Donor‐Stabilized Phosphenium Adducts as New Efficient and Immobilizing Ligands in Palladium‐Catalyzed Alkynylation and Platinum‐Catalyzed Hydrogenation in Ionic Liquids

The straightforward synthesis of a new donor‐stabilized phosphenium ligand 3d by addition of bromodifurylphosphine to 1,3‐dimethylimidazolium‐2‐carboxylate 1 is described. The obtained ligand exhibits a very strong π‐acceptor character, comparable to that of triphenyl phosphite [P(OPh)₃] or of tris‐halogenophosphines, with a ν_CO(A₁) at 2087 cm⁻¹ for its nickel tricarbonyl complex. This ligand, as well as the related 3a which was obtained from chlorodiphenylphosphine, were tested in palladium‐catalyzed aryl alkynylation and in the platinum‐catalyzed selective hydrogenation of chloronitrobenzenes, both in an ionic liquid phase. In C C bond cross‐coupling we observed that the increase of the π‐acceptor character in ligand 3d , due to the introduction of an additional electron‐withdrawing group, provides a very efficient catalyst in the alkynylation reaction of aryl bromides with phenylacetylene, including the deactivated 4‐bromoanisole or the sterically hindered 2‐bromonaphthalene. The catalytic activity decreases with recycling due to the sensitiveness of ligands to protonation in the ionic phase. Conversely, a multiple recycling of the metal/ligand system in non‐acidic media was achieved from platinum‐catalyzed hydrogenation of m‐chloronitrobenzene. The catalytic results obtained by employing the complex of platinum(II) chloride with 3a [trans‐PtCl₂( 3a )₂] in comparison with the non‐ionic related trans‐tris(triphenylphosphine)platinum dichloride [trans‐PtCl₂(PPh₃)₂] complex clearly indicate that the simultaneous existence of a strong π‐acceptor character and a positive charge within the ligand 3a significantly increases the life‐time of the platinum catalyst. The selectivity of the reaction is also improved by decreasing the undesirable formation of dehalogenation products. This cationic platinum complex trans‐PtCl₂( 3a )₂ is the first example of a highly selective catalyst for hydrogenation of chloronitroarenes immobilized in an ionic liquid phase. The system was recycled six times without noticeable metal leaching in the organic phase, and no loss of activity.     

High Regioselective Diels–‐Alder Reaction of Myrcene with Acrolein Catalyzed by Zinc‐Containing Ionic Liquids

The ambient zinc‐containing ionic liquids, MX‐ZnCl₂, functioning as both Lewis acid catalyst and green solvent, are employed for a high regioselective Diels–Alder reaction of myrcene with acrolein for the first time, where MX is either 1‐butyl‐3‐methylimidazolium chloride (BmimCl), 1‐ethyl‐3‐methylimidazolium bromide (EmimBr), N‐butylpyridinium bromide (BPyBr), or N‐ethylpyridinium bromide (EtPyBr). Compared with the analogous reaction performed over a ZnCl₂ catalyst in the conventional solvent dichloromethane, higher regioselectivity of the ‘para’ cycloadduct and excellent yield were achieved at shorter reaction time in these ionic liquids with optimized molar compositions of MX and ZnCl₂. These moisture‐insensitive ionic liquids can be easily separated from reaction products after simple washing with hexane, allowing their reuse with no obvious loss in activity.     

Efficient Heterogeneous Asymmetric Catalysis of the Mukaiyama Aldol Reaction by Silica‐ and Ionic Liquid‐Supported Lewis Acid Copper(II) Complexes of Bis(oxazolines)

Lewis acid complexes based on copper(II) and an imidazolium‐tagged bis(oxazoline) have been used to catalyse the asymmetric Mukaiyama aldol reaction between methyl pyruvate and 1‐methoxy‐1‐trimethylsilyloxypropene under homogeneous and heterogeneous conditions. Although the ees obtained in ionic liquid were similar to those found in dichloromethane, there was a significant rate enhancement in the ionic liquid with reactions typically reaching completion within 2 min compared with only 55 % conversion after 60 min in dichloromethane. However, this rate enhancement was offset by lower chemoselectivity in ionic liquids due to the formation of 3‐hydroxy‐1,3‐diphenylbutan‐1‐one as a by‐product. Supporting the catalyst on silica or an imidazolium‐modified silica using the ionic liquid or in an ionic liquid‐diethyl ether system completely suppressed the formation of this by‐product without reducing the enantioselectivity. Although the heterogeneous systems were characterised by a drop in catalytic activity the system could be recycled up to five times without any loss in conversion or ee.     

Lewis Basic Ionic Liquids‐Catalyzed Conversion of Carbon Dioxide to Cyclic Carbonates

A series of easily prepared Lewis basic ionic liquids were developed for cyclic carbonate synthesis from epoxide and carbon dioxide at low pressure without utilization of any organic solvents or additives. Notably, quantitative yields together with excellent selectivity were attained when 1,8‐diazabicyclo[5.4.0]undec‐7‐enium chloride ([HDBU]Cl) was used as a catalyst. Furthermore, the catalyst could be recycled over five times without appreciable loss of catalytic activity. The effects of the catalyst structure and various reaction parameters on the catalytic performance were investigated in detail. This protocol was found to be applicable to a variety of epoxides producing the corresponding cyclic carbonates in high yields and selectivity. Therefore, this solvent‐free process thus represents an environmentally friendly example for the catalytic conversion of carbon dioxide into value‐added chemicals by employing Lewis basic ionic liquids as catalyst. A possible catalytic cycle for the hydrogen bond‐assisted ring‐opening of epoxide and activation of carbon dioxide induced by the nucleophilic tertiary nitrogen of the ionic liquid was also proposed.     

Three‐Component One‐Pot Synthesis of α‐Hydroxylamino Phosphonates using Ionic Liquids

α‐Hydroxylamino phosphonates are synthesised in a one‐pot operation by three‐component coupling reactions of aldehydes, hydroxylamines and diethyl phosphite using 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([bmim]BF₄) or 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([bmim]PF₆) ionic liquids under mild and neutral conditions. The recovered ionic liquids can be recycled for four to five runs without loss of activity.     

Improvement of melt stability and degradation efficiency of poly (lactic acid) by using phosphite

Concurrent improvement of melt processing stability and degradation efficiency of poly(lactic acid) (PLA) is still a challenge for the industry. This article presents the use of phosphites: tris(nonylphenyl) phosphite (TNPP) and tris (2,4-di-tert-butylphenyl) phosphite (TDBP), to control the thermal stabilization, mechanical performance, and hydrolytic degradation ability of the compressed PLA films. The hydrolysis process is followed as a function of time at 45, 60, and 75°C. During melt extrusion, both phosphites function as a processing aid, besides acting as a chain extender stabilizing the PLA molecular weight. The phosphite structure plays a crucial role over crystallinity and water absorption, in controlling the hydrolytic degradation of PLA. The application of TNPP significantly catalyzes the hydrolysis of PLA, which is the initial step of the biodegradation process. The optimum amount of TNPP for best hydrolytic degradation efficiency and thermal stabilization of PLA is 0.5 wt%. The excessive TNPP loadings cause a drastic drop in PLA molecular weight and, as a consequence, a reduction of flexural strength. The reactions between PLA and phosphite molecules are discussed.     

Synthesis,characterization, and application of oligomer‐type‐based phosphites

Organic alkyl and aryl phosphites are effective antioxidants and photostabilizers with applications in a wide range of polymers. The primary role of phosphites is to decompose hydroperoxide. However, aryl phosphites are also capable of reacting as antioxidants by affecting the kinetics. In particular, oligomer‐type phosphites have a greater effect on polymer degradation because of their high compatibility, reactivity, and solubility with almost all polymers. Generally, phosphites are sensitive to hydrolysis. In order to overcome this hydrolytic sensitivity in phosphites, a novel hydrolytically stable oligomeric phosphite incorporating a sterically hindered aromatic alcohol (2,4‐di‐tert‐butyl‐6‐methylphenol) that gives hydrolytic stability to the phosphite was synthesized and characterized, and its performance as an antioxidant for polypropylene was investigated. J. VINYL ADDIT. TECHNOL., 22:146–155, 2016. © 2014 Society of Plastics Engineers     

Supported Ionic Liquid Enzymatic Catalysis for the Production of Biodiesel

Pseudomonas cepacia lipase supported in the 1‐n‐butyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquid is an alternative “green” method for the production of biodiesel from the alcoholysis of soybean oil. The transesterification reaction catalyzed by this ionic liquid‐supported enzyme can be performed at room temperature, in the presence of water and without the use of organic solvents. It is also compatible with various alcohols (including isoamyl alcohol). The biodiesel is separated by simple decantation and the recovered ionic liquid/enzyme catalytic system can be re‐used at least four times without loss of catalytic activity and selectivity.     

Sulfonic Acid‐Functionalized Ionic Liquids as Metal‐Free,Efficient and Reusable Catalysts for Direct Amination of Alcohols

A series of sulfonic acid‐functionalized (SO₃H‐functionalized) ionic liquids was synthesized and used as metal‐free, highly selective and efficient catalysts for the direct amination of alcohols. Notably, the activities of the series of SO₃H‐functionalized ionic liquids were compared and a 92% isolated yield was obtained using 3‐tetradecyl‐1‐(butyl‐4‐ sulfonyl)imidazolium trifluoromethanesulfonate ([BsTdIM][OTf]) as the catalyst. Importantly, the catalytic system has wide substrate scope including benzylic, allyl, propargylic, aliphatic alcohols with sulfonamide, amide, carbamate, aromatic amine and N‐heterocyclic compounds. Interestingly, the system was also suitable for a multi‐gram scale direct amination of alcohols. Additionally, the reusable nature of [BsTdIM][OTf] makes this protocol more attractive and avoids the disposal and neutralization of acidic catalysts. Moreover, preliminary experiments indicated that this reaction should proceed via an S_N1 pathway.     

Lewis酸离子液体催化的苯和氯乙烷烷基化反应

以Lewis酸离子液体为催化剂,考察了Lewis阴离子催化剂、加料方式、AlCl3/[Et3NH]Cl摩尔比、反应温度、苯/氯乙烷摩尔比、催化剂用量等因素对苯和氯乙烷烷基化反应的影响及离子液体的重复可用性. 结果表明,在AlCl3/[Et3NH]Cl摩尔比为2的离子液体的催化作用下,苯和氯乙烷的烷基化反应在温度为70℃、苯/氯乙烷摩尔比为10:1、催化剂用量为苯和氯乙烷总质量10%的条件下,苯转化率为9.48%,乙苯选择性为93.65%;离子液体可循环使用10次,苯的转化率和乙苯的选择性均无明显变化.     

Synthesis and antioxidative properties of novel multifunctional stabilizers

New multifunctional stabilizers containing hindered amino, phosphite, and in some cases also free phenolic moieties have been synthesized starting from tris(diethylamino)phosphine. Some of them proved to be efficient stabilizers for model hydrocarbons and for polypropylene during processing, thermo‐, and photooxidation. Various sterically hindered phenols, amines (HAS), and phosphites have been modified by the reaction with isophorone diisocyanate (IPDI) to get new multifunctional stabilizers for polymers. The synthesized products have been investigated regarding their thermal and antioxidative behavior. The novel urethane stabilizers are, depending during the polymer processing to release the antioxidatively active parent phenols.     

Ionic liquid as surfactant in microwave‐assisted emulsion polymerization

The aim of this work is to study the use of an ionic liquid (IL) as surfactant in emulsion polymerization reactions and to evaluate its effect when these reactions are heated under microwave irradiation. The IL 1‐n‐dodecyl‐3‐methylimidazolium chloride was chosen to replace the surfactant dodecyltrimethylammonium bromide (DTAB) in methyl methacrylate emulsion polymerizations. The conversion evolutions and the final average diameter of polymeric particles were quite similar for reactions using the surfactant DTAB or the IL, showing that the IL acted efficiently as surfactant in emulsion polymerizations. Comparing the polymerization reactions performed under microwave irradiation and conventional heating, reaction rate enhancements were obtained for both DTAB and IL. Using a pulsed scheme, under high‐power microwave irradiation, slightly higher reaction rates and molecular weights were obtained in reactions using IL, in comparison with surfactant DTAB, indicating the existence of some specific effects linked to IL–microwaves interaction. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

氯铝酸离子液体催化苯与1-己烯的烷基化反应

研究了在具有 Lewis酸性的氯铝酸离子液体体系中进行的苯与 1 -己烯的烷基化反应。以溴化 1 -乙基 - 3 -甲基咪唑 (emim Br) ,溴化 1 -丁基 - 3 -甲基咪唑 (bmim Br) ,盐酸三乙胺 (Et3NHCl) ,溴化四丁基铵 (C4 H9NBr) ,十六烷基三甲基溴化铵 (C19H4 2 Br N)分别与 Al Cl3原位合成法制备离子液体催化体系。结果表明以上各种离子液体均有很高的催化活性 ,反应转化率在短时间内达到1 0 0 %。其中 Et3NHCl- Al Cl3离子液体单烷基选择性达到 98.1 %。而且催化剂易于分离并能重复使用 ,反应转化率没有明显降低     

Biphasic Hydrogenation of Olefins by Functionalized Ionic Liquid‐Stabilized Palladium Nanoparticles

Palladium nanoparticles in the size range of 5–6 nm were prepared conveniently by reducing palladium(II) with atmospheric pressure hydrogen and stabilized by 2,2′‐dipyridylamine‐functionalized imidazolium cations according to our approach. The efficient catalytic conversion of cyclohexene into cyclohexane by the functionalized ionic liquid‐stabilized palladium nanoparticles has been performed under very mild hydrogen pressure (0.1 MPa) and at 35 °C. It was found that the concentration of palladium and the reaction temperature considerably affected the size and degree of aggregation of Pd nanoparticles in ionic liquid, which further changed the performance of the catalyst activity. The synthesized nanocatalysts can be recycled at least five times without any loss of the activity. Finally, the scope of substrates was also investigated. The excellent catalytic activity of the present system can be attributed to good stabilization and high dispersion of palladium nanoparticles.     

六氟锑酸盐离子液体的研究进展

六氟锑酸盐离子液体具有常规离子液体的特性,如低蒸汽压、不挥发、物质溶解性好等,不仅可以作为溶剂,还可以通过调配阴阳离子比例或离子交换得到路易斯酸催化剂,在多种类型反应中得到应用。主要对近年来六氟锑酸盐离子液体的合成、结构、性质及其在反应中的应用进行综述。     

Oxybromination of Ethynylbenzene Catalysed by Molybdenum Complexes in Organic Solvent and in Ionic Liquids

The molybdenum(VI)‐catalysed oxybromination of ethynylbenzene was performed with hydrogen peroxide as oxidant and potassium bromide as source of bromine, in a two‐phase water/solvent system, where solvent was either dichloromethane or an ionic liquid. The selectivity was toward 1,2‐dibromostyrene when performed in water/dichloromethane. In ionic liquids better yields and shorter reaction times were obtained that, together with the complete ethynylbenzene conversion and the preferred formation of α,α‐dibromoacetophenone, make the reaction synthetically useful.     

High‐performance phosphite stabilizer

The initial rates of air oxidation of eight aromatic phosphites were measured at 200°C in hydrocarbon solvents. The phosphites were oxidized to the corresponding phosphates, and, in every case, a small amount of the corresponding substituted phenol was also detected. The phenolic compounds likely arose from hydrolysis of the phosphites by water generated during oxidation. In general, alkyl substitution caused a decrease in the rate of oxidation. Phosphite 7 [bis(2,4‐dicumylphenyl) pentaerythritol diphosphite] and, to a lesser extent, phosphite 6 [bis(2,6‐di‐t‐butyl‐4‐methylphenyl) pentaerythritol diphosphite] had a combination of high rate of oxidation and good resistance towards hydrolysis in the bulk state, a combination that is not usual with most commercially available phosphites (1).     

Metal Triflate‐Catalyzed Regio‐ and Stereoselective Friedel–Crafts Alkenylation of Arenes with Alkynes in an Ionic Liquid: Scope and Mechanism

In the metal triflate‐catalyzed hydroarylation of alkynes, employing an ionic liquid dramatically enhanced the catalytic activities, resulting in broadening the scope of substrates (arenes and alkynes). In some cases, even reactions that were not possible in conventional organic solvents proceeded smoothly in ionic liquids. Moreover, the ionic liquid phase containing catalyst could be readily recovered by simple decantation of the organic layer after reaction and reused for the following runs without any significant loss of activity. Mechanistic studies including ¹³C NMR analysis of reaction intermediates and isotope experiments confirmed for the first time that this type of reaction proceeds via vinyl cationic intermediates.     

己内酰胺苯磺酸类离子液体催化甲苯选择性硝化反应的研究

制备了己内酰胺对甲基苯磺酸和苯磺酸离子液体作为催化剂和溶剂,用于催化甲苯与等摩尔67%(m/m)硝酸的硝化反应,并用1H NMR进行了表征。研究了不同的反应温度、时间和离子液体用量及不同的离子液体等因素对甲苯硝化反应的影响。结果表明:该离子液体对甲苯的硝化有较好的对位选择性,产物中邻、对异构体质量比为1.2,较硝硫混酸硝化(邻、对异构体质量比约2.0)显著降低,收率可达37.1%,且可重复使用。     

Butanol alcoholysis reaction of polyethylene terephthalate using acidic ionic liquid as catalyst

The alcoholysis reaction of polyethylene terephthalate (PET) and n‐butanol to produce dibutyl terephthalate (DBTP) and ethylene glycol (EG) was investigated in the presence of a Brönsted–Lewis acidic ionic liquid (IL). It was found that a synergetic effect of Brönsted and Lewis acid sites enhanced the IL catalytic performance, and (3‐sulfonic acid) propyltriethylammonium chlorozincinate [HO₃S‐(CH₂)₃‐NEt₃]Cl‐ZnCl₂ (molar fraction of ZnCl₂ (x) was 0.67) was a good catalyst for the reaction. The conversion of PET was 100%, and the yields of DBTP and EG were 95.3% and 95.7% at 205°C for 8 h, respectively. The reusability of IL was good and after it was used seven times, PET conversion and the yields of DBTP and EG did not significantly decrease. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1840–1844, 2013