Kinetic evaluation of tin‐POMS catalyst for urethane reactions

We report the activity for a new tin‐polyhedral oligomeric metal silsesquioxane (POMS) catalyst in 1‐butanol and 2‐butanol model reactions with 4,4′‐methylenebis(cyclohexylisocyanate) (H₁₂MDI) in toluene and N,N‐dimethylformamide (DMF). Kinetic rate constants for varying levels of tin‐POMS ranging between 100 ppm and 1000 ppm tin are reported. We observed urethane reactions in toluene to follow second order reaction kinetics, whereas similar reactions in DMF followed first order reaction kinetics. We determined tin‐POMS is an efficient catalyst system for urethane reactions and found the new catalyst to be easy to handle, soluble, and very effective for catalyzing urethane reactions. By direct comparison of a model reaction between tin‐POMS and dibutyltin dilaurate (DBTDL), tin‐POMS was found to be quite similar to DBTDL for urethane catalytic activity. In addition, we show the efficacy for tin‐POMS to be an excellent polyurethane reaction catalyst through a model reaction of H12MDI with 2000 g/mol poly(ε‐caprolactone) diol. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Study of TATP: Influence of Reaction Conditions on Product Composition

The influence of reaction conditions (temperature, catalyst type, catalyst concentration – represented as molar ratio catalyst/acetone n_c/n_a) on the composition of the product formed from the reaction of acetone and hydrogen peroxide (30%) under acid catalysis was studied. 3,3,6,6,9,9‐Hexamethyl‐1,2,4,5,7,8‐hexoxonane (TATP) was found to be the major product when the content of the catalyst in the reaction mixture is low (n_c/n_a ≤ 0.5). A single side product (peak 10.2) in an amount ranging from 1.5 to 8% of the total peak area was present in all the prepared samples. Three other side products were found when catalyzing by hydrochloric and nitric acids. Temperature and catalyst type did not have a significant influence on the composition of the product at low catalyst concentration. Increasing the catalyst concentration led to the formation of 3,3,6,6‐tetramethyl‐1,2,4,5‐tetroxane (DADP) either as a co‐product of TATP or as an exclusive product depending on the concentration of the catalyst.     

Controlled Reversible Anchoring of η6‐Arene/TsDPEN‐ Ruthenium(II) Complex onto Magnetic Nanoparticles: A New Strategy for Catalyst Separation and Recycling

A new catalyst separation and recycling protocol combining magnetic nanoparticles and host‐guest assembly was developed. The catalyst, (η⁶‐arene)[N‐(para‐toluenesulfonyl)‐1,2‐diphenylethylenediamine]ruthenium trifluoromethanesulfonate [Ru(OTf)(TsDPEN)(η⁶‐arene)] bearing a dialkylammonium salt tag, was easily separated from the reaction mixtures by magnet‐assisted decantation, on basis of the formation of a pseudorotaxane complex by using dibenzo[24]crown‐8‐modified Fe₃O₄ nanoparticles. The ruthenium catalyst has been successfully reused at least 5 times with the retention of enantioselectivity but at the expense of relatively low catalytic activities in the asymmetric hydrogenation of 2‐methylquinoline.     

Evaluation of the performance of catalytic oxidation of VOCs by a mixed oxide at a semi‐pilot scale†

Volatile organic compounds (VOCs) are one of the main contributors to air pollution. To reduce anthropogenic emissions, it is necessary to improve existing techniques such as catalytic oxidation through the development of new cost‐effective catalysts. Although many studies deal with the development and testing of new materials, most are performed at laboratory scale, of which only a few study mixtures of VOCs. To assess their viability for industrial applications, further tests are required, namely, mixture tests at intermediate scale in relevant environment and extrapolated on an industrial scale. In this work, the catalytic performance of a new mixed oxide Co‐Al‐Ce was investigated towards the oxidation of the n‐butanol and toluene on a semi‐pilot scale (TRL 4). Single component and mixture experiments were performed for several concentrations at a fixed flow rate. A commercial catalyst Pd/γ‐Al₂O₃ was used as the benchmark to evaluate the performance of the mixed oxide. The Co‐Al‐Ce catalyst enables complete oxidation of n‐butanol at the same temperature as the reference catalyst. Moreover, it provides a better selectivity for n‐butanol, while providing an equivalent one for the oxidation of toluene. In mixtures, the presence of n‐butanol promotes the oxidation of toluene for both catalysts but more significantly for the Co‐Al‐Ce catalyst. The presence of toluene inhibits the oxidation of n‐butanol for the Co‐Al‐Ce and promotes it for high conversions of n‐butanol for the Pd/γ‐Al₂O₃ catalyst.     

Evolutionary Catalyst Screening: Iridium‐Catalyzed Imine Hydrogenation

A high throughput catalyst screening is presented employing an evolutionary approach. The method comprises the optimization of initial leads by subjecting the catalysts to iterative rounds of optimization, including structural elaboration of the ligands by creating new focused libraries. Highly modular supramolecular ligands, robotized synthesis combined by high throughput experimentation creates a platform for fast catalyst development. An illustrative example for the asymmetric hydrogenation of cyclic 2,3,3‐trimethyl‐3H‐indole using iridium catalysts is presented. The kinetic investigation of the best catalyst yields an unusual second order in iridium, first order in hydrogen and zeroth order in substrate. Under optimized reaction conditions a TOF of 100 mol mol⁻¹ h⁻¹ with 96% ee could be obtained with the best catalyst. A full catalyst screening and kinetic study was conducted within a three‐week time‐frame.     

New Indenylidene‐Schiff Base‐Ruthenium Complexes for Cross‐Metathesis and Ring‐Closing Metathesis

We here report on the stability and catalytic activity of new indenylidene‐Schiff base‐ruthenium complexes 3a – f through representative cross‐metathesis (CM) and ring‐closing metathesis (RCM) reactions. Excellent activity of the new complexes was found for the two selected RCM reactions; prominent conversion was obtained compared to the commercial Hoveyda–Grubbs catalyst 2 . Moreover, excellent results were obtained for a standard CM reaction. Higher conversions were achieved with one of the indenylidene catalysts compared with Hoveyda–Grubbs catalyst. Unexpectedly, an isomerization reaction was observed during the CM reaction of allylbenzene. To the best of our knowledge, isomerization reactions in this model CM reaction in closed systems have never been described using first generation catalysts, including the Hoveyda–Grubbs catalyst. The first model CM reactions as well as the RCM reactions have been monitored using ¹H NMR. The course of the CM reaction of 3‐phenylprop‐1‐ene ( 8 ) and cis‐1,4‐diacetoxybut‐2‐ene ( 9 ) was monitored by GC. The isomerization reaction was studied by means of GC‐mass spectrometry and in situ IR spectroscopy. All catalysts were structurally characterized by means of ¹H, ¹³C, and ³¹P NMR spectroscopy.     

Conjugated linoleic acid formation by hydrogenation/isomerisation of safflower oil over bifunctional structured catalyst Rh/SBA‐15

Directed isomerisation of safflower oil under very low hydrogen partial pressure of 7 psi over a novel bifunctional highly structured rhodium‐based catalyst (Rh/SBA‐15), having narrow pore size distribution ranging from 4 to 8 nm, and BET‐specific surface of ≈1,000 m² g^?1, was investigated as a new chemocatalytic approach for vegetable oil hardening and simultaneously producing health‐beneficial conjugated linoleic acids (CLA). Time course profiles of (cis‐9, trans‐11)‐; (cis‐10, trans‐12)‐; (trans‐10, cis‐12)‐; (cis,cis)‐ and (trans, trans)‐octadecadienoic isomers (CLAs) as well as the other fatty acids traditionally encountered during the hydrogenation of vegetable oils are presented and discussed under selected process conditions. Preliminary results show that it is possible to tailor characteristics of the hydrogenation catalyst in such way to confer its bi‐functional activity: hydrogenation and conjugation isomerisation. © 2011 Canadian Society for Chemical Engineering     

Primary Amine‐Thioureas with Improved Catalytic Properties for “Difficult” Michael Reactions: Efficient Organocatalytic Syntheses of (S)‐Baclofen, (R)‐Baclofen and (S)‐Phenibut

Among the class of primary amine‐thioureas based on tert‐butyl esters of α‐amino acids, the most efficient organocatalyst for “difficult” Michael reactions was identified. The derivative based on (S)‐di‐tert‐butyl aspartate and (1R,2R)‐diphenylethylenediamine provided the products of the reaction between aryl methyl ketones and nitroolefins in excellent yields and enantioselectivities. In addition, this new catalyst can be used at low catalyst loading (5 mol%). The utility of this methodology was highlighted by the efficient synthesis of (S)‐baclofen, (R)‐baclofen and (S)‐phenibut.     

Combination of 8‐aminoquinoline nickel dichloride and Cp2ZrCl2 catalysts for ethylene polymerization

Polyethylene has been modified and synthesized in situ by a combination of Cp₂ZrCl₂ and 8‐aminoquinoline nickel dichloride catalysts with methylaluminoxane co‐catalyst. The results indicate that the crystallinity and T_m of polyethylene both decrease with increasing Ni/Zr mol ratio when the Ni catalyst is added first. Oligomers formed by 8‐aminoquinoline nickel dichloride within a certain Ni/Zr mol ratio could be completely converted into polymer. Three methods used to introduce catalysts to the reaction system resulted in different products. Polyethylene with the lowest melting point, crystallinity and the highest degree of branching resulted when the Zr catalyst was added after that of the Ni compound. © 2001 Society of Chemical Industry     

Copper Pincer Complexes as Advantageous Catalysts for the Heteroannulation of ortho‐Halophenols and Alkynes

A new, non‐symmetrical copper(II) pincer complex catalyzes much more efficiently the formation of benzofuran by the reaction between ortho‐iodophenols and alkynes. The lowest catalyst loadings are realized for this reaction, and bromo‐ and chlorophenols are heteroannulated for the first time. Strong evidence for hydrophenoxylation and intramolecular halogen atom‐transfer steps catalyzed by this remarkably active, recyclable homogeneous catalyst is provided.

     

Direct Use of Benzylic Alcohols for Gold(III)‐Catalyzed S‐Benzylation of Mercaptobenzoic Acids in Water

We demonstrate the gold(III)‐catalyzed direct substitution of benzylic alcohols in water. These atom economic and environmentally benign protocols afford S‐benzylated products in moderate to excellent yields. In contrast, common Lewis or Brønsted acids as catalyst, and organic solvents such as dichloromethane or toluene were ineffective for the S‐benzylation of mercaptobenzoic acids. Water can be an attractive tool for new transition metal‐catalyzed reactions. A Hammett study for the rate constants with various substituted alcohols shows a good correlation (R²=0.97) between the log(k_X/k_H) and the σ⁺ value of the respective substituents. From the slope negative ρ values of 2.35 are obtained, suggesting that there is a build‐up of positive charge in the transition state. Our catalytic system can be performed with the use of only 2 mol% of gold(III) catalyst without any other additives in water, and scaled up to 10 mmol scale (85% isolated yield). Notably, the present method can accomplish the S‐benzylation of unprotected mercaptobenzoic acids, which is chemoselective and leaves the carboxyl group intact. Furthermore, the direct substitution of allylic and propargylic alcohols also proceeded smoothly in good yields.

     

A Practical and Effective Ruthenium Trichloride‐Based Protocol for the Regio‐ and Stereoselective Catalytic Hydroamidation of Terminal Alkynes

A rational catalyst development based on mechanistic and spectroscopic investigations led to the discovery of a new protocol for catalytic hydroamidation reactions that draws on easily available ruthenium trichloride trihydrate (RuCl₃⋅3 H₂O) as the catalyst precursor instead of the previously employed, expensive bis(2‐methylallyl)(1,5‐cyclooctadiene)ruthenium(II). This practical and easy‐to‐use protocol dramatically improves the synthetic applicability of Ru‐catalyzed hydroamidations. The catalyst, generated in situ from ruthenium(III) chloride hydrate, tri‐n‐butylphosphine, 4‐(dimethylamino)pyridine and potassium carbonate, effectively promotes the addition of secondary amides, lactams and carbamates to terminal alkynes under formation of (E)‐anti‐Markovnikov enamides. The scope of the new protocol is demonstrated by the synthesis of 24 functionalized enamide derivatives, among them valuable intermediates for organic synthesis.     

Synthesis of ultra‐high molecular weight polystyrene with rare earth–magnesium alkyl catalyst system: general features of bulk polymerization

Bulk polymerization of styrene (St) with an in‐situ‐activated Ziegler‐catalyst containing neodymium 2‐ethylhexyl phosphonate [Nd(P₂₀₄)₃], magnesium–aluminum alkyls and hexamethyl phosphoramide (HMPA) was studied. The new rare‐earth catalyst exhibited high activity for polymerization of styrene, and its catalytic efficiency reached 14 730 g PSt/g Nd. The influence of reaction parameters, such as Mg/Nd, Mg/Al, St/Nd molar ratios, temperature, etc, on the catalyst performance was examined in detail. The molecular weight of the resulting polystyrene is ultra‐high (M_W = 40 × 10⁴ ∼ 120 × 10⁴ g mol⁻¹) and the distribution of molecular weight is broad (M_W/M_n = 2.1 ∼ 2.8). The microstructure of the polystyrene was characterized by IR and ¹³C NMR spectroscopies and found to be atactic. © 2001 Society of Chemical Industry     

Chemically and enzymatically catalyzed synthesis of C6–C10 alkyl benzoates

The esterification of benzoic acid with n‐hexanol, n‐octanol, 2‐ethyl hexanol and n‐decanol was investigated in detail. An analysis of the reaction kinetics of esterification in the presence of different commercially available chemical catalysts was carried out. The effects of catalyst type and loading on the reaction rate were studied. Although the considered reaction is bimolecular, it showed a first‐order behavior, and a linear dependence with respect to the catalyst concentration was observed. Hence, a new approach is presented to describe the reaction kinetics accurately over a wide range. The application of biotechnological synthesis applying different enzymes as catalysts offers an interesting alternative besides chemical synthesis. Especially an esterase from Bacillus subtilis immobilized on Sepabeads EC‐EP showed high stability and was applied for 2 days in the synthesis of hexyl benzoate. Nevertheless, the chemical reaction route remains superior with respect to the catalyst activities under the applied conditions, which were 25 kU/g for the chemical reaction and 0.7 kU/g for the best enzymatic conversion.     

A new catalytic process for high‐efficiency synthesis of p‐xylene by methylation of toluene with CH3Br

A new catalytic process for p‐xylene synthesis from the methylation of toluene with CH₃Br was proposed. CH₃Br was prepared from the catalytic bromination of natural gas (CH₄), by using H₂O + HBr + O₂ as mediator over supported Rh catalyst. The methylation conditions were investigated using HZSM‐5 or modified HZSM‐5 catalyst. Under optimal reaction conditions, p‐xylene selectivity is up to 93%, and p‐xylene yield is more than 21% at 673 k over the Si—P modified HZSM‐5 catalyst. Compared to the processes using MeOH or dimethyl carbonate (DMC) as methylation agent, this new process is very attractive in an economic standpoint since CH₄ is much cheaper than MeOH and DMC. In addition, the process has other advantages, such as mild reaction conditions, simple operation, high‐product yield, and so on. It is predicted that the process has good industrial potential for para‐xylene production. © 2012 American Institute of Chemical Engineers AIChE J, 59: 532–540, 2013     

Bismuth Triflate‐Catalyzed Addition of Allylsilanes to N‐Alkoxycarbonylamino Sulfones: Convenient Access to 3‐Cbz‐Protected Cyclohexenylamines

Bismuth triflate was found to be an efficient catalyst in the Sakurai reaction of allyltrimethylsilanes with N‐alkoxycarbonylamino sulfones. The reaction proceeded smoothly with a low catalyst loading of Bi(OTf)₃⋅4 H₂O (2–5 mol%) to afford the corresponding protected homoallylic amines in very good yields (up to 96%). A sequential allylation reaction followed by ring‐closing metathesis delivers 6–8 membered 3‐Cbz‐protected cycloalkenylamines.     

A First Example of Cobalt‐Catalyzed Remote C?H Functionalization of 8‐Aminoquinolines Operating through a Single Electron Transfer Mechanism

The development of new C H functionalization protocols based on inexpensive cobalt catalysts is currently attracting significant interest. Functionalized 8‐aminoquinoline compounds are high‐potential building blocks in organic chemistry and pharmaceutical compounds and new facile routes for their preparation would be highly valuable. Recently, copper has been applied as catalyst for the functionalization of 8‐aminoquinoline compounds and found to operate through a single electron transfer (SET) mechanism, although requiring elevated reaction temperatures. Herein, we described the first example of a cobalt‐catalyzed remote C H functionalization of 8‐aminoquinoline compounds operating through a SET mechanism, exemplified using a practical and mild nitration protocol. The reaction uses inexpensive cobalt nitrate hexahydrate [Co(NO₃)₂⋅6 H₂O] as catalyst and tert‐butyl nitrite (TBN) as nitro source. This methodology offers the basis for the facile preparation of many new functionalized 8‐aminoquinoline derivatives.

     

Gold‐Catalyzed Cyclizations: A Comparative Study of ortho,ortho′‐Substituted KITPHOS Monophosphines with their Biaryl Monophosphine Counterpart SPHOS

Electrophilic gold(I) triflimide (trifluoromethanesulfonimide) complexes of electron‐rich ortho,ortho′‐disubstituted KITPHOS (11‐dicyclohexylphosphino‐12‐phenyl‐9,10‐ethenoanthracene) monophosphines are efficient catalysts for intramolecular cycloisomerizations that afford phenols, 3‐acylindenes and methylene‐oxazolines; comparative catalyst testing showed that these catalysts either competed with or outperformed that based on SPHOS [2‐(2′,6′‐dimethoxybiphenyl)dicyclohexylphosphine]. An electron‐rich biarylmonophosphine containing a single ortho‐methoxy substituent, prepared by rhodium‐catalyzed [2+2+2] cycloaddition between a 1‐alkynyl(dicyclohexylphosphine) oxide and 1,7‐octadiyne, also formed a highly efficient catalyst for the same transformations. Monitoring of comparative catalyst testing between a KITPHOS‐based gold(I) triflimide complex containing a coordinated tetrahydrothiophene and its counterpart coordinated solely by the triflimide anion revealed that the former is an order of magnitude less efficient than the latter, confirming that tetrahydrothiophene can be an effective catalyst inhibitor.     

Thermal and crystallization behaviors of polyethylene blends synthesized by binary late transition metal catalysts combinations

A series of reactor blends of linear and branched polyethylenes have been prepared, in the presence of modified methylaluminoxane, using a combination of 2,6‐bis[1‐(2,6‐dimethyphenylimino) pyridyl]‐cobalt(II) dichloride ( 1 ), known as an active catalyst for producing linear polyethylene, and [1,4‐bis(2,6‐diidopropylphenyl)] acenaphthene diimine nickel(II) dibromide ( 2 ), which is active for the production of branched polyethylene. The polymerizations were performed at various levels of catalyst feed ratio at 10 bar. The linear correlation between catalyst activity and concentration of catalyst 2 suggested that the catalysts performed independently from each other. The weight‐average molecular weights , crystalline structures, and phase structures of the blends were investigated, using a combination of gel permeation chromatography, differential scanning calorimetry, wide‐angle X‐ray diffraction, and small angle X‐ray scattering techniques. It was found that the polymerization activities and MWs and crystallization rate of the polymers took decreasing tendency with the increase of the catalyst 2 ratios, while melting temperatures (T_m), crystalline temperatures (T_c), and crystalline degrees took decreasing tendency. Long period was distinctly influenced by the amorphous component concentration. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4188–4198, 2007     

A Mixed Ligand Approach for the Asymmetric Hydrogenation of 2‐Substituted Pyridinium Salts

Herein we describe a new methodology for the asymmetric hydrogenation (AH) of 2‐substituted pyridinium salts. An iridium catalyst based on a mixture of a chiral monodentate phosphoramidite and an achiral phosphine was shown to hydrogenate N‐benzyl‐2‐arylpyiridinium bromides to the corresponding N‐benzyl‐2‐arylpiperidines with full conversion and good enantioselectivity. The mechanism of the reaction under optimized conditions was investigated via kinetic measurements and isotopic labeling experiments. Our study suggests that the hydrogenation starts with a 1,4‐hydride addition and that the enantiodiscriminating step involves the reduction of an iminium intermediate.