2-Bromo-2-methylpropionyl bromide → Methyl {5-[4-(2-bromo-2-methylpropanoyl)phenyl]bicyclo[3.2.2]non-1-yl}acetate

HRID 908122Notes

Reaction equation

HRID 908122 reaction equation
[C:1]1([C:7]23[CH2:15][CH2:14][C:11]([CH2:16][C:17]([O:19][CH3:20])=[O:18])([CH2:12][CH2:13]2)[CH2:10][CH2:9][CH2:8]3)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Cl-].[Al+3].[Cl-].[Cl-].[Br:25][C:26]([CH3:31])([CH3:30])[C:27](Br)=[O:28]>C(Cl)Cl>[Br:25][C:26]([CH3:31])([CH3:30])[C:27]([C:4]1[CH:3]=[CH:2][C:1]([C:7]23[CH2:15][CH2:14][C:11]([CH2:16][C:17]([O:19][CH3:20])=[O:18])([CH2:12][CH2:13]2)[CH2:10][CH2:9][CH2:8]3)=[CH:6][CH:5]=1)=[O:28]

Participants

5

Reactant 3

HCID 886852-Bromo-2-methylpropionyl bromideHCID 6451240Aluminum(III) ChlorideHCID 25258104Methyl (5-phenylbicyclo[3.2.2]non-1-yl)acetate2×

Product 1

HCID 25258351Methyl {5-[4-(2-bromo-2-methylpropanoyl)phenyl]bicyclo[3.2.2]non-1-yl}acetateYield 26%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

To an ice water cooled solution of methyl (5-phenylbicyclo[3.2.2]non-1-yl)acetate (Intermediate 23; 229 mg, 0.79 mmol) in DCM (10 mL) was added aluminium chloride (318 mg, 2.38 mmol) followed by the dropwise addition of 2-bromoisobutyryl bromide (0.10 mL, 0.79 mmol). The reaction mixture was allowed to stir at 0° C. for 40 mins then poured onto ice-water (100 mL). The organic phase was separated and the aqueous phase washed with DCM (3×50 mL), the organic washings were combined, dried (MgSO4) and concentrated to leave a yellow gum. This was purified on a 12 g Crawford silicyle cartridge, loading in DCM and eluting with 0-10%-20% isohexane-EtOAc to provide the title compound (85 mg, 0.202 mmol, 26%) as a pale yellow gum; 1H NMR (CDCl3) δ 1.09 (d, 3H), 1.50-1.57 (m, 3H), 1.67-1.74 (m, 3H), 1.82-1.86 (m, 6H), 2.03 (s, 6H), 2.27 (q, 1H), 3.67 (s, 3H), 7.37 (d, 2H), 8.11 (d, 2H); GC-MS CI m/e MH+ 421.

Workup

  1. additionthen poured onto ice-water (100 mL)
  2. customThe organic phase was separated
  3. washthe aqueous phase washed with DCM (3×50 mL)
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated
  6. customto leave a yellow gum
  7. customThis was purified on a 12 g Crawford silicyle cartridge, loading in DCM
  8. washeluting with 0-10%-20% isohexane-EtOAc

Sources & evidence

ORD record
ord-0d83bb16db314395836101f93b8a23c9
Source dataset
uspto-grants-2011_09
Patent number
US08017603B2

Reaction notes

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