Methyl acetoacetate → HCID 17821749, compound

HRID 1609568Notes

Reaction equation

HRID 1609568 reaction equation
[C:1]([O:7][CH3:8])(=[O:6])[CH2:2][C:3]([CH3:5])=[O:4].[H-].[Na+].C([Li])CCC.[F:16][C:17]1[CH:22]=[CH:21][C:20]([C:23]2[C:28](/[CH:29]=[CH:30]/[CH:31]=[O:32])=[C:27]([CH:33]([CH3:35])[CH3:34])[C:26]([CH2:36][OH:37])=[C:25]([CH:38]([CH3:40])[CH3:39])[N:24]=2)=[CH:19][CH:18]=1.[Cl-].[NH4+]>O1CCCC1.CCCCCC.[Br-].[Zn+2].[Br-]>[F:16][C:17]1[CH:22]=[CH:21][C:20]([C:23]2[C:28](/[CH:29]=[CH:30]/[CH:31]([OH:32])[CH2:5][C:3](=[O:4])[CH2:2][C:1]([O:7][CH3:8])=[O:6])=[C:27]([CH:33]([CH3:34])[CH3:35])[C:26]([CH2:36][OH:37])=[C:25]([CH:38]([CH3:40])[CH3:39])[N:24]=2)=[CH:19][CH:18]=1

Participants

9

Reactant 5

HCID 7757Methyl acetoacetateHCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 20081821HCID 20081821, compoundHCID 178418339Butyllithium

Product 1

HCID 17821749HCID 17821749, compound

Reagents, catalysts & solvents 3

HCID 10421208Zinc bromideCatalystHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Procedure

0.5 ml (4.5 mmol) of methyl acetoacetate are added dropwise at 0° C.-5° C. under argon to a suspension of 0.15 g(5 mmol) of 80% pure sodium hydride in 6.5 ml of tetrahydrofuran p.a. After 15 minutes in each case, 3.65 ml (6 mmol) of 15% strength butyllithium in hexane are first added dropwise at 0° C. during the course of 10 minutes then a solution of 1.01 g (4.5 mmol) of dry zinc bromide in 4.5 ml of tetrahydrofuran and finally 0.51 g (1.5 mmol) of the compound from Example 123. The mixture is stirred overnight at room temperature, saturated ammonium chloride solution is added slowly, the aqueous phase is extracted using ethyl acetate, and the combined organic phases are washed using saturated sodium chloride solution, dried over sodium sulphate and concentrated. After column chromatography (φ3 cm) on 20 g of silica gel (230-400 mesh) using petroleum ether-ethyl acetate (1:1), 0.17 g (25% of theory) of yellowish oil is obtained. Rf =0.35 (petroleum ether-ethyl acetate (1:1)).

Workup

  1. extractionthe aqueous phase is extracted
  2. washthe combined organic phases are washed
  3. dry with materialdried over sodium sulphate
  4. concentrationconcentrated
  5. customis obtained

Sources & evidence

ORD record
ord-001f4445d8614a9dbea340227d7aa335
Source dataset
uspto-grants-1995_03
Patent number
US05401746

Reaction notes

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