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A method for synthesizing 1,2,2-triarylethanone and derivatives thereof

A synthesis method and technology of diphenyl ethyl ketone are applied in the field of synthesizing 1,2,2-triaryl ethyl ketone and derivatives thereof, which can solve the problems of poor atom economy of the synthesis method and achieve the effect of high yield

Active Publication Date: 2019-10-18
LANZHOU UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] Although new transition-metal-catalyzed synthesis of 1,2,2-triarylethanones has been reported, it requires expensive transition metals such as palladium and ligands or requires aryl halides or aryl pseudohalides (such as phenol esters) , and generally requires basic reaction conditions, the atom economy of the synthesis method is not good

Method used

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  • A method for synthesizing 1,2,2-triarylethanone and derivatives thereof
  • A method for synthesizing 1,2,2-triarylethanone and derivatives thereof
  • A method for synthesizing 1,2,2-triarylethanone and derivatives thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0041] Using phenyl benzyl ketone and p-xylene as raw materials (reaction formula 2)

[0042]

[0043] Dissolve benzophenone (39.3 mg, 0.2 mmol) and p-xylene (74.0 μL, 0.6 mmol, 3.0 eq) in the solvent 1,2-dichloroethane DCE in a reaction tube under argon atmosphere at room temperature (1.0 mL), add oxidant DDQ (54.5 mg, 0.24 mmol) and catalyst FeCl 3 (6.5 mg, 0.04 mmol, 0.04 eq), placed in an 80°C oil bath to stir the reaction, after the reaction stopped, add 1.0 mL petroleum ether PE to dilute, the mixture was directly put on the column, and petroleum ether and ethyl acetate (volume ratio 95 :5) The product 2-(2,5-dimethylphenyl)-1,2-diphenylethanone (amorphous solid, 46.3 mg, 77%) was obtained by direct column chromatography as the mobile phase.

[0044] The product detection data are as follows:

[0045] 1H NMR (400 MHz, CDCl3): δ 7.94-7.92 (m, 2 H), 7.49-7.45 (m, 1 H), 7.39-7.35 (m, 2 H), 7.33-7.29 (m, 2 H), 7.26-7.23 (m, 1 H), 7.22-7.18 (m, 2H), 7.09 (d, J = 7.6 Hz,...

Embodiment 2

[0047] Using phenyl benzyl ketone and o-iodoanisole as raw materials (reaction formula 3)

[0048]

[0049] Under an argon atmosphere at room temperature, benzophenone (39.3 mg, 0.2 mmol) and o-iodoanisole (140.4 mg, 0.6 mmol, 3.0 eq) were dissolved in DCE (1.0 mL) in a reaction tube, followed by To this was added DDQ (54.5 mg, 0.24 mmol) and FeCl 3(6.5 mg, 0.04 mmol, 0.04 eq), placed in an 80°C oil bath to stir the reaction, after the reaction stopped, add 1.0 mL petroleum ether to dilute, the mixture was directly put on the column, and petroleum ether and ethyl acetate (volume ratio 95: 5) The product 2-(3-iodo-4-methoxyphenyl)-1,2-diphenylethanone (amorphous solid, 57.4 mg, 67%) was obtained by direct column chromatography as the mobile phase.

[0050] The product detection data are as follows:

[0051] 2-(3-iodo-4-methoxyphenyl)-1,2-diphenylethan-1-one, amorphous solid (67%).

[0052] 1H NMR (400 MHz, CDCl3): δ 7.99-7.97 (m, 2 H), 7.69-7.68 (m, 1 H), 7.54-7.49 (m, 1 ...

Embodiment 3

[0054] Take tert-butyl benzyl ketone and p-xylene as raw materials (reaction formula 4)

[0055]

[0056] Under an argon atmosphere at room temperature, tert-butylbenzyl ketone (35.2 mg, 0.2 mmol) and p-xylene (74.0 μL, 0.6 mmol, 3.0 eq) were dissolved in DCE (1.0 mL) in a reaction tube, followed by To this was added DDQ (54.5 mg, 0.24 mmol) and FeCl 3 (6.5 mg, 0.04 mmol, 0.04 eq), placed in an 80°C oil bath to stir the reaction, after the reaction stopped, add 1.0 mL petroleum ether to dilute, the mixture was directly put on the column, and petroleum ether and ethyl acetate (volume ratio 95: 5) The product 2-(2,5-dimethylphenyl)-,3,3-dimethyl-1-phenylbutyl ketone (amorphous solid, 38.1 mg, 68 %).

[0057] The product detection data are as follows:

[0058] 1-(2,5-dimethylphenyl)-3,3-dimethyl-1-phenylbutan-2-one, amorphous solid (68%).

[0059] 1 H NMR (400 MHz, CDCl 3 ): δ 7.28-7.24 (m, 2 H), 7.21-7.17 (m, 1 H),7.14-7.12 (m, 2 H), 7.06-7.04 (m, 2 H), 6.99-6.97 (m, 1 ...

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Abstract

The invention provides a method for synthesizing 1,2,2-triaryl ethyl ketone and derivatives thereof. The method comprises the following steps: dissolving a phenylbenzyl ketone derivative and an aryl compound, adding an oxidizing agent and a catalyst, carrying out a reaction in a certain temperature range, and separating the reaction products, so as to obtain the product, wherein the catalyst is ferric trichloride, ferric sesquibromide or aluminum trichloride; the oxidizing agent is 4,5-dichloro-3,6-dioxo-1,4-cyclohexadiene-1,2-carbonitrile (DDQ); the solvent is one of 1,2-dichloroethane, dichloromethane, normal hexane, n-nonane, acetonitrile and n-heptane. According to the invention, cheap ferric trichloride, ferric sesquibromide or aluminum trichloride serves as the catalyst, the DDQ serves as the oxidizing agent, synthesis of the 1,2,2-triaryl ethyl ketone and derivatives thereof can be economically and efficiently realized under the oxidation condition, the reaction process is simple, and the method is easy to operate and high in yield.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a new method for synthesizing 1,2,2-triarylethanone and derivatives thereof. Background technique [0002] 1,2,2-Triarylethanone and related structural fragments widely exist in natural products and drug molecules, and are also used as key building blocks for the synthesis of multiple natural products and drug molecules. Moreover, 1,2,2-triarylethanone and its related structural fragments can be used as starting materials for active heterocyclic compounds and the like by constructing new carbon-carbon (nitrogen) bonds. In addition, they are also used as Single-electron acceptors are used in the study of photochemical reaction mechanisms. [0003] Although new transition-metal-catalyzed synthesis of 1,2,2-triarylethanones has been reported, it requires expensive transition metals such as palladium and ligands or requires aryl halides or aryl pseudohalides (s...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07B41/06C07C45/68C07C49/215C07C49/255C07C49/233C07C201/12C07C205/45C07C319/20C07C323/22C07D319/24
Inventor 张辅民彭蕊陈涛
Owner LANZHOU UNIVERSITY