Methyl acetoacetate → HCID 17821749, compound

HRID 1681263Notes

Reaction equation

HRID 1681263 reaction equation
[C:1]([O:7][CH3:8])(=[O:6])[CH2:2][C:3]([CH3:5])=[O:4].[H-].[Na+].[CH2:11]([Li])[CH2:12][CH2:13]C.[F:16][C:17]1[CH:22]=[CH:21][C:20]([C:23]2[CH:28](/[CH:29]=[CH:30]/[CH:31]=[O:32])[C:27](C(C)C)([CH:33]([CH3:35])[CH3:34])[C:26]([CH2:39][OH:40])=[CH:25][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]([CH2:39][OH:40])=[C:25]([CH:12]([CH3:13])[CH3:11])[N:24]=2)=[CH:19][CH:18]=1

Participants

9

Reactant 5

HCID 7757Methyl acetoacetateHCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 86746403HCID 86746403, 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.

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-35bc1a738d24451c87ef678cec627a6d
Source dataset
uspto-grants-1992_12
Patent number
US05169857

Reaction notes

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