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Method for synthesizing aryl ketone compound by taking AQ as photocatalyst

A technology for photocatalysts and aldehyde-based compounds, which is applied in the preparation of carbon-based compounds, the preparation of organic compounds, catalysts, etc. Effect

Pending Publication Date: 2020-09-04
HAINAN NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, this protocol utilizing the pyridine carboxamide ligand reduces the yield of aliphatic aldehydes with high pKa C–H bonds

Method used

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  • Method for synthesizing aryl ketone compound by taking AQ as photocatalyst
  • Method for synthesizing aryl ketone compound by taking AQ as photocatalyst
  • Method for synthesizing aryl ketone compound by taking AQ as photocatalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0040]

[0041] Reaction conditions: bromobenzene (0.4mmol), cyclohexane formaldehyde (0.6mmol), AQ (10mol%, 0.04mmol), Pd(OAc) 2 (5mol%, 0.02 mmol), Xantphos is 4,5-bis(diphenylphosphine)-9,9-dimethylxanthene (5mol%, 0.02mmol), potassium bicarbonate (110mol%, 0.44 mmol) and acetone (5.0ml). In a PhotoRedOx Box equipped with a fan, the mixture was irradiated with a 427 nm Kessil lamp (Kessil LED photocatalytic lamp PR160) at room temperature under an Ar atmosphere for 24 h. The mixture was then quenched with saturated NaCl solution (10 mL) and extracted with ethyl acetate (3 x 10 mL). The organic layers were combined, washed with brine (1 x 30 mL), and concentrated under vacuum. The product was purified by flash column chromatography on silica gel with hexane / ethyl acetate to give the pure product cyclohexyl(phenyl)methanone as a colorless liquid. Using diphenylmethane as an internal standard, the yield was determined by 1H-NMR, and the product yield was 90%. The produc...

Embodiment 2

[0045] The difference between this example and Example 1 is that the bromobenzene replaces the equimolar amount of 4-chlorophenyl trifluoromethanesulfonate, and 0.48 mmol TBAB (120 mol%) is added.

[0046]

[0047] The pure product was obtained as a white solid with a yield of 75%. The product hydrogen spectrum, carbon spectrum data are as follows:

[0048]1 H-NMR (400MHz, CDCl 3 )δ7.88(d, J=6.9Hz, 2H), 7.42(d, J=8.5Hz, 2H), 3.20(tt, J=11.3, 3.2Hz, 1H), 1.91-1.78(m, 4H), 1.73(m,1H),1.54-1.32(m,4H),1.31-1.22(m,1H).

[0049] 13 C-NMR (100MHz, CDCl 3 )δ202.5, 139.1, 134.7, 129.7, 128.9, 45.6, 29.4, 25.9, 25.8.

[0050] The product structure is as follows:

[0051]

Embodiment 3

[0053] The difference between this example and Example 1 is that the cyclohexanecarbaldehyde is replaced by an equimolar amount of 3,3-dimethylbutyraldehyde.

[0054]

[0055] The pure product was obtained as a colorless liquid with a product yield of 87%. The product hydrogen spectrum, carbon spectrum data are as follows:

[0056] 1 H-NMR (400MHz, CDCl 3 )δ7.97-7.87(m,2H),7.56-7.47(m,1H),7.42(m,2H),2.84(s,2H),1.04(s,9H)

[0057] 13 C-NMR (100MHz, CDCl 3 )δ200.4, 137.6, 131.6, 127.4, 127.2, 49.0, 30.4, 29.0.

[0058] The structure of the product was confirmed as:

[0059]

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Abstract

The invention provides a method for synthesizing an aryl ketone compound by taking AQ as a photocatalyst. The method comprises the following steps that AQ serves as a photocatalyst; under the conditions of a palladium catalyst, a phosphine ligand, weak base and an organic solvent, a 390-to-430-nm photocatalysis lamp is used for irradiation at room temperature in an inert protective atmosphere, soan aldehyde group-containing compound reacts with Ar-X, wherein Ar-X is aryl halide or aryl trifluoromethanesulfonic acid, the aryl halide is aryl bromide or aryl iodide, and the aldehyde group-containing compound is one selected from aryl aldehyde, alkyl aldehyde, linear primary aldehyde and acyclic secondary aldehyde. According to the invention, the anthraquinone (AQ) HAT photocatalyst and palladium catalyst are combined for use, C-H arylation and alkenylation reactions of aldehyde can be directly carried out to synthesize ketone, and reaction efficiency is high. The method has the advantages of mild reaction conditions, high yield and a wide substrate application range, and can be used for synthesizing natural products in medicinal plants.

Description

technical field [0001] The invention relates to the technical field of organic synthesis, in particular to a method for synthesizing aryl ketones using AQ as a photocatalyst. Background technique [0002] Direct functionalization of aldehyde C–H bonds coupled with carbon electrophiles, such as aryl halides and alkenyl halides, which are readily available under palladium catalysis, is an ideal approach for the synthesis of ketones, which are used in pharmaceuticals, natural products, organic materials , an important structural motif ubiquitously found in photosensitizers, flavorants and fragrances. [0003] Changing the structure of aldehydes under palladium catalysis is particularly challenging due to the high bond dissociation energy and low acidity of the C–H bond structure of aldehydes. Kuninobu and Kanai recently reported palladium-catalyzed C–H arylation of aldehydes at high temperatures, in which newly designed ligands were used to facilitate the deprotonation of alde...

Claims

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Application Information

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IPC IPC(8): C07C49/792C07C45/68C07C49/813C07C49/76C07C49/82C07D263/56C07C49/84B01J31/02
CPCC07C45/68C07D263/56B01J31/0205C07C2601/14B01J2231/4205C07C2531/02C07C49/792C07C49/813C07C49/76C07C49/82C07C49/84
Inventor 郑超王璐王倩刘天鑫李小宝宋鑫明郑彩娟秦家艳魏俊杰成贵娟苗梦茹
Owner HAINAN NORMAL UNIV