Tetraethyl methylenediphosphonate → HCID 86641295, compound

HRID 1841910Notes

Reaction equation

HRID 1841910 reaction equation
[CH2:1]([P:10](=[O:17])([O:14][CH2:15][CH3:16])[O:11][CH2:12][CH3:13])[P:2](=[O:9])([O:6][CH2:7][CH3:8])[O:3][CH2:4][CH3:5].[H-].[Na+].Br[CH2:21][C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23]>CN(C=O)C>[CH2:15]([O:14][P:10]([CH:1]([P:2]([O:6][CH2:7][CH3:8])([O:3][CH2:4][CH3:5])=[O:9])[CH2:21][C:22]([O:24][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:23])([O:11][CH2:12][CH3:13])=[O:17])[CH3:16]

Participants

5

Reactant 3

HCID 15455Tetraethyl methylenediphosphonateHCID 24758Sodium hydrideHCID 79177tert-Butyl bromoacetate

Product 1

HCID 86641295HCID 86641295, compoundYield 50.2%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of tetraethyl methylenebisphosphonate (3.00 g, 10.4 mmol) in dry DMF (9 mL) was added NaH (60% suspension in mineral oil, 0.46 g, 11.5 mmol) portionwise. The resulting slurry was stirred for 30 min at room temperature, after which t-butyl bromoacetate (1.7 mL, 11.5 mmol) was quickly added neat. The reaction mixture was stirred for 1 h and quenched by adding 2 mL of a saturated solution of NH4Cl. The reaction mixture was evaporated and purified by flash chromatography on silica gel eluting with 5% methanol/ethyl acetate to give pure 40 (2.1 g, 50%) as a clear colourless oil. 1H NMR (400 MHz, CDCl3) δ 1.33 (bt, J=7.0, 12H), 1.46 (s, 9H), 2H), 2.76 (dt, J=16.0, 6.1, 2H), 3.07 (tt, J=24.0, 6.1, 1H), 4.10-4.25 (m, 8H).

Workup

  1. stirringThe reaction mixture was stirred for 1 h
  2. customquenched
  3. additionby adding 2 mL of a saturated solution of NH4Cl
  4. customThe reaction mixture was evaporated
  5. custompurified by flash chromatography on silica gel eluting with 5% methanol/ethyl acetate

Sources & evidence

ORD record
ord-c71d115c103f40a9b26fb81995519480
Source dataset
uspto-grants-2015_02
Patent number
US08946144B2

Reaction notes

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