Aniline → 1-Phenoxy-2,2,6,6-tetramethylpiperidine

HRID 1369336Notes

Reaction equation

HRID 1369336 reaction equation
[OH:1][N:2]1[C:7]([CH3:9])([CH3:8])[CH2:6][CH2:5][CH2:4][C:3]1([CH3:11])[CH3:10].N(OC(C)(C)C)=O.N[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1>C(#N)C.[Cu](F)F>[O:1]([N:2]1[C:7]([CH3:9])([CH3:8])[CH2:6][CH2:5][CH2:4][C:3]1([CH3:11])[CH3:10])[C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1

Participants

6

Reactant 3

HCID 6115Aniline2×HCID 10906Tert-Butyl nitriteHCID 5499762,2,6,6-Tetramethylpiperidin-1-ol

Product 1

HCID 132131751-Phenoxy-2,2,6,6-tetramethylpiperidineYield 74.1%

Reagents, catalysts & solvents 2

HCID 522688Copper fluorideCatalystHCID 6342AcetonitrileSolvent

Procedure

To a suspension of 3.9 g (25 mmol) of 1-oxyl-2,2,6,6-tetramethylpiperidine, 11.76 g (114 mmol) of tert-butyl nitrite and 25 mg (0.25 mmol) of copper(II) fluoride in 120 mL of acetonitrile at 65° C. under a nitrogen atmosphere is added dropwise over 30 minutes 6.98 g (75 mmol) of aniline. The evolution of gas is observed during the addition of the aniline. The dark red reaction mixture is kept at 65° C. for an additional ten minutes followed by cooling to ambient temperature. The reaction mixture is then concentrated to a thick oil which turns into a semi-solid upon standing. The residue is purified by vacuum flash chromatography (heptane) to give 4.3 g of a colorless oil in 74.1% yield based on nitroxyl. The structure is confirmed by 1Hnmr analysis, mass spectroscopy and elemental analyses.

Workup

  1. customThe dark red reaction mixture
  2. waitis kept at 65° C. for an additional ten minutes
  3. concentrationThe reaction mixture is then concentrated to a thick oil which
  4. customThe residue is purified by vacuum flash chromatography (heptane)

Sources & evidence

ORD record
ord-2d2626e4583049cea9cff98ae7f327e1
Source dataset
uspto-grants-2003_06
Patent number
US06579328B2

Reaction notes

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