Isopropanol → Phosphorochloridothioic acid, O,O-diisopropyl ester

HRID 1080620Notes

Reaction equation

HRID 1080620 reaction equation
[H-].[Na+:2].[CH:3]([OH:6])([CH3:5])[CH3:4].[P:7]([Cl:11])(Cl)(Cl)=[S:8]>C1COCC1>[CH3:4][CH:3]([CH3:5])[O-:6].[Na+:2].[P:7]([Cl:11])([O:6][CH:3]([CH3:5])[CH3:4])([O:6][CH:3]([CH3:5])[CH3:4])=[S:8]

Participants

6

Reactant 3

HCID 3776IsopropanolHCID 19883Thiophosphoryl chlorideHCID 24758Sodium hydride

Product 2

HCID 75652Phosphorochloridothioic acid, O,O-diisopropyl esterYield 117.1%HCID 109204432-Propanol, sodium salt (1:1)

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent4×

Conditions

Temperature
-40 °C

Procedure

A solution of sodium isopropoxide in THF was prepared by the reaction of 45 g (1125 mmole) of 60% sodium hydride with 84 ml (1100 mmole) of isopropyl alcohol in 400 ml of THF. This solution was added, with mechanical stirring, to 83.4 g (490 mmole) of thiophosphorylchloride in 300 ml of THF and cooled to -40° C. internal. After the addition was complete the reaction mixture was slowly warmed to 25° C. When gas chromatography showed the reaction to be complete the THF was removed in vacuo and the product partitioned between hexanes and water. The organic layer was dried over anhydrous magnesium sulfate and concentrated in vacuo yielding 93 g of the title compound, an oil. nmr 1.4 d 12H, 4.9 m 2H.

Workup

  1. additionAfter the addition
  2. temperaturewas slowly warmed to 25° C
  3. customthe reaction
  4. customwas removed in vacuo
  5. customthe product partitioned between hexanes and water
  6. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  7. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-cbe97f5467334983bada0d42dda47b83
Source dataset
uspto-grants-1996_12
Patent number
US05583124

Reaction notes

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