3-Nitrobenzaldehyde → Methyl 2,6-dimethyl-4-(3-nitrophenyl)-5-diisopropoxyphosphinyl-1,4-dihydropyridine-3-carboxylate

HRID 485076Notes

Reaction equation

HRID 485076 reaction equation
[CH2:1]([P:5](=[O:14])([O:10][CH:11]([CH3:13])[CH3:12])[O:6][CH:7]([CH3:9])[CH3:8])[C:2]([CH3:4])=O.[NH2:15]/[C:16](/[CH3:22])=[CH:17]\[C:18]([O:20][CH3:21])=[O:19].[N+:23]([C:26]1[CH:27]=[C:28]([CH:31]=[CH:32][CH:33]=1)[CH:29]=O)([O-:25])=[O:24].C(O)(=O)C.N1CCCCC1>C(O)(C)C>[CH3:22][C:16]1[NH:15][C:2]([CH3:4])=[C:1]([P:5]([O:10][CH:11]([CH3:13])[CH3:12])([O:6][CH:7]([CH3:9])[CH3:8])=[O:14])[CH:29]([C:28]2[CH:31]=[CH:32][CH:33]=[C:26]([N+:23]([O-:25])=[O:24])[CH:27]=2)[C:17]=1[C:18]([O:20][CH3:21])=[O:19]

Participants

6

Reactant 4

HCID 74493-NitrobenzaldehydeHCID 643918Methyl 3-aminocrotonateHCID 9793820Piperidine, acetateHCID 12616936Diisopropyl acetonylphosphonate

Product 1

HCID 13363673Methyl 2,6-dimethyl-4-(3-nitrophenyl)-5-diisopropoxyphosphinyl-1,4-dihydropyridine-3-carboxylateYield 34.7%

Reagents, catalysts & solvents 1

HCID 3776IsopropanolSolvent

Procedure

A mixture of 2.44 grams of diisopropyl acetonylphosphonate, 1.15 grams of methyl 3-aminocrotonate, and 1.51 grams of m-nitrobenzaldehyde was dissolved in 10 ml of isopropanol, then 290 mg of piperidine acetate was added thereto, and the mixture was heated to reflux for sixteen hours with stirring. The reaction solution was concentrated in vacuo, to the residue was added ether, the resulting crystals were collected by filtration, washed with ether and then with water, dried, and recrystallized from ethyl acetate to afford 1.57 grams (yield 34%) of methyl 2,6-dimethyl-4-(3-nitrophenyl)-5-diisopropoxyphosphinyl-1,4-dihydropyridine-3-carboxylate, melting point 205°-7° C.

Workup

  1. temperaturethe mixture was heated
  2. temperatureto reflux for sixteen hours
  3. concentrationThe reaction solution was concentrated in vacuo, to the residue
  4. additionwas added ether
  5. filtrationthe resulting crystals were collected by filtration
  6. washwashed with ether
  7. dry with materialwith water, dried
  8. customrecrystallized from ethyl acetate

Sources & evidence

ORD record
ord-5e7b399ae93040c0a64d3db56cffb65e
Source dataset
uspto-grants-1985_08
Patent number
US04535073

Reaction notes

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