Hydrochloric Acid → HCID 21107911, compound

Temperature

-78 °C

A solution of 11.1 ml (27.72 mmol) n-BuLi (2.5 M in hexanes) was added dropwise to a cooled to −78° C. solution of 3.4 g (13.2 mmol) 1,1′:4′,1″-terphenyl-2′,3′-diamine in 110 ml THF. The reaction mixture was stirred at −78° C. for 1 hour and 2.4 ml (13.5 mmol) dry ethyl diethoxyacetate were added dropwise over 1 min. The solution was then stirred at 78° C. for 30 min, allowed to slowly warm up room temperature, stirred for another 30 min and the heated at reflux for 2 hours. Formation of white precipitate (LiOH) was observed during the reflux. After cooling to room temperature and addition of 60 ml water the reaction mixture was carefully neutralized with the addition of 5N acetic acid. Diethyl ether (200 ml) was then added, the formed biphasic mixture was vigorously stirred and the organic layer separated. It was washed with water (3×100 ml) and dried over anhydrous sodium sulfate. Evaporation of the solvent afforded an yellow-brown oil which was dissolved in 15 ml THF and 60 ml 4N HCl were added. The mixture was stirred at reflux for 2 hours, cooled to room temperature and 120 ml icy water was added. The mixture was stirred vigorously for 10 min at ˜0° C. and then filtered. The solid was suspended in 70 ml water and neutralized with 10% aqueous sodium carbonate. The solid was filtered again, washed with water and dried at room temperature under reduced pressure. Yield—2.85 g (72.4%). 1H NMR (250 MHz, CDCl3), δ, ppm: 7.54 (m, 10H), 8.03 (br. s, 2H), 10.06 (s, 1H), 10.31 (br. s, 1H).

1. stirringThe solution was then stirred at 78° C. for 30 min
2. temperatureto slowly warm up room temperature
3. stirringstirred for another 30 min
4. temperaturethe heated
5. temperatureat reflux for 2 hours
6. temperatureAfter cooling to room temperature
7. stirringthe formed biphasic mixture was vigorously stirred
8. customthe organic layer separated
9. washIt was washed with water (3×100 ml)
10. dry with materialdried over anhydrous sodium sulfate
11. customEvaporation of the solvent
12. customafforded an yellow-brown oil which
13. stirringThe mixture was stirred
14. temperatureat reflux for 2 hours
15. temperaturecooled to room temperature
16. stirringThe mixture was stirred vigorously for 10 min at ˜0° C.
17. filtrationfiltered
18. filtrationThe solid was filtered again
19. washwashed with water
20. customdried at room temperature under reduced pressure

ORD record

ord-51613850875d42b6bb56effa36fef637

Source dataset

uspto-grants-2007_06

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07229943B2