Hydrochloric Acid → HCID 54747359, compound

HRID 2046258Notes

Reaction equation

HRID 2046258 reaction equation
[C:1]([C:3]1[CH:4]=[C:5]([CH2:9][N:10]2[C:15](=[O:16])[C:14]([C:17](OCC)=[O:18])=[C:13]([OH:22])[C:12]([CH:23]([CH3:25])[CH3:24])=[N:11]2)[CH:6]=[CH:7][CH:8]=1)#[N:2].[H-].[Na+].BrCC1C=CC=C(C#[N:37])C=1.Cl.CC[O:41][C:42]([CH3:44])=[O:43]>CN(C)C=O.O>[C:1]([C:3]1[CH:4]=[C:5]([CH2:9][N:10]2[C:15](=[O:16])[C:14]([C:17]([NH:37][CH2:44][C:42]([OH:41])=[O:43])=[O:18])=[C:13]([OH:22])[C:12]([CH:23]([CH3:24])[CH3:25])=[N:11]2)[CH:6]=[CH:7][CH:8]=1)#[N:2]

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 8857Ethyl AcetateHCID 24758Sodium hydrideHCID 97249Benzonitrile, 3-(bromomethyl)-HCID 68814917HCID 68814917, compound

Product 1

HCID 54747359HCID 54747359, compoundYield 52%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

Ethyl 2-[(3-cyanophenyl)methyl]-5-hydroxy-6-(1-methylethyl)-3-oxo-2,3-dihydro-4-pyridazinecarboxylate. Sodium hydride (53 mg, 1.33 mmol) was added to a solution of the compound from example 14a) (120 mg, 0.53 mmol) in N,N-Dimethylformamide (DMF) (2.5 mL) at 0° C. The reaction was brought to room temperature and stirred for 30 minutes. The temperature was then reduced to 0° C. and α-bromo-m-tolunitrile (104 mg, 0.53 mmol) was added. The reaction was brought to room temperature and stirred for 3 h followed by the addition of 1N HCl. The solution was diluted with EtOAc and H2O 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, 30-60% EtOAc/Hexanes) to give the title compound (95 mg, 52%). 1H NMR (400 MHz, DMSO-d6) δ ppm 12.35 (s, 1H) 7.78 (dt, J=6.88, 1.74 Hz, 1H) 7.72 (s, 1H) 7.52-7.63 (m, 2H) 5.20 (s, 2H) 4.27 (q, J=7.16 Hz, 2H) 3.16 (sept, J=6.82 Hz, 1H) 1.26 (t, J=7.07 Hz, 3H) 1.16 (d, J=6.82 Hz, 6H).

Workup

  1. customwas brought to room temperature
  2. customwas then reduced to 0° C.
  3. customwas brought to room temperature
  4. stirringstirred for 3 h
  5. customthe layers separated
  6. washThe combined organic layers were washed with Brine
  7. dry with materialdried (MgSO4)
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe product was purified by column chromatography (SiO2, 30-60% EtOAc/Hexanes)

Sources & evidence

ORD record
ord-cf8fda7184a64f429e5c32501108223d
Source dataset
uspto-grants-2013_11
Patent number
USRE044613E1

Reaction notes

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