Bulletin of the Chemical Society of Japan p. 2232 - 2242 (2007)
Update date:2022-08-03
Topics:
Sugi, Yoshihiro
Maekawa, Hiroyoshi
Ito, Akira
Ozawa, Chikako
Shibata, Tomoko
Niimi, Amhiro
Asaoka, Chihara
Komura, Kenichi
Kubota, Yoshihiro
Lee, Jae-Youl
Kim, Jong-Ho
Seo, Gon
Alkylation, i.e., isopropylation, s-butylation, and t-butylation, of biphenyl (BP) was examined over one-dimensional twelve-membered (12-MR) zeolites: Mordenite (MOR) and SSZ-24 (AFI) with straight channels, and SSZ-55 (ATS) and SSZ-42 (IFR) with corrugated channels. Types of zeolites and alkylating agents highly influenced the selectivities for dialkylbiphenyl (DABP) isomers. Shape-selective formation of 4,4'-diisopropylbiphenyl (4,4'-DIPB) was observed over MOR and AFI; however, ATS and IFR gave 4,4'-DIPB only in low selectivities at 250°C: 87% over MOR, 60% over AFI, 20% over ATS, and 30% over IFR. The selectivities for 4,4'-di-s-butylbiphenyl (4,4'-DSBB) in the,s-butyl-ation were higher than those for 4,4'-DIPB: 95% over MOR, 85% over AFI, 75% over ATS, and 50% over IFR. The t-butylation afforded selectively 4,4'-di-t-butylbiphenyl (4,4'-DTBB) over the zeolites: 96-97% over MOR and AFI, 90% over ATS, and 80% over IFR. These results in the alkylation indicate the exclusion of 4,4'-DABP from other bulky DABP isomers by steric restriction in zeolite channels is an important key for the high shape-selectivity. Even zeolites with large channels, such as ATS and IFR, can have shape-selective nature if the bulky moieties, such as,s-butyl and t- butyl groups, are large enough to differentiate the transition state of the least bulky 4,4'-DABP from those of the other isomers inside their channels. The selectivity for 4,4'-DABP decreased at high temperatures in some alkylations: isopropylation over MOR, and s-butylation and t-butylation over MOR, AFI, and ATS. The decreases are due to the iso-merization of 4,4'-DABP at external acid sites, because the channels are not large enough for the isomerization of 4,4'-DABP to bulkier 3,4'-DABP. However, the isopropylation over AFI was accompanied by the isomerization of 4,4'-DIPB at external and internal acid sites, because the channels are large enough for the isomerization of 4,4'-DIPB.
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