Methanethioamide → HCID 13175941, compound

HRID 370598Notes

Reaction equation

HRID 370598 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 thioformamide (0.3 g) in dry tetrahydrofuran (23 cc) is stirred for 3 hours at 20° and then heated for 90 minutes at 50° C. The reaction mixture is diluted with ethyl acetate (160 cc) and washed with a saturated solution of sodium bicarbonate (100 cc) and then with a semi-saturated solution of sodium chloride (100 cc). After drying of the organic layer over magnesium sulphate and evaporation of 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 a saturated solution of sodium bicarbonate (100 cc)
  2. dry with materialAfter drying of the organic layer over magnesium sulphate and evaporation of the solvent under reduced pressure (30 mm Hg; 4 kPa) at 30° C.
  3. customthe residue obtained
  4. washis subjected to chromatography on a column (height: 30 cm; diameter: 2.5 cm) of silica gel (0.04-0.06 mm), elution
  5. 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
  6. custombeing collected
  7. additionFractions 16 to 25, containing the pure product
  8. concentrationconcentrated to dryness under reduced pressure (30 mm Hg; 4 kPa) at 30° C.
  9. customthe residue is triturated in isopropyl ether (50 cc)
  10. filtrationAfter filtration
  11. customdrying

Sources & evidence

ORD record
ord-1c90e2d2d83a4ffb85c12ef301e1bdb3
Source dataset
uspto-grants-1985_07
Patent number
US04526962

Reaction notes

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