Iodine → HCID 67517274, compound

HRID 1508489Notes

Reaction equation

HRID 1508489 reaction equation
[I:1]I.[CH3:3][O:4][C:5]1[CH:10]=[CH:9][C:8]([C:11]2[C:15]([CH3:16])=[C:14]([C:17]([O:19][CH3:20])=[O:18])[N:13]([CH3:21])[N:12]=2)=[CH:7][CH:6]=1>CCO.S([O-])([O-])(=O)=O.[Ag+2]>[I:1][C:10]1[CH:9]=[C:8]([C:11]2[C:15]([CH3:16])=[C:14]([C:17]([O:19][CH3:20])=[O:18])[N:13]([CH3:21])[N:12]=2)[CH:7]=[CH:6][C:5]=1[O:4][CH3:3]

Participants

5

Reactant 2

HCID 807IodineHCID 86704595HCID 86704595, compound

Product 1

HCID 67517274HCID 67517274, compound

Reagents, catalysts & solvents 2

HCID 178418844HCID 178418844, compoundCatalystHCID 702EthanolSolvent

Procedure

Silver sulfate (261 mg, 0.837 mmol) and iodine (212 mg, 0.837 mmol) were added successively to a solution of methyl 3-(4-methoxyphenyl)-1,4-dimethyl-1H-pyrazole-5-carboxylate (217.8 mg, 0.837 mmol) in EtOH (8.4 mL) at 25° C. and the reaction was stirred vigorously overnight. The reaction mixture was filtered through a plug of Celite®. The filtrate was diluted with EtOAc (80 mL) and washed with satd Na2SO3 (30 mL). The organic layer was washed with brine (2×30 mL), 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 1125 mL) to afford methyl 3-(3-iodo-4-methoxyphenyl)-1,4-dimethyl-1H-pyrazole-5-carboxylate, as a colorless solid. Rf=0.31 (20% EtOAc/hexanes). LCMS calc.=387.02. found=386.91 (M+H)+. 1H NMR (600 MHz, CDCl3): δ 7.99 (d, J=2.1 Hz, 1H); 7.48 (dd, J=8.5, 2.2 Hz, 1H); 6.82 (d, J=8.5 Hz, 1H); 4.12 (s, 3H); 3.89 (s, 3H); 3.86 (s, 3H); 2.31 (s, 3H).

Workup

  1. filtrationThe reaction mixture was filtered through a plug of Celite®
  2. additionThe filtrate was diluted with EtOAc (80 mL)
  3. washwashed with satd Na2SO3 (30 mL)
  4. washThe organic layer was washed with brine (2×30 mL)
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated in vacuo
  7. customto give the crude product
  8. 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 1125 mL)

Sources & evidence

ORD record
ord-6fa4111dac194845ac243e70f2a120b5
Source dataset
uspto-grants-2015_12
Patent number
US09221834B2

Reaction notes

Loading…