Formaldehyde → t-Butyl 2-(2-phenylethyl)acrylate

HRID 1995106Notes

Reaction equation

HRID 1995106 reaction equation
C([Li:5])CCC.[CH:6]([NH:9][CH:10]([CH3:12])[CH3:11])([CH3:8])[CH3:7].C(=O)=O.CC(C)=O.[C:20]([O:24][C:25](=[O:38])[CH:26]([CH2:30][CH2:31][C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1)[C:27](=O)C)([CH3:23])([CH3:22])[CH3:21].C=O>O1CCCC1>[CH:6]([N-:9][CH:10]([CH3:12])[CH3:11])([CH3:8])[CH3:7].[Li+:5].[C:20]([O:24][C:25](=[O:38])[C:26](=[CH2:27])[CH2:30][CH2:31][C:32]1[CH:33]=[CH:34][CH:35]=[CH:36][CH:37]=1)([CH3:23])([CH3:22])[CH3:21]

Participants

8

Reactant 5

HCID 712FormaldehydeHCID 7912DiisopropylamineHCID 13195717Tert-butyl 3-oxo-2-phenethylbutanoateHCID 18522661Acetone cardiceHCID 178418339Butyllithium

Product 2

HCID 2724682Lithium diisopropylamideHCID 14552295t-Butyl 2-(2-phenylethyl)acrylateYield 27%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of lithium diisopropylamide in tetrahydrofuran was prepared by addition of n-butyllithium (4.2 ml, 11 mmol) to a solution of diisopropylamine (1.1 g, 11 mmol) in anhydrous THF (22 ml) cooled to -78° (dry-ice acetone bath). After additon of t-butyl-2-(2-phenylethyl)-3-oxobutyrate (2.62 g, 10 mmol), the mixture was stirred for 10 minutes, then dry paraformaldehyde (1.4 g) was added all at once. The mixture was allowed to warm to room temperature, stirred for one hour at this temperature, then heated at reflux for one hour. The mixture was cooled, filtered, and concentrated, and the residue was purified by chromatography on neutral alumina, giving the title product (0.62 g, 2.7 mmol, 27%) as a colorless oil. NMR (CDCl3); 1.48 (9H,s), 2.3-3.0 (4H,m), 5.2 (1H, broad s), 6.05 (1H,d,J=1 Hz), 7.13 (5H,s). IR (CHCl3); 1700, 1630, 1590 cm-1. MS (m/e); 232 (M+).

Workup

  1. temperatureheated
  2. temperatureat reflux for one hour
  3. temperatureThe mixture was cooled
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customthe residue was purified by chromatography on neutral alumina

Sources & evidence

ORD record
ord-c3639d5176e6450b83975940af938c52
Source dataset
uspto-grants-1983_09
Patent number
US04402969

Reaction notes

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