Acetic Acid → [1-Cyano-2-(tetrahydro-pyran-4-yl)-vinyl]-phosphonic acid diethyl ester

HRID 502867Notes

Reaction equation

HRID 502867 reaction equation
[C:1]([CH2:3][P:4](=[O:11])([O:8][CH2:9][CH3:10])[O:5][CH2:6][CH3:7])#[N:2].C([O-])(=O)C.[NH4+].C(O)(=O)C.[O:21]1[CH2:26][CH2:25][CH:24]([CH:27]=O)[CH2:23][CH2:22]1>C1(C)C=CC=CC=1>[CH2:6]([O:5][P:4]([C:3]([C:1]#[N:2])=[CH:27][CH:24]1[CH2:25][CH2:26][O:21][CH2:22][CH2:23]1)(=[O:11])[O:8][CH2:9][CH3:10])[CH3:7]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 75676Diethyl (cyanomethyl)phosphonateHCID 517165Ammonium AcetateHCID 9964078Tetrahydro-2H-pyran-4-carboxaldehyde

Product 1

HCID 72481733[1-Cyano-2-(tetrahydro-pyran-4-yl)-vinyl]-phosphonic acid diethyl ester

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a stirred solution of diethyl cyanomethylphosphonate (50.0 g, 282 mmol), ammonium acetate (9.0 g, 117 mmol), acetic acid (9 ml) in toluene (200 mL), tetrahydropyran-4-carbaldehyde (32.2 g, 282 mmol) were added. The reaction mixture was stirred at room temperature for two hours and then heated at reflux for 1.5 hours. After cooling down, the reaction mixture washed with saturated sodium bicarbonate solution three times, brine one time and then dried over magnesium sulfate. The reaction mixture was filtered and concentrated to yield a residue. The residue was purified by Kugelrohr distillation to yield [1-cyano-2-(tetrahydropyran-4-yl)-vinyl]-phosphonic acid diethyl ester as a colorless oil.

Workup

  1. temperatureheated
  2. temperatureat reflux for 1.5 hours
  3. temperatureAfter cooling down
  4. washthe reaction mixture washed with saturated sodium bicarbonate solution three times, brine one time
  5. dry with materialdried over magnesium sulfate
  6. filtrationThe reaction mixture was filtered
  7. concentrationconcentrated
  8. customto yield a residue
  9. distillationThe residue was purified by Kugelrohr distillation

Sources & evidence

ORD record
ord-843a4dc3c7434bc48072f19891de31da
Source dataset
uspto-grants-2010_08
Patent number
US07776882B2

Reaction notes

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