Triethylamine → methyl N-[2-(4-formyl-4,5,6,7-tetrahydropyrazolo[1,5-a]pyrimidin-3-yl)ethyl]carbamate

HRID 349564Notes

Reaction equation

HRID 349564 reaction equation
[CH:1]([N:3]1[CH2:8][CH2:7][CH2:6][N:5]2[N:9]=[CH:10][C:11]([CH2:12][CH2:13]C(O)=O)=[C:4]12)=[O:2].C([N:19](CC)CC)C.Cl[C:25]([O:27][CH2:28]C)=[O:26].[N-]=[N+]=[N-].[Na+]>O.C(Cl)Cl.O1CCCC1>[CH:1]([N:3]1[CH2:8][CH2:7][CH2:6][N:5]2[N:9]=[CH:10][C:11]([CH2:12][CH2:13][NH:19][C:25](=[O:26])[O:27][CH3:28])=[C:4]12)=[O:2]

Participants

8

Reactant 4

HCID 8471TriethylamineHCID 10928Ethyl chloroformateHCID 33557Sodium AzideHCID 179620213-(4-Formyl-4,5,6,7-tetrahydropyrazolo[1,5-a]pyrimidin-3-yl)propionic acid

Product 1

HCID 17962023methyl N-[2-(4-formyl-4,5,6,7-tetrahydropyrazolo[1,5-a]pyrimidin-3-yl)ethyl]carbamate

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a mixture of 3-(4-formyl-4,5,6,7-tetrahydropyrazolo[1,5-a]pyrimidin-3-yl)propionic acid (18.0 g), triethylamine (9.8 g) and tetrahyrofuran (300 ml) was added dropwise ethyl chloroformate (9.6 g) under ice-cooling. The mixture was stirred under ice-cooling for 30 minutes. To the reaction mixture was added a solution of sodium azide (6.68 g) in water (100 ml), and the mixture was stirred at room temperature for 30 minutes. To the reaction mixture was added methylene chloride, and the aqueous layer was separated. The organic layer was washed with water, dried over anhydrous magnesium sulfate, filtered, and concentrated in vacuo. To the oily residue was added methanol (100 ml), and the mixture was stirred under reflux for 1.5 hours. The reaction mixture was concentrated in vacuo to give crude methyl N-[2-(4-formyl-4,5,6,7-tetrahydropyrazolo[1,5-a]pyrimidin-3-yl)ethyl]carbamate as an oil. This product was used in the next step without further purification.

Workup

  1. temperaturecooling
  2. temperaturecooling for 30 minutes
  3. stirringthe mixture was stirred at room temperature for 30 minutes
  4. customthe aqueous layer was separated
  5. washThe organic layer was washed with water
  6. dry with materialdried over anhydrous magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. additionTo the oily residue was added methanol (100 ml)
  10. stirringthe mixture was stirred
  11. temperatureunder reflux for 1.5 hours
  12. concentrationThe reaction mixture was concentrated in vacuo

Sources & evidence

ORD record
ord-ab18594ba0424da1bb4bcd6d308f9b82
Source dataset
uspto-grants-2007_02
Patent number
US07179801B2

Reaction notes

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