Diisopropylamine → HCID 131723198, compound

HRID 843396Notes

Reaction equation

HRID 843396 reaction equation
C([Li:5])CCC.[CH:6]([NH:9][CH:10]([CH3:12])[CH3:11])([CH3:8])[CH3:7].[CH2:13]([O:20][C:21]1[CH:26]=[CH:25][C:24]([CH2:27][C:28]([O:30][CH3:31])=[O:29])=[CH:23][CH:22]=1)[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1.C([N-]C(C)C)(C)C.[Li+].Br[CH2:41][C:42]([O:44][C:45]([CH3:48])([CH3:47])[CH3:46])=[O:43]>CCCCCC.C1COCC1>[CH:6]([N-:9][CH:10]([CH3:12])[CH3:11])([CH3:8])[CH3:7].[Li+:5].[C:45]([O:44][C:42]([CH2:41][CH:27]([C:24]1[CH:25]=[CH:26][C:21]([O:20][CH2:13][C:14]2[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=2)=[CH:22][CH:23]=1)[C:28]([O:30][CH3:31])=[O:29])=[O:43])([CH3:48])([CH3:47])[CH3:46]

Participants

9

Reactant 5

HCID 7912DiisopropylamineHCID 79177tert-Butyl bromoacetateHCID 2724682Lithium diisopropylamideHCID 2756645Methyl 2-(4-benzyloxyphenyl)acetateHCID 178418339Butyllithium

Product 2

HCID 2724682Lithium diisopropylamideHCID 131723198HCID 131723198, compoundYield 86%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolvent

Conditions

Temperature
0 °C

Procedure

Lithium diisopropylamide (LDA) was prepared by the addition of 2.5 M n-butyllithium in hexane (8.4 mL) to a solution of diisopropylamine (2.94 mL, 21 mmol) in THF (30 mL) at −78° C. followed by stirring at 0° C. for 20 min. A solution of methyl 4-benzyloxyphenylacetate (4.8 g, 18.7 mmol) in THF (50 mL) was cooled to −78° C. and to it was added the prepared LDA solution. The mixture was stirred at −78° C. for 1 h and t-butyl bromoacetate (3.1 mL, 21 mmol) in THF (20 mL) was added. The mixture was allowed to warm to 0° C., stirred for an additional 1.5 h at 0° C., quenched with MeOH and concentrated in vacuo. The residue was taken up in EtOAc and the solution was washed with citric acid and brine, dried over MgSO4 and concentrated. Purification on a silica gel column by eluting with 40% EtOAc/hexane afforded the desired product (6.0 g, 86%) as a solid. MS (CI—NH3): (M+H)+=371.

Workup

  1. stirringThe mixture was stirred at −78° C. for 1 h
  2. temperatureto warm to 0° C.
  3. stirringstirred for an additional 1.5 h at 0° C.
  4. customquenched with MeOH
  5. concentrationconcentrated in vacuo
  6. washthe solution was washed with citric acid and brine
  7. dry with materialdried over MgSO4
  8. concentrationconcentrated
  9. customPurification on a silica gel column
  10. washby eluting with 40% EtOAc/hexane

Sources & evidence

ORD record
ord-e0bec602390a4fd8bd7f7abe1175d295
Source dataset
uspto-grants-2002_04
Patent number
US06376665B1

Reaction notes

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