Hydrogen Bromide → 7-Bromo-7-(2-chlorophenyl)-2,2-dimethylheptanoic acid ethyl ester

HRID 1801528Notes

Reaction equation

HRID 1801528 reaction equation
[CH2:1]([O:3][C:4](=[O:20])[C:5]([CH3:19])([CH3:18])[CH2:6][CH2:7][CH2:8][CH:9]=[CH:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=1[Cl:17])[CH3:2].[BrH:21]>C(O)(=O)C>[CH2:1]([O:3][C:4](=[O:20])[C:5]([CH3:19])([CH3:18])[CH2:6][CH2:7][CH2:8][CH2:9][CH:10]([Br:21])[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=1[Cl:17])[CH3:2]

Participants

4

Reactant 2

HCID 260Hydrogen BromideHCID 675123837-(2-Chlorophenyl)-2,2-dimethylhept-6-enoic acid ethyl ester

Product 1

HCID 675123617-Bromo-7-(2-chlorophenyl)-2,2-dimethylheptanoic acid ethyl esterYield 86%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

7-(2-Chlorophenyl)-2,2-dimethylhept-6-enoic acid ethyl ester (11.75 g, 0.040 mole) was dissolved in acetic acid (80 mL) under an argon atmosphere. The flask was cooled in an ice-water bath. Hydrogen bromide gas was passed slowly through the solution for 3 hours while the solution slowly warmed to room temperature. Ice (250 g) was added and after mixing, the product was extracted with ethyl acetate (2×100 mL). The ethyl acetate extracts were combined and washed with saturated sodium bicarbonate solution (3×75 mL) and water (100 mL). The solution was dried over sodium sulfate, filtered, and concentrated under reduced pressure. The remaining oil (14.06 g) was purified by column chromatography on silica gel (250 g), eluting with 3:1 (followed by 2:1) heptane/ethyl acetate. The product-containing fractions were combined and concentrated under reduced pressure to provide 7-bromo-7-(2-chlorophenyl)-2,2-dimethylheptanoic acid ethyl ester (12.9 g, 86% yield) as a clear oil. 1H NMR (300 MHz, CDCl3/TMS): δ=7.57 (d, 1H, J=7.50 Hz), 7.33-7.15 (m, 3H), 5.43 (t, 1H, J=6.9 Hz), 4.08 (q, 2H, J=7.2 Hz), 2.30-2.21 (m, 2H), 1.55-1.42 (m, 3H), 1.34-1.19 (m, 5H), 1.13 (s, 6H). 13C NMR (75 MHz, CDCl3/TMS): δ=177.72, 139.41, 132.69, 129.67, 129.28, 128.92, 127.48, 60.36, 50.17, 42.26, 40.57, 39.19, 28.59, 25.38, 25.34, 24.45, 14.50. MS (HR, DIP-CI): Calculated for (MH+): 375.0726, found 375.0726.

Workup

  1. temperatureThe flask was cooled in an ice-water bath
  2. additionafter mixing
  3. extractionthe product was extracted with ethyl acetate (2×100 mL)
  4. washwashed with saturated sodium bicarbonate solution (3×75 mL) and water (100 mL)
  5. dry with materialThe solution was dried over sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated under reduced pressure
  8. customThe remaining oil (14.06 g) was purified by column chromatography on silica gel (250 g)
  9. washeluting with 3:1 (followed by 2:1) heptane/ethyl acetate
  10. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-cb838a6834db434fb86ee994bb1a91aa
Source dataset
uspto-grants-2013_01
Patent number
US08349833B2

Reaction notes

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