Dimethylformamide dimethyl acetal → 2-Benzhydryloxycarbonyl-7-t-butoxycarbonylamino-3-(2-dimethylaminomethyleneamino-thiazol-5-yl)-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene

HRID 2413429Notes

Reaction equation

HRID 2413429 reaction equation
[NH2:1][C:2]1[S:3][C:4]([C:7]2[CH2:14][S:13][CH:12]3[N:9]([C:10](=[O:23])[CH:11]3[NH:15][C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[C:8]=2[C:24]([O:26][CH:27]([C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)[C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)=[O:25])=[CH:5][N:6]=1.CO[CH:42](OC)[N:43]([CH3:45])[CH3:44]>O1CCCC1.C(OCC)(=O)C>[CH:27]([O:26][C:24]([C:8]1[N:9]2[CH:12]([S:13][CH2:14][C:7]=1[C:4]1[S:3][C:2]([N:1]=[CH:42][N:43]([CH3:45])[CH3:44])=[N:6][CH:5]=1)[CH:11]([NH:15][C:16]([O:18][C:19]([CH3:22])([CH3:21])[CH3:20])=[O:17])[C:10]2=[O:23])=[O:25])([C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1)[C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1

Participants

5

Reactant 2

HCID 78373Dimethylformamide dimethyl acetalHCID 131759453-(2-Aminothiazol-5-yl)-2-benzhydryloxycarbonyl-7-t-butoxycarbonylamino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene

Product 1

HCID 539806132-Benzhydryloxycarbonyl-7-t-butoxycarbonylamino-3-(2-dimethylaminomethyleneamino-thiazol-5-yl)-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-eneYield 51.3%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
20 °C

Procedure

A solution of 3-(2-amino-thiazol-5-yl)-2-benzhydryloxycarbonyl-7-t-butoxycarbonylamino-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene (4 g) in tetrahydrofuran (50 cc) is treated with dimethoxy(dimethylamino)methane (1.13 g). The reaction mixture is stirred for 25 minutes at 20° C., then diluted with ethyl acetate (150 cc), washed with distilled water (4×150 cc) and with a saturated sodium chloride solution (150 cc) and dried ove magnesium sulphate. The residue obtained after evaporation of the solvent under reduced pressure (30 mm Hg; 4 kPa) at 30° C. is chromatographed on a column (height: 28 cm; diameter: 5 cm) of silica gel (0.04-0.06 mm), elution being carried out under a pressure of 0.6 bar (60 kPa) with ethyl acetate, and 100 cc fractions being collected. Fractions 9 to 23, containing the pure product, are combined and concentrated to dryness under reduced pressure (30 mm Hg; 4 kPa) at 30° C. 2-Benzhydryloxycarbonyl-7-t-butoxycarbonylamino-3-(2-dimethylaminomethyleneamino-thiazol-5-yl)-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene (E-form) (2.25 g) is obtained in the form of an orange froth whose characteristics are identical to those of the product obtained in A.

Workup

  1. washwashed with distilled water (4×150 cc) and with a saturated sodium chloride solution (150 cc)
  2. dry with materialdried ove magnesium sulphate
  3. customThe residue obtained
  4. customafter evaporation of the solvent under reduced pressure (30 mm Hg; 4 kPa) at 30° C.
  5. customis chromatographed on a column (height: 28 cm; diameter: 5 cm) of silica gel (0.04-0.06 mm), elution
  6. custombeing collected
  7. additionFractions 9 to 23, containing the pure product
  8. concentrationconcentrated to dryness under reduced pressure (30 mm Hg; 4 kPa) at 30° C

Sources & evidence

ORD record
ord-4384ec66c5d5424c877ff2facb5d7a95
Source dataset
uspto-grants-1985_01
Patent number
US04496560

Reaction notes

Loading…