Acetic Acid → 2-(6-bromo-1-oxo-2,3-dihydro-1H-inden-2-yl)acetic acid

HRID 1585163Notes

Reaction equation

HRID 1585163 reaction equation
[Br:1][C:2]1[CH:10]=[C:9]2[C:5]([CH2:6][CH2:7][C:8]2=[O:11])=[CH:4][CH:3]=1.C(=O)(OC)OC.[H-].[Na+].[C:20]([OH:23])(=[O:22])[CH3:21]>O1CCCC1>[Br:1][C:2]1[CH:10]=[C:9]2[C:5]([CH2:6][CH:7]([CH2:21][C:20]([OH:23])=[O:22])[C:8]2=[O:11])=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 12021Dimethyl CarbonateHCID 24758Sodium hydrideHCID 1397781-Indanone, 6-bromo-

Product 1

HCID 212218342-(6-bromo-1-oxo-2,3-dihydro-1H-inden-2-yl)acetic acid

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

6-Bromo-1-indanone (142 g, 672 mmol) in tetrahydrofuran (1200 mL) was added slowly to refluxing dimethyl carbonate (143 mL, 1680 mmol), sodium hydride (80.6 g, 2020 mmol, 60% in oil, washed with pentane after weighing) and tetrahydrofuran (1200 mL). After refluxing the mixture for 2.5 hours, acetic acid (240 mL) was added dropwise at 0° C. and then allowed to warm to room temp. The mixture was partitioned between diethyl ether/dichloromethane and dilute aqueous hydrochloric acid. The organic layer was washed with 2N hydrochloric acid, water, aqueous sodium bicarbonate, and brine and was then dried over sodium sulfate to obtain a brown solid after removing solvent under vacuum, (176 g, 97%, crude), 124.5-127.5° C. m.p. 1H-NMR (300 MHz, CDCl3) (a ratio of approximately 3:1 enol to ketone tautomers) 7.91 (d, 0.27H), 7.77 (d, 0.73H, J=1.8), 7.73 (dd, 0.27H), 7.54 (dd, 0.73H, J=8.1, 1.8), 7.39 (d, 0.27H), 7.34 (d, 0.73H, J=7.9), 3.86 (s, 2.19H), 3.83 (m, 0.27H), 3.80 (s, 0.81H), 3.50 (m, 0.27H), 3.47 (s, 1.46H), 3.32 (m, 0.27H).

Workup

  1. temperatureAfter refluxing the mixture for 2.5 hours
  2. customThe mixture was partitioned between diethyl ether/dichloromethane and dilute aqueous hydrochloric acid
  3. washThe organic layer was washed with 2N hydrochloric acid, water, aqueous sodium bicarbonate, and brine
  4. dry with materialwas then dried over sodium sulfate
  5. customto obtain a brown solid
  6. customafter removing solvent under vacuum, (176 g, 97%, crude), 124.5-127.5° C.

Sources & evidence

ORD record
ord-7be2f647679146638553a274c3040ce8
Source dataset
uspto-grants-1999_08
Patent number
US05936000

Reaction notes

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