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

HRID 1945348Notes

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.[N:14](OCCC(C)C)=[O:15]>CCOCC.O1CCCC1.Cl.CCOCC>[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[C:11](=[O:12])/[C:10](=[N:14]/[OH:15])/[CH2:9][CH2:8][CH2:7][C:6]=2[CH:13]=1

Participants

Conditions

Temperature: 24 °C

Procedure

J.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 ether/tetrahydrofuran (120 mL) and 1N HCl in ether (9 mL) was added. The solution was cooled to 0° C. before addition of isoamyl nitrite (1.2 mL, 9 mmol) and the reaction was stirred 18 h at 24° C., concentrated, and applied to 25 (M) Biotage silica gel column. Gradient elution from 15-100% B (A=Hexanes; B=ethyl acetate) over 1 L and gave J.3a (E)-2-bromo-6-(hydroxyimino)-6,7,8,9-tetrahydro-5H-benzo[7]annulen-5-one 1 g (64%). LC (Cond.-J1); RT=1.9 min; LC/MS: Anal. Calcd. for [M+H]+ C11H10NBrO2: 268; found: 268.

Workup

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

Sources & evidence

ORD record: ord-0da3e6a5d11046fbb2f4eff728645b11
Source dataset: uspto-grants-2013_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08394968B2

Reaction notes

Loading…