1-Chloro-4-(chloromethyl)benzene → 1-(4-chlorobenzyl)-1H-1,2,4-triazol-3-amine

Sodium metal (460 mg, 20 mmol) was dissolved in 30 ml of methanol and 3-amino-1,2,4-triazole (1.682 g, 20 mmol) added. The resulting clear solution was stirred for 1 hour at room temperature, evaporated to dryness and the sodium salt suspended in 45 ml DMF. A solution of 4-chlorobenzyl chloride (3.221 g, 20 mmol) in 5 ml DMF was slowly added to the heavily stirred suspension obtained previously. After 3 hours at room temperature, a cloudy solution was obtained, which was stirred overnight at 20° C. The resulting mixture was concentrated in the rotatory evaporator and the oily residue treated with 100 ml of dichloromethane. Insoluble material was filtered off and the filtrate concentrated to give a brownish oil which solidified on standing. Chromatography on silica gel using dichloromethane/methanol 98:2 v/v as an eluent gave a poor separation of the two regioisomers. However, a pure fraction (215 mg, 5%) of the title compound could be obtained as a colorless solid after trituration with diethyl ether. MS ISP (m/e): 209.0 & 211.0 (100 & 43) [(M+H)+].

1. customevaporated to dryness
2. customobtained previously
3. waitAfter 3 hours at room temperature
4. customa cloudy solution was obtained
5. stirringwhich was stirred overnight at 20° C
6. concentrationThe resulting mixture was concentrated in the rotatory evaporator
7. additionthe oily residue treated with 100 ml of dichloromethane
8. filtrationInsoluble material was filtered off
9. concentrationthe filtrate concentrated
10. customto give a brownish oil which
11. customgave
12. customa poor separation of the two regioisomers

ORD record

ord-fdb848dd6f364d57b5cb5746a2e7590b

Source dataset

uspto-grants-2012_10

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US08288403B2