Imidazole → HCID 131716793, compound

HRID 981551Notes

Reaction equation

HRID 981551 reaction equation
[C:1]1(=[O:14])[O:13][C@@H:6]([C@@H:7]([C@@H:9]([CH2:11][OH:12])[OH:10])[OH:8])[C@@H:4]([OH:5])[C@H:2]1[OH:3].N1C=CN=C1.CN(C=O)C.[C:25]([Si:29](Cl)([C:36]1[CH:41]=[CH:40][CH:39]=[CH:38][CH:37]=1)[C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1)([CH3:28])([CH3:27])[CH3:26]>C(OCC)(=O)C.O>[Si:29]([O:12][CH2:11][C@@H:9]([OH:10])[C@@H:7]([OH:8])[C@@H:6]1[O:13][C:1](=[O:14])[C@H:2]([OH:3])[C@@H:4]1[OH:5])([C:25]([CH3:28])([CH3:27])[CH3:26])([C:36]1[CH:37]=[CH:38][CH:39]=[CH:40][CH:41]=1)[C:30]1[CH:35]=[CH:34][CH:33]=[CH:32][CH:31]=1

Participants

7

Reactant 4

HCID 795ImidazoleHCID 6228DimethylformamideHCID 94078tert-ButyldiphenylchlorosilaneHCID 2723843Heptono-1,4-lactone

Product 1

HCID 131716793HCID 131716793, compoundYield 55%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent2×

Conditions

Temperature
0 °C

Procedure

D-glycero-D-gulo-Heptono-1,4-lactone (6) (10 g, 48.08 mmol) and imidazole (4.98 g, 1.5 equiv) were added to dry DMF (25 ml) and the mixture stirred at 0° C. under nitrogen. tert-Butylchlorodiphenylsilane (13.74 ml, 1.1 equiv) was added slowly, after which the reaction mixture was allowed to warm up to room temperature over three hours. After 22 hours, t.l.c. (eluant ethyl acetate) indicated that the mixture contained the desired monosilyl derivative (Rf 0.65) and a smaller amount of another carbohydrate derivative (Rf 0.9). The crude reaction mixture was shaken with water (50 ml), causing a white precipitate to form. Ethyl acetate (90 ml) was added and the layers separated after shaking. The aqueous layer was back-extracted with more ethyl acetate (25 ml). The combined organic extracts were washed with saturated aqueous sodium chloride (4×25 ml) and dried (magnesium sulphate). Evaporation of the solvent followed by dry column chromatography (eluant hexane:ethyl acetate, 2:1, increasing the eluant polarity with each fraction), yielding 7 -O-tert-butyldiphenylsilyl-D-glycero-D-gulo-heptono-1,4-lactone (7) (11.02 g, 55%) as a white solid, m.p. 54°-57° C. (Found: C, 61.58; H, 6.86%. C23H30O7Si requires: C, 61.87; H, 6.77%); [α]d20 -10.56° (c, 0.99 in CHCl3); vmax (CHCl3) 3410 (broad, OH) and 1790 cm-1 (γ-lactone); and 2,7-di-O-tert-butyldiphenylsilyl-D-glycero-D-gulo-heptono-1,4-lactone (8) (5.94 g, 18%) as a colorless, viscous oil [α]D20 -4.08° (c, 1.20 in CHCl3); vmax (CHCl3) 3440 (broad, OH) and 1790 cm-1 (γ-lactone).

Workup

  1. temperatureto warm up to room temperature over three hours
  2. customThe crude reaction mixture
  3. customto form
  4. customthe layers separated
  5. stirringafter shaking
  6. extractionThe aqueous layer was back-extracted with more ethyl acetate (25 ml)
  7. washThe combined organic extracts were washed with saturated aqueous sodium chloride (4×25 ml)
  8. dry with materialdried (magnesium sulphate)
  9. customEvaporation of the solvent
  10. dry with materialby dry column chromatography (eluant hexane
  11. temperatureethyl acetate, 2:1, increasing the eluant polarity with each fraction),

Sources & evidence

ORD record
ord-488d1087529c469dbf138b57bb0f5509
Source dataset
uspto-grants-1991_02
Patent number
US04992460

Reaction notes

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