Dicyclohexylcarbodiimide → HCID 86736633, compound

HRID 1862888Notes

Reaction equation

HRID 1862888 reaction equation
[CH2:1]1[C:4](=[O:5])[N:3]2[C@@H:6](C(O)=O)/[C:7](/[O:11][C@H:2]12)=[CH:8]/[CH2:9][OH:10].[Cl:15][C:16]1[CH:21]=[CH:20][CH:19]=[C:18]([C:22]([O:24]O)=[O:23])[CH:17]=1.C1(N=C=NC2CCCCC2)CCCCC1>COCCOC.C(Cl)Cl.C(OCC)(=O)C>[Cl:15][C:16]1[CH:17]=[C:18]([CH:19]=[CH:20][CH:21]=1)[C:22]([O:24][C@@H:6]1[N:3]2[C@H:2]([O:11]/[C:7]/1=[CH:8]\[CH2:9][OH:10])[CH2:1][C:4]2=[O:5])=[O:23]

Participants

6

Reactant 3

HCID 10868DicyclohexylcarbodiimideHCID 70297m-Chloroperbenzoic acidHCID 5280980Clavulanic Acid

Product 1

HCID 86736633HCID 86736633, compoundYield 11.4%

Reagents, catalysts & solvents 2

HCID 8857Ethyl AcetateSolventHCID 86634710Dimethoxyethane methylene chlorideSolvent

Procedure

Clavulanic acid (containing ca 0.5 meq. ethyl acetate; 410 mg., 1.7 mmole) was dissolved in dry 1,2-dimethoxyethane/methylene chloride (1:1, 10 ml.). The solution was stirred and ice-cooled with exclusion of moisture while m-chloroperbenzoic acid (380 mg.) and dicyclohexylcarbodiimide (400 mg.) were added. The mixture was stirred with exclusion of moisture for 3 hours at 0° and then for 15 hours at room temperature. The mixture was diluted with ethyl acetate (50 ml.) and was filtered. The filtrate was washed with saturated sodium bicarbonate solution and then with saturated brine. The solution was dried (magnesium sulphate and the solvent was evaporated under reduced pressure to yield a yellow gum. The gum was chromatographed on silica gel (25 g.) using ethyl acetate/petroleum ether (b.p. 60°-80°) to give the title compound as a colourless gum (60 mg., 11% yield). [α]D21 +88.8° (c=1.0 CHCl3). νmax (CHCl3): 3320 (hydroxyl OH), 1805 (β-lactam C=O), 1730 (ester C=O), 1700 (olefinic C=C)cm-1. δ (CDCl3): 2.28 (br.s, 1H, OH), 3.11 (d, J 16 Hz, 1H, C(6)H), 3.48 (dd, J 16, J' 2 Hz, 1H, C(6)H), 4.26 (d, J 7 Hz, 2H, CH2O), 5.03 (t, J 7 Hz, 1H, olefinic H), 5.77 (d, J 2 Hz, 1H, C(5)H), 6.70 (s, 1H, C(2)H), 7.25-7.60 (m, 2H, Ar-H), 7.80-8.00 (m, 2H, Ar-H).

Workup

  1. additionwere added
  2. stirringThe mixture was stirred with exclusion of moisture for 3 hours at 0°
  3. filtrationwas filtered
  4. washThe filtrate was washed with saturated sodium bicarbonate solution
  5. dry with materialThe solution was dried (magnesium sulphate
  6. customthe solvent was evaporated under reduced pressure
  7. customto yield a yellow gum
  8. customThe gum was chromatographed on silica gel (25 g.)

Sources & evidence

ORD record
ord-7ba42693ccec42dab00e46cdbd79ddb4
Source dataset
uspto-grants-1979_09
Patent number
US04166904

Reaction notes

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