Sodium hydride → 4-(4-methoxy-2-nitrobenzylidene)tetrahydro-2H-pyran

HRID 1914680Notes

Reaction equation

HRID 1914680 reaction equation
C(OP([CH2:9][C:10]1[CH:15]=[CH:14][C:13]([O:16][CH3:17])=[CH:12][C:11]=1[N+:18]([O-:20])=[O:19])(=O)OCC)C.C1OCCOCCOCCOCCOC1.[H-].[Na+].[O:38]1[CH2:43][CH2:42][C:41](=O)[CH2:40][CH2:39]1>C1COCC1.O>[CH3:17][O:16][C:13]1[CH:14]=[CH:15][C:10]([CH:9]=[C:41]2[CH2:42][CH2:43][O:38][CH2:39][CH2:40]2)=[C:11]([N+:18]([O-:20])=[O:19])[CH:12]=1

Participants

7

Reactant 4

HCID 24758Sodium hydrideHCID 3633615-Crown-5HCID 121599Tetrahydro-4H-pyran-4-oneHCID 10614363Diethyl (4-methoxy-2-nitrobenzyl)phosphonate

Product 1

HCID 593531074-(4-methoxy-2-nitrobenzylidene)tetrahydro-2H-pyranYield 73%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of diethyl-(4-methoxy-2-nitrobenzyl)phosphonate (3 g; 9.89 mmol; 1 eq) and 15-crown-5 (196.31 μL; 0.99 mmol; 0.1 eq) in THF (30 mL) at 0° C. is added portionwise sodium hydride (431.65 mg; 9.89 mmol; 1 eq). After 15 min, a solution of tetrahydro-2H-pyran-4-one (990.43 mg; 9.89 mmol; 1 eq) in THF (30 mL) is added dropwise at 0° C. After stirring at room temperature for 3 h, the reaction is complete. The mixture is diluted with water at 0° C. and the product is extracted with EtOAc. The organic layer is washed with saturated aqueous NaHCO3 and brine then dried over MgSO4. The solvent is removed under reduced pressure and the yellow residue is washed with pentane (to remove the oil from NaH) to afford 1.8 g (73%) of the title compound as an orange powder. 1H NMR (DMSO-d6) δ 7.53 (d, J=2.3 Hz, 1H), 7.32-7.24 (m, 2H), 6.39 (s, 1H), 3.84 (s, 3H), 3.67-3.63 (m, 2H), 3.55-3.51 (m, 2H), 2.34-2.31 (m, 2H), 2.19-2.16 (m, 2H). HPLC (max plot) 87%; Rt 3.96 min.

Workup

  1. extractionthe product is extracted with EtOAc
  2. washThe organic layer is washed with saturated aqueous NaHCO3 and brine
  3. dry with materialthen dried over MgSO4
  4. customThe solvent is removed under reduced pressure
  5. washthe yellow residue is washed with pentane (
  6. customto remove the oil from NaH)

Sources & evidence

ORD record
ord-4a8b9d29aa464b89ad4dc729b914477a
Source dataset
uspto-grants-2013_12
Patent number
US08614215B2

Reaction notes

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