Phenyl Isothiocyanate → tert-butyl 5,5-dimethyl-2-(3-phenylthioureido)-5,7-dihydro-4H-thieno[2,3-c]pyran-3-carboxylate

HRID 2207763Notes

Reaction equation

HRID 2207763 reaction equation
[NH2:1][C:2]1[S:12][C:5]2[CH2:6][O:7][C:8]([CH3:11])([CH3:10])[CH2:9][C:4]=2[C:3]=1[C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14].[C:20]1([N:26]=[C:27]=[S:28])[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1>O1CCCC1>[CH3:10][C:8]1([CH3:11])[O:7][CH2:6][C:5]2[S:12][C:2]([NH:1][C:27]([NH:26][C:20]3[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=3)=[S:28])=[C:3]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[C:4]=2[CH2:9]1

Participants

4

Reactant 2

HCID 7673Phenyl IsothiocyanateHCID 86731954tert-butyl 2-amino-5,5-dimethyl-5,7-dihydro-4H-thieno[2,3-c]pyran-3-carboxylate

Product 1

HCID 86731953tert-butyl 5,5-dimethyl-2-(3-phenylthioureido)-5,7-dihydro-4H-thieno[2,3-c]pyran-3-carboxylateYield 30.6%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of tert-butyl 2-amino-5,5-dimethyl-5,7-dihydro-4H-thieno[2,3-c]pyran-3-carboxylate (0.100 g, 0.353 mmol, 1 eq) in dry tetrahyrofuran (5 mL) under argon was added phenyl isothiocyanate (0.05 mL, 0.388 mmol, 1.1 eq). The mixture was heated at reflux for 16 hours. The solvent was evaporated in vacuo. Purification by reverse-phase chromatography (0-100% CH3CN: Water ramp over 20 min) afforded the desired product tert-butyl 5,5-dimethyl-2-(3-phenylthioureido)-5,7-dihydro-4H-thieno[2,3-c]pyran-3-carboxylate as a yellow solid (0.045 g, 0.108 mmol, 30% yield). 1H NMR (400 MHz, DMSO) δ 11.92 (s, 1H), 11.05 (s, 1H), 7.50 (d, J=7.6, 2H), 7.42 (t, J=7.9, 2H), 7.26 (t, J=7.3, 1H), 4.61 (s, 2H), 2.65 (s, 2H), 1.53 (s, 9H), 1.23 (s, 6H).

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux for 16 hours
  3. customThe solvent was evaporated in vacuo
  4. customPurification by reverse-phase chromatography (0-100% CH3CN: Water ramp over 20 min)

Sources & evidence

ORD record
ord-5f5c12aca220491f9014900dbd424a2a
Source dataset
uspto-grants-2016_06
Patent number
US09376452B2

Reaction notes

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