Thiourea → Di-tert-butyl (3-fluoro-4-formylphenyl)(methyl)malonate

HRID 500663Notes

Reaction equation

HRID 500663 reaction equation
[O:1]1CCO[CH:2]1[C:6]1[CH:11]=[CH:10][C:9]([C:12]([CH3:27])([C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21])[C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])=[CH:8][C:7]=1[F:28].NC(N)=S>CCO.O>[F:28][C:7]1[CH:8]=[C:9]([C:12]([CH3:27])([C:20]([O:22][C:23]([CH3:26])([CH3:25])[CH3:24])=[O:21])[C:13]([O:15][C:16]([CH3:17])([CH3:18])[CH3:19])=[O:14])[CH:10]=[CH:11][C:6]=1[CH:2]=[O:1]

Participants

4

Reactant 2

HCID 2723790ThioureaHCID 57443965Di-tert-butyl [4-(1,3-dioxolan-2-yl)-3-fluorophenyl](methyl)malonate

Product 1

HCID 57443966Di-tert-butyl (3-fluoro-4-formylphenyl)(methyl)malonateYield 100%

Reagents, catalysts & solvents 1

HCID 19096565Water ethanolSolvent

Procedure

Di-tert-butyl [4-(1,3-dioxolan-2-yl)-3-fluorophenyl](methyl)malonate (0.91 g, 2.30 mmol) and thiourea (0.87 g, 11.4 mmol) were stirred in refluxing EtOH/H2O (6.7 mL/6.7 mL) for 7 hours. Room temperature was attained and the solvent removed in vacuo. H2O (100 mL) was added to the residue and the products extracted into EtOAc (2×100 mL). The combined organic extracts were washed with brine, dried over MgSO4 and concentrated in vacuo to give 0.81 g of clean product (pale yellow gum, 100%). 1H NMR (CDCl3) δ 10.33 (s, 1H), 7.82 (t, J=8.1 Hz, 1H), 7.31 (dd, J=8.1, 1.8 Hz, 1H), 7.27 (dd, J=12.0, 1.8 Hz, 1H), 1.77 (s, 3H), 1.46 (s, 18H).

Workup

  1. customRoom temperature
  2. customthe solvent removed in vacuo
  3. additionH2O (100 mL) was added to the residue
  4. extractionthe products extracted into EtOAc (2×100 mL)
  5. washThe combined organic extracts were washed with brine
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-9ca2db67a9054dc89de1580a4b2dfc10
Source dataset
uspto-grants-2010_08
Patent number
US07772238B2

Reaction notes

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