Methanethioamide → HCID 13175941, compound

HRID 2413410Notes

Reaction equation

HRID 2413410 reaction equation
[CH:1]([O:14][C:15]([C:17]1[N:18]2[CH:21]([S:22][CH2:23][C:24]=1[CH:25](Br)[CH:26]=O)[CH:20]([NH:29][C:30]([O:32][C:33]([CH3:36])([CH3:35])[CH3:34])=[O:31])[C:19]2=[O:37])=[O:16])([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH:38]([NH2:40])=[S:39]>O1CCCC1.C(OCC)(=O)C>[CH:1]([O:14][C:15]([C:17]1[N:18]2[CH:21]([S:22][CH2:23][C:24]=1[C:25]1[S:39][CH:38]=[N:40][CH:26]=1)[CH:20]([NH:29][C:30]([O:32][C:33]([CH3:34])([CH3:36])[CH3:35])=[O:31])[C:19]2=[O:37])=[O:16])([C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1)[C:8]1[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=1

Participants

5

Reactant 2

HCID 3005587MethanethioamideHCID 13175928HCID 13175928, compound

Product 1

HCID 13175941HCID 13175941, compound

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
50 °C

Procedure

A solution of 2-benzhydryloxycarbonyl-3-(1-bromo-2-oxoethyl)-7-t-butoxycarbonylamino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene (mixture of the epimeric bromoaldehydes) (2.34 g) and of thioformamide (0.3 g) in dry tetrahydrofuran (23 cc) is stirred for 3 hours at 20° C. and then heated at 50° C. for 90 minutes. The reaction mixture is diluted with ethyl acetate (160 cc) and washed with saturated sodium bicarbonate solution (100 cc) and then with half-saturated sodium chloride solution (100 cc). After having dried the organic layer over magnesium sulphate and evaporated the solvent under reduced pressure (30 mm Hg; 4 kPa) at 30° C., the residue obtained is subjected to chromatography on a column (height: 30 cm; diameter: 2.5 cm) of silica gel (0.04-0.06 mm), elution being carried out under a pressure of 0.8 bar (80 kPa) with a 70:30 (by volume) mixture of cyclohexane and ethyl acetate, and 50 cc fractions being collected. Fractions 16 to 25, containing the pure product, are combined and concentrated to dryness under reduced pressure (30 mm Hg; 4 kPa) at 30° C., and the residue is triturated in isopropyl ether (50 cc). After filtration and drying, 2-benzhydryloxycarbonyl-7-t-butoxycarbonylamino-8-oxo-3-(thiazol-5-yl)-5-thia-1-azabicyclo[4.2.0]oct-2-ene (0.85 g) is obtained in the form of a cream-coloured solid.

Workup

  1. washwashed with saturated sodium bicarbonate solution (100 cc)
  2. dry with materialAfter having dried the organic layer over magnesium sulphate
  3. customevaporated the solvent under reduced pressure (30 mm Hg; 4 kPa) at 30° C.
  4. customthe residue obtained
  5. washis subjected to chromatography on a column (height: 30 cm; diameter: 2.5 cm) of silica gel (0.04-0.06 mm), elution
  6. additionbeing carried out under a pressure of 0.8 bar (80 kPa) with a 70:30 (by volume) mixture of cyclohexane and ethyl acetate, and 50 cc fractions
  7. custombeing collected
  8. additionFractions 16 to 25, containing the pure product
  9. concentrationconcentrated to dryness under reduced pressure (30 mm Hg; 4 kPa) at 30° C.
  10. customthe residue is triturated in isopropyl ether (50 cc)
  11. filtrationAfter filtration
  12. customdrying

Sources & evidence

ORD record
ord-7ac2b3adcf0b4d65b44de9470aaca61e
Source dataset
uspto-grants-1985_01
Patent number
US04496560

Reaction notes

Loading…