Triphenylphosphine Oxide → HCID 131711010, compound

HRID 462318Notes

Reaction equation

HRID 462318 reaction equation
[C:1]([NH:4][CH:5]1[C:30](=[O:31])[N:7]2[C:8]([C:14]([O:16][CH:17]([C:24]3[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=3)[C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)=[O:15])=[C:9](CO)[CH2:10][S:11][C@H:6]12)(=[O:3])[CH3:2].C(NC1C(=O)N2[C:39]([C:45]([O:47][CH:48](C3C=CC=CC=3)C3C=CC=CC=3)=[O:46])=[C:40](C=O)CS[C@H]12)(=O)C.C(C=P(C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)(OC)=O.C1(P(=O)(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>CC(C)=O.OS(O)(=O)=O.O=[Cr](=O)=O.C(O)(C)C.C1C=CC=CC=1.CC(C)=O>[C:1]([NH:4][CH:5]1[C:30](=[O:31])[N:7]2[C:8]([C:14]([O:16][CH:17]([C:24]3[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=3)[C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)=[O:15])=[C:9]([CH:40]=[CH:39][C:45]([O:47][CH3:48])=[O:46])[CH2:10][S:11][C@H:6]12)(=[O:3])[CH3:2]

Participants

9

Reactant 4

HCID 13097Triphenylphosphine OxideHCID 17453Acetic acid, 2-(triphenylphosphoranylidene)-, methyl esterHCID 70638849HCID 70638849, compoundHCID 88821743HCID 88821743, compound

Product 1

HCID 131711010HCID 131711010, compound

Reagents, catalysts & solvents 4

HCID 131709961Jones' reagentCatalystHCID 180AcetoneSolventHCID 241BenzeneSolventHCID 3776IsopropanolSolvent

Procedure

To a stirred cooled (0°-5° C.) solution containing 220 mg. of benzhydryl 7-acetamido-3-hydroxymethyl-3-cephem-4-carboxylate dissolved in 10 ml. of dry acetone there was added 15 drops of Jones reagent. The mixture was stirred at 0°-5° C. for 1 minute and then quenched with isopropanol and a small amount of saturated sodium bicarbonate solution. Ethyl acetate was added and the resulting solution was washed with saturated aqueous sodium chloride solution, saturated aqueous sodium bicarbonate solution, saturated aqueous sodium chloride solution again, dried over magnesium sulfate, filtered and evaporated under reduced pressure to give 225 mg. of benzhydryl 7-acetamido-3-formyl-3-cephem-4-carboxylate (one spot on a thin layer chromatogram). This aldehyde material was dissolved in a mixture of 10 ml. of dry benzene and 10 ml. of isopropanol. Then 1 equivalent of (carbmethoxymethylene)-triphenylphosphorane was added as a solid. The mixture was stirred for 1 hour at room temperature, evaporated under reduced pressure to dryness, taken up in ethyl acetate and washed with cold 5 percent v/v hydrochloric acid solution, saturated aqueous sodium bicarbonate solution, saturated aqueous sodium chloride solution, dried over magnesium sulfate, filtered and evaporated to give 293 mg. of the crude titled product mixed with triphenylphosphine oxide bi-product. When the crude product was applied to two commercially available preparative thin layer chromatography plates (solvent, 1:1 v/v ethyl acetate:benzene), there was obtained 90 mg. of the purified titled product whose NMR, IR and UV spectra were consistent with the assigned structure.

Workup

  1. temperatureTo a stirred cooled (0°-5° C.) solution
  2. additioncontaining 220 mg
  3. customquenched with isopropanol
  4. additionEthyl acetate was added
  5. washthe resulting solution was washed with saturated aqueous sodium chloride solution, saturated aqueous sodium bicarbonate solution, saturated aqueous sodium chloride solution again
  6. dry with materialdried over magnesium sulfate
  7. filtrationfiltered
  8. customevaporated under reduced pressure
  9. customto give 225 mg
  10. stirringThe mixture was stirred for 1 hour at room temperature
  11. customevaporated under reduced pressure to dryness
  12. washwashed with cold 5 percent v/v hydrochloric acid solution, saturated aqueous sodium bicarbonate solution, saturated aqueous sodium chloride solution
  13. dry with materialdried over magnesium sulfate
  14. filtrationfiltered
  15. customevaporated
  16. customto give 293 mg

Sources & evidence

ORD record
ord-665d0124143a424ba287425bb87d3839
Source dataset
uspto-grants-1977_12
Patent number
US04065620

Reaction notes

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