Thionyl Chloride → Ethyl 2-(5-(Chloromethyl)-3-nitro-1H-pyrazol-1-yl)acetate

HRID 407792Notes

Reaction equation

HRID 407792 reaction equation
O[CH2:2][C:3]1[N:7]([CH2:8][C:9]([O:11][CH2:12][CH3:13])=[O:10])[N:6]=[C:5]([N+:14]([O-:16])=[O:15])[CH:4]=1.O=S(Cl)[Cl:19]>C(Cl)(Cl)Cl>[Cl:19][CH2:2][C:3]1[N:7]([CH2:8][C:9]([O:11][CH2:12][CH3:13])=[O:10])[N:6]=[C:5]([N+:14]([O-:16])=[O:15])[CH:4]=1

Participants

4

Reactant 2

HCID 24386Thionyl ChlorideHCID 86684029Ethyl 2-(5-(Hydroxymethyl)-3-nitro-1H-pyrazol-1-yl)acetate

Product 1

HCID 86684030Ethyl 2-(5-(Chloromethyl)-3-nitro-1H-pyrazol-1-yl)acetateYield 68%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Conditions

Temperature
0 °C

Procedure

To a mixture of 151a (1.50 g, 6.55 mmol) in CHCl3 (60 mL) cooled at 0° C. was slowly added SOCl2 (2.34 g, 19.6 mmol) while maintaining the internal temperature below 5° C. This reaction mixture was warmed to 50° C. and stirred at this temperature for 3 h. It was then cooled to 0° C. and quenched with water. The organic layer was separated and evaporated under reduced pressure. The residue was purified by silica-gel column chromatography eluting with 30:1 dichloromethane/methanol to afford 151b (1.1 g, 68%) as a yellow solid. MS-ESI: [M+H]+ 247.9

Workup

  1. temperaturewhile maintaining the internal temperature below 5° C
  2. temperatureThis reaction mixture was warmed to 50° C.
  3. temperatureIt was then cooled to 0° C.
  4. customquenched with water
  5. customThe organic layer was separated
  6. customevaporated under reduced pressure
  7. customThe residue was purified by silica-gel column chromatography
  8. washeluting with 30:1 dichloromethane/methanol

Sources & evidence

ORD record
ord-7738180cbf3e4c3097f7fdd66286dd03
Source dataset
uspto-grants-2014_06
Patent number
US08754077B2

Reaction notes

Loading…