Diethyl Ether → Ethyl 4-methylidenecyclohexane-1-carboxylate

HRID 1614986Notes

Reaction equation

HRID 1614986 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].O=[C:8]1[CH2:13][CH2:12][CH:11]([C:14]([O:16][CH2:17][CH3:18])=[O:15])[CH2:10][CH2:9]1.[CH2:19](OCC)C>>[CH2:17]([O:16][C:14]([CH:11]1[CH2:12][CH2:13][C:8](=[CH2:19])[CH2:9][CH2:10]1)=[O:15])[CH3:18]

Participants

4

Reactant 3

HCID 3283Diethyl Ether2×HCID 317638Ethyl 4-oxocyclohexanecarboxylateHCID 21226445Aluminium lithium hydride

Product 1

HCID 15151435Ethyl 4-methylidenecyclohexane-1-carboxylate

Procedure

4-Methylenecyclohexanecarboxylic acid ethyl ester is prepared from the Wittig reaction on ethyl 4-oxocyclohexanecarboxylate using Method 3. This ester is reduced to compound III-5 according to the following procedure: To a solution of lithium aluminum hydride (4.0 equiv) in diethyl ether (1.0 M with respect to hydride) is added ethyl 4-oxocyclohexanecarboxylate in diethyl ether (2.0 M with respect to ester). The reaction is heated to reflux for 2 h after which it is cooled in an ice bath and quenched with by subsequent additions of isopropanol, 50% NaOH in water, and water. The mixture is then filtered and the filter cake is washed with excess diethyl ether. The filtrate is then washed with water and brine, dried over sodium sulfate, and concentrated in vacuo to provide a clear oil that is used without further purification.

Workup

  1. temperatureThe reaction is heated
  2. temperatureto reflux for 2 h after which it
  3. temperatureis cooled in an ice bath
  4. customquenched with by subsequent additions of isopropanol, 50% NaOH in water, and water
  5. filtrationThe mixture is then filtered
  6. washthe filter cake is washed with excess diethyl ether
  7. washThe filtrate is then washed with water and brine
  8. dry with materialdried over sodium sulfate
  9. concentrationconcentrated in vacuo
  10. customto provide a clear oil that
  11. customis used without further purification

Sources & evidence

ORD record
ord-872466a0c14840f69eee40f2af45a5a8
Source dataset
uspto-grants-2014_07
Patent number
US08765735B2

Reaction notes

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