N,N'-Dimethylethylenediamine → HCID 66930609, compound

HRID 1364122Notes

Reaction equation

HRID 1364122 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([N:8]2[CH:17]=[C:16]3[C:10]([CH2:11][CH2:12][N:13]([C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[CH2:14][CH2:15]3)=[N:9]2)=[CH:4][CH:3]=1.[O:25]1[CH2:29][CH2:28][NH:27][C:26]1=[O:30].C(=O)([O-])[O-].[K+].[K+].CNCCNC>O1CCOCC1.[Cu]I>[O:30]=[C:26]1[N:27]([C:2]2[CH:7]=[CH:6][C:5]([N:8]3[CH:17]=[C:16]4[C:10]([CH2:11][CH2:12][N:13]([C:18]([O:20][C:21]([CH3:24])([CH3:23])[CH3:22])=[O:19])[CH2:14][CH2:15]4)=[N:9]3)=[CH:4][CH:3]=2)[CH2:28][CH2:29][O:25]1

Participants

7

Reactant 4

HCID 8070N,N'-Dimethylethylenediamine4×HCID 11430Potassium CarbonateHCID 739492-Oxazolidinone4×HCID 66931029HCID 66931029, compound

Product 1

HCID 66930609HCID 66930609, compound

Reagents, catalysts & solvents 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)Catalyst4×HCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of 1,1-dimethylethyl 2-(4-bromophenyl)-4,5,7,8-tetrahydropyrazolo[3,4-d]azepine-6(2H)-carboxylate (may be prepared as described in Description 12) (160 mg, 0.41 mmol), 2-oxazolidinone (71 mg, 0.82 mmol), potassium carbonate (170 mg, 1.23 mmol), copper (I) iodide (24 mg, 0.12 mmol) and N,N′-dimethyl-1,2-ethanediamine (13 μl, 0.12 mmol) in dioxane (10 ml) was heated at reflux overnight. The same amounts again of 2-oxazolidinone, copper (I) iodide and N,N′-dimethyl-1,2-ethanediamine were added and the mixture heated for 6 hours. The reaction mixture was transferred to a microwave vial, the same amounts again of 2-oxazolidinone, copper (I) iodide and N,N′-dimethyl-1,2-ethanediamine were added and the mixture heated at 100° C. in microwave for 1 hour. The same amounts again of 2-oxazolidinone, copper (I) iodide and N,N′-dimethyl-1,2-ethanediamine were added and the mixture heated at 100° C. in microwave for a further 2 hours. Crude mixture was filtered through a celite pad washing with methanol. The solvent was evaporated in vacuo, the residue was taken up into ethyl acetate, washed with water and brine, then dried over magnesium sulphate. After evaporation of the solvent in vacuo, the residue was purified by column chromatography on silica gel, eluting with a 50% mixture of ethyl acetate in hexane to afford the title compound (D26). MS (ES+) m/e 343 [M-tBu]+.

Workup

  1. temperaturewas heated
  2. temperatureat reflux overnight
  3. temperaturethe mixture heated for 6 hours
  4. temperaturethe mixture heated at 100° C. in microwave for a further 2 hours
  5. filtrationCrude mixture was filtered through a celite pad
  6. washwashing with methanol
  7. customThe solvent was evaporated in vacuo
  8. washwashed with water and brine
  9. dry with materialdried over magnesium sulphate
  10. customAfter evaporation of the solvent in vacuo
  11. customthe residue was purified by column chromatography on silica gel
  12. washeluting with a 50% mixture of ethyl acetate in hexane

Sources & evidence

ORD record
ord-835a9e2a285c4b65b27eb060d9661558
Source dataset
uspto-grants-2011_02
Patent number
US07888347B2

Reaction notes

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