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

HRID 261922

반응식

HRID 261922 반응식
[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]

참가 물질

8

반응물 4

HCID 406CID 406HCID 12958Dimethyl methylphosphonateHCID 10889502Methyl 3-(1-adamantyl)propanoateHCID 178418339Butyllithium

생성물 1

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

시약·촉매·용매 3

HCID 176Acetic Acid용매HCID 8028Tetrahydrofuran용매HCID 8058Hexane용매

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-d74267ae4f9840bd8c5b44a792da3ddb
출처 데이터셋
uspto-grants-1979_05
특허 번호
US04152527

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