m-Chloroperbenzoic acid → HCID 54226983, compound

HRID 1450206Notes

Reaction equation

HRID 1450206 reaction equation
[C:1]1([CH2:7][C:8]([NH:10][C@@H:11]2[C:37](=[O:38])[N:13]3[CH:14]([C:25]([O:27][CH2:28][C:29]4[CH:34]=[CH:33][C:32]([O:35][CH3:36])=[CH:31][CH:30]=4)=[O:26])[C:15]([CH:18]4[CH2:22][CH2:21][CH2:20][S:19]4(=[O:24])=[O:23])=[CH:16][S:17][C@H:12]23)=[O:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.ClC1C=CC=C(C(OO)=[O:47])C=1>ClCCl>[O:47]=[S:17]1[C@@H:12]2[C@H:11]([NH:10][C:8](=[O:9])[CH2:7][C:1]3[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=3)[C:37](=[O:38])[N:13]2[C:14]([C:25]([O:27][CH2:28][C:29]2[CH:34]=[CH:33][C:32]([O:35][CH3:36])=[CH:31][CH:30]=2)=[O:26])=[C:15]([CH:18]2[CH2:22][CH2:21][CH2:20][S:19]2(=[O:24])=[O:23])[CH2:16]1

Participants

4

Reactant 2

HCID 70297m-Chloroperbenzoic acidHCID 131719839HCID 131719839, compound

Product 1

HCID 54226983HCID 54226983, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

4-Methoxybenzyl (6R, 7R)-7-phenylacetamido-3-(1,1-dioxotetrahydrothien-2-yl)ceph-2-em-4-carboxylate (0.973 g) in dichloromethane (20 ml) was cooled in ice-water and treated with 3-chloroperbenzoic acid (0.343 g) and warmed to room temperature for 1 h. The solution was washed with saturated sodium metabisulphite, brine and then dried. Afar removal of solvent, the residue was flash chromatographed on silica gel eluting initially with 80, 90% ethyl acetate-hexane and then ethyl acetate. The first product eluted was the least polar isomer of the title compound, obtained as a pale yellow foam, (0.309 g, 31%); 5H (CDCl3) 2.02-2.39 (4H, m), 2.91-3.03 (1H, m), 3.11-3.20 (1H, m), 3.49 and 3.79 (2H, ABq, J 8.6 Hz), 3.58 and 3.66 (2H, ABq, J 15.9 Hz), 3.81 (3H, s), 4.52 (1H, d, J 4.7 Hz), 5.02 (1H, dd, J 7.3, 11.2 Hz), 5.20 and 5.26 (2H, ABq, J 11.4 Hz), 6.03 (1H, dd, J 4.7, 10.0 hz), 6.69 (1H, d, J 10.0 Hz), 6.90 (2H, d, J 8.7 Hz) and 7.26-7.39 (7H, m). Further elution with 10% ethanol-ethyl acetate provided the second more polar isomer as an off white, amorphous solid, (0.166g, 17%); 5H (CDCl3) 1.90-2.30 (4H, m), 2.88-3.20 (2H, m), 3.06 a 4.13 (2H, ABq, J 18.4 Hz), 3.57 (2H, s), 3.77 (3H, s), 4.43 (1H, d, J 4.1 Hz), 4.61 (1H, t, J 8.3 Hz), 5.18 (3H, m), 5.98 (1H, dd J 4.8, 9.6 Hz), 6.84 (2H, d, J 8.7 Hz) and 7.17-7.36 (7H, m).

Workup

  1. washThe solution was washed with saturated sodium metabisulphite, brine
  2. customdried
  3. customAfar removal of solvent
  4. customchromatographed on silica gel eluting initially with 80, 90% ethyl acetate-hexane
  5. washThe first product eluted
  6. customobtained as a pale yellow foam, (0.309 g, 31%)
  7. washFurther elution with 10% ethanol-ethyl acetate
  8. customprovided the second more polar isomer as an off white, amorphous solid, (0.166g, 17%)

Sources & evidence

ORD record
ord-832803eb1fca477bb38fdbd00d147715
Source dataset
uspto-grants-1997_02
Patent number
US05602117

Reaction notes

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