m-Chloroperbenzoic acid → 2-Benzhydryloxycarbonyl-7-{2-[(2-t-butoxycarbonylprop-2-yl)-oxyimino]-2-(2-tritylaminothiazol-4-yl)-acetamido}-8-oxo-3-[2-(pyridin-3-yl-amino)-thiazol-5-yl]-5-thia-1-azabicyclo[4.2.0]oct-2-ene 5-oxide

HRID 1980423Notes

Reaction equation

HRID 1980423 reaction equation
ClC1C=CC=C(C(OO)=[O:9])C=1.[CH:12]([O:25][C:26]([C:28]1[N:29]2[CH:32]([S:33][CH2:34][C:35]=1[C:36]1[S:40][C:39]([NH:41][C:42]3[CH:43]=[N:44][CH:45]=[CH:46][CH:47]=3)=[N:38][CH:37]=1)[CH:31]([NH:48][C:49](=[O:88])[C:50](=[N:76][O:77][C:78]([C:81]([O:83][C:84]([CH3:87])([CH3:86])[CH3:85])=[O:82])([CH3:80])[CH3:79])[C:51]1[N:52]=[C:53]([NH:56][C:57]([C:70]3[CH:75]=[CH:74][CH:73]=[CH:72][CH:71]=3)([C:64]3[CH:69]=[CH:68][CH:67]=[CH:66][CH:65]=3)[C:58]3[CH:63]=[CH:62][CH:61]=[CH:60][CH:59]=3)[S:54][CH:55]=1)[C:30]2=[O:89])=[O:27])([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1>C(Cl)Cl>[CH:12]([O:25][C:26]([C:28]1[N:29]2[CH:32]([S:33](=[O:9])[CH2:34][C:35]=1[C:36]1[S:40][C:39]([NH:41][C:42]3[CH:43]=[N:44][CH:45]=[CH:46][CH:47]=3)=[N:38][CH:37]=1)[CH:31]([NH:48][C:49](=[O:88])[C:50](=[N:76][O:77][C:78]([C:81]([O:83][C:84]([CH3:87])([CH3:86])[CH3:85])=[O:82])([CH3:80])[CH3:79])[C:51]1[N:52]=[C:53]([NH:56][C:57]([C:58]3[CH:59]=[CH:60][CH:61]=[CH:62][CH:63]=3)([C:64]3[CH:65]=[CH:66][CH:67]=[CH:68][CH:69]=3)[C:70]3[CH:71]=[CH:72][CH:73]=[CH:74][CH:75]=3)[S:54][CH:55]=1)[C:30]2=[O:89])=[O:27])([C:19]1[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1)[C:13]1[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1

Participants

4

Reactant 2

HCID 70297m-Chloroperbenzoic acidHCID 538049402-Benzhydryloxycarbonyl-7-[2-(2-t-butoxycarbonylprop-2-yl-oxyimino)-2-(2-tritylaminothiazol-4-yl)-acetamido]-8-oxo-3-[2-(pyridin-3-yl-amino)-thiazol-5-yl]-5-thia-1-azabicyclo[4.2.0]oct-2-ene

Product 1

HCID 542707772-Benzhydryloxycarbonyl-7-{2-[(2-t-butoxycarbonylprop-2-yl)-oxyimino]-2-(2-tritylaminothiazol-4-yl)-acetamido}-8-oxo-3-[2-(pyridin-3-yl-amino)-thiazol-5-yl]-5-thia-1-azabicyclo[4.2.0]oct-2-ene 5-oxideYield 5.1%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Conditions

Temperature
0 °C

Procedure

A solution of m-chloroperbenzoic acid (2.59 g) in methylene chloride (52 cc) is run, in the course of 30 minutes, into a solution, cooled to 0° C., of the syn isomer of 2-benzhydryloxycarbonyl-7-{2-[(2-t-butoxycarbonylprop-2-yl)-oxyimino]-2-(2-tritylaminothiazol-4-yl)acetamido}-8-oxo-3-[2-(pyridin-3-yl-amino)-thiazol-5-yl]-5-thia-1-azabicyclo[4.2.0]oct-2-ene (13.46 g) in methylene chloride (123 cc). The mixture is stirred for 15 minutes at 0° C. and the reaction solution is then diluted with methylene chloride (200 cc). The mixture is washed successively with a semi-saturated solution of sodium bicarbonate (200 cc) and distilled water (2×200 cc). The organic phase is then dried over anhydrous magnesium sulphate and filtered and the filtrate is then concentrated under reduced pressure (100 mm Hg; 13.3 kPa) at 30° C. The residue is purified by chromatography on a column (height=29 cm, diameter=5.8 cm) containing silica gel (0.04-0.06 mm), elution being carried out under a pressure of 0.4 bar with a mixture of cyclohexane and ethyl acetate (10/90 by volume) (2 liters) and 125 cc fractions being collected. Fractions 11 to 15 are combined and concentrated to dryness under reduced pressure (30 mm Hg; 4 kPa) at 30° C. to give the syn isomer of 2-benzhydryloxycarbonyl-7-{2-[(2-t-butoxycarbonylprop-2-yl)-oxyimino]-2-(2-tritylaminothiazol-4-yl)-acetamido}-8-oxo-3-[2-(pyridin-3-yl-amino)-thiazol-5-yl]-5-thia-1-azabicyclo[4.2.0]oct-2-ene 5-oxide (0.70 g) in the form of a hard yellow foam.

Workup

  1. customis run, in the course of 30 minutes, into a solution
  2. washThe mixture is washed successively with a semi-saturated solution of sodium bicarbonate (200 cc)
  3. distillationdistilled water (2×200 cc)
  4. dry with materialThe organic phase is then dried over anhydrous magnesium sulphate
  5. filtrationfiltered
  6. concentrationthe filtrate is then concentrated under reduced pressure (100 mm Hg; 13.3 kPa) at 30° C
  7. customThe residue is purified by chromatography on a column (height=29 cm, diameter=5.8 cm)
  8. additioncontaining
  9. washsilica gel (0.04-0.06 mm), elution
  10. additionbeing carried out under a pressure of 0.4 bar with a mixture of cyclohexane and ethyl acetate (10/90 by volume) (2 liters) and 125 cc fractions
  11. custombeing collected
  12. concentrationconcentrated to dryness under reduced pressure (30 mm Hg; 4 kPa) at 30° C.

Sources & evidence

ORD record
ord-78c59c98e61346f697b71c4b832f35a5
Source dataset
uspto-grants-1985_04
Patent number
US04508717

Reaction notes

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