1,8-Diazabicyclo(5.4.0)undec-7-ene → 1-[(1S)-1-azidoethyl]-3-nitrobenzene

HRID 572199Notes

Reaction equation

HRID 572199 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([C@H:10](O)[CH3:11])[CH:7]=[CH:8][CH:9]=1)([O-:3])=[O:2].C1(P([N:27]=[N+:28]=[N-:29])(C2C=CC=CC=2)=O)C=CC=CC=1.N12CCCN=C1CCCCC2>O1CCCC1.C(OCC)(=O)C.O>[N:27]([C@H:10]([C:6]1[CH:7]=[CH:8][CH:9]=[C:4]([N+:1]([O-:3])=[O:2])[CH:5]=1)[CH3:11])=[N+:28]=[N-:29]

Participants

7

Reactant 3

HCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 199401P,P-Diphenylphosphinic azideHCID 11147933(R)-1-(3-nitrophenyl)ethanol

Product 1

HCID 866418551-[(1S)-1-azidoethyl]-3-nitrobenzeneYield 130.1%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of (1R)-1-(3-nitrophenyl)ethanol (12 g, 72 mmol) in tetrahydrofuran (220 mL), cooled to 0° C., was added diphenylphosphoryl azide (31 mL, 145 mmol) in one portion followed by 1,8-diazabicyclo[5.4.0]undec-7-ene (22 mL, 145 mmol) dropwise over 30 minutes. The reaction mixture was allowed to warm slowly to room temperature and was stirred for 38 hours after which time the mixture was diluted with ethyl acetate (100 mL) and water (100 mL), the two phases separated and the aqueous phase extracted with ethyl acetate (2×100 mL). The combined organic phases were washed with brine (100 mL), dried (MgSO4) and concentrated under reduced pressure to give a black liquid. The crude liquid was purified by flash chromatography (silica, ethyl acetate/hexanes) to give 1-[(1S)-1-azidoethyl]-3-nitrobenzene (18 g) as a yellow liquid in acceptable purity.

Workup

  1. customthe two phases separated
  2. extractionthe aqueous phase extracted with ethyl acetate (2×100 mL)
  3. washThe combined organic phases were washed with brine (100 mL)
  4. dry with materialdried (MgSO4)
  5. concentrationconcentrated under reduced pressure
  6. customto give a black liquid
  7. customThe crude liquid was purified by flash chromatography (silica, ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-6fcb51e3926d484a9945561bbc922c07
Source dataset
uspto-grants-2015_05
Patent number
US09029386B2

Reaction notes

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