Sodium Hydroxide → 2-(((Benzyloxy)carbonyl)amino)malonic acid

HRID 986610Notes

Reaction equation

HRID 986610 reaction equation
C([O:3][C:4](=[O:22])[CH:5]([NH:11][C:12]([O:14][CH2:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)=[O:13])[C:6]([O:8]CC)=[O:7])C.[OH-].[Na+]>C(O)C>[CH2:15]([O:14][C:12]([NH:11][CH:5]([C:6]([OH:8])=[O:7])[C:4]([OH:22])=[O:3])=[O:13])[C:16]1[CH:17]=[CH:18][CH:19]=[CH:20][CH:21]=1

Participants

4

Reactant 2

HCID 14798Sodium HydroxideHCID 259787Diethyl 2-(benzyloxycarbonylamino)malonate

Product 1

HCID 2729702-(((Benzyloxy)carbonyl)amino)malonic acidYield 96.4%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

Compound 2 (3.49 mmol, 1.08 g) was dissolved in 3 mL 95% ethanol and treated with 3.49 mL 2N NaOH. The clear, colorless solution was left at room temperature for 19 hours until no starting material could be detected by tlc on silica gel (benzene:ethyl acetate, 4:1). Ethanol was evaporated under reduced pressure at room temperature. The aqueous solution was washed once with ether and then acidified with concentrated HCl to pH 2.5. The milky solution was extracted with ethyl acetate (3x). The pooled extract was washed with brine, dried over anhydrous Na2SO4 and evaporated to dryness. The product was crystallized from ether to yield 0.852 g of compound 3; mp 144°-145° C.; homogeneous by the tlc on silic gel (CHCl3 :methanol:acetate acid, 5:13:1); 250 MHz nmr (acetone-d6, ppm) 5.00 (1H, d, J=8 Hz, α--H), 5.10 (2H, s, ArCH2 --), 6.84 (1H, d, J=8 Hz, amide H), 7.36 (5H, m, ArH5). In a 60 MHz spectrum run in low water content acetone, a 9.7 ppm (2H, broad s, exchangeable with D2O) was also observed.

Workup

  1. customEthanol was evaporated under reduced pressure at room temperature
  2. washThe aqueous solution was washed once with ether
  3. extractionThe milky solution was extracted with ethyl acetate (3x)
  4. extractionThe pooled extract
  5. washwas washed with brine
  6. dry with materialdried over anhydrous Na2SO4
  7. customevaporated to dryness
  8. customThe product was crystallized from ether

Sources & evidence

ORD record
ord-3f0fa60dfef54291b52ee10d29954322
Source dataset
uspto-grants-1987_12
Patent number
US04714619

Reaction notes

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