p-Toluidine → 1-Azido-4-methylbenzene

HRID 850041

Reaction equation

HRID 850041 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][CH:3]=1.N([O-])=O.[Na+].[N-:13]=[N+:14]=[N-].[Na+]>Cl.O>[N:1]([C:2]1[CH:7]=[CH:6][C:5]([CH3:8])=[CH:4][CH:3]=1)=[N+:13]=[N-:14]

Participants

6

Reactant 3

HCID 7813p-ToluidineHCID 33557Sodium AzideHCID 23668193Sodium Nitrite

Product 1

HCID 1374301-Azido-4-methylbenzene

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 962WaterSolvent

Procedure

p-Toluidine (9.3 mM) was dissolved in hydrochloric acid (5M; 10 ml), and the mixture cooled to <0° C. Sodium nitrite (10.28 mM) was dissolved in a minimum amount of water, and this solution was added dropwise to the reaction over 30 minutes. The solution was stirred for 20 minutes, then the presence of the oxidising agent was tested for using starch/iodide paper. Sodium azide (37.38 mM) was then added slowly to the reaction mixture over a period of 1 hour (due to vigorous effervescing). The reaction was quenched, once all the sodium azide had been added, in water (50 ml), and quantitatively transferred to a conical flask with water (50 ml). The mixture was neutralised with sodium carbonate, until pH=6. The organics were extracted into dichloromethane (3×30 ml), washed with water (2×20 ml), dried over magnesium sulphate, and excess solvent removed under vacuum. The p-azidotoluene thus obtained was an oil and was isolated via chromatography (100% petroleum/ether 40-60). 1H NMR: d6DMSO: δ: 2.37 (s; 3H; CH3); 7.0 (d;2H; H3 ;H5); 7.3 (d; 2H; H2 ; H6)

Workup

  1. temperaturethe mixture cooled to <0° C
  2. additionthis solution was added dropwise to the reaction over 30 minutes
  3. customThe reaction was quenched
  4. additiononce all the sodium azide had been added, in water (50 ml)
  5. customquantitatively transferred to a conical flask with water (50 ml)
  6. extractionThe organics were extracted into dichloromethane (3×30 ml)
  7. washwashed with water (2×20 ml)
  8. dry with materialdried over magnesium sulphate, and excess solvent
  9. customremoved under vacuum

Sources & evidence

ORD record
ord-744a169087b440a5892d8b09c0f4cbdd
Source dataset
uspto-grants-2000_01
Patent number
US06015827

Linked notes

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