CID 406 → HCID 21321734、化合物

HRID 261921ノート

反応式

HRID 261921 の反応式
[CH3:1][P:2](=[O:7])([O:5][CH3:6])[O:3][CH3:4].P(=O)([O-])[O-].C([Li])CCC.[C:17]12([CH2:27][C:28](OC)=[O:29])[CH2:26][CH:21]3[CH2:22][CH:23]([CH2:25][CH:19]([CH2:20]3)[CH2:18]1)[CH2:24]2>O1CCCC1.CCCCCC.C(O)(=O)C>[O:29]=[C:28]([CH2:27][C:17]12[CH2:26][CH:21]3[CH2:22][CH:23]([CH2:25][CH:19]([CH2:20]3)[CH2:18]1)[CH2:24]2)[CH2:1][P:2](=[O:7])([O:5][CH3:6])[O:3][CH3:4]

参加物

8

反応物 4

HCID 406CID 406HCID 12958Dimethyl methylphosphonateHCID 141339Tricyclo(3.3.1.13,7)decane-1-acetic acid, methyl esterHCID 178418339Butyllithium

生成物 1

HCID 21321734HCID 21321734、化合物

試薬・触媒・溶媒 3

HCID 176Acetic Acid溶媒HCID 8028Tetrahydrofuran溶媒HCID 8058Hexane溶媒

実験手順

A solution of 49.6 g (0.400 moles) dimethyl methylphosphonate (Aldrich) in 500 ml dry tetrahydrofuran was cooled to -78° in a dry nitrogen atmosphere. To the stirred phosphonate solution was added 188 ml of 2.34 M n-butyllithium in hexane solution (Alfa Inorganics, Inc. dropwise over a period of 40 minutes at such a rate that the reaction temperature never rose above -65°. After an additional 5 minutes stirring at -78°, 41.7 g (0.200 mole) methyl (1-adamantyl)-acetate was added dropwise at a rate that kept the reaction temperature less than -70° (20 minutes). After 1.0 hour at -78°, the reaction mixture was allowed to warm to ambient temperature, neutralized with 25 ml acetic acid and rotary evaporated to a white gel. The gelatinous material was taken up in 50 ml water, the aqueous phase extracted with 100 ml portions of methylene chloride (4x), the combined orgaic extracts were backwashed with water (4 × 100 ml), dried (MgSO4), and concentrated (water aspirator) to a crude residue and distilled, b.p 209°-212° (<0.02 mm) to give dimethyl 2-oxo-3-(1-adamantyl)propylphosphonate (2a ).

後処理

  1. customthe reaction temperature less than -70° (20 minutes)
  2. waitAfter 1.0 hour at -78°
  3. customrotary evaporated to a white gel
  4. extractionthe aqueous phase extracted with 100 ml portions of methylene chloride (4x)
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated (water aspirator) to a crude residue
  7. distillationdistilled, b.p 209°-212° (<0.02 mm)

出典と根拠

ORDレコード
ord-704c97ff8fdf44a189a2bfd360863807
出典データセット
uspto-grants-1979_05
特許番号
US04152527

反応ノート

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