乙基二茂铁是合成二茂铁衍生物的重要中间体,在航天、制药等领域有着广泛的应用。目前烷基二茂铁的合成主要采用间接法[1]：先进行二茂铁的酰化反应，然 后经还原后制得烷基二茂铁(Scheme1)间接法制备乙基二茂铁步骤多，过程长，而且在还原过程中用到有毒，易爆的危险药品，造成了环境污染。这里，我 们以氯铝酸离子液体作为催化剂和溶剂，将二茂铁与卤代烷直接反应进行Friedel-Crafts烷基化反应。氯铝酸离子液体不但可以有效地催化合成乙基 二茂铁，而且可以控制副产物的生成，提高了目标产物的选择性。在离子液体反应体系中，最优条件下(反应温度60℃，压力3MPa，反应时间6h)，二茂铁 的转化率大于80%，目标产物乙基二茂铁的选择性可达到80%。一步法合成乙基二茂铁缩短了反应路线，避免了危险品的使用，从而达到了绿色合成的目的。

刘士民,王利国,杨本群,等. 氯铝酸离子液体中一步法合成乙基二茂铁[C]. 第二十八届中国化学会年会第1分会场摘要集.2012,16.

A series of silica, glass and molecular sieves supported chloroaluminate ionic liquids (ILs) were prepared and their catalytic performance on the trimerization of isobutene based on C4 mixture was investigated. Interestingly, it was found that the carrier played a key role in the reaction route. Among these supported catalysts, silica supported chloroaluminate ionic liquid was highly efficient for the trimerization of isobutene. X-ray photoelectron spectroscopy (XPS) and differential scanning calorimetry (DSC) characterizations suggested that the synergy between Al2Cl7− anion and silica induced the catalytic activity for isobutene oligomerization due to the strong interaction between ILs and silanol group. The reaction conditions including loading amount, temperature, reactant concentration, and space velocity for the isobutene oligomerization were optimized. Ultimately, complete conversion of isobutene and 91.4% selectivity of trimers were obtained over the IL/silica (30 wt.%) catalyst at mild conditions. Moreover, catalyst stability and deactivation were preliminarily studied.

Keywords: Ionic liquid; Silica supported; Isobutene; Trimerization; C4 feed

★★★☆☆ Liu SM,Shang JP,Zhang SG,et al. Highly Efficient Trimerization Of Isobutene Over Silica Supported Chloroaluminate Ionic Liquid Using C4 Feed[J]. Catalysis Today,2012,200:41-48.

A new series of low-melting ammonium salts based on the [nido-7,8-C2B9H12]– anion have been synthesized and characterized, and their physicochemical properties including spectroscopic properties, thermal properties, surface properties, solubility, density, viscosity, electrochemical properties, and tribological properties have been studied in detail. In comparison with previously reported carborane-derivatized imidazolium or pyridinium salts, these diether-functionalized ammonium salts display lower phase transition temperatures (Tg = –76 to –57 °C), and four exist as liquids at room temperature due to their flexible alkoxy chains. TGA analysis revealed that the weight loss rates of these carborane-derivatized low-melting salts were ca. 30–80 wt.-% after thermal decomposition, which is different from the traditional RTILs. SEM images showed that the resulting residue had hollow reticular shell morphology, and XPS and XRD analyses indicate that the main components of the skeleton are B2O3 and amorphous carbon. This provides a new strategy for preparing new inorganic porous materials by thermal decomposition of these low-melting salts.

Keywords: Ionic liquids / Carboranes / Boron / Carbon / Raman spectroscopy / IR spectrocsopy

★★★☆☆ Liu SM,Chen ZJ,Zhang QH,et al. Carborane-derivatized Low-melting Salts With Ether-functionalized Cations—preparation And Properties[J]. Eur. J. Inorg. Chem.,2011:1910–1920.