Sodium Cyanide → Ethyl oxane-4-carboxylate

HRID 1584380Notes

Reaction equation

HRID 1584380 reaction equation
[CH2:1]([O:3][C:4]([C:6]1(C(OCC)=O)[CH2:11][CH2:10][O:9][CH2:8][CH2:7]1)=[O:5])[CH3:2].[I-].[Li+].[C-]#N.[Na+]>CN(C)C=O>[CH2:1]([O:3][C:4]([CH:6]1[CH2:11][CH2:10][O:9][CH2:8][CH2:7]1)=[O:5])[CH3:2]

Participants

5

Reactant 3

HCID 8929Sodium CyanideHCID 66321Lithium iodideHCID 239606Diethyl tetrahydropyran-4,4-dicarboxylate

Product 1

HCID 13467581Ethyl oxane-4-carboxylateYield 92%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
140 °C

Procedure

To a solution of tetrahydropyran-4,4-dicarboxylic acid diethyl ester (400 mg, 1.74 mmol) in N,N-dimethylformamide (4 mL), was added lithium iodide (1.16 g, 8.66 mmol), followed by sodium cyanide (94 mg, 1.91 mmol). The mixture was heated at 130° C. for 7 hours, 140° C. for 25 hours, after which GC analysis indicated the reaction to be >95% complete. The mixture was partitioned between 33% diethyl ether/hexanes (100 mL) and brine (25 mL). The organic layer was washed with additional brine (25 mL), dried (MgSO4) and concentrated in vacuo to afford the tetrahydropyran-4-carboxylic acid ethyl ester (253 mg, 92%). Note: Substitution of 2 equivalents of sodium acetate for 1.1 equivalents of sodium cyanide in this reaction and heating 12 hours longer provides identical results.

Workup

  1. customthe reaction
  2. customThe mixture was partitioned between 33% diethyl ether/hexanes (100 mL) and brine (25 mL)
  3. washThe organic layer was washed with additional brine (25 mL)
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-92ec246d8ae549a48c648e80ac22db55
Source dataset
uspto-grants-1999_08
Patent number
US05932595

Reaction notes

Loading…