1,4-Dihydroxy-2,2,6,6-tetramethylpiperidine → 1-(2-Nitro-4-chlorophenoxy)-2,2,6,6-tetramethyl-4-hydroxypiperidine

HRID 1369353Notes

Reaction equation

HRID 1369353 reaction equation
[OH:1][N:2]1[C:7]([CH3:9])([CH3:8])[CH2:6][CH:5]([OH:10])[CH2:4][C:3]1([CH3:12])[CH3:11].N(OC(C)(C)C)=O.[Cl:20][C:21]1[CH:27]=[CH:26][C:24](N)=[C:23]([N+:28]([O-:30])=[O:29])[CH:22]=1>[Cu](F)F.N1C=CC=CC=1>[N+:28]([C:23]1[CH:22]=[C:21]([Cl:20])[CH:27]=[CH:26][C:24]=1[O:1][N:2]1[C:7]([CH3:8])([CH3:9])[CH2:6][CH:5]([OH:10])[CH2:4][C:3]1([CH3:12])[CH3:11])([O-:30])=[O:29]

Participants

6

Reactant 3

HCID 53951,4-Dihydroxy-2,2,6,6-tetramethylpiperidineHCID 69794-Chloro-2-nitroanilineHCID 10906Tert-Butyl nitrite

Product 1

HCID 225950341-(2-Nitro-4-chlorophenoxy)-2,2,6,6-tetramethyl-4-hydroxypiperidineYield 84.8%

Reagents, catalysts & solvents 2

HCID 522688Copper fluorideCatalystHCID 1049PyridineSolvent

Procedure

The procedure of Example 1 is repeated using 4.31 g (25 mmol) of 1-oxyl-2,2,6,6-tetramethyl-4-hydroxypiperidine, 7.73 g (75 mmol) of tert-butyl nitrite, 25 mg (0.25 mmol) of copper(II) flouride, 70 mL of pyridine and 5.61 g (32.5 mmol) of 4-chloro-2-nitroaniline at 70° C. The crude product obtained is purified by vacuum flash chromatography (70:30/heptane:ethyl acetate) to give 4.28 g of the title compound in 84.8% yield as a light yellow solid melting at 124-125.5° C. The structure is confirmed by 1Hnmr and elemental analysis.

Workup

  1. customat 70° C
  2. customThe crude product obtained
  3. customis purified by vacuum flash chromatography (70:30/heptane:ethyl acetate)

Sources & evidence

ORD record
ord-4a4e32f9ea7a46409f97423686fd2b3b
Source dataset
uspto-grants-2003_06
Patent number
US06579328B2

Reaction notes

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