Methyl acetoacetate → HCID 13826418, compound

HRID 1906921Notes

Reaction equation

HRID 1906921 reaction equation
[C:1]([O:7][CH3:8])(=[O:6])[CH2:2][C:3]([CH3:5])=[O:4].[H-].[Na+].C([Li])CCC.CCCCCC.[Cl:22][C:23]1[CH:32]=[C:31]([Cl:33])[C:30]2[C:25](=[CH:26][C:27]([Cl:34])=[CH:28][CH:29]=2)[C:24]=1[CH2:35][CH2:36][CH:37]=[O:38]>O1CCCC1>[Cl:22][C:23]1[CH:32]=[C:31]([Cl:33])[C:30]2[C:25](=[CH:26][C:27]([Cl:34])=[CH:28][CH:29]=2)[C:24]=1[CH2:35][CH2:36][CH:37]([OH:38])[CH2:5][C:3](=[O:4])[CH2:2][C:1]([O:7][CH3:8])=[O:6]

Participants

7

Reactant 5

HCID 7757Methyl acetoacetateHCID 8058HexaneHCID 24758Sodium hydrideHCID 13826417HCID 13826417, compoundHCID 178418339Butyllithium

Product 1

HCID 13826418HCID 13826418, compoundYield 88.5%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
5 °C

Procedure

A solution of methyl acetoacetate (0.088 g, 0.76 mmole) in dry tetrahydrofuran (2 ml) was added dropwise (5 minutes) to a mixture of sodium hydride (0.036 g, 0.75 mmole) in tetrahydrofuran (3 ml) under nitrogen and with cooling (ice bath). After stirring at about 5° C. for 20 minutes, a solution of n-butyl lithium in hexane (0.55 ml, 0.77 mole) was added dropwise (5 minutes) and the mixture stirred at 5° C. for 30 minutes. The ice bath was replaced by a dry ice-acetone bath and a solution of 3-(2,4,7-trichloronaphthalen-1-yl)propanal (0.20 g, 0.7 mmole) in tetrahydrofuran (5 ml) was added (5 minutes). The reaction mixture was stirred at -70° C. for about 10 minutes and at room temperature for 5 hours and then poured into ice water containing 0.5 ml conc. HCl. After extraction with ether, the ether extracts were combined, washed with cold water and brine and dried over MgSO4. The solution was filtered and concentrated in vacuo to give 0.25 g of the title compound as a yellow oil.

Workup

  1. temperaturewith cooling (ice bath)
  2. stirringthe mixture stirred at 5° C. for 30 minutes
  3. stirringThe reaction mixture was stirred at -70° C. for about 10 minutes and at room temperature for 5 hours
  4. extractionAfter extraction with ether
  5. washwashed with cold water and brine
  6. dry with materialdried over MgSO4
  7. filtrationThe solution was filtered
  8. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-e1470172fdae4aefa630762672b802fd
Source dataset
uspto-grants-1987_03
Patent number
US04654363

Reaction notes

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