Microwave Heating Outperforms Conventional Heating for a Thermal Reaction that Produces a Thermally Labile Product: Observations Consistent with Selective Microwave Heating

Microwave (MW) heating is more effective than conventional (CONV) heating for promoting a high‐temperature oxidative cycloisomerization reaction that was previously reported as a key step in a total synthesis of the natural product illudinine. The thermal reaction pathway as envisioned is an inverse electron‐demand dehydro‐Diels–Alder reaction with in situ oxidation to generate a substituted isoquinoline, which itself is unstable to the reaction conditions. Observed reaction yields were higher at a measured bulk temperature of 200 °C than at 180 °C or 220 °C; at 24 hours than at earlier or later time points; and when the reaction solution was heated using MW energy as opposed to CONV heating with a metal heat block. Selective MW heating of polar solute aggregates is postulated to explain these observations.     

Heat-treatment influence on Ni–Fe–Cu–Mo nanocrystalline alloy obtained by mechanical alloying

The 77Ni14Fe5Cu4Mo (wt%) powders have been obtained by dry mechanical alloying of elemental powders in a planetary mill under argon atmosphere for milling durations ranging from 2 to 28?h. The alloy formation is obtained after 12?C16?h of milling, as shown by the X-ray diffraction and magnetic studies. The crystallite mean size is 13?±?2?nm after 28?h of milling. An optimal heat-treatment temperature was chosen after the analysis of the DSC signals. and the samples were heated at 350?°C for different durations ranging from 0.5 to 4?h. The heat treatment was continued to enhance the alloy formation and to eliminate the internal stresses induced during the milling process. The evolution of the phases amount during the heat treatment was calculated from the X-ray patterns using the Rietveld procedure.     

Influence of mechanical activation time,annealing, and Fe/O ratio on Fe3O4/Fe composites formation from Fe2O3 and Fe powders mixture

Commercially, iron (α-Fe) and hematite (α-Fe₂O₃) powders were used for the synthesis of composite powders of Fe₂O₃/Fe type by mechanical milling. Several ratios of Fe₂O₃/Fe were chosen for the composite synthesis; the atomic percent of oxygen in the starting mixtures ranged from 21 to 46 %. The Fe₂O₃/Fe composite samples with various Fe/O ratios were milled for different milling times. The milled composite samples were subjected to the heat treatments in argon up to 900 °C. During the heat treatment at temperatures that do not exceed 550 °C, Fe₃O₄/Fe composite particles are formed by the reaction between the Fe₂O₃ and Fe. Further increase of the heat treatment up to 700 °C leads to the reaction of the Fe₃O₄/Fe composite component phases, resulting thus in the formation of FeO/Fe composite. The heat treatment up to 900 °C of the Fe₂O₃/Fe leads to the formation of a composite of FeO/Fe₃O₄/Fe independent of the milling time and Fe₂O₃/Fe ratios. The onset temperatures of the Fe₃O₄ and FeO formations decrease upon increasing the milling time. Another important aspect is that, in the case of the same milling time but with a large amount of iron into the composite powder the formations temperatures of Fe₃O₄ and FeO are also decreasing. The influence of the mechanical activation time, heat treatment temperature, and Fe/O ratio on the formation of the (Fe₃O₄, FeO)/Fe composite from Fe₂O₃+Fe precursor mixtures was studied by differential scanning calorimetry and X-ray diffraction techniques.     

Economizing on Precious Metals in Three‐Way Catalysts: Thermally Stable and Highly Active Single‐Atom Rhodium on Ceria for NO Abatement under Dry and Industrially Relevant Conditions**

We show for the first time that atomically dispersed Rh cations on ceria, prepared by a high‐temperature atom‐trapping synthesis, are the active species for the (CO+NO) reaction. This provides a direct link with the organometallic homogeneous Rh^I complexes capable of catalyzing the dry (CO+NO) reaction. The thermally stable Rh cations in 0.1 wt % Rh₁/CeO₂ achieve full NO conversion with a turn‐over‐frequency (TOF) of around 330 h^?1 per Rh atom at 120 °C. Under dry conditions, the main product above 100 °C is N₂ with N₂O being the minor product. The presence of water promotes low‐temperature activity of 0.1 wt % Rh₁/CeO₂. In the wet stream, ammonia and nitrogen are the main products above 120 °C. The uniformity of Rh ions on the support, allows us to detect the intermediates of (CO+NO) reaction via IR measurements on Rh cations on zeolite and ceria. We also show that NH₃ formation correlates with the water gas shift (WGS) activity of the material and detect the formation of Rh hydride species spectroscopically.     

The RuO4-catalyzed ketohydroxylation. Part 1. Development, scope, and limitation

A new straightforward oxidation of C,C-double bonds to unsymmetrical alpha-hydroxy ketones using catalytic amounts of RuCl(3) and stoichiometric amounts of Oxone under buffered conditions has been developed, a reaction for which we coined the expression "ketohydroxylation". The transformation allows the direct formation of alpha-hydroxy ketones (acyloins) from olefins without intermediate formation of syn-diols. The present paper will provide detailed information starting with the underlying concept and the subsequent development of the reaction. The effect of base, solvent stoichiometry, and temperature will be discussed resulting in an improved mechanistic model that might help to explain the influence of different reaction parameters on reactivity and selectivity in RuO(4)-catalyzed oxidations of C,C-double bonds. Furthermore, an improved workup procedure allows the recovery of the ruthenium catalyst by precipitation while simplifying the overall product purification. The second part of the paper focuses on exploration of scope and limitation. A variety of substituted olefins are oxidized to alpha-hydroxy ketones in good to excellent regioselectivities and yield. Cyclic substrates proved to be problematic to oxidize; however, a careful analysis of temperature effects resulted in the development of a successful protocol for the ketohydroxylation of cyclic substrates by simply decreasing the reaction temperature.     

A Single‐Molecule‐Level Mechanistic Study of Pd‐Catalyzed and Cu‐Catalyzed Homocoupling of Aryl Bromide on an Au(111) Surface

On‐surface Pd‐ and Cu‐catalyzed C?C coupling reactions between phenyl bromide functionalized porphyrin derivatives on an Au(111) surface have been investigated under ultra‐high vacuum conditions by using scanning tunneling microscopy and kinetic Monte Carlo simulations. We monitored the isothermal reaction kinetics by allowing the reaction to proceed at different temperatures. We discovered that the reactions catalyzed by Pd or Cu can be described as a two‐phase process that involves an initial activation followed by C?C bond formation. However, the distinctive reaction kinetics and the C?C bond‐formation yield associated with the two catalysts account for the different reaction mechanisms: the initial activation phase is the rate‐limiting step for the Cu‐catalyzed reaction at all temperatures tested, whereas the later phase of C?C formation is the rate‐limiting step for the Pd‐catalyzed reaction at high temperature. Analysis of rate constants of the Pd‐catalyzed reactions allowed us to determine its activation energy as (0.41±0.03) eV.     

Solvent‐free synthesis of polyacrylamide by frontal polymerization

Polymerization and characterization of polyacrylamide prepared by frontal polymerization are described. Frontally polymerized polyacrylamide is imidized and crosslinked during polymerization. Imide formation was determined by elemental analysis. The addition of commercial polyacrylamide or barium carbonate to the monomer (acrylamide) and initiator (potassium persulfate) decreased the reaction temperature from 235 °C to < 100 °C, thereby reducing imide formation. The commercial polyacrylamide‐diluted product, frontally polymerized polyacrylamide‐diluted product, and the barium carbonate‐diluted product were characterized by IR, TGA, and elemental analysis. Molecular weights of barium carbonate‐diluted samples were determined by light scattering and found to be on the order of one million. Conversion of the barium carbonate‐diluted product was determined to be 76 ± 6%, independent of the amount of diluent over the range 0.8:1–1.5:1. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1129–1135, 2000     

Temperature‐responsive Catalyst for the Coupling Reaction of Carbon Dioxide and Propylene Oxide

The selective synthesis of polypropylene carbonate (PPC) and cyclic propylene carbonate (CPC) from coupling reaction of CO₂ and propylene oxide (PO) is a long term pursuing target. Here we report that a temperature controllable porphyrin aluminum catalyst using 5,10,15,20‐tetra(1,2,3,4,5,6, 7,8‐octahydro‐1,4:5,8‐dimethanoanthracen‐9‐yl)porphyrin as ligand, once in conjunction with suitable onium salt, achieved single cycloaddition or copolymerization reaction. Only cycloaddition reaction happened at temperature above 75 °C to produce 100% CPC, whereas copolymerization became dominant to afford PPC with selectivity over 99% at 25 °C, and the obtained PPC showed over 99% carbonate linkage and 92% head‐to‐tail structure. Based on systematic analysis of the electronic and steric feature in the porphyrin ligand, it was found that the electronic feature of the substituent in porphyrin ligand was decisive for PPC selectivity, porphyrin ligand bearing strong electron‐donating substituents displayed a significantly reduced tolerance towards increased temperature with respect to PPC formation. Therefore, temperature‐responsive catalyst could be designed by suitable modification in porphyrin ligand, and such accurate synthesis of target product by one catalyst may create a useful and facile platform for selective PPC or CPC production.     

Synthesis of N‐Arylated 1,2‐Dihydroheteroaromatics Through the Three‐Component Reaction of Arynes with N‐Heteroaromatics and Terminal Alkynes or Ketones

The reaction of benzynes with N‐heteroaromatics including quinolines, isoquinolines, and pyridines and various terminal alkynes or ketones with an α‐hydrogen in the presence of KF and 18‐crown‐6 in THF at room temperature for 8 h gave various N‐arylated 1,2‐dihydroheteroaromatics in good to moderate yields. Some of these product structures are found in various naturally occurring and biologically active heterocyclic compounds. The reaction involves an unusual multiple construction of new C? C, C? N, and C? H bonds and the cleavage of a C? H bond in one pot. It is likely that the three‐component coupling proceeds through the nucleophilic addition of quinoline to benzyne, which generates a zwitterionic species. The latter then attracts a proton from terminal alkyne (or ketone) to generate an N‐arylated quinolinium cation and an acetylide anion. Further reaction of these two ions provides the final substituted 1,2‐dihydroquinolines. In the reaction, the terminal alkyne acts first as a proton donor and then as a nucleophile. The application of a three‐component coupling reaction product, 1,2‐dihydro‐2‐pyridinyl alkyne in a stereospecific [4+2] Diels–Alder cycloaddition reaction with N‐phenyl maleimide to give an isoquinuclidine derivative, an important core present in various natural products, is demonstrated.     

Complex formation and degradation in poly(acrylonitrile‐co‐vinyl acetate) containing copper nitrate

The pyrolysis of polymers containing metal nitrates may provide a relatively simple, rapid, and advantageous method of producing high‐temperature superconductors (HTSCs). The advantage lies in the ability to use conventional polymer processing or microlithographic patterning before pyrolysis. A copolymer of acrylonitrile and vinyl acetate [P(AN‐VA)], a well‐known fiber‐forming polymer, was investigated as a potential HTSC precursor. Complex formation with the highly polar acrylonitrile groups was expected to enhance atomic‐level mixing and hinder nitrate recrystallization. The metal nitrates were found to have a profound effect on P(AN‐VA) pyrolysis. P(AN‐VA) containing copper nitrate (CuN) exhibited complex formation and an exothermic decomposition that began at about 170 °C (reaction 1‐CuN). Reaction 1‐CuN had a heat of about 3.5 kJ/g_NO3 and a mass loss of about 0.99 g/g_NO3. As reaction 1‐CuN also involved the nitrile groups, it disrupted the nitrile cyclization reaction at about 290 °C. For a P(AN‐VA)/CuN ratio of 2/1, there was no nitrile cyclization, and the thermooxidative degradation temperature was reduced by approximately 200 °C. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1023–1032, 2004     

Flexible transparent fluorinated nanohybrid with innovative heat‐resistance property—new technology proposal for fabrication of transparent materials using “crystalline” polymer

A new technology for the production of transparent material, using a “crystalline” polymer, is proposed in this study. In addition, a heat‐resistant transparent flexible plastic film with a high hydrophobic surface and a thermal decomposition temperature near 400 °C was created. Partially fluorinated crystalline polymer with switchboard‐type lamellae results high transparency as a consequence of the formation of a high‐density amorphous structure based on high‐temperature drawing just below the melting point at 250 °C. Melt‐compounding with montmorillonite modified by the long‐chain quaternary phosphonium with high coverage induces formation of a nanohybrid that retains transparency and also results in an increase in the thermal degradation temperature by over 50 °C. Through this technology, which results in heat‐resistance, transparency, and flexibility, the nano‐micro‐millimeter structures of solid‐state polymers are hierarchically controlled, which enables the creation of new materials. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1674–1690     

A conjugated alkyne functional bicyclic polybenzoxazine with superior heat resistance

A difunctional benzoxazine (coPh‐apa) with a conjugated alkyne group is synthesized by the oxidative coupling reaction from a monocycle‐benzoxazine (Ph‐apa) containing an alkyne group. A model compound, 1,4‐diphenylbutadiyne (coPa), is used to study the curing reaction process of coPh‐apa by DSC, Fourier transform infrared spectroscopy, and ¹³C NMR, and the results suggest that the conjugated alkyne groups are involved in the crosslinking reaction via the trimerization reaction of the conjugated alkynyl groups and the Diels–Alder reaction. Furthermore, thermal properties of the polybenzoxazine are studied by dynamic thermomechanical analysis and thermogravimetric analysis. A glass‐transition temperature (T_gs) of as high as 412 °C and a char yield of 75.6% at 800 °C under nitrogen are obtained with the aid of the conjugated alkyne groups. Its excellent heat resistance dominates most thermosetting resins and will serve for heat shields. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1587–1592     

Coupling of Titanacyclopentadienes with a Cp Ligand and Elimination of One Substituent

Titanacyclopentadienes, prepared from [Cp₂TiBu₂] and either two equivalents of an alkyne or a diyne, were treated with PMe₃ (3 equiv) at 50 °C for 3 h and then with azobenzene at room temperature for 12 h to give 4,5,6‐trisubstituted indene derivatives with the loss of one substituent in good yields. This reaction contrasts sharply with our previously reported reaction for the formation of 4,5,6,7‐tetrasubstituted indene derivatives without the loss of substituents by the treatment of titanacyclopentadienes with azobenzene without PMe₃. ¹³C NMR spectroscopy of the product derived from a ¹³C‐enriched complex revealed that the five carbon atoms originating from a Cp ligand were arranged linearly in the trisubstituted indene derivatives, in contrast to the 4,5,6,7‐tetrasubsituted indene derivatives, in which the corresponding five carbon atoms are arranged in a ring.     

Ethylene Epoxidation with Nitrous Oxide over Fe–BTC Metal–Organic Frameworks: A DFT Study

The epoxidation of ethylene with N₂O over the metal‐organic framework Fe–BTC (BTC=1,3,5‐benzentricarboxylate) is investigated by means of density functional calculations. Two reaction paths for the production of ethylene oxide or acetaldehyde are systematically considered in order to assess the efficiency of Fe–BTC for the selective formation of ethylene oxide. The reaction starts with the decomposition of N₂O to form an active surface oxygen atom on the Fe site of Fe–BTC, which subsequently reacts with an ethylene molecule to form an ethyleneoxy intermediate. This intermediate can then be selectively transformed either by 1,2‐hydride shift into the undesired product acetaldehyde or into the desired product ethylene oxide by way of ring closure of the intermediate. The production of ethylene oxide requires an activation energy of 5.1 kcal mol^?1, which is only about one‐third of the activation energy of acetaldehyde formation (14.3 kcal mol^?1). The predicted reaction rate constants for the formation of ethylene oxide in the relevant temperature range are approximately 2–4 orders of magnitude higher than those for acetaldehyde. Altogether, the results suggest that Fe–BTC is a good candidate catalyst for the epoxidation of ethylene by molecular N₂O.     

Theoretical study of enantiomeric and geometric control in chiral guanidine‐catalyzed asymmetric 1,4‐addition of 5H‐oxazol‐4‐ones

Density functional theory calculations are used to study the reaction mechanism and origins of high stereoselectivity in chiral guanidine‐catalyzed asymmetric 1,4‐addition of 5H‐oxazol‐4‐ones. The reaction involves proton abstraction of 5H‐oxazol‐4‐one, C—C bond formation, and proton transfer. N1 atom of chiral guanidine exchanges its character as base and acid to activate 5H‐oxazol‐4‐one and to facilitate the product formation. The role of N2—H2 is not only H‐bond donor for 5H‐oxazol‐4‐one but also electron accepter for N1. The enantioselectivity related with rate‐limiting step 1 and Z/E selectivity determined in step 2 are primarily influenced by a five to six‐membered ring link in the backbone of chiral guanidine. The reaction proceeds along the favorable path with smaller rotations of the linked bonds. The enantioselectivity is improved with guanidine involving an electron‐deficient and bulky substituent. With methyl ether‐protected hydroxy in structure, the catalytic ability and enantioselective control of guanidine are extraordinarily low, affording the opposite enantiomer as major product. Z‐isomers are preferred in all cases. © 2013 Wiley Periodicals, Inc.     

Synthesis of C3‐Fluorinated Oxindoles through Reagent‐Free Cross‐Dehydrogenative Coupling

Reported herein is an unprecedented synthesis of C3‐fluorinated oxindoles through cross‐dehydrogenative coupling of C(sp³)‐H and C(sp²)‐H bonds from malonate amides. Under the unique and mild electrochemical conditions, the requisite oxidant and base are generated in a continuous fashion, allowing the formation of the base‐ and heat‐sensitive 3‐fluorooxindoles in high efficiency with broad substrate scope. The synthetic usefulness of the electrochemical method is further highlighted by its easy scalability and the diverse transformations of the electrolysis product.     

Lewis Acid Catalyzed Synthesis of 1‐Aryl‐1,2‐dihydro‐naphtho[1,2‐e][1,3]oxazin‐3‐ones under Solvent Free Conditions: A Mechanistic Approach

Lewis acids catalyzed highly efficient one‐pot three component coupling of β‐naphthol, benzaldehydes and urea to produce 1‐aryl‐1,2‐dihydro‐naphtho[1,2‐e][1,3]oxazin‐3‐one derivatives under solvent free conditions is described. Mechanistic studies confirmed that product formation is possible only at very high temperature (140–150°C) and at lower temperature (90–100°C) formation of 14‐aryl‐14H‐dibenzo(a,j)xanthenes was observed. Among the nine Lewis acids screened, iodine, P₂O₅ and Yb(OTf)₃ are found to be most effective catalyst for this multicomponent reaction.     

New Insights into the Diels–Alder Reaction of Graphene Oxide

Graphene oxide is regarded as a major precursor for graphene‐based materials. The development of graphene oxide based derivatives with new functionalities requires a thorough understanding of its chemical reactivity, especially for canonical synthetic methods such as the Diels–Alder cycloaddition. The Diels–Alder reaction has been successfully extended with graphene oxide as a source of diene by using maleic anhydride as a dienophile, thereby outlining the presence of the cis diene present in the graphene oxide framework. This reaction provides fundamental information for understanding the exact structure and chemical nature of graphene oxide. On the basis of high‐resolution ¹³C‐SS NMR spectra, we show evidence for the formation of new sp³ carbon centers covalently bonded to graphene oxide following hydrolysis of the reaction product. DFT calculations are also used to show that the presence of a cis dihydroxyl and C vacancy on the surface of graphene oxide are promoting the reaction with significant negative reaction enthalpies.     

Unusual Investigation of Polycyclic Saturated Tetrazine: A Breakthrough to 1,2,4,5‐Tetrazine

The theoretical investigation of polycyclic saturated tetrazine is a novel process, and the reaction of 1,2,4,5‐tetrazine with diazomethane that undergoes polymerization reaction has been studied by using a computational method, and it gives dinitrogen (N₂) as the major product. The spectroscopic studies, bond length, bond angle, heat of formation, and densities are measure of investigations in this communication. The theoretical evidence of the possibility to synthesize polycyclic saturated tetrazine is a major challenge for nitrogen‐rich chemistry.     

The Reductive Dehydration of Cellulose by Solid/Gas Reaction with TiCl4 at Low Temperature: A Cheap,Simple, and Green Process for Preparing Anatase Nanoplates and TiO2/C Composites

Metal oxides and metal oxide/carbon composites are entering the development of new technologies and should therefore to be prepared by sustainable chemistry processes. Therefore, a new aspect of the reactivity of cellulose is presented through its solid/gas reaction with vapour of titanium(IV) chloride in anhydrous conditions at low temperature (80 °C). This reaction leads to two transformations both for cellulose and titanium(IV) chloride. A reductive dehydration of cellulose is seen at the lowest temperature ever reported and results in the formation of a carbonaceous fibrous solid as the only carbon‐containing product. Simultaneously, the in situ generation of water leads to the formation of titanium dioxide with an unexpected nanoplate morphology (ca. 50 nm thickness) and a high photocatalytic activity. We present the evidence showing the evolution of the cellulose and the TiO₂ nanostructure formation, along with its photocatalytic activity. This low‐temperature process avoids any other reagents and is among the greenest processes for the preparation of anatase and also for TiO₂/carbon composites. The anisotropic morphology of TiO₂ questions the role of the cellulose on the growing process of these nanoparticles.