4.2.8. Reductive Coupling 3109 5. Reaction of Aromatic Compounds 3110 5.1. Electrophilic Substitutions 3110 5.2. Radical Substitution 3111 5.3. Oxidative Coupling 3111 5.4. Photochemical Reactions 3111 6. Reaction of Carbonyl Compounds 3111 6.1. Nucleophilic Additions 3111 6.1.1. Allylation 3111 6.1.2. Propargylation 3120 6.1.3. Benzylation 3121 6.1.4. Arylation/Vinylation 3121 6.1.5. Alkynylation 3121 6.1.6. Alkylation 3121 6.1.7. Reformatsky-Type Reaction 3122 6.1.8. Direct Aldol Reaction 3122 6.1.9. Mukaiyama Aldol Reaction 3124 6.1.10. Hydrogen Cyanide Addition 3125 6.2. Pinacol Coupling 3126 6.3. Wittig Reactions 3126 7. Reaction of R,â-Unsaturated Carbonyl Compounds 3127

Organic Reactions in Aqueous Media with a Focus on Carbon−Carbon Bond Formations: A Decade Update

Great attention has been given to metal–organic frameworks (MOFs)-derived solid bases because of their attractive structure and catalytic performance in various organic reactions. The extraordinary skeleton structure of MOFs provides many possibilities for incorporation of diverse basic functionalities, which is unachievable for conventional solid bases. The past decade has witnessed remarkable advances in this vibrant research area; however, MOFs for heterogeneous basic catalysis have never been reviewed until now. Therefore, a review summarizing MOFs-derived base catalysts is highly expected. In this review, we present an overview of the recent progress in MOFs-derived solid bases covering preparation, characterization, and catalytic applications. In the preparation section, the solid bases are divided into two categories, namely, MOFs with intrinsic basicity and MOFs with modified basicity. The basicity can originate from either metal sites or organic ligands. Different approaches used for generation o...

Metal-Organic Frameworks for Heterogeneous Basic Catalysis.

Magnetocaloric effect: From materials research to refrigeration devices

Heterocycles constitute the largest and the most diverse family of organic compounds Among them, aromatic heterocycles represent structural motifs found in a great number of biologically active natural and synthetic compounds, drugs, and agrochemicals Moreover, aromatic heterocycles are widely used for synthesis of dyes and polymeric materials of high value 1 There are numerous reports on employment of aromatic heterocycles as intermediates in organic synthesis 2

Although, a variety of highly efficient methodologies for synthesis of aromatic heterocycles and their derivatives have been reported in the past, the development of novel methodologies is in cuntinious demand Particlularly, development of new synthetic approaches toward heterocycles, aiming at achieving greater levels of molecular complexity and better functional group compatibilities in a convergent and atom economical fashions from readily accessible starting materials and under mild reaction conditions, is one of a major research endeavor in modern synthetic organic chemistry Transition metal-catalyzed transformations, which often help to meet the above criteria, are among the most attractive synthetic tools

Several excellent reviews dealing with transition metal-catalyzed synthesis of heterocyclic compounds have been published in literature during recent years Many of them highlighted the use of a particular transition metal, such as gold,3 silver,4 palladium,5 copper,6 cobalt,7 ruthenium,8 iron,9 mercury,10 rare-earth metals,11 and others Another array of reviews described the use of a specific kind of transformation, for instance, intramolecular nucleophilic attack of heteroatom at multiple C–C bonds,12 Sonogashira reaction,13 cycloaddition reactions,14 cycloisomerization reactions,15 C–H bond activation processes,16 metathesis reactions,17 etc Reviews devoted to an application of a particular type of starting materials have also been published Thus, for example, applications of isocyanides,18 diazocompounds,19 or azides20 have been discussed In addition, a significant attention was given to transition metal-catalyzed multicomponent syntheses of heterocycles21 Finally, syntheses of heterocycles featuring formation of intermediates, such as nitrenes,22 vinylidenes,23 carbenes, and carbenoids24 have also been reviewed

The main focus of the present review is a transition metal-catalyzed synthesis of aromatic monocyclic heterocycles The organization of the review is rather classical and is based on a heterocycle, categorized in the following order: (a) ring size of heterocycle, (b) number of heteroatoms, (c) type of heterocycle, and (d) a class of transformation involved A brief mechanistic discussion is given to provide information about a possible reaction pathway when necessary The review mostly discusses recent literature, starting from 200425 until the end of 2011, however, some earlier parent transformations are discussed when needed

Transition Metal-Mediated Synthesis of Monocyclic Aromatic Heterocycles

Advances in the chemistry of tetrahydroquinolines.

A simple method of tuning PID controllers for stable and unstable FOPTD systems

Montmorillonite KSF clay catalyzed one-pot synthesis of α-aminonitriles

Inert gas atomized (IGA) superalloy Inconel 718 powders with varied oxygen levels of 275, 180 and 140 ppm were consolidated by hot isostatic pressing (HIPing) at 1200 °C/120 MPa/3 h. The microstructural characterization of as-HIPed alloys has shown that the densification phenomenon of the powder does not depend on its oxygen content. However, the formation of deleterious phases such as prior particle boundaries (PPBs) occur more predominantly in the HIPed material produced from the powder with high oxygen content. It was also observed that the recrystallization and formation of annealing twins in the HIPed alloy are greatly influenced by the oxygen content. Transmission electron microscopy (TEM) studies have revealed that the precipitation of γ″, γ′ and δ phases does not depend on oxygen level of HIPed alloy during heat treatment as per AMS 5662J standard schedule but the MC carbides enriched with Nb and Ti precipitated preferentially at the PPBs for the alloy with high oxygen content of 275 ppm. In contrast, the carbides were found to be precipitated more uniformly in the matrix of the alloy with low oxygen content of 140 ppm. Tensile properties of the as-HIPed and HIP + heat treated alloys have shown that the yield strength (YS), ultimate tensile strength (UTS) do not get influenced by the oxygen content, but the ductility was found to be deteriorated drastically at elevated temperatures with increasing the oxygen content of the alloy. Stress rupture properties of the heat treated alloys at 650 °C under a stress level of 690 MPa have maintained a direct relation with the oxygen content, as the alloy with 275 ppm of oxygen content has shown inferior rupture life of 27 h with 2.1% ductility as compared to 84.5 h of life with 4.5% ductility and 116 h of life with 6% ductility offered by the alloys with 180 and 140 ppm of oxygen content, respectively. A better combination of mechanical properties achieved by use of prealloyed powder with low oxygen content makes it possible to explore the near net shape advantage of HIP technology to its maximum potential for alloy 718 components.

Effect of oxygen content of powder on microstructure and mechanical properties of hot isostatically pressed superalloy Inconel 718

Inert gas atomized (IGA) superalloy Inconel 718 powder was consolidated by hot isostatic pressing (HIPing) at 1200 °C under 120 MPa pressure for 3 h. The HIPed alloy heat treated as per the aerospace materials specification (AMS) 5662J standard schedule, viz. solution treatment (ST) at 980 °C for 1 h/water quenching (WQ) to room temperature (RT) and a two-step ageing treatment (AT) at 720 °C for 8 h/furnace cooling (FC) at 55 °C h −1 to 620 °C and holding at 620 °C for 8 h and air cooling (AC) to room temperature has exhibited the yield strength (YS) and ultimate tensile strength (UTS) comparable to that of the conventionally processed (forged and heat treated) IN 718. However, its ductility and stress rupture properties at 650 °C were found to be poor due to the presence of prior particle boundary (PPB) networks decorated with highly stable oxides (Al 2 O 3 and TiO 2 ) and brittle MC (Nb, Ti)C carbides. To mitigate this problem, the HIPed alloy was subjected to solution treatment at 1270 °C for 1 h followed by re-HIPing at 1100 °C/130 MPa/3 h before heat-treating it as per AMS 5662J standard schedule. Optical and scanning electron microscopy (SEM) of the alloy processed under modified HIPing and heat treatment conditions have shown the dissolution of MC-carbides, breaking up of PPB networks and formation of equiaxed grains with an average diameter of about 50 μm. Transmission electron microscopy (TEM) of this alloy has revealed uniform distribution of γ″ and γ′ strengthening precipitates in the γ-matrix and the presence of δ(Ni 3 Nb) phase as well as very fine oxide particles near the grain boundaries. The tensile properties of the alloy processed under modified conditions have shown quite satisfactory levels of YS and UTS combined with a significantly improved elongation (EL) values at room temperature (19.5%) and at 650 °C (8.0%). The improvement in alloy ductility was found to correlate well with the fractography of the tensile tested specimens, which showed the predominance of transgranular fracture with fine dimples at room temperature and fine dimples together with the particle boundary facets at 650 °C. The stress rupture properties of modified processed alloy at 650 °C and at a stress level of 690 MPa have shown a vastly improved rupture life of 80 h combined with 5% ductility. The improvement in tensile and stress rupture properties accomplished by the modified processing makes it possible to explore the near net shape capability of HIP technology to its full potential in the development of alloy 718 components.

M. Srinivas

Papers

A simple method of tuning PID controllers for stable and unstable FOPTD systems

Montmorillonite KSF clay catalyzed one-pot synthesis of α-aminonitriles

Effect of oxygen content of powder on microstructure and mechanical properties of hot isostatically pressed superalloy Inconel 718

Influence of modified processing on structure and properties of hot isostatically pressed superalloy Inconel 718

Transesterification of glycerol with dimethyl carbonate for the synthesis of glycerol carbonate over Mg/Zr/Sr mixed oxide base catalysts