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

HRID 236049

反応式

HRID 236049 の反応式
[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

参加物

6

反応物 3

HCID 9865ThiiraneHCID 114724-Hydroxymethylpyridine2 回HCID 62406Trifluoromethanesulfonic acid

生成物 1

HCID 201592114-Hydroxymethyl-1-(2-mercaptoethyl)pyridinium trifluoromethanesulfonate

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 6344Dichloromethane溶媒

反応条件

温度
60 °C

実験手順

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-pyridine-methanol (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 oilwhich was further dried in vacuo over P2O5 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).

後処理

  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 oilwhich
  9. dry with materialwas further dried in vacuo over P2O5
  10. customto give the product (4.64 g, 97% as a colourless oil

出典と根拠

ORDレコード
ord-30b9f5b1a6854349a937653162526066
出典データセット
uspto-grants-1987_02
特許番号
US04642341

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