Hydrochloric Acid → (1R)-2-Azido-1-(2,2-dimethyl-4H-1,3-benzodioxin-6-yl)ethanol

HRID 2118198Notes

Reaction equation

HRID 2118198 reaction equation
B.C1COCC1.[N:7]([CH2:10][C:11]([C:13]1[CH:24]=[CH:23][C:16]2[O:17][C:18]([CH3:22])([CH3:21])[O:19][CH2:20][C:15]=2[CH:14]=1)=[O:12])=[N+:8]=[N-:9].Cl>C1(C)C=CC=CC=1.C1COCC1>[N:7]([CH2:10][C@@H:11]([C:13]1[CH:24]=[CH:23][C:16]2[O:17][C:18]([CH3:22])([CH3:21])[O:19][CH2:20][C:15]=2[CH:14]=1)[OH:12])=[N+:8]=[N-:9]

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 2723981Borane;tetrahydrofuranHCID 114023652-Azido-1-(2,2-dimethyl-4H-1,3-benzodioxin-6-yl)ethanone

Product 1

HCID 86595260(1R)-2-Azido-1-(2,2-dimethyl-4H-1,3-benzodioxin-6-yl)ethanolYield 68.2%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

R-(+)-2-Methyl-CBS-oxazaborolidine solution in toluene (1M, 7.5 ml) was added to THF (75 ml) and the solution was diluted to 0° C. Borane-THF complex (1M solution in THF, 125 ml) was added and the mixture was stirred under nitrogen for 15 min. A solution of 2-azido-1-(2,2-dimethyl-4H-1,3-benzodioxin-6-yl)ethanone (24.7 g) in THF (250 ml) was added dropwise over 1.5 h at 5° C. The mixture was stirred for a further 1 h and then cautiously treated with 2M HCl (100 ml). The reaction mixture was extracted with ether and the organic layer was washed with 2M HCl, NaHCO3, brine, dried (MgSO4). The solvent was removed by evaporation and the residue was chromatographed on a Biotage column eluting with diethyl ether-petrol (40-60° C.) (1:9; 1:1) to give the title compound (16.99 g). ES+ve 250 (MH)+.

Workup

  1. additionthe solution was diluted to 0° C
  2. stirringThe mixture was stirred for a further 1 h
  3. extractionThe reaction mixture was extracted with ether
  4. washthe organic layer was washed with 2M HCl, NaHCO3, brine
  5. dry with materialdried (MgSO4)
  6. customThe solvent was removed by evaporation
  7. customthe residue was chromatographed on a Biotage column
  8. washeluting with diethyl ether-petrol (40-60° C.) (1:9; 1:1)

Sources & evidence

ORD record
ord-d4748a9a1dd5497cad775c583055b072
Source dataset
uspto-grants-2008_10
Patent number
US07442836B2

Reaction notes

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