Thiirane → 4-Hydroxymethyl-1-(2-mercaptoethyl)pyridinium trifluoromethanesulfonate

HRID 1583513Notes

Reaction equation

HRID 1583513 reaction equation
[N:1]1[CH:6]=[CH:5][C:4]([CH2:7][OH:8])=[CH:3][CH:2]=1.[F:9][C:10]([F:16])([F:15])[S:11]([OH:14])(=[O:13])=[O:12].[CH2:17]1[S:19][CH2:18]1>C(Cl)Cl.O>[F:9][C:10]([F:16])([F:15])[S:11]([O-:14])(=[O:13])=[O:12].[OH:8][CH2:7][C:4]1[CH:5]=[CH:6][N+:1]([CH2:17][CH2:18][SH:19])=[CH:2][CH:3]=1

Participants

6

Reactant 3

HCID 9865ThiiraneHCID 114724-Hydroxymethylpyridine2×HCID 62406Trifluoromethanesulfonic acid

Product 1

HCID 201592114-Hydroxymethyl-1-(2-mercaptoethyl)pyridinium trifluoromethanesulfonateYield 97%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
60 °C

Procedure

To a solution of 4-pyridinemethanol (1.635 g, 0.015 mol) in 10 mL of CH2Cl2, at 0° C. under N2, was added dropwise trifluoromethanesulfonic acid (1.327 mL, 0.015 mol). A yellow-brown oil rapidly separated out. An additional equivalent of 4-pyridinemethanol (1.635 g, 0.015 mol) was added to this mixture and the solvent was removed under reduced pressure to give an oil. To this oil was added ethylene sulfide (0.891 mL, 0.015 mol) and the resulting homogeneous mixture was heated (oil bath) at about 60° C. for 3 h. The reaction mixture was then taken up in 15 mL of H2O and the aqueous solution was washed with CH2Cl2 (5×5 mL). After removing residual organic solvent in vacuo the aqueous solution was applied to a C18 reverse-phase column. Elution with H2O and subsequent evaporation of the relevant fractions afforded an oil which was further dried in vacuo over P 2 O5 to give the product (4.64 g, 97%) as a colourless oil. ir (film) νmax : 3455 (s, OH), 2565, (w, SH) cm-1 ; 1Hnmr (d6 -acetone) δ: 9.07, 8.18 (ABq, J=6.8 Hz, 4H, aromatic), 5.03 (s, 2H, CH2OH), 4.96 (t, J=6.5 Hz, 2H, N--CH2), 4.09 (br s, 1H, --OH), 3.5-3.1 (m, 2H, S--CH2), 2.25 (brs, 1H, --SH).

Workup

  1. customA yellow-brown oil rapidly separated out
  2. customthe solvent was removed under reduced pressure
  3. customto give an oil
  4. washthe aqueous solution was washed with CH2Cl2 (5×5 mL)
  5. customAfter removing residual organic solvent in vacuo the aqueous solution
  6. washElution
  7. customwith H2O and subsequent evaporation of the relevant fractions
  8. customafforded an oil which
  9. customwas further dried in vacuo over P 2

Sources & evidence

ORD record
ord-fbb39967c5594f8e95781f23076a0705
Source dataset
uspto-grants-1985_11
Patent number
US04552696

Reaction notes

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