No abstract

No abstract

The concept of an organic reaction between two macroscopic solid particles is investigated. Thus, we study several reactions that have been recently reported to proceed "in the solid phase" and clearly show that, in most cases, grinding the two solid reactants together results in the formation of a liquid phase. This is true both for catalytic transformations (e.g., aldol condensations and oligomerization of benzylic compounds) and for noncatalytic reactions (Baeyer-Villiger oxidations, oxidative coupling of naphthols using iron chloride, condensation of amines and aldehydes to form azomethines, homo-etherification of benzylic alcohols using p-toluenesulfonic acid, and nuclear aromatic bromination with NBS). This liquefaction implies the existence of a eutectic mixture with T(fusion) below ambient temperature (although both reagents have higher than ambient melting points). In cases where heating is required, it is again clear that a phase change (from solid to liquid) occurs, explaining the observed reaction kinetics. On the basis of 19 experimental examples, we discuss the possibility of solid-phase organic reactions and the implications of these findings to the reaction between two solid reagents. A general description of such reactive systems is proposed, based on a consideration of the potential for eutectic (or peritectic) formation between the constituents of the liquid phases that arise during the process of mechanical mixing of the solid reagents and products.

Graphite is exfoliated into graphene by shearing vortex fluidic films of N-methyl-pyrrolidone (NMP), as a controlled process for preparing oxide free graphene, and for exfoliating the corresponding boron nitride sheets.

Organic chemistry is continually evolving to improve the syntheses of value added and bioactive compounds. Through this progression, a concomitant advancement in laboratory technology has occurred. Many researchers now choose to mediate transformations in continuous-flow systems given the many benefits over round bottom flasks. Furthermore, reaction scale up is often less problematic as this is addressed at the inception of the science. Although single-step transformations in continuous-flow systems are common, multi-step transformations are more valuable. In these systems, molecular complexity is accrued through sequential transformations to a mobile scaffold, much like an in vitro version of Nature's polyketide synthases. Utilizing this methodology, multi-step continuous-flow systems have improved the syntheses of active pharmaceutical ingredients (APIs), natural products, and commodity chemicals. This Review details these advancements while highlighting the rapid progress, benefits, and diversification of this expanding field.

Until recently the spectacular developments in nanotechnology have been with little regard to their potential effect on human health and the environment. There are no specific regulations on nanoparticles except existing regulations covering the same material in bulk form. Difficulties abound in devising such regulations, beyond self-imposed regulations by responsible companies, because of the likelihood of different properties exhibited by any one type of nanoparticle, which are tuneable by changing their size, shape and surface characteristics. Green chemistry metrics need to be incorporated into nanotechnologies at the source. This review scopes this issue in the context of potential health effects of nanoparticles, along with medical applications of nanoparticles including imaging, drug delivery, disinfection, and tissue repair. Nanoparticles can enter the human body through the lungs, the intestinal tract, and to a lesser extent the skin, and are likely to be a health issue, although the extent of effects on health are inconclusive. Nanoparticles can be modified to cross the brain blood barrier for medical applications, but this suggests other synthetic nanoparticles may unintentionally cross this barrier.

A paradigm shift away from using solvents in organic synthesis as solventless reactions can lead to improved outcomes, and more benign synthetic procedures, in for example aldol condensation reactions, sequential aldol and Michael addition reactions en route to Kröhnke type pyridines, reactions leading to 3-carboxycoumarins, benzylidenes, 4-aryl-1,4-dihydropyridines and 2-aryl-1,2,3,4-tetrahydroquinazolines, and oligomerisation reactions for the synthesis of cavitands; kinetic considerations for the reaction of two solids can only be explained if a eutectic melt is formed during the reaction.

A vortex fluidic device (VFD) involving a rapidly rotating tube open at one end forms dynamic thin films at high rotational speed for finite sub-millilitre volumes of liquid, with shear within the films depending on the speed and orientation of the tube. Continuous flow operation of the VFD where jet feeds of solutions are directed to the closed end of the tube provide additional tuneable shear from the viscous drag as the liquid whirls along the tube. The versatility of this simple, low cost microfluidic device, which can operate under confined mode or continuous flow is demonstrated in accelerating organic reactions, for model Diels-Alder dimerization of cyclopentadienes, and sequential aldol and Michael addition reactions, in accessing unusual 2,4,6-triarylpyridines. Residence times are controllable for continuous flow processing with the viscous drag dominating the shear for flow rates >0.1 mL/min in a 10 mm diameter tube rotating at >2000 rpm.