1,8-Diazabicyclo(5.4.0)undec-7-ene → 3-(2-methylsulfanyl-pyrimidin-4-yl)-1-oxo-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazole-2-carboxylic acid ethyl ester

HRID 1455250Notes

Reaction equation

HRID 1455250 reaction equation
[CH2:1]([O:3][C:4](=[O:23])[CH2:5][C:6]([N:8]1[CH2:12][CH2:11][CH2:10][N:9]1[C:13]([C:15]1[CH:20]=[CH:19][N:18]=[C:17]([S:21][CH3:22])[N:16]=1)=O)=[O:7])[CH3:2].N12CCCN=C1CCCCC2>CN(C=O)C.O>[CH2:1]([O:3][C:4]([C:5]1[C:6](=[O:7])[N:8]2[CH2:12][CH2:11][CH2:10][N:9]2[C:13]=1[C:15]1[CH:20]=[CH:19][N:18]=[C:17]([S:21][CH3:22])[N:16]=1)=[O:23])[CH3:2]

Participants

5

Reactant 2

HCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 574380843-[2-(2-Methylsulfanyl-pyrimidine-4-carbonyl)-pyrazolidin-1-yl]-3-oxo-propionic acid ethyl ester

Product 1

HCID 574380853-(2-methylsulfanyl-pyrimidin-4-yl)-1-oxo-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazole-2-carboxylic acid ethyl ester

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

To a solution of 3-[2-(2-methylsulfanyl-pyrimidine-4-carbonyl)-pyrazolidin-1-yl]-3-oxo-propionic acid ethyl ester, 12, (9.6 g, 28.4 mmol) in DMF (280 mL) was added 1.8-diazabicyclo[5.4.0]-undec-7-ene (12.7 mL, 85.2 mmol). The reaction solution is stirred for 2 hours at room temperature then diluted with H2O. The aqueous phase is extracted three times with CHCl3. The combined organic phases are washed with aqueous saturated NH4Cl (×3), dried (MgSO4), filtered and concentrated in vacuo. The residue is purified over silica (5% MeOH/CHCl3) to afford 3.1 g of the desired product. 1H NMR (300 MHz, CDCl3) δ 8.67 (d, J=5.1 Hz, 1H), 7.61 (d, J=5.1 Hz, 1H), 4.33 (q, J=7.2 Hz, 2H), 4.31 (t, J=7.2 Hz, 2H), 4.09 (t, J=7.2 Hz, 2H), 2.74 (dddd, 7.2, 7.2, 7.2, 7.2 Hz, 2H), 2.61 (s, 3H), 1.35 (t, J=7.2 Hz, 3H); ESI+ MS: m/z (rel intensity) 321.1 (100, M++H).

Workup

  1. extractionThe aqueous phase is extracted three times with CHCl3
  2. washThe combined organic phases are washed with aqueous saturated NH4Cl (×3)
  3. dry with materialdried (MgSO4)
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe residue is purified over silica (5% MeOH/CHCl3)

Sources & evidence

ORD record
ord-d9387b3fce2e4daeb78b9a9ed912c8fb
Source dataset
uspto-grants-2009_01
Patent number
US07482356B2

Reaction notes

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