1,4-Dihydroxy-2,2,6,6-tetramethylpiperidine → 1-(2-Nitro-4-trifluoromethylphenoxy)-2,2,6,6-tetramethylpiperidine

HRID 1369338Notes

Reaction equation

HRID 1369338 reaction equation
[OH:1][N:2]1[C:7]([CH3:9])([CH3:8])[CH2:6][CH:5](O)[CH2:4][C:3]1([CH3:12])[CH3:11].N(OC(C)(C)C)=O.[N+:20]([C:23]1[CH:29]=[C:28]([C:30]([F:33])([F:32])[F:31])[CH:27]=[CH:26][C:24]=1N)([O-:22])=[O:21]>[Cu](F)F.C(#N)C>[N+:20]([C:23]1[CH:29]=[C:28]([C:30]([F:31])([F:32])[F:33])[CH:27]=[CH:26][C:24]=1[O:1][N:2]1[C:7]([CH3:9])([CH3:8])[CH2:6][CH2:5][CH2:4][C:3]1([CH3:12])[CH3:11])([O-:22])=[O:21]

Participants

6

Reactant 3

HCID 53951,4-Dihydroxy-2,2,6,6-tetramethylpiperidineHCID 10906Tert-Butyl nitriteHCID 67865Benzenamine, 2-nitro-4-(trifluoromethyl)-

Product 1

HCID 225982761-(2-Nitro-4-trifluoromethylphenoxy)-2,2,6,6-tetramethylpiperidineYield 69.3%

Reagents, catalysts & solvents 2

HCID 522688Copper fluorideCatalystHCID 6342AcetonitrileSolvent

Procedure

The procedure of Example 1 is repeated using 3.9 g (25 mmol) of 1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine, 7.84 g (76 mmol) of tert-butyl nitrite, 25 mg (0.25 mmol) of copper(II) fluoride, 120 mL of acetonitrile and 10.3 g (50 mmol) of 2-nitro-4-trifluoromethylaniline at 65° C. The crude product obtained is purified by vacuum flash chromatography (heptane) to give 6.0 g of light yellow crystals melting at 54-55° C., a 68.9% yield based on nitroxyl. The structure is confirmed by 1Hnmr, mass spectroscopy and elemental analyses.

Workup

  1. customat 65° C
  2. customThe crude product obtained
  3. customis purified by vacuum flash chromatography (heptane)

Sources & evidence

ORD record
ord-2094db77b75142c6ac67e1690ac34faa
Source dataset
uspto-grants-2003_06
Patent number
US06579328B2

Reaction notes

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