Dibromomethane → HCID 67403052, compound

HRID 2095227Notes

Reaction equation

HRID 2095227 reaction equation
[CH3:1][C:2]1([CH3:11])[C:6]([CH3:7])=[CH:5][CH2:4][C@@H:3]1[CH:8]([OH:10])[CH3:9].Br[CH2:13]Br>C(Br)(=O)C.C(OCC)C.[Zn]>[CH3:7][C:6]12[CH2:13][CH:5]1[CH2:4][C@H:3]([CH:8]([OH:10])[CH3:9])[C:2]2([CH3:1])[CH3:11]

Participants

6

Reactant 2

HCID 3024DibromomethaneHCID 59637687HCID 59637687, compound

Product 1

HCID 67403052HCID 67403052, compoundYield 12.5%

Reagents, catalysts & solvents 3

HCID 10482Acetyl bromideCatalystHCID 23994ZincCatalystHCID 3283Diethyl EtherSolvent

Procedure

A drop of acetyl bromide (1 drop) was added to a mixture of activated (with 1N HCl) zinc (19.6 g, 0.3 mol), cuprous bromide (1.5 g, 0.01 mol) and 1-((1S)-2,2,3-trimethylcyclopent-3-enyl)ethanol (ca. 20% ee, 15.4 g, 0.3 mol) in diethyl ether (50 ml). After 10 minutes stirring, dibromomethane (52.0 g, 0.3 mol) was added and stirring at reflux continued for 6 h. The solid was filtered off and washed with MTBE. The combined organic phases were washed with water and diluted citric acid solution, dried (MgSO4), concentrated in vacuo and distilled using a 5 cm Widmer-column to give 1-((3S)-1,2,2-trimethylbicyclo[3.1.0]hex-3-yl)ethanol (2.1 g, 12.5% yield, colourless liquid; GC/MS: 3 main diastereomeric pairs of enantiomers 33+30.5+20%). Analytical samples of the three main pairs of enantiomers were obtained by flash chromatography (MTBE/hexane 1:3)

Workup

  1. stirringstirring
  2. temperatureat reflux
  3. waitcontinued for 6 h
  4. filtrationThe solid was filtered off
  5. washwashed with MTBE
  6. washThe combined organic phases were washed with water and diluted citric acid solution
  7. dry with materialdried (MgSO4)
  8. concentrationconcentrated in vacuo
  9. distillationdistilled

Sources & evidence

ORD record
ord-d9439628cc0f4c19a7fa3e5c3cb1f8ae
Source dataset
uspto-grants-2013_05
Patent number
US08445732B2

Reaction notes

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