Triacetoxyperiodinane → (4,6-dichloropyrimidin-5-yl)[1-methyl-5-(4-methylphenyl)-1H-pyrazol-4-yl]methanone

HRID 72699Notes

Reaction equation

HRID 72699 reaction equation
[Cl:1][C:2]1[C:7]([CH:8]([C:10]2[CH:11]=[N:12][N:13]([CH3:22])[C:14]=2[C:15]2[CH:20]=[CH:19][C:18]([CH3:21])=[CH:17][CH:16]=2)[OH:9])=[C:6]([Cl:23])[N:5]=[CH:4][N:3]=1.CC(OI1(OC(C)=O)(OC(C)=O)OC(=O)C2C=CC=CC1=2)=O>C(Cl)(Cl)Cl>[Cl:23][C:6]1[C:7]([C:8]([C:10]2[CH:11]=[N:12][N:13]([CH3:22])[C:14]=2[C:15]2[CH:20]=[CH:19][C:18]([CH3:21])=[CH:17][CH:16]=2)=[O:9])=[C:2]([Cl:1])[N:3]=[CH:4][N:5]=1

Participants

4

Reactant 2

HCID 159087TriacetoxyperiodinaneHCID 86712557(4,6-dichloropyrimidin-5-yl)[1-methyl-5-(4-methylphenyl)-1H-pyrazol-4-yl]methanol

Product 1

HCID 86712558(4,6-dichloropyrimidin-5-yl)[1-methyl-5-(4-methylphenyl)-1H-pyrazol-4-yl]methanone

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

To a mixture of (4,6-dichloropyrimidin-5-yl)[1-methyl-5-(4-methylphenyl)-1H-pyrazol-4-yl]methanol (C4) (60 g, 170 mmol) and chloroform (1.8 L) was added Dess-Martin periodinane (110 g, 258 mmol) in portions at room temperature. After the addition was complete, the reaction mixture was stirred at room temperature for 2 hours, and then concentrated in vacuo. The residue was taken up in ethyl acetate and washed with aqueous sodium hydroxide solution (0.5 N, 2×800 mL), then with saturated aqueous sodium chloride solution, dried over sodium sulfate, and concentrated under reduced pressure. Recrystallization from methanol afforded the product as a light yellow solid. Yield: 31.3 g, 90.1 mmol, 53%. LCMS m/z 346.9 (M+1). 1H NMR (400 MHz, CDCl3) δ 2.33 (s, 3H), 3.69 (s, 3H), 7.07-7.15 (br AB quartet, JAB=8 Hz, ΔνAB=8 Hz, 4H), 8.15 (s, 1H), 8.49 (s, 1H).

Workup

  1. additionAfter the addition
  2. concentrationconcentrated in vacuo
  3. washwashed with aqueous sodium hydroxide solution (0.5 N, 2×800 mL)
  4. dry with materialwith saturated aqueous sodium chloride solution, dried over sodium sulfate
  5. concentrationconcentrated under reduced pressure
  6. customRecrystallization from methanol

Sources & evidence

ORD record
ord-8b5835b556ba4cb6a07b7c3bb8ba2bc2
Source dataset
uspto-grants-2014_09
Patent number
US08829010B2

Reaction notes

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