Iodine → HCID 67184064, compound

HRID 2425558Notes

Reaction equation

HRID 2425558 reaction equation
C[Mg]Cl.[CH3:4][C:5]([S@:8](/[N:10]=[CH:11]/[C:12]1[CH:13]=[N:14][N:15]([CH3:21])[C:16]=1[C:17]([F:20])([F:19])[F:18])=[O:9])([CH3:7])[CH3:6].[Cl-].[NH4+].[CH2:24](Cl)Cl.CO.[NH4+].[OH-].II>ClCCl.O.CO>[CH3:21][N:15]1[C:16]([C:17]([F:18])([F:20])[F:19])=[C:12]([C@@H:11]([NH:10][S@@:8]([C:5]([CH3:4])([CH3:6])[CH3:7])=[O:9])[CH3:24])[CH:13]=[N:14]1

Participants

9

Reactant 5

HCID 807IodineHCID 25517Ammonium ChlorideHCID 21896990Dichloromethane methanol ammonium hydroxideHCID 87323718HCID 87323718, compoundHCID 178418332HCID 178418332, compound

Product 1

HCID 67184064HCID 67184064, compound

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

Methyl magnesium chloride (3M in diethyl ether, 3.56 ml, 0.0107 moles) was added dropwise to a stirred solution of (R,E)-2-methyl-N-((1-methyl-5-(trifluoromethyl)-1H-pyrazol-4-yl)methylene)propane-2-sulfinamide (1.0 g, 0.035 moles) in dichloromethane (30 ml) at −70° C. under nitrogen. The mixture was allowed to warm to RT to give a cloudy solution and the solution was stirred overnight at RT under nitrogen. Ammonium chloride solution (saturated) was added slowly dropwise to quench the reaction. The mixture was diluted with water and extracted with ethyl acetate (3×20 ml). The organic layer was separated and back-washed with brine (2×30 ml). The organic layer was separated, dried (Na2SO4), filtered and evaporated to give an oil. Yield 1.1 g. 1H NMR (300 MHz CDCl3) ratio 4.5:1 of diastereoisomers. The diastereoisomers were separated by silica gel chromatography using IPA/Heptane 20:80. The top diastereoisomer (100% de) was isolated. Yield 660 mg, 62%. 1H NMR (400 MHz CD30D) δ 7.48 (s, 1H) 4.79, 4.78, 4.76, 4.75, 4.73 (quin, 1H) 3.23, 3.21 (d, 1H) 1.58, 1.57 (d, 3H) 1.21 (s, 9H). MS (ESI) m/z 298 (M+H)+. GC-MS Cl+298 (M+H)+. TLC CH2Cl2:MeOH:NH4OH 95:5:0.5 0.3 UV−ve I2+ve. [α]D=−13.94° (c 1.65, CH3OH).

Workup

  1. customto give a cloudy solution
  2. customto quench
  3. customthe reaction
  4. extractionextracted with ethyl acetate (3×20 ml)
  5. customThe organic layer was separated
  6. washback-washed with brine (2×30 ml)
  7. customThe organic layer was separated
  8. dry with materialdried (Na2SO4)
  9. filtrationfiltered
  10. customevaporated
  11. customto give an oil
  12. customThe diastereoisomers were separated by silica gel chromatography
  13. customThe top diastereoisomer (100% de) was isolated

Sources & evidence

ORD record
ord-34a350b12b354bb483878fc085789ccb
Source dataset
uspto-grants-2011_06
Patent number
US07964732B2

Reaction notes

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