Diethyl Carbonate → HCID 135974540, compound

HRID 2054409Notes

Reaction equation

HRID 2054409 reaction equation
[O-]CC.[Na+].[Na].[C:6]([OH:9])(=O)C.[Cl:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=1[C:17]1[CH:18]=[C:19]([NH:22][CH:23]=[NH:24])[NH:20][N:21]=1.C(OC(=O)OCC)C>C(O)C>[Cl:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=1[C:17]1[CH:18]=[C:19]2[N:22]=[CH:23][NH:24][C:6](=[O:9])[N:20]2[N:21]=1

Participants

6

Reactant 4

HCID 7766Diethyl CarbonateHCID 2723922Sodium ethoxideHCID 5360545SodiumHCID 178476698HCID 178476698, compound

Product 1

HCID 135974540HCID 135974540, compoundYield 57.2%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

To an ethanolic solution of sodium ethoxide, generated by portionwise addition of sodium metal (4.2 g, 185 mmol) to stirred ethanol (250 ml), was added N-[5-(2-chlorophenyl)-2H-pyrazol-3-yl]-formamidine, acetate salt (I-3A-9b; 5.2 g, 18.5 mmol) in one portion. Diethylcarbonate (17.8 ml, 148 mmol) was added, dropwise, and the mixture was heated at reflux for 2 hours. After cooling to room temperature, the reaction was concentrated, in vacuo, and then extracted with ethyl acetate from water after adjusting to pH 7 with 3 M aqueous HCL. The combined organic layers were washed with water and then brine, dried (MgSO4), filtered, and then concentrated, in vacuo, to one-third volume at which time a precipitate began to form. After stirring overnight, the product was collected by vacuum filtration and then dried, in vacuo, to afford I-3A-9c as a solid (2.61 g, 57%). A second crop of the intermediate was collected from the filtrate after standing an additional 24 hours (600 mg, 19%): +ESI MS (M+1) 247.1; 1H NMR (400 MHz, CD3OD) δ 7.97 (s, 1H), 7.86-7.82 (m, 1H), 7.55-7.51 (m, 1H), 7.45-7.39 (m, 2H), 6.92 (s, 1H).

Workup

  1. temperaturedropwise, and the mixture was heated
  2. temperatureat reflux for 2 hours
  3. concentrationthe reaction was concentrated, in vacuo
  4. extractionextracted with ethyl acetate from water
  5. washThe combined organic layers were washed with water
  6. dry with materialbrine, dried (MgSO4)
  7. filtrationfiltered
  8. concentrationconcentrated, in vacuo, to one-third volume at which time a precipitate
  9. customto form
  10. filtrationthe product was collected by vacuum filtration
  11. customdried, in vacuo

Sources & evidence

ORD record
ord-6f51c90041e94fda84d2195f1135e3b2
Source dataset
uspto-grants-2008_02
Patent number
US07329658B2

Reaction notes

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