Acetic Acid → 10-Chloro-4,4-diethyl-2-propan-2-yl-2,6,9,11-tetrazabicyclo[5.4.0]undeca-7,9,11-trien-5-one

HRID 2234469Notes

Reaction equation

HRID 2234469 reaction equation
[Cl:1][C:2]1[N:7]=[C:6](Cl)[C:5]([N+:9]([O-])=O)=[CH:4][N:3]=1.C([O-])([O-])=O.[K+].[K+].C[O:19][C:20](=O)[C:21]([CH2:29][CH3:30])([CH2:24][NH:25][CH:26]([CH3:28])[CH3:27])[CH2:22][CH3:23].C(O)(=O)C>CC(C)=O.[Fe]>[Cl:1][C:2]1[N:7]=[C:6]2[C:5]([NH:9][C:20](=[O:19])[C:21]([CH2:22][CH3:23])([CH2:29][CH3:30])[CH2:24][N:25]2[CH:26]([CH3:28])[CH3:27])=[CH:4][N:3]=1

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 11430Potassium CarbonateHCID 5212662,4-Dichloro-5-nitropyrimidineHCID 86617586Methyl2-ethyl-2-[(propan-2-ylamino)methyl]butanoate2×

Product 1

HCID 8661758510-Chloro-4,4-diethyl-2-propan-2-yl-2,6,9,11-tetrazabicyclo[5.4.0]undeca-7,9,11-trien-5-one

Reagents, catalysts & solvents 2

HCID 23925IronCatalystHCID 180AcetoneSolvent2×

Procedure

To a solution of 2,4-dichloro-5-nitropyrimidine (Aldrich; 5.1 g, 26.4 mmol) and K2CO3 (4.4 g, 31.6 mmol) in acetone (150 mL) was slowly added methyl2-ethyl-2-[(propan-2-ylamino)methyl]butanoate (Intermediate 200; 5.3 g, 26.4 mmol) in acetone (30 mL). The mixture was stirred at room temperature for 18 hours. The reaction was filtered and the solvent evaporated. The residue and iron (4.4 g, 79.2 mmol) were added to acetic acid (175 mL) and heated at 80° C. overnight. The resulting solution was filtered and the solvent evaporated and the residue quenched with 2.0 N NaOH(aq) (75 mL), to the resultant emulsion, was added 10% MeOH/DCM (100 ml) and the suspension filtered through a pad of celite. The obtained filtrate was extracted with 10% MeOH/DCM (3×150 mL, dried and the solvent removed. The resultant material was dissolved in DCM and filtered. Acetonitrile was added to the DCM and the DCM was slowly removed in vacuo to give a precipitate, which was filtered and dried to yield the title compound as a white solid. (3.1 g, 33%)

Workup

  1. filtrationThe reaction was filtered
  2. customthe solvent evaporated
  3. temperatureheated at 80° C. overnight
  4. filtrationThe resulting solution was filtered
  5. customthe solvent evaporated
  6. customthe residue quenched with 2.0 N NaOH(aq) (75 mL)
  7. additionto the resultant emulsion, was added 10% MeOH/DCM (100 ml)
  8. filtrationthe suspension filtered through a pad of celite
  9. extractionThe obtained filtrate was extracted with 10% MeOH/DCM (3×150 mL
  10. customdried
  11. customthe solvent removed
  12. dissolutionThe resultant material was dissolved in DCM
  13. filtrationfiltered
  14. additionAcetonitrile was added to the DCM
  15. customthe DCM was slowly removed in vacuo
  16. customto give a precipitate, which
  17. filtrationwas filtered
  18. customdried

Sources & evidence

ORD record
ord-6ebc2b18a3d14831af24cf18814440cc
Source dataset
uspto-grants-2010_05
Patent number
US07709471B2

Reaction notes

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