Tert-Butyl nitrite → 2-Azido-8-bromo-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulene

HRID 628070Notes

Reaction equation

[Br:1][C:2]1[CH:16]=[CH:15][C:5]2[C:6]3[N:7]=[C:8]([NH2:14])[S:9][C:10]=3[CH2:11][CH2:12][O:13][C:4]=2[CH:3]=1.N(OC(C)(C)C)=O.C[Si]([N:28]=[N+:29]=[N-])(C)C>C(#N)C>[N:14]([C:8]1[S:9][C:10]2[CH2:11][CH2:12][O:13][C:4]3[CH:3]=[C:2]([Br:1])[CH:16]=[CH:15][C:5]=3[C:6]=2[N:7]=1)=[N+:28]=[N-:29]

Participants

Conditions

Temperature: 0 °C

Procedure

To a suspension of 8-bromo-4,5-dihydro-6-oxa-3-thia-1-aza-benzo[e]azulen-2-ylamine (2.38 g, 8 mmol) in acetonitrile at 0° C. was added tert-butyl nitrite (1.43 mL, 12 mmol) followed by trimethylsilyl azide (1.26 mL, 9.6 mmol) dropwise. The reaction mixture was stirred at 0° C. for 90 mins, allowed to warm up to RT and concentrated in vacuo. The resulting residue was purified by flash chromatography (SiO2, 10% ethyl acetate in cyclohexane) to yield the title compound as a red oil which solidified upon standing (956 mg, 37%). 1H NMR (CDCl3): 8.21 (1H, d, J=8.6 Hz), 7.24 (1H, dd, J=8.6, 2.1 Hz), 7.20 (1H, d, J=2.1 Hz), 4.34 (2H, t, J=5.1 Hz), 3.21 (2H, t, J=5.1 Hz).

Workup

temperatureto warm up to RT
concentrationconcentrated in vacuo
customThe resulting residue was purified by flash chromatography (SiO2, 10% ethyl acetate in cyclohexane)

Sources & evidence

ORD record: ord-f8f100f2618f4103ac4b491950f77782
Source dataset: uspto-grants-2016_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09309265B2

Reaction notes

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