Methyl iodide → 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfinyl-1H-pyrazole-3-carboxaldehyde O-(methyl)oxime

HRID 2301365Notes

Reaction equation

HRID 2301365 reaction equation
[NH2:1][C:2]1[N:6]([C:7]2[C:12]([Cl:13])=[CH:11][C:10]([C:14]([F:17])([F:16])[F:15])=[CH:9][C:8]=2[Cl:18])[N:5]=[C:4]([CH:19]=[N:20][OH:21])[C:3]=1[S:22]([CH3:24])=[O:23].[O-][CH2:26]C.[Na+].IC>C(O)C>[CH3:26][O:21][N:20]=[CH:19][C:4]1[C:3]([S:22]([CH3:24])=[O:23])=[C:2]([NH2:1])[N:6]([C:7]2[C:12]([Cl:13])=[CH:11][C:10]([C:14]([F:17])([F:16])[F:15])=[CH:9][C:8]=2[Cl:18])[N:5]=1

Participants

5

Reactant 3

HCID 6328Methyl iodide2×HCID 2723922Sodium ethoxideHCID 1363524165-amino-1-[2,6-dichloro-4-(trifluoromethyl)-phenyl]-4-methylsulfinyl-1H-pyrazole-3-carboxaldehyde oxime

Product 1

HCID 545293625-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfinyl-1H-pyrazole-3-carboxaldehyde O-(methyl)oximeYield 39.3%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent2×

Procedure

A solution of 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)-phenyl]-4-methylsulfinyl-1H-pyrazole-3-carboxaldehyde oxime (0.15 g) in ethanol was added to a solution of sodium ethoxide (0.025 g)in ethanol at 20° C., followed by iodomethane (0.023 ml). The reaction was monitored by HPLC and over the next 24 hours three additional equivalents of iodomethane were added. The reaction mixture was then concentrated and partitioned between dichloromethane and water. The organic layer was water-washed, dried (MgSO4) and concentrated. This was then combined with crude product from another identical preparation and chromatographed on a silica gel column, eluting with hexane/ethyl acetate, to give 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-methylsulfinyl-1H-pyrazole-3-carboxaldehyde O-(methyl)oxime (0.06 g)as a yellow solid m.p.80° C. Compound 17.

Workup

  1. additionwere added
  2. concentrationThe reaction mixture was then concentrated
  3. custompartitioned between dichloromethane and water
  4. washwashed
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated
  7. customThis was then combined with crude product from another identical preparation
  8. customchromatographed on a silica gel column
  9. washeluting with hexane/ethyl acetate

Sources & evidence

ORD record
ord-c076540eefbb45c89e9ab6efe6a9bfd7
Source dataset
uspto-grants-2002_12
Patent number
US06500850B2

Reaction notes

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