Chloride → HCID 13191407, compound

HRID 1074429Notes

Reaction equation

HRID 1074429 reaction equation
[C:1]([NH:4][C@@H:5]1[C@@H:18]([O:19][CH2:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)[C@H:17]([OH:27])[C@@H:16]([CH2:28][O:29][CH2:30][C:31]2[CH:36]=[CH:35][CH:34]=[CH:33][CH:32]=2)[O:15][C@@H:6]1[O:7][CH2:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)(=[O:3])[CH3:2].N1C(C)=CC(C)=CC=1C.[C:46]([O:49][C@H:50]1[C@H:55]([O:56][C:57](=[O:59])[CH3:58])[C@@H:54]([CH2:60][O:61][C:62](=[O:64])[CH3:63])[O:53][C@@H:52](Cl)[C@@H:51]1[N:66]1[C:70](=[O:71])[C:69]2=[CH:72][CH:73]=[CH:74][CH:75]=[C:68]2[C:67]1=[O:76])(=[O:48])[CH3:47].[Cl-]>[N+](C)([O-])=O.C(Cl)(Cl)Cl.[O-]S(C(F)(F)F)(=O)=O.FC(F)(F)S([O-])(=O)=O.[Ag+2].[O-]S(C(F)(F)F)(=O)=O.[Ag+]>[C:1]([NH:4][C@@H:5]1[C@@H:18]([O:19][CH2:20][C:21]2[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=2)[C@H:17]([O:27][C@@H:52]2[O:53][C@H:54]([CH2:60][O:61][C:62](=[O:64])[CH3:63])[C@@H:55]([O:56][C:57](=[O:59])[CH3:58])[C@H:50]([O:49][C:46](=[O:48])[CH3:47])[C@H:51]2[N:66]2[C:67](=[O:76])[C:68]3=[CH:75][CH:74]=[CH:73][CH:72]=[C:69]3[C:70]2=[O:71])[C@@H:16]([CH2:28][O:29][CH2:30][C:31]2[CH:32]=[CH:33][CH:34]=[CH:35][CH:36]=2)[O:15][C@@H:6]1[O:7][CH2:8][C:9]1[CH:10]=[CH:11][CH:12]=[CH:13][CH:14]=1)(=[O:3])[CH3:2]

Participants

9

Reactant 4

HCID 312ChlorideHCID 79532,4,6-Trimethylpyridine2×HCID 10994087HCID 10994087, compoundHCID 11827086HCID 11827086, compound

Product 1

HCID 13191407HCID 13191407, compound

Reagents, catalysts & solvents 4

HCID 76223Silver(I) trifluoromethanesulfonateCatalystHCID 178527656HCID 178527656, compoundCatalystHCID 6212ChloroformSolventHCID 6375NitromethaneSolvent2×

Procedure

To a solution of benzyl 2-acetamido-3,6-di-O-benzyl-2-deoxy-α-D-glucopyranoside [prepared by the process set forth in J. C. Jacquinet, et al., Carbohydr. Res., 38, 305 (1974)] (2.95 g, 6.00 mmol), silver trifluoromethanesulfonate (triflate) (1.90 g, 7.39 mmol), and 2,4,6-collidine (0.90 g, 7.42 mmol) in dry nitromethane (45 ml) stirred at room temperature under an atmosphere of nitrogen is added a solution of 3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-β-D-glucopyranosyl chloride [prepared by the process set forth in S. Akiya et al., Chem. Pharm. Bull., 8, 583 (1960)](3.35 g, 7.38 mmol) in dry nitromethane (45 ml). After stirring for 6 hours at room temperature, additional chloride (1.73 g, 3.81 mmol), silver triflate (0.98 g, 3.81 mmol), and collidine (0.46 g, 3.80 mmol) are added, and stirring is continued overnight with exclusion of moisture. The mixture is then diluted with chloroform (150 ml), undissolved solids removed by filtration, and the filter washed with chloroform (60 ml). The combined filtrates are washed successively with cold water, 3% aqueous hydrochloric acid, saturated aqueous sodium bicarbonate, and water. The dried (sodium sulfate) organic solution is evaporated and the resulting syrup is treated for 6 hours with acetic anhydride (30 ml) and pyridine (40 ml). The mixture is then evaporated and coevaporated several times with toluene. The residue is dissolved in the minimal volume of dichloromethane and the solution applied to a column of silica gel (E. Merck, No. 7734, 70-230 mesh) (900 g packed as a slurry in 9:1 dichloromethane-diethyl ether). Elution with 90:10:0.25 dichloromethane-diethyl ether-methanol and evaporation of the appropriate fractions affords benzyl 2-acetamido-4-O-(3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-β-D-glucopyranosyl)-3,6-di-O-benzyl-2-deoxy-α-D-glucopyranoside as an amorphous solid; yield 2.17 g (39.8%), [α]D25 +57.1° (c, 1, chloroform). The 300-MHz nmr spectrum in chloroform-d is in accord with the desired structure.

Workup

  1. customprepared by the process
  2. stirringstirring
  3. waitis continued overnight with exclusion of moisture
  4. customremoved by filtration
  5. washthe filter washed with chloroform (60 ml)
  6. washThe combined filtrates are washed successively with cold water, 3% aqueous hydrochloric acid, saturated aqueous sodium bicarbonate, and water
  7. dry with materialThe dried (sodium sulfate) organic solution
  8. customis evaporated
  9. additionthe resulting syrup is treated for 6 hours with acetic anhydride (30 ml) and pyridine (40 ml)
  10. customThe mixture is then evaporated
  11. dissolutionThe residue is dissolved in the minimal volume of dichloromethane
  12. washElution
  13. customwith 90:10:0.25 dichloromethane-diethyl ether-methanol and evaporation of the appropriate fractions

Sources & evidence

ORD record
ord-3067a65c5e7540628ff667e0a7d751d3
Source dataset
uspto-grants-1983_07
Patent number
US04391800

Reaction notes

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