Bromine → 1-(2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosyl)-3-(5-bromo-2-thienylmethyl)-4-methylbenzene

HRID 221013Notes

Reaction equation

HRID 221013 reaction equation
[C:1]([O:4][C@@H:5]1[C@@H:10]([O:11][C:12](=[O:14])[CH3:13])[C@H:9]([O:15][C:16](=[O:18])[CH3:17])[C@@H:8]([CH2:19][O:20][C:21](=[O:23])[CH3:22])[O:7][C@H:6]1[C:24]1[CH:29]=[CH:28][C:27]([CH3:30])=[C:26]([CH2:31][C:32]2[S:33][CH:34]=[CH:35][CH:36]=2)[CH:25]=1)(=[O:3])[CH3:2].[Br:37]Br.S([O-])([O-])(=O)=S.[Na+].[Na+].C(=O)([O-])O.[Na+]>C(Cl)(Cl)Cl>[C:1]([O:4][C@@H:5]1[C@@H:10]([O:11][C:12](=[O:14])[CH3:13])[C@H:9]([O:15][C:16](=[O:18])[CH3:17])[C@@H:8]([CH2:19][O:20][C:21](=[O:23])[CH3:22])[O:7][C@H:6]1[C:24]1[CH:29]=[CH:28][C:27]([CH3:30])=[C:26]([CH2:31][C:32]2[S:33][C:34]([Br:37])=[CH:35][CH:36]=2)[CH:25]=1)(=[O:3])[CH3:2]

Participants

6

Reactant 4

HCID 24408BromineHCID 24477Sodium ThiosulfateHCID 516892Sodium BicarbonateHCID 666079831-(2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosyl)-4-methyl-3(2-thienylmethyl)benzene

Product 1

HCID 666079031-(2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosyl)-3-(5-bromo-2-thienylmethyl)-4-methylbenzeneYield 55.9%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent2×

Conditions

Temperature
0 °C

Procedure

1-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-4-methyl-3-(2-thienylmethyl)benzene (11.08 g) obtained in Example 158-(1) was dissolved in chloroform (100 ml), and added dropwise thereto at 0° C. was a solution of bromine (3.71 g) in chloroform (13 ml). The mixture was stirred at 0° C. for 1.5 hours, and then, at room temperature for 1 hour, and the mixture was poured into a 10% aqueous sodium thiosulfate solution and a saturated aqueous sodium hydrogen carbonate solution. The mixture was extracted twice with chloroform, washed with brine, and dried over magnesium sulfate. The solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography (hexane:ethyl acetate=80:20-67:33) to give 1-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyl)-3-(5-bromo-2-thienylmethyl)-4-methylbenzene (7.13 g) as a colorless solid. APCI-Mass m/Z 614/616 (M+NH4). (2) The above 1-(2,3,4,6-tetra-O-acetyl-β-Dglucopyranosyl)-3-(5-bromo-2-thienylmethyl)-4-methylbenzene was treated in a manner similar to Example 106-(3) to give the desired 1-(β-D-glucopyranosyl)-3-(5-bromo-2-thienylmethyl)-4-methylbenzene as colorless powder. APCI-Mass m/Z 446/448 (m+NH4).

Workup

  1. additionadded dropwise
  2. customat 0° C.
  3. waitat room temperature for 1 hour
  4. extractionThe mixture was extracted twice with chloroform
  5. washwashed with brine
  6. dry with materialdried over magnesium sulfate
  7. customThe solvent was evaporated under reduced pressure
  8. customthe residue was purified by silica gel column chromatography (hexane:ethyl acetate=80:20-67:33)

Sources & evidence

ORD record
ord-0784101da5104c7d8eef619c6e0c1afe
Source dataset
uspto-grants-2012_06
Patent number
US08202984B2

Reaction notes

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