Hydrogen Bromide → 8-Bromo-8-(2-chlorophenyl)-2,2-dimethyloctanoic acid ethyl ester

HRID 1801543Notes

Reaction equation

HRID 1801543 reaction equation
[CH2:1]([O:3][C:4](=[O:21])[C:5]([CH3:20])([CH3:19])[CH2:6][CH2:7][CH2:8][CH2:9][CH:10]=[CH:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[Cl:18])[CH3:2].[BrH:22]>C(O)(=O)C>[CH2:1]([O:3][C:4](=[O:21])[C:5]([CH3:20])([CH3:19])[CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH:11]([Br:22])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[Cl:18])[CH3:2]

Participants

4

Reactant 2

HCID 260Hydrogen BromideHCID 675131248-(2-Chlorophenyl)-2,2-dimethyl-oct-7-enoic acid ethyl ester

Product 1

HCID 675129798-Bromo-8-(2-chlorophenyl)-2,2-dimethyloctanoic acid ethyl esterYield 81.8%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Conditions

Temperature
15 °C

Procedure

8-(2-Chlorophenyl)-2,2-dimethyl-oct-7-enoic acid ethyl ester (7 g, 22.8 mmol) was dissolved in glacial acetic acid (60 mL). The solution was cooled in an ice-bath (ca. 15° C.), while dry hydrogen bromide was passed into the solution for 8 h. The reaction mixture was poured into ice-water (130 mL) and extracted with ethyl acetate (3×50 mL). The combined organic layers were washed with saturated NaHCO3 solution (100 mL), dried over Na2SO4, and concentrated under reduced pressure. The crude product (10 g) was purified by column chromatography (200 g silica gel, eluting with ethyl acetate/heptane=1/20 to 1/10) to furnish 8-bromo-8-(2-chlorophenyl)2,2-dimethyloctanoic acid ethyl ester (7.46 g, 81.8% yield) as a yellow oil. 1H NMR (Field: 300 MHz, Solvent: CDCl3/TMS) δ (ppm): 7.59 (d, 1H, J=7.8 Hz), 7.34 (t, 1H, J=7.5 Hz), 7.26 (d, 1H, J=6.9 Hz), 7.19 (t, 1H, J=7.2 Hz), 5.45 (t, 1H, J=7.5 Hz), 4.09 (q, 2H, J=7.2 Hz), 2.26-2.09 (m, 4H), 1.52-1.46 (m, 2H), 1.41-1.31 (m, 2H), 1.28-1.18 (m, 2H), 1.20 (t, 3H, J=7.2 Hz), 1.14 (s, 6H). 13C NMR (Field: 75 MHz, Solvent: CDCl3/TMS) δ (ppm): 177.80, 139.43, 132.65, 129.64, 129.24, 128.88, 127.45, 60.28, 50.30, 42.25, 39.21, 29.48, 27.98, 25.36, 24.88, 14.49. HRMS (GC-CI): Calculated for C18H26BrClO2 (M+H)+389.0883, found 389.0867.

Workup

  1. extractionextracted with ethyl acetate (3×50 mL)
  2. washThe combined organic layers were washed with saturated NaHCO3 solution (100 mL)
  3. dry with materialdried over Na2SO4
  4. concentrationconcentrated under reduced pressure
  5. customThe crude product (10 g) was purified by column chromatography (200 g silica gel, eluting with ethyl acetate/heptane=1/20 to 1/10)

Sources & evidence

ORD record
ord-a273e67613f54376a9cc07c464a11bc2
Source dataset
uspto-grants-2013_01
Patent number
US08349833B2

Reaction notes

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