N,N'-Dimethylethylenediamine → 4-Azidoaniline

HRID 2174219Notes

Reaction equation

HRID 2174219 reaction equation
I[C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[CH:4][CH:3]=1.O=C1O[C@H]([C@H](CO)O)C(O)=C1O.[Na].[N-:22]=[N+:23]=[N-:24].[Na+].CNCCNC>CS(C)=O.O.[Cu](I)I>[N:22]([C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[CH:4][CH:3]=1)=[N+:23]=[N-:24]

Participants

8

Reactant 4

HCID 8070N,N'-DimethylethylenediamineHCID 108934-IodoanilineHCID 33557Sodium AzideHCID 66586226sodium L-ascorbic acid

Product 1

HCID 846744-AzidoanilineYield 61.2%

Reagents, catalysts & solvents 3

HCID 83717Copper iodideCatalystHCID 679Dimethyl SulfoxideSolventHCID 962WaterSolvent2×

Conditions

Temperature
100 °C

Procedure

4-iodoaniline (400 mg, 1.8263 mmol) was mixed with sodium L-ascorbic acid (90 mg, 0.46 mmol) in DMSO (25 mL). A solution of sodium azide (241 mg, 3.65 mmol) in water (6.5 mL) was added followed by N,N′-dimethylethane-1,2-diamine (30 mg, 0.4 mmol) and copper iodide (30 mg, 0.2 mmol). The mixture was then heated at 100° C. for 6 h. The mixture was then mixed with a large amount of water (80 mL) and then extracted with EtOAc (3 times). The organics were dried (MgSO4), filtered and concentrated in vacuo to give a residue that was purified by flash chromatography (silica, eluting with MeOH in DCM) to give 4-azidoaniline (150 mg). 1H NMR (400 MHz, DMSO) δ 6.81-6.75 (m, 2H), 6.63-6.57 (m, 2H), 5.13 (s, 2H).

Workup

  1. extractionextracted with EtOAc (3 times)
  2. dry with materialThe organics were dried (MgSO4)
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo
  5. customto give a residue that
  6. customwas purified by flash chromatography (silica, eluting with MeOH in DCM)

Sources & evidence

ORD record
ord-52a1f47fdba54377b584b946ca97b40f
Source dataset
uspto-grants-2015_06
Patent number
US09060515B2

Reaction notes

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