Hexane → 2-(1-Methylethyl)-5,9,13-trimethyl-1-trimethylsiloxy-2,4,8,12-cyclotetradecatetraene-1-carbonitrile

HRID 1886200Notes

Reaction equation

HRID 1886200 reaction equation
C[Si](C)(C)[N-][Si](C)(C)C.[Li+].Cl[CH2:12][C:13]([CH3:38])=[CH:14][CH2:15][CH2:16][C:17]([CH3:37])=[CH:18][CH2:19][CH2:20][C:21]([CH3:36])=[CH:22][CH:23]=[C:24]([CH:33]([CH3:35])[CH3:34])[CH:25]([O:28][Si:29]([CH3:32])([CH3:31])[CH3:30])[C:26]#[N:27].CCCCCC>O1CCCC1.[Cl-].[Na+].O>[CH3:34][CH:33]([C:24]1[C:25]([O:28][Si:29]([CH3:32])([CH3:31])[CH3:30])([C:26]#[N:27])[CH2:12][C:13]([CH3:38])=[CH:14][CH2:15][CH2:16][C:17]([CH3:37])=[CH:18][CH2:19][CH2:20][C:21]([CH3:36])=[CH:22][CH:23]=1)[CH3:35].[CH3:35][CH:33]([C:24]1[C:25](=[O:28])[CH2:26][C:13]([CH3:38])=[CH:14][CH2:15][CH2:16][C:17]([CH3:37])=[CH:18][CH2:19][CH2:20][C:21]([CH3:36])=[CH:22][CH:23]=1)[CH3:34]

Participants

7

Reactant 3

HCID 8058HexaneHCID 2733832Lithium HexamethyldisilazideHCID 53993800HCID 53993800, compound

Product 2

HCID 544770112-(1-Methylethyl)-5,9,13-trimethyl-1-trimethylsiloxy-2,4,8,12-cyclotetradecatetraene-1-carbonitrileYield 83%HCID 570081642-(1-Methylethyl)-5,9,13-trimethyl-2,4,8,12-cyclotetradecatetraen-1-oneYield 16%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 57417360Sodium chloride; waterSolvent

Procedure

To a solution of lithium hexamethyldisilazide in tetrahydrofuran (20 ml, 5.0 mmol, 0.25M) was dropwise added with stirring on an oil bath at 55° C. under argon atmosphere a solution of 15-chloro-3-(1-methylethyl)-6,10,14-trimethyl-2-trimethylsiloxy-3,5,9,13-pentadecatetraenenitrile (378 mg, 0.895 mmol) in tetrahydrofuran (15 ml) in 50 minutes. The resultant mixture was stirred at this temperature for 20 minutes and poured into a mixture of saturated brine (30 ml)-hexane (20 ml) containing ice (50 g) for stopping the reaction. The organic layer was separated, and the aqueous layer was extracted with hexane-ether (5:1, 30 ml). The extract was dried over sodium sulfate and concentrated under reduced pressure. The resultant residue was chromatographed on a silica gel column to give 2-(1-methylethyl)-5,9,13-trimethyl-1-trimethylsiloxy-2,4,8,12-cyclotetradecatetraen-1-carbonitrile (H) (288 mg, 83%) and 2-(1-methylethyl)-5,9,13-trimethyl-2,4,8,12-cyclotetradecatetraen-1-one (42.9 mg, 0.11 mmol, 16%).

Workup

  1. customthe reaction
  2. customThe organic layer was separated
  3. extractionthe aqueous layer was extracted with hexane-ether (5:1, 30 ml)
  4. dry with materialThe extract was dried over sodium sulfate
  5. concentrationconcentrated under reduced pressure
  6. customThe resultant residue was chromatographed on a silica gel column

Sources & evidence

ORD record
ord-ad6868eb775048e28e695567d9ec3837
Source dataset
uspto-grants-1992_09
Patent number
US05149843

Reaction notes

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