Acetic Acid → HCID 89619658, compound

HRID 515550Notes

Reaction equation

HRID 515550 reaction equation
C[O-].[Na+].C[O:5][C:6](=[O:9])OC.[Cl:10][C:11]1[CH:12]=[C:13]([CH2:18][C:19]#[N:20])[CH:14]=[C:15]([Cl:17])[CH:16]=1.[C:21](O)(=O)C>C1(C)C=CC=CC=1.O.CO>[CH3:21][C:12]1[C:11]([Cl:10])=[CH:16][C:15]([Cl:17])=[CH:14][C:13]=1[CH:18]([C:19]#[N:20])[C:6]([OH:5])=[O:9]

Participants

8

Reactant 4

HCID 176Acetic AcidHCID 12021Dimethyl CarbonateHCID 10942334Sodium MethoxideHCID 126899782-(3,5-Dichlorophenyl)acetonitrile

Product 1

HCID 89619658HCID 89619658, compoundYield 76.2%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolventHCID 1140TolueneSolvent2×

Procedure

A mixture of sodium methoxide (25% in methanol, 225.9 g, 1.045 mol) and toluene (996 mL) was boiled to remove the methanol/toluene azeotrope. Toluene was added as necessary in portions during the course of the distillation. When the head temperature reached 110° C. the distillation was continued for 20 min. The mixture was allowed to cool to room temperature and toluene was added so that the volume was the same as it was prior to distillation. Methanol (74 mL) and dimethylcarbonate (118.4 g, 1.31 mol) were added to the reaction mixture. The mixture was warmed to 50° C. and 3,5-dichlorophenylacetonitrile (148.2 g, 0.796 mol) in toluene (140 mL) was added over 3.5 h. The resulting mixture was allowed to cool to room temperature overnight, then warmed to 50° C. for a further 2 h. The mixture was allowed to cool to room temperature and acetic acid (80 g, 1.33 mol) was added drop-wise. Water (350 mL) was added to the reaction mixture and the organic phase separated and the solvent removed under reduced pressure. Crystallisation of the resulting residue from methanol (171 mL) gave the product as a white solid (148 g, 76%) melting at 97-99° C.

Workup

  1. customto remove the methanol/toluene azeotrope
  2. additionToluene was added as necessary in portions
  3. distillationduring the course of the distillation
  4. customreached 110° C.
  5. distillationthe distillation
  6. additiontoluene was added so that the volume
  7. distillationto distillation
  8. temperatureThe mixture was warmed to 50° C.
  9. temperatureto cool to room temperature overnight
  10. temperaturewarmed to 50° C. for a further 2 h
  11. temperatureto cool to room temperature
  12. customthe organic phase separated
  13. customthe solvent removed under reduced pressure
  14. customCrystallisation of the resulting residue from methanol (171 mL)

Sources & evidence

ORD record
ord-2664debfbd674896867ec955ef30dc51
Source dataset
uspto-grants-2015_08
Patent number
US09108965B2

Reaction notes

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