Carbon tetrabromide → Di-tert-butyl phosphorobromidate

HRID 416418

Reaction equation

HRID 416418 reaction equation
C(Br)(Br)(Br)[Br:2].[OH-].[Na+].[C:8]([O:12][P:13]([O-:19])[O:14][C:15]([CH3:18])([CH3:17])[CH3:16])([CH3:11])([CH3:10])[CH3:9].P([O-])([O-])[O-]>[Cl-].C([N+](CC)(CC)CC)C1C=CC=CC=1.ClCCl>[P:13]([Br:2])(=[O:19])([O:12][C:8]([CH3:11])([CH3:10])[CH3:9])[O:14][C:15]([CH3:18])([CH3:17])[CH3:16]

Participants

7

Reactant 4

HCID 11205Carbon tetrabromideHCID 14798Sodium HydroxideHCID 107908PhosphiteHCID 21959072Di-tert-butyl phosphite

Product 1

HCID 10934607Di-tert-butyl phosphorobromidateYield 172.1%

Reagents, catalysts & solvents 2

HCID 66133Benzyl triethylammonium chlorideCatalystHCID 6344DichloromethaneSolvent3×

Procedure

A 500 mL 3-neck flask equipped with dropping funnel and thermometer was charged with carbon tetrabromide (16.58 g, 50 mmol), benzyltriethylammonium chloride (1.14 g, 5.0 mmol) and dichloromethane (50 mL). A 20% w/w NaOH solution (50 mL) was added with vigorous stirring, followed by dropwise addition of a solution of di-tert-butylphosphite (20 g, 100 mmol) in dichloromethane (20 mL), the rate of addition was controlled to keep the temperature of reaction mixture not to exceed to 25° C. After addition of phosphite, the mixture was further stirred at room temperature for 3 h, diluted with dichloromethane (20 mL) and separated. The organic phase was washed with saturated sodium bisulfite, water, brine, dried (Na2SO4), filtered and concentrated at RT. After removing the solvent, the residue was further pumped in vacuo for 1 h to give di-tert-butyl phosphorobromidate as a colorless oil (23.5 g, 86%).

Workup

  1. customA 500 mL 3-neck flask equipped
  2. additionthe rate of addition
  3. customthe temperature of reaction mixture not
  4. customto exceed to 25° C
  5. customseparated
  6. washThe organic phase was washed with saturated sodium bisulfite, water, brine
  7. dry with materialdried (Na2SO4)
  8. filtrationfiltered
  9. concentrationconcentrated at RT
  10. customAfter removing the solvent
  11. waitthe residue was further pumped in vacuo for 1 h

Sources & evidence

ORD record
ord-47f2d9d209f04415a33207330d3d3ad2
Source dataset
uspto-grants-2012_01
Patent number
US08088793B2

Linked notes

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