9-Bromo-2,3-diiodo-4,5-dihydro-6-oxa-1,3a-diaza-benzo[e]azulene → 10-Bromo-2-iodo-5,6-dihydrobenzo[F]imidazo[1,2-D][1,4]oxazepine

HRID 575012Notes

Reaction equation

[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[O:14][CH2:13][CH2:12][N:11]3[C:7](=[N:8][C:9]([I:16])=[C:10]3I)[C:6]=2[CH:17]=1.CC[Mg+].[Br-]>O1CCCC1>[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[O:14][CH2:13][CH2:12][N:11]3[C:7](=[N:8][C:9]([I:16])=[CH:10]3)[C:6]=2[CH:17]=1

Participants

Conditions

Temperature: -30 °C

Procedure

Into a 20 L 4-necked round-bottom flask purged and maintained with an inert atmosphere of nitrogen was placed a solution of 9-Bromo-2,3-diiodo-4,5-dihydro-6-oxa-1,3a-diaza-benzo[e]azulene (900 g, 1.74 mol, 1.00 equiv) in tetrahydrofuran (9 L), followed by the addition of EtMgBr (755 mL, 1.30 equiv) dropwise with stirring at −30° C. over 60 min. The resulting solution was stirred at −30-15° C. for 10 min, quenched by the addition of 1500 mL of saturated aqueous NH4Cl and extracted with 3×3000 mL of tetrahydrofuran. The combined organic layers were washed with 2×2000 mL of brine, dried over anhydrous sodium sulfate and concentrated under vacuum to afford 450 g (66%) of 9-Bromo-2-iodo-4,5-dihydro-6-oxa-1,3a-diaza-benzo[e]azulene as a yellow solid.

Workup

customInto a 20 L 4-necked round-bottom flask purged
temperaturemaintained with an inert atmosphere of nitrogen
stirringThe resulting solution was stirred at −30-15° C. for 10 min
customquenched by the addition of 1500 mL of saturated aqueous NH4Cl
extractionextracted with 3×3000 mL of tetrahydrofuran
washThe combined organic layers were washed with 2×2000 mL of brine
dry with materialdried over anhydrous sodium sulfate
concentrationconcentrated under vacuum

Sources & evidence

ORD record: ord-eae76786b9314025af427cf368a34186
Source dataset: uspto-grants-2015_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09034866B2

Reaction notes

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