CID 406 → HCID 21321734, compound

HRID 261921Notes

Reaction equation

HRID 261921 reaction equation
[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]

Participants

8

Reactant 4

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

Product 1

HCID 21321734HCID 21321734, compound

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Procedure

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 ).

Workup

  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)

Sources & evidence

ORD record
ord-704c97ff8fdf44a189a2bfd360863807
Source dataset
uspto-grants-1979_05
Patent number
US04152527

Reaction notes

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