Synthetic method of diaryl-substituted dicarbonyl compound

Abstract

The invention relates to a synthetic method of a diaryl-substituted dicarbonyl compound shown as the following formula (III), the equation is shown in the description, and the synthetic method specifically comprises the steps of adding 100 mmol of a compound shown as formula (I), 130 mmol of a compound shown as formula (II), 12 mmol of a catalyst (composed of 6 mmol of 1,3-bi(diphenylphosphine propane) nickel dichloride and 6 mmol of hexafluoroacetylacetone copper), 240 mmol of 2-iodoxybenzoic acid, 110 mmol of dimethylaminopyridine and 17 mmol od tetraphenylporphyrin, then stirring and heating to 90 DEG C, and stirring for reacting for 7 hours under 90 DEG C; after the reaction is finished, quenching the reaction with deionized water, filtering, washing the filter liquor sufficiently withdeionized water, extracting an organic phase for 2 to 3 times by using ethyl acetate, combining the organic phase and drying with anhydrous sodium sulfate, finally performing reduced pressure distillation to perform chromatographic separation on the obtained thick residue by a 300 to 400-mesh silicagel column, wherein an elution solvent is a mixture of acetone and chloroform with the volume ratioof 1 to 2, thus obtaining the compound of the formula (II).

Description

[0001] This application is a divisional application with an application date of October 14, 2016, an application number of 201610895883.6, and an invention title of "a synthesis method of a diaryl-substituted dicarbonyl compound". technical field

[0002] The invention relates to a synthesis method of a dicarbonyl compound, more particularly to a synthesis method of a diaryl-substituted dicarbonyl compound, and belongs to the technical field of organic chemical synthesis. Background technique

[0003] The carbonyl structure is a very important type of active group in organic chemical synthesis, which can expand and change the group through a variety of reactions, so it plays an important role in organic chemical synthesis. For example, dicarbonyl compounds are a class of highly functional structural units, which are very important in drug design and functional group modification.

[0004] Therefore, the development of synthetic methods for dicarbonyl compounds has attracted ...

Examples

Embodiment 1

[0036]

[0037] In an appropriate amount of organic solvent at room temperature (a mixture of dimethyl sulfoxide (DMSO) and acetonitrile at a volume ratio of 3:1), add 100 mmol of the above formula (I) compound, 120 mmol of the above formula (II) compound, 20 mmol Two-component composite catalyst (composed of 10mmol 1,3-bis(diphenylphosphinopropane) nickel dichloride and 10mmol copper hexafluoroacetylacetonate), 200mmol oxidant 2-iodylbenzoic acid (IBX), 150mmol base dimethyl Aminopyridine (DMPA) and 14mmol auxiliary tetraphenylporphyrin, then heated to 70°C while stirring, and stirred and reacted at this temperature for 9 hours;

[0038] After the reaction is completed, quench the reaction with deionized water, filter, fully wash the filtrate with deionized water, then extract the organic phase with ethyl acetate for 2-3 times, combine the organic phases and dry them with anhydrous sodium sulfate, and finally distill under reduced pressure. The viscous residue obtained was...

Embodiment 2

[0041]

[0042] To an appropriate amount of organic solvent at room temperature (a mixture of dimethyl sulfoxide (DMSO) and acetonitrile at a volume ratio of 3:1), add 100 mmol of the above formula (I) compound, 180 mmol of the above formula (II) compound, 10 mmol Two-component composite catalyst (composed of 5mmol 1,3-bis(diphenylphosphinopropane) nickel dichloride and 5mmol copper hexafluoroacetylacetonate), 250mmol oxidant 2-iodylbenzoic acid (IBX), 100mmol alkali dimethyl Aminopyridine (DMPA) and 18mmol auxiliary tetraphenylporphyrin, then heated to 100°C while stirring, and stirred and reacted at this temperature for 6 hours;

[0043] After the reaction is completed, quench the reaction with deionized water, filter, fully wash the filtrate with deionized water, then extract the organic phase with ethyl acetate for 2-3 times, combine the organic phases and dry them with anhydrous sodium sulfate, and finally distill under reduced pressure. The viscous residue obtained wa...

Embodiment 3

[0046]

[0047] In an appropriate amount of organic solvent at room temperature (a mixture of dimethyl sulfoxide (DMSO) and acetonitrile at a volume ratio of 3:1), add 100 mmol of the above formula (I) compound, 150 mmol of the above formula (II) compound, 16 mmol Two-component composite catalyst (composed of 8mmol 1,3-bis(diphenylphosphinopropane) nickel dichloride and 8mmol copper hexafluoroacetylacetonate), 225mmol oxidant 2-iodylbenzoic acid (IBX), 125mmol alkali dimethyl Aminopyridine (DMPA) and 16mmol auxiliary tetraphenylporphyrin, then heated to 80°C while stirring, and stirred and reacted at this temperature for 8 hours;

[0048] After the reaction is completed, quench the reaction with deionized water, filter, fully wash the filtrate with deionized water, then extract the organic phase with ethyl acetate for 2-3 times, combine the organic phases and dry them with anhydrous sodium sulfate, and finally distill under reduced pressure. The viscous residue obtained was...

[0001] This application is a divisional application with an application date of October 14, 2016, an application number of 201610895883.6, and an invention title of "a synthesis method of a diaryl-substituted dicarbonyl compound". technical field

[0002] The invention relates to a synthesis method of a dicarbonyl compound, more particularly to a synthesis method of a diaryl-substituted dicarbonyl compound, and belongs to the technical field of organic chemical synthesis. Background technique

[0003] The carbonyl structure is a very important type of active group in organic chemical synthesis, which can expand and change the group through a variety of reactions, so it plays an important role in organic chemical synthesis. For example, dicarbonyl compounds are a class of highly functional structural units, which are very important in drug design and functional group modification.

[0004] Therefore, the development of synthetic methods for dicarbonyl compounds has attracted ...

Examples

Embodiment 1

[0036]

[0037] In an appropriate amount of organic solvent at room temperature (a mixture of dimethyl sulfoxide (DMSO) and acetonitrile at a volume ratio of 3:1), add 100 mmol of the above formula (I) compound, 120 mmol of the above formula (II) compound, 20 mmol Two-component composite catalyst (composed of 10mmol 1,3-bis(diphenylphosphinopropane) nickel dichloride and 10mmol copper hexafluoroacetylacetonate), 200mmol oxidant 2-iodylbenzoic acid (IBX), 150mmol base dimethyl Aminopyridine (DMPA) and 14mmol auxiliary tetraphenylporphyrin, then heated to 70°C while stirring, and stirred and reacted at this temperature for 9 hours;

[0038] After the reaction is completed, quench the reaction with deionized water, filter, fully wash the filtrate with deionized water, then extract the organic phase with ethyl acetate for 2-3 times, combine the organic phases and dry them with anhydrous sodium sulfate, and finally distill under reduced pressure. The viscous residue obtained was...

Embodiment 2

[0041]

[0042] To an appropriate amount of organic solvent at room temperature (a mixture of dimethyl sulfoxide (DMSO) and acetonitrile at a volume ratio of 3:1), add 100 mmol of the above formula (I) compound, 180 mmol of the above formula (II) compound, 10 mmol Two-component composite catalyst (composed of 5mmol 1,3-bis(diphenylphosphinopropane) nickel dichloride and 5mmol copper hexafluoroacetylacetonate), 250mmol oxidant 2-iodylbenzoic acid (IBX), 100mmol alkali dimethyl Aminopyridine (DMPA) and 18mmol auxiliary tetraphenylporphyrin, then heated to 100°C while stirring, and stirred and reacted at this temperature for 6 hours;

[0043] After the reaction is completed, quench the reaction with deionized water, filter, fully wash the filtrate with deionized water, then extract the organic phase with ethyl acetate for 2-3 times, combine the organic phases and dry them with anhydrous sodium sulfate, and finally distill under reduced pressure. The viscous residue obtained wa...

Embodiment 3

[0046]

[0047] In an appropriate amount of organic solvent at room temperature (a mixture of dimethyl sulfoxide (DMSO) and acetonitrile at a volume ratio of 3:1), add 100 mmol of the above formula (I) compound, 150 mmol of the above formula (II) compound, 16 mmol Two-component composite catalyst (composed of 8mmol 1,3-bis(diphenylphosphinopropane) nickel dichloride and 8mmol copper hexafluoroacetylacetonate), 225mmol oxidant 2-iodylbenzoic acid (IBX), 125mmol alkali dimethyl Aminopyridine (DMPA) and 16mmol auxiliary tetraphenylporphyrin, then heated to 80°C while stirring, and stirred and reacted at this temperature for 8 hours;

[0048] After the reaction is completed, quench the reaction with deionized water, filter, fully wash the filtrate with deionized water, then extract the organic phase with ethyl acetate for 2-3 times, combine the organic phases and dry them with anhydrous sodium sulfate, and finally distill under reduced pressure. The viscous residue obtained was...

Images