HCID 20435949, compound → HCID 20435995, compound

HRID 1154050Notes

Reaction equation

HRID 1154050 reaction equation
[Br:1][CH2:2][CH:3]([CH2:29]Br)[C:4]([N:6]1[CH:11]([C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])[CH2:10][CH2:9][CH2:8][N:7]1C(OCC1C=CC=CC=1)=O)=[O:5]>C(O)(=O)C.CO.[Pd]>[Br:1][CH2:2][CH:3]1[CH2:29][N:7]2[CH2:8][CH2:9][CH2:10][CH:11]([C:12]([O:14][C:15]([CH3:16])([CH3:17])[CH3:18])=[O:13])[N:6]2[C:4]1=[O:5]

Participants

5

Reactant 1

HCID 20435949HCID 20435949, compound

Product 1

HCID 20435995HCID 20435995, compoundYield 15.5%

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 176Acetic AcidSolventHCID 887MethanolSolvent

Procedure

13.3 g of 1-benzyl 3-tert.butyl 2-(3-bromo-2-bromomethyl-propanoyl)-hexahydropyridazine-1,3-dicarboxylate in 122 ml of acetic acid and 122 ml of methanol was hydrogenated undera pressure of 1 atmosphere for 16 hours in the presence of 1.4 g of 10% palladium/charcoal, the hydrogenation being carried out under a soda-lime trap. The catalyst was removed by filtration, the filtrate was treated with 3.2 g of sodium acetate trihydrate and then evaporated. The residue was extracted with 300 ml of ethyl acetate and the solution was chromatographed on 400 g of silica gel using diethyl ether/hexane for the elution. There were obtained 1.25 g of tert.butyl 2-bromomethyl-hexahydro-3-oxo-1H-pyrazolo[1,2-a]pyridazine-5-carboxylate (diastereomer A) having a melting point of 109°-111° C. (from hexane), 2.45 g of tert.butyl 2-bromomethyl-hexahydro-3-oxo-1H-pyrazolo[1,2-a]-pyridazine-5-carboxylate (diastereomer B) having a melting point of 88°-89° C. (from hexane) and 1.20 g of a mixture of the aforementioned diastereomers.

Workup

  1. customThe catalyst was removed by filtration
  2. additionthe filtrate was treated with 3.2 g of sodium acetate trihydrate
  3. customevaporated
  4. extractionThe residue was extracted with 300 ml of ethyl acetate
  5. customthe solution was chromatographed on 400 g of silica gel
  6. washfor the elution

Sources & evidence

ORD record
ord-827ec970968744189b065ac75c111618
Source dataset
uspto-grants-1984_12
Patent number
US04487929

Reaction notes

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