Toluene → Methanefluorodiphosphonate

HRID 1181910Notes

Reaction equation

HRID 1181910 reaction equation
[F:1][CH:2]([P:13](=[O:22])([O:18]C(C)C)[O:14]C(C)C)[P:3](=[O:12])([O:8]C(C)C)[O:4]C(C)C.C[Si](Br)(C)C.C1(C)C=CC=CC=1.C(N(CCCC)CCCC)CCC>ClCCCl.CN(C=O)C>[F:1][CH:2]([P:13](=[O:14])([OH:22])[OH:18])[P:3](=[O:4])([OH:12])[OH:8]

Participants

7

Reactant 4

HCID 1140TolueneHCID 7622TributylamineHCID 76113BromotrimethylsilaneHCID 12722940Tetrapropan-2-yl (fluoromethylene)bis(phosphonate)

Product 1

HCID 471181MethanefluorodiphosphonateYield 269.5%

Reagents, catalysts & solvents 2

HCID 111,2-DichloroethaneSolventHCID 6228DimethylformamideSolvent

Conditions

Temperature
41 °C

Procedure

To a stirred solution of tetraisopropyl fluoromethylenediphosphonate (320 mg, 0.88 mmol) in 1,2-dichloroethane (5 mL) was added dropwise trimethylsilyl bromide (0.70 mL, 5.28 mmol). The resulting solution was stirred at 40-42° C. for 24 h and 3 mL of anhydrous toluene was added. The mixture was concentrated to dryness, and coevaporated with toluene once. The residue was redissolved in DMF (3 mL)/water (2 mL) mixture and concentrated. The residue was mixed with DMF (2 mL) and tributylamine (0.42 mL, 1.76 mmol) and then concentrated to dryness. The residue was coevaporated with anhydrous DMF two times. The resulting residue was dried in a vacuum oven at 30° C. overnight to give a slightly yellow residue (460 mg).

Workup

  1. concentrationThe mixture was concentrated to dryness
  2. dissolutionThe residue was redissolved in DMF (3 mL)/water (2 mL) mixture
  3. concentrationconcentrated
  4. concentrationconcentrated to dryness
  5. customThe resulting residue was dried in a vacuum oven at 30° C. overnight

Sources & evidence

ORD record
ord-cce75287da804760b74a693eba9eca36
Source dataset
uspto-grants-2007_10
Patent number
US07285658B2

Reaction notes

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