Diethyl Oxalate → HCID 66958407, compound

HRID 1984494Notes

Reaction equation

HRID 1984494 reaction equation
CC(C)([O-])C.[Na+].[C:7]([O:14][CH2:15][CH3:16])(=[O:13])[C:8](OCC)=O.[OH:17][C:18]([CH3:24])([CH3:23])[CH2:19][C:20](=O)[CH3:21].C([O-])(=O)C.[K+].C(O)(=O)C(O)=O.[CH2:36]([NH:40][NH2:41])[CH2:37][CH2:38][CH3:39]>C(O)(=O)C.C(O)C>[CH2:36]([N:40]1[C:20]([CH2:19][C:18]([OH:17])([CH3:24])[CH3:23])=[CH:21][C:8]([C:7]([O:14][CH2:15][CH3:16])=[O:13])=[N:41]1)[CH2:37][CH2:38][CH3:39]

Participants

8

Reactant 5

HCID 7268Diethyl OxalateHCID 31256Diacetone AlcoholHCID 162021Butylhydrazine oxalateHCID 517044Potassium AcetateHCID 23676156Sodium t-butoxide

Product 1

HCID 66958407HCID 66958407, compoundYield 48.4%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 702EthanolSolvent

Procedure

A mixture sodium tert-butoxide (23.0 g, 0.240 mol) and ethanol (200 mL) was stirred for 30 minutes at 0° C.; most of the solid was dissolved. A mixture of diethyl oxalate (32.6 mL, 0.240 mol) and 4-hydroxy4-methyl-2-pentanone (25.0 mL, 0.200 mol) was added slowly, and the reaction was stirred for ten minutes at 0° C. before the addition of acetic acid (100 mL). The reaction was warmed to ambient temperature and stirred for ten minutes. Potassium acetate (29.4 g, 0.300 mol) and butylhydrazine oxalate (30.0 g, 0.200 mol) were sequentially added. The reaction was stirred overnight at ambient temperature, and the acetic acid was removed under reduced pressure. The residue was adjusted to pH 14 with the addition of 50% w/w aqueous sodium hydroxide while maintaining the temperature at 0° C. with the addition of ice. The mixture was extracted with dichloromethane; the combined extracts were dried over sodium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by chromatography on a HORIZON HPFC system (65+M cartridge, eluting with 0 to70% ethyl acetate in hexanes) to provide 26 g of ethyl 1-butyl-5-(2-hydroxy-2-methylpropyl)-1H-pyrazole-3-carboxylate as a yellow oil.

Workup

  1. dissolutionmost of the solid was dissolved
  2. additionwas added slowly
  3. stirringThe reaction was stirred overnight at ambient temperature
  4. customthe acetic acid was removed under reduced pressure
  5. additionThe residue was adjusted to pH 14 with the addition of 50% w/w aqueous sodium hydroxide
  6. temperaturewhile maintaining the temperature at 0° C.
  7. additionwith the addition of ice
  8. extractionThe mixture was extracted with dichloromethane
  9. dry with materialthe combined extracts were dried over sodium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated under reduced pressure
  12. customThe crude product was purified by chromatography on a HORIZON HPFC system (65+M cartridge, eluting with 0 to70% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-4591968c857a4708b4a88b35f7cbfcba
Source dataset
uspto-grants-2009_06
Patent number
US07544697B2

Reaction notes

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