Water → 3-Amino-4-(2,5-dimethylphenylthio)benzonitrile

HRID 1184370Notes

Reaction equation

HRID 1184370 reaction equation
O.O.[Sn](Cl)Cl.[CH3:6][C:7]1[CH:12]=[CH:11][C:10]([CH3:13])=[CH:9][C:8]=1[S:14][C:15]1[CH:22]=[CH:21][C:18]([C:19]#[N:20])=[CH:17][C:16]=1[N+:23]([O-])=O.CCOC(C)=O.O>CCO.Cl>[NH2:23][C:16]1[CH:17]=[C:18]([CH:21]=[CH:22][C:15]=1[S:14][C:8]1[CH:9]=[C:10]([CH3:13])[CH:11]=[CH:12][C:7]=1[CH3:6])[C:19]#[N:20]

Participants

7

Reactant 4

HCID 962WaterHCID 8857Ethyl AcetateHCID 61436Stannous chloride dihydrateHCID 291067464-(2,5-Dimethylphenylthio)-3-nitrobenzonitrile

Product 1

HCID 435183713-Amino-4-(2,5-dimethylphenylthio)benzonitrileYield 74%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 702EthanolSolvent

Conditions

Temperature
70 °C

Procedure

A mixture of Tin (II) chloride dihydrate (25.218 g, 112.0 mmol) in EtOH (85.0 mL) and conc. HCl (12 M, 15.0 mL) was stirred at 70° C. until a clear solution was formed. Compound 24 (8.0 g, 28.14 mmol) was then added over 10 min. The solution was kept slightly refluxing during addition. The reaction was monitored with TLC (25% EtOAc in hexanes, Rf=0.65). The reaction was complete after refluxing for 1.5 hrs as indicated by the absence of the starting material (TLC). Water (35 mL) was added and the resulting solution was allowed to cool to room temperature. Precipitation occurred during cooling. The mixture was further cooled and stirred for 30 min at 15° C. The precipitate was filtered, washed with water, and dried under vacuum to yield compound 25 as a white solid (5.30 g, 95% HPLC purity, 65% yield). 1H NMR (500 MHz, DMSO-d6): δ 7.20 (d, J=8 Hz, 1H), 7.07 (d, J=2 Hz, 1H), 7.04 (d, J=8 Hz, 1H), 7.00 (d, J=8 Hz, 1H), 6.90 (dd, J1=2 Hz, J2=8 Hz, 1H), 6.85 (s, 1H), 5.72 (s, 2H), 2.26 (s, 3H), 2.18 (s, 3H).

Workup

  1. customwas formed
  2. temperatureThe solution was kept slightly refluxing during addition
  3. temperatureafter refluxing for 1.5 hrs
  4. temperatureto cool to room temperature
  5. customPrecipitation
  6. temperatureduring cooling
  7. temperatureThe mixture was further cooled
  8. stirringstirred for 30 min at 15° C
  9. filtrationThe precipitate was filtered
  10. washwashed with water
  11. customdried under vacuum

Sources & evidence

ORD record
ord-4aef13768f2541bdb8a3435ae85f1392
Source dataset
uspto-grants-2014_03
Patent number
US08669247B2

Reaction notes

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