Hydrogen Peroxide → 2,4-Bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino}-6-chloro-s-triazine

HRID 1276638Notes

Reaction equation

HRID 1276638 reaction equation
OO.[OH:3][N:4]1[C:9]([CH3:11])([CH3:10])[CH2:8][CH:7]([CH2:12][CH2:13][CH2:14][CH2:15][NH:16][C:17]2[N:22]=[C:21]([NH:23][CH2:24][CH2:25][CH2:26][CH2:27][CH:28]3[CH2:33][C:32]([CH3:35])([CH3:34])[N:31]([OH:36])[C:30]([CH3:38])([CH3:37])[CH2:29]3)[N:20]=[C:19]([Cl:39])[N:18]=2)[CH2:6][C:5]1([CH3:41])[CH3:40].S([O-])([O-])=O.[Na+].[Na+].[C:48]([OH:52])([CH3:51])([CH3:50])[CH3:49]>O.C(OCC)(=O)C>[OH:52][C:48]([CH3:51])([CH3:50])[CH2:49][O:36][N:31]1[C:32]([CH3:35])([CH3:34])[CH2:33][CH:28]([CH2:27][CH2:26][CH2:25][CH2:24][NH:23][C:21]2[N:22]=[C:17]([NH:16][CH2:15][CH2:14][CH2:13][CH2:12][CH:7]3[CH2:6][C:5]([CH3:41])([CH3:40])[N:4]([O:3][CH2:49][C:48]([CH3:51])([OH:52])[CH3:50])[C:9]([CH3:11])([CH3:10])[CH2:8]3)[N:18]=[C:19]([Cl:39])[N:20]=2)[CH2:29][C:30]1([CH3:38])[CH3:37]

Participants

7

Reactant 4

HCID 784Hydrogen Peroxide2×HCID 6386tert-ButanolHCID 24437Sodium SulfiteHCID 570971972,4-bis[N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-chloro-s-triazine

Product 1

HCID 571517592,4-Bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]butylamino}-6-chloro-s-triazineYield 99.9%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
42.5 °C

Procedure

A total of 40 g (0.59 mol) of 50% aqueous hydrogen peroxide is added in two portions over five hours to a mixture of 43.2 g (0.076 mol) of 2,4-bis[N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-chloro-s-triazine and 7.0 g (0.035 mol) of ferrous chloride tetrahydrate in 150 g of tert-butyl alcohol and 15 g of water. Another portion of 50% aqueous hydrogen peroxide (3 g, 0.044 mol) is added to the reaction mixture while the temperature is maintained at 40-45° C. for 2.25 hours. The reaction mixture is diluted with 100 g of ethyl acetate. A solution of 100 g of 20% aqueous sodium sulfite is added and the reaction mixture is heated at 60° C. for one hour to decompose residual peroxide. The aqueous layer is extracted with ethyl acetate, and the combined organic layers are concentrated. The crude product is purified by flash chromatography on silica gel with 1:1 (v/v) hexane/ethyl acetate to afford 54.1 g of the title compound.

Workup

  1. temperaturethe reaction mixture is heated at 60° C. for one hour
  2. extractionThe aqueous layer is extracted with ethyl acetate
  3. concentrationthe combined organic layers are concentrated
  4. customThe crude product is purified by flash chromatography on silica gel with 1:1 (v/v) hexane/ethyl acetate

Sources & evidence

ORD record
ord-58be3852bd6842ce8f69b23e5266a5d9
Source dataset
uspto-grants-2000_12
Patent number
US06166212

Reaction notes

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