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

HRID 591018
Notes
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Reaction equation

HRID 591018 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
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

5

Reactant 3

HCID 24247Perchloric AcidHCID 516892Sodium BicarbonateHCID 86717835Methyl 2-{1-bromothieno[3,2-f]quinolin-2-yl}-2-hydroxyacetate

Product 1

HCID 86717834Methyl 2-{1-bromothieno[3,2-f]quinolin-2-yl}-2-(tert-butoxy)acetateYield 60.5%

Reagents, catalysts & solvents 1

HCID 10908tert-Butyl acetate
Solvent

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

  1. temperaturewarmed at room temperature for 1 hour more
  2. extractionThe aqueous layer was extracted with ethyl acetate
  3. washThe organic layer was washed with brine
  4. dry with materialdried over sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. 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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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes