934-55-4Relevant articles and documents
Aromatization modulates the activity of small organic molecules as promoters for carbon-halogen bond activation
Yang, Huan,Chu, De-Zhao,Jiao, Lei
, p. 1534 - 1539 (2018/02/14)
The combination of small organic molecules and a base serves as a unique system for the activation carbon-halogen bonds in haloarenes by single electron transfer (SET). However, most of the molecules employed as promoters only allow for the activation of aryl iodides, and efficient activation of aryl bromides and chlorides under this mode is still rather challenging. Herein, we report the discovery of a structurally simple yet powerful promoter molecule, indoline, which exhibits unusually high activity in promoting the activation of haloarenes by SET. In the presence of t-BuOK and a trace amount of oxygen, indoline promotes the formation of aryl radicals not only from aryl iodides and bromides, but also from unactivated aryl chlorides (e.g., chlorobenzene) under relatively mild conditions. Mechanistic studies reveal the molecular basis for its high activity, for which the aromatization process plays a key role in modulating the electron transfer process.
Very efficient conversion of glucose to 5-hydroxymethylfurfural in DBU-based ionic liquids with benzenesulfonate anion
Wu, Lingqiao,Song, Jinliang,Zhang, Binbin,Zhou, Baowen,Zhou, Huacong,Fan, Honglei,Yang, Yingying,Han, Buxing
, p. 3935 - 3941 (2014/08/05)
Efficient conversion of glucose to 5-hydroxymethylfurfural (HMF), an important platform molecular for fuels and chemicals, is a promising topic in green chemistry. In this work, several new DBU-based (DBU = 1,8-diazabicyclo[5. 4.0]undec-7-ene) ionic liquids (ILs) with benzene sulfonate (BS) anion were synthesized and used as the solvents for the dehydration of glucose to HMF. It was found that all the ILs were excellent solvents for the dehydration of glucose to form HMF using CrCl3 as the catalyst. The effects of various factors, such as kind of catalysts, catalyst amount, reaction time and reaction temperature, on the yields of HMF were studied systematically in the Et-DBUBS/CrCl3 catalytic system. The yield of HMF from glucose could reach 83.4% under the optimized reaction conditions, and the reasons for the high yield were investigated on the basis of control experiments. The Et-DBUBS/CrCl3 system could be reused at least five times without considerable reduction in the efficiency. Further study indicated that the catalytic system was also very efficient for transformation of fructose, inulin, and cellobiose to HMF. This journal is the Partner Organisations 2014.
On the positional reactivity order in the sulfur trioxide sulfonation of benzene, halogenobenzenes, halogenonaphthalenes, and chloroanthracenes
Cerfontain,Zou,Bakker,van de Griendt
, p. 1966 - 1971 (2007/10/02)
The reaction of sulfur trioxide with benzene, the four halogenobenzenes, and six halogenonaphthalenes in dichloromethane as solvent, and with four chlorinated anthracenes in nitromethane as solvent, has been studied by analysis of the resulting mixture of the sulfo derivatives with 1H NMR. The sulfonation of benzene yields initially benzenesulfonic acid and subsequently the 1,3-disulfonic acid (1,3-S2). The initial sulfonation of the four halogenobenzenes yields ? 98% of the 4-S. Their subsequent sulfonation gives the 2,4-S2 and in the case of fluoro- and iodobenzene also the 2,4,6-S3. Monosulfonation of 1-fluoronaphthalene yields only the 4-S, whereas the three other 1-halogenonapthalenese yield in addition some 5-S. Further sulfonation on any of the four 1-halogenonaphthalene-4-sulfonic acids yields a mixture of the 2,4-S2 and 4,7-S2, and eventually also some 2,4,7-S3, whereas the 1-halogeno-5-sulfonic acids give the corresponding 5,7-S2. Sulfonation of 2-chloro- and 2-bromonaphthalene yields initially 85% 8-S and 15% 4-S, which are subsequently converted into the 6,8-S2 and 4,7-S2, respectively. On reaction with 1.0 mol-equiv. of SO3, 2-chloroanthracene gives the 9-S, and 9-chloroanthracene gives an 18:82 mixture of the 4-S and 10-S. Both 1,5- and 1,8-dichloroanthracene yield initially the 4-S and subsequently the 4,8-S2 and 4,5-S2, respectively.