Hydrochloric Acid → HCID 54739191, compound

HRID 1822422Notes

Reaction equation

HRID 1822422 reaction equation
C(O[C:4](=[O:18])[C:5](=[N:10][NH:11][CH:12]1[CH2:17][CH2:16][CH2:15][CH2:14][CH2:13]1)[C:6]([CH3:9])([CH3:8])[CH3:7])C.CC(C)(C)[C:21](=O)[C:22]([OH:24])=[O:23].C1CCN2C(=[N:32]CCC2)CC1.BrCC.[C:42]([O-:45])(O)=O.[Na+].Cl.C1(NN)CCCCC1.Cl.[CH3:57][C:58]([O:61]C)(C)C>O.CCOC(C)=O>[CH:12]1([N:11]2[C:58](=[O:61])[C:57]([C:42]([NH:32][CH2:21][C:22]([OH:24])=[O:23])=[O:45])=[C:4]([OH:18])[C:5]([C:6]([CH3:7])([CH3:8])[CH3:9])=[N:10]2)[CH2:13][CH2:14][CH2:15][CH2:16][CH2:17]1

Participants

11

Reactant 8

HCID 313Hydrochloric AcidHCID 6332Ethyl BromideHCID 13150Trimethylpyruvic acidHCID 15413tert-Butyl methyl etherHCID 811841,8-Diazabicyclo(5.4.0)undec-7-ene2×HCID 207836Cyclohexylhydrazine hydrochlorideHCID 516892Sodium BicarbonateHCID 86623017HCID 86623017, compound

Product 1

HCID 54739191HCID 54739191, compoundYield 57%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
120 °C

Procedure

Ethyl-2-(cyclohexylhydrazono)-3,3-dimethylbutanoate. To a solution of trimethylpyruvic acid (0.6 g, 2.77 mmol) in MTBE (4.0 ml) was added DBU (0.58 ml, 3.85 mmol) followed by bromoethane (0.5 ml, 6.70 mmol) at room temperature. The reaction was heated in the microwave at 120° C. for 20 minutes. The reaction was cooled and 10% NaHCO3 (aq) added. The layers were separated and the organic layer was washed again with 10% NaHCO3 (aq). The aqueous layer backextracted with Et2O several times. The combined organic layers were washed with Brine, dried (MgSO4), filtered and concentrated. The resulting oil was redissolved in Ethanol (5.0 mL) and cyclohexylhydrazine hydrochloride (0.500 g, 3.32 mmol) and DBU (0.500 ml, 3.32 mmol) were added. The reaction was heated in the microwave at 150° C. for 25 minutes. The reaction was cooled to room temperature and 1N HCl added. The solution was diluted with H2O and EtOAc and the layers separated. The aqueous layer was backextracted with EtOAc several times. The combined organic layers were washed with Brine, dried (MgSO4), filtered and concentrated. The product was purified by column chromatography (SiO2, 5-15% EtOAc/Hexanes) to give the title compound as a colorless oil (0.403 g, 57%). 1H NMR (400 MHz, DMSO-d6) d ppm 9.32 (d, J=4.80 Hz, 1H) 4.20 (q, J=7.07 Hz, 2H) 3.08-3.26 (m, 1H) 1.79-1.94 (m, 2H) 1.48-1.74 (m, 3H) 1.26 (t, J=7.07 Hz, 3H) 1.22-1.37 (m, 5H) 1.15 (s, 9H).

Workup

  1. temperatureThe reaction was cooled
  2. customThe layers were separated
  3. washthe organic layer was washed again with 10% NaHCO3 (aq)
  4. washThe combined organic layers were washed with Brine
  5. dry with materialdried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated
  8. dissolutionThe resulting oil was redissolved in Ethanol (5.0 mL)
  9. temperatureThe reaction was heated in the microwave at 150° C. for 25 minutes
  10. temperatureThe reaction was cooled to room temperature
  11. customthe layers separated
  12. washThe combined organic layers were washed with Brine
  13. dry with materialdried (MgSO4)
  14. filtrationfiltered
  15. concentrationconcentrated
  16. customThe product was purified by column chromatography (SiO2, 5-15% EtOAc/Hexanes)

Sources & evidence

ORD record
ord-25a0a94488c64f649d534bfdd139d0e0
Source dataset
uspto-grants-2009_10
Patent number
US07608621B2

Reaction notes

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