Sodium Iodide → HCID 86614397, compound

HRID 1673322Notes

Reaction equation

HRID 1673322 reaction equation
[OH:1][CH2:2][CH2:3][N:4]1[C:12]2[C:7](=[C:8]([CH2:13][CH2:14][C:15]3[CH:20]=[CH:19][C:18]([OH:21])=[CH:17][CH:16]=3)[CH:9]=[CH:10][CH:11]=2)[C:6]([O:22][C@@H:23]2[O:49][C@H:48]([CH2:50][O:51][C:52](=[O:57])[C:53]([CH3:56])([CH3:55])[CH3:54])[C@@H:40]([O:41][C:42](=[O:47])[C:43]([CH3:46])([CH3:45])[CH3:44])[C@H:32]([O:33][C:34](=[O:39])[C:35]([CH3:38])([CH3:37])[CH3:36])[C@H:24]2[O:25][C:26](=[O:31])[C:27]([CH3:30])([CH3:29])[CH3:28])=[N:5]1.[C:58](=[O:61])([O-])[O-].[Cs+].[Cs+].[I-].[Na+].Br[CH2:67][CH2:68][CH2:69][O:70][CH2:71][C:72]1[CH:77]=[CH:76][CH:75]=[CH:74][CH:73]=1>CN(C)C=O.O>[CH2:71]([O:70][CH2:69][CH2:68][CH2:67][O:21][C:18]1[CH:19]=[CH:20][C:15]([CH2:14][CH2:13][C:8]2[CH:9]=[CH:10][CH:11]=[C:12]3[C:7]=2[C:6]([O:22][C@@H:23]2[O:49][C@H:48]([CH2:50][O:51][C:52](=[O:57])[C:53]([CH3:56])([CH3:55])[CH3:54])[C@@H:40]([O:41][C:42](=[O:47])[C:43]([CH3:44])([CH3:45])[CH3:46])[C@H:32]([O:33][C:34](=[O:39])[C:35]([CH3:38])([CH3:37])[CH3:36])[C@H:24]2[O:25][C:26](=[O:31])[C:27]([CH3:28])([CH3:29])[CH3:30])=[N:5][N:4]3[CH2:3][CH2:2][O:1][C:58](=[O:61])[C:7]([CH3:12])([CH3:8])[CH3:6])=[CH:16][CH:17]=1)[C:72]1[CH:77]=[CH:76][CH:75]=[CH:74][CH:73]=1

Participants

7

Reactant 4

HCID 5238Sodium IodideHCID 10796Cesium carbonateHCID 2776064Benzyl 3-Bromopropyl EtherHCID 67341380HCID 67341380, compound

Product 1

HCID 86614397HCID 86614397, compoundYield 163.4%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

To a mixture of 1-(2-hydroxyethyl)-4-[2-(4-hydroxy-phenyl)ethyl]-3-(2,3,4,6-tetra-O-pivaloyl-β-D-glucopyranosyloxy)-1H-indazole (2 g), cesium carbonate (1.64 g) and sodium iodide (0.38 g) in N,N-dimethylformamide (10 mL) was added benzyl 3-bromopropyl ether (0.86 g), and the mixture was stirred at room temperature overnight. The reaction mixture was poured into water, and the resulting mixture was extracted with diethyl ether. The extract was washed with water and brine, and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure, and the residue was dissolved in dichloromethane (15 mL). To the solution were added triethylamine (1.22 mL) and pivaloyl chloride (0.93 mL), and the mixture was stirred at room temperature overnight. The reaction mixture was poured into 0.5 mol/L hydrochloric acid, and the resulting mixture was extracted with diethyl ether. The extract was washed with water, a saturated aqueous sodium hydrogen carbonate solution and brine, and dried over anhydrous sodium sulfate. The solvent was removed under reduced pressure, and the residue was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate=3/1) to give 4-{2-[4-(3-benzyloxypropoxy)phenyl]ethyl}-3-(2,3,4,6-tetra-O-pivaloyl-β-D-glucopyranosyloxy)-1-(2-pivaloyloxyethyl)-1H-indazole (2.11 g). This material was dissolved in ethyl acetate (20 mL). To the solution was added 10% palladium-carbon powder (0.5 g), and the mixture was stirred at room temperature under a hydrogen atmosphere for 2 hours. The insoluble material was removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate=2/1-1/1) to give the title compound (1.59 g).

Workup

  1. extractionthe resulting mixture was extracted with diethyl ether
  2. washThe extract was washed with water and brine
  3. dry with materialdried over anhydrous sodium sulfate
  4. customThe solvent was removed under reduced pressure
  5. dissolutionthe residue was dissolved in dichloromethane (15 mL)
  6. additionTo the solution were added triethylamine (1.22 mL) and pivaloyl chloride (0.93 mL)
  7. stirringthe mixture was stirred at room temperature overnight
  8. additionThe reaction mixture was poured into 0.5 mol/L hydrochloric acid
  9. extractionthe resulting mixture was extracted with diethyl ether
  10. washThe extract was washed with water
  11. dry with materiala saturated aqueous sodium hydrogen carbonate solution and brine, and dried over anhydrous sodium sulfate
  12. customThe solvent was removed under reduced pressure
  13. customthe residue was purified by column chromatography on silica gel (eluent: n-hexane/ethyl acetate=3/1)

Sources & evidence

ORD record
ord-80ea8ba8d1cf43bf8ff2d0fce58096b3
Source dataset
uspto-grants-2011_08
Patent number
US07998975B2

Reaction notes

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