Ammonium Chloride → Ethyl 4-methylidenecyclohexane-1-carboxylate

HRID 2368994Notes

Reaction equation

HRID 2368994 reaction equation
[Li+].[CH3:2]C([N-]C(C)C)C.O=[C:10]1[CH2:15][CH2:14][CH:13]([C:16]([O:18][CH2:19][CH3:20])=[O:17])[CH2:12][CH2:11]1.[NH4+].[Cl-]>C1COCC1>[CH2:2]=[C:10]1[CH2:15][CH2:14][CH:13]([C:16]([O:18][CH2:19][CH3:20])=[O:17])[CH2:12][CH2:11]1

Participants

5

Reactant 3

HCID 25517Ammonium ChlorideHCID 317638Ethyl 4-oxocyclohexanecarboxylateHCID 2724682Lithium diisopropylamide

Product 1

HCID 15151435Ethyl 4-methylidenecyclohexane-1-carboxylate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a suspension of MePh3PBr (37.1 g, 104 mmol) in THF (500 mL) at 0° C. was added slowly LDA (1.2 eq) over 1 h. The resulting orange solution was stirred for 30 min before ethyl 4-oxocyclohexanecarboxylate (16.1 g, 94.4 mmol) was added dropwise. The resulting suspension was warmed to rt and stirred overnight (may not necessary). A saturated NH4Cl (aq) was added and THF was removed. The aqueous residue was extracted with EtOAc (100*3). The combined organic layers were washed with brine, dried over Na2SO4 and concentrated. The residue was purified by passing through a short silica gel plug (hexanes/EtOAc 7:1). After being concentrated, ethyl 4-methylenecyclohexanecarboxylate was obtained as pale yellow oil (12.1 g, 76%).

Workup

  1. additionwas added dropwise
  2. customTHF was removed
  3. extractionThe aqueous residue was extracted with EtOAc (100*3)
  4. washThe combined organic layers were washed with brine
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated
  7. customThe residue was purified
  8. concentrationAfter being concentrated

Sources & evidence

ORD record
ord-2f6d067100324d13b6c714e95666e61f
Source dataset
uspto-grants-2014_04
Patent number
US08703784B2

Reaction notes

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