Chemical oxidative polymerization of m-phenylenediamine and its derivatives using aluminium triflate as a co-catalyst

Aromatic diamine monomers, including m-phenylenediamine (mPD), 2-methyl-m-phenylenediamine (2Me-mPD), 4-methyl-m-phenylenediamine (4Me-mPD) and trimethyl-m-phenylenediamine (tMe-mPD), were polymerized by chemical oxidation using ammonium persulfate as an oxidant. Aluminium triflate (Al(OTf)₃) was also used for the first time as a co-catalyst under various polymerization conditions. The polymerization yield was improved when Al(OTf)₃ was introduced to the polymerization reaction for most polymers. The poly(2-methyl-m-phenylenediamine) (P(2Me-mPD)), poly(4-methyl-m-phenylenediamine) (P(4Me-mPD)) and poly(trimethyl-m-phenylenediamine) (P(tMe-mPD)) polymers exhibited better solubility than poly(m-phenylenediamine) (P(mPD)) polymers in most common solvents. The homopolymers obtained were characterized by FT-IR, ¹H and ¹³C NMR, WAXD and TGA. The results showed that the yield, solubility and structure of the polymers are significantly dependent on the polymerization conditions. TGA measurements indicated that the polymers have good thermal stability and decompose above 400 °C in nitrogen.     

Highly efficient TfOH-catalyzed head-to-tail dimerization of vinylarenes

A convenient and efficient TfOH-catalyzed head-to-tail dimerization of vinylarenes has been realized under mild conditions. The present protocol provides an attractive approach to a diverse range of higher olefins in good to excellent yields.     

Reductive coupling reaction of aldehydes using indium(III) triflate as the catalyst

A reductive coupling reaction was effectively developed to convert an aldehyde to its symmetrical ether. The successful reactions required Et₃SiH and CH₂Cl₂ as the suitable solvent in the presence of a catalytic amount of In(OTf)₃. Various aldehydes were subjected to the method, and each afforded the expected ethers in good to excellent yields.     

Highly effective peroxidic epoxidation of olefins using hexathiocyanatorhenate(IV) as catalyst and bicarbonate as co-catalyst

In the presence of bicarbonate as co-catalyst hexathiocyanatorhenate(IV) functions as an extremely effective catalyst in the epoxidation of olefins using aqueous hydrogen peroxide as the terminal oxidant.     

Olefinpolymerization with highly active soluble zirconium compounds using aluminoxane as co-catalyst

The homogeneous Ziegler-Natta–catalysts, consisting of a zirconocene compound and methyl-aluminoxane, lead to extremely high polymerization activities. With bis(cyclopentadienyl)zirconium dichloride pure atactic polypropylene and polyethylene with activities up to 30.10⁶ g PE/g Zr·h are formed. The higher the degree of oligomerization of the aluminoxane the more active are the catalysts. The density of polyethylene (LLDPE) can be lowered by using 1-butene or 1-hexene as comonomers. Incorporation of dienes gives EPDM-elastomers. Highly isotactic polypropylene can be prepared by using chiral rac-ethylene bis–(tetrahydroindenyl) zirconium dichloride together with methylaluminoxane as cocatalyst. The toluene soluble part here consists of less than 0.2 weight percent. After resolution of this racemate it is also possible to produce optically active polypropylene and polybutene.     

Lewis Acid trapping of an elusive copper-tosylnitrene intermediate using scandium triflate

High-valent copper-nitrene intermediates have long been proposed to play a role in copper-catalyzed aziridination and amination reactions. However, such intermediates have eluded detection for decades, preventing the unambiguous assignments of mechanisms. Moreover, the electronic structure of the proposed copper-nitrene intermediates has also been controversially discussed in the literature. These mechanistic questions and controversy have provided tremendous motivation to probe the accessibility and reactivity of Cu(III)-NR/Cu(II)N(?)R species. In this paper, we report a breakthrough in this field that was achieved by trapping a transient copper-tosylnitrene species, 3-Sc, in the presence of scandium triflate. The sufficient stability of 3-Sc at -90 °C enabled its characterization with optical, resonance Raman, NMR, and X-ray absorption near-edge spectroscopies, which helped to establish its electronic structure as Cu(II)N(?)Ts (Ts = tosyl group) and not Cu(III)NTs. 3-Sc can initiate tosylamination of cyclohexane, thereby suggesting Cu(II)N(?)Ts cores as viable reactants in oxidation catalysis.     

An extraction study of gallium, indium and thallium using TPASO as an extractant

A method is proposed for the extraction and individual separation of trivalent gallium, indium and thallium from salicylate media using triphenylarsine oxide dissolved in toluene as an extractant. The optimum extraction conditions are evaluated and described. The extracted metal ions are stripped and estimated spectrophotometrically following complexation with 4-(2-pyridylazo) resorcinol. A possible mechanism of the extraction is discussed. The method permits rapid and precise individual separation of gallium (III), indium (III) and thallium (III) and is applicable to the analysis of alloy samples.     

Intermolecular and intramolecular alpha-amidoalkylation reactions using bismuth triflate as the catalyst

Bismuth(III) triflate was found to promote the formation of stable cyclic N-acyliminium species in remarkable catalytic amounts (1 mol %). The alpha-amidoalkylation process seems to be effective in intermolecular and intramolecular manners leading to alpha-substituted lactams and heterocyclic systems containing azacycles, respectively. By comparing our results with those obtained with the classical Lewis acids as catalysts, it was evidenced clearly that the use of bismuth(III) triflate had been efficient for nearly all alpha-acetoxy lactams we used, except for N-acyliminium precursors bearing a sulfur atom. Also, the process seems to be easy, general, and clean, having diastereoselectivity comparable to protocols using classical Lewis acids and resulting in the formation of polyheterocyclic systems in good to excellent yields (64-99% in acetonitrile as solvent).     

Silica triflate as an efficient reagent for the solvent-free synthesis of coumarins

Silica triflate,as a new silica-based reagent,can be used for the efficient synthesis of 4-substituted coumarins via a Pechmann reaction under solvent-free reaction conditions.All reactions were performed at 80℃in good to high yields.     

An effective ostrich oil bleaching technique using peroxide value as an indicator

Ostrich oil has been used extensively in the cosmetic and pharmaceutical industries. However, rancidity causes undesirable chemical changes in flavour, colour, odour and nutritional value. Bleaching is an important process in refining ostrich oil. Bleaching refers to the removal of certain minor constituents (colour pigments, free fatty acid, peroxides, odour and non-fatty materials) from crude fats and oils to yield purified glycerides. There is a need to optimize the bleaching process of crude ostrich oil prior to its use for therapeutic purposes. The objective of our study was to establish an effective method to bleach ostrich oil using peroxide value as an indicator of refinement. In our study, we showed that natural earth clay was better than bentonite and acid-activated clay to bleach ostrich oil. It was also found that 1 hour incubation at a 150 °C was suitable to lower peroxide value by 90%. In addition, the nitrogen trap technique in the bleaching process was as effective as the continuous nitrogen flow technique and as such would be the recommended technique due to its cost effectiveness.     

Pd-catalysed methoxycarbonylation of vinylarenes using chiral monodentate phosphetanes and phospholane as ligands. Effect of substrate substituents on enantioselectivity

Palladium complexes bearing phospholane 1 and phosphetane 2-4 ligands have been synthesised to be used as catalyst precursors in the asymmetric methoxycarbonylation of vinyl arenes. Single crystals of the complex [PdCl2(2)2] II were obtained from a toluene solution and analysed by X-ray crystallography. Using these complexes, excellent regioselectivity (up to 99%) to the branched esters was obtained. Phosphetane ligands provide higher enantioselectivity than the phospholane under the same reaction conditions and an important influence of the substrate was observed. Enantioselectivity up to 50% was obtained using 4-methoxystyrene.     

Yttrium triflate as an efficient and useful catalyst for chemoselective protection of carbonyl compounds

Carbonyl compounds have been successfully converted into their corresponding oxathiolane, dithiolane, and dithiane derivatives with 2-mercaptoethanol, 1,2-ethanedithiol, and 1,3-propanedithiol using catalytic amount of yttrium triflate. In addition, by using this catalyst, high chemoselective protection of carbonyl compounds has been achieved.     

Exfoliated and reorganized graphite oxide on titania nanoparticles as an auxiliary co-catalyst for photocatalytic solar conversion

The hybrid of graphite oxide (GO)/TiO(2) was prepared through the spontaneous exfoliation of bulky graphite oxide and reorganization with TiO(2) nanoparticles as a solar conversion and hydrogen-generating photocatalyst. GO/TiO(2) showed enhanced activities for both photocurrent generation (in an electrode form) and hydrogen production (in a slurry form) than those of bare TiO(2) under UV light irradiation. The enhanced photocatalytic activity of GO/TiO(2) is ascribed to the ability of graphitic layers in accepting and transporting electrons from excited TiO(2), promoting the charge separation. When GO was hybridized with platinized TiO(2) (Pt/TiO(2)), it showed a marked synergistic effect for the photocatalytic hydrogen production compared with GO/TiO(2) and Pt/TiO(2). This indicates that the cheap and abundant carbon material can be a good candidate for an electron attracting reservoir and an auxiliary co-catalyst for the photocatalytic hydrogen production.     

Pentafluorophenylammonium triflate as a suitable and effective metal-free catalyst for the synthesis of quinazoline derivatives via one-pot multicomponent method

Research on Chemical Intermediates - A simple and facile synthesis of highly functionalized quinazoline derivatives has been successfully developed by treatment of aldehydes, ammonium acetate, and...     

Highly efficient Pd(acac)2/TFA catalyzed head-to-tail dimerization of vinylarenes at room temperature

Pd(acac)₂ catalyzed dimerization of vinylarenes to form dimers under mild condition with excellent yields and stereoselectivities. In particular, the use of TFA highly promoted the activity and selectivity of the dimerization. The studies on mechanism for the reaction displayed clearly that the dimerization of styrenes is 100% atom economic reaction.     

Novel method for catalyst immobilization using an ionic polymer: a case study using recyclable ytterbium triflate

A series of ionic polymers prepared by quarternization of cross-linked poly(4-vinylpyridine/styrene) (P/S) resins with several alkylating agents, including short-length PEG mesylate were used as polymeric supports to immobilize Yb(OTf)₃. The efficacy of the polymer-bound catalyst was examined in a Mannich-type reaction.     

Synthesis of novel 3,4‐dihydropyrimidinones on water soluble solid support catalyzed by indium triflate

Syntheses of several new 3,4‐dihydropyrimidinones (DHPMs) on sodium sulfate solid support have been reported. The microwave enhanced rapid synthesis of the title compounds yielded a good percentage of the DHPMs. The catalytic activity of indium triflate enables to prepare a wide range of DHPMs. Syntheses of 2‐hydroxyphenyl, 2‐hydroxy‐4‐methoxyphenyl pendant groups on DHPMs scaffold are advantages of the present method, which are rather prone towards cyclization and the presence of free hydroxyl groups on the phenyl ring is confirmed via D₂O exchange study. The mechanism of the reaction is expected to proceed via absorption of substrates on the solid support followed by promotion of the reaction by In(OTf)₃ coupled with microwave irradiation.     

A simple phenylation of heteroaromatic compounds using diphenyliodonium triflate

In this study a novel method for direct synthesis of 2-phenyl heteroaromatic arenes was successfully developed. The title compounds were synthesized by reaction of heteroaromatic compounds with diphenylene iodonium trifluoromethanesulfonate in the presence of 5?mol% Pd(OAc)₂ under mild reaction conditions (THF, 60?°C, 24?h). The proposed reaction mechanism was studied by HPLC.