Hydrazine → 2-Aminoethyl methyl 1,4-dihydro-2,6-dimethyl-4-(3-nitrophenyl)pyridine-3,5-dicarboxylate

HRID 256722Notes

Reaction equation

HRID 256722 reaction equation
[CH3:1][C:2]1[NH:3][C:4]([CH3:37])=[C:5]([C:21]([O:23][CH2:24][CH2:25][N:26]2C(=O)C3=CC=CC=C3C2=O)=[O:22])[CH:6]([C:12]2[CH:17]=[CH:16][CH:15]=[C:14]([N+:18]([O-:20])=[O:19])[CH:13]=2)[C:7]=1[C:8]([O:10][CH3:11])=[O:9].O.NN.NN>C(O)C.C(Cl)Cl>[CH3:1][C:2]1[NH:3][C:4]([CH3:37])=[C:5]([C:21]([O:23][CH2:24][CH2:25][NH2:26])=[O:22])[CH:6]([C:12]2[CH:17]=[CH:16][CH:15]=[C:14]([N+:18]([O-:20])=[O:19])[CH:13]=2)[C:7]=1[C:8]([O:10][CH3:11])=[O:9]

Participants

6

Reactant 3

HCID 9321HydrazineHCID 24654Hydrazine hydrate (1:1)HCID 137998311,4-Dihydro-2,6-dimethyl-3-methoxycarbonyl-4-(3-nitrophenyl)-5-(2-phthalimidoethoxy)carbonyl-pyridine

Product 1

HCID 135634192-Aminoethyl methyl 1,4-dihydro-2,6-dimethyl-4-(3-nitrophenyl)pyridine-3,5-dicarboxylateYield 98.7%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 6344DichloromethaneSolvent

Procedure

A solution of 2.32 g (4.59 mmol) of (±)-2,6-dimethyl-3-carbomethoxy-4-(3-nitrophenyl)-5-(2-phthalimidoethyloxycarbonyl)-1,4-dihydropyridine and 344 mg of hydrazine monohydrate in 100 ml of ethanol is heated at reflux for 2 hr. TLC indicates the reaction is incomplete so another 1.5 equivalents of hydrazine monhydrate is added and the mixture refluxed for an additional hr. After cooling, the precipitate is collected by filtration, washed with ethanol, and the filtrate evaporated under vacuum to leave a yellow solid. This solid is taken up in 125 ml of CH2Cl2, washed twice with 0.5N KOH, once with water, dried (MgSO4), filtered, and the solvent removed under vacuum to give 1.70 g of (±)-2,6-dimethyl-3-carbomethoxy-4-(3-nitrophenyl)-5 (2-aminoethoxycarbonyl)-1,4-dihydropyridine as a yellow solid. 1H-NMR (CDCl3); δ 1.85 (s, 2H); 2.40 (d, 6H); 3.40 (t, 2H); 3.68 (s, 3 H); 4.35 (s, 2H); 5.15 (s, 1H); 5.90 (s, 1H); 7.40 (t, 1H) 7.68 (d, 1H); 8.03 (d, 1H); 8.13 (s, 1H).

Workup

  1. temperatureat reflux for 2 hr
  2. additionis added
  3. temperaturethe mixture refluxed for an additional hr
  4. temperatureAfter cooling
  5. filtrationthe precipitate is collected by filtration
  6. washwashed with ethanol
  7. customthe filtrate evaporated under vacuum
  8. customto leave a yellow solid
  9. washwashed twice with 0.5N KOH, once with water
  10. dry with materialdried (MgSO4)
  11. filtrationfiltered
  12. customthe solvent removed under vacuum

Sources & evidence

ORD record
ord-d005d79cc282482bb83da4ff22c94ce1
Source dataset
uspto-grants-1993_11
Patent number
US05258519

Reaction notes

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