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Carbon-carbon cross coupling catalyzed by transition metals on solid supports

一种固体载体、偶联的技术，应用在制备二芳基化合物,偶联芳基化合物领域，能够解决难以使用、去除炭载体困难、不能大批量使用等问题

Inactive Publication Date: 2006-12-27
WYETH LLC
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] However, some of the catalysts mentioned above are expensive and generally cannot be used in large quantities
Additionally, carbon supports, including palladium on activated carbon, are difficult to work with due to the tendency of the reaction mixture to turn black, making any reaction changes that may have occurred in the reaction unclear
It is also difficult to remove the carbon support from the equipment used for the reaction

Method used

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  • Carbon-carbon cross coupling catalyzed by transition metals on solid supports

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0084] Example 1-catalyst in the preparation of 3-chloro-5-(4,4-dimethyl-2-oxo-1,4-dihydro-2H-benzo[b][1,3]oxazine-6 -base) comparison in benzonitrile

[0085] To each reaction vessel of a Mettler-Toledo(R) Bohdan parallel synthesizer was added 3-bromo-5-chlorobenzonitrile (0.42 g, 1.94 mmol), 4,4-dimethyl-2-oxo- 1,4-Dihydro-2H-benzo[b][1,3]oxazine-6-boronic acid (0.45g, 2.04mmol), soda ash (0.23g, 2.17mmol), ethanol SDA 3A 190 standard strength ( 6 mL) and 0.045 g (1 mol%) of the catalyst described in Table 1.

[0086] reaction

catalyst

Product conversion %

1

5% reduced Pd / BaSO 4

85

2

5% unreduced Pd / BaSO 4

93

3

5% unreduced Pd / CaCO 3

95

[0087] The suspension was stirred vigorously and heated to 80 °C overnight. After dilution with THF (25 mL), the diluted solution was analyzed by high performance liquid chromatography (HPLC).

[0088] As shown in Table 1, the conversion of product w...

Embodiment 2

[0090] Example 2-Solvent in the preparation of 3-chloro-5-(4,4-dimethyl-2-oxo-1,4-dihydro-2H-benzo[b by Pd on carbonate or sulfate ][1,3]Oxazin-6-yl)Comparison in benzonitrile

[0091] 4,4-Dimethyl-2-oxo-1,4-dihydro-2H-benzo[b][1,3]oxazine-6-boronic acid (0.45g, 2.04mmol) in soda ash (0.23 g, 2.17mmol) and 5% Pd / BaSO 4 or 5%Pd / CaCO 3 Heating with 3-bromo-5-chlorobenzonitrile (0.42 g, 1.94 mmol) in the presence of alcohol SDA 3A 190 standard strength gave 3-chloro-5-(4,4-dimethyl-2-oxo- 1,4-Dihydro-2H-benzo[b][1,3]oxazin-6-yl)benzonitrile in good yield and purity.

[0092] When the same reaction was carried out using tetrahydrofuran (THF) instead of alcohol, 3-chloro-5-(4,4-dimethyl-2-oxo-1,4-dihydro-2H-benzo[b] [1,3]oxazin-6-yl)benzonitrile, but when 5% Pd / BaSO 4 When used as a catalyst, the above products are contaminated with raw materials. When 5%Pd / CaCO 3 When used as a catalyst, only traces of 3-chloro-5-(4,4-dimethyl-2-oxo-1,4-dihydro-2H-benzo[b][1,3] azin-6-yl)...

Embodiment 3

[0094] Example 3-solvent in the preparation of 3-chloro-5-(4,4-dimethyl-2-oxo-1,4-dihydro-2H-benzo[b][1,3] using Pd / charcoal (Oxazin-6-yl) benzonitrile comparison

[0095] 4,4-Dimethyl-2-oxo-1,4-dihydro-2H-benzo[b][1,3]oxazine-6-boronic acid (0.45g, 2.04mmol) in soda ash (0.23 g, 2.17 mmol) and 5% Pd / C catalyst in the presence of 3-bromo-5-chlorobenzonitrile (0.42 g, 1.94 mmol) in a solvent heated together to give 3-chloro-5-(4,4-di Methyl-2-oxo-1,4-dihydro-2H-benzo[b][1,3]oxazin-6-yl)benzonitrile in good yield and purity. See Table 2.

[0096] 5%Pd / C catalyst

[0097] The inventors also noticed that when the reaction was carried out in methanol, impurities were produced. Without being bound by theory, the inventors suspect that the impurity arises from the addition of methanol to the nitrile moiety in the feed and product.

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Abstract

The present invention provides methods of coupling carbon-containing compounds using a transition metal or transition metal complex on a solid support. The solid support can include alkaline earth metal salts, including carbonate and sulfate salts. The transition metals can include palladium or nickel metal. The method can include combining two carbon containing compounds and a transition metal or transition metal complex on a solid support in the presence of a solvent, desirably an alcohol.

Description

Background of the invention [0001] The present invention relates to heterogeneous catalysts for coupling carbonaceous compounds. [0002] Homogeneous catalysts containing solubilizing ligands have been used for the coupling of carbon-containing compounds, often with high catalytic activity, leading to high yields of desired products. However, after the catalyst is used in the reaction, its removal is very difficult, especially on a large scale. Homogeneous catalysts have ligands that dissociate from the catalyst and are difficult to remove, thus creating purification problems. As a result, painstaking detection, cleanup and crystallization efforts must be undertaken to remove and / or reduce the presence of catalyst and / or reduce free ligand to acceptable levels. [0003] To avoid the use of homogeneous catalysts, heterogeneous catalysts have been used to couple carbon-containing compounds. A variety of heterogeneous catalysts are known in the art which include metals on soli...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D265/18B01J21/00B01J23/00B01J23/44B01J23/58B01J23/62B01J23/755B01J23/78B01J27/053B01J27/232B01J31/00B01J31/02B01J31/18B01J31/24C07B37/04C07C1/20C07C2/68
CPCB01J27/053C07B37/04B01J2531/90B01J23/628B01J23/78B01J23/58B01J2231/4211B01J2531/847B01J2531/824B01J31/0202B01J23/755B01J31/1805C07D265/18B01J23/44B01J31/24B01J27/232B01J21/00C07D265/00B01J23/00
Inventor B·K·维尔克
Owner WYETH LLC
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