Copper catalyst system for sonogashira coupling reaction

A technology of coupling reaction and copper catalyst, which is applied in the field of copper catalyst system, can solve the problems of high reaction temperature, metal palladium toxicity, narrow substrate range, etc., and achieve the effects of low reaction temperature, cost saving and high selectivity

Inactive Publication Date: 2012-06-20
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Yet adopt above-mentioned catalyst to have following problem: 1. the price of palladium is expensive, thus cost is higher; 2. metal palladium has stronger toxicity; 3. palladium is easy to remain in the product, thus has influenced its application in occasions such as drug synthesis; 4. The above reactions usually have high reactivity for bromo-, iodo-alkenes and aromatic hydrocarbons, but for chlorinated compounds, their reactivity is often very low; although so far, this compound can also get the desired Conjugated products, but there are still many limitations; therefore overcoming this limitation is also an urgent technical problem in this field
But its disadvantages are: high amount of catalyst, too high reaction temperature, narrow substrate range
In addition, the current catalyst system can only meet the reaction of aromatic iodides, but can not do anything for aromatic bromides or chlorides which are cheap but less reactive.
Therefore, the current catalyst system is difficult to achieve large-scale application or industrial production in terms of cost, difficulty of operation and degree of danger.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] In a pressure-resistant Schlenk test tube, CuI (0.0000005 mmol), triarylphosphine (PPh 3 ) (0.02 mmol), potassium carbonate (1.0 mmol), and H 2 O (3 mL), the system was evacuated and replaced with argon three times. Under gas protection, iodobenzene (0.5 mmol) and phenylacetylene (0.6 mmol) were added with a micro-injector, and then the system was sealed and placed in Heated in an oil bath at 85°C for about 24 hours, first added 4 mL of water to quench the reaction, then extracted with ethyl acetate (4 mL×3), combined the organic phases and dried with anhydrous sodium sulfate, concentrated and passed simple column chromatography (Petroleum ether (60-90°C) was used as the eluent) to obtain the coupling product 1,2-diphenylacetylene (88.5 mg), with a yield of 99%. The melting point is 58~59°C. GC-MS showed that no alkyne self-coupling product was detected in the system after the reaction. Its NMR data are: 1 H NMR (CDCl 3, 400MHz) (δ, ppm) 7.59-7.48 (m, 4H), 7.39-7.2...

Embodiment 2

[0030] In a pressure-resistant Schlenk test tube, CuI (0.0000005 mmol), PPh 3 (0.02 mmol), potassium carbonate (1.0 mmol), and H 2 O (3 mL), the system was evacuated and replaced with argon three times. Under gas protection, p-chloroiodobenzene (0.5 mmol) and phenylacetylene (0.6 mmol) were added with a micro-injector. Then the system was sealed and heated in an oil bath at 85°C for about 24 hours. First, 4 mL of water was added to quench the reaction, and then extracted with ethyl acetate (4 mL×3). The organic phases were combined and dried with anhydrous sodium sulfate. After concentration, The coupling product 4-chlorophenylethynylbenzene (105.2 mg) was obtained by simple column chromatography (petroleum ether (60-90°C) as the eluent), with a yield of 98%. The melting point is 83~84°C. Its NMR data are: 1 H NMR (CDCl 3 , 400MHz) (δ, ppm) 7.53 (t, J = 7.6 Hz, 2H), 7.46 (d, J = 8.4 Hz, 2H), 7.36─7.34 (m, 4H), 7.32 (s, 1H); 13 C NMR (CDCl 3 ,100 MHz) (δ, ppm) 135.9 (C)...

Embodiment 3

[0032] In a pressure-resistant Schlenk test tube, CuI (0.0000005 mmol), PPh 3 (0.02 mmol), potassium carbonate (1.0 mmol), and H 2 O (3 mL), the system was evacuated and replaced with argon three times. Under gas protection, p-methoxyiodobenzene (0.5 mmol) and 4-fluorophenylacetylene (0.6 mmol) were added with a micro-injector . Then the system was sealed and heated in an oil bath at 85°C for about 24 hours. First, 4 mL of water was added to quench the reaction, and then extracted with ethyl acetate (4 mL×3). The organic phases were combined and dried with anhydrous sodium sulfate. After concentration, The cross-coupling product 1fluoro-4-(2-(4-methoxyphenyl)ethynyl)benzene (113.1 mg ), the yield was 99%. Its NMR data are: 1 H NMR (CDCl 3 , 400MHz) (δ, ppm) 3.84 (s, OCH 3 ), 6.89 (d, J = 8.8 Hz, 2H, ArH), 7.02-7.06 (m, 2H, ArH), 7.46-7.51 (m, 4H, ArH ); 13 C NMR (CDCl 3 ,75 MHz) (δ, ppm) 164.2 (d, J = 247.5 Hz, C), 159.9 (CH), 133.5 (d, J = 7.5 Hz, CH), 133.2 (CH), 11...

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Abstract

The invention discloses a copper catalyst system for sonogashira coupling reaction. The copper catalyst system comprises copper salt, phosphine ligands and inorganic alkaline according to a mol ratio of 1: (50000-200000): (200000-1000000), wherein the copper salt is selected from one kind of materials or a mixture of more than one kind of materials from copper iodide, copper acetylacetonate, copper bromide, copper sulfate and copper powder, and the phosphine ligands are trivalent phosphine ligands. The invention discloses the novel copper catalyst system for sonogashira coupling reaction. Compared with the existing noble-metal-containing catalyst system, the catalyst system has the advantages that the cheap copper salt is used for replacing the noble metal, the cost is greatly reduced, inaddition, the environmental-friendly water can be adopted as reaction solvents, the environment is favorably protected, the cost is favorably saved, and the reaction also obtains great progress in green chemistry.

Description

technical field [0001] The invention belongs to the field of catalysts, and in particular relates to a copper catalyst system used for the sordium coupling reaction, which can catalyze the sormonium coupling reaction in water to prepare alkyne compounds. Background technique [0002] Catalyzed terminal alkynes and sp by Pd / Cu hybrid catalyst 2 The cross-coupling reaction between carbon halides (aryl halohydrocarbons) is usually called Sonogashira coupling reaction (Sonogashira reaction for short). This reaction was first discovered independently by Heck, Cassar and Sonogashira in 1975. After nearly 30 years of development, it has gradually become known to people and has become an important name reaction. At present, the Sonogashira reaction has been widely used in the synthesis of substituted alkynes and large conjugated alkynes, and is considered to be the most effective and direct method for the synthesis of alkyne compounds. It has been widely used in the synthesis of m...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B37/04C07C15/54C07C2/86C07C17/266C07C25/24C07C43/225C07C43/215C07C41/30C07C15/48C07C15/58C07C22/08C07C205/06C07C201/12C07C211/45C07C209/68C07C67/293C07C69/07C07C69/157
Inventor 毛金成李廷义屈孝铭孙鹏
Owner SUZHOU UNIV
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