Hydrochloric Acid → 4-But-2-ynyloxy-benzenethiol

HRID 278315Notes

Reaction equation

HRID 278315 reaction equation
C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CN(C=O)C.[CH2:25]([O:29][C:30]1[CH:35]=[CH:34][C:33]([S:36](Cl)(=O)=O)=[CH:32][CH:31]=1)[C:26]#[C:27][CH3:28].Cl>ClCCl.[Cl-].[Na+].O>[CH2:25]([O:29][C:30]1[CH:31]=[CH:32][C:33]([SH:36])=[CH:34][CH:35]=1)[C:26]#[C:27][CH3:28]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 6228DimethylformamideHCID 11776TriphenylphosphineHCID 111959284-But-2-ynyloxy-benzenesulfonyl chloride

Product 1

HCID 235138844-But-2-ynyloxy-benzenethiolYield 42.3%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 57417360Sodium chloride; waterSolvent

Procedure

To a solution of 11.8 g (0.045 mol) of triphenylphosphine dissolved in 10 mL of dichloromethane and 0.3 mL of DMF was added 3.67 g (0.015 mol) of the 4-but-2-ynyloxy-benzenesulfonyl chlorid, dissolved in 15 mL of dichloromethane and the resulting mixture was stirred for 2 h at room temperature. After the addition of 5 mL of 1N HCl solution the reaction was stirred for 0.5 h followed by the addition of 15 mL of brine. The organics were separated and concentrated in vacuo and the residue was diluted with ether and 2.5N sodium hydroxide solution. The resulting precipitate was filtered off and the aqueous layer was acidified to pH2 and extracted with ether. The combined organics were washed with brine, dried over Na2SO4, filtered through Magnesol® and concentrated in vacuo. The residue was chromatographed on silica gel eluting with hexanes/ether (4:1) to provide 1.13 g (42%) of the thiol as a yellow oil. CI Mass Spec: 179 (M+H).

Workup

  1. stirringwas stirred for 0.5 h
  2. customThe organics were separated
  3. concentrationconcentrated in vacuo
  4. additionthe residue was diluted with ether and 2.5N sodium hydroxide solution
  5. filtrationThe resulting precipitate was filtered off
  6. extractionextracted with ether
  7. washThe combined organics were washed with brine
  8. dry with materialdried over Na2SO4
  9. filtrationfiltered through Magnesol®
  10. concentrationconcentrated in vacuo
  11. customThe residue was chromatographed on silica gel eluting with hexanes/ether (4:1)

Sources & evidence

ORD record
ord-4c4f50311bb34a90a6acedcb632bdc8f
Source dataset
uspto-grants-2002_03
Patent number
US06358980B1

Reaction notes

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