Water → 2-(1-Methylethyl)-5,9,13-trimethyl-2,4,8,12-tetradecatetraenenitrile

HRID 5665

Reaction equation

HRID 5665 reaction equation
C(OP([CH:9]([CH:12]([CH3:14])[CH3:13])[C:10]#[N:11])(OCC)=O)C.C[Si]([N-][Si](C)(C)C)(C)C.[K+].O[CH2:26][CH:27]=[C:28]([CH2:30][CH2:31][CH:32]=[C:33]([CH2:35][CH2:36][CH:37]=[C:38]([CH3:40])[CH3:39])[CH3:34])[CH3:29].O>C1(C)C=CC=CC=1>[CH3:14][CH:12]([C:9](=[CH:26][CH:27]=[C:28]([CH3:29])[CH2:30][CH2:31][CH:32]=[C:33]([CH3:34])[CH2:35][CH2:36][CH:37]=[C:38]([CH3:40])[CH3:39])[C:10]#[N:11])[CH3:13]

Participants

6

Reactant 4

HCID 962WaterHCID 3327a FarnesolHCID 3251421Potassium bis(trimethylsilyl)amideHCID 11031342Phosphonic acid, (1-cyano-2-methylpropyl)-, diethyl ester

Product 1

HCID 536571452-(1-Methylethyl)-5,9,13-trimethyl-2,4,8,12-tetradecatetraenenitrileYield 96%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Conditions

Temperature
-70 °C

Procedure

To a solution of 2-(diethylphosphono)isovaleronitrile (8.72 g, 40 mmol) in toluene (75 ml) was gradually added a 0.5 M solution of potassium bis(trimethylsilyl)amide in toluene (75 ml) with stirring at -70° C. under argon atmosphere. The cooling bath was removed, and the reaction mixture was stirred at room temperature for 30 minutes. The reaction mixture was cooled to -70° C. again, and farnesol (5.88 g, 26.7 mmol) was added thereto with stirring, and the mixture was allowed to warm to room temperature. After addition of water, the organic layer was separated, washed with saturated aqueous sodium bicarbonate and then saturated aqueous sodium chloride, and dried over MgSO4. The organic layer was separated from MgSO4 by filtration and concentrated to give a residue, which was purified with silica gel column chromatography (solvent: n-hexane/ethyl acetate=100:1) to obtain the aimed 2 -(1-methylethyl)-5,9,13-trimethyl-2,4,8,12-tetradecatetraenenitrile (7.23 g, 96%; 2Z:2E=25.6:1).

Workup

  1. customThe cooling bath was removed
  2. stirringthe reaction mixture was stirred at room temperature for 30 minutes
  3. temperatureThe reaction mixture was cooled to -70° C. again
  4. stirringwith stirring
  5. temperatureto warm to room temperature
  6. customthe organic layer was separated
  7. washwashed with saturated aqueous sodium bicarbonate
  8. dry with materialsaturated aqueous sodium chloride, and dried over MgSO4
  9. customThe organic layer was separated from MgSO4 by filtration
  10. concentrationconcentrated
  11. customto give a residue, which
  12. customwas purified with silica gel column chromatography (solvent: n-hexane/ethyl acetate=100:1)

Sources & evidence

ORD record
ord-d891efc28e36422aa4bc843ada73ddc3
Source dataset
uspto-grants-1993_09
Patent number
US05245085

Linked notes

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