Ethyl 4-(5-amino-3-methyl-4-oxo-1,4-dihydroquinolin-8-yl)cyclohex-3-ene-1-carboxylate → HCID 178472343, compound

HRID 1948111Notes

Reaction equation

HRID 1948111 reaction equation
[NH2:1][C:2]1[CH:11]=[CH:10][C:9]([C:12]2[CH2:17][CH2:16][CH:15]([C:18]([O:20][CH2:21][CH3:22])=[O:19])[CH2:14][CH:13]=2)=[C:8]2[C:3]=1[C:4](=[O:24])[C:5]([CH3:23])=[CH:6][NH:7]2>CCO.[Pd]>[NH2:1][C:2]1[CH:11]=[CH:10][C:9]([C@@H:12]2[CH2:13][CH2:14][C@H:15]([C:18]([O:20][CH2:21][CH3:22])=[O:19])[CH2:16][CH2:17]2)=[C:8]2[C:3]=1[C:4](=[O:24])[C:5]([CH3:23])=[CH:6][NH:7]2

Participants

4

Reactant 1

HCID 67254617Ethyl 4-(5-amino-3-methyl-4-oxo-1,4-dihydroquinolin-8-yl)cyclohex-3-ene-1-carboxylate2×

Product 1

HCID 178472343HCID 178472343, compound

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 702EthanolSolvent

Procedure

A mixture of ethyl 4-(5-amino-3-methyl-4-oxo-1,4-dihydroquinolin-8-yl)cyclohex-3-ene-1-carboxylate (Compound 304C, 0.270 g, 0.83 mmol) and palladium 10% wt on activated carbon (88.0 mg, 0.083 mmol) in EtOH (2.17 mL) was evacuated and purged with hydrogen (3×) and subsequently stirred under one atmosphere of hydrogen at rt for 16 hrs. The reaction mixture was filtered and the filtrate was concentrated in vacuo to an orange oil. The product was purified by mass directed purification which resolved the cis and trans isomers. Compound 304A, the trans isomer eluted first: 1H NMR (400 MHz, MeOD) δ ppm 1.27 (t, J=7.07 Hz, 3H) 1.53-1.73 (m, 4H) 1.79 (d, J=4.29 Hz, 2H) 2.02 (d, J=0.76 Hz, 3H) 2.26 (d, J=13.14 Hz, 2H) 2.70-2.82 (m, 2H) 4.17 (q, J=7.07 Hz, 2H) 6.38 (d, J=8.34 Hz, 1H) 7.12 (d, J=8.34 Hz, 1H) 7.63 (s, 1H). MS (ES+): m/z 329.16/329.36 (100/70) [MH+]. HPLC: tR=1.28 min (Micromass TOF: polar—3 min). Compound 304B, the cis isomer eluted after: 1H NMR (400 MHz, CDCl3) δ ppm 1.25 (t, J=7.07 Hz, 3H) 1.54 (br. s., 1H) 1.70 (d, J=12.63 Hz, 1H) 1.87 (br. s., 1H) 2.02 (d, J=0.51 Hz, 1H) 2.07 (br. s., 1H) 2.35-2.45 (m, 1H) 2.69-2.81 (m, 1H) 4.12 (q, J=7.07 Hz, 1H) 6.39 (d, J=8.34 Hz, 1H) 7.20 (d, J=8.34 Hz, 1H) 7.64 (d, J=0.76 Hz, 1H). MS (ES+): m/z 329.14/329.35 (100/70) [MH+]. HPLC: tR=1.30 min (Micromass TOF: polar—3 min).

Workup

  1. customwas evacuated
  2. custompurged with hydrogen (3×)
  3. filtrationThe reaction mixture was filtered
  4. concentrationthe filtrate was concentrated in vacuo to an orange oil
  5. customThe product was purified by mass
  6. custompurification which
  7. washCompound 304A, the trans isomer eluted first
  8. customHPLC: tR=1.28 min (Micromass TOF: polar—3 min)
  9. washCompound 304B, the cis isomer eluted after: 1H NMR (400 MHz, CDCl3) δ ppm 1.25 (t, J=7.07 Hz, 3H) 1.54 (br. s., 1H) 1.70 (d, J=12.63 Hz, 1H) 1.87 (br. s., 1H) 2.02 (d, J=0.51 Hz, 1H) 2.07 (br. s., 1H) 2.35-2.45 (m, 1H) 2.69-2.81 (m, 1H) 4.12 (q, J=7.07 Hz, 1H) 6.39 (d, J=8.34 Hz, 1H) 7.20 (d, J=8.34 Hz, 1H) 7.64 (d, J=0.76 Hz, 1H)
  10. customHPLC: tR=1.30 min (Micromass TOF: polar—3 min)

Sources & evidence

ORD record
ord-8d5214c8426f4fdab2fa191069f0f593
Source dataset
uspto-grants-2013_03
Patent number
US08399433B2

Reaction notes

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