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

HRID 511539Notes

Reaction equation

HRID 511539 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, 3 H) 1.53-1.73 (m, 4 H) 1.79 (d, J=4.29 Hz, 2 H) 2.02 (d, J=0.76 Hz, 3 H) 2.26 (d, J=13.14 Hz, 2 H) 2.70-2.82 (m, 2 H) 4.17 (q, J=7.07 Hz, 2 H) 6.38 (d, J=8.34 Hz, 1 H) 7.12 (d, J=8.34 Hz, 1 H) 7.63 (s, 1 H). 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, 3 H) 1.54 (br. s., 1 H) 1.70 (d, J=12.63 Hz, 1 H) 1.87 (br. s., 1 H) 2.02 (d, J=0.51 Hz, 1 H) 2.07 (br. s., 1 H) 2.35-2.45 (m, 1 H) 2.69-2.81 (m, 1 H) 4.12 (q, J=7.07 Hz, 1 H) 6.39 (d, J=8.34 Hz, 1 H) 7.20 (d, J=8.34 Hz, 1 H) 7.64 (d, J=0.76 Hz, 1 H). 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, 3 H) 1.54 (br. s., 1 H) 1.70 (d, J=12.63 Hz, 1 H) 1.87 (br. s., 1 H) 2.02 (d, J=0.51 Hz, 1 H) 2.07 (br. s., 1 H) 2.35-2.45 (m, 1 H) 2.69-2.81 (m, 1 H) 4.12 (q, J=7.07 Hz, 1 H) 6.39 (d, J=8.34 Hz, 1 H) 7.20 (d, J=8.34 Hz, 1 H) 7.64 (d, J=0.76 Hz, 1 H)
  10. customHPLC: tR=1.30 min (Micromass TOF: polar—3 min)

Sources & evidence

ORD record
ord-84404ce12c84430a96b23938a8b644f5
Source dataset
uspto-grants-2015_08
Patent number
US09096624B2

Reaction notes

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