TY - JOUR
T1 - Mechanistic Study on the Efficient Conversion of d -Sorbitol to Iodohexanes Mediated by Hydroiodic Acid
AU - Li, Teng
AU - Jin, Ping
AU - Zhang, Yekai
AU - Huang, Kexin
AU - Long, Jingen
AU - Jiang, Jun
AU - Liu, Shengqin
AU - Sen, Ayusman
AU - Yang, Weiran
N1 - Funding Information:
This work was financially supported by funds from the National Natural Science Foundation of China (Grant 21808100), “Thousand Young Talents” Program of China, “Thousand Talents” Entrepreneurship Program of Jiangxi Province, and China Postdoctoral Science Foundation Funded Project (Project 2019M652285). We thank Peng Zhou from the School of Foreign Studies of Nanchang University for the language revision.
Publisher Copyright:
© 2020 American Chemical Society.
PY - 2020/9/30
Y1 - 2020/9/30
N2 - As an important biomass-derived chemical, d-sorbitol can be converted to a variety of useful chemicals and fuels. Because of the strong nucleophilicity of I- and reducibility of hydrogen iodide (HI), hydroiodic acid has been used for polyol hydrogenolysis with high selectivity. Here, d-sorbitol was converted by HI, rhodium, and hydrogen to give a high yield of iodohexanes (94.2%) at 373 K in a water/cyclohexane biphasic system. Rhodium and hydrogen were used to regenerate HI in situ. The reaction mechanism was studied in detail by using model molecules. The substitution-elimination-addition (SEA) mechanism was proven to be the most possible pathway. The high concentration of both proton and iodide was found to be necessary for the efficient conversion of d-sorbitol and the selective formation of iodohexanes. Besides, water could inhibit the conversion of d-sorbitol dramatically. These findings were explained by kinetic study and demonstrated in the reaction kinetic equation. This catalytic system, including HI and RhCl3, was proven to be reusable. In addition, iodohexanes can be quantitatively converted to hexenes over ZrO2 at 473 K.
AB - As an important biomass-derived chemical, d-sorbitol can be converted to a variety of useful chemicals and fuels. Because of the strong nucleophilicity of I- and reducibility of hydrogen iodide (HI), hydroiodic acid has been used for polyol hydrogenolysis with high selectivity. Here, d-sorbitol was converted by HI, rhodium, and hydrogen to give a high yield of iodohexanes (94.2%) at 373 K in a water/cyclohexane biphasic system. Rhodium and hydrogen were used to regenerate HI in situ. The reaction mechanism was studied in detail by using model molecules. The substitution-elimination-addition (SEA) mechanism was proven to be the most possible pathway. The high concentration of both proton and iodide was found to be necessary for the efficient conversion of d-sorbitol and the selective formation of iodohexanes. Besides, water could inhibit the conversion of d-sorbitol dramatically. These findings were explained by kinetic study and demonstrated in the reaction kinetic equation. This catalytic system, including HI and RhCl3, was proven to be reusable. In addition, iodohexanes can be quantitatively converted to hexenes over ZrO2 at 473 K.
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U2 - 10.1021/acs.iecr.9b06348
DO - 10.1021/acs.iecr.9b06348
M3 - Article
AN - SCOPUS:85095135999
SN - 0888-5885
VL - 59
SP - 17173
EP - 17181
JO - Industrial and Engineering Chemistry Research
JF - Industrial and Engineering Chemistry Research
IS - 39
ER -