7152-15-0Relevant articles and documents
Preparation process of isobutyryl ethyl acetate
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Paragraph 0021-0027; 0036; 0037; 0042-0052, (2021/02/13)
The invention provides an isobutyryl ethyl acetate preparation process which is characterized by comprising the following specific steps: step one, adding 125 mL of ethyl acetate and 13.6 g (80 mmol)of potassium mono-ethyl malonate into a three-neck flask, stirring and cooling to 0-5 DEG C, then sequentially adding 9.12 g (96 mmol) of anhydrous magnesium chloride and 27.8 mL (0.2 mol) of triethylamine, heating to 65 DEG C within 0.5 h, and stirring for 6 hours at the temperature of 65 DEG C; step two, cooling to 0 DEG C, dropwise adding 6 mL (57 mmol) of isobutyryl chloride within one hour, and carrying out reactions at the room temperature for 12 hours; step three, cooling to 0 DEG C, carefully adding 70 mL of 13% hydrochloric acid, keeping the temperature not higher than 20 DEG C in theprocess; step four, separating out an organic phase, extracting a water layer with toluene (40 mL*3), merging the organic phase, washing with a saturated sodium bicarbonate solution until the organicphase is neutral, and washing with 25 mL of saturated edible salt water, and carrying out reduced pressure distillation to remove the solvent; and step five, carrying out reduced pressure distillation on the crude product to obtain 5.5 g of colorless liquid. The method provided by the invention solves the problems of low productivity and low purity during production and manufacturing of isobutyryl ethyl acetate at present.
General [4 + 1] Cyclization Approach to Access 2,2-Disubstituted Tetrahydrofurans Enabled by Electrophilic Bifunctional Peroxides
Gao, Min,Zhao, Yukun,Zhong, Chen,Liu, Shengshu,Liu, Pengkang,Yin, Qi,Hu, Lin
supporting information, p. 5679 - 5684 (2019/08/01)
A general [4 + 1] cyclization reaction of carbonyl nucleophiles with 2-iodomethylallyl peroxides, which function as unique electrophilic oxygen synthons, for the synthesis of a broad range of 2,2-disubstituted tetrahydrofurans is achieved under operationally simple conditions. The unprecedented asymmetric version of such reaction is also realized via chiral auxiliary-assisted cyclization, thus providing a distinct approach to access chiral tetrahydrofurans with high diastereoselectivities. The new method can be applied to the synthesis of core structure of posaconazole drug.
Five Roads That Converge at the Cyclic Peroxy-Criegee Intermediates: BF3-Catalyzed Synthesis of β-Hydroperoxy-β-peroxylactones
Vil, Vera A.,Gomes, Gabriel Dos Passos,Ekimova, Maria V.,Lyssenko, Konstantin A.,Syroeshkin, Mikhail A.,Nikishin, Gennady I.,Alabugin, Igor V.,Terent'Ev, Alexander O.
, p. 13427 - 13445 (2018/11/02)
We have discovered synthetic access to β-hydroperoxy-β-peroxylactones via BF3-catalyzed cyclizations of a variety of acyclic precursors, β-ketoesters and their silyl enol ethers, alkyl enol ethers, enol acetates, and cyclic acetals, with H2O2. Strikingly, independent of the choice of starting material, these reactions converge at the same β-hydroperoxy-β-peroxylactone products, i.e., the peroxy analogues of the previously elusive cyclic Criegee intermediate of the Baeyer-Villiger reaction. Computed thermodynamic parameters for the formation of the β-hydroperoxy-β-peroxylactones from silyl enol ethers, enol acetates, and cyclic acetals confirm that the β-peroxylactones indeed correspond to a deep energy minimum that connects a variety of the interconverting oxygen-rich species at this combined potential energy surface. The target β-hydroperoxy-β-peroxylactones were synthesized from β-ketoesters, and their silyl enol ethers, alkyl enol ethers, enol acetates, and cyclic acetals were obtained in 30-96% yields. These reactions proceed under mild conditions and open synthetic access to a broad selection of β-hydroperoxy-β-peroxylactones that are formed selectively even in those cases when alternative oxidation pathways can be expected. These β-peroxylactones are stable and can be useful for further synthetic transformations.