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Synthesizing method of (E)-2-methylene-1,4-butanedione compound

A synthesis method and compound technology, applied in the fields of organic chemistry, organic chemistry, carbon monoxide reaction preparation, etc., can solve the problems of poor functional group compatibility, difficult preparation of raw materials, complicated reaction steps, etc., and achieve mild conditions, reduce waste emissions, and selectivity. high effect

Active Publication Date: 2018-12-11
HENAN NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Although the above method can effectively synthesize 2-methylene-1,4-butanedione compounds, there are still some shortcomings, such as difficult preparation of raw materials, poor functional group compatibility, severe reaction conditions, cumbersome reaction steps, and product formation. It is easy to generate a mixture of E / Z configurations, etc., so that its practicability is limited

Method used

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  • Synthesizing method of (E)-2-methylene-1,4-butanedione compound
  • Synthesizing method of (E)-2-methylene-1,4-butanedione compound
  • Synthesizing method of (E)-2-methylene-1,4-butanedione compound

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0011]

[0012] Add compound 1a (0.3mmol, 67mg) and acetonitrile (CH 3 CN, 2mL), then add compound 2a (0.6mmol, 67μL), palladium acetate (Pd(OAc) 2 ,0.03mmol,7mg), trifurylphosphine (P(furyl) 2 , 0.12mmol, 28mg) and triethylamine (Et 3 N, 1.5 mmol, 208 μL). The reaction was stirred at 80°C for 8 hours under a CO (1 atm) atmosphere, then 10 mL of saturated ammonium chloride solution was added to quench the reaction, extracted with ethyl acetate (10 mL×3), the organic phases were combined, and dried over anhydrous sodium sulfate. Filtered, spin-dried, separated by silica gel column (petroleum ether / ethyl acetate=20:1) to obtain yellow solid product (E)-2-benzylidene-1,4-diphenylbutane-1,4- Diketone 3a (80 mg, 82%). The characterization data of the compound are as follows: mp 87-89°C; 1 H NMR (400MHz, CDCl 3 )δ:4.49(s,2H),7.28-7.38(m,5H),7.44(s,1H),7.51(t,J=7.6Hz,4H),7.59(t,J=8.4Hz,2H), 7.97(d, J=7.2Hz, 2H), 8.05(d, J=8.4Hz, 2H). 13 C NMR (100MHz, CDCl 3 )δ: 38.6, 128...

Embodiment 2

[0014] Add compound 1a (0.3mmol, 67mg) and acetonitrile (2mL) to a 25mL reaction flask, then add compound 2a (0.3mmol, 34μL), palladium acetate (0.03mmol, 7mg), trifurylphosphine (0.12mmol, 28mg ) and triethylamine (1.5mmol, 208μL). The reaction was stirred at 80°C for 8 hours under a CO (1 atm) atmosphere, then 10 mL of saturated ammonium chloride solution was added to quench the reaction, extracted with ethyl acetate (10 mL×3), the organic phases were combined, and dried over anhydrous sodium sulfate. Filtered, spin-dried, separated by silica gel column (petroleum ether / ethyl acetate=20:1) to obtain yellow solid product (E)-2-benzylidene-1,4-diphenylbutane-1,4- Diketone 3a (50 mg, 51%).

Embodiment 3

[0016] Add compound 1a (0.3mmol, 67mg) and acetonitrile (2mL) to a 25mL reaction flask, then add compound 2a (0.6mmol, 67μL), palladium acetate (0.06mmol, 13mg), trifurylphosphine (0.12mmol, 28mg ) and triethylamine (1.5mmol, 208μL). The reaction was stirred at 80°C for 8 hours under a CO (1 atm) atmosphere, then 10 mL of saturated ammonium chloride solution was added to quench the reaction, extracted with ethyl acetate (10 mL×3), the organic phases were combined, and dried over anhydrous sodium sulfate. Filtered, spin-dried, separated by silica gel column (petroleum ether / ethyl acetate=20:1) to obtain yellow solid product (E)-2-benzylidene-1,4-diphenylbutane-1,4- Diketone 3a (72 mg, 74%).

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Abstract

The invention discloses a synthesizing method of a (E)-2-methylene-1,4-butanedione compound, and belongs to the technical field of organic synthesis. The synthesizing method is technically characterized in that the (E)-2-methylene-1,4-butanedione compound is shown in the attached figure. Compared with the prior art, the synthesizing method has the advantages that (1) by adopting one-pot cascade reaction, the complicated separation and purifying process of intermediates is avoided, the emission of wastes is reduced, and the burden to environment is reduced; (2) the raw materials are easy to prepare; (3) the reaction is performed at the temperature of 100 DEG C, the conditions are mild, and the operation is simple and convenient; (4) the application range of the primer is broad; (5) the selectivity of the product configuration is high.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and specifically relates to a synthesis method of (E)-2-methylene-1,4-butanedione compounds. Background technique [0002] 2-Methylene-1,4-butanedione belongs to 1,4-dicarbonyl compounds. It has important application value in the fields of organic synthesis, materials, chemical industry and medicine because of its lively and diverse reactivity. At present, the methods for synthesizing 2-methylene-1,4-butanedione mainly include the ring-opening reaction of copper-catalyzed acetyl-substituted three-membered ring alcohols, and the synthesis of 2-methylene-1,4-butanediol. Oxidation and condensation reactions of pyridinium salts with 2-butene-1,4-dione compounds, etc. Although the above method can effectively synthesize 2-methylene-1,4-butanedione compounds, there are still some shortcomings, such as difficult preparation of raw materials, poor functional group compatibility, severe reactio...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C45/49C07C49/796C07C49/84C07C49/813C07D333/22
CPCC07B2200/09C07C45/49C07D333/22C07C49/796C07C49/84C07C49/813
Inventor 何艳刘奇梦刘云飞柴欣媛宋桂娴
Owner HENAN NORMAL UNIV