Ethanol → Sodium 1-(2-chlorophenyl)-3-cyano-6-oxo-1,6-dihydropyridine-2-thiolate

HRID 1455523Notes

Reaction equation

HRID 1455523 reaction equation
C[Si]([N-][Si](C)(C)C)(C)C.[Na+:10].[Cl:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[N:18]=[C:19]=[S:20].[CH3:21][CH2:22][OH:23]>C1COCC1.C(#N)C>[Cl:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[N:18]1[C:22](=[O:23])[CH:21]=[CH:17][C:12]([C:13]#[N:18])=[C:19]1[S-:20].[Na+:10]

Participants

6

Reactant 3

HCID 702EthanolHCID 1231711-Chloro-2-isothiocyanatobenzeneHCID 2724254Sodium bis(trimethylsilyl)amide

Product 1

HCID 68805809Sodium 1-(2-chlorophenyl)-3-cyano-6-oxo-1,6-dihydropyridine-2-thiolateYield 88%

Reagents, catalysts & solvents 2

HCID 6342AcetonitrileSolventHCID 8028TetrahydrofuranSolvent

Procedure

NaHMDS (13.2 mL, 1.0M in THF, 13.2 mmol) was added slowly to a solution of 2-chlorophenyl isothiocyanate (1.02 g, 6.0 mmol) in THF (50 mL) and acetonitrile (5 mL) at −78° C. The mixture was warmed to r.t. over 1 h. N,N-Dimethyluracil (841 mg, 6.0 mmol) and EtOH (75 mL) were added and the mixture heated at reflux for 4 h. Volatiles were removed in vacuo and the residue was dissolved in hot EtOH (10 mL). Et2O (˜100 mL) was added slowly to precipitate out the product. The solid was filtered off, washed with Et2O (2×30 mL) and dried to give the title compound (1.5 g, 88%) (v. hygroscopic). δH (DMSO-d6) 7.35-7.32 (1H, m), 7.25-7.20 (2H, m), 7.15 (1H, d, J 9.1 Hz), 7.05-7.01 (1H, m), 5.85 (1H, br s), 5.58 (1H, d, J 9.1 Hz). LCMS (ES+) RT 3.06 minutes, 285 (M+H)+.

Workup

  1. temperaturethe mixture heated
  2. temperatureat reflux for 4 h
  3. customVolatiles were removed in vacuo
  4. dissolutionthe residue was dissolved in hot EtOH (10 mL)
  5. additionEt2O (˜100 mL) was added slowly
  6. customto precipitate out the product
  7. filtrationThe solid was filtered off
  8. washwashed with Et2O (2×30 mL)
  9. customdried

Sources & evidence

ORD record
ord-de1cb130da004ac0845fb39695e6848f
Source dataset
uspto-grants-2009_01
Patent number
US07482452B2

Reaction notes

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