Ammonia → 4-Chloro-2-(3-aminomethyl-2-methysulfanyl-phenoxy)-benzonitrile fumarate

HRID 1178542Notes

Reaction equation

HRID 1178542 reaction equation
[NH3:1].[Cl:2][C:3]1[CH:10]=[CH:9][C:6]([C:7]#[N:8])=[C:5]([O:11][C:12]2[CH:17]=[CH:16][CH:15]=[C:14]([CH2:18]Cl)[C:13]=2[S:20][CH3:21])[CH:4]=1.[C:22]([OH:29])(=[O:28])/[CH:23]=[CH:24]/[C:25]([OH:27])=[O:26]>CO>[C:22]([OH:29])(=[O:28])/[CH:23]=[CH:24]/[C:25]([OH:27])=[O:26].[Cl:2][C:3]1[CH:10]=[CH:9][C:6]([C:7]#[N:8])=[C:5]([O:11][C:12]2[CH:17]=[CH:16][CH:15]=[C:14]([CH2:18][NH2:1])[C:13]=2[S:20][CH3:21])[CH:4]=1

Participants

5

Reactant 3

HCID 222AmmoniaHCID 444972Fumaric AcidHCID 219304424-Chloro-2-(3-chloromethyl-2-methysulfanyl-phenoxy)-benzonitrile2×

Product 1

HCID 694233764-Chloro-2-(3-aminomethyl-2-methysulfanyl-phenoxy)-benzonitrile fumarate

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent2×

Procedure

7N Ammonia in methanol (30 mL, 210 mmol) was added to 4-chloro-2-(3-chloromethyl-2-methysulfanyl-phenoxy)-benzonitrile (240 mg, 0.8 mmol). After stirring for 17 h, TLC still showed some 4-chloro-2-(3-chloromethyl-2-methysulfanyl-phenoxy)-benzonitrile. The reaction mixture was concentrated to about 10 mL by evaporation in vacuo, concentrated ammonia (7 mL) was added and the mixture was heated with stirring at 60° C. for 17 h. Sodium carbonate solution (4 mL) and ethyl acetate (6 mL) were added and the organic layer was separated and dried with MgSO4. To this, was added fumaric acid (84 mg, 0.64 mmol) in methanol (3 mL). Immediately, the solvent was removed in vacuo and diethyl ether (40 mL) was added to the residue. After stirring for 17 h, 4-chloro-2-(3-aminomethyl-2-methysulfanyl-phenoxy)-benzonitrile fumarate (134.7 mg, 53%) was filtered off as a white solid.

Workup

  1. concentrationThe reaction mixture was concentrated to about 10 mL by evaporation in vacuo, concentrated ammonia (7 mL)
  2. additionwas added
  3. temperaturethe mixture was heated
  4. stirringwith stirring at 60° C. for 17 h
  5. additionSodium carbonate solution (4 mL) and ethyl acetate (6 mL) were added
  6. customthe organic layer was separated
  7. dry with materialdried with MgSO4
  8. customImmediately, the solvent was removed in vacuo and diethyl ether (40 mL)
  9. additionwas added to the residue
  10. stirringAfter stirring for 17 h
  11. filtration4-chloro-2-(3-aminomethyl-2-methysulfanyl-phenoxy)-benzonitrile fumarate (134.7 mg, 53%) was filtered off as a white solid

Sources & evidence

ORD record
ord-aec6b75d3fe74cd6a2468909fd4852b2
Source dataset
uspto-grants-2007_10
Patent number
US07276528B2

Reaction notes

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