9-Bromo-3,4-diiodo-2,5-diazatetracyclo[11.1.1.0[2,6].0[7,12]]pentadeca-3,5,7,9,11-pentaene → 10-Bromo-2-iodo-6,7-dihydro-5H-5,7-methanobenzo[c]imidazo[1,2-a]azepine

HRID 575042Notes

Reaction equation

[Br:1][C:2]1[CH:3]=[C:4]2[C:13](=[CH:14][CH:15]=1)[CH:12]1[CH2:16][CH:10]([CH2:11]1)[N:9]1[C:5]2=[N:6][C:7]([I:18])=[C:8]1I.CC[Mg+].[Br-]>O1CCCC1>[Br:1][C:2]1[CH:3]=[C:4]2[C:13](=[CH:14][CH:15]=1)[CH:12]1[CH2:11][CH:10]([CH2:16]1)[N:9]1[C:5]2=[N:6][C:7]([I:18])=[CH:8]1

Participants

Conditions

Temperature: -40 °C

Procedure

Into a 3-L 4-necked round-bottom flask purged and maintained with an inert atmosphere of nitrogen was placed tetrahydrofuran (1200 mL), 9-bromo-3,4-diiodo-2,5-diazatetracyclo[11.1.1.0[2,6].0[7,12]]pentadeca-3,5,7,9,11-pentaene (119.3 g, 226.40 mmol, 1.00 equiv), followed by the addition of EtMgBr (90.7 mL, 1.20 equiv) dropwise with stirring at −40° C. The resulting solution was stirred at −40° C. for 1 h. This reaction was repeated for 2 more times. The reaction was then quenched by the addition of 500 mL of 5% hydrogen chloride and extracted with 3×500 mL of dichloromethane. The organic layers were combined, dried over anhydrous sodium sulfate and concentrated under vacuum to afford 259 g (97%) of 9-bromo-4-iodo-2,5-diazatetracyclo[11.1.1.0[2,6].0[7,12]]pentadeca-3,5,7,9,11-pentaene as a brown solid.

Workup

customInto a 3-L 4-necked round-bottom flask purged
temperaturemaintained with an inert atmosphere of nitrogen
stirringThe resulting solution was stirred at −40° C. for 1 h
customThe reaction was then quenched by the addition of 500 mL of 5% hydrogen chloride
extractionextracted with 3×500 mL of dichloromethane
dry with materialdried over anhydrous sodium sulfate
concentrationconcentrated under vacuum

Sources & evidence

ORD record: ord-f45c7622e1374600ad0a3409bc205c02
Source dataset: uspto-grants-2015_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09034866B2

Reaction notes

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