4-(Methylsulfonyl)aniline → HCID 178491240, compound

HRID 1352945Notes

Reaction equation

HRID 1352945 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.[F:16][C:17]1[CH:18]=[C:19]([CH:22]=[CH:23][C:24]=1[O:25][CH3:26])[C:20]#[N:21]>C1(C)C=CC=CC=1.C(Cl)(Cl)Cl>[F: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[O:25][CH3:26]

Participants

6

Reactant 3

HCID 796174-(Methylsulfonyl)anilineHCID 27745483-Fluoro-4-methoxybenzonitrileHCID 16682925Trimethylaluminum

Product 1

HCID 178491240HCID 178491240, 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-fluoro-4-methoxybenzonitrile (5 g, 33 mmol) in toluene (100 mL) was added over 10 minutes and the reaction mixture was heated to 80–85° 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, 1000 mL). The intermediate was filtered and washed with more hexane/ether (2/1). The pale yellow solid 3-fluoro-4-methoxy-N-[4-(methylsulfonyl)phenyl]benzenecarboximidamide (3.95 g, 74%) was used in the next reaction without further purification: mp (DSC) 195° C. Anal. Calc'd. for C15H15N2SO3F: C, 55.89; H, 4.69; N, 8.69. Found: C, 55.92; H, 4.74; N, 8.53.

Workup

  1. additionwas added over 15 minutes
  2. temperaturethe reaction mixture was heated to 80–85° 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, 1000 mL)
  9. filtrationThe intermediate was filtered
  10. washwashed with more hexane/ether (2/1)
  11. customThe pale yellow solid 3-fluoro-4-methoxy-N-[4-(methylsulfonyl)phenyl]benzenecarboximidamide (3.95 g, 74%) was used in the next reaction without further purification

Sources & evidence

ORD record
ord-33ac5e8a1b134c19a83211d6c374ce09
Source dataset
uspto-grants-2007_05
Patent number
US07220770B2

Reaction notes

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