4-Toluenesulfonyl chloride → 3-(Hydroxymethyl)-1H-pyrazol-5-yl 4-methylbenzenesulfonate

HRID 1016395Notes

Reaction equation

HRID 1016395 reaction equation
[OH:1][CH2:2][C:3]1[NH:7][N:6]=[C:5]([OH:8])[CH:4]=1.[C:9]1([CH3:19])[CH:14]=[CH:13][C:12]([S:15](Cl)(=[O:17])=[O:16])=[CH:11][CH:10]=1.C(N(CC)CC)C>ClCCl>[OH:1][CH2:2][C:3]1[NH:7][N:6]=[C:5]([O:8][S:15]([C:12]2[CH:13]=[CH:14][C:9]([CH3:19])=[CH:10][CH:11]=2)(=[O:17])=[O:16])[CH:4]=1

Participants

5

Reactant 3

HCID 73974-Toluenesulfonyl chlorideHCID 8471TriethylamineHCID 178519777HCID 178519777, compound

Product 1

HCID 874174943-(Hydroxymethyl)-1H-pyrazol-5-yl 4-methylbenzenesulfonateYield 54.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a stirred suspension of 5-hydroxymethyl-1H-pyrazol-3-ol (J. Heterocycl. Chem., 1979, 16, 505-508) (1.0245 g, 8.98 mmol) in anhydrous dichloromethane (50 ml), under nitrogen, was added p-toluenesulfonyl chloride (1.8825 g, 9.87 mmol), then, dropwise over 5 min, anhydrous triethylamine (1.50 ml, 10.8 mmol). The mixture was stirred at room temperature for 16.5 h under nitrogen, then washed with brine (50 ml). The aqueous layer was further extracted with dichloromethane, and the combined organic extracts were dried (Na2SO4) and evaporated in vacuo. The residue was purified by flash chromatography (silica gel, 5-7% MeOH/CH2Cl2) to afford 1.3067 g (54%) of the title compound as a pale green solid; 1H NMR (360 MHz, d6-DMSO) δ 2.42 (3H, s), 4.38 (2H, d, J=5.7 Hz), 5.32 (1H, t, J=5.7 Hz), 5.82 (1H, d, J=2.2 Hz), 7.47 (2H, d, J=8.3 Hz), 7.77 (2H, d, J=8.3 Hz), 12.55 (1H, s).

Workup

  1. washwashed with brine (50 ml)
  2. extractionThe aqueous layer was further extracted with dichloromethane
  3. dry with materialthe combined organic extracts were dried (Na2SO4)
  4. customevaporated in vacuo
  5. customThe residue was purified by flash chromatography (silica gel, 5-7% MeOH/CH2Cl2)

Sources & evidence

ORD record
ord-b3087e37cc944168b4b0cc8f72522204
Source dataset
uspto-grants-2002_11
Patent number
US06476030B1

Reaction notes

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