Diethyl Oxalate → HCID 66958401, compound

HRID 1984443Notes

Reaction equation

HRID 1984443 reaction equation
[CH3:1][C:2]([CH3:5])([O-])[CH3:3].[Na+].[C:7]([O:14][CH2:15][CH3:16])(=[O:13])[C:8](OCC)=O.[C:17]([O-])(=O)[CH3:18].[K+].[ClH:22].C(O)(=O)C(O)=O.[C:29]([NH:33][NH2:34])(C)([CH3:31])[CH3:30]>C(O)(=O)C.C(O)C>[C:2]([N:33]1[C:29]([CH2:31][CH2:17][CH2:18][Cl:22])=[CH:30][C:8]([C:7]([O:14][CH2:15][CH3:16])=[O:13])=[N:34]1)([CH3:5])([CH3:3])[CH3:1]

Participants

7

Reactant 4

HCID 7268Diethyl OxalateHCID 517044Potassium AcetateHCID 23676156Sodium t-butoxideHCID 86604923HCID 86604923, compound

Product 1

HCID 66958401HCID 66958401, compound

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 702EthanolSolvent2×

Conditions

Temperature
0 °C

Procedure

Under a nitrogen atmosphere, a mixture sodium tert-butoxide (88.45 g, 0.920 mol) and ethanol (625 mL) was stirred for 5 minutes and then cooled to 0° C. A solution of diethyl oxalate (119 mL, 0.877 mol) and 6-chloro-2-pentanone (100 mL, 0.877 mol) in a minimal amount of ethanol was added and a precipitate formed immediately. The reaction was stirred for 5 minutes, then acetic acid (438 mL of 2 M) was added and a solution was obtained. Potassium acetate (129.0 g, 1.314 mol) was added and the reaction mixture was stirred for 3 minutes at which time it solidified. tert-Butylhydrazine oxalate hydrochloride (120.1 g, 0.964 mol) was added. The reaction was allowed to warm to ambient temperature with stirring overnight and then concentrated under reduced pressure. The residue was diluted with dichloromethane and water and the mixture was adjusted to pH 11 with the addition of 2 M aqueous sodium carbonate. The aqueous layer was extracted with dichloromethane; the combined organics were dried over sodium sulfate, filtered, and concentrated under reduced pressure to provide ethyl 1-tert-butyl-5-(3-chloropropyl)-1H-pyrazole-3-carboxylate that was used without purification.

Workup

  1. customa precipitate formed immediately
  2. customa solution was obtained
  3. stirringthe reaction mixture was stirred for 3 minutes at which time it
  4. temperatureto warm to ambient temperature
  5. stirringwith stirring overnight
  6. concentrationconcentrated under reduced pressure
  7. additionThe residue was diluted with dichloromethane and water
  8. additionthe mixture was adjusted to pH 11 with the addition of 2 M aqueous sodium carbonate
  9. extractionThe aqueous layer was extracted with dichloromethane
  10. dry with materialthe combined organics were dried over sodium sulfate
  11. filtrationfiltered
  12. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-6b089a4d6f054dd48d0b79a2ee58e614
Source dataset
uspto-grants-2009_06
Patent number
US07544697B2

Reaction notes

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