Molecular Behaviors of Formaldehyde Encapsulated in Supercages of Zeolite NaY with Different Loadings and its Intrinsic Reactivity for the Carbonyl-ene Reaction with alpha-Methylstyrene

作者：Sato Kei ichi; Masui Yoichi; Onaka Makoto^*

来源：Bulletin of the Chemical Society of Japan, 2017, 90(12): 1318-1324.

DOI：10.1246/bcsj.20170252

The reactivity of formaldehyde (HCHO) adsorbed in the supercages of zeolite NaY toward alpha-methylstyrene for the carbonyl-ene reaction was very dependent on the loading amount of HCHO in the NaY pores. We first prepared a series of NaY samples with different amounts of HCHO, and applied them to the carbonyl-ene reaction with excess amounts of alpha-methylstyrene to evaluate their intrinsic reactivities. It was found that one formaldehyde molecule adsorbed in one supercage of NaY produced 3-phenylbut-3-en-1-ol in the highest yield (83%), while for higher loading amounts of HCHO on NaY, lower yields of the product were obtained because the supercages were narrowed by the HCHO molecules as well as the homoallylic alcohol product and its over-reaction products. We next investigated their states of HCHO adsorbed in the pores by (CDD)-C-13/CPMASNMR analysis. When three HCHO molecules were adsorbed in a supercage, it was clarified that all the HCHO was exclusively encapsulated in a monomeric form, while most of the adsorbed HCHO with much higher loading amounts was transformed into 1,3,5-trioxane inside the supercages of NaY as well as paraformaldehyde outside the supercages.

• 出版日期2017-12