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

HRID 1255822Notes

Reaction equation

HRID 1255822 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-8fb5db18e66447ec93f3327bc56d3e98
Source dataset
uspto-grants-2013_06
Patent number
US08461161B2

Reaction notes

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