Sodium hydride → HCID 68681876, compound

HRID 1865461Notes

Reaction equation

HRID 1865461 reaction equation
C([Si]([S:11][Si:12]([CH:19]([CH3:21])[CH3:20])([CH:16]([CH3:18])[CH3:17])[CH:13]([CH3:15])[CH3:14])(C(C)C)C(C)C)(C)C.[H-].[Na+].[C:24]([C:26]1([CH2:49][CH:50]2[CH2:52][CH2:51]2)[CH2:31][CH2:30][C:29](OS(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)(=O)=O)=[CH:28][CH2:27]1)#[N:25]>O1CCCC1.C1(C)C=CC=CC=1>[CH:50]1([CH2:49][C:26]2([C:24]#[N:25])[CH2:31][CH2:30][C:29]([S:11][Si:12]([CH:13]([CH3:14])[CH3:15])([CH:16]([CH3:17])[CH3:18])[CH:19]([CH3:20])[CH3:21])=[CH:28][CH2:27]2)[CH2:52][CH2:51]1

Participants

6

Reactant 3

HCID 24758Sodium hydrideHCID 11163810HCID 11163810, compoundHCID 86638754HCID 86638754, compound

Product 1

HCID 68681876HCID 68681876, compoundYield 100.1%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a degassed, cooled (0° C.) solution of triisopropylsilylsulfide (11.1 g, 58.6 mmol) in tetrahydrofuran (60 ml) was added portionwise over 10 minutes sodium hydride (2.34 g, 60% dispersion in oil) and the mixture stirred until a clear solution formed. 1,1,2,2,3,3,4,4,4-Nonafluorobutane-1-sulfonic acid 4-cyano-4-cyclopropylmethylcyclohex-1-enyl ester (26.9 g, 58.6 mmol) was dissolved in anhydrous toluene (170 ml) and degassed for 30 minutes before addition of TIPS sodium sulfide solution and tetrakis triphenylphosphine palladium (0) (3.38 g, 2.93 mmol). On complete addition the mixture was plunged into an oil bath preheated to 90° C. After 15 min the mixture becomes dark brown in colour. After a further 15 min the mixture was allowed to cool to ambient temperature. The mixture was poured on to ice (200 g) and extracted with diethyl ether (2×200 ml). The combined organic layer was washed with water (200 ml), dried over anhydrous sodium sulphate, filtered and evaporated to give a brown oil. The oil was purified by dry flash column chromatography on silica eluting with isohexane on a gradient of dichloromethane (5-30%). Collecting appropriate fractions followed by evaporation gave a brown oil (20.5 g, 100%). 1H NMR δ (ppm)(CDCl3): 5.92 (1H, s), 2.61-2.54 (2H, m), 2.38-2.28 (1H, m), 2.21-2.10 (3H, m), 1.67-1.44 (2H, m), 1.33-1.23 (3H, m), 1.14 (18H, d, J=7.2 Hz), 0.95-0.85 (1H, m), 0.58-0.55 (2H, m), 0.20-0.18 (2H, m).

Workup

  1. customformed
  2. additionOn complete addition the mixture
  3. customwas plunged into an oil bath
  4. custompreheated to 90° C
  5. waitAfter a further 15 min the mixture was allowed
  6. extractionextracted with diethyl ether (2×200 ml)
  7. washThe combined organic layer was washed with water (200 ml)
  8. dry with materialdried over anhydrous sodium sulphate
  9. filtrationfiltered
  10. customevaporated
  11. customto give a brown oil
  12. customThe oil was purified
  13. dry with materialby dry flash column chromatography on silica eluting with isohexane on a gradient of dichloromethane (5-30%)
  14. customCollecting appropriate fractions
  15. customfollowed by evaporation

Sources & evidence

ORD record
ord-d408dfa9bd7d4e629169515f9e02ebe7
Source dataset
uspto-grants-2009_12
Patent number
US07626056B2

Reaction notes

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