4-(Methylsulfonyl)aniline → HCID 178425633, compound

HRID 52312

Reaction equation

HRID 52312 reaction equation
[CH3:1][S:2]([C:5]1[CH:11]=[CH:10][C:8]([NH2:9])=[CH:7][CH:6]=1)(=[O:4])=[O:3].C[Al](C)C.[Cl:16][C:17]1[CH:18]=[C:19]([CH:22]=[CH:23][C:24]=1[CH3:25])[C:20]#[N:21]>C1(C)C=CC=CC=1.C(Cl)(Cl)Cl>[Cl:16][C:17]1[CH:18]=[C:19]([C:20](=[NH:21])[NH:9][C:8]2[CH:10]=[CH:11][C:5]([S:2]([CH3:1])(=[O:3])=[O:4])=[CH:6][CH:7]=2)[CH:22]=[CH:23][C:24]=1[CH3:25]

Participants

6

Reactant 3

HCID 796174-(Methylsulfonyl)anilineHCID 888943-Chloro-p-toluonitrileHCID 16682925Trimethylaluminum

Product 1

HCID 178425633HCID 178425633, compound

Reagents, catalysts & solvents 2

HCID 1140TolueneSolvent2×HCID 6212ChloroformSolvent

Procedure

To a suspension of 4-(methylsulfonyl)aniline (2.82 g, 16.5 mmol) in toluene (150 mL), trimethylaluminum (2M solution in toluene, 12.5 mL, 24.7 mmol) was added over 15 minutes. The reaction mixture was warmed to room temperature and stirred for 2.5 hours. A solution of 3-chloro-4-methylbenzonitrile (5 g, 33 mmol) in toluene (100 mL) was added over 10 minutes and the reaction mixture was heated to 90°-95° C. After 20 hours, the reaction mixture was cooled to room temperature and poured over a slurry of silica gel in chloroform. After filtration, the residue was washed with a mixture of methylene chloride/methanol (2/1). The combined filtrates were concentrated in vacuo and the resulting yellowish solid was stirred with a mixture of hexane/ether (2/1, 700 mL). The intermediate was filtered and washed with more of hexane/ether (2/1). The pale yellow solid 3-chloro-4-methyl-N-[4-(methylsulfonyl)phenyl]benzenecarboximidamide (4.7 g, 88%) was used in the next reaction without further purification: mp (DSC) 179° C. Anal. Calc'd. for C15H15N2SO2Cl: C, 55.81, H, 4.68, N, 8.68. Found: C, 55.65, H, 4.63, N, 8.59.

Workup

  1. additionwas added over 15 minutes
  2. temperaturethe reaction mixture was heated to 90°-95° C
  3. waitAfter 20 hours
  4. temperaturethe reaction mixture was cooled to room temperature
  5. filtrationAfter filtration
  6. washthe residue was washed with a mixture of methylene chloride/methanol (2/1)
  7. concentrationThe combined filtrates were concentrated in vacuo
  8. stirringthe resulting yellowish solid was stirred with a mixture of hexane/ether (2/1, 700 mL)
  9. filtrationThe intermediate was filtered
  10. washwashed with more of hexane/ether (2/1)
  11. customThe pale yellow solid 3-chloro-4-methyl-N-[4-(methylsulfonyl)phenyl]benzenecarboximidamide (4.7 g, 88%) was used in the next reaction without further purification

Sources & evidence

ORD record
ord-b3b0a34bbebd4c4f8d05de58db324efd
Source dataset
uspto-grants-1997_04
Patent number
US05616601

Linked notes

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