126-39-6Relevant academic research and scientific papers
Control of morphology and catalytic activity of a cationic layered material
Swanson, Claudia H.,Shaikh, Harris A.,Abdollahian, Yashar,Hauser, Jesse L.,Ikehata, Mariko,Oliver, Scott R.J.
, p. 93 - 98 (2012)
We have discovered three new synthetic pathways to our two-dimensional cationic inorganic material, antimony oxide hydroxide ethanedisulfonate, [Sb4O4(OH)2](O3SCH 2CH2SO3)?H2O. These new methods include room temperature conditions and allow control of crystal size and morphology for improved catalytic performance of the material. As a benchmark reaction, we studied ketalization of 2-butanone with 1,2-ethanediol, a common step for carbonyl group protection. Our material is easily recovered for reuse and gives a higher yield and turnover rates than the typical iodine or toluenesulfonate homogeneous catalyst. The yield ranged between 79 and 92%, with the crystals from reflux conditions giving the highest yield when used as-synthesized. The morphology and properties for each crystal growth method are described in detail. A repeated catalysis study with powdered samples increases the yield to ca. 97%.
Three-dimensional phosphine metal-organic frameworks assembled from Cu(I) and pyridyl diphosphine
Tan, Xin,Li, Lei,Zhang, Jianyong,Han, Xiaorui,Jiang, Long,Li, Fuwei,Su, Cheng-Yong
, p. 480 - 485 (2012)
Metal-organic frameworks (MOFs) with phosphine based ligands are extremely attractive for catalysis. In this paper, phosphine has been successfully incorporated for the first time into three-dimensional (3D) MOFs. The MOFs are based on rigid L2M2 dimeric secondary building blocks assembled from Cu(I) and a pyridyl diphosphine ligand, 4-(3,5- bis(diphenylphosphino)phenyl)pyridine, with Br- (CuL-Br), Cl - (CuL-Br), or PF6- (CuL-PF6) as counteranions. The structures have a 4.122 net topology, which can be further simplified to 64.82-qtz. The MOFs contain 1D homochiral channels. The PF6- anions hosted in the 1D channel of CuL-PF6 can be readily exchanged with Br- or Cl- while keeping the framework intact. The materials show anion-tunable flexible porosity. CuL-Br reveals gradual uptake of MeOH, while CuL-PF6 exhibits stepwise sorption for MeOH. The heterogeneous Lewis acid catalytic activity of the MOFs has been shown in ketalization reaction. CuL-Br and CuL-PF6 are active in the reactions between ethylene glycol and 2-butanone/cyclohexanone, up to 93% yield with 0.2 mol % catalyst loading. In contrast, no reaction happens between ethylene glycol and bulky benzophenone, suggesting profound size selectivity. The catalysts can be reused with the framework left intact for three runs without loss of activity.
Synthesis of 1-bromo-3-buten-2-one
Westerlund, Andreas,Carlson, Rolf
, p. 4035 - 4042 (1999)
A synthetic method for 1-bromo-3-buten-2-one is given. The compound is prepared through the following sequence: 2-butanone to 2-methyl-2-ethyl-1,3- dioxolane to 2-(1-bromoethyl)-2-bromomethyl-1,3-dioxolane to 2-bromomethyl-2- vinyl-1,3-dioxolane to the final product. Full experimental details including spectral data are given.
Cationic two-dimensional inorganic networks of antimony oxide hydroxide for Lewis acid catalysis
Yin, Jinlin,Fei, Honghan
, p. 4054 - 4058 (2018)
We have successfully synthesized a rare example of inorganic layered materials possessing a positive charge, which is well outside the isostructural set of layered double hydroxides. This layered architecture consists of two-dimensional corrugated [Sb2O2(OH)]+ layers with linear α,ω-alkanedisulfonate anions residing in the interlamellar space. This cationic material displays a chemical robustness under highly acidic aqueous conditions (pH = 1). Combining the robust nature and the high density of SbIII sites on the exposed crystal facets, our cationic layered material is an efficient, recyclable catalyst for cyanosilylation of benzaldehyde derivatives with trimethylsilyl cyanide. In addition, the Lewis acidity of the SbIII sites also catalyzes the ketalization of carbonyl groups under "green" solvent-free conditions.
Solvothermal synthesis, structure and catalytic activity of a mixed-valence CuI/CuII complex with 1-D chain structure
Han, Zhi-Ping,Li, Yahong
, p. 73 - 76 (2012)
A complex of composition [CuI4CuII(mtpo) 4(H2O)2Cl2]n (1) was synthesized from reaction of Hmtpo (Hmtpo = 5-methyl-[l,2,4]-triazolo-[l,5-a]- pyrimidin-7-o1) with one equivalent of CuCl2·2H2O in water at 100 °C under autogenous pressure. Complex 1 was fully characterized by X-ray single crystal diffraction, elemental analysis and IR spectroscopy. X-ray analysis reveals that complex 1 is a mixed-valence coordination polymer and displays 1-D chain structure. Compound 1 was able to heterogeneously catalyze the ketalization reaction of 2-butanone and ethylene glycol to afford 2-ethyl-2-methyl-[1,3]-dioxolane in excellent yield under mild conditions.
Synthesis of a novel melamine-formaldehyde resin-supported ionic liquid with Bronsted acid sites and its catalytic activities
Xing, Guiying
, p. 1369 - 1374 (2013)
Bronsted acidic ionic liquid immobilized on a melamine-formaldehyde resin (AIL-MFR) was synthesized through the reaction of melamine-formaldehyde resin (MFR) with 1,4-butanesulfonate. Using PEG-2000 as the additive, the MFR can be prepared in regular microspheres with an average diameter of 3.97 μm and surface area of 9.09 m2 g-1. The AIL-MFR had high acidity of 2.93 mmol g-1, mainly from the sulfonic groups. The catalysis results showed that the AIL-MFR had high activity and stability for acetalization with excellent conversions and yields for most substrates. Furthermore, immobilization of the acidic ionic liquid on the MFR made the recycling of the catalyst convenient.
First Example of a Nonanuclear Silver Sulfate Hybrid Cluster: Green Approach for Synthesis of Lewis Acid Catalyst
Paul, Avijit Kumar,Naveen, Kumari,Kumar, Nikhil,Kanagaraj, Rajendiran,Vidya,Rom, Tanmay
, p. 6411 - 6416 (2018)
Finding a high nuclearity hybrid framework with novel structure and properties by an environmentally benign approach is a really challenging task. Herein, a green strategy for synthesis of a new inorganic-organic hybrid framework solid has been described. The framework contains silver sulfate clusters with nine different silver ions with shortest silver-silver connectivity. The present compound is the first example of nonanuclear silver sulfate hybrid framework with a new topology. The hybrid solid compound shows a highly active Lewis acidic nature for the various heterogeneous catalytic reactions such as cyanosilylation, ketalization, and esterification with quantitative transformation and recyclability.
Hydrothermal synthesis of two cationic bismuthate clusters: An alkylenedisulfonate bridged hexamer, [Bi6O4(OH) 4(H2O)2][(CH2)2(SO 3)2]3 and a rare nonamer templated by triflate, [Bi9O8(OH)6][CF3SO 3]5
Rogow, David L.,Fei, Honghan,Brennan, Daniel P.,Ikehata, Mariko,Zavalij, Peter Y.,Oliver, Allen G.,Oliver, Scott R. J.
, p. 5619 - 5624 (2010)
This paper reports the synthesis, characterization, and application of two cationic bismuthate clusters by anion templating. The compounds were synthesized under mild hydrothermal treatment and characterized by powder and single-crystal X-ray diffraction, infrared spectroscopy, and thermogravimetric analysis. The first material consists of a cationic hexanuclear bismuthate cluster octahedral in geometry and linked by 1,2-ethanedisulfonate molecules. This structure is thermally stable to about 235 °C. In the second compound, discrete cationic nonanuclear bismuthate clusters interact electrostatically with trifluoromethanesulfonate anions to pack into a nearly layered assembly. The material undergoes a transformation to Bi2O3 upon loss of the triflate groups at about 385 °C. Both materials demonstrate the use of sulfonate groups for the anion-directed assembly of these rare cationic inorganic structures. The application of the 3D octahedral bismuth cluster material toward acidic heterogeneous catalysis is also reported.
Facile preparation of ionic liquid functionalized magnetic nano-solid acid catalysts for acetalization reaction
Wang, Ping,Kong, Aiguo,Wang, Wenjuan,Zhu, Haiyan,Shan, Yongkui
, p. 159 - 164 (2010)
The facile two-step preparation procedure of a novel magnetic nano-solid acid catalyst is described, which includes grafting an ionic liquid onto Fe 3O4 nanoparticles, followed by the sulfonation of phenyl groups in the ionic liquid. The catalytic performance of this novel material has been systematically studied in the acetal formation of benzaldehyde and ethylene glycol. The experimental results testify this catalyst possesses high catalytic activity with a yield of 97% under mild reaction conditions. Furthermore, the catalyst is readily separated using a permanent magnet and it is reusable without any significant decrease in catalytic activity.
Polyacrylonitrile fiber mat supported solid acid catalyst for acetalization
Shao, Linjun,Du, Yijun,Xing, Guiying,Lv, Weixi,Liang, Xuezheng,Qi, Chenze
, p. 1199 - 1203 (2012)
A novel polyacrylonitrile hybrid fiber mat supported solid acid catalyst was prepared by electrospin-ning, and its catalytic activities were carefully investigated through acetalization reactions. The results showed that this hybrid fiber mat exhibits high activity for the reactions, with average yields over 95%. Besides having catalytic activities similar to the solid acid, the heterogeneous solid acid/polyacrylonitrile mat can be reused in six runs without significant loss of catalytic activities. The large size of the hybrid fiber mat greatly facilitates recovery of the catalyst from the reaction mixture. The high and stable catalytic activities of the hybrid fiber mat hold great potential for green chemical processes and preparation of membrane reactors in the future.
