p-Chlorothiophenol → HCID 21186643, compound

HRID 1003629Notes

Reaction equation

HRID 1003629 reaction equation
[H-].[Na+].[Cl:3][C:4]1[CH:9]=[CH:8][C:7]([SH:10])=[CH:6][CH:5]=1.[H][H].FC(F)(F)S(O[CH:19]1[CH2:25][CH:24]2[N:26]([CH3:27])[CH:21]([CH2:22][CH2:23]2)[CH2:20]1)(=O)=O>>[Cl:3][C:4]1[CH:9]=[CH:8][C:7]([S:10][CH:19]2[CH2:20][CH:21]3[N:26]([CH3:27])[CH:24]([CH2:23][CH2:22]3)[CH2:25]2)=[CH:6][CH:5]=1

Participants

5

Reactant 4

HCID 7815p-ChlorothiophenolHCID 24758Sodium hydrideHCID 21186581HCID 21186581, compoundHCID 178418361HCID 178418361, compound2×

Product 1

HCID 21186643HCID 21186643, compoundYield 65.2%

Procedure

In a 3 neck round bottom flask equipped for overhead mechanical stirring sodium hydride (2.03 g, 50.91 mmol, 60% oil dispersion) was rinsed free of oil with hexane (2 washes) and tetrahydrofuran (200 mL) was added followed by 4-chlorothiophenol (6.69 g, 46.28 mmol in 20 mL of tetrahydrofuran). Hydrogen gas freely evolved from the reaction. Upon cessation of hydrogen evolution, 3-trifluoromethanesulfonyloxy-8-methyl-8-azabicyclo-(3.2.1)-octane (9.5 g, 46.28 mmol in 70 mL of tetrahydrofuran) was added. The reaction was refluxed overnight, then cooled and filtered through Diatomaceous earth (with ether rinse). The filtrate was concentrated at reduced pressure and residue was taken up in ether. The organic phase was washed with water and brine, dried over calcium sulfate and concentrated to afford 8.08 g (65%) of 3-(4-chlorophenylsulfanyl)-8-methyl-8-azabicyclo-(3.2.1)-octane as atan oil which had: NMR δ 7.42-7.23 (m, 4 H), 3.22 (sym m, 1 H), 3.20-3.11 (m, 2 H), 2.24 (s, 3 H), 2.03-1.97 (m, 2 H), 1.82-1.66 (m, 4 H), 1.53 (ABq, Δv1-3 =14.5 Hz, J=6.5 Hz, 2 H).

Workup

  1. customIn a 3 neck round bottom flask equipped for overhead
  2. washwas rinsed free of oil with hexane (2 washes) and tetrahydrofuran (200 mL)
  3. additionwas added
  4. temperatureThe reaction was refluxed overnight
  5. temperaturecooled
  6. filtrationfiltered through Diatomaceous earth (with ether rinse)
  7. concentrationThe filtrate was concentrated at reduced pressure and residue
  8. washThe organic phase was washed with water and brine
  9. dry with materialdried over calcium sulfate
  10. concentrationconcentrated

Sources & evidence

ORD record
ord-94d86d1565a54e51bd6009fc5bed277a
Source dataset
uspto-grants-2000_04
Patent number
US06046213

Reaction notes

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