Formaldehyde → 8-Oxo-2,2,5,7-tetramethyl-7-(hydroxymethyl)-3-oxa-1-azabicyclo[4.2.0]octane

HRID 443457ノート

反応式

HRID 443457 の反応式
C([N-]C(C)C)(C)C.[Li+].[O:9]=[C:10]1[N:17]2[CH:12]([CH:13]([CH3:20])[CH2:14][O:15][C:16]2([CH3:19])[CH3:18])[CH:11]1[CH3:21].[CH2:22]=[O:23].[Cl-].[Na+]>O1CCCC1.O>[O:23]=[C:22]1[N:17]2[CH:12]([CH:13]([CH3:20])[CH2:14][O:15][C:16]2([CH3:18])[CH3:19])[C:11]1([CH3:21])[CH2:10][OH:9]

参加物

7

反応物 4

HCID 712FormaldehydeHCID 5234Sodium ChlorideHCID 2724682Lithium diisopropylamideHCID 204494518-Oxo-2,2,5,7-tetramethyl-3-oxa-1-azabicyclo[4.2.0]octane

生成物 1

HCID 204494488-Oxo-2,2,5,7-tetramethyl-7-(hydroxymethyl)-3-oxa-1-azabicyclo[4.2.0]octane

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒2 回

反応条件

温度
-78 °C

実験手順

To a solution of 1.1 equivalents of freshly prepared lithium diisopropylamide in anhydrous tetrahydrofuran under a nitrogen atmosphere at -78° is added a solution of 8-oxo-2,2,5,7-tetramethyl-3-oxa-1-azabicyclo-[4.2.0]octane in anhydrous tetrahydrofuran which has been cooled to -78° C. After two minutes, the resulting lithium enolate is treated with excess formaldehyde, introduced as a gas just above the surface of the stirred solution. The solution is stirred for 30 minutes at -78° and then poured into water. The aqueous phase is saturated with sodium chloride and extracted with ethyl acetate. The combined ethyl acetate solutions are dried over magnesium sulfate and filtered. The filtrate is evaporated under reduced pressure to give the crude product. Purification by chromatographed on silica gel using ethyl acetate/benzene gives 8-oxo-2,2,5,7-tetramethyl-7-(hydroxymethyl)-3-oxa-1-azabicyclo[4.2.0]octane.

後処理

  1. additionintroduced as a gas just above the surface of the stirred solution
  2. extractionextracted with ethyl acetate
  3. dry with materialThe combined ethyl acetate solutions are dried over magnesium sulfate
  4. filtrationfiltered
  5. customThe filtrate is evaporated under reduced pressure
  6. customto give the crude product
  7. customPurification
  8. customby chromatographed on silica gel

出典と根拠

ORDレコード
ord-834b25dae12b42b99631f2b610b10d2c
出典データセット
uspto-grants-1981_04
特許番号
US04260627

反応ノート

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