Microwave-Assisted Esterification of Oleic Acid Using an Ionic Liquid Catalyst

The combination of 1-butyl-3-methylimidazolium hydrogen sulfate ([Bmim]HSO₄) ionic liquid (IL) and microwave heating was used to esterify oleic acid as a green approach in biodiesel synthesis. To compare the heating systems, conventional heating and the ultrasonic method were employed but the microwave method was found to be more effective. H₂SO₄ and 1-methyl imidazole hydrogen sulfate ([Hmim]HSO₄) were also used in the esterification of oleic acid and their catalytic activities were compared to that of [Bmim]HSO₄. ILs provided some advantages such as reusability, easy recyclability, and very stable activity. There was only a small decrease in the catalytic activity of [Bmim]HSO₄ after four successive applications, which means that ILs can be reused, contrary to homogeneous catalysts. The combination of IL catalysts and microwave irradiation proved to be a potential alternative method for biodiesel production.     

SiO_2固化SO_3H-功能化离子液体催化合成油酸甲酯

以1,3-丙烷磺内酯和巯基改性纳米二氧化硅球为原料,采用化学键合接枝法获得固化SO_3H-功能化离子液体的酸催化材料(SiO_2-IL)。采用NMR、FTIR和热分析方法对SiO_2-IL的结构和热稳定性进行了表征。考察了SiO_2-IL在油酸与甲醇酯化反应中的催化活性,分析了影响其催化性能的关键因素及原因。结果表明,该离子液体自身所具有的酸性以及固化过程中化学键合接枝程度均对其催化性能有所影响。对反应工艺条件进行了优化。结果表明,在反应温度60℃、n(甲醇)∶n(油酸)=12∶1、m(SiO_2-IL)∶m(油酸)=0.09∶1.00、反应时间5 h条件下,油酸甲酯收率最高为94%,催化材料经重复使用5次后,油酸甲酯收率仍可达74%。     

Novel SO<Subscript>3</Subscript>H-Functionalized Ionic Liquids Based on Benzimidazolium Cation: Efficient and Recyclable Catalysts for One-Pot Synthesis of Biscoumarin Derivatives

Abstract  

In this article, a new group of SO₃H-functionalized ionic liquids based on benzimidazolium cation was synthesized and used as environmentally benign catalysts for the one-pot synthesis of biscoumarin derivatives. The ionic liquids showed high catalytic activities and reusabilities with good to excellent yields of the desired products. H ₀ (Hammett function) values and the minimum-energy geometries of SO₃H-functionalized ionic liquids were determined and the results revealed that the acidities and catalytic activities of ionic liquids in the synthesis of biscoumarin derivatives were related to their structures.     

酸性离子液体催化合成N-甲酰吗啉

合成了7种酸性离子液体,并将其应用于催化合成N-甲酰吗啉的反应中,筛选出了一种可以重复使用的离子液体[HSO3-pmim]HSO4,并对其进行了表征。以吗啉和甲酸为原料,离子液体[HSO3-pmim]HSO4为催化剂,以一种环保的工艺合成了N-甲酰吗啉。用红外光谱对产品结构进行了分析表征,和N-甲酰吗啉标准谱图一致,用气相色谱测定产品质量分数大于99.8%。考察了影响反应的主要因素,确定了较佳反应条件:n(甲酸)∶n(吗啉)=1.15∶1,反应温度85~95℃,反应时间8.0 h。在该条件下[HSO3-pmim]HSO4重复使用7次后,没有明显消耗,N-甲酰吗啉的收率大于81.3%。     

Synthesis of Phytosteryl Esters by Using Alumina-Supported Zinc Oxide (ZnO/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>) from Esterification Production of Phytosterol with Fatty Acid

The feasibility of zinc oxide-catalyzed esterification of natural phytosterols with oleic acid was investigated well by a chemical process. The influences of various reaction parameters were evaluated. Basic solid zinc oxide is the most desirable catalyst due to its high selectivity (more than 90%), reusability, activity and less corrosivity, whereas sterol selectivity with other catalysts, such as H₂SO₄, NaHSO₄ and NaOMe, did not exceed 80%. Further results showed that during zinc oxide-catalyzed synthesis, the nature of the acyl donor was of paramount importance with direct esterification with fatty acids, which gives better results with higher conversion rate selectivity and more mild reaction conditions than transesterification with methyl esters. The substrate molar ratio of 2:1 (oleic acid/phytosterol) was optimal. Other parameters such as optimal catalyst load (0.5%) and temperature (170 °C) showed a maximum production of steryl esters close to 98% after 8 h. It was also found that the amount of trans fatty acid formed in esterification was low, and the trans fatty acid content (%) in the phytosterol oleate ester fraction (3.26%) was much lower than that in free oleic oil (7.35%), which suggested that fatty acids in esters were more stable than free fatty acids regarding the combination with sterol. Immobilized ZnO could be a promising catalyst for replacing homogeneous and corrosive catalysts for esterification reactions of sterol.     

Synthesis and Characterization of Ferromagnetic BaFe<Subscript>2</Subscript>O<Subscript>4</Subscript> Nanocrystals Using Novel Ionic Precursor Complex [Fe(opd)<Subscript>3</Subscript>]<Subscript>2</Subscript>[Ba(CN)<Subscript>8</Subscript>]

The following investigation reports the synthesis of novel complex [Fe(opd)₃]₂[Ba(CN)₈] and preparation of BaFe₂O₄ nanoparticles through thermal decomposition without using any surfactant. The complex was characterized via Furrier transform infrared spectroscopy (FT-IR), ultra violet-visible spectroscopy (UV–vis), conductivity measurement and elemental analysis. The synthesized crystals of inorganic precursor complex was transferred to furnace, where they were calcined under normal atmosphere condition at 900 °C for 4 h. Formation of BaFe₂O₄ was supported by FT-IR and energy-dispersive X-ray analysis. Hexagonal structure of nano-oxide was confirmed on powder X-ray diffraction. Furthermore, uniform morphology of nanocrystals were reported by scanning electron microscopy. The saturation magnetization (22 emu/g), remanent magnetization (6 emu/g) and coercivity (400 Oe) reported on vibrating sample magnetometer curve illustrates the promising industrial and medicinal applications of prepared mixed oxide.     

酸性离子液体催化合成N，N’-亚甲基双丙烯酰胺

以N-甲基咪唑、2-氯乙基苯、硫酸氢钾合成1-甲基-3-[α-甲基-(4-磺酸苄基)]咪唑硫酸氢盐酸性离子液体.考察了酸性离子液体在甲醛和丙烯腈的反应中的催化性能,确定了最佳反应条件:n(甲醛):n(丙烯腈)=1.2:1.0,酸性离子液体用量为丙烯腈质量的8.0%,反应温度70℃,反应时间2.0h.在该条件下N,N'-亚甲基双丙烯酰胺的收率大于92%,纯度为98%以上,且反应结束后产物易于分离,酸性离子液体循环使用5次以上.     

Solution-Combustion Synthesis of LiNi<Subscript>1/3</Subscript>Co<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>O<Subscript>2</Subscript> as a Cathode Material for Lithium-Ion Batteries

A cathode material for lithium-ion batteries–LiNi_1/3Co_1/3Mn_1/3O₂–was prepared by solution combustion synthesis and characterized by XRD, SEM, and galvanostatic charge/discharge cycling. The sample calcined at 950°C for 10 h showed best charge/discharge performance. An initial discharge capacity (C) of 150.5 mA h g^–1 retained 95.7% of its value after 75 charge/discharge cycles at I_c = 14 mA g^–1 (0.2C rate), I_d = 70 mA g^–1 (0.5C rate).     

Syndiospecific Polymerization of Styrene Using Half-Titanocene Catalyst Covalently Supported on MgCl<Subscript>2</Subscript>/AlEt<Subscript>n</Subscript>(OEt)<Subscript>3-n</Subscript>

The novel half-titanocene catalyst bearing reactive functional amino group, η⁵-pentamethylcyclopentadienyltri(p-amino-phenoxyl) titanium [Cp^∗Ti(p-OC₆H₄NH₂)₃], was easily synthesized by the reaction of η⁵-pentamethylcyclopentadienyltrichloride titanium (Cp^∗TiCl₃) with p-amino phenol in the presence of triethyl amine (NEt₃). Cp^∗Ti(p-OC₆H₄NH₂)₃ covalently anchored on MgCl₂/AlEt_n(OEt)_3-n support obtained from the reaction of triethylaluminium (AlEt₃) with the adduct of magnesium chloride (MgCl₂) and ethanol (EtOH), has been investigated and used to catalyze syndiospecific polymerization of styrene. Influences of the support structure, cocatalyst, and the molar ratio of Al in methylaluminoxane (MAO) and Ti (Al_MAO/Ti) on catalytic activity, syndiotacticity and molecular weight of the resultant polystyrene were investigated. Compared with the corresponding Cp^∗Ti(p-OC₆H₄NH₂)₃ homogeneous catalyst, a considerable increase in activity and molecular weight of syndiotactic polystyrene (sPS) was observed for the Cp^∗Ti(p-OC₆H₄NH₂)₃-MgCl₂/AlEt_n(OEt)_3-n supported catalyst even at a relatively low Al_MAO/Ti ratio of 50, and the kinetics of polymerization was stable during the reaction process.     

Efficient Synthesis of the Very-Long-Chain n-3 Fatty Acids,Tetracosahexaenoic Acid (C<Subscript>24</Subscript>:6n-3) and Tricosahexaenoic Acid (C<Subscript>23</Subscript>:6n-3)

Tetracosahexaenoic acid (C₂₄:6n-3, THA, 3) is an essential biosynthetic precursor in mammals of docosahexaenoic acid (C₂₂:6n-3, DHA, 1), the end-product of the metabolism of n-3 fatty acids. THA 3 is present in commercially valuable fishes, such as flathead flounder. Tricosahexaenoic acid (C₂₃:6n-3, TrHA, 2), an odd-numbered-chain fatty acid, has been identified from marine organisms such as the dinoflagellate, Amphidinium carterae. To date, few studies have examined THA 3 and TrHA 2 due to difficulties in detecting and identifying these compounds, so their chemical and biological properties remain poorly characterized. Only one methodology for the chemical synthesis of THA 3 has been presented, and no method for the synthesis of TrHA 2 has been reported. We report here the efficient synthesis of THA 3 in four steps in 56% overall yield, and the synthesis of TrHA 2 in six steps in 48% overall yield. We also present the synthesis of Δ²-THA 4, an intermediate of β-oxidation of THA 3 to DHA 1, in three steps in 73% overall yield.