Iodine → HCID 67516452, compound

HRID 1508487Notes

Reaction equation

HRID 1508487 reaction equation
[I:1]I.[CH3:3][O:4][C:5]1[CH:10]=[CH:9][C:8]([C:11]2[CH:15]=[C:14]([C:16]([O:18][CH3:19])=[O:17])[N:13]([CH3:20])[N:12]=2)=[CH:7][CH:6]=1>CCO.S([O-])([O-])(=O)=O.[Ag+2]>[I:1][C:15]1[C:11]([C:8]2[CH:7]=[CH:6][C:5]([O:4][CH3:3])=[CH:10][CH:9]=2)=[N:12][N:13]([CH3:20])[C:14]=1[C:16]([O:18][CH3:19])=[O:17]

Participants

5

Reactant 2

HCID 807IodineHCID 13370529HCID 13370529, compound

Product 1

HCID 67516452HCID 67516452, compound

Reagents, catalysts & solvents 2

HCID 178418844HCID 178418844, compoundCatalystHCID 702EthanolSolvent

Procedure

Silver sulfate (640 mg, 2.053 mmol) and iodine (0.106 mL, 2.053 mmol) were added successively to a solution of methyl 3-(4-methoxyphenyl)-1-methyl-1H-pyrazole-5-carboxylate (405.8 mg, 1.648 mmol) in EtOH (20.0 mL) at 25° C. and the reaction was stirred vigorously for 4 h. The reaction mixture was filtered through a plug of Celite®. The filtrate was diluted with EtOAc (20 mL) and washed with satd Na2SO3 (10 mL). The organic layer was dried (Na2SO4) and concentrated in vacuo to give the crude product. This was purified by flash chromatography (Biotage Horizon, 25M, Si, ˜20 mL/min, 100% hexanes for 144 mL, gradient to 20% EtOAc in hexanes over 2394 mL) to afford methyl 4-iodo-3-(4-methoxyphenyl)-1-methyl-1H-pyrazole-5-carboxylate, as a colorless solid. Rf=0.33 (20% EtOAc/hexanes). LCMS calc.=373.01. found=372.89 (M+H)+. 1H NMR (600 MHz, CDCl3): δ 7.68 (d, J=8.6 Hz, 2H); 6.97 (d, J=8.6 Hz, 2H); 4.22 (s, 3H); 3.96 (s, 3H); 3.85 (s, 3H).

Workup

  1. filtrationThe reaction mixture was filtered through a plug of Celite®
  2. additionThe filtrate was diluted with EtOAc (20 mL)
  3. washwashed with satd Na2SO3 (10 mL)
  4. dry with materialThe organic layer was dried (Na2SO4)
  5. concentrationconcentrated in vacuo
  6. customto give the crude product
  7. customThis was purified by flash chromatography (Biotage Horizon, 25M, Si, ˜20 mL/min, 100% hexanes for 144 mL, gradient to 20% EtOAc in hexanes over 2394 mL)

Sources & evidence

ORD record
ord-84f7d53f894f45d893110ad930ed9fdf
Source dataset
uspto-grants-2015_12
Patent number
US09221834B2

Reaction notes

Loading…