Chloroform → HCID 70635581, compound

HRID 596828Notes

Reaction equation

HRID 596828 reaction equation
[S:1]1[CH:5]=[CH:4][CH:3]=[C:2]1[CH2:6][C:7]([NH:9][CH:10]1[C:39](=[O:40])[N:12]2[CH:13]([C:23]([O:25][CH:26]([C:33]3[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=3)[C:27]3[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=3)=[O:24])[C:14]([C:17]([O:19][CH2:20][CH2:21][Br:22])=[O:18])=[CH:15][S:16][C@H:11]12)=[O:8].C(Cl)(Cl)Cl.ClC1C=CC=C(C(OO)=O)C=1.P(Cl)(Cl)Cl>C(OCC)(=O)C.CN(C)C=O>[S:1]1[CH:5]=[CH:4][CH:3]=[C:2]1[CH2:6][C:7]([NH:9][CH:10]1[C:39](=[O:40])[N:12]2[C:13]([C:23]([O:25][CH:26]([C:27]3[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=3)[C:33]3[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=3)=[O:24])=[C:14]([C:17]([O:19][CH2:20][CH2:21][Br:22])=[O:18])[CH2:15][S:16][C@H:11]12)=[O:8]

Participants

7

Reactant 4

HCID 6212Chloroform2×HCID 24387Phosphorus trichlorideHCID 70297m-Chloroperbenzoic acidHCID 70636258HCID 70636258, compound

Product 1

HCID 70635581HCID 70635581, compoundYield 53%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
5 °C

Procedure

To a cooled (5° C.) stirred solution of benzhydryl 7-(2-thienylacetamido)-3-(2-bromoethoxycarbonyl)-2-cephem-4-carboxylate (0.29 g., 0.453 mmol.) in 30 ml. chloroform was added 85% m-chloroperbenzoic acid (0.101 g., .497 mmol.) in 3 ml. chloroform. The mixture was allowed to stir with cooling for 30 minutes, and then was washed with sodium bicarbonate solution (2X) and sodium chloride solution and dried over Na2SO4. Evaporation in vacuo gave 301 mg. of the Δ3 sulfoxide. The sulfoxide was dissolved in 25 ml. dimethylformamide, cooled briefly, and then treated with 0.06 ml. (0.678 mmol. 1.5 eq.) phosphorous trichloride. The mixture was allowed to stir at ambient temperature for 30 minutes. Ethyl acetate was added to the reaction mixture, and then it was washed successively with water (2X), aqueous sodium bicarbonate (2X) and brine. The organic layer was dried over anhydrous Na2SO4 and evaporated in vacuo to dryness. The crude product was chromatographed on 5 g. of silica gel using a benzene-ethyl acetate gradient providing benzhydryl 7-(2-thienylacetamido)-3-(2-bromoethoxycarbonyl)-3-cephem-4-carboxylate (0.154 g., 53%) as a colorless solid: ir (CHCl3) 1799 cm-1 (β-lactam C = O); nmr (DMSO-d6) δ3.34 (m, 2, CH2Br), 3.76 (s, 2, side chain CH2), 3.8-4.4 (m), 5.20 (d, 1, J = 5.0 Hz, C6 --H) and 5.86 (q, 1, J = 5.0 and 9.0 Hz, C7 --H).

Workup

  1. temperaturewith cooling for 30 minutes
  2. washwas washed with sodium bicarbonate solution (2X) and sodium chloride solution
  3. dry with materialdried over Na2SO4
  4. customEvaporation in vacuo
  5. customgave 301 mg
  6. additiontreated with 0.06 ml
  7. stirringto stir at ambient temperature for 30 minutes
  8. washit was washed successively with water (2X), aqueous sodium bicarbonate (2X) and brine
  9. dry with materialThe organic layer was dried over anhydrous Na2SO4
  10. customevaporated in vacuo to dryness
  11. customThe crude product was chromatographed on 5 g

Sources & evidence

ORD record
ord-3ddf1cc01f13407984825832fbd6e4e3
Source dataset
uspto-grants-1977_03
Patent number
US04012380

Reaction notes

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