Adenaphtho-imidazolyl nitrogen heterocyclic carbene metal palladium complex catalyst and preparation and application thereof

A technology of acenaphthoimidazolyl nitrogen and heterocyclic carbene, which is applied in the field of metal ligand catalysts and chemical synthesis, to achieve the effects of mild reaction conditions, promotion of catalytic cycle, and enhancement of σ electron donating ability

Inactive Publication Date: 2019-05-24
LANZHOU INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Abstract
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  • Application Information

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Problems solved by technology

However, there are relatively few examples of the application of azacarbene transition metal complexes in carbonylation reactions, especially the application of catalyzing o-iodoaniline, terminal alkynes, and carbon monoxide carbonylation to obtain 4-quinolones has not been reported.

Method used

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  • Adenaphtho-imidazolyl nitrogen heterocyclic carbene metal palladium complex catalyst and preparation and application thereof
  • Adenaphtho-imidazolyl nitrogen heterocyclic carbene metal palladium complex catalyst and preparation and application thereof
  • Adenaphtho-imidazolyl nitrogen heterocyclic carbene metal palladium complex catalyst and preparation and application thereof

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Experimental program
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Effect test

Embodiment 1

[0039] Embodiment 1: Synthesis of acenaphthoimidazolyl nitrogen heterocyclic carbene metal palladium complex Pd-NHC-1

[0040] (1) Synthesis of α-diimine compounds: Weigh 0.7g (3.84 mmol) of acenaphthenequinone into a 100mL three-neck flask, add 35mL of acetonitrile and heat at 80°C for 15 minutes, then add 6.5mL of glacial acetic acid. Also in a beaker, dissolve 1.63 g (9.2 mmol) of 2,6-diisopropylaniline with 30 mL of acetonitrile and pour it into a constant pressure burette. After the acenaphthylquinone is completely dissolved, slowly drop the acetonitrile solution substituted for aniline into the three-necked flask, the reaction device is carried out under the protection of nitrogen, continue to heat and react for 5 hours, cool at room temperature, filter, and wash with n-hexane to obtain α-diimine compounds The target product is 1.78 g, and the yield is 92%.

[0041](2) Synthesis of azacyclic carbene salt (imidazolium salt): add 1.00 g (2 mmol) of α-diimine compound, 3.2...

Embodiment 2

[0045] Embodiment 2: Synthesis of acenaphthoimidazolyl nitrogen heterocyclic carbene metal palladium complex Pd-NHC-2

[0046] 3-chloropyridine is replaced by pyridine, and others are the same as in Example 1. The acenaphthoimidazolyl nitrogen heterocyclic carbene metal palladium complex Pd-NHC-2 was obtained, yield: 0.280 g. Its NMR characterization data are as follows:

[0047] 1 H NMR (400 MHz, CDCl 3 ) δ 8.64 (d, J = 5.0 Hz, 2H), 7.70 (d, J = 8.3 Hz,2H), 7.63 (t, J = 7.8 Hz, 2H), 7.56 (s, 2H), 7.48 (d, J = 7.8 Hz, 4H), 7.34(m, 2H), 7.13 (m, 2H), 6.79 (d, J = 7.0 Hz, 2H), 3.42 (m, 4H), 1.46 (d, J =6.6 Hz, 12H), 0.92 (d, J = 6.9 Hz, 12H). 13 C NMR (101 MHz, CDCl 3 ) δ 151.58(s), 147.26(s), 130.59(s), 127.99(s), 127.24(s), 124.71(s), 123.97(s),122.12(s), 28.89(s), 25.79(s ), 24.29 (s).

Embodiment 3

[0048] Embodiment 3: Synthesis of 2-phenylquinolin-4(1H)-one

[0049] In an autoclave with a volume of 75 mL, add 5 mL of N,N-dimethylformamide, 1 mmol of o-iodoaniline, 1.2 mmol of phenylacetylene, 4.0 mmol of dimethylamine, and 0.5 mol% of acenaphthoimidazolyl nitrogen Heterocyclic carbene metal palladium complex Pd-NHC-1 (relative to ortho-iodoaniline). Seal the reactor, replace the reactor with carbon monoxide 3 times, and seal the reactor. The CO gas pressure is 2.0 MPa, and the temperature is controlled by the temperature controller to slowly rise to 100 o C, reacted for 15 hours, cooled to room temperature, unloaded, and the liquid obtained by the reaction was qualitatively analyzed with an Agilent 6890 / 5973 gas chromatography spectrometer, the selectivity of the target product 2-phenylquinolin-4(1H)-one was greater than 99%, separated The yield is 95%. Product characterization data are as follows:

[0050] 1 H NMR (400 MHz, DMSO) δ 11.74 (s, 1H), 8.11 (m, 1H), 7.8...

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Abstract

The invention discloses an acenaphtho-imidazolyl nitrogen heterocyclic carbene metal palladium complex catalyst, which is prepared by the following steps: 3-chloropyridine or pyridine is taken as an axial ligand, acenaphtho-imidazole salt is taken as a framework, and coordination is carried out on the 3-chloropyridine or pyridine and a metal ligand PdCl2 in the presence of potassium carbonate under the protection of nitrogen so as to obtain the acenaphtho-imidazole nitrogen heterocyclic carbene metal palladium complex catalyst. According to the acenaphtho-imidazole nitrogen heterocyclic carbene metal palladium complex, due to the introduction of the anthraquinone skeleton, the coordination of carbon 2 as atoms and metals is affected, the charge density of the metal center is increased, thesigma electron-donating capacity is enhanced, the oxidation addition reaction is facilitated, and the catalytic circulation is further promoted. The experimental results show that the selectivity ofthe carbonylation cyclization reaction is high (the selectivity is more than 99%) and the conversion rate is high (more than 85%) by using the acenaphtho-imidazole nitrogen heterocyclic carbene metalpalladium complex catalyst. In addition, the dosage of the catalyst is small, the reaction conditions are mild, the use of toxic phosphine ligands is avoided, and the method is safe and environment-friendly.

Description

technical field [0001] The present invention relates to a metal palladium complex catalyst, in particular to an acenaphthoimidazolyl nitrogen heterocyclic carbene metal palladium complex catalyst and a preparation method thereof; -The application of quinolones belongs to the technical field of chemical synthesis and the field of metal ligand catalyst. Background technique [0002] Quinolones are the most widely used synthetic antibacterial drugs in the world. In recent years, with the deepening of research on quinolones, it has been found that quinolone derivatives have many other biological properties besides antibacterial activity. Activities such as antimalarial, antituberculosis, antitumor, anxiolytic, antiischemic, anti-HSV-1, and as HIV-1 integrase inhibitor and CB2 receptor agonist (Curr Med Chem, 2009, 16: 1746 -1767). Among them, the 4-quinolone structure has become one of the popular advantageous structures in medicinal chemistry research due to its easy chemical...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/22C07D215/233
Inventor 刘建华汪兵洋杨磊夏春谷许传芝
Owner LANZHOU INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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