Potassium Carbonate → 10-Chloro-2-cyclopentyl-4,4-diethyl-2,6,9,11-tetrazabicyclo[5.4.0]undeca-7,9,11-trien-5-one

HRID 2234506Notes

Reaction equation

HRID 2234506 reaction equation
CO[C:3](=[O:16])[C:4]([CH2:9][NH:10][CH:11]1[CH2:15][CH2:14][CH2:13][CH2:12]1)([CH2:7][CH3:8])[CH2:5][CH3:6].C(=O)([O-])[O-].[K+].[K+].[Cl:23][C:24]1[N:29]=[C:28](Cl)[C:27]([N+:31]([O-])=O)=[CH:26][N:25]=1>CC(C)=O.C(O)(=O)C.[Fe]>[Cl:23][C:24]1[N:29]=[C:28]2[C:27]([NH:31][C:3](=[O:16])[C:4]([CH2:5][CH3:6])([CH2:7][CH3:8])[CH2:9][N:10]2[CH:11]2[CH2:12][CH2:13][CH2:14][CH2:15]2)=[CH:26][N:25]=1

Participants

7

Reactant 3

HCID 11430Potassium CarbonateHCID 5212662,4-Dichloro-5-nitropyrimidineHCID 68684960Methyl2-[(cyclopentylamino)methyl]-2-ethyl-butanoate2×

Product 1

HCID 8661759110-Chloro-2-cyclopentyl-4,4-diethyl-2,6,9,11-tetrazabicyclo[5.4.0]undeca-7,9,11-trien-5-oneYield 30.2%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 176Acetic AcidSolventHCID 180AcetoneSolvent

Procedure

To a solution of methyl2-[(cyclopentylamino)methyl]-2-ethyl-butanoate (Intermediate 252; 7.1 g, 31.3 mmol) in acetone (150 mL) was added potassium carbonate (5.3 g, 38.0 mmol) followed by 2,4-dichloro-5-nitropyrimidine (Aldrich; 6.1 g, 31.3 mmol). The black mixture was stirred at room temperature for 18 hours. The reaction was filtered and the solvent removed in vacuo to yield a black gum, which was dissolved in acetic acid (175 mL) and iron (7.0 g, 125 mmol) added and the reaction heated at 80° C. overnight. The resulting solution was filtered and the solvent removed in vacuo, the black solid/gum was quenched with water (75 mL) and to this was added sodium carbonate until basic, the resultant black emulsion was filtered through a pad of celite. The obtained mixture was extracted with DCM (3×150 mL), dried and the solvent removed in vacuo to yield a black solid. This was passed through a bond elute column (50 g) eluting with 0-1% MeOH in DCM to afford a brown solid, which was triturated with diethyl ether to yield the title compound as a white solid (3.05 g, 30%)

Workup

  1. filtrationThe reaction was filtered
  2. customthe solvent removed in vacuo
  3. customto yield a black gum, which
  4. temperaturethe reaction heated at 80° C. overnight
  5. filtrationThe resulting solution was filtered
  6. customthe solvent removed in vacuo
  7. customthe black solid/gum was quenched with water (75 mL)
  8. additionto this was added sodium carbonate until basic, the resultant black emulsion
  9. filtrationwas filtered through a pad of celite
  10. extractionThe obtained mixture was extracted with DCM (3×150 mL)
  11. customdried
  12. customthe solvent removed in vacuo
  13. customto yield a black solid
  14. washelute column (50 g)
  15. washeluting with 0-1% MeOH in DCM
  16. customto afford a brown solid, which
  17. customwas triturated with diethyl ether

Sources & evidence

ORD record
ord-89bfa4c9016348aba9ad103df24bea5d
Source dataset
uspto-grants-2010_05
Patent number
US07709471B2

Reaction notes

Loading…