Oxime-based method for synthesis of pyridine derivative by [2+2+2] cycloaddition

A technology of cycloaddition and derivatives, which is applied in the field of addition synthesis of pyridine derivatives, to achieve the effects of novel synthetic routes, reduced toxicity, and good reaction effects

Inactive Publication Date: 2013-01-16
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] At present, there are many reports on the reaction of pyridine derivatives prepared by this [2+2+2] cycloaddition method, but there are no reports on the use of oxime as the starting material. The present invent

Method used

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  • Oxime-based method for synthesis of pyridine derivative by [2+2+2] cycloaddition
  • Oxime-based method for synthesis of pyridine derivative by [2+2+2] cycloaddition
  • Oxime-based method for synthesis of pyridine derivative by [2+2+2] cycloaddition

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Embodiment 1

[0015] The novel reaction synthesis steps and product structural formula are as follows:

[0016]

[0017] The specific steps of this reaction are as follows:

[0018] Take three-necked reaction flask, add hydroxylamine hydrochloride (66mmol, 4.6g), add ethanol after inert gas replacement three times, add ethyl glyoxylate 6 (66mmol, 13.5g), add Et under stirring 3 N (66mmol, 9.3mL), react at room temperature. Adjust the pH value of the reaction solution to close to 7 with hydrochloric acid, extract the aqueous phase with ether (50mL×3), combine the organic phases, and wash the organic phase with anhydrous Na 2 SO 4 After drying, filtering and evaporating the solvent, compound 7 was obtained by column chromatography (yield: 62%).

[0019] Get the Schlenk reaction tube, weigh Rh(NBD) in the glove box 2 BF 4 (0.025mmol, 9.3mg) and BINAP (0.025mmol, 15.6mg) and molecular sieves (137.8mg), DCE (2mL) was added under the protection of an inert gas, and compound 7 (0.1ml) was ...

Embodiment 2

[0023] The novel reaction synthesis steps and product structural formula are as follows:

[0024]

[0025] The specific steps of this reaction are as follows:

[0026] Take three-necked reaction flask, add hydroxylamine hydrochloride (66mmol, 4.6g), add ethanol after inert gas replacement three times, add ethyl glyoxylate 6 (66mmol, 13.5g), add Et under stirring 3 N (66mmol, 9.3mL), react at room temperature. Adjust the pH value of the reaction solution to close to 7 with hydrochloric acid, extract the aqueous phase with ether (50mL×3), combine the organic phases, and wash the organic phase with anhydrous Na 2 SO 4 After drying, filtering and evaporating the solvent, compound 7 was obtained by column chromatography (yield: 62%).

[0027] Get the Schlenk reaction tube, weigh Rh(NBD) in the glove box 2 BF 4 (0.05mmol, 18.7mg) and BINAP (0.05mmol, 31.1mg) and molecular sieves (208.2mg), under the protection of inert gas, add DCE, after stirring for a while, add compound 7...

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Abstract

The invention relates to a new oxime-based method for synthesis of a pyridine derivative by [2+2+2] cycloaddition. According to the invention, corresponding oxime is synthesized from aldehyde, Rh(NBD)2BF4 is taken as a metal precursor, BINAP is adopted as a diphosphine ligand, DCE is employed as a solvent, a molecular sieve is used as an additive, and diyne is added to react with the materials for 48h at a temperature of 80DEG C, thus obtaining the corresponding pyridine derivative. Compared with previous nitrile raw materials, the starting material required by the method has the characteristics of simple synthesis, high yield, substantially reduced toxicity, stability in water and air, and strong operability.

Description

technical field [0001] The present invention relates to a new method for synthesizing pyridine derivatives through [2+2+2] cycloaddition based on oxime. Compared with the previous nitrile raw materials, the starting materials required by the method have the advantages of simple synthesis, high yield, greatly reduced toxicity and enhanced air stability. This reaction realizes the synthesis of pyridine derivatives by [2+2+2] cycloaddition by replacing nitriles with oximes. Background technique [0002] According to literature 1 [Chang H T.; Jeganmohan M.; Cheng C H. Org. Lett.2007, 9, 505-508], literature 2 [Cioni P,; Diversi P,; Ingrosso G, et al.J.Mol .Catal.1987,40,337-357], and document 3 [Diversi P,; Ingrosso G,; Catalyze the [2+2+2] cycloaddition reaction between diynes and nitriles, and then prepare multi-substituted pyridine derivatives. The previous synthesis often goes through the following routes: [0003] [0004] This synthetic route uses nitriles as startin...

Claims

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Application Information

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IPC IPC(8): C07D471/04C07D221/04
Inventor 万伯顺徐粉吴凡
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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