Methyl iodide → (S)-Methyl 2-((tert-butoxycarbonyl)amino)-3-(4-nitrophenyl)propanoate

HRID 393485Notes

Reaction equation

HRID 393485 reaction equation
[N+:1]([C:4]1[CH:22]=[CH:21][C:7]([CH2:8][C@@H:9]([C:18]([OH:20])=[O:19])[NH:10][C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12])=[CH:6][CH:5]=1)([O-:3])=[O:2].[C:23](=O)([O-])[O-].[Na+].[Na+].CI>CN(C=O)C>[CH3:23][O:19][C:18](=[O:20])[C@H:9]([CH2:8][C:7]1[CH:21]=[CH:22][C:4]([N+:1]([O-:3])=[O:2])=[CH:5][CH:6]=1)[NH:10][C:11]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[O:12]

Participants

5

Reactant 3

HCID 6328Methyl iodideHCID 10340Sodium CarbonateHCID 7021882N-(tert-Butoxycarbonyl)-4-nitro-L-phenylalanine

Product 1

HCID 11558856(S)-Methyl 2-((tert-butoxycarbonyl)amino)-3-(4-nitrophenyl)propanoateYield 98.1%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To suspesion of of 4-nitro-N-[(1,1-dimethylethoxy)carbonyl]-L-phenylalanine (226.2 mmol, 70.2 g) and sodium carbonate (1.13 mol, 95 g) in DMF (500 mL) was added methyl iodide (1.13 mol, 70.4 InL) at room temperature. The suspesion was stirred for 15 h at room temperature at this time TLC analysis of the mixture indicated the absence of starting acid and the excess methyl iodide and some DMF were removed under high vacuum. The residue was poured into water (2 L) and stirred at room temperature as a precipitate formed slowly over 72 h. The precipitated solids were collected by filtration and washed with water (2 L). After air and vacuum drying, 72 g (98%) of a light yellow solid, mp 95-96° C. were obtained. 1H-NMR, (DMSO-d6) (400 MHz) δ 8.16 (d, 2H, J=20 Hz), 7.53 (d, 2H, J=20 Hz), 7.39 (d, 1H, J=22 Hz), 4.26-4.28 (m, 1H), 3.6 (s, 3H), 2.96-3.19 (m, 2H), 1.25 (s, 9H). 13C NMR, CDCl3 (100 Mhz) δ 172.04, 155.29, 146.27, 145.96, 130.48, 123.18, 78.36, 54.44, 51.9, 36.1, 27.99. HR MS: Obs. mass, 325.1404. Calcd. mass, 325.1400 (M+H).

Workup

  1. customthe excess methyl iodide and some DMF were removed under high vacuum
  2. additionThe residue was poured into water (2 L)
  3. stirringstirred at room temperature as a precipitate
  4. customformed slowly over 72 h
  5. filtrationThe precipitated solids were collected by filtration
  6. washwashed with water (2 L)
  7. customAfter air and vacuum drying

Sources & evidence

ORD record
ord-8a538a48ab7947fbb7a45aac89daa3a7
Source dataset
uspto-grants-2004_10
Patent number
US06806365B2

Reaction notes

Loading…