Sulfuric Acid → Ethyl 2-cyano-5-phenyl-1,3-thiazole-4-carboxylate

HRID 383931Notes

Reaction equation

HRID 383931 reaction equation
N[C:2]1[S:3][C:4]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)=[C:5]([C:7]([O:9][CH2:10][CH3:11])=[O:8])[N:6]=1.S(=O)(=O)(O)O.N([O-])=O.[Na+].[C:27]([Cu])#[N:28].[C-]#N.[Na+].C([O-])(O)=O.[Na+]>CCOC(C)=O.C(O)(=O)C>[C:27]([C:2]1[S:3][C:4]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)=[C:5]([C:7]([O:9][CH2:10][CH3:11])=[O:8])[N:6]=1)#[N:28]

Participants

9

Reactant 6

HCID 1118Sulfuric AcidHCID 8929Sodium CyanideHCID 516892Sodium BicarbonateHCID 12603728Ethyl 2-amino-5-phenyl-1,3-thiazole-4-carboxylateHCID 23668193Sodium NitriteHCID 178418546HCID 178418546, compound

Product 1

HCID 59291286Ethyl 2-cyano-5-phenyl-1,3-thiazole-4-carboxylate

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a mixed solution of ethyl 2-amino-5-phenyl-1,3-thiazole-4-carboxylate, acetic acid, and sulfuric acid was slowly added an aqueous NaNO2 solution (5 mL) at 0° C., followed by stirring at the same temperature for 1 hour. This solution was added to an aqueous solution (40 mL) containing CuCN, NaCN, and NaHCO3 (30 g) over 30 minutes, followed by stirring at the same temperature for 1 hour. EtOAc was added thereto, and the insolubles were filtered through Celite. The filtrate was extracted with EtOAc, the organic layer was dried, and the solvent was removed by evaporation under reduced pressure. The residue was purified by silica gel column chromatography (hexane:EtOAc=from 5:1 to 3:1 to 2:1) to obtain ethyl 2-cyano-5-phenyl-1,3-thiazole-4-carboxylate as a yellow solid.

Workup

  1. stirringby stirring at the same temperature for 1 hour
  2. filtrationthe insolubles were filtered through Celite
  3. extractionThe filtrate was extracted with EtOAc
  4. customthe organic layer was dried
  5. customthe solvent was removed by evaporation under reduced pressure
  6. customThe residue was purified by silica gel column chromatography (hexane:EtOAc=from 5:1 to 3:1 to 2:1)

Sources & evidence

ORD record
ord-d184072c5da9451f9c16c669c262b828
Source dataset
uspto-grants-2013_02
Patent number
US08367696B2

Reaction notes

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