Sulfuric Acid-Catalyzed Dehydration of Sorbitol: Mechanistic Study on Preferential Formation of 1,4-Sorbitan

被引：33

作者：

Yabushita, Mizuho ^{[1
,2
]}

Kobayashi, Hirokazu ^{[1
]}

Shrotri, Abhijit ^{[1
]}

Hara, Kenji ^{[1
]}

Ito, Shogo ^{[1
,2
]}

Fukuoka, Atsushi ^{[1
]}

机构：

[1] Hokkaido Univ, Catalysis Res Ctr, Kita Ku, Sapporo, Hokkaido 0010021, Japan

[2] Hokkaido Univ, Grad Sch Chem Sci & Engn, Div Chem Sci & Engn, Kita Ku, Sapporo, Hokkaido 0608628, Japan

来源：

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN | 2015年 / 88卷 / 07期

基金：

日本学术振兴会;

关键词：

SUGAR ALCOHOLS; HYDROLYTIC HYDROGENATION; LIGNOCELLULOSIC BIOMASS; BIMETALLIC CATALYSTS; SELECTIVE CONVERSION; NICKEL-CATALYSTS; AQUEOUS-SOLUTION; SOLID ACID; CELLULOSE; ISOSORBIDE;

D O I：

10.1246/bcsj.20150080

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

1,4-Sorbitan is a precursor to environmentally benign surfactants, which can be produced from biomass via sorbitol. Currently, sulfuric acid-catalyzed dehydration of sorbitol is the most widely used route for industrial synthesis of 1,4-sorbitan. In this work, we have studied the mechanism of the sorbitol dehydration by sulfuric acid. Our results show that both thermodynamic and kinetic parameters play significant roles to determine the yield of 1,4-sorbitan. Sorbitol preferentially forms an adduct with sulfuric acid, thereby inhibiting the subsequent dehydration of 1,4-sorbitan to isosorbide. Furthermore, a reaction mechanism is proposed for the dehydration reaction, which involves an S(N)2 reaction on primary C1 of sorbitol attacked by OH of secondary C4.

引用

页码：996 / 1002

页数：7

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