4-Methoxyphenol → HCID 67856655, compound

HRID 2253997Notes

Reaction equation

HRID 2253997 reaction equation
[C:1]([O:5][C:6]([NH:8][CH:9]1[C:34](=[O:35])[N:11]2[C:12]([C:18]([O:20][CH:21]([C:28]3[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=3)[C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=3)=[O:19])=[C:13]([CH2:16][OH:17])[CH2:14][S:15][C@H:10]12)=[O:7])([CH3:4])([CH3:3])[CH3:2].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[CH3:55][O:56][C:57]1[CH:62]=[CH:61][C:60](O)=[CH:59][CH:58]=1.N(C(OCC)=O)=NC(OCC)=O>O1CCCC1.C(OCC)(=O)C>[C:1]([O:5][C:6]([NH:8][CH:9]1[C:34](=[O:35])[N:11]2[C:12]([C:18]([O:20][CH:21]([C:28]3[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=3)[C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=3)=[O:19])=[C:13]([CH2:16][O:17][C:60]3[CH:61]=[CH:62][C:57]([O:56][CH3:55])=[CH:58][CH:59]=3)[CH2:14][S:15][C@H:10]12)=[O:7])([CH3:4])([CH3:2])[CH3:3]

Participants

7

Reactant 4

HCID 90154-MethoxyphenolHCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 70147912HCID 70147912, compound

Product 1

HCID 67856655HCID 67856655, compoundYield 21.2%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

5.00 g (10.1 mmol) of Diphenylmethyl 7-tert-butoxycarbonylamino-3-hydroxymethyl-3-cephem-4-carboxylate, 7.93 g (30.2 mmol) of triphenylphosphine, and 7.28 g (60.2 mmol) of p-methoxyphenol were dissolved in 25 ml of tetrahydrofuran under argon atmosphere, and the reaction solution was cooled to -40°-35° C., and 4.76 ml (30.2 mmol) of diethyl azodicarboxylate were added dropwise, and then the stirring was effected for 6 hrs. at the same temperature. This solution was added to a suspension of 300 ml of ice cold 1N hydrochloric acid and 300 ml of ethyl acetate, and stirred, and then separated, and the layer of ethyl acetate was washed with water and saturated saline solution, and dried over anhydrous magnesium sulfate. Benzene was added to a caramel obtained by evaporating off the solvent so that the insoluble material was removed by filtering off, and the residue obtained by evaporating off the benzene filtrate was dissolved in diethyl ether. This ether solution was washed with 20% potassium carbonate aqueous solution until unreacted p-methoxyphenol was removed, and further washed with saturated potassium dihydrogen phosphate aqueous solution, water, and saturated saline solution. The layer of ether was dried over anhydrous magnesium sulfate, and then, ether was evaporated off to give 2.80 g of a caramel. The caramel was column chromatographed on silica gel by eluting with benzene-acetone (V:V;100:1), and then, powdered with ether-hexane to give 1.29 g of diphenylmethyl 7-tert-butoxycarbonylamino-3-(4-methoxyphenoxymethyl)-3cephem-4-carboxylate.

Workup

  1. temperaturethe reaction solution was cooled to -40°-35° C.
  2. customseparated
  3. washthe layer of ethyl acetate was washed with water and saturated saline solution
  4. dry with materialdried over anhydrous magnesium sulfate
  5. additionBenzene was added to a caramel
  6. customobtained
  7. customby evaporating off the solvent so that the insoluble material
  8. customwas removed
  9. filtrationby filtering off
  10. customthe residue obtained
  11. customby evaporating off the benzene filtrate
  12. dissolutionwas dissolved in diethyl ether
  13. washThis ether solution was washed with 20% potassium carbonate aqueous solution until unreacted p-methoxyphenol
  14. customwas removed
  15. washfurther washed with saturated potassium dihydrogen phosphate aqueous solution, water, and saturated saline solution
  16. dry with materialThe layer of ether was dried over anhydrous magnesium sulfate
  17. customether was evaporated off
  18. customto give 2.80 g of a caramel
  19. customchromatographed on silica gel
  20. washby eluting with benzene-acetone (V:V;100:1)

Sources & evidence

ORD record
ord-2ee57a83a5df47aab3bf60930ee03707
Source dataset
uspto-grants-1993_08
Patent number
US05233035

Reaction notes

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