Thiophenol → HCID 131710157, compound

HRID 1606519Notes

Reaction equation

HRID 1606519 reaction equation
[S:1]1[CH:5]=[CH:4][CH:3]=[C:2]1[CH2:6][C:7]([NH:9][CH:10]1[C:36](=[O:37])[N:12]2[CH:13]([C:20]([O:22][CH:23]([C:30]3[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=3)[C:24]3[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=3)=[O:21])[C:14]([C:17]([OH:19])=O)=[CH:15][S:16][C@H:11]12)=[O:8].CN1CCOCC1.ClC(OCC)=O.[C:51]1([SH:57])[CH:56]=[CH:55][CH:54]=[CH:53][CH:52]=1>C(OCC)(=O)C.C(Cl)Cl>[S:1]1[CH:5]=[CH:4][CH:3]=[C:2]1[CH2:6][C:7]([NH:9][CH:10]1[C:36](=[O:37])[N:12]2[CH:13]([C:20]([O:22][CH:23]([C:30]3[CH:31]=[CH:32][CH:33]=[CH:34][CH:35]=3)[C:24]3[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=3)=[O:21])[C:14]([C:17]([S:57][C:51]3[CH:56]=[CH:55][CH:54]=[CH:53][CH:52]=3)=[O:19])=[CH:15][S:16][C@H:11]12)=[O:8]

Participants

7

Reactant 4

HCID 7969ThiophenolHCID 79724-MethylmorpholineHCID 10928Ethyl chloroformateHCID 70635149HCID 70635149, compound

Product 1

HCID 131710157HCID 131710157, compoundYield 66.5%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-10 °C

Procedure

To a cooled (-10° C.), stirred solution of benzhydryl 7-(2-thienylacetamido)-3-carboxy-2-cephem-4-carboxylate (.267 g., 0.5 mmol.) in 25 ml. of methylene chloride under an argon atmosphere was added 0.152 g. (1.5 mmol.) of N-methylmorpholine. The reaction mixture was then cooled to -20° C. and 0.135 g. (1.25 mmol.) of ethyl chloroformate was added. The mixture was stirred at 0° for 30 minutes after which time the mixture was cooled to -10° and 0.165 g. of thiophenol was added. After stirring the reaction mixture at 0° for 1 hour, ethyl acetate was added, and the resulting solution was washed successively with aqueous sodium bicarbonate, water, and brine and then dried over anhydrous sodium sulfate. Evaporation in vacuo to dryness gave a product which was chromatographed on a silica gel column using a tolueneethyl acetate gradient to provide 0.208 g. (66.5%) of the title product: ir (CHCl3) 1798 cm-1 (β-lactam C = 0); nmr (CDCl3) 3.80 (s, 2, side chain CH2), 5.06 (d, 1, J = 4.0 Hz, C6 --H), 5.42 (q, 1, J = 4.0 and 8.0 Hz, C7 --H), 5.70 (s, 1, C4 --H) and 7.87 ppm (s, 1, C 2 --H).

Workup

  1. temperatureThe reaction mixture was then cooled to -20° C.
  2. temperaturewas cooled to -10°
  3. stirringAfter stirring the reaction mixture at 0° for 1 hour
  4. washthe resulting solution was washed successively with aqueous sodium bicarbonate, water, and brine
  5. dry with materialdried over anhydrous sodium sulfate
  6. customEvaporation in vacuo to dryness
  7. customgave a product which
  8. customwas chromatographed on a silica gel column
  9. customto provide 0.208 g

Sources & evidence

ORD record
ord-29dec73603ad411d89bdd48f9a4a52c3
Source dataset
uspto-grants-1976_04
Patent number
US03953436

Reaction notes

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