Реакция #94359

Уравнение реакции

methyl 2-(3-methylacetonylmercapto)acetate

sodium hydride

→

4-methyltetrahydrothiopyran-3,5-dione

Выход 76.3%

Растворители

tetrahydrofuran

tetrahydrofuran

Условия реакции

Обработка

1. 1
   КонцентрированиеThe resulting yellow reaction mixture is concentrated to a small volume at temperature below 40° C. under reduced pressure
2. 2
   workup.ADDITIONpoured into ice-cold water
3. 3
   Экстракцияextracted with ether
4. 4
   Экстракцияextracted several times with chloroform
5. 5
   ПромывкаThe extracts are washed with a small portion of an aqueous sodium chloride solution
6. 6
   Сушкаdried over anhydrous sodium sulfate
7. 7
   ДругоеThe solvent is removed in vacuo
8. 8
   Другоеthe residue is crystallized from methylene chloride - ether

Методика

A solution of 101.3 g (0.57 mole) of methyl 2-(3-methylacetonylmercapto)acetate in 2.3 liter of dry tetrahydrofuran is added dropwise over a period of 3 hours to a stirred suspension of 0.57 mole of sodium hydride (27.4 g of 50% mineral oil suspension) in 1.1 liter of dry tetrahydrofuran at room temperature under nitrogen. Stirring is continued for an additional 3 hours. The resulting yellow reaction mixture is concentrated to a small volume at temperature below 40° C. under reduced pressure, poured into ice-cold water and then extracted with ether. The aqueous layer is acidified at pH 2-3 with dilute hydrochloric acid and extracted several times with chloroform. The extracts are washed with a small portion of an aqueous sodium chloride solution and dried over anhydrous sodium sulfate. The solvent is removed in vacuo and the residue is crystallized from methylene chloride - ether to give 62.7 g (75.6% yield) of 4-methyltetrahydrothiopyran-3,5-dione, mp. 131°-133° C. Recrystallization from acetone - ether gives an analytical specimen, mp. 132.5°-133° C. IR: νmaxCHCl3 cm-1 : 1735, 1705, 1631; νmaxNujol cm-1 :1635, 1553. UV: λmax95%EtOH mμ (ε): 275 (9500), 315 (2400); λmaxN-HCl mμ (ε): 272 (9900); λmaxN-NaOH mμ (ε): 289 (11600), 316 (12900). NMR: ppm (CDCl3): 1.28 (doublet, 3H, J = 7, Me), 3.44 (singlet, 4H, 2-H2 and 6-H2), 3.73 (quartet, 1H, J = 7, 4-H); ppm (CD3OD): 1.69 (broad singlet, 3H, vinyl-Me), 3.34 (broad singlet, 4H, 2-H2 and 6-H2). Anal. Calcd. for C6H8O2S (%): C, 49.98; H, 5.59; S, 22.24. Found (%): C, 50.17; H, 5.50; S, 22.14.

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