Hydrochloric Acid → 2-(2-Aminophenyl)-N-methyl-N-[(1S)-1-(3-aminophenyl)-2-(1-pyrrolidinyl)ethyl]acetamide

HRID 353261Notes

Reaction equation

HRID 353261 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[CH2:10][C:11]([N:13]([CH3:30])[C@@H:14]([C:21]1[CH:26]=[CH:25][CH:24]=[C:23]([N+:27]([O-])=O)[CH:22]=1)[CH2:15][N:16]1[CH2:20][CH2:19][CH2:18][CH2:17]1)=[O:12])([O-])=O.O.NN.Cl>[Ni].CCO>[NH2:1][C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[CH2:10][C:11]([N:13]([CH3:30])[C@@H:14]([C:21]1[CH:26]=[CH:25][CH:24]=[C:23]([NH2:27])[CH:22]=1)[CH2:15][N:16]1[CH2:17][CH2:18][CH2:19][CH2:20]1)=[O:12]

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 24654Hydrazine hydrate (1:1)HCID 117742682-(2-Nitrophenyl)-N-methyl-N-[(1S)-1-(3-nitrophenyl)-2-(1-pyrrolidinyl)ethyl]acetamide

Product 1

HCID 99776132-(2-Aminophenyl)-N-methyl-N-[(1S)-1-(3-aminophenyl)-2-(1-pyrrolidinyl)ethyl]acetamide

Reagents, catalysts & solvents 2

HCID 935NickelCatalystHCID 702EthanolSolvent

Conditions

Temperature
55 °C

Procedure

With stirring at 55° C., Raney nickel was added in small quantities to a mixture of 10 (0.9857 g, 2.3899 mmol) and hydrazine hydrate (55%, 2 mL) in EtOH (30 mL) until gas evolution stopped in about 10 min. The mixture was then filtered through celite, and the Raney nickel was washed with hot MeOH (100 mL). The filtrate was evaporated and dried in vacuo before the residue was partitioned between sat'd NaHCO3 and CH2Cl2, which was dried (Na2SO4), filtered through celite, and evaporated. The product was gravity column chromatographed eluting with CHCl3:2% NH3:2% MeOH before it was converted to the HCl salt with Et2O—HCl to yield 9 3HCl.(0.3159 g, 29%, unoptimized): m.p. (HCl salt) 219-222° C.; 1H NMR (HCl salt, DMSO-d6) δ1.98 (br s, 4H, —CH2CH2—), 2.87 (s, 3H, —NCH3), 3.2-4.3 (complex, 8H, 4 —CH2—), 6.1 (m, 1H, —CH—), 7.11-7.45 (complex, 8H, aromatic). MS(FAB) m/z 353. Anal. (C, H, N) C21H28N4O. 3HCl0.25H2O.

Workup

  1. filtrationThe mixture was then filtered through celite
  2. washthe Raney nickel was washed with hot MeOH (100 mL)
  3. customThe filtrate was evaporated
  4. customdried in vacuo before the residue
  5. customwas partitioned between sat'd NaHCO3 and CH2Cl2, which
  6. dry with materialwas dried (Na2SO4)
  7. filtrationfiltered through celite
  8. customevaporated
  9. customchromatographed
  10. washeluting with CHCl3
  11. customto yield 9 3HCl

Sources & evidence

ORD record
ord-a94a3996857745c69b77ca4a8ad472f9
Source dataset
uspto-grants-2004_06
Patent number
US06750216B2

Reaction notes

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