−1) 2934, 2203, 1642, 1321, 1004, 725。
Example 19
A50 mL autoclave was charged with 5mL of toluene, 1 mmol of 3-methyl iodobenzene, 1.2 mmol of phenylacetylene, 2.0 mmol of triethylamine, and 0.5 mol% of benzimidazole N-heterocyclic carbene palladium metal complex (relative to iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 18 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1- (3-tolyl) -3-phenyl-2-propyne-1-one is more than 99 percent, and the separation yield is 98 percent.
1H NMR (400 MHz, CDCl3) δ 8.23 (dd, J = 7.8, 1.2 Hz, 1H), 7.59 (m, 2H), 7.35 (m, 5H), 7.20 (m, 1H), 2.61 (s, 3H)。
13C NMR (100 MHz, CDCl3) δ 179.80 (s), 140.51 (s), 135.76 (s), 133.19 (s), 132.94 (s), 132.19 (s), 130.60 (s), 128.66 (s), 125.90 (s), 120.38 (s), 91.82 (s), 88.40 (s), 21.96 (s)。
HRMS (ESI) calcd. for C16H13O [M+H]: 221.0961, found: 221.0961。
IR (KBr, cm−1) 2934, 2203, 1642, 1321, 1004, 725。
Example 20
A50 mL autoclave was charged with 5mL of toluene, 1 mmol of 4-methyl iodobenzene, 1.2 mmol of phenylacetylene, 2.0 mmol of triethylamine, and 0.5 mol% of benzimidazole N-heterocyclic carbene palladium metal complex (relative to iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 18 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1- (4-tolyl) -3-phenyl-2-propyne-1-one is more than 99 percent, and the separation yield is 87 percent.
1H NMR (400 MHz, CDCl3) δ 7.99 (d, J = 8.2 Hz, 2H), 7.54 (dd, J = 8.3, 1.4 Hz, 2H), 7.30 (m, 3H), 7.17 (d, J = 8.0 Hz, 2H), 2.30 (s, 3H)。
13C NMR (100 MHz, CDCl3) δ 177.68 (s), 145.28 (s), 134.64 (s), 133.05 (s), 130.74 (s), 129.72 (s), 129.40 (s), 128.71 (s), 120.25 (s), 92.63 (s), 87.04 (s), 21.86 (s)。
HRMS (ESI) calcd. for C16H13O [M+H]: 221.0961, found: 221.0953。
IR (KBr, cm−1) 2913, 2203, 1637, 1288, 1009, 765。
Example 21
A50 mL autoclave was charged with 5mL of toluene, 1 mmol of 4-methoxyiodobenzene, 1.2 mmol of phenylacetylene, 2.0 mmol of triethylamine, and 0.5 mol% of benzimidazole N-heterocyclic carbene palladium metal complex (relative to iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 18 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1- (4-methoxyphenyl) -3-phenyl-2-propyne-1-one is more than 99 percent, and the separation yield is 70 percent.
1H NMR (400 MHz, CDCl3) δ 8.20 (d, J = 8.9 Hz, 2H), 7.68 (d, J = 6.8 Hz, 2H), 7.44 (m, 3H), 6.99 (d, J = 8.9 Hz, 2H), 3.90 (s, 3H).
13C NMR (100 MHz, CDCl3) δ 55.6, 86.9, 92.3, 113.9, 120.4, 128.7, 130.3, 130.6,132.0, 133.0, 164.5, 176.7.
HRMS (ESI) calcd.for C17H15O2 [M+H]: 251.1073, found: 251.1076.
IR (KBr, cm−1) 2203, 1630, 1487, 1254, 1004, 750
Example 22
A50 mL autoclave was charged with 5mL of toluene, 1 mmol of 3-methoxyiodobenzene, 1.2 mmol of phenylacetylene, 2.0 mmol of triethylamine, and 0.5 mol% of benzimidazole N-heterocyclic carbene palladium metal complex (relative to iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 18 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, and obtaining the target product 1- (3-methoxyphenyl) -3-phenyl-2-propyne-1-one with the selectivity of more than 99 percent and the separation yield of 85 percent.
1H NMR (400 MHz, CDCl3) δ 7.76 (m, 1H), 7.58 (m, 3H), 7.33 (tdd, J = 8.5, 6.8, 3.7 Hz, 4H), 7.07 (ddd, J = 8.2, 2.7, 0.9 Hz, 1H), 3.77 (s, 3H)。
13C NMR (101 MHz, CDCl3) δ 176.69 (s), 158.78 (s), 137.22 (s), 132.03 (s), 129.78 (s), 128.62 (s), 127.66 (s), 121.79 (s), 119.88 (s), 119.06 (s), 111.84 (s), 91.94 (s), 85.94 (s), 54.42 (s)。
HRMS (ESI) calcd. for C17H15O2 [M+H]: 251.1073, found: 251.1076。
IR (KBr, cm−1) 2203, 1634, 1521, 1302, 1159, 757。
Example 23
A50 mL autoclave was charged with 5mL of toluene, 1 mmol of 2-methoxyiodobenzene, 1.2 mmol of phenylacetylene, 2.0 mmol of triethylamine, and 0.5 mol% of benzimidazole N-heterocyclic carbene palladium metal complex (relative to iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 18 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1- (2-methoxyphenyl) -3-phenyl-2-propyne-1-one is more than 99 percent, and the separation yield is 80 percent.
1H NMR (400 MHz, CDCl3) δ 7.95 (m, 1H), 7.48 (m, 2H), 7.39 (dd, J = 8.3, 7.4 Hz, 1H), 7.26 (m, 3H), 6.89 (m, 2H), 3.80 (d, J = 2.1 Hz, 3H)。
13C NMR (100 MHz, CDCl3) δ 176.70 (s), 159.85 (s), 135.16 (s), 132.96 (s), 132.56 (s), 130.54 (s), 128.66 (s), 126.68 (s), 120.64 (s), 120.35 (s), 112.30 (s), 91.63 (s), 89.31 (s), 55.93 (s)。
HRMS (ESI) calcd. for C17H15O2 [M+Na]: 259.0735, found: 259.0715。
IR (KBr, cm−1) 2203, 1630, 1268, 1016, 757。
Example 24
A50 mL autoclave was charged with 5mL of toluene, 1 mmol of 4-fluoroiodobenzene, 1.2 mmol of phenylacetylene, 2.0 mmol of triethylamine, and 0.5 mol% of benzimidazole N-heterocyclic carbene palladium metal complex (relative to iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 18 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1- (4-fluorophenyl) -3-phenyl-2-propyne-1-ketone is more than 99 percent, and the separation yield is 90 percent.
1H NMR (400 MHz, CDCl3) δ 8.11 (dd, J = 8.9, 5.4 Hz, 2H), 7.54 (dd, J= 8.3, 1.3 Hz, 2H), 7.31 (m, 3H), 7.05 (m, 2H)。
13C NMR (100 MHz, CDCl3) δ 176.68 (s), 164.51 (s), 132.97 (s), 132.00 (s), 130.58 (s), 130.36 (s), 128.66 (s), 120.40 (s), 113.90 (s), 92.31 (s), 86.95 (s), 55.61 (s)。
HRMS (ESI) calcd. for C15H10FO [M+H]: 225.0710, found: 225.0705。
IR (KBr, cm−1) 2210, 1630, 1222, 1028, 845, 730。
Example 25
A50 mL autoclave was charged with 5mL of toluene, 1 mmol of 4-chloroiodobenzene, 1.2 mmol of phenylacetylene, 2.0 mmol of triethylamine, and 0.5 mol% of benzimidazole N-heterocyclic carbene palladium metal complex (relative to iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 18 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1- (4-chlorphenyl) -3-phenyl-2-propyne-1-ketone is more than 99 percent, and the separation yield is 79 percent.
1H NMR (400 MHz, CDCl3)δ 8.15-8.17 (m, 2H), 7.68-7.70 (m, 3H), 7.42-7.7.51 (m,5H)。
13C NMR (100 MHz, CDCl3) δ 86.6, 93.6, 12.0, 128.7, 129.0, 130.9, 131.0, 133.1,135.3, 140.7 176.7。
HRMS (ESI) calcd. for C15H10ClO [M+H]: 241.0415, found: 241.0407。
IR (KBr, cm−1) 2203, 1657, 1213, 1002, 743, 675。
Example 26
A50 mL autoclave was charged with 5mL of toluene, 1 mmol of 4-trifluoromethyl iodobenzene, 1.2 mmol of phenylacetylene, 2.0 mmol of triethylamine, and 0.5 mol% of benzimidazole N-heterocyclic carbene palladium metal complex (relative to iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 18 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1- (4-trifluoromethylphenyl) -3-phenyl-2-propyne-1-ketone is more than 99 percent, and the separation yield is 95 percent.
1H NMR (400 MHz, CDCl3) δ 8.31 (d, J = 8.1 Hz, 2H), 7.77 (d, J = 8.2 Hz, 2H), 7.69 (m, 2H), 7.50 (t, J = 7.4 Hz, 1H), 7.43 (m, 2H)。
13C NMR (100 MHz, CDCl3) δ 176.66 (s), 139.40 (s), 133.21 (s), 131.21 (s), 129.80 (s), 128.80 (s), 125.70 (d, J = 3.7 Hz), 119.68 (s), 94.47 (s), 86.60 (s)。
Example 27
A50 mL autoclave was charged with 5mL of toluene, 1 mmol of 1-iodonaphthalene, 1.2 mmol of phenylacetylene, 2.0 mmol of triethylamine, and 0.5 mol% of benzimidazole N-heterocyclic carbene palladium metal complex (relative to iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 18 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1- (1-naphthyl) -3-phenyl-2-propyne-1-one is more than 99 percent, and the separation yield is 92 percent.
1H NMR (400 MHz, CDCl3) δ 8.31 (d, J = 8.1 Hz, 2H), 7.77 (d, J = 8.2 Hz, 2H), 7.69 (m, 2H), 7.50 (t, J = 7.4 Hz, 1H), 7.43 (m, 2H)。
13C NMR (100 MHz, CDCl3) δ 176.66 (s), 139.40 (s), 133.21 (s), 131.21 (s), 129.80 (s), 128.80 (s), 125.70 (d, J = 3.7 Hz), 119.68 (s), 94.47 (s), 86.60 (s)。
Example 28
A50 mL autoclave was charged with 5mL of toluene, 1 mmol of methyl 4-iodobenzoate, 1.2 mmol of phenylacetylene, 2.0 mmol of triethylamine, and 0.5 mol% of benzimidazole N-heterocyclic carbene palladium metal complex (relative to iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 18 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1- (4-methyl formate phenyl) -3-phenyl-2-propyne-1-ketone is more than 99 percent, and the separation yield is 66 percent.
1H NMR (400 MHz, CDCl3) δ 8.19 (m, 2H), 8.10 (m, 2H), 7.62 (dd, J = 5.2, 3.3 Hz, 2H), 7.38 (m, 3H), 3.88 (d, J = 4.0 Hz, 3H)。
13C NMR (100 MHz, CDCl3)δ 176.17 (s), 165.10 (s), 138.89 (s), 133.66 (s), 132.16 (s), 130.08 (s), 128.79 (s), 128.38 (s), 127.75 (s), 118.78 (s), 93.17 (s), 85.79 (s), 51.52 (s)。
IR (KBr, cm−1) 2210, 1734, 1637, 1281, 1111, 702
Example 29
A50 mL autoclave was charged with 5mL of toluene, 1 mmol of iodobenzene, 1.2 mmol of 4-fluoroacetylene, 2.0 mmol of triethylamine, and 0.5 mol% of benzimidazole N-heterocyclic carbene palladium metal complex (relative to the iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 18 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1-phenyl-3- (4-fluorophenyl) -2-propyne-1-ketone is more than 99 percent, and the separation yield is 88 percent.
1H NMR (400 MHz, CDCl3) δ 8.21 (m, 2H), 7.69 (m, 3H), 7.53 (t, J = 7.6 Hz, 2H), 7.13 (t, J = 8.7 Hz, 2H)。
13C NMR (100 MHz, CDCl3) δ 177.90 (s), 165.31 (s), 162.79 (s), 136.84 (s), 135.37 (d, J = 9.0 Hz), 134.19 (s), 129.56 (s), 128.67 (s), 116.38 (s), 116.16 (s), 91.98 (s), 86.83 (s)。
HRMS (ESI) calcd.for C15H10FO, 225.0710; found 225.0716。
IR (KBr, cm−1) 2199, 1648, 1259, 1012, 775。
Example 30
A50 mL autoclave was charged with 5mL of toluene, 1 mmol of iodobenzene, 1.2 mmol of 4-bromophenylacetylene, 2.0 mmol of triethylamine, and 0.5 mol% of benzimidazole N-heterocyclic carbene palladium metal complex (relative to iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 18 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1-phenyl-3- (4-bromophenyl) -2-propyne-1-one is more than 99 percent, and the separation yield is 65 percent.
1H NMR (400 MHz, CDCl3) δ 8.13 (dd, J = 8.3, 1.2 Hz, 2H), 7.56 (m, 1H), 7.47 (m, 6H)。
13C NMR (100 MHz, CDCl3) δ 177.82 (s), 136.74 (s), 134.32 (d, J = 6.8 Hz), 132.13 (s), 130.59 (s), 129.60 (s), 125.62 (s), 119.08 (s), 91.65 (s), 87.70 (s)。
HRMS (ESI) calculated for C15H9BrO[M+H]+, 284.9915; found284.9918。
IR (KBr, cm−1) 2208, 1654, 1254, 1012, 775。
Example 31
A50 mL autoclave was charged with 5mL of toluene, 1 mmol of iodobenzene, 1.2 mmol of 4-methylphenylacetylene, 2.0 mmol of triethylamine, and 0.5 mol% of benzimidazole N-heterocyclic carbene palladium metal complex (relative to the iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 18 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1-phenyl-3- (4-tolyl) -2-propyne-1-one is more than 99 percent, and the separation yield is 98 percent.
1H NMR (400 MHz, CDCl3) δ 8.12 (dd, J = 8.3, 1.3 Hz, 2H), 7.46 (m, 5H), 7.11 (d, J = 8.0 Hz, 2H), 2.28 (s, 3H)。
13C NMR (100 MHz, CDCl3) δ 176.99 (s), 140.53 (s), 135.92 (s), 132.97 (s), 132.07 (s), 128.47 (d, J = 3.0 Hz), 127.55 (s), 115.93 (s), 92.79 (s), 85.75 (s), 76.37 (s), 76.05 (s), 75.73 (s), 20.71 (s)。
HRMS (ESI) calcd. for C16H13O [M+H]+: 221.0961, found: 221.0953。
IR (KBr, cm−1) 2203, 1637, 1275, 1008, 811, 702。
Example 32
A50 mL autoclave was charged with 5mL of toluene, 1 mmol of iodobenzene, 1.2 mmol of 4-ethylphenylacetylene, 2.0 mmol of triethylamine, and 0.5 mol% of benzimidazole N-heterocyclic carbene palladium metal complex (relative to the iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 18 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1-phenyl-3- (4-ethylphenyl) -2-propyne-1-one is more than 99 percent, and the separation yield is 85 percent.
1H NMR (400 MHz, CDCl3) δ 8.23 (m, 2H), 7.62 (dd, J = 11.6, 4.6 Hz, 3H), 7.52 (t, J = 7.6 Hz, 2H), 7.26 (m, 2H), 2.70 (q, J = 7.6 Hz, 2H), 1.26 (t, J = 7.6 Hz, 3H)。
13C NMR (101 MHz, CDCl3) δ 178.10 (s), 147.78 (s), 137.04 (s), 134.00 (s), 133.26 (s), 129.57 (s), 128.60 (s), 128.33 (s), 117.27 (s), 93.86 (s), 86.78 (s), 29.06 (s), 15.18 (s)。
HRMS (ESI) calculated for C17H15O[M+H]+:235.1117; found 235.1112。
IR (KBr, cm−1)2194, 1630, 1209, 1171, 1007, 696。
Example 33
A50 mL autoclave was charged with 5mL of toluene, 1 mmol of iodobenzene, 1.2 mmol of 4-n-butylbenzene acetylene, 2.0 mmol of triethylamine, and 0.5 mol% of benzimidazole N-heterocyclic carbene palladium metal complex (relative to iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 18 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1-phenyl-3- (4-n-butylphenyl) -2-propyne-1-ketone is more than 99 percent, and the separation yield is 97 percent.
1H NMR (400 MHz, CDCl3) δ 8.09 (m, 2H), 7.42 (dd, J = 34.5, 7.9 Hz, 5H), 7.08 (d, J = 8.2 Hz, 2H), 2.49 (m, 2H), 1.46 (dd, J = 8.6, 6.8 Hz, 2H), 1.21 (dd, J = 15.0, 7.4 Hz, 2H), 0.79 (d, J = 7.4 Hz, 3H)。
13C NMR (100 MHz, CDCl3) δ 178.00 (s), 146.54 (s), 137.03 (s), 134.04 (s), 133.20 (s), 129.55 (s), 128.89 (s), 128.63 (s), 117.20 (s), 93.91 (s), 86.86 (s), 77.53 (s), 77.21 (s), 76.90 (s), 35.80 (s), 33.24 (s), 22.34 (s), 13.95 (s)。
HRMS (ESI) calcd. for C19H19O [M+H]+: 263.1430, found: 263.1440。
IR (KBr, cm−1 ) 2926, 2203, 1644, 1288, 1009, 695。
Example 34
A50 mL autoclave was charged with 5mL of toluene, 1 mmol of iodobenzene, 1.2 mmol of 4-tert-butylacetylene, 2.0 mmol of triethylamine, and 0.5 mol% of benzimidazole N-heterocyclic carbene palladium metal complex (relative to the iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 18 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1-phenyl-3- (4-tert-butylphenyl) -2-propyne-1-ketone is more than 99 percent, and the separation yield is 90 percent.
1H NMR (400 MHz, CDCl3) δ 8.23 (dd, J = 8.3, 1.2 Hz, 2H), 7.61 (t, J = 8.5 Hz, 3H), 7.50 (t, J = 7.6 Hz, 2H), 7.43 (d, J = 8.5 Hz, 2H), 1.33 (s, 9H)。
13C NMR (100 MHz, CDCl3) δ 178.07 (s), 154.61 (s), 137.05 (s), 134.03 (s), 133.03 (s), 129.57 (s), 128.63 (s), 125.79 (s), 117.07 (s), 93.82 (s), 86.80 (s), 35.12 (s), 31.08 (s)。
HRMS (ESI) calculated for C19H19O[M+H]+:263.1430; found 263.1435。
IR (KBr, cm−1)2195, 1650, 1597, 1509, 1298, 839, 705。
Example 35
A50 mL autoclave was charged with 5mL of toluene, 1 mmol of iodobenzene, 1.2 mmol of 4-methoxyphenylacetylene, 2.0 mmol of triethylamine, and 0.5 mol% of benzimidazole N-heterocyclic carbene palladium metal complex (relative to the iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 18 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1-phenyl-3- (4-methoxyphenyl) -2-propyne-1-one is more than 99 percent, and the separation yield is 95 percent.
1H NMR (400 MHz, CDCl3) δ 8.12 (m, 2H), 7.49 (m, 5H), 6.84 (m, 2H), 3.75 (s, 3H)。
13C NMR (100 MHz, CDCl3) δ 178.05 (s), 161.77 (s), 137.07 (s), 135.18 (s), 133.94 (s), 129.50 (s), 128.59 (s), 114.46 (s), 111.89 (s), 94.37 (s), 86.91 (s), 77.41 (s), 77.10 (s), 76.78 (s), 55.46 (s)。
HRMS (ESI) calcd. for C16H13O2 [M+H]+: 237.0910, found: 237.0906。
IR (KBr, cm−1 ) 2920, 2203, 1657, 1288, 1002, 839, 689。
Example 36
A50 mL autoclave was charged with 5mL of toluene, 1 mmol of iodobenzene, 1.2 mmol of 4-n-pentyloxyphenylacetylene, 2.0 mmol of triethylamine, and 0.5 mol% of benzimidazole N-heterocyclic carbene palladium metal complex (relative to the iodobenzene). The reaction kettle is sealed, replaced by carbon monoxide for 3 times, and the reactor is sealed. Introducing CO gas under the pressure of 2.0 MPa, slowly raising the temperature to 100 ℃ by using a temperature controller, reacting for 18 hours, cooling to room temperature, discharging the kettle, carrying out qualitative analysis on the liquid obtained by the reaction by using an Agilent 6890/5973 gas chromatograph-mass spectrometer, wherein the selectivity of the target product 1-phenyl-3- (4-n-pentyloxyphenyl) -2-propyn-1-one is more than 99 percent, and the separation yield is 90 percent.
1H NMR (400 MHz, CDCl3) δ 8.13 (m, 2H), 7.53 (m, 3H), 7.43 (d, J = 7.8 Hz, 2H), 6.82 (d, J = 8.8 Hz, 2H), 3.89 (t, J = 6.6 Hz, 2H), 1.71 (m, 2H), 1.32 (dd, J = 7.8, 4.7 Hz, 4H), 0.85 (t, J = 7.1 Hz, 3H)。
13C NMR (100 MHz, CDCl3) δ 178.04 (s), 161.42 (s), 137.11 (s), 135.18 (s), 133.89 (s), 129.49 (s), 128.57 (s), 114.92 (s), 111.58 (s), 94.58 (s), 86.92 (s), 68.27 (s), 28.80 (s), 28.14 (s), 22.44 (s), 14.02 (s)。
HRMS (ESI) calcd.for C20H21O2[M+H]: 293.1542; found 293.1549。
IR (KBr, cm−1) 2208, 1634, 1254, 1012, 785。
Claims (3)
1. The pyrene-labeled benzimidazole nitrogen heterocyclic carbene palladium metal complex is characterized in that: the pyrene-labeled benzimidazole nitrogen heterocyclic carbene palladium metal complex prepared by taking benzimidazole as a framework and pyridine as an axial ligand has the structural formula:
。
2. the method for preparing pyrene-labeled benzimidazole n-heterocyclic carbene palladium metal complex according to claim 1, comprising the following steps:
synthesizing 1- (2-bromoethoxy) pyrene:
taking acetone as a solvent, and mixing 1-hydroxypyrene, cesium carbonate and 1, 2-dibromoethane according to a molar ratio of 1: 1.5-2.5: 3.5-4.5, heating at 60-80 ℃, reacting under reflux for 4-15 hours, and separating and purifying the product after the reaction is finished to obtain 1- (2-bromoethoxy) pyrene;
synthesizing 1-pyreneoxyethyl benzimidazole:
taking acetonitrile as a reaction solvent, and mixing the 1- (2-bromoethoxy) pyrene, benzimidazole and potassium hydroxide according to a molar ratio of 1: 1.3-2.0: 1.1-1.5, heating at 80-100 ℃, reacting under reflux for 20-30 hours, and separating and purifying the product after the reaction is finished to obtain 1-pyreneoxyethyl benzimidazole;
synthesizing 1-pyreneoxyethyl-3-benzyl benzimidazole bromide:
taking acetonitrile as a reaction solvent, and reacting the 1-pyreneoxyethyl benzimidazole and benzyl bromide according to a molar ratio of 1: 1.0 to 1.5, and heating, reacting and refluxing for 20 to 30 hours at a temperature of between 80 and 100 ℃; separating and purifying the product after the reaction is finished to obtain 1-pyreneoxyethyl-3-benzyl benzimidazole bromide;
step four, synthesizing a pyrene-marked benzimidazole nitrogen heterocyclic carbene palladium metal complex:
taking pyridine as a reaction solvent, and reacting palladium chloride, the 1-pyreneoxyethyl-3-benzyl benzimidazole bromide, potassium carbonate and potassium bromide in a molar ratio of 1: 1.0-1.5: 3-10: 8-20, heating and refluxing for 20-30 hours at 80-100 ℃, and separating and purifying the product after the reaction is finished to obtain the pyrene-labeled benzimidazole nitrogen heterocyclic carbene palladium metal complex.
3. The application of the pyrene-labeled benzimidazole N-heterocyclic carbene palladium metal complex as claimed in claim 1, wherein: the pyrene-labeled benzimidazole nitrogen heterocyclic carbene palladium metal complex is used as a catalyst to synthesize an intermediate alpha, beta-unsaturated alkynone in a one-step reaction in a Sonogashira carbonylation reaction of three components of aryl iodide, carbon monoxide and terminal alkyne; the addition amount of the benzimidazole nitrogen heterocyclic carbene palladium metal complex is 0.5-3 mol% of the molar amount of the iodo-aromatic hydrocarbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910139773.0A CN109810147B (en) | 2019-02-26 | 2019-02-26 | Pyrene-labeled benzimidazole nitrogen heterocyclic carbene palladium metal complex, and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910139773.0A CN109810147B (en) | 2019-02-26 | 2019-02-26 | Pyrene-labeled benzimidazole nitrogen heterocyclic carbene palladium metal complex, and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109810147A CN109810147A (en) | 2019-05-28 |
| CN109810147B true CN109810147B (en) | 2021-02-26 |
Family
ID=66607537
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910139773.0A Active CN109810147B (en) | 2019-02-26 | 2019-02-26 | Pyrene-labeled benzimidazole nitrogen heterocyclic carbene palladium metal complex, and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109810147B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11691135B2 (en) * | 2020-10-15 | 2023-07-04 | King Fahd University Of Petroleum & Minerals | Synthesis of alkynones via carbonylative Sonogashira coupling reactions catalyzed by Pd(II)-N-Heterocyclic carbene-pyridine complexes |
| CN112275322B (en) * | 2020-11-03 | 2022-01-25 | 中国科学院兰州化学物理研究所 | Preparation method and application of supported CNTs @ NHC-Cu catalytic material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104607248A (en) * | 2015-01-23 | 2015-05-13 | 齐鲁工业大学 | Pyrene-4,5,9,10-quadri-imine-(arylamine) palladium chloride and application thereof in Heck reaction |
-
2019
- 2019-02-26 CN CN201910139773.0A patent/CN109810147B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104607248A (en) * | 2015-01-23 | 2015-05-13 | 齐鲁工业大学 | Pyrene-4,5,9,10-quadri-imine-(arylamine) palladium chloride and application thereof in Heck reaction |
Non-Patent Citations (3)
| Title |
|---|
| Aryl-palladium-NHC complex: efficient phosphine-free catalyst precursors for the carbonylation of aryl iodides with amines or alkynes;Chunyan Zhang et al.;《Org. Biomol. Chem.》;20141017;第12卷;9702-9706页 * |
| Novel (N‐heterocyclic carbene)Pd(pyridine)Br2 complexes for carbonylative Sonogashira coupling reactions: Catalytic efficiency and scope for arylalkynes, alkylalkynes and dialkynes;Mansur Ibrahim et al.;《Appl Organometal Chem.》;20180228;e4280 * |
| Phenylene- and Biphenylene-Bridged Bis-Imidazolylidenes of Palladium. Influence of the Presence of Pyrene Tags on the Catalytic Activity of the Complexes;Sheila Ruiz-Botella et al.;《Organometallics》;20140917;第33卷;5509-5516页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109810147A (en) | 2019-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | pH-Responsive N-heterocyclic carbene copper (I) complexes: syntheses and recoverable applications in the carboxylation of arylboronic esters and benzoxazole with carbon dioxide | |
| CN107011145B (en) | Method for preparing 2-iodopent-2-ene-1, 4-dione derivative by visible light catalysis | |
| CN107880079B (en) | Cyclic N-heterocyclic bis-carbene-palladium complex and preparation method and application thereof | |
| CN109912809B (en) | Non-noble metal-metal organic framework composite material, preparation method and application thereof | |
| CN111393480B (en) | Gold complex containing biphosphine ortho-carborane ligand and preparation method and application thereof | |
| CN109810147B (en) | Pyrene-labeled benzimidazole nitrogen heterocyclic carbene palladium metal complex, and preparation and application thereof | |
| CN114478362A (en) | Preparation method of chiral pyridinol derivative | |
| Saito et al. | A Macrocyclic Phenanthroline–Copper Complex with Less Steric Hindrance: Synthesis, Structure, and Application to the Synthesis of a [2] Rotaxane | |
| CN109939737B (en) | Cobalt carbene catalysts, method for the production thereof, and use thereof for the catalytic hydrogenation of aldehyde and ketone compounds | |
| CN114653404B (en) | Ruthenium compound catalyst and application thereof in olefin metathesis | |
| CN103748065B (en) | The manufacture method of 2-alkenyl amine compound | |
| CN111233830B (en) | C2-sulfonylamino indole derivative and preparation method and application thereof | |
| JPWO2015170688A1 (en) | Metal-supported porous coordination polymer catalyst | |
| CN111718262B (en) | Simple preparation method of 9-hydroxyfluorene-9-carboxylic ester compound | |
| CN112694489B (en) | Preparation method of N-heterocyclic carbene copper catalyst | |
| CN107629049B (en) | Synthesis method of pyridine [2,1-a ] isoindole compound | |
| CN111039767B (en) | Method for preparing deuterated aldehyde by using triazole carbene as catalyst | |
| JP2014528911A (en) | Process for the production of palladium (I) tri-t-butylphosphine bromide dimer and process using it in isomerization reactions | |
| CN114478372A (en) | Asymmetric preparation method of pyridinol nitrogen oxide | |
| JP4413507B2 (en) | Pincer metal complex, method for producing the same, and pincer metal complex catalyst | |
| EP3438115A1 (en) | Ruthenium based complexes | |
| CN107935803B (en) | Synthetic method of 1, 2-diketone compound | |
| CN111574569A (en) | Coordination compound of rhodium, preparation method and application thereof | |
| Yuan et al. | Halide-bridged tetranuclear organocopper (i) clusters supported by indolyl-based NCN pincer ligands and their catalytic activities towards the hydrophosphination of alkenes | |
| CN113845550B (en) | Flexible large-steric-hindrance N-heterocyclic carbene palladium complex containing halogenated benzene ring, preparation method and application thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |