Diethyl methylmalonate → Diethyl 2-methyl-2-(pent-4-ynyl)malonate

HRID 129309

反応式

HRID 129309 の反応式
[CH3:1][CH:2]([C:8]([O:10][CH2:11][CH3:12])=[O:9])[C:3]([O:5][CH2:6][CH3:7])=[O:4].[H-].[Na+].CS(O[CH2:20][CH2:21][CH2:22][C:23]#[CH:24])(=O)=O>O1CCCC1>[CH3:1][C:2]([CH2:24][CH2:23][CH2:22][C:21]#[CH:20])([C:3]([O:5][CH2:6][CH3:7])=[O:4])[C:8]([O:10][CH2:11][CH3:12])=[O:9]

参加物

5

反応物 3

HCID 11857Diethyl methylmalonateHCID 24758Sodium hydrideHCID 12476209Pent-4-yn-1-yl methanesulfonate

生成物 1

HCID 19373418Diethyl 2-methyl-2-(pent-4-ynyl)malonate

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒3 回

実験手順

A solution of diethyl methylmalonate (Aldrich Chemical Company, 35.6 ml) in dry tetrahydrofuran (200 ml) was added, dropwise, to a stirred suspension of sodium hydride (60% dispersion in mineral oil, 9.1 g) in tetrahydrofuran (50 ml) under nitrogen. After the addition was complete, the mixture was heated to gentle reflux for 1 hour and then allowed to cool before a solution of pent-4-ynyl methanesulphonate (35.2 g) in tetrahydrofuran (50 ml) was added. The resulting mixture was heated to gentle reflux for a further 2 hours. The bulk of the solvent was then removed in vacuo and the residue was partitioned between diethyl ether and water. The organic phase was separated and washed with water and brine before drying over anhydrous magnesium sulphate and evaporation under reduced pressure. Distillation gave diethyl 2-methyl-2-(pent-4-ynyl)malonate (45.8 g) as a colourless oil (b.p. 92°-97°, 0.5 mm Hg)

後処理

  1. additionAfter the addition
  2. temperaturethe mixture was heated
  3. temperatureto gentle reflux for 1 hour
  4. additionwas added
  5. temperatureThe resulting mixture was heated
  6. temperatureto gentle reflux for a further 2 hours
  7. customThe bulk of the solvent was then removed in vacuo
  8. customthe residue was partitioned between diethyl ether and water
  9. customThe organic phase was separated
  10. washwashed with water and brine
  11. dry with materialbefore drying over anhydrous magnesium sulphate and evaporation under reduced pressure
  12. distillationDistillation

出典と根拠

ORDレコード
ord-d0e7030d8e3547a68a2f7ea0306aa4cf
出典データセット
uspto-grants-1995_11
特許番号
US05466710

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