Synthesis And Characterization Of Triazine/Hindered Amine Cyclohexyl Ethers

Studies on the synthesis and characterization of triazine/hindered amine derivatives were carried out.The synthetic routes of six intermediates for 2,4-bis(1-Cyclohexyloxy-4-butylamine-2,2,6,6-tetramethylpiperidine)-6-chloro-1,3,5-triazine were investigated.1-oxyl-2,2,6,6-tetramethylpiperid-4-one was synthesized by using 2,2,6,6-tetramethylpiperid-4-one as the raw material,ion exchange resin loaded Mg(Ⅱ) and magnesium hydroxide as catalyst,hydrogen peroxide as oxidant and water as solvent.The structure was charaterized by electron-spin resonance(ESR), ESI-MS,NMR.The effect of catalyst amount on yield was also investigated.1-Cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-one was synthesized by 1-oxyl-2,2,6,6-tetramethylpiperid-4-one and cyclohexane as the raw material, hydrogen peroxide and ferrous sulfate heptahydrate as oxidation-reduction initiator, and tetrabutyl ammonium bromide as phase transfer catalyst.The structure was charaterized by ESI-MS,NMR.In the synthesis of the sterically hindered alkoxyamine the use of acetic acid and phase transfer catalyst was advantageous to the synthesis efficiency and yield.n-butylamine reacted with 1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-one and 2,2,6,6-tetramethylpiperid-4-one,then vacuumize to remove water.The imine obtained was hydrogenated with methods of sodium borohydride and high-pressure hydrogenation to get 1-cyclohexyloxy-4-butylamine-2,2,6,6-tetramethylpiperidine. The structure was charaterized by ESI-MS,NMR.Compared to 2,2,6,6-tetramethyl piperid-4-one,cyclohexyl ethers used to replace base group showed differences in the physico-chemical properties and reactions.The former need methanol as co-solvent, the latter could react in the condition of molten state.Sodium borohydride as an efficient hydrogen raw materials,has shortcomings of cost and purify.Pd/C as a catalyst for hydrogenation process in the production was advantageous to the efficiency and the recycle of catalyst.4-butylamine-2,2,6,6-tetramethylpiperidine and 1-cyclohexyloxy-4-butylamine-2,2,6,6-tetramethylpiperidine were used to react with cyanuric chloride.The former obtained one-substitution product 2-(4-butylamine-2,2,6,6-tetramethylpiperidine) -4,6-dichloro-1,3,5-triazine and two-substitution product 2,4-bis(4-butylamine-2,2,6,6-tetrarnethylpiperidine)-6-chloro-1,3,5-triazine.The latter obtained onesubstitution product 2-(1-cyclohexyloxy-4-butylamine-2,2,6,6-tetramethylpiperidine) -4,6-dichloro-1,3,5-triazine and two-substitution product 2,4-bis(1-cyclohexyloxy-4-butylamine-2,2,6,6-tetramethylpiperidine)-6-chloro-1,3,5-triazine.The molecular weight was measured by ESI-MS.Compared to the synthesis of triazine/hindered amine,steric factor of hindered amine cyclohexyl ethers increased significantly. One-substitution product could be generated in the ice bath,while two-substitution product couldn't be got even if the temperature was of 70℃.The yield of two-substitution product was increased considerably when the reaction temperature was of 85℃.