1,8-Diazabicyclo(5.4.0)undec-7-ene → Methyl 4-((3-(azido(phenyl)methyl)phenoxy)methyl)benzoate

HRID 332675Notes

Reaction equation

HRID 332675 reaction equation
[C:1]([C:9]1[CH:10]=[C:11]([CH:24]=[CH:25][CH:26]=1)[O:12][CH2:13][C:14]1[CH:23]=[CH:22][C:17]([C:18]([O:20][CH3:21])=[O:19])=[CH:16][CH:15]=1)(=O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[BH4-].[Na+].C1(P([N:43]=[N+:44]=[N-:45])(C2C=CC=CC=2)=O)C=CC=CC=1.N12CCCN=C1CCCCC2>CO.O.C1(C)C=CC=CC=1.C(OCC)(=O)C>[N:43]([CH:1]([C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)[C:9]1[CH:10]=[C:11]([CH:24]=[CH:25][CH:26]=1)[O:12][CH2:13][C:14]1[CH:23]=[CH:22][C:17]([C:18]([O:20][CH3:21])=[O:19])=[CH:16][CH:15]=1)=[N+:44]=[N-:45]

Participants

9

Reactant 4

HCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 199401P,P-Diphenylphosphinic azideHCID 4311764Sodium borohydrideHCID 71093281Methyl 4-((3-benzoylphenoxy)methyl)benzoate

Product 1

HCID 71093296Methyl 4-((3-(azido(phenyl)methyl)phenoxy)methyl)benzoateYield 92%

Reagents, catalysts & solvents 4

HCID 887MethanolSolventHCID 962WaterSolventHCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Procedure

To an ice-cooled suspension of methyl 4-((3-benzoylphenoxy)methyl)benzoate (1.62 g, 4.88 mmol) in methanol (20 mL), was added sodium borohydride (0.27 g, 7.32 mmol). The reaction mixture was allowed to warm to room temperature over 2 hours. The reaction mixture was diluted with water and extracted with ethyl acetate. The organic extracts were washed with brine, dried (MgSO4), and concentrated under reduced pressure to afford an oil. To a solution of the oil in toluene (25 mL), was added diphenylphosphoryl azide (1.26 mL, 5.85 mmol) and 1,8-diazabicyclo[5.4.0]undec-7-ene (881 μL, 5.85 mmol). The reaction mixture was stirred at 100° C. for 3 hours. The reaction mixture was allowed to cool to room temperature, diluted with ethyl acetate and washed with water, brine, dried (magnesium sulphate), filtered and concentrated. The crude material was purified by silica gel chromatography eluting with 0-10% ethyl acetate in iso-hexane to afford the title compound (1.62 g, 92% over 2 steps).

Workup

  1. extractionextracted with ethyl acetate
  2. washThe organic extracts were washed with brine
  3. dry with materialdried (MgSO4)
  4. concentrationconcentrated under reduced pressure
  5. customto afford an oil
  6. temperatureto cool to room temperature
  7. washwashed with water, brine
  8. dry with materialdried (magnesium sulphate)
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customThe crude material was purified by silica gel chromatography
  12. washeluting with 0-10% ethyl acetate in iso-hexane

Sources & evidence

ORD record
ord-fc30da4df7bc4038811871cf1ec0d557
Source dataset
uspto-grants-2014_11
Patent number
US08877774B2

Reaction notes

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