Methyl morpholine oxide → HCID 86761924, compound

HRID 448799Notes

Reaction equation

HRID 448799 reaction equation
[Br:1][C:2]1[C:3]([C:14]([P:17](=[O:24])([O:21][CH2:22][CH3:23])[O:18][CH2:19][CH3:20])([F:16])[F:15])=[CH:4][C:5]2[C:10]([CH:11]=1)=[CH:9][CH:8]=[C:7]([CH2:12]Br)[CH:6]=2.C[N+]1([O-])CC[O:29]CC1>O1CCOCC1>[Br:1][C:2]1[C:3]([C:14]([P:17](=[O:24])([O:21][CH2:22][CH3:23])[O:18][CH2:19][CH3:20])([F:16])[F:15])=[CH:4][C:5]2[C:10]([CH:11]=1)=[CH:9][CH:8]=[C:7]([CH:12]=[O:29])[CH:6]=2

Participants

4

Reactant 2

HCID 82029Methyl morpholine oxideHCID 59157924HCID 59157924, compound

Product 1

HCID 86761924HCID 86761924, compoundYield 86.6%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

To a solution of diethyl [3-bromo-7-(bromomethyl)-2-naphthyl](difluoro)methylphosphonate (0.2 g from step 5, example 2) in 5 mL, of dioxane was added N-methylmorpholine N-oxide (0.17 g). The reaction mixture was refluxed for 1 h. The mixture was quenched with a saturated solution of NH4Cl and the mixture was extracted with EtOAc and the extract dried over Na2SO4 and evaporated. The residue was purified by flash chromatography eluting with 10-20% EtOAc/hexanes to afford diethyl (3-bromo-7-formyl-2-naphthyl)(difluoro)methylphosphonate (0.15 grams) which was hydrolyzed with TMSBr (2 mL) in CH2Cl2 (1 mL) at rt. overnight. The mixture was evaporated to dryness and the residue was dissolved in ethanol. It was evaporated to dryness again and the process was repeated 3 times. The reaction residue was dissolved in water and treated with NaOH 1N to afford the titled product as a sodium salt.

Workup

  1. temperatureThe reaction mixture was refluxed for 1 h
  2. customThe mixture was quenched with a saturated solution of NH4Cl
  3. extractionthe mixture was extracted with EtOAc
  4. dry with materialthe extract dried over Na2SO4
  5. customevaporated
  6. customThe residue was purified by flash chromatography
  7. washeluting with 10-20% EtOAc/hexanes

Sources & evidence

ORD record
ord-95e4b7f9027147d3bc8be7b0c9cca78b
Source dataset
uspto-grants-2013_07
Patent number
US08481742B2

Reaction notes

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