Iodine → Ethyl 2-amino-2-cyanoacetate

HRID 1350445Notes

Reaction equation

HRID 1350445 reaction equation
C(=O)(O)[O-].[Na+].[C:6]([C:8](=[N:14]O)[C:9]([O:11][CH2:12][CH3:13])=[O:10])#[N:7].S(S([O-])=O)([O-])=O.[Na+].[Na+].II>CCOC(C)=O.O>[CH2:12]([O:11][C:9](=[O:10])[CH:8]([NH2:14])[C:6]#[N:7])[CH3:13]

Participants

7

Reactant 4

HCID 807IodineHCID 24489Sodium DithioniteHCID 516892Sodium BicarbonateHCID 6399078Ethyl 2-cyano-2-(hydroxyimino)acetate

Product 1

HCID 288716Ethyl 2-amino-2-cyanoacetateYield 31%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

Dilute aqueous saturated sodium bicarbonate (560 mL) with deionized water (700 mL). and stir the solution while adding ethyl cyanoglyoxylate-2-oxime (70.0 g, 493 mmol) in portions (note: some off-gassing and a gentle endotherm were observed). Add sodium dithionite (238 g, 1.37 mol, 2.8 eq.) in portions and stir at rt. After 2.5–3 hours, during this time the reaction was monitored by TLC (EtOAc, I2 stain), saturate the solution with sodium chloride (400 g), and extract the product CH2Cl2 (1×500 mL, 3×250 mL), making sure solid NaCl was visible (more added if necessary) during the extractions. Combine the organic layers, dry over (MgSO4), filter, and concentrate the filtrate to dryness in vacuo on a rotovapor at low bath temperature (30–35° C.) to afford 19.6 g (31%) crude amino-cyano-acetic acid ethyl ester which was used immediately in the next reaction.

Workup

  1. waitAfter 2.5–3 hours
  2. concentrationsaturate the solution with sodium chloride (400 g)
  3. extractionextract the product CH2Cl2 (1×500 mL, 3×250 mL)
  4. additionmore added if necessary)
  5. extractionduring the extractions
  6. dry with materialCombine the organic layers, dry over (MgSO4)
  7. filtrationfilter
  8. concentrationconcentrate the filtrate to dryness in vacuo on a rotovapor at low bath temperature (30–35° C.)

Sources & evidence

ORD record
ord-c6619c64668b40569f6872c0b2e608c4
Source dataset
uspto-grants-2007_05
Patent number
US07214673B2

Reaction notes

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