Copper catalyst system for decarboxylation coupling reaction

A copper catalyst, decarboxylation coupling technology, applied in physical/chemical process catalysts, organic compounds/hydrides/coordination complex catalysts, organic chemistry, etc., can solve problems such as palladium product residue, application impact, toxicity, etc., to achieve Cost reduction, environmental protection, high selectivity effect

Inactive Publication Date: 2012-08-01
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, thereby cost is higher; 2. metal palladium has stronger toxicity; So far, this compound can also get the desired coupling product under some conditions, but there are still many limitations; therefore overcoming this limitation is also an urgent technical problem in this field.
[0005] However, the above three iron-copper-catalyzed decarboxylation coupling reactions can only activate C sp -H, C sp2 -H and N-H, there is no information about C which is more difficult to activate sp3 Report on Decarboxylation Coupling Reaction of -H

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Cinnamic acid (0.5mmol), CuO (0.05mmol), and toluene (2mL) were sequentially loaded into a pressure-resistant Schlenk test tube, and the system was evacuated and replaced with argon three times. Di-tert-butyl peroxide (1mmol) was added to the device, and then the system was sealed and heated in an oil bath at 110°C for about 24 hours. After the reaction was completed, the solvent was distilled off, and after concentration, it was concentrated and passed through simple column chromatography (petroleum ether was used as the eluent). (60-90° C.)) to obtain the decarboxylation coupling product (3-phenyl-propenyl)-benzene (89.4 mg), with a yield of 92%. Its NMR data are: 1 H NMR (300MHz, CDCl 3 ) (δ, ppm) 7.40-7.28 (m, 6H), 7.26-7.15 (m, 3H), 6.46 (d, J=15.9Hz, 1H), 6.40-6.30 (m, 1H), 3.55 (d, J = 6.2Hz, 2H); 13 C NMR (75MHz, CDCl 3)(δ, ppm) 140.6, 137.9, 131.5, 129.7, 129.2, 129.1, 129.0, 127.6, 126.6, 126.6, 39.8; high-resolution mass spectrometry data are: HRMS calcd ...

Embodiment 2

[0029] 4-Chlorocinnamic acid (0.5mmol), CuO (0.05mmol), and toluene (2mL) were sequentially loaded into a pressure-resistant Schlenk test tube, and the system was evacuated and replaced with argon three times under gas protection. Di-tert-butyl peroxide (1mmol) was added into the micro-injector, and then the system was sealed and heated in an oil bath at 110°C for about 24 hours. The decarboxylation coupling product 1-chloro-4-(3-phenyl-propenyl)-benzene (101.8 mg) can be obtained by using petroleum ether (60-90° C.) with a yield of 89%. Its NMR data are: 1 H NMR (300MHz, CDCl 3 ) (δ, ppm) 7.35-7.28 (m, 2H), 7.23 (d, J = 10.2Hz, 6H), 6.44-6.26 (m, 2H), 3.53 (d, J = 5.6Hz, 2H); 13 C NMR (100MHz, CDCl 3 )(δ, ppm) 140.0, 136.1, 132.8, 130.2, 123.0, 128.8, 128.8, 128.7, 127.5, 126.4, 39.5; high-resolution mass spectrometry data is: HRMS calcd.for[C 15 h 13 Cl] + requires m / z 228.0706, found 228.0705.

Embodiment 3

[0031] 4-Fluorocinnamic acid (0.5mmol), CuO (0.05mmol), and toluene (2mL) were successively loaded into a pressure-resistant Schlenk test tube, and the system was evacuated and replaced with argon three times under gas protection. Di-tert-butyl peroxide (1mmol) was added into the micro-injector, and then the system was sealed and heated in an oil bath at 110°C for about 24 hours. The decarboxylation coupling product 1-fluoro-4-(3-phenyl-propenyl)-benzene (96.6 mg) can be obtained by using petroleum ether (60-90° C.) with a yield of 91%. Its NMR data are: 1 H NMR (300MHz, CDCl 3 ) (δ, ppm) 7.32-7.22 (m, 6Hz), 6.97 (t, J = 8.7Hz, 2H), 6.41 (d, J = 15.8Hz, 1H), 6.33-6.20 (m, 1H), 3.53 ( d, J=6.4Hz, 2H); 13 C NMR (101MHz, CDCl 3 )(δ, ppm) 162.5(d, 1 J=244.5Hz), 140.5, 134.1(d, 4 J=2.8Hz), 130.3, 129.5, 129.1 (d, 3 J=9.8Hz, ), 128.8, 128.0(d, 3 J=7.9Hz), 126.7, 115.9, (d, 2 J=21.4Hz), 39.8; The high-resolution mass spectrometry data is: HRMS calcd.for[C 15 h 13 F] + req...

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Abstract

The invention discloses a copper catalyst system for decarboxylation coupling reaction, which comprises a copper-containing compound and an oxidant in a mol ratio of 1:(10-40), wherein the copper-containing compound is one or mixture of cuprous iodide, cupric acetylacetonate, cuprous bromide, cupric sulfate and copper powder; and the oxidant is tert-butyl hydroperoxide, di-tert-butyl peroxide or dicumyl peroxide. The catalyst system can catalyze the decarboxylation coupling reaction of cinnamic acid and methylbenzene compounds to prepare olefin compounds. Compared with the existing noble-metal-containing catalyst system, the catalyst system disclosed by the invention uses the cheap copper-containing compound instead of noble metal, thereby lowering the cost; and the byproduct is only carbon dioxide, thereby being beneficial to environment protection and cost saving, and satisfying the requirement for green chemistry.

Description

technical field [0001] The invention belongs to the field of catalysts, and in particular relates to a copper catalyst system for the decarboxylation coupling reaction of cinnamic acid and toluene compounds. The catalyst system can catalyze the decarboxylation coupling reaction of cinnamic acid and toluene compounds to prepare olefin compounds. Background technique [0002] The reaction of intramolecular or intermolecular coupling of carboxylic acid, carboxylate or carboxylate compounds after removal of carbon dioxide by transition metal catalysis or alkali is usually called decarboxylative coupling reaction (Decarboxylative Coupling). After the concept of decarboxylation coupling was proposed, the German scientist Gooβen (see: Science.2006, 313, 662) and the American scientist Myers (see: J.Am.Chem.Soc.2005, 127, 10323) respectively made pioneering work. Decarboxylation coupling can form negative synthons needed in organic chemical synthesis in a new way, allowing stable a...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/28C07B37/00C07C1/20C07C15/50C07C17/263C07C25/24C07C41/30C07C43/215C07C43/225
Inventor 毛金成杨海龙朱研孙鹏
Owner SUZHOU UNIV
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