Ammonium Chloride → HCID 25135997, compound

HRID 1353541Notes

Reaction equation

HRID 1353541 reaction equation
[Cl-:1].[NH4+].[CH3:3][O:4][C:5](=[O:29])[C@H:6]([NH:18][C:19]([O:21][CH2:22][C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)=[O:20])[CH2:7][C:8]1[CH:13]=[CH:12][C:11]([N+:14]([O-])=O)=[C:10]([OH:17])[CH:9]=1>[Fe]>[ClH:1].[CH3:3][O:4][C:5](=[O:29])[C@H:6]([NH:18][C:19]([O:21][CH2:22][C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)=[O:20])[CH2:7][C:8]1[CH:13]=[CH:12][C:11]([NH2:14])=[C:10]([OH:17])[CH:9]=1

Participants

4

Reactant 2

HCID 25517Ammonium ChlorideHCID 25135996HCID 25135996, compound

Product 1

HCID 25135997HCID 25135997, compound

Reagents, catalysts & solvents 1

HCID 23925IronCatalyst

Procedure

Powdered iron (3.7 g, 66.4 mmol) and ammonium chloride (5.9 g, 111 mmol) were added at 0° C. to a solution of (R)-2-benzyloxycarbonylamino-3-(3-hydroxy-4-nitro-phenyl)-propionic acid methyl ester (2.07 g, 5.53 mmol) in degassed 1:1 methanol/water (400 mL). The resulting mixture was stirred at room temperature for 48 h. Trifluoroacetic acid (7 mL) was added, and the mixture was swirled until it was a clear dark red solution containing a suspension of unreacted iron powder. The mixture was filtered and the filtrate was concentrated in vacuo. The residue was extracted with ethyl acetate (2×150 mL), the combined organic layers were washed with brine and dried over sodium sulfate. After filtration, hydrochloric acid (4.2 mL, 4M in dioxane) was added. Solvents were removed in vacuo, and the title compound was obtained as a tan foamy solid (80%). 1H-NMR (CD3OD, 500 MHz) δ 7.34–7.28 (m, 5H), 7.20 (d, J=8.0 hz, 1H), 6.88 (s, 1H), 6.78 (d, J=7.5 Hz, 1H), 5.05–5.00 (m, 2H), 4.42 (dd, J=8.5, 5.0 Hz, 1H), 3.70 (s, 3H), 3.65 (s, 1H), 3.33 (br s, 2H), 3.11 (dd, J=14.0, 5.0 hz, 1H), 2.90 (dd, J=13.5, 9.0 Hz, 1H). 13CNMR (CD3OD, 125 MHz) 172.5, 157.4, 151.2, 140.2, 137.0, 128.5, 128.0, 127.7, 123.8, 120.9, 117.0, 116.9, 67.2, 55.7, 52.0, 37.2. Mass spec.: 345.20 (MH)+.

Workup

  1. customin degassed 1:1 methanol/water (400 mL)
  2. additionTrifluoroacetic acid (7 mL) was added
  3. additioncontaining
  4. additiona suspension of unreacted iron powder
  5. filtrationThe mixture was filtered
  6. concentrationthe filtrate was concentrated in vacuo
  7. extractionThe residue was extracted with ethyl acetate (2×150 mL)
  8. washthe combined organic layers were washed with brine
  9. dry with materialdried over sodium sulfate
  10. filtrationAfter filtration, hydrochloric acid (4.2 mL, 4M in dioxane)
  11. additionwas added
  12. customSolvents were removed in vacuo

Sources & evidence

ORD record
ord-55262f7ecfbe4545b4e9f4e4cbdb0d8e
Source dataset
uspto-grants-2007_05
Patent number
US07220862B2

Reaction notes

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