Chlorotrimethylsilane → HCID 56605983, compound

HRID 1648833Notes

Reaction equation

HRID 1648833 reaction equation
[C:1]([NH:4][CH2:5][CH2:6][S:7][C:8]1[CH2:14][C@H:13]2[N:10]([C:11](=[O:18])[C@H:12]2[C@@H:15]([OH:17])[CH3:16])[C:9]=1[C:19]([O:21][CH2:22][C:23]1[CH:28]=[CH:27][C:26]([N+:29]([O-:31])=[O:30])=[CH:25][CH:24]=1)=[O:20])(=O)[CH3:2].Cl[Si:33]([CH3:36])([CH3:35])[CH3:34].[N-:37]=[N+:38]=[N-:39].CN(C)C(=[NH2+])N(C)C.[N-]=[N+]=[N-]>N1C=CC=CC=1.ClCCl.O>[CH3:2][C:1]1[N:4]([CH2:5][CH2:6][S:7][C:8]2[CH2:14][C@H:13]3[N:10]([C:11](=[O:18])[C@H:12]3[C@@H:15]([O:17][Si:33]([CH3:36])([CH3:35])[CH3:34])[CH3:16])[C:9]=2[C:19]([O:21][CH2:22][C:23]2[CH:24]=[CH:25][C:26]([N+:29]([O-:31])=[O:30])=[CH:27][CH:28]=2)=[O:20])[N:39]=[N:38][N:37]=1

Participants

8

Reactant 4

HCID 6397ChlorotrimethylsilaneHCID 33558Azide2×HCID 53962945HCID 53962945, compoundHCID 178484365HCID 178484365, compound

Product 1

HCID 56605983HCID 56605983, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 1049PyridineSolventHCID 6344DichloromethaneSolvent2×

Procedure

p-Nitrobenzyl (5R, 6R)-3-(2-acetamidoethylthio)-6-[(1S)-1-hydroxyethyl]-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylate, e1 (232 mg) was suspended in pyridine (3 ml) and treated with chlorotrimethylsilane (350 mg). After 15 min. the pyridine was evaporated in vacuo and ethyl acetate (20 ml) and water (20 ml) were added to the residue. After shaking, the layers were separated and the ethyl acetate layer was washed with brine, dried (MgSO4) and evaporated in vacuo. Toluene (10 ml) was added to the residue and evaporated in vacuo. The resultant trimethylsilyl ether was taken up in dry dichloromethane (6 ml), cooled to -30° and N-methylmorpholine (0.25 ml) was added. A solution of phosgene in toluene (0.90 ml; 12.5% w/w, d 0.91), diluted with dry CH2Cl2 (1 ml), was added dropwise. The mixture was allowed to warm to room temperature and the i.r. spectrum of the reaction mixture indicated that the imidoyl chloride had formed. Tetramethylguanidinium azide in dichloromethane (0.90 ml, 100 mg/ml) was added and after stirring at room temperature for 15 min. a further portion (0.20 ml) of the azide solution was added, and after another 15 min. more azide solution (0.15 ml) was added. After 15 min. the solution was diluted with dichloromethane (15 ml), water (15 ml) was added, the layers separated and the dichloromethane layer was washed with brine, dried (MgSO4) and evaporated in vacuo to dryness. Toluene (2×20 ml) was added to the residue and evaporated in vacuo. The product was chromatographed on silica gel (230-400 mesh ASTM) (15 g) eluting with ethyl acetate to give, after combination and evaporation of appropriate fractions, the title compound, e2, (210 mg), λmax (EtOH) 311 (ε10932) and 265 (11509) nm, νmax (CH2Cl2) 1785, 1705, 1525, 1345, 1150, 845 cm-1, [M+ found m/e 546.1677; C23H30N6O6SSi requires m/e 546.1714].

Workup

  1. customAfter 15 min. the pyridine was evaporated in vacuo and ethyl acetate (20 ml) and water (20 ml)
  2. additionwere added to the residue
  3. customthe layers were separated
  4. washthe ethyl acetate layer was washed with brine
  5. dry with materialdried (MgSO4)
  6. customevaporated in vacuo
  7. additionToluene (10 ml) was added to the residue
  8. customevaporated in vacuo
  9. temperaturecooled to -30°
  10. additionN-methylmorpholine (0.25 ml) was added
  11. additionA solution of phosgene in toluene (0.90 ml; 12.5% w/w, d 0.91), diluted with dry CH2Cl2 (1 ml)
  12. additionwas added dropwise
  13. customhad formed
  14. additionwas added
  15. additionwas added
  16. customthe layers separated
  17. washthe dichloromethane layer was washed with brine
  18. dry with materialdried (MgSO4)
  19. customevaporated in vacuo to dryness
  20. additionToluene (2×20 ml) was added to the residue
  21. customevaporated in vacuo
  22. customThe product was chromatographed on silica gel (230-400 mesh ASTM) (15 g)
  23. washeluting with ethyl acetate
  24. customto give
  25. customafter combination and evaporation of appropriate fractions

Sources & evidence

ORD record
ord-ebe2c0528a4143f5a59fda2da05c3474
Source dataset
uspto-grants-1983_11
Patent number
US04413000

Reaction notes

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