Ammonia → 8'-Bromo-4'-methyl-3',4'-dihydro-2'H-spiro[1,3-dioxane-2,10'-pyrimido[1,2-a]indole]

HRID 853879Notes

Reaction equation

[Br:1][C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][CH:10]=1)[N:7]([CH:11]([CH3:15])[CH2:12][C:13]#[N:14])[C:6](=O)[C:5]12[O:21][CH2:20][CH2:19][CH2:18][O:17]1.N>[Ni].CCO>[Br:1][C:2]1[CH:10]=[CH:9][C:8]2[N:7]3[CH:11]([CH3:15])[CH2:12][CH2:13][N:14]=[C:6]3[C:5]3([O:21][CH2:20][CH2:19][CH2:18][O:17]3)[C:4]=2[CH:3]=1

Participants

Conditions

Temperature: 135 °C

Procedure

A mixture of 3-(5′-bromo-2′-oxospiro[1,3-dioxane-2,3′-indol]-1′(2′H)-yl)butanenitrile (0.751 g, 2.14 mmol), and wet Raney Nickel (0.75 g) in 2M EtOH.NH3 (10 mL) was hydrogenated in a Parr Hydrogenation Bottle (500 mL) at 55 lb/in2 H2 for 23 hr. The Raney Nickel was removed by filtration through Sulka Floc and the filtrate was poured into a steel pressure vessel and heated at 135° C. for 69 hr. The reaction mixture was cooled to room temperature and concentrated. The crude product was purified on Biotage KP silica gel eluting with CH2Cl2/CH3OH/NH4OH (98/2/1) to give the title compound as a white solid (0.097 g, 13% yield). Anal. Calc'd for C15H17BrN2O2: C, 53.43; H, 5.08; N, 8.31. Found: C, 53.61; H, 5.12; N, 8.11. NMR (300 Mz, DMSO-d6): consistent. MS: (ES+) m/z 337/339 [M+H]; one Br pattern observed. m.p.: 69-72° C.

Workup

customfor 23 hr
customThe Raney Nickel was removed by filtration through Sulka Floc
additionthe filtrate was poured into a steel pressure vessel
temperatureThe reaction mixture was cooled to room temperature
concentrationconcentrated
customThe crude product was purified on Biotage KP silica gel eluting with CH2Cl2/CH3OH/NH4OH (98/2/1)

Sources & evidence

ORD record: ord-7a7e85a9a8b44e1aa58520d05bb19d8f
Source dataset: uspto-grants-2007_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07256198B2

Reaction notes

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