Toluene → HCID 10188276, compound

HRID 2307740Notes

Reaction equation

HRID 2307740 reaction equation
[C:1]([O:7][C@@H:8]1[C@@H:14]([O:15][C:16](=[O:21])[C:17]([CH3:20])([CH3:19])[CH3:18])[C@H:13]([O:22][C:23](=[O:28])[C:24]([CH3:27])([CH3:26])[CH3:25])[C@@H:12]([CH2:29][O:30][C:31](=[O:36])[C:32]([CH3:35])([CH3:34])[CH3:33])[O:11][CH:9]1[OH:10])(=[O:6])[C:2]([CH3:5])([CH3:4])[CH3:3].CC(C)([O-])C.[K+].C([O:50][C:51](=[O:54])[CH2:52]Br)C1C=CC=CC=1.C1(C)C=CC=CC=1>[Cl-].C([N+](CCCC)(CCCC)CCCC)CCC.CC(N(C)C)=O>[C:1]([O:7][C@@H:8]1[C@@H:14]([O:15][C:16](=[O:21])[C:17]([CH3:18])([CH3:20])[CH3:19])[C@H:13]([O:22][C:23](=[O:28])[C:24]([CH3:27])([CH3:26])[CH3:25])[C@@H:12]([CH2:29][O:30][C:31](=[O:36])[C:32]([CH3:35])([CH3:34])[CH3:33])[O:11][CH:9]1[O:10][CH2:52][C:51]([OH:54])=[O:50])(=[O:6])[C:2]([CH3:5])([CH3:4])[CH3:3]

Participants

7

Reactant 4

HCID 1140TolueneHCID 62576Benzyl bromoacetateHCID 11114005HCID 11114005, compoundHCID 23665647Potassium tert-butoxide

Product 1

HCID 10188276HCID 10188276, compound

Reagents, catalysts & solvents 2

HCID 70681Tetrabutylammonium ChlorideCatalystHCID 31374DimethylacetamideSolvent

Conditions

Temperature
0 °C

Procedure

A mixture that consists of 54.1 g (100 mmol) of 2,3,4,6-tetra-O-pivaloyl-glucopyranose, 1.39 g (5 mmol) of tetrabutylammonium chloride and 11.22 g of potassium-t-butoxide (100 mmol) in 500 ml of dimethylacetamide is cooled to 0° C. At 0° C., 34.36 g (150 mmol) of bromoacetic acid benzyl ester is added in drops over 20 minutes while being stirred vigorously. It is stirred for 0.5 hour at 0° C. 250 toluene is added, the organic phase is separated, it is filtered, and it is evaporated to the dry state in a vacuum. The residue is taken up in 400 ml of methanol, mixed with 5 g of palladium (10%) on activated carbon and hydrogenated until hydrogen absorption is completed. Catalyst is filtered out, it is rewashed with a little methanol, and the combined organic solutions are evaporated to the dry state in a vacuum. The residue is chromatographed on silica gel (mobile solvent: dichloromethane/n-hexane/ethanol/acetic acid=20:5:3:0.5). The product-containing fractions are concentrated by evaporation, dissolved in 400 ml of ethyl acetate and shaken out three times with 200 ml of water. Then, the organic phase is separated and evaporated to the dry state in a vacuum.

Workup

  1. stirringIt is stirred for 0.5 hour at 0° C
  2. customthe organic phase is separated
  3. filtrationit is filtered
  4. customit is evaporated to the dry state in a vacuum
  5. additionmixed with 5 g of palladium (10%) on activated carbon and hydrogenated until hydrogen absorption
  6. filtrationCatalyst is filtered out
  7. customthe combined organic solutions are evaporated to the dry state in a vacuum
  8. customThe residue is chromatographed on silica gel (mobile solvent: dichloromethane/n-hexane/ethanol/acetic acid=20:5:3:0.5)
  9. concentrationThe product-containing fractions are concentrated by evaporation
  10. dissolutiondissolved in 400 ml of ethyl acetate
  11. stirringshaken out three times with 200 ml of water
  12. customThen, the organic phase is separated
  13. customevaporated to the dry state in a vacuum

Sources & evidence

ORD record
ord-b211f513ce094bb1ac894bd90d2536b1
Source dataset
uspto-grants-2004_12
Patent number
US06831164B2

Reaction notes

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