Diphenylmethylidenehydrazine → HCID 86758631, Verbindung

An oven-dried, 1-L, 3necked flask was equipped with Teflon-coated magnetic stirring bar, reflux condenser, and argon inlet. The apparatus was flushed with Ar for 30 minutes. The flask was charged with 3 (10.0 g, 27.2 mmol), Pd(OAc)2 (143 mg, 0.64 mmol), 2-dicyclohexylphosphino-2′-(N,N-dimethylamino)biphenyl (490 mg, 1.23 mmol), sodium tert-butoxide (9.4 g, 98 mmol), and benzophenone hydrazone (9.6 g, 49.0 mmol). The apparatus was purged for 5 more minutes with Ar and then placed under a static Ar atmosphere (balloon). Toluene (120 mL) was added via cannula and stirring initiated. The resulting mixture was placed in an 80° C. oil bath (external temperature) for 20 h. The reaction mixture was allowed to cool to ambient temperature, and the toluene was removed in vacuo. The crude product was dissolved in 200 mL acetonitrile and filtered through a pad of silica gel (150 g in a 350 mL fritted funnel). The plug was washed with 6×100 mL acetonitrile then 10×100 mL MeOH. The product containing fractions were combined and concentrated to produce a red solid, which was dissolved in hot EtOH (30 mL) and treated with hexanes (20 mL) to induce crystallization. The flask was cooled to ambient temperature and then placed in an ice bath for 1 h. The resultant solid (4) was collected by filtration and washed with cold hexanes (2×30 mL) to provide 13.75 g (76% yield).

1. temperaturereflux condenser, and argon inlet
2. customThe apparatus was flushed with Ar for 30 minutes
3. customThe apparatus was purged for 5 more minutes with Ar
4. additionToluene (120 mL) was added via cannula
5. customwas placed in an 80° C.
6. customfor 20 h
7. customthe toluene was removed in vacuo
8. dissolutionThe crude product was dissolved in 200 mL acetonitrile
9. filtrationfiltered through a pad of silica gel (150 g in a 350 mL fritted funnel)
10. washThe plug was washed with 6×100 mL acetonitrile
11. additionThe product containing fractions
12. concentrationconcentrated
13. customto produce a red solid, which
14. customcrystallization
15. temperatureThe flask was cooled to ambient temperature
16. filtrationThe resultant solid (4) was collected by filtration
17. washwashed with cold hexanes (2×30 mL)
18. customto provide 13.75 g (76% yield)

ORD-Eintrag

ord-66634853c15a483ba9b7e9a824a1a8a9

Quelldatensatz

uspto-grants-2002_12

DOI

10.6084/m9.figshare.5104873.v1

Patentnummer

US06489512B1