Acetophenone → HCID 53758701, compound

HRID 36168Notes

Reaction equation

HRID 36168 reaction equation
[C:1]([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1)(=[O:3])[CH3:2].C[Si]([N-][Si](C)(C)C)(C)C.[Li+].[CH2:20]([O:22][P:23]([C:28]([P:30](=[O:37])([O:34][CH2:35][CH3:36])[O:31][CH2:32][CH3:33])=[CH2:29])(=[O:27])[O:24][CH2:25][CH3:26])[CH3:21].[Cl:38]N1C(=O)CCC1=O>C1COCC1>[CH2:35]([O:34][P:30]([C:28]([P:23](=[O:27])([O:24][CH2:25][CH3:26])[O:22][CH2:20][CH3:21])([Cl:38])[CH2:29][CH2:2][C:1](=[O:3])[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1)(=[O:37])[O:31][CH2:32][CH3:33])[CH3:36]

Participants

6

Reactant 4

HCID 7410AcetophenoneHCID 31398ChlorosuccinimideHCID 2733832Lithium HexamethyldisilazideHCID 11022954Tetraethyl vinylidene phosphonate

Product 1

HCID 53758701HCID 53758701, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

Acetophenone (1.17 ml) is dissolved in THF (20 ml), cooled to -78° and treated with lithium bis(trimethylsilyl)amide. The solution is stirred for 30 minutes and a solution of ethenylidenebisphosphonic acid tetraethyl ester (I, 2.7g) in THF (5 ml) is added. The solution is stirred for several minutes then warmed to 0° for 1 hour. N-Chlorosuccinimide (1.33 g) is added and the solution was stirred at 22° for 18 hours. The reaction is quenched with aqueous ammonium chloride and concentrated. The residue is diluted with ethyl acetate and washed with sulfuric acid (2N, 2×), water, sodium bicarbonate, saline and dried with magnesium sulfate and concentrated. The resultant mixture is chromatographed eluting with ethyl acetate, slowly increased from 1 to 5% ethanol/ethyl acetate. The appropriate fractions are pooled and concentrated to give the title compound, MS (m/e) 454, 426, 322 and 105; IR (neat) 1686, 1599, 1581, 1448, 1391, 1368, 1259, 1214 and 1163 cm-1 ; NMR (CDCl3) 8.02-7.99, 7.59-7.54, 7.49-7.44, 4.37-4.25, 3.50, 2.78-2.64 and 1.38 δ. Another compound is formed by the reaction which is not within the scope of the invention.

Workup

  1. temperaturecooled to -78°
  2. stirringThe solution is stirred for several minutes
  3. temperaturethen warmed to 0° for 1 hour
  4. stirringthe solution was stirred at 22° for 18 hours
  5. customThe reaction is quenched with aqueous ammonium chloride
  6. concentrationconcentrated
  7. additionThe residue is diluted with ethyl acetate
  8. washwashed with sulfuric acid (2N, 2×), water, sodium bicarbonate, saline
  9. dry with materialdried with magnesium sulfate
  10. concentrationconcentrated
  11. customThe resultant mixture is chromatographed
  12. washeluting with ethyl acetate
  13. temperatureslowly increased from 1 to 5% ethanol/ethyl acetate
  14. concentrationconcentrated

Sources & evidence

ORD record
ord-44afd46340bb4667bff2c15721db9e74
Source dataset
uspto-grants-1995_05
Patent number
US05412141

Reaction notes

Loading…