Trimethylsilyl triflate → HCID 53919135, compound

HRID 1281697Notes

Reaction equation

HRID 1281697 reaction equation
[Br:1][C:2]1[NH:3][C:4]2[CH:10]=[C:9]([Cl:11])[C:8]([Cl:12])=[CH:7][C:5]=2[N:6]=1.C/C(/O[Si](C)(C)C)=N\[Si](C)(C)C.FC(F)(F)S(O[Si](C)(C)C)(=O)=O.C(O[C@H:41]1[O:58][CH2:57][C@H:52]([O:53][C:54](=[O:56])[CH3:55])[C@@H:47]([O:48][C:49](=[O:51])[CH3:50])[C@@H:42]1[O:43][C:44](=[O:46])[CH3:45])(=O)C.C(=O)(O)[O-].[Na+]>ClCCCl>[Br:1][C:2]1[N:3]([C@H:57]2[O:58][CH2:41][C@H:42]([O:43][C:44](=[O:46])[CH3:45])[C@@H:47]([O:48][C:49](=[O:51])[CH3:50])[C@@H:52]2[O:53][C:54](=[O:56])[CH3:55])[C:4]2[CH:10]=[C:9]([Cl:11])[C:8]([Cl:12])=[CH:7][C:5]=2[N:6]=1

Participants

7

Reactant 5

HCID 65367Trimethylsilyl triflateHCID 4660172-bromo-5,6-dichloro-1H-benzimidazoleHCID 516892Sodium BicarbonateHCID 6913588N,O-bis(trimethylsilyl)acetamideHCID 26175765HCID 26175765, compound

Product 1

HCID 53919135HCID 53919135, compoundYield 56%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Conditions

Temperature
50 °C

Procedure

As described in General Procedure III, 2-bromo-5,6-dichlorobenzimidazole (1.0 g, 3.8 mmol), N,O-bis(trimethylsilyl) acetamide (Aldrich, 1.0 ml, 4.1 mmol), and 1,2-dichloroethane (Aldrich Sure Seal, 25 ml) were combined and refluxed under nitrogen for 0.5 h. The solution was cooled to 50° C. and trimethylsilyl trifluoromethanesulfonate (Aldrich, 0.8 ml, 4.1 mmol) was added. Immediately, 1.4 g (4.4 mmol) solid 1,2,3,4-tetra-O-acetyl-beta-L-xylopyranose was added. The solution was stirred under nitrogen at reflux for 0.25 h, then poured into 7% aqueous sodium bicarbonate and extracted with dichloromethane. The organic layers were dried with magnesium sulfate (anhyd), filtered, and evaporated. The crude residue was crystallized from chloroform and hexane to give 1.11 g (56% yield) of 2-bromo-5,6-dichloro-1-(2,3,4-tri-O-acetyl-beta-L-xylopyranosyl)-1H-benzimidazole. 1H NMR (CDCl3) δ7.80 (s,1H), 7.76 (s, 1H), 5.68-5.64 (m, 1H), 5.55-5.51 (m, 1H), 5.32-5.25 (m, 1H), 4.48-4.43 (dd, 1H), 3.69-3.61 (t, 1H), 2.15 (s, 3H), 2.10 (s, 3H), 1.90 (s, 3H).

Workup

  1. temperaturerefluxed under nitrogen for 0.5 h
  2. temperatureat reflux for 0.25 h
  3. extractionextracted with dichloromethane
  4. dry with materialThe organic layers were dried with magnesium sulfate (anhyd)
  5. filtrationfiltered
  6. customevaporated
  7. customThe crude residue was crystallized from chloroform and hexane

Sources & evidence

ORD record
ord-3c7e9c15f1394d499779c68a2936bf32
Source dataset
uspto-grants-2002_09
Patent number
US06455507B1

Reaction notes

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