Nitrogen → 2675-80-1

HRID 1891416Notes

Reaction equation

HRID 1891416 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[C:5]([CH:7]=[C:8]([O:12][CH3:13])[C:9]=1[O:10][CH3:11])N.N([O-])=O.[Na+].N#N.[ClH:20].O>O.Cl.Cl[Cu]>[Cl:20][C:5]1[CH:7]=[C:8]([O:12][CH3:13])[C:9]([O:10][CH3:11])=[C:3]([O:2][CH3:1])[CH:4]=1

Participants

8

Reactant 4

HCID 947NitrogenHCID 322853,4,5-TrimethoxyanilineHCID 21885828Hydrate;hydrochlorideHCID 23668193Sodium Nitrite2×

Product 1

HCID 236178472675-80-1Yield 67%

Reagents, catalysts & solvents 3

HCID 62652Cuprous chlorideCatalystHCID 313Hydrochloric AcidSolventHCID 962WaterSolvent

Procedure

To a stirred suspension of 3,4,5-trimethoxyaniline (6.27 g, 34.2 mmol) in 37% HCl:H2O (75:25) at 0° C. was added dropwise a solution of NaNO2 (2.51 g, 36.4 mmol) in H2O. The temperature was maintained below 5° C. during the addition. Upon complete addition of NaNO2, an ice cold solution of CuCl (4.41 g, 44.6 mmol) in 37% HCl was added and the solution allowed to warm to room temperature. The stirred suspension was warmed to 60° C. until evolution of N2 ceased. The product was filtered and washed with cold H2O. The crude product was purified by flash chromatography (silica gel, EtOAc/Petroleum Spirit 3:17) to give the title compound as a white solid (4.68 g, 67%). 1H NMR (300 MHz, CDCl3) δ 6.58 (s, 2H), 3.85 (s, 6H), 3.82 (s, 3H), ESIMS m/z [M+H]+ 203.2.

Workup

  1. temperatureThe temperature was maintained below 5° C. during the addition
  2. filtrationThe product was filtered
  3. washwashed with cold H2O
  4. customThe crude product was purified by flash chromatography (silica gel, EtOAc/Petroleum Spirit 3:17)

Sources & evidence

ORD record
ord-c24108f8381c4c2880d21ab2b2dcedd9
Source dataset
uspto-grants-2013_08
Patent number
US08507539B2

Reaction notes

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