Aniline → Azidobenzene

HRID 1618881Notes

Reaction equation

HRID 1618881 reaction equation
N([O-])=O.[Na+].[NH2:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1.[N-:12]=[N+:13]=[N-].[Na+]>O.Cl>[N:5]([C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][CH:7]=1)=[N+:12]=[N-:13]

Participants

6

Reactant 3

HCID 6115AnilineHCID 33557Sodium AzideHCID 23668193Sodium Nitrite

Product 1

HCID 69319Azidobenzene

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 962WaterSolvent2×

Procedure

A solution of NaNO2 (5.7 g, 82.5 mmol)) in water (20 mL) was added dropwise to a solution of aniline (3.06 g, 33 mmol) in 4M HCl (330 mL) at 0-5° C. After stirring the mixture at this temperature for 45 min, a solution of NaN3 (429 g, 66 mmol) in water (20 mL) was slowly added to the mixture at the same temperature. Stirring was continued for 30 min below 5° C. and then for overnight at room temperature. The reaction mixture was extracted with diethyl ether (50×3), washed with water and dried over anhydrous MgSO4. The solvent was removed under reduced pressure and the crude liquid was purified by silica gel column chromatography using hexane/EAC 0-5% as eluent. Yield: 1.70 g (43%). IR (neat) 2925, 2093, 1933, 1620, 1492, 1295, 1175 cm−1; 1H NMR (400 MHz, CDCl3) δ7.10-7.21 (m, 2H), 7.22-7.24 (m, 1H), 7.42-7.46 (m, 2H); 13C NMR (CDCl3) δ 140.02, 129.72, 124.88, 109.00.

Workup

  1. stirringStirring
  2. waitwas continued for 30 min below 5° C.
  3. waitfor overnight at room temperature
  4. extractionThe reaction mixture was extracted with diethyl ether (50×3)
  5. washwashed with water
  6. dry with materialdried over anhydrous MgSO4
  7. customThe solvent was removed under reduced pressure
  8. customthe crude liquid was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-7709fb9b26f54913807afb454c386756
Source dataset
uspto-grants-2014_07
Patent number
US08772048B2

Reaction notes

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