Iodine → 2-iodo-3-(2-methylsulfanyl-pyrimidin-4-yl)-6,7-dihydro-5H-pyrazolo[1,2-a]pyrazol-1-one

HRID 1455258Notes

Reaction equation

HRID 1455258 reaction equation
[CH3:1][S:2][C:3]1[N:8]=[C:7]([C:9]2[N:13]3[CH2:14][CH2:15][CH2:16][N:12]3[C:11](=[O:17])[CH:10]=2)[CH:6]=[CH:5][N:4]=1.[I:18]I>C(Cl)(Cl)(Cl)Cl.N1C=CC=CC=1>[I:18][C:10]1[C:11](=[O:17])[N:12]2[CH2:16][CH2:15][CH2:14][N:13]2[C:9]=1[C:7]1[CH:6]=[CH:5][N:4]=[C:3]([S:2][CH3:1])[N:8]=1

Participants

4

Reactant 2

HCID 807IodineHCID 574380973-(2-Methylsulfanyl-pyrimidin-4-yl)-6,7-dihydro-5h-pyrazolo[1,2-a]pyrazol-1-one

Product 1

HCID 575317902-iodo-3-(2-methylsulfanyl-pyrimidin-4-yl)-6,7-dihydro-5H-pyrazolo[1,2-a]pyrazol-1-one

Reagents, catalysts & solvents 1

HCID 68848382Carbon tetrachloride pyridineSolvent2×

Conditions

Temperature
0 °C

Procedure

To a cold (0° C.) solution of 3-(2-methylsulfanyl-pyrimidin-4-yl)-6,7-dihydro-5H-pyrazolo[1,2-a]pyrazol-1-one, 20, (4.7 g, 19.1 mmol), in carbon tetrachloride/pyridine (140 mL of 1:1 mixture) is added dropwise a solution of iodine in carbon tetrachloride/pyridine (80 mL of 1:1 mixture). After stirring at 0° C. for 30 min, the ice-bath is removed at the mixture was stirred at room temperature. After stirring at room temperature for 1 hour, the reaction mixture was poured into aqueous saturated Na2S2O3. The aqueous phase is extracted with EtOAc (×3). The combined organic phases are dried (MgSO4), filtered and concentrated in vacuo. The resulting yellow solid is purified by silica gel chromatography (5% MeOH/chloroform) to afford 4.2 g of the desired product. 1H NMR (300 MHz, CDCl3) δ 8.72 (d, J=5.1 Hz, 1H), 7.97 (d, J=5.1 Hz, 1H), 4.31 (t, J=6.9 Hz, 2H), 4.10 (t, J=6.9 Hz, 2H), 2.74 (dddd, J=6.9, 6.9, 6.9, 6.9 Hz, 2H), 2.62 (s, 3H); ESI+ MS: m/z (rel intensity) 375.0 (100, M++H).

Workup

  1. customthe ice-bath is removed at the mixture
  2. stirringwas stirred at room temperature
  3. stirringAfter stirring at room temperature for 1 hour
  4. additionthe reaction mixture was poured into aqueous saturated Na2S2O3
  5. extractionThe aqueous phase is extracted with EtOAc (×3)
  6. dry with materialThe combined organic phases are dried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe resulting yellow solid is purified by silica gel chromatography (5% MeOH/chloroform)

Sources & evidence

ORD record
ord-01beb012cef44e0b801af9fd56108d4e
Source dataset
uspto-grants-2009_01
Patent number
US07482356B2

Reaction notes

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