Formaldehyde → Tetraethyl vinylidene phosphonate

HRID 1588045Notes

Reaction equation

HRID 1588045 reaction equation
C=O.[CH2:3](NCC)C.[CH2:8]([P:17](=[O:24])([O:21][CH2:22][CH3:23])[O:18][CH2:19][CH3:20])[P:9](=[O:16])([O:13][CH2:14][CH3:15])[O:10][CH2:11][CH3:12]>CO>[CH2:22]([O:21][P:17]([C:8]([P:9](=[O:16])([O:13][CH2:14][CH3:15])[O:10][CH2:11][CH3:12])=[CH2:3])(=[O:24])[O:18][CH2:19][CH3:20])[CH3:23]

Participants

5

Reactant 3

HCID 712FormaldehydeHCID 8021DiethylamineHCID 15455Tetraethyl methylenediphosphonate

Product 1

HCID 11022954Tetraethyl vinylidene phosphonate

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

Paraformaldehyde (104.2 g) and diethylamine (50.8 g) are combined in methanol (2 1), warmed until clear, then treated with methylene bisphosphonic acid, tetraethyl ester (190.09 g) and refluxed for 18 hrs. The sample is then concentrated, methanol added, the methanol removed by heat and reduced pressure, toluene is added and removed by heat and reduced pressure. The residue is dissolved in toluene (1 1), treated with p-TSA (0.5 g) and refluxed through a Dean Stark trap for 18 hrs. The sample is concentrated under reduced pressure with heat, dissolved in methylene chloride washed twice with water, dried with magnesium sulfate, and concentrated under reduced pressure with heat. The sample is purified by distillation at reduced pressure to give the title compound, bp=140° (0.6 torr); MS (m/e) 300, 285, 273, 255, 245, 227, 217, 199, 192, 181, 163, 153 and 135; IR (neat) 2984, 2934, 2909, 1651, 1580, 1479, 1444, 1392, 1254, 1166, 1098, 1042, 1025, 974, 855, 813 and 800 cm-1 ; NMR (CDCl3) 7.1, 6.7, 4.1 and 1.3 δ.

Workup

  1. temperaturewarmed until clear,
  2. temperaturerefluxed for 18 hrs
  3. concentrationThe sample is then concentrated
  4. additionmethanol added
  5. customthe methanol removed
  6. temperatureby heat
  7. additionreduced pressure, toluene is added
  8. customremoved
  9. temperatureby heat
  10. dissolutionThe residue is dissolved in toluene (1 1)
  11. additiontreated with p-TSA (0.5 g)
  12. temperaturerefluxed through a Dean Stark trap for 18 hrs
  13. concentrationThe sample is concentrated under reduced pressure
  14. temperaturewith heat
  15. dissolutiondissolved in methylene chloride
  16. washwashed twice with water
  17. dry with materialdried with magnesium sulfate
  18. concentrationconcentrated under reduced pressure
  19. temperaturewith heat
  20. distillationThe sample is purified by distillation at reduced pressure

Sources & evidence

ORD record
ord-807e5c9d2609410883e51560287d330b
Source dataset
uspto-grants-1993_06
Patent number
US05220021

Reaction notes

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