Sodium hydride → HCID 86586358, compound

HRID 989769Notes

Reaction equation

HRID 989769 reaction equation
[H-].[Na+].[C:3]([CH2:5]P(=O)(OCC)OCC)#[N:4].[CH3:14][C:15]1[CH:20]=[CH:19][C:18]([S:21]([O:24][CH2:25][C@@H:26]2[O:31][C:30]3[C:32]([CH:39]=O)=[C:33]([N+:36]([O-:38])=[O:37])[CH:34]=[CH:35][C:29]=3[O:28][CH2:27]2)(=[O:23])=[O:22])=[CH:17][CH:16]=1>CN(C=O)C>[N:4]#[C:3][CH:5]=[CH:39][C:32]1[C:30]2[O:31][CH:26]([CH2:25][O:24][S:21]([C:18]3[CH:19]=[CH:20][C:15]([CH3:14])=[CH:16][CH:17]=3)(=[O:22])=[O:23])[CH2:27][O:28][C:29]=2[CH:35]=[CH:34][C:33]=1[N+:36]([O-:38])=[O:37]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 75676Diethyl (cyanomethyl)phosphonateHCID 12082209HCID 12082209, compound

Product 1

HCID 86586358HCID 86586358, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a suspension of 0.44 g (11 mmole) of 60% sodium hydride/mineral oil dispersion in 100 mL of DMF was add 1.8 g (10 mmole) of diethyl cyanomethylphosphonate. The mixture was stirred for 30 minutes at room temperature under nitrogen and then 3.0 g (7.6 mmole) of [(2R)-8-formyl-7-nitro-2,3-dihydro-1,4-benzodioxin-2-yl]methyl 4-methylbenzenesulfonate added and stirring at room temperature continued overnight. The solvent was then removed in vacuum and replaced with 400 mL of dichloromethane. The solution was washed with 300 mL portions of water and saturated brine, dried over sodium sulfate, filtered and concentrated in vacuum to a yellow oil. This was column chromatographed on silica gel with methylene chloride as eluant to give 2.5 g of the (R)-enantiomer of the title compound as a yellow solid (m.p. 117-118° C.).

Workup

  1. stirringstirring at room temperature
  2. waitcontinued overnight
  3. customThe solvent was then removed in vacuum
  4. washThe solution was washed with 300 mL portions of water and saturated brine
  5. dry with materialdried over sodium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated in vacuum to a yellow oil
  8. customThis was column chromatographed on silica gel with methylene chloride as eluant

Sources & evidence

ORD record
ord-bbdb43a616134cadb149618286aa0204
Source dataset
uspto-grants-2002_10
Patent number
US06458802B1

Reaction notes

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