Acetamide, 2-(trimethylsilyl)- → HCID 131712017, compound

HRID 1733748Notes

Reaction equation

HRID 1733748 reaction equation
[O:1]1[C:6]([C:7](=[N:11][O:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH3:18])[C:8]([OH:10])=O)=[CH:5][S:4][CH2:3][CH2:2]1.[NH2:19][CH:20]1[C:30](=[O:31])[N:22]2[C:23]([C:27]([OH:29])=[O:28])=[CH:24][CH2:25][S:26][C@H:21]12.C[Si](CC(N)=O)(C)C.C[Si](C([Si](C)(C)C)C(N)=O)(C)C>C(OCC)(=O)C.O>[O:1]1[C:6]([C:7](=[N:11][O:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH3:18])[C:8]([NH:19][CH:20]2[C:30](=[O:31])[N:22]3[C:23]([C:27]([OH:29])=[O:28])=[CH:24][CH2:25][S:26][C@H:21]23)=[O:10])=[CH:5][S:4][CH2:3][CH2:2]1

Participants

7

Reactant 4

HCID 357676Acetamide, 2-(trimethylsilyl)-HCID 11708267BistrimethylsilylacetamidHCID 12941984(6R)-7-amino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acidHCID 54300440HCID 54300440, compound

Product 1

HCID 131712017HCID 131712017, compoundYield 72.2%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent3×

Procedure

N,N-Dimethylformamide (0.579 g.), phosphoryl chloride (1.214 g.) and ethyl acetate (3 ml.) were treated in a conventional manner to give a Vilsmeier reagent and the reagent was added to ethyl acetate (7 ml.). To the solution was added 2-(2,3-dihydro-1,4-oxathiin-6-yl)-2-n-hexyloxyiminoacetic acid (syn isomer, 2.00 g.) under stirring to give an activated acid solution. On the other hand, 7-amino-3-cephem-4-carboxylic acid (1.46 g.), trimethylsilylacetamide (3.84 g.), bis(trimethylsilyl)acetamide (4.40 ml.) and ethyl acetate (24 ml.) were stirred to prepare a solution. To the solution was added all at once the activated acid solution at -10° C., and stirred at the same temperature for 1.5 hours. After adding water (30 ml.) and ethyl acetate (15 ml.) to the resultant solution, the solution was shaken sufficiently and the organic layer was separated. An aqueous solution of sodium bicarbonate (30 ml.) was added to the organic solution, shaken sufficiently and the aqueous layer was separated. The solution was adjusted to pH 2.0 with conc. hydrochloric acid and extracted with ethyl acetate (60 ml.). The extract was washed with water (20 ml.) twice, dried over magnesium sulfate and concentrated in vacuo. The residue was pulverized with diisopropyl ether (50 ml.) and the precipitates were collected by filtration to give 7-[2-(2,3-dihydro-1,4-oxathiin-6yl)-2-n-hexyloxyiminoacetamido]-3-cephem-4-carboxylic acid (syn isomer, 2.40 g.).

Workup

  1. customto give an activated acid solution
  2. customto prepare a solution
  3. additionTo the solution was added all at once the activated acid solution at -10° C.
  4. stirringstirred at the same temperature for 1.5 hours
  5. stirringthe solution was shaken sufficiently
  6. customthe organic layer was separated
  7. additionAn aqueous solution of sodium bicarbonate (30 ml.) was added to the organic solution
  8. stirringshaken sufficiently
  9. customthe aqueous layer was separated
  10. extractionextracted with ethyl acetate (60 ml.)
  11. washThe extract was washed with water (20 ml.) twice
  12. dry with materialdried over magnesium sulfate
  13. concentrationconcentrated in vacuo
  14. filtrationthe precipitates were collected by filtration

Sources & evidence

ORD record
ord-194e06b34afe4b72928faf95e4044f45
Source dataset
uspto-grants-1980_12
Patent number
US04242510

Reaction notes

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