Chloroform → HCID 131710677, compound

HRID 596844Notes

Reaction equation

HRID 596844 reaction equation
[S:1]1[CH:5]=[CH:4][CH:3]=[C:2]1[CH2:6][C:7]([NH:9][CH:10]1[C:37](=[O:38])[N:12]2[CH:13]([C:21]([O:23][CH:24]([C:31]3[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=3)[C:25]3[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=3)=[O:22])[C:14]([C:17](=[O:20])[CH2:18][CH3:19])=[CH:15][S:16][C@H:11]12)=[O:8].C(Cl)(Cl)Cl.ClC1C=CC=C(C(OO)=O)C=1>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:37](=[O:38])[N:12]2[C:13]([C:21]([O:23][CH:24]([C:25]3[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=3)[C:31]3[CH:32]=[CH:33][CH:34]=[CH:35][CH:36]=3)=[O:22])=[C:14]([C:17](=[O:20])[CH2:18][CH3:19])[CH2:15][S:16][C@H:11]12)=[O:8]

Participants

5

Reactant 3

HCID 6212Chloroform2×HCID 70297m-Chloroperbenzoic acidHCID 131710678HCID 131710678, compound

Product 1

HCID 131710677HCID 131710677, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
5 °C

Procedure

To a cooled (5° C.), stirred solution of 0.363 g. of benzhydryl 7-(2-thienylacetamido)-3-propionyl-2-cephem-4-carboxylate in 30 ml. of chloroform was added dropwise a solution of 0.149 g. of 85 percent m-chloroperbenzoic acid in 3 ml. of chloroform. The reaction was allowed to stir with cooling for one hour, after which time it was washed twice with aqueous sodium bicarbonate solution and twice with brine and then dried over anhydrous sodium sulfate. The solution was then evaporated in vacuo to provide a gel which was dissolved in 15 ml. of dimethylformamide. This solution was cooled for five minutes in an ice bath, removed from the ice bath, and subsequently treated with 0.145 ml. of phosphorous trichloride. This mixture was allowed to stir at room temperature for 45 minutes, after which time it was transferred to a separatory funnel with the aid of ethyl acetate and washed successively with aqueous sodium bicarbonate (2X), water (4X), and brine (2X) and then dried over anhydrous sodium sulfate. Evaporation in vacuo to dryness gave a product which when chromatographed on silica gel using a toluene-ethyl acetate gradient provided 0.267 g. (74 percent) of the title product as a white solid which crystallized as white needles from methylene chloride/hexane (m.p. 220°-221° decomp.): nmr (DMSO d-6) δ0.80 (t, 3, J = 7.0 Hz, --CH2CH3), 2.5 (m), 3.84 (s, 2, side chain CH2), 5.22 (d, 1, J = 4.0 Hz, C6 --H), 5.92 (q, 1, J = 4.0 and 8.0 Hz, C7 --H).

Workup

  1. stirringto stir
  2. temperaturewith cooling for one hour
  3. washafter which time it was washed twice with aqueous sodium bicarbonate solution and twice with brine
  4. dry with materialdried over anhydrous sodium sulfate
  5. customThe solution was then evaporated in vacuo
  6. customto provide a gel which
  7. dissolutionwas dissolved in 15 ml
  8. temperatureThis solution was cooled for five minutes in an ice bath
  9. customremoved from the ice bath
  10. additionsubsequently treated with 0.145 ml
  11. stirringto stir at room temperature for 45 minutes
  12. customafter which time it was transferred to a separatory funnel with the aid of ethyl acetate
  13. washwashed successively with aqueous sodium bicarbonate (2X), water (4X), and brine (2X)
  14. dry with materialdried over anhydrous sodium sulfate
  15. customEvaporation in vacuo to dryness
  16. customgave a product which when
  17. customchromatographed on silica gel using a toluene-ethyl acetate gradient
  18. customprovided 0.267 g
  19. custom(74 percent) of the title product as a white solid which crystallized as white needles from methylene chloride/hexane (m.p. 220°-221° decomp.)

Sources & evidence

ORD record
ord-f5cd95a16adb4a1fbbfe263d23b35814
Source dataset
uspto-grants-1977_03
Patent number
US04012380

Reaction notes

Loading…