Methyl N-(triethylammoniosulfonyl)carbamate → 1-((Trimethylsilyl)ethynyl)-2-(4-fluoro-3-methylphenyl)-4,4,6,6-tetramethylcyclohexene

HRID 6520Notes

Reaction equation

HRID 6520 reaction equation
[CH3:1][Si:2]([C:5]#[C:6][C:7]1(O)[C:12]([CH3:14])([CH3:13])[CH2:11][C:10]([CH3:16])([CH3:15])[CH2:9][CH:8]1[C:17]1[CH:22]=[CH:21][C:20]([F:23])=[C:19]([CH3:24])[CH:18]=1)([CH3:4])[CH3:3].CC[N+](S(N=C(OC)[O-])(=O)=O)(CC)CC>C(#N)C.O>[CH3:3][Si:2]([C:5]#[C:6][C:7]1[C:12]([CH3:14])([CH3:13])[CH2:11][C:10]([CH3:16])([CH3:15])[CH2:9][C:8]=1[C:17]1[CH:22]=[CH:21][C:20]([F:23])=[C:19]([CH3:24])[CH:18]=1)([CH3:1])[CH3:4]

Participants

5

Reactant 2

HCID 2724994Methyl N-(triethylammoniosulfonyl)carbamateHCID 197938911-((Trimethylsilyl)ethynyl)-2-(4-fluoro-3-methylphenyl)-4,4,6,6-tetramethyl-cyclohexan-1-ol

Product 1

HCID 197939071-((Trimethylsilyl)ethynyl)-2-(4-fluoro-3-methylphenyl)-4,4,6,6-tetramethylcyclohexeneYield 67%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6342AcetonitrileSolvent

Procedure

To a solution of the hydroxy acetylene from Example 1, Step C above (20 g, 55.5 mmol) in acetonitrile (250 ml) is added 20 g (83 mmol) of Burgess reagent. The reaction mixture is heated at reflux for 14 hours, cooled to room temperature and diluted with H2O (1 L). The aqueous solution is extracted with ether and the combined ether layers are washed with H2O. The ether fraction is dried over MgSO4 and the solvent is removed under reduced pressure. Purification by silica gel chromatography (100% hexane) provides 12.7 g (67%) of 1-((trimethylsilyl)ethynyl)-2-(4-fluoro-3-methylphenyl)-4,4,6,6-tetramethylcyclohexene as an oil: 1H NMR δ=0.0 (s,9), 0.95 (s,6), 1.15 (s,6), 1.4 ((s,2), 2.1 (s,2), 2.2 (s,3), 6.85 (t,1), 7.25 (m,2).

Workup

  1. temperatureThe reaction mixture is heated
  2. temperatureat reflux for 14 hours
  3. extractionThe aqueous solution is extracted with ether
  4. washthe combined ether layers are washed with H2O
  5. dry with materialThe ether fraction is dried over MgSO4
  6. customthe solvent is removed under reduced pressure
  7. customPurification by silica gel chromatography (100% hexane)

Sources & evidence

ORD record
ord-5ce452de6da847909012d9a70df1b395
Source dataset
uspto-grants-1993_09
Patent number
US05248830

Reaction notes

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