4-Chlorobenzonitrile → 4-chloro-N-[4-(methylsulfonyl)phenyl]benzenecarboximidamide

To a suspension of 4-(methylsulfonyl)aniline (7 g, 41 mmol) in toluene (400 mL), trimethylaluminum (2M solution in toluene, 30.5 mL, 61 mmol) was added over 15 minutes. The reaction mixture was warmed to room temperature and stirred for 2.5 hours. A solution of 4-chlorobenzonitrile (11.3 g, 82 mmol) in toluene (200 mL) was added over 10 minutes and the reaction mixture was heated to 80°-85° C. After 16 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. 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 of hexane/ether (2/1). The pale yellow solid 4-chloro-N-[4-(methylsulfonyl)phenyl]benzenecarboximidamide (10.93 g, 86%) was used in the next reaction without further purification: mp (DSC) 191° C. Anal. Calc'd. for C14H13N2SO2Cl: C, 54.46, H, 4.24, N, 9.07. Found: C, 54.42, H, 4.30, N, 9.07.

1. additionwas added over 15 minutes
2. temperaturethe reaction mixture was heated to 80°-85° C
3. waitAfter 16 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
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 of hexane/ether (2/1)
11. customThe pale yellow solid 4-chloro-N-[4-(methylsulfonyl)phenyl]benzenecarboximidamide (10.93 g, 86%) was used in the next reaction without further purification

ORD record

ord-45e2e30cff9d4228995f8b63eba08d26

Source dataset

uspto-grants-1997_04

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US05616601