Ammonium Chloride → 5,5-Di[(diethoxyphosphoryl)methyl]-2,2-dimethyl-1,3-dioxane

HRID 578607Notes

Reaction equation

[P:1]([O-:8])([O:5][CH2:6][CH3:7])[O:2][CH2:3][CH3:4].[Na+].Br[CH2:11][C:12]1([CH2:20]Br)[CH2:17][O:16][C:15]([CH3:19])([CH3:18])[O:14][CH2:13]1.[Cl-].[NH4+]>C1COCC1.CN(C=O)C>[CH2:3]([O:2][P:1]([CH2:11][C:12]1([CH2:20][P:1]([O:5][CH2:6][CH3:7])([O:2][CH2:3][CH3:4])=[O:8])[CH2:17][O:16][C:15]([CH3:19])([CH3:18])[O:14][CH2:13]1)([O:5][CH2:6][CH3:7])=[O:8])[CH3:4]

Participants

Conditions

Temperature: 68 °C

Procedure

Sodium diethyl phosphite (63.6 g, 400 mmol, 6.0 eq.) was added to a solution of 5,5-di(bromomethyl)-2,2-dimethyl-1,3-dioxane (20.0 g, 66 mmol) in an anhydrous mixture of THF/DMF (9:1, 600 ml). The reaction mixture was stirred for 15 h at 68° C. and subsequently mixed with a saturated aqueous solution of ammonium chloride (20.0 ml) and the volatile constituents were removed in vacuo. The residue was diluted with deionized water (200 ml) and the solution formed was extracted with methylene chloride (3×200 ml). The combined organic phases were dried with anhydrous sodium sulphate and the solvent was then removed under reduced pressure. The obtained crude product was purified by flash column chromatography (eluent: ethyl acetate/methanol 9:1). 19.6 g (71% yield) of the product was obtained as a colorless oil.

Workup

customthe volatile constituents were removed in vacuo
additionThe residue was diluted with deionized water (200 ml)
customthe solution formed
extractionwas extracted with methylene chloride (3×200 ml)
dry with materialThe combined organic phases were dried with anhydrous sodium sulphate
customthe solvent was then removed under reduced pressure
customThe obtained crude product
customwas purified by flash column chromatography (eluent: ethyl acetate/methanol 9:1)

Sources & evidence

ORD record: ord-e0c8aa747f3c49bfa9c9c3df46ec71e1
Source dataset: uspto-grants-2015_05
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09040602B2

Reaction notes

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