Methyl N-(3-nitrobenzoyl)-3-amino-3-(3,4-dimethoxyphenyl)propionate → Methyl N-(3-aminobenzoyl)-3-amino-3-(3,4-dimethoxyphenyl)propionate

HRID 1594650Notes

Reaction equation

HRID 1594650 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([CH:26]=[CH:27][CH:28]=1)[C:7]([NH:9][CH:10]([C:16]1[CH:21]=[CH:20][C:19]([O:22][CH3:23])=[C:18]([O:24][CH3:25])[CH:17]=1)[CH2:11][C:12]([O:14][CH3:15])=[O:13])=[O:8])([O-])=O.C(OCC)(=O)C.C(Cl)Cl>C(OCC)(=O)C.CO.[Pd]>[NH2:1][C:4]1[CH:5]=[C:6]([CH:26]=[CH:27][CH:28]=1)[C:7]([NH:9][CH:10]([C:16]1[CH:21]=[CH:20][C:19]([O:22][CH3:23])=[C:18]([O:24][CH3:25])[CH:17]=1)[CH2:11][C:12]([O:14][CH3:15])=[O:13])=[O:8]

Participants

6

Reactant 2

HCID 15547129Methyl N-(3-nitrobenzoyl)-3-amino-3-(3,4-dimethoxyphenyl)propionateHCID 21226138Dichloromethane ethylacetate

Product 1

HCID 15547130Methyl N-(3-aminobenzoyl)-3-amino-3-(3,4-dimethoxyphenyl)propionateYield 93%

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 887MethanolSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of methyl N-(3-nitrobenzoyl)-3-amino-3-(3,4-dimethoxyphenyl)propionate (1.25 grams, 3.22 mmol) in a mixture of 150 milliliters of ethyl acetate and 75 milliliters of methanol (mixture gently warmed to dissolve all solid and then allowed to cool to room temperature) was added 0.25 grams of 10% Pd/C. The mixture was then treated with 60 psi of H2 for 2.5 hours on a Parr Type Shaker. Reaction progress was monitored by TLC (1/9 ethyl acetate/methylene chloride, UV) and was complete after 2.5 hours. The reaction mixture was filtered through celite to remove catalyst. The filtrate was concentrated in vacuo to afford a white solid which was dried in vacuo (60 ° C., <1 mm) to afford 1.07 grams (93%) of the desired product: 1H NMR (dmso-d6, 250 MHz) δ 8.60 (d, J=8.5 Hz, 1 H, NH), 7.15-6.8 (m, 6 H, Ar), 6.67 (m, 1 H, Ar), 5.40 (m, 1 H, CHCO), 5.24 (m 2 H, ArNH2), 3.75 (s, 3 H, OCH3), 3.72 (s, 3 H, OCH3), 3.56 (s, 3 H, CO2CH3), 2.95 (dd, J=8.9, 15.4 Hz, 1 H), 2.81 (dd, J=6.3, 15.4 Hz, 1 H); 13C NMR (dmso-d6) δ 170.9, 166.4, 148.6, 148.6, 147.8, 135.6, 135.1, 128.6, 118.5, 116.4, 114.4, 112.8, 111.6, 110.6, 55.5, 55.5, 51.4, 49.6, 40.7.

Workup

  1. temperaturegently warmed
  2. dissolutionto dissolve all solid
  3. additionThe mixture was then treated with 60 psi of H2 for 2.5 hours on a Parr Type Shaker
  4. customReaction progress
  5. filtrationThe reaction mixture was filtered through celite
  6. customto remove catalyst
  7. concentrationThe filtrate was concentrated in vacuo
  8. customto afford a white solid which
  9. customwas dried in vacuo (60 ° C., <1 mm)

Sources & evidence

ORD record
ord-c31d891c724846fcba72947b0febdf6a
Source dataset
uspto-grants-2001_09
Patent number
US06284780B1

Reaction notes

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