Chloroacetonitrile → HCID 71059752, compound

HRID 2402341Notes

Reaction equation

HRID 2402341 reaction equation
Cl[CH2:2][C:3]#[N:4].[F:5][C:6]1([F:15])[CH2:11][CH2:10][N:9]([C:12]([NH2:14])=[S:13])[CH2:8][CH2:7]1.[C:16]1([C:22](=O)[CH2:23][C:24](=O)[C:25]([O:27][CH2:28][CH3:29])=[O:26])[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1.C([O-])(=O)C.[Na+]>CO>[CH2:28]([O:27][C:25]([C:24]1[CH:23]=[C:22]([C:16]2[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=2)[N:4]=[C:3]2[N:14]=[C:12]([N:9]3[CH2:8][CH2:7][C:6]([F:5])([F:15])[CH2:11][CH2:10]3)[S:13][C:2]=12)=[O:26])[CH3:29]

Participants

6

Reactant 4

HCID 7856ChloroacetonitrileHCID 2265032,4-Dioxo-4-phenyl-butyric acid ethyl esterHCID 517045Sodium AcetateHCID 45118489HCID 45118489, compound

Product 1

HCID 71059752HCID 71059752, compoundYield 86.7%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

Chloroacetonitrile (0.32 mL, 5.06 mmol) was added to a solution of 4,4-difluoropiperidinothiocarboxamide (839 mg, 4.66 mmol) prepared above in methanol (15 mL), followed by heating overnight under reflux. The reaction solution was concentrated, and the residue was dissolved in acetic acid (15 mL), followed by addition of commercially available ethyl 4-phenyl-2,4-dioxobutyrate (1.03 g, 4.68 mmol) and sodium acetate (573 mg, 6.99 mmol) thereto. The mixture was heated for 1.5 hr under reflux in an argon atmosphere. The reaction solution was concentrated, and the residue was put into a saturated aqueous solution of sodium hydrogen carbonate. The precipitated crystals were collected by filtration, washed with water, and dried to obtain 2-(4,4-difluoropiperidino)-5-phenyl-7-thiazolo[4,5-b]pyridinecarboxylic acid ethyl ester (1.63 g, 4.04 mmol) as a brown powder.

Workup

  1. temperatureby heating overnight
  2. temperatureunder reflux
  3. concentrationThe reaction solution was concentrated
  4. dissolutionthe residue was dissolved in acetic acid (15 mL)
  5. temperatureThe mixture was heated for 1.5 hr
  6. temperatureunder reflux in an argon atmosphere
  7. concentrationThe reaction solution was concentrated
  8. filtrationThe precipitated crystals were collected by filtration
  9. washwashed with water
  10. customdried

Sources & evidence

ORD record
ord-3ffc5db66d46451babae691d5262c7b4
Source dataset
uspto-grants-2014_08
Patent number
US08796320B2

Reaction notes

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