Ethanethiol → 4-bromo-3-oxothiobutyric acid-S-ethyl ester

HRID 65518

反応式

HRID 65518 の反応式
[CH2:1]=[C:2]1[O:6][C:4](=[O:5])[CH2:3]1.[Br:7]Br.[CH2:9]([SH:11])[CH3:10].C1OC1C.C(=O)([O-])O.[Na+]>C(Cl)Cl.O>[CH2:9]([S:11][C:4](=[O:5])[CH2:3][C:2](=[O:1])[CH2:6][Br:7])[CH3:10]

参加物

8

反応条件

温度
-40 °C

実験手順

In 40 ml of anhydrous methylene chloride was dissolved 8.4 g of diketene, and the resulting solution was cooled to -40° C. Then, 14.4 g of bromine was added dropwise to the solution while maintaining the temperature at -40° to -35° C. over a period of 1 hour, and the resulting mixture was subjected to reaction at -30° to -20° C. for 30 minutes. On the other hand, 7.48 g of ethanethiol and 5.84 g of propylene oxide were dissolved in 60 ml of anhydrous methylene chloride, and the resulting solution was cooled to -40° C. Into this solution was introduced the above-mentioned reaction mixture. Then, the temperature of the reaction mixture was raised up to room temperature over a period of 1 hour, and the mixture was further subjected to reaction at the same temperature for 1 hour. The reaction mixture was introduced into 100 ml of water at 5° C., and the pH was adjusted to 6.0 with sodium hydrogencarbonate. The organic layer was separated, washed with 30 ml of saturated aqueous sodium chloride solution and then dried over anhydrous magnesium sulfate. The solvent was removed by distillation under reduced pressure and the residue obtained was distilled under reduced pressure to obtain 11.8 g (yield, 58.0%) of 4-bromo-3-oxothiobutyric acid-S-ethyl ester having a boiling point of 110°-120° C./4 mmHg.

後処理

  1. temperaturewhile maintaining the temperature at -40° to -35° C. over a period of 1 hour
  2. customthe resulting mixture was subjected to reaction at -30° to -20° C. for 30 minutes
  3. temperaturethe resulting solution was cooled to -40° C
  4. additionInto this solution was introduced the above-mentioned reaction mixture
  5. temperatureThen, the temperature of the reaction mixture was raised up to room temperature over a period of 1 hour
  6. customthe mixture was further subjected to reaction at the same temperature for 1 hour
  7. customThe organic layer was separated
  8. washwashed with 30 ml of saturated aqueous sodium chloride solution
  9. dry with materialdried over anhydrous magnesium sulfate
  10. customThe solvent was removed by distillation under reduced pressure
  11. customthe residue obtained
  12. distillationwas distilled under reduced pressure

出典と根拠

ORDレコード
ord-717b35c4eb894f3b96a55ccdf92a5903
出典データセット
uspto-grants-1986_09
特許番号
US04614819

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