Sodium hydride → HCID 19737418, compound

HRID 258340Notes

Reaction equation

HRID 258340 reaction equation
O1CCOC1.[O:6]([C:13]1[CH:18]=[CH:17][C:16]([C:19]2([CH2:26][N:27]3[CH:31]=[N:30][CH:29]=[N:28]3)[O:23][CH:22]([CH2:24][OH:25])[CH2:21][O:20]2)=[CH:15][CH:14]=1)[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.[H-].[Na+].[Cl:34][C:35]1[CH:42]=[CH:41][C:38]([CH2:39]Br)=[CH:37][CH:36]=1>O1CCOCC1>[O:6]([C:13]1[CH:18]=[CH:17][C:16]([C:19]2([CH2:26][N:27]3[CH:31]=[N:30][CH:29]=[N:28]3)[O:23][CH:22]([CH2:24][O:25][CH2:39][C:38]3[CH:41]=[CH:42][C:35]([Cl:34])=[CH:36][CH:37]=3)[CH2:21][O:20]2)=[CH:15][CH:14]=1)[C:7]1[CH:8]=[CH:9][CH:10]=[CH:11][CH:12]=1

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 693291-(Bromomethyl)-4-chlorobenzeneHCID 67855966HCID 67855966, compound

Product 1

HCID 19737418HCID 19737418, compound

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent3×

Procedure

14,1 parts of 2-[p-(Phenoxy)-phenyl]-2-(1H-1,2,4-triazolyl-methyl)-4-hydroxymethyl-1,3-dioxolane dioxolane dissolved in 100 ml absolute dioxane and then 1,8 parts of 55 % sodium hydrid dispersion in 100 ml absolute dioxane are stirred in at room temperature while introducing nitrogen. The mixture is heated 3 hours to 80° C., then cooled to room temperaLure, treated dropwise within 30 minutes with 8,6 parts of p-chlorobenzylbromide dissolved in 50 parts of absolute dioxane. The reaction mixture is beated 3 hours to 50° C., then cooled to room temperature, diluted with 1200 ml ice-water and extracted with three 200 ml portions of ethyl acetate. The combined extracts are washed with two 70 ml portions of water, dried over sodium sulfate, filtered and the solvent removed by evaporation. The remaining diastereoisomers are separated by column chromatography (silica gel/ethyl acetate). The eluant is then removed by evaporation to give the diastereoisomer B in the form of crystals with a melting point of 83°-85° C. The diastereoisomer A is obtained after the evaporation of the solvent in form of a viscous slightly brownish oil; nD26 : 1.5865.

Workup

  1. additionwhile introducing nitrogen
  2. temperatureThe mixture is heated 3 hours to 80° C.
  3. temperaturecooled to room temperaLure
  4. extractionextracted with three 200 ml portions of ethyl acetate
  5. washThe combined extracts are washed with two 70 ml portions of water
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. customthe solvent removed by evaporation
  9. customThe remaining diastereoisomers are separated by column chromatography (silica gel/ethyl acetate)
  10. customThe eluant is then removed by evaporation
  11. customto give the diastereoisomer B in the form of crystals with a melting point of 83°-85° C
  12. customThe diastereoisomer A is obtained
  13. customafter the evaporation of the solvent in form of a viscous slightly brownish oil

Sources & evidence

ORD record
ord-504e6b35d1614041b0be5e2d9fdfab66
Source dataset
uspto-grants-1993_11
Patent number
US05266585

Reaction notes

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