ncp ligand, its iridium complex, synthesis method, intermediate and application

A technology of iridium complexes and ligands, applied in the field of NCP ligands, can solve the problems of low catalytic efficiency, harsh reaction conditions, poor selectivity, etc.

Active Publication Date: 2018-07-13
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] The technical problem to be solved by the present invention is to provide NCP ligands, its iridium complexes, synthesis methods, intermediates and application

Method used

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  • ncp ligand, its iridium complex, synthesis method, intermediate and application
  • ncp ligand, its iridium complex, synthesis method, intermediate and application
  • ncp ligand, its iridium complex, synthesis method, intermediate and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0156] Embodiment 1: preparation of the present invention H NCP ligand

[0157]

[0158] Add 3-methoxyphenylboronic acid (5.0g, 32.8mmol), K 2 CO 3 (9.4g, 68.0mmol), then set up a reflux device, pump and change the gas 3 times, add 2-bromopyridine (4.4g, 27.8mmol), solvent ethylene glycol dimethyl ether (50mL) and Distilled water (33 mL). Then the system was bubbled with a long needle for 30 min, and tetrakistriphenylphosphopalladium (1.3 g, 1.1 mmol) was added. The system was heated to reflux for 12h in an argon atmosphere. After the reaction, the system was cooled to room temperature, extracted with ethyl acetate (30mL×3), the collected organic phase was backwashed with saturated brine, dried over anhydrous sodium sulfate, concentrated by filtration, and purified by column chromatography (petroleum ether: ethyl acetate = 1:20), to obtain 3.2g of colorless oil 2-(3-methoxyphenyl)pyridine, yield 61%.

[0159] Add 2-(3-methoxyphenyl)pyridine (3.2g, 17.3mmol) and 40% aq...

Embodiment 2

[0163] Embodiment 2: preparation of the present invention Me NCP ligand

[0164]

[0165] Add 3-methoxyphenylboronic acid (5.0 g, 32.6 mmol), K 2 CO 3 (9.8g, 71mmol), then set up the reflux device, pump and change the gas 3 times, add 2-bromo-6-methylpyridine (5.1g, 29.8mmol) and solvent ethylene glycol dimethyl ether under argon protection gas (60mL) and distilled water (38mL). Then the system was bubbled with a long needle for 30 min, and tetrakistriphenylphosphopalladium (1.7 g, 1.5 mmol) was added. The system was heated to reflux for 12h in an argon atmosphere. After the reaction, the system was cooled to room temperature, extracted with ethyl acetate (30mL×3), the collected organic phase was backwashed with saturated brine, dried over anhydrous sodium sulfate, concentrated by filtration, and purified by column chromatography (petroleum ether: ethyl acetate = 1:50), and 3.0 g of colorless oil 2-(3-methoxyphenyl)-6-picoline was obtained with a yield of 51%.

[0166...

Embodiment 3

[0171] Embodiment 3: preparation of the present invention tBu NCP ligand

[0172]

[0173] Add 3-methoxyphenylboronic acid (3.1g, 20.0mmol), K 2 CO 3 (5.8g, 42.0mmol), then set up the reflux device, pump and change the gas 3 times, add 2-bromo-6-tert-butylpyridine (3.6g, 16.8mmol) and solvent ethylene glycol di methyl ether (30 mL) and distilled water (20 mL). Then the system was bubbled with a long needle for 30 minutes and tetrakistriphenylphosphopalladium (1.0 g, 0.9 mmol) was added. The system was heated to reflux for 12h in an argon atmosphere. After the reaction, the system was cooled to room temperature, extracted with ethyl acetate (30mL×3), the collected organic phase was backwashed with saturated brine, dried over anhydrous sodium sulfate, concentrated by filtration, and purified by column chromatography (petroleum ether: ethyl acetate = 1:100), to obtain 2.7g of colorless oil 2-(3-methoxyphenyl)-6-tert-butylpyridine, yield 67%.

[0174] 1 H NMR (400MHz, CD...

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Abstract

The invention discloses an NCP ligand, iridium complex, synthetic method, intermediate and application thereof. The invention provides an NCP ligand and an NCP ligand iridium complex, wherein R1, R2, R3, R4, R5, R6 and R7 separately represent hydrogen atom or C1-C30 alkyl, R' and R'' independently represent C1-C30 alkyl. The invention provides the application of the NCP ligand iridium complex to the catalysis of alkane dehydrogenation reaction, olefin isomerization reaction, alcohol dehydrogenation reaction, ester alpha alkylation reaction, and amide alpha alkylation reaction. The NCP ligand provided by the invention contains dialkyl substituted phosphine, which has strong electron donating ability and can form a NCP ligand iridium complex by complexing with iridium. The NCP ligand iridium complex uses pyridine to replace a conventional alkyl phosphate electron donor, and has the advantages of good stability, high selectivity on alkane dehydrogenation reaction, mild reaction conditions, good catalytic effect, and industrial production prospect.

Description

technical field [0001] The present invention relates to NCP ligand, its iridium complex, synthesis method, intermediate and application. Background technique [0002] Alkanes are abundant in nature, and alkenes are important industrial raw materials. If people can convert cheap and abundant alkanes into alkenes with higher application value, the application prospects of alkanes will be greatly improved. At present, some homogeneous catalysts have been applied to alkane dehydrogenation reaction (J.Am.Chem.Soc.1999,121,4086-4087; J.Am.Chem.Soc.2004,126,1804-1811; Organometallics2009,28, 5432-5444; Angew.Chem.Int.Ed.2001, 40, 3596-3600; Organometallics2006, 25, 5466-5476; Organometallics2012, 31, 7359-7367.), but they still have the disadvantages of poor olefin selectivity and high reaction temperature . Therefore, it is an urgent problem to develop catalysts with high selectivity to olefins, mild reaction conditions and high catalytic efficiency. There are also synthesis of...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F9/58C07F19/00C07D213/30B01J31/24C07C13/263C07C5/52C07C5/25C07C11/02C07C15/44C07C251/08C07C249/02C07C69/612C07C67/343C07D307/33C07C53/128C07C51/09C07C233/11C07C231/12
Inventor 黄正贾香清郭乐
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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