Tert-butyl acetoacetate → HCID 54272216, compound

HRID 330675Notes

Reaction equation

HRID 330675 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([C:20]2[CH:25]=[CH:24][C:23]([F:26])=[CH:22][C:21]=2[CH3:27])=[C:9]([C:14]2[N:18]([CH3:19])[N:17]=[N:16][N:15]=2)[CH:10]=[CH:11][CH:12]=[O:13])=[C:4]([CH3:28])[CH:3]=1.[C:29]([O:35][C:36]([CH3:39])([CH3:38])[CH3:37])(=[O:34])[CH2:30][C:31]([CH3:33])=[O:32].[H-].[Na+].C([Li])CCC>O1CCCC1>[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]([C:20]2[CH:25]=[CH:24][C:23]([F:26])=[CH:22][C:21]=2[CH3:27])=[C:9]([C:14]2[N:18]([CH3:19])[N:17]=[N:16][N:15]=2)[CH:10]=[CH:11][CH:12]([OH:13])[CH2:33][C:31](=[O:32])[CH2:30][C:29]([O:35][C:36]([CH3:39])([CH3:38])[CH3:37])=[O:34])=[C:4]([CH3:28])[CH:3]=1

Participants

6

Reactant 4

HCID 15538Tert-butyl acetoacetate2×HCID 24758Sodium hydrideHCID 53912652HCID 53912652, compoundHCID 178418339Butyllithium

Product 1

HCID 54272216HCID 54272216, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
-30 °C

Procedure

To a solution of 5,5-bis(4-fluoro-2-methylphenyl)-4-(1-methyl-1H-tetrazol-5-yl)-2,4-pentadienal (1.0 g, 2.5 mmoles) in tetrahydrofuran at -50° C. was added the dianion of t-butyl acetoacetate (2.5 mL of a 1M solution, 2.5 mmoles) prepared by adding t-butyl acetoacetate (4.0 g, 25.0 mmoles) in tetrahydrofuran (4 mL) to a suspension of sodium hydride (1.0 g of 60% dispersion, 25.0 mmoles) in tetrahydrofuran at -5° C. followed by cooling to -30° C. and the addition of butyl lithium (11.4 mL of 2.2M solution, 25 mmoles). After stirring for 1.5 hours, analytical TLC indicated starting aldehyde and another 0.5 mL of dianion solution was added. The solution was stirred an additional 0.5 hour and quenched with 1N hydrochloric acid. The mixture was extracted with methylene chloride. The extracts were dried and concentrated in vacuo. The residue was purified by column chromatography on silica gel eluting with methanol in methylene chloride to produce 0.6 g of the title compound; m.p.=65°-72° C.

Workup

  1. customprepared
  2. additionanother 0.5 mL of dianion solution was added
  3. stirringThe solution was stirred an additional 0.5 hour
  4. customquenched with 1N hydrochloric acid
  5. extractionThe mixture was extracted with methylene chloride
  6. customThe extracts were dried
  7. concentrationconcentrated in vacuo
  8. customThe residue was purified by column chromatography on silica gel eluting with methanol in methylene chloride

Sources & evidence

ORD record
ord-1280e92bad6543588ed1cc958e90a50a
Source dataset
uspto-grants-1990_01
Patent number
US04897490

Reaction notes

Loading…