Ethyl Acetoacetate → (3-Acetyl-4-ethoxy-4-oxobutylidene)bisphosphonic acid tetraethyl ester

HRID 1450208Notes

Reaction equation

HRID 1450208 reaction equation
[CH2:1]([O:3][P:4]([C:9]([P:11](=[O:18])([O:15][CH2:16][CH3:17])[O:12][CH2:13][CH3:14])=[CH2:10])(=[O:8])[O:5][CH2:6][CH3:7])[CH3:2].[C:19]([O:25][CH2:26][CH3:27])(=[O:24])[CH2:20][C:21]([CH3:23])=[O:22].C1CCN2C(=NCCC2)CC1>C1COCC1.C(OCC)(=O)C>[CH2:16]([O:15][P:11]([CH:9]([P:4](=[O:8])([O:5][CH2:6][CH3:7])[O:3][CH2:1][CH3:2])[CH2:10][CH:20]([C:21](=[O:22])[CH3:23])[C:19]([O:25][CH2:26][CH3:27])=[O:24])(=[O:18])[O:12][CH2:13][CH3:14])[CH3:17]

Participants

6

Reactant 3

HCID 8868Ethyl AcetoacetateHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 11022954Tetraethyl vinylidene phosphonate

Product 1

HCID 23176330(3-Acetyl-4-ethoxy-4-oxobutylidene)bisphosphonic acid tetraethyl ester

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

Ethenylidenebisphosphonic acid tetraethyl ester (I, 3.00 g), ethyl acetoacetate (II, 1.4 ml), and DBU (0.25 ml) are heated to 50° in THF (20 ml) for 1.5 hours. The reaction is cooled, diluted with ethyl acetate, filtered through magnesium sulfate and concentrated under reduced pressure. The concentrate is chromatographed eluting with ethyl acetate, ethyl acetate/acetone (1/1). The appropriate fractions are pooled and concentrated to give the title compound, MS (m/e) 430 (M+), 388, 339, 301 and 288; IR (neat) 2984, 1740, 1716, 1478, 1444, 1392, 1368 and 1250 cm-1 ; NMR (CDCl3) 4.20, 2.43, 2.29, 1.35 and 1.28 δ.

Workup

  1. temperatureThe reaction is cooled
  2. filtrationfiltered through magnesium sulfate
  3. concentrationconcentrated under reduced pressure
  4. customThe concentrate is chromatographed
  5. washeluting with ethyl acetate, ethyl acetate/acetone (1/1)
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-9518e5d6fc4141f58213640271683374
Source dataset
uspto-grants-1997_02
Patent number
US05602115

Reaction notes

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