Formaldehyde → Methyl 4-(3-(tert-butoxycarbonyl)but-3-en-2-yl)benzoate

HRID 931395Notes

Reaction equation

HRID 931395 reaction equation
[C:1](=O)([O-])[O-].[K+].[K+].C=O.[C:9]([O:13][C:14](=[O:36])[CH:15](P(OCC)(OCC)=O)[CH:16]([C:18]1[CH:27]=[CH:26][C:21]([C:22]([O:24][CH3:25])=[O:23])=[CH:20][CH:19]=1)[CH3:17])([CH3:12])([CH3:11])[CH3:10]>C1COCC1>[C:9]([O:13][C:14]([C:15](=[CH2:1])[CH:16]([C:18]1[CH:19]=[CH:20][C:21]([C:22]([O:24][CH3:25])=[O:23])=[CH:26][CH:27]=1)[CH3:17])=[O:36])([CH3:10])([CH3:11])[CH3:12]

Participants

5

Reactant 3

HCID 712FormaldehydeHCID 11430Potassium CarbonateHCID 118022782Methyl 4-(4-(tert-butoxy)-3-(diethoxyphosphoryl)-4-oxobutan-2-yl)benzoate

Product 1

HCID 90010903Methyl 4-(3-(tert-butoxycarbonyl)but-3-en-2-yl)benzoate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

Potassium carbonate (9.16 g, 66.2 mmol) and paraformaldehyde (2.48 g, 82.7 mmol) were added to a solution of methyl 4-(4-(tert-butoxy)-3-(diethoxyphosphoryl)-4-oxobutan-2-yl)benzoate (13.7 g, 33.1 mmol) in anhydrous THF (250 mL), respectively. The reaction mixture was heated at reflux for 20 h, then cooled, and concentrated. The residue was purified by flash chromatography on silica gel eluting with 5% ethyl acetate in petroleum ether to give the title compound. MS: m/z=235.0 (M−tBu); 1H NMR (400 MHz, CDCl3): δ 7.97 (d, 2H, J=8.5 Hz), 7.28 (d, 2H, J=8.5 Hz), 6.26-6.32 (m, 1H), 5.56-5.61 (m, 1H), 4.01 (q, 1H, J=7.1 Hz), 3.92 (s, 3H), 1.42 (d, 3H, J=7.0 Hz), 1.33 (s, 9H).

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureat reflux for 20 h
  3. temperaturecooled
  4. concentrationconcentrated
  5. customThe residue was purified by flash chromatography on silica gel eluting with 5% ethyl acetate in petroleum ether

Sources & evidence

ORD record
ord-036e9bb8c47f4e82a6dd1b92b7a33bc0
Source dataset
uspto-grants-2016_03
Patent number
US09296750B2

Reaction notes

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