Dibromomethane → Methyl 1-methyl-4-methylidenecyclohexane-1-carboxylate

HRID 2225497Notes

Reaction equation

HRID 2225497 reaction equation
Br[CH2:2]Br.[CH3:4][C:5]1([C:12]([O:14][CH3:15])=[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]([O:14][CH3:15])=[O:13])[CH2:10][CH2:9][C:8](=[CH2:2])[CH2:7][CH2:6]1

Participants

7

Reactant 3

HCID 3024DibromomethaneHCID 5234Sodium ChlorideHCID 12568255Methyl 1-methyl-4-oxocyclohexane-1-carboxylate

Product 1

HCID 19004635Methyl 1-methyl-4-methylidenecyclohexane-1-carboxylate

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 24193Titanium TetrachlorideCatalystHCID 8028TetrahydrofuranSolvent2×

Procedure

Under an argon stream, 5.3 ml of dibromomethane and 28 ml of titanium tetrachloride (methylene chloride 2M solution) were added to a solution of 15 g of zinc suspended in 250 ml of THF, under ice cooling. The resultant solution was stirred for one hour. Then, a solution of 8.5 g of methyl 1-methyl-4-oxo-1-cyclohexanecarboxylate in 50 ml of THF was added to the solution. The solution was reacted for 15 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 sodium chloride solution and dried over magnesium sulfate. The solvent was removed in vacuo. The oily substance formed was subjected to column chromatography using 100 g of silica gel. From the fraction eluted with hexane and ethyl acetate=50:1, the solvent was removed in vacuo, yielding 7 g of methyl 1-methyl-4-methylene-1-cyclohexanecarboxylate as a colorless oil, which had the following physiochemical properties:

Workup

  1. customThe solution was reacted for 15 hours
  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 sodium chloride solution
  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=50:1
  10. customthe solvent was removed in vacuo

Sources & evidence

ORD record
ord-a36a2e00ac4543edba6be24783447017
Source dataset
uspto-grants-1994_09
Patent number
US05344845

Reaction notes

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