Dimethylformamide → HCID 90418142, compound

HRID 2177363Notes

Reaction equation

HRID 2177363 reaction equation
C([S:4][CH:5]([CH3:12])[C:6](=[O:11])[C:7]([F:10])([F:9])[F:8])(=O)C.CN(C)C=O.[C:18]([CH2:20][C:21]([O:23][CH2:24][CH3:25])=[O:22])#[N:19]>CC(=O)OCC>[NH2:19][C:18]1[S:4][CH:5]([CH3:12])[C:6]([OH:11])([C:7]([F:10])([F:9])[F:8])[C:20]=1[C:21]([O:23][CH2:24][CH3:25])=[O:22]

Participants

5

Reactant 3

HCID 6228DimethylformamideHCID 7764Ethyl cyanoacetateHCID 90418133HCID 90418133, compound

Product 1

HCID 90418142HCID 90418142, compound

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

Into a 100-mL round-bottom flask, was placed 3-(acetylsulfanyl)-1,1,1-trifluorobutan-2-one (5.8 g, 28.97 mmol, 1.00 equiv), N,N-dimethylformamide (10 mL). This was followed by the addition of TEA (3 g, 29.65 mmol, 1.02 equiv) and ethyl 2-cyanoacetate (3.27 g, 28.91 mmol, 1.00 equiv) dropwise with stirring at 0° C. The resulting solution was stirred overnight at 25° C. Then it was diluted with 20 mL of EA. The organic phase was separated and washed with 3×20 mL of H2O. The mixture was dried over anhydrous sodium sulfate. The solids were filtered out. The resulting mixture was concentrated under vacuum. The residue was applied onto a silica gel column with ethyl acetate/petroleum ether (30/70). The collected fractions were combined and concentrated under vacuum. This resulted in 6.5 g (79%) of ethyl 2-amino-4-hydroxy-5-methyl-4-(trifluoromethyl)-4,5-dihydrothiophene-3-carboxylate as a dark red liquid.

Workup

  1. customInto a 100-mL round-bottom flask, was placed
  2. stirringThe resulting solution was stirred overnight at 25° C
  3. customThe organic phase was separated
  4. washwashed with 3×20 mL of H2O
  5. dry with materialThe mixture was dried over anhydrous sodium sulfate
  6. filtrationThe solids were filtered out
  7. concentrationThe resulting mixture was concentrated under vacuum
  8. concentrationconcentrated under vacuum
  9. customThis resulted in 6.5 g (79%) of ethyl 2-amino-4-hydroxy-5-methyl-4-(trifluoromethyl)-4,5-dihydrothiophene-3-carboxylate as a dark red liquid

Sources & evidence

ORD record
ord-d560489600754cf3a547f75d413d57cd
Source dataset
uspto-grants-2015_06
Patent number
US09067898B1

Reaction notes

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