Ethyl 1-[3-[(2,4-dioxoimidazolidin-5-ylidene)methyl]-4-nitrophenyl]-4-piperidinecarboxylate → HCID 13987620, compound

HRID 256185Notes

Reaction equation

HRID 256185 reaction equation
[O:1]=[C:2]1[NH:6][C:5](=O)[C:4](=[CH:8][C:9]2[CH:10]=[C:11]([N:18]3[CH2:23][CH2:22][CH:21]([C:24]([O:26][CH2:27]C)=[O:25])[CH2:20][CH2:19]3)[CH:12]=[CH:13][C:14]=2[N+:15]([O-])=O)[NH:3]1>CN(C)C=O.[Pd]>[O:1]=[C:2]1[NH:6][C:5]2=[N:15][C:14]3[CH:13]=[CH:12][C:11]([N:18]4[CH2:23][CH2:22][CH:21]([C:24]([O:26][CH3:27])=[O:25])[CH2:20][CH2:19]4)=[CH:10][C:9]=3[CH:8]=[C:4]2[NH:3]1

Participants

4

Reactant 1

HCID 53966207Ethyl 1-[3-[(2,4-dioxoimidazolidin-5-ylidene)methyl]-4-nitrophenyl]-4-piperidinecarboxylate

Product 1

HCID 13987620HCID 13987620, compound

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 6228DimethylformamideSolvent

Procedure

Ethyl 1-[3-[(2,4-dioxoimidazolidin-5-ylidene)methyl]-4-nitrophenyl]-4-piperidinecarboxylate (35.8 g, 92 mmol) in dimethylformamide (500 mL) was hydrogenated over 10% palladium on charcoal (3.6 g) at 200 psi pressure. After 42 hours, the mixture was filtered through kieselguhr, the solvent evaporated, and the residue diluted with 50% methanol/ether ether (500 mL). A light spray powder (25.0 g) was collected in two crops. The powder was added to methanol (500 mL) containing p-toluene sulfonic acid (1.5 g), and heated at reflux for 18 hours. Upon cooling, the mixture was filtered to give 19.5 g of an off white solid consisting of a mixture of ethyl 1-(1,3,9,9a-tetrahydro-2-oxo-1H-imidazo[4,5-b]quinolin-7-yl)-4-piperidinecarboxylate and the corresponding oxidized 2,3-dihydro compound (ethyl ester of the title compound). The solid was added to methanol (500 mL), heated to reflux, iodine (13.7 g, 54 mmol) added portionwise, and reflux continued for 2.5 hours. Upon cooling, 10% sodium thiosulfate and 10% sodium carbonate solution were added until pH=7. Water (300 mL) was added, and the precipitate consisting of the title compound collected (19.4 g, 65%).

Workup

  1. filtrationthe mixture was filtered through kieselguhr
  2. customthe solvent evaporated
  3. additionthe residue diluted with 50% methanol/ether ether (500 mL)
  4. customA light spray powder (25.0 g) was collected in two crops
  5. additionThe powder was added to methanol (500 mL)
  6. additioncontaining p-toluene sulfonic acid (1.5 g)
  7. temperatureheated
  8. temperatureat reflux for 18 hours
  9. temperatureUpon cooling
  10. filtrationthe mixture was filtered
  11. customto give 19.5 g of an off white solid

Sources & evidence

ORD record
ord-58c263adda3e48148f252143a817e691
Source dataset
uspto-grants-1987_10
Patent number
US04701459

Reaction notes

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