CID 406 → Dimethyl 2-Oxo-4-(1-Adamantyl)butylphosphonate

HRID 261922

反応式

HRID 261922 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][CH2:28][C:29](OC)=[O:30])[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:30]=[C:29]([CH2:28][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 10889502Methyl 3-(1-adamantyl)propanoateHCID 178418339Butyllithium

生成物 1

HCID 21321716Dimethyl 2-Oxo-4-(1-Adamantyl)butylphosphonate収率 100%

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 24.8 g (0.200 moles) dimethyl methyl-phosphonate (Aldrich) in 250 ml dry tetrahydrofuran was cooled to -78° in a dry nitrogen atomsphere. To the stirred phosphonate solution was added 92 ml of 2.38 M n-butyllithium in hexane solution (Alfa Inorganics, Inc.) dropwise over a period of 30 minutes at such a rate that the reaction temperature never rose above -65°. After an additional 5 minutes stirring at -78°, 22.2 g (0.100 mole) methyl 3-(1-adamantyl)propionate 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 55 ml acetic acid and rotary evaporated to a white gel. The gelatenous material was taken up to 50 ml water, the aqueous phase extracted with 100 ml portions of methylene chloride (4X), the combined organic extracts were backwashed with water (4 × 100 ml), dried (MgSO4), and concentrated (water aspirator) to a crude residue and distilled, b.p. 195-200° (<0.02 mm) to give dimethyl 2-oxo-4-(1-adamantyl)butylphosphonate (2b) weighing 36.6 g (100% yield).

後処理

  1. customthe reaction temperature less than -70° (20 minutes)
  2. waitAfter 1.0 hour at -78° the reaction mixture was allowed
  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

出典と根拠

ORDレコード
ord-d74267ae4f9840bd8c5b44a792da3ddb
出典データセット
uspto-grants-1979_05
特許番号
US04152527

関連ノート

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