Volume 83, Issue 7

The 3rd International Conference on Green Chemistry (ICGC-3) was held in Ottawa, Canada, 15-18 August 2010, with the theme “The Road to Greener Industry”. Bringing together academia and industry to trade ideas about green chemistry was the purpose of the meeting. Dedicated sessions on industrial aspects, presented by industry speakers, were well attended by both academics and industrial representatives. Academic sessions, in turn, presented new ideas to both groups. Major topics in the conference were green energy (biofuels, H 2 production, CO 2 capture), green engineering (energy efficiency, greener processes, separations), policy (industry, government, NGOs), green chemistry education, green transportation (materials, additives, powertrain) and green chemical synthesis (benign routes, solvents, catalysts, biopolymers). The 348 delegates travelled to Ottawa from 33 countries, making it a truly international discussion. This issue contains five important lectures from the conference. Peter Wells gives us a rather sobering discussion of some of the unintended consequences of green improvements. Zheng Cui, Evan S. Beach, and Paul T. Anastas describe many of the exciting green chemistry developments coming from China in the past three years. John Andraos announces a new database and algorithm that allows industry to evaluate the efficiency of synthesis plans. Achim Stolle and Bernd Ondruschka compare the performance and energy efficiency of solvent-free reactions performed by ball milling versus other methods such as microwave. Ken Seddon describes the use of new ionic liquids as catalysts for the oligomerization of linear terminal olefins to make lubricant oils. May these articles continue the discussion, stimulate more ideas, and help us all go down the Road to Greener Industry. Philip G. Jessop Conference Chair and Conference Editor

This contribution presents two solvent-free reactions of terminal alkynes in ball mills: Pd-catalyzed Sonogashira cross-coupling and Cu-catalyzed homo-coupling (Glaser reaction). The results are compared to other solvent-free reaction protocols, which have been published up to date for those types of reactions. Reactions are assessed on the basis of reaction variables like type of catalyst and base or reaction time. Furthermore, performance-based parameters (yield, selectivity, turnover number, TON, and turnover frequency, TOF) are considered and evaluated. Findings from ball-milling experiments indicate that those processes are comparable to the energy entry by microwave irradiation with respect to reaction time and TOF.

In order to sensibly design green policy, at least three separate disciplines need to be involved. Clearly, technology will be required to design new processes and redesign old ones. Government policy makers will need to ensure that new regulatory structures adapt and reflect societal goals of decreasing our impact on the planet. Lastly, we need to hear from the economists to make certain that our efforts to develop green processes actually have a net positive effect. This last point is not as obvious as it might appear. James Watt’s invention of the external condenser for steam engines, which he patented in 1769, dramatically reduced coal requirements for a unit of output. Not surprisingly, demand for coal dropped as new steam engines incorporating that design became common after the patent expired in 1794. However, in the period 1830–1860 coal use in England actually increased by an order of magnitude. This is the efficiency paradox. As the effective cost of the product falls because more can be produced from the same raw materials, demand increases. The net result is higher overall consumption. While the focus of green chemistry is the effect emissions are having on the environment, to date we have tended to concentrate on inputs and processes, and not the emissions themselves. In designing policy and new processes, we need to keep phenomena such as the efficiency paradox in mind to ensure that our efforts to improve the environment actually have that effect in practice.

After 20 years of green chemistry research, a complete algorithm for the determination of material and synthetic strategy efficiencies for synthesis plans to any chemical target has been achieved. This paper presents the first announcement of a comprehensive database consisting of green metrics calculations for 1060 plans to 220 targets of interest to the chemical industry in the following categories: commodity industrial chemicals, pharmaceuticals, agrichemicals, dyestuffs and colorants, natural products, flavorings, fragrances, and sweeteners, and molecules of theoretical interest. Data mining of the original literature covered the period 1828–2010. A summary of trends in achieving green chemistry strategies is presented, including an unbiased method of ranking plans using a suite of parameters, ring construction strategies, and implications on the development of new kinds of smart structure search databases. The take-home message is that targeted optimization is a multivariable problem that requires synergistic maximization and minimization of key variables. Problems in the reporting of chemical syntheses in scientific journals and patents are discussed as well as setting guidelines for their standardization and normalization. The merits of spreadsheet tools are presented from decision making in route selection all the way to fast and accurate proofreading of the final plan chosen.

The principles of green chemistry provide a framework for rational design of environmentally friendly chemicals and chemical processes having reduced intrinsic hazard. In China, the academic community has made advances in key areas, developing new catalysts, solvents, polymers, plastics additives, and biomass transformations that add to the “toolbox” of alternative, more benign, and transformative technologies. Educational and outreach activities have also flourished in recent years. This perspective highlights examples of green chemistry breakthroughs in China, focusing on literature reports from 2008 to 2010. While we cannot hope to be comprehensive, we aim to provide examples that demonstrate the scope of the current research field.

A Lewis acidic chlorogallate(III) ionic liquid, 1-ethyl-3-methylimidazolium hepta-chlorodigallate(III), [C 2 mim][Ga 2 Cl 7 ], was successfully used to oligomerise 1-pentene. The influence of temperature, time, catalyst concentration, and stirring rate on conversion and product distribution was modelled using a design of experiment (DoE) approach (chemo-metrics). The process was optimised for lubricant base oils production; the C20–C50 fraction (where C n indicates the number of carbons in the oligomer) was maximised, while the heavier oligomer fraction (>C50) was minimised.

An explosion occurs when a large amount of energy is suddenly released. This energy may come from an over-pressurized steam boiler, from the products of a chemical reaction involving explosive materials, or from a nuclear reaction that is uncontrolled. In order for an explosion to occur, there must be a local accumulation of energy at the site of the explosion, which is suddenly released. This release of energy can be dissipated as blast waves, propulsion of debris, or by the emission of thermal and ionizing radiation. Modern explosives or energetic materials are nitrogen-containing organic compounds with the potential for self-oxidation to small gaseous molecules (N 2 , H 2 O, and CO 2 ). Explosives are classified as primary or secondary based on their susceptibility of initiation. Primary explosives are highly susceptible to initiation and are often used to ignite secondary explosives, such as TNT (2,4,6-trinitrotoluene), RDX (1,3,5-trinitroperhydro-1,3,5-triazine), HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazocane), and tetryl ( N -methyl- N -2,4,6-tetranitro-aniline).

The IUPAC/IUPAP Joint Working Party (JWP) on the priority of claims to the discovery of new elements 113–116 and 118 has reviewed the relevant literature pertaining to several claims. In accordance with the criteria for the discovery of elements previously established by the 1992 IUPAC/IUPAP Transfermium Working Group (TWG), and reinforced in subsequent IUPAC/IUPAP JWP discussions, it was determined that the Dubna-Livermore collaborations share in the fulfillment of those criteria both for elements Z = 114 and 116. A synopsis of experiments and related efforts is presented.