3-Chlorobenzoic Acid → 5-[2-Ethoxy-5-(4-ethyl-4-oxidopiperazin-1-ylsulphonyl)pyridin-3-yl]-3-ethyl-2-(pyridin-2-yl)methyl-2,6-dihydro-7h-pyrazolo[4,3-d]pyrimidin-7-one

HRID 990235Notes

Reaction equation

HRID 990235 reaction equation
[CH2:1]([O:3][C:4]1[C:9]([C:10]2[NH:11][C:12](=[O:28])[C:13]3[C:14](=[C:16]([CH2:26][CH3:27])[N:17]([CH2:19][C:20]4[CH:25]=[CH:24][CH:23]=[CH:22][N:21]=4)[N:18]=3)[N:15]=2)=[CH:8][C:7]([S:29]([N:32]2[CH2:37][CH2:36][N:35]([CH2:38][CH3:39])[CH2:34][CH2:33]2)(=[O:31])=[O:30])=[CH:6][N:5]=1)[CH3:2].ClC1C=C(C=CC=1)C(O)=[O:45].ClC1C=C(C=CC=1)C(OO)=O>ClCCl>[CH2:1]([O:3][C:4]1[C:9]([C:10]2[NH:11][C:12](=[O:28])[C:13]3[C:14](=[C:16]([CH2:26][CH3:27])[N:17]([CH2:19][C:20]4[CH:25]=[CH:24][CH:23]=[CH:22][N:21]=4)[N:18]=3)[N:15]=2)=[CH:8][C:7]([S:29]([N:32]2[CH2:37][CH2:36][N+:35]([CH2:38][CH3:39])([O-:45])[CH2:34][CH2:33]2)(=[O:30])=[O:31])=[CH:6][N:5]=1)[CH3:2]

Participants

5

Reactant 3

HCID 4473-Chlorobenzoic AcidHCID 70297m-Chloroperbenzoic acidHCID 1355816594-{6-Ethoxy-5-[3-ethyl-6,7-dihydro-7-oxo-2-(2-pyridylmethyl)-2H-pyrazolo [4,3-d]pyrimidin-5-yl]-3-pyridylsulfonyl}-1-ethylpiperazine

Product 1

HCID 1358163985-[2-Ethoxy-5-(4-ethyl-4-oxidopiperazin-1-ylsulphonyl)pyridin-3-yl]-3-ethyl-2-(pyridin-2-yl)methyl-2,6-dihydro-7h-pyrazolo[4,3-d]pyrimidin-7-oneYield 180.3%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A mixture of the title compound of Example 1 (180 mg, 0.32 mmol), 3-chlorobenzoic acid (13 mg, 0.08 mmol) and dichloromethane (10 ml) was stirred at room temperature for 20 minutes, 3-chloroperoxybenzoic acid (112 mg, 0.32 mmol) added and the reaction mixture stirred for a further 18 hours, then partitioned between dichloromethane (20 ml) and aqueous sodium bicarbonate solution (10 ml). The phases were separated, the aqueous phase extracted with dichloromethane (2×20 ml) and the combined organic solutions dried (MgSO4) and evaporated under reduced pressure. The residue was purified by column chromatography on silica gel, using dichloromethane:methanol (80:20) as eluant, to furnish the title compound (82 mg, 45%) as a white powder. Found: C, 52.73; H, 5.67; N, 17.69. C26H32N8O5S; 0.50 CH2Cl2 requires C, 52.08; H, 5.44; N, 18.34%. δ (CDCl3): 1.30 (3H, t), 1.40 (3H,t), 1.58 (3H, t), 3.02 (2H, q), 3.20 (2H, m), 3.32 (4H, m), 3.48 (2H, m), 3.72 (2H, m), 4.76 (2H, q), 5.68 (2H, s), 7.08 (1H, d), 7.22 (1H, m), 7.63 (1H, m), 8.58 (1H, d), 8.65 (1H, s), 9.03 (1H, s), 10.70 (1H, s).

Workup

  1. stirringthe reaction mixture stirred for a further 18 hours
  2. custompartitioned between dichloromethane (20 ml) and aqueous sodium bicarbonate solution (10 ml)
  3. customThe phases were separated
  4. extractionthe aqueous phase extracted with dichloromethane (2×20 ml)
  5. dry with materialthe combined organic solutions dried (MgSO4)
  6. customevaporated under reduced pressure
  7. customThe residue was purified by column chromatography on silica gel

Sources & evidence

ORD record
ord-7d6e37cc1e2244e7866e806b448ec50f
Source dataset
uspto-grants-2002_10
Patent number
US06458951B2

Reaction notes

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