Isoamyl Nitrite → (6E)-2-bromo-6-hydroxyimino-8,9-dihydro-7H-benzo[7]annulen-5-one

HRID 1684865

Reaction equation

[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[C:11](=[O:12])[CH2:10][CH2:9][CH2:8][CH2:7][C:6]=2[CH:13]=1.C([O:19][N:20]=O)CC(C)C>CCOCC.C1COCC1.Cl.CCOCC>[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[C:11](=[O:12])/[C:10](=[N:20]/[OH:19])/[CH2:9][CH2:8][CH2:7][C:6]=2[CH:13]=1

Participants

Conditions

Temperature: 24 °C

Procedure

Example 3, 2-Bromo-6,7,8,9-tetrahydro-5H-benzo[7]annulen-5-one (1.5 g, 5.9 mmol) was dissolved in 2:1 Et2O/THF (120 mL) and 1N HCl in Et2O (9 mL) was added. The solution was cooled to 0° C. before addition of iso-amylnitrite (1.2 mL, 9 mmol) and the reaction was stirred 18 hours at 24° C., concentrated, and applied to 25 (M) Biotage® silica gel column. Gradient elution from 15-100% B (A=Hexanes; B=EtOAc) over 1 L and gave Example 6, (E)-2-bromo-6-(hydroxyimino)-6,7,8,9-tetrahydro-5H-benzo[7]annulen-5-one 1 g (64%). RT=1.9 minutes (condition 1). LCMS: Anal. Calcd. For C11H10NBrO2: 268. found: 268 (M+H).

Workup

additionwas added
concentrationconcentrated
washGradient elution from 15-100% B (A=Hexanes

Sources & evidence

ORD record: ord-97d0b54758784c8087f2917a9a7a75c3
Source dataset: uspto-grants-2012_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08147818B2

Linked notes

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