Dibromomethane → HCID 19004549, compound

HRID 2225487Notes

Reaction equation

HRID 2225487 reaction equation
Br[CH2:2]Br.[CH3:4][C:5]1([C:12]([OH:14])=[O:13])[CH2:10][CH2:9][C:8](=O)[CH2:7][CH2:6]1.[Cl-].[Na+]>C1COCC1.[Ti](Cl)(Cl)(Cl)Cl.[Zn]>[CH3:4][C:5]1([C:12]([OH:14])=[O:13])[CH2:10][CH2:9][C:8](=[CH2:2])[CH2:7][CH2:6]1

Participants

7

Reactant 3

HCID 3024DibromomethaneHCID 5234Sodium ChlorideHCID 226099431-Methyl-4-oxocyclohexane-1-carboxylic acid

Product 1

HCID 19004549HCID 19004549, compound

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 24193Titanium TetrachlorideCatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

Under an argon stream, 3 ml of dibromomethane and 30 ml of titanium tetrachloride (methylene chloride 2M solution) were added to a solution of 7 g of zinc suspended in 200 ml of THF, under ice-cooling. The resultant solution was stirred for one hour. Then, a solution of 4.1 g of 1-methyl-4-oxo-1-cyclohexanecarboxylic acid (Example 26) in 40 ml of THF was added to the solution. The resultant solution was reacted for 12 hours. After reaction, 500 ml of an aqueous sodium chloride solution was added to the reaction solution. The solution was extracted three times with 100 ml of ethyl acetate. The organic layer obtained was washed three times with an aqueous solution of sodium chloride and dried over magnesium sulfate. The solvent was removed in vacuo. The oily substance formed was subjected to column chromatography using 20 g of silica gel. From the fraction eluted with hexane and ethyl acetate=2:1, the solvent was removed in vacuo, yielding 1.3 g of 1-methyl-4-methylene-1-cyclohexanecarboxylic acid as a colorless oil, which had the following physiochemical properties:

Workup

  1. temperaturecooling
  2. additionwas added to the reaction solution
  3. extractionThe solution was extracted three times with 100 ml of ethyl acetate
  4. customThe organic layer obtained
  5. washwas washed three times with an aqueous solution of sodium chloride
  6. dry with materialdried over magnesium sulfate
  7. customThe solvent was removed in vacuo
  8. customThe oily substance formed
  9. washFrom the fraction eluted with hexane and ethyl acetate=2:1
  10. customthe solvent was removed in vacuo

Sources & evidence

ORD record
ord-d88a3973b0b9453b8f5605d0a30b37d9
Source dataset
uspto-grants-1994_09
Patent number
US05344845

Reaction notes

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