m-Chloroperbenzoic acid → HCID 54375593, compound

HRID 1980419Notes

Reaction equation

HRID 1980419 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]([CH2:41][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:79])[C:50](=[N:76][O:77][CH3:78])[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:80])=[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]([CH2:41][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:79])[C:50](=[N:76][O:77][CH3:78])[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:80])=[O:27])([C:13]1[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1)[C:19]1[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1

Participants

4

Reactant 2

HCID 70297m-Chloroperbenzoic acidHCID 54463668HCID 54463668, compound

Product 1

HCID 54375593HCID 54375593, compoundYield 60.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Conditions

Temperature
3 °C

Procedure

A solution of m-chloroperbenzoic acid (1.46 g) in methylene chloride (30 cc) is added dropwise, in the course of 15 minutes, to a solution, cooled to 3° C., of the syn isomer of 2-benzhydryloxycarbonyl-7-[2-methoxyimino-2-(2-tritylaminothiazol-4-yl)-acetamido]-8-oxo-3-[2-(pyridin-3-yl-methyl)-thiazol-5-yl]-5-thia-1-azabicyclo[4.2.0]oct-2-ene (8.30 g) in methylene chloride (85 cc). The mixture is stirred at 3° C. for 4 hours 30 minutes and then diluted with methylene chloride (100 cc). The organic phase is washed successively with a semi-saturated solution of sodium bicarbonate (150 cc), distilled water (100 cc) and then a saturated solution of sodium chloride (100 cc). It is then dried over anhydrous sodium sulphate; the mixture is filtered and the filtrate is concentrated to dryness under reduced pressure (30 mm Hg; 4 kPa) at 30° C. The residue is purified by chromatography on a column (height=30 cm, diameter=2.5 cm) containing silica gel (0.05-0.2 mm), elution being carried out with ethyl acetate (1.2 liters) and then with a mixture of ethyl acetate and methanol (95/5 by volume) (0.8 liter) and 60 cc fractions being collected. Fractions 19 to 33, containing the pure product, are combined and concentrated under reduced pressure (30 mm Hg; 4 kPa) at 30° C. to give the syn isomer of 2-benzhydryloxycarbonyl-7-[2-methoxyimino-2-(2-tritylaminothiazol-4-yl)-acetamido]-8-oxo-3-[2-(pyridin-3-yl-methyl)-thiazol- 5-yl]-5-thia-1-azabicyclo[4.2.0]oct-2-ene 5-oxide (5 g) in the form of a hard yellow foam.

Workup

  1. washThe organic phase is washed successively with a semi-saturated solution of sodium bicarbonate (150 cc)
  2. distillationdistilled water (100 cc)
  3. dry with materialIt is then dried over anhydrous sodium sulphate
  4. filtrationthe mixture is filtered
  5. concentrationthe filtrate is concentrated to dryness under reduced pressure (30 mm Hg; 4 kPa) at 30° C
  6. customThe residue is purified by chromatography on a column (height=30 cm, diameter=2.5 cm)
  7. additioncontaining
  8. washsilica gel (0.05-0.2 mm), elution
  9. additionwith a mixture of ethyl acetate and methanol (95/5 by volume) (0.8 liter) and 60 cc fractions
  10. custombeing collected
  11. additionFractions 19 to 33, containing the pure product
  12. concentrationconcentrated under reduced pressure (30 mm Hg; 4 kPa) at 30° C.

Sources & evidence

ORD record
ord-cd50715e304145ef90654c9fcf8dfa88
Source dataset
uspto-grants-1985_04
Patent number
US04508717

Reaction notes

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