Fumaric Acid → HCID 25066885, compound

HRID 2190221Notes

Reaction equation

HRID 2190221 reaction equation
Cl.[NH2:2][C@@H:3]([CH2:14][C:15]1[CH:20]=[CH:19][C:18]([O:21][C:22]([O:24][CH2:25][CH3:26])=[O:23])=[C:17]([O:27][C:28]([O:30][CH2:31][CH3:32])=[O:29])[CH:16]=1)[C:4]([O:6][C@H:7]([CH3:13])[CH2:8][O:9][C:10](=[O:12])[CH3:11])=[O:5].[C:33]([OH:40])(=[O:39])/[CH:34]=[CH:35]/[C:36]([OH:38])=[O:37]>C(OCC)(=O)C>[C:33]([OH:40])(=[O:39])/[CH:34]=[CH:35]/[C:36]([OH:38])=[O:37].[NH2:2][C@@H:3]([CH2:14][C:15]1[CH:20]=[CH:19][C:18]([O:21][C:22]([O:24][CH2:25][CH3:26])=[O:23])=[C:17]([O:27][C:28]([O:30][CH2:31][CH3:32])=[O:29])[CH:16]=1)[C:4]([O:6][C@H:7]([CH3:13])[CH2:8][O:9][C:10](=[O:12])[CH3:11])=[O:5]

Participants

4

Reactant 2

HCID 444972Fumaric AcidHCID 66951003HCID 66951003, compound

Product 1

HCID 25066885HCID 25066885, compoundYield 83%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent2×

Procedure

(1R)-2-Acetyloxy-1-methylethyl (2S)-2-amino-3-[3,4-bis(ethoxycarbonyloxy)phenyl]propanoate hydrochloride (14) (10.5 g, 21.7 mmol) was mixed with ethyl acetate (250 mL), and then quickly washed with 5% sodium bicarbonate (100 mL) at 0° C. The organic layer was separated, dried over MgSO4, and then transferred to a flask charged with a mixture of fumaric acid (2.5 g, 21.8 mmol) and ethyl acetate. The mixture was stirred at room temperature for 30 min. The title compound (21) (9.1 g, 83% yield) was crystallized and collected by filtration. M.p.: 78.1-80.7° C. (uncorrected). The melting point as determined using differential scanning calorimeter (DSC) was 82.05° C. (melting enthalpy was 102 μg). 1H NMR (400 MHz, CD3OD): δ 1.20 (d, J=6.4 Hz, 3H), 1.35 (t, J=6.8 Hz, 3H), 1.36 (t, J=6.8 Hz, 3H), 2.03 (s, 3H), 3.17 (dd, J=14.0, 6.8 Hz, 1H), 3.22 (dd, J=14.0, 6.8 Hz, 1H), 4.03 (dd, J=12.0, 6.4 Hz, 1H), 4.22 (dd, J=12.0, 3.2 Hz, 1H), 4.23 (t, J=6.8 Hz, 1H), 4.29 (q, J=7.2 Hz, 2H), 4.30 (q, J=7.2 Hz, 2H), 5.17 (m, 1H), 6.69 (s, 2H), 7.23 (dd, J=8.0, 2.0 Hz, 1H), 7.27 (d, J=2.0 Hz, 1H), 7.30 (d, J=8.0 Hz, 1H). MS (ESI) m/z 442.2 (M+H)+. Calc. For C20H27NO10.2H2O: C, 48.57; H, 5.94; N, 2.36. Found: C, 48.64; H, 5.51; N, 2.38.

Workup

  1. washquickly washed with 5% sodium bicarbonate (100 mL) at 0° C
  2. customThe organic layer was separated
  3. dry with materialdried over MgSO4
  4. customtransferred to a flask

Sources & evidence

ORD record
ord-067f8eafa6cb435ca6d10d64e4c97e89
Source dataset
uspto-grants-2012_12
Patent number
US08324273B2

Reaction notes

Loading…