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Method for synthesizing aryl ketone compound by taking TBADT as photocatalyst

A technology for photocatalysts and aldehyde-based compounds, which is applied in the fields of condensation preparation of carbonyl compounds, organic chemistry methods, chemical instruments and methods, etc., can solve the problems of reducing the yield of aliphatic aldehydes, etc. rate effect

Pending Publication Date: 2020-09-11
HAINAN NORMAL UNIVERSITY
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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 TBADT as photocatalyst
  • Method for synthesizing aryl ketone compound by taking TBADT as photocatalyst
  • Method for synthesizing aryl ketone compound by taking TBADT as photocatalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0041]

[0042] Reaction conditions: bromobenzene (0.4mmol), cyclohexane formaldehyde (0.6mmol), TBADT (2mol%, 0.008mmol), Pd(OAc) 2 (5mol%, 0.02mmol), Xantphos is 4,5-bis(diphenylphosphine)-9,9-dimethylxanthene (5mol%, 0.02mmol), potassium bicarbonate (110mol%, 0.44mmol ) and acetone (5.0ml). In a PhotoRedOx Box equipped with a fan, the mixture was irradiated with a 34W 390 nm Kessil lamp (Kessil LED photocatalytic lamp PR160) at room temperature under an Ar atmosphere for 48 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 product cyclohexyl(phenyl)methanone as a colorless liquid in 88% yield. The hydrogen spectrum and carbon spectrum data of the product are as follows:

[0043] 1 H-NMR (400MHz, CDCl ...

Embodiment 2

[0046] The difference between this example and Example 1 is that the bromobenzene replaces an equimolar amount of 3,4,5-trimethoxyphenyl trifluoromethanesulfonate.

[0047]

[0048] The pure product was obtained as a white solid with a product yield of 81%. The product hydrogen spectrum, carbon spectrum data are as follows:

[0049] 1 H-NMR (400MHz, CDCl 3)δ7.13(s,2H),3.84(s,6H),3.83(s,3H),3.14(tt,J=11.4,3.2Hz,1H),1.86-1.73(m,4H),1.70-1.62 (m,1H),1.49-1.25(m,4H),1.25-1.13(m,1H).

[0050] 13 C-NMR (100MHz, CDCl 3 )δ202.6, 153.1, 142.4, 131.6, 105.9, 60.9, 56.3, 45.4, 29.6, 25.9, 25.8.

[0051] The structure of the product was confirmed as:

[0052]

Embodiment 3

[0054] The difference between this example and Example 1 is that the bromobenzene is replaced by an equimolar amount of p-iodotoluene, and 0.48 mmol TBAB (120 mol%) is added.

[0055]

[0056] The pure product was obtained as a colorless liquid with a product yield of 84%. The product hydrogen spectrum, carbon spectrum data are as follows:

[0057] 1 H-NMR (400MHz, CDCl 3 )δ7.85(d, J=8.2Hz, 2H), 7.25(d, J=8.1Hz, 2H), 3.24(tt, J=11.5, 3.1Hz, 1H), 2.41(s, 3H), 1.93- 1.80(m,4H),1.78-1.69(m,1H),1.56-1.33(m,4H),1.32-1.22(m,1H).

[0058] 13 C-NMR (100MHz, CDCl 3 )δ203.5, 143.4, 133.8, 129.2, 128.3, 45.5, 29.5, 26.0, 25.9, 21.6.

[0059] The structure of the product was confirmed as:

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Abstract

The invention provides a method for synthesizing an aryl ketone compound by taking TBADT as a photocatalyst. The method comprises the following steps: with TBADT as a photocatalyst, under the conditions of a palladium catalyst, a phosphine ligand, weak base and an organic solvent, irradiating the reactants under a 380-400 nm photocatalysis lamp at the room temperature under the inert protective atmosphere, so that an aldehyde group-containing compound reacts with Ar-X, wherein the Ar-X is aryl halide or aryl trifluoromethanesulfonate, and the aryl halide is aryl bromide or aryl iodide; the aldehyde group-containing compound is one of aryl aldehyde, alkyl aldehyde, linear primary aldehyde, acyclic secondary aldehyde and N-methylformamide. According to the invention, the tetrabutylammonium sebacate (TBADT)HAT photocatalyst and palladium catalysis are combined for use, and aldehyde C-H arylation and alkenylation reactions can be directly carried out to synthesize ketone. The method has the advantages of mild reaction conditions, high yield and 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 TBADT 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 a...

Claims

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Application Information

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IPC IPC(8): C07B61/00C07B41/06C07C45/45C07C49/792C07C49/84C07C49/76C07C49/563C07D263/56B01J31/04B01J31/24
CPCC07B61/00C07B41/06C07C45/45C07D263/56B01J31/04B01J31/2409C07C2601/14B01J2231/46B01J2231/4205B01J2531/824B01J35/19B01J35/39C07C49/792C07C49/84C07C49/76C07C49/563
Inventor 郑超王璐李小宝王倩宋鑫明郑彩娟周文利魏俊杰成贵娟苗梦茹
Owner HAINAN NORMAL UNIVERSITY