CID 406 → HCID 14560275, compound

HRID 261929Notes

Reaction equation

HRID 261929 reaction equation
[CH3:1][P:2](=[O:7])([O:5][CH3:6])[O:3][CH3:4].P(=O)([O-])[O-].C([Li])CCC.[CH2:17]1[C:25]2[C:20](=[CH:21][CH:22]=[CH:23][CH:24]=2)[CH2:19][CH:18]1[C:26](OC)=[O:27]>O1CCCC1.CCCCCC.C(O)(=O)C>[O:27]=[C:26]([CH:18]1[CH2:19][C:20]2[C:25](=[CH:24][CH:23]=[CH:22][CH:21]=2)[CH2:17]1)[CH2:1][P:2](=[O:7])([O:5][CH3:6])[O:3][CH3:4]

Participants

8

Reactant 4

HCID 406CID 406HCID 12958Dimethyl methylphosphonateHCID 9964238Methyl indane-2-carboxylateHCID 178418339Butyllithium

Product 1

HCID 14560275HCID 14560275, compoundYield 86.4%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Procedure

A solution of 20.4 g (164 mmoles) dimethyl methylphosphonate (Aldrich) in 200 ml dry tetrahydrofuran was cooled to -78° in a dry nitrogen atmosphere. To the stirred phosphonate solution was added 82.6 ml of 2.25M n-butyllithium in hexane solution (Alfa Inorganics, Inc.) dropwise over a period of 20 minutes at such a rate that the reaction temperature never rose above -65°. After an additional 5 minutes stirring at -78°, 14.0 g (73.5 mmole) methyl indane-2-carboxylate 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 20 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 75 ml portions of methylene chloride (4x), the combined organic extracts were backwashed (75 ml H2O), dried (MgSO4), and concentrated (water aspirator) to a crude residue and distilled, b.p. 150°-160° (0.1 mm) to give 17.0 g (86.4%) dimethyl 2-oxo-2-(2-indany)ethylphsphonate (2i).

Workup

  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 75 ml portions of methylene chloride (4x)
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated (water aspirator) to a crude residue
  7. distillationdistilled

Sources & evidence

ORD record
ord-ad182aa9a7304ca4b3c929b03f694e67
Source dataset
uspto-grants-1979_05
Patent number
US04152527

Reaction notes

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