2-[(2-chloro-phenyl)-hydroxy-methyl]-3-(2-methylsulfanyl-pyrimidin-4-yl)-6,7-dihydro-5H-pyrazolo[1,2-a]pyrazol-1-one → 2-(2-chlorobenzoyl)-3-(2-methylsulfanyl-pyrimidin-4-yl)-6,7-dihydro-5H-pyrazolo[1,2-a]pyrazol-1-one

HRID 1455260Notes

Reaction equation

HRID 1455260 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[CH:8]([OH:26])[C:9]1[C:16](=[O:17])[N:12]2[CH2:13][CH2:14][CH2:15][N:11]2[C:10]=1[C:18]1[CH:23]=[CH:22][N:21]=[C:20]([S:24][CH3:25])[N:19]=1>C(Cl)Cl.[O-2].[Mn+4].[O-2]>[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8]([C:9]1[C:16](=[O:17])[N:12]2[CH2:13][CH2:14][CH2:15][N:11]2[C:10]=1[C:18]1[CH:23]=[CH:22][N:21]=[C:20]([S:24][CH3:25])[N:19]=1)=[O:26]

Participants

4

Reactant 1

HCID 575317942-[(2-chloro-phenyl)-hydroxy-methyl]-3-(2-methylsulfanyl-pyrimidin-4-yl)-6,7-dihydro-5H-pyrazolo[1,2-a]pyrazol-1-one

Product 1

HCID 574381002-(2-chlorobenzoyl)-3-(2-methylsulfanyl-pyrimidin-4-yl)-6,7-dihydro-5H-pyrazolo[1,2-a]pyrazol-1-oneYield 69%

Reagents, catalysts & solvents 2

HCID 178418406HCID 178418406, compoundCatalystHCID 6344DichloromethaneSolvent

Procedure

To a solution of 2-[(2-chloro-phenyl)-hydroxy-methyl]-3-(2-methylsulfanyl-pyrimidin-4-yl)-6,7-dihydro-5H-pyrazolo[1,2-a]pyrazol-1-one, 22, (0.22 g, 0.56 mmol) in CH2Cl2 (3 mL) is added manganese (IV) oxide (0.30 g, 3.40 mmol). After stirring for 18 hours at room temperature, the mixture is filtered through celite and washed with CH2Cl2. The filtrate is concentrated in vacuo. The crude residue is purified over silica (5% MeOH/chloroform) to afford 165 mg (69% yield) of the desired product. 1H NMR (300 MHz, CDCl3) δ 8.69 (d, J=5.1 Hz, 1H), 7.78 (dd, J=7.2, 1.8 Hz, 1H), 7.81 (d, J=5.1 Hz, 1H), 7.46-7.33 (m, 4H), 4.44 (t, J=7.2 Hz, 2H), 4.03 (t, J=7.2 Hz, 2H), 2.76 (dddd, J=7.2, 7.2, 7.2, 7.2 Hz, 2H), 2.63 (s, 3H); ESI+ MS: m/z (rel intensity) 387.1 (100, M++H).

Workup

  1. filtrationthe mixture is filtered through celite
  2. washwashed with CH2Cl2
  3. concentrationThe filtrate is concentrated in vacuo
  4. customThe crude residue is purified over silica (5% MeOH/chloroform)

Sources & evidence

ORD record
ord-ee77d6a2dc084b26b24f58444852a03b
Source dataset
uspto-grants-2009_01
Patent number
US07482356B2

Reaction notes

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