Ethyl Acetate → 4-(2,5-Dimethylphenylthio)-3-nitrobenzonitrile

HRID 1946837Notes

Reaction equation

HRID 1946837 reaction equation
Cl[C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][C:3]=1[N+:10]([O-:12])=[O:11].[CH3:13][C:14]1[CH:19]=[CH:18][C:17]([CH3:20])=[CH:16][C:15]=1[SH:21].C([O-])([O-])=O.[K+].[K+].CCOC(C)=O>C1COCC1>[CH3:13][C:14]1[CH:19]=[CH:18][C:17]([CH3:20])=[CH:16][C:15]=1[S:21][C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][C:3]=1[N+:10]([O-:12])=[O:11]

Participants

6

Reactant 4

HCID 8857Ethyl AcetateHCID 11430Potassium CarbonateHCID 13655Benzonitrile, 4-chloro-3-nitro-HCID 776152,5-Xylenethiol

Product 1

HCID 291067464-(2,5-Dimethylphenylthio)-3-nitrobenzonitrileYield 95%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 4-chloro-3-nitrobenzonitrile (5.4 g, 29.67 mmol) in THF (100 mL) was added 2,5-dimethylthiophenol (4.921 g, 35.60 mmol) and K2CO3 (20.45 g, 148.0 mmol). The reaction was monitored with TLC (25% EtOAc in hexanes). After refluxing for 16 hrs, the reaction was complete. The solid was filtered and washed with copious amounts of EtOAc. The filtrate was washed sequentially with saturated NaHCO3, water, saturated NaCl solution, dried over MgSO4, filtered, and evaporated in vacuo. The resulting solid was then sonicated in hexanes and filtered to yield compound 24 as a yellow/white solid (8.00 g, 97.8% HPLC purity, 95% yield). 1H NMR (500 MHz, DMSO-d6): δ 8.77 (d, J=2 Hz, 1H), 7.94 (dd, J1=2 Hz, J2=8 Hz, 1H), 7.46 (s, 1H), 7.41 (d, J=8 Hz, 1H), 7.36 (d, J=8 Hz, 1H), 6.76 (d, J=8 Hz, 1H), 2.32 (s, 3H), 2.23 (s, 3H).

Workup

  1. temperatureAfter refluxing for 16 hrs
  2. filtrationThe solid was filtered
  3. washwashed with copious amounts of EtOAc
  4. washThe filtrate was washed sequentially with saturated NaHCO3, water, saturated NaCl solution
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. customevaporated in vacuo
  8. customThe resulting solid was then sonicated in hexanes
  9. filtrationfiltered

Sources & evidence

ORD record
ord-dcbba5cf002d405885597bb8fd737a07
Source dataset
uspto-grants-2013_03
Patent number
US08399456B2

Reaction notes

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