Sodium Chloride → 2-[4-Cyano-4-(3-cyclopentyloxy-4-methoxyphenyl)cyclohexylidene]-1,3-dithiane

HRID 741770Notes

Reaction equation

HRID 741770 reaction equation
C[Si](C)(C)[CH:3]1[S:8][CH2:7][CH2:6][CH2:5][S:4]1.C([Li])CCC.[C:16]([C:18]1([C:25]2[CH:30]=[CH:29][C:28]([O:31][CH3:32])=[C:27]([O:33][CH:34]3[CH2:38][CH2:37][CH2:36][CH2:35]3)[CH:26]=2)[CH2:23][CH2:22][C:21](=O)[CH2:20][CH2:19]1)#[N:17].[Cl-].[Na+]>O1CCCC1.O>[C:16]([C:18]1([C:25]2[CH:30]=[CH:29][C:28]([O:31][CH3:32])=[C:27]([O:33][CH:34]3[CH2:38][CH2:37][CH2:36][CH2:35]3)[CH:26]=2)[CH2:19][CH2:20][C:21](=[C:3]2[S:8][CH2:7][CH2:6][CH2:5][S:4]2)[CH2:22][CH2:23]1)#[N:17]

Participants

7

Reactant 4

HCID 5234Sodium ChlorideHCID 834132-Trimethylsilyl-1,3-dithianeHCID 9861604SB-200473HCID 178418339Butyllithium

Product 1

HCID 107880172-[4-Cyano-4-(3-cyclopentyloxy-4-methoxyphenyl)cyclohexylidene]-1,3-dithianeYield 272%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

To a solution of 2-trimethylsilyl-1,3-dithiane (9.25 mL, 48.7 mmol) in dry tetrahydrofuran (80 mL) at 0°C. under an argon atmosphere was added rapidly n-butyllithium (2.5M in hexanes, 19.2 mL, 48 mmol). After 10 min, the mixture was cooled to -78°C. and a solution of 4-cyano-4-(3-cyclopentyloxy-4-methoxyphenyl)cyclohexan-1-one (7.53 g, 23 mmol) in tetrahydrofuran (40 mL) was added. After 10 min, aqueous sodium chloride was added, the mixture was allowed to warm to room temperature and was diluted with water. This mixture was combined with the product of three substantially similar reactions conducted on ketone (3.04, 6.01 and 6.1 g, 48.3 mmol total), the combined mixture was extracted three times with methylene chloride, the extract was dried (magnesium sulfate) and evaporated. Purification by flash chromatography, eluting with 10% ethyl acetate/hexanes, provided a white solid (26 g, 87%): m.p. 115°-116° C.

Workup

  1. waitAfter 10 min
  2. temperatureto warm to room temperature
  3. extractionthe combined mixture was extracted three times with methylene chloride
  4. dry with materialthe extract was dried (magnesium sulfate)
  5. customevaporated
  6. customPurification by flash chromatography
  7. washeluting with 10% ethyl acetate/hexanes

Sources & evidence

ORD record
ord-0dfb6e6ca8214db4a7079bd3127196bb
Source dataset
uspto-grants-1996_09
Patent number
US05552438

Reaction notes

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