Perchloric Acid → Methyl 2-{1-bromothieno[3,2-f]quinolin-2-yl}-2-(tert-butoxy)acetate

HRID 591018Notes

Reaction equation

[Br:1][C:2]1[C:6]2=[C:7]3[C:12](=[CH:13][CH:14]=[C:5]2[S:4][C:3]=1[CH:15]([OH:20])[C:16]([O:18][CH3:19])=[O:17])[N:11]=[CH:10][CH:9]=[CH:8]3.Cl(O)(=O)(=O)=O.C(=O)(O)[O-].[Na+]>C(OC(=O)C)(C)(C)C>[Br:1][C:2]1[C:6]2=[C:7]3[C:12](=[CH:13][CH:14]=[C:5]2[S:4][C:3]=1[CH:15]([O:20][C:6]([CH3:7])([CH3:2])[CH3:5])[C:16]([O:18][CH3:19])=[O:17])[N:11]=[CH:10][CH:9]=[CH:8]3

Participants

Conditions

Temperature: -5 °C

Procedure

To a suspension of methyl 2-{1-bromothieno[3,2-f]quinolin-2-yl}-2-hydroxyacetate (16h) (152 mg, 0.43 mmol) in tert-butylacetate (2.3 mL) at −10° C. was added perchloric acid (69.4 μL). The mixture was stirred at −5° C. for 5 hours and then warmed at room temperature for 1 hour more. The mixture was then basified with a saturated aqueous solution of sodium bicarbonate until pH 8. The aqueous layer was extracted with ethyl acetate. The organic layer was washed with brine, dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by 2 preparative TLC (cyclohexane/ethyl acetate 60/40) to afford the desired product (16i) (55 mg, 0.13 mmol, 31%) as beige powder.

Workup

temperaturewarmed at room temperature for 1 hour more
extractionThe aqueous layer was extracted with ethyl acetate
washThe organic layer was washed with brine
dry with materialdried over sodium sulfate
filtrationfiltered
concentrationconcentrated in vacuo
customThe residue was purified by 2 preparative TLC (cyclohexane/ethyl acetate 60/40)

Sources & evidence

ORD record: ord-28555d43918f4061aaf848a17db85192
Source dataset: uspto-grants-2016_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09238026B2

Reaction notes

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