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Green Chemistry Metrics : Material Efficiency and Strategic Synthesis Design

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Encyclopedia of Sustainability Science and Technology

Definition of the Subject and Its Importance

Over the last 2 decades, the topic of “green metrics ” has grown rapidly in conjunction with the field of green chemistry. Green metrics promise to provide a rigorous, thorough, and quantitative understanding of material, energy, and cost efficiencies for individual chemical reactions and synthesis plans. Indeed, before the advent of green chemistry, good synthetic strategy and elegance were ill-defined, yet intuitive concepts couched less in quantitative terms and more by subjective ones. The quest for a reliable method of measuring material efficiency or “greenness” of a chemical reaction, synthesis, or process is of fundamental importance in the field of organic synthesis when various routes to a given target molecule are considered for selection. Such a method should be robust in its application to any kind of reaction or plan regardless of complexity. It should standardize the ranking of efficiencies of...

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Abbreviations

Atom economy:

Ratio of molecular weight of target molecule to sum of molecular weights of reactants assuming a balanced chemical equation.

B/M:

Ratio of sum of number of target bonds made in a synthesis plan to total number of reaction steps.

By-product of a reaction:

A product formed in a reaction between reagents as a direct mechanistic consequence of producing the target product assuming a balanced chemical equation that accounts for the production of that target product.

Degree of asymmetry:

A parameter determined from the shape of a synthesis tree diagram for a synthesis plan that describes the degree of skewness of a triangle whose vertices are the target product node, the origin, and the node for the last reagent along the ordinate axis.

Degree of convergence:

A parameter determined from the shape of a synthesis tree diagram for a synthesis plan that describes the ratio of the angle subtended at the actual product node vertex to that at a product node vertex corresponding to the hypothetical case of all reaction substrates in a plan reacting in a single step.

E-factor with respect to molecular weight (Emw):

Ratio of sum of molecular weights of by-products in a reaction to molecular weight of target product in a given reaction or synthesis plan.

E-factor with respect to mass (Em):

The ratio of mass of total waste from all sources to mass of target product collected in a given reaction or synthesis plan.

Ekernel :

Contribution to the total or overall E-factor with respect to mass from reaction by-products, reaction side products, and unreacted starting materials.

Eexcess :

Contribution to the total or overall E-factor with respect to mass from excess reagents.

Eauxiliaries :

Contribution to the total or overall E-factor with respect to mass from auxiliary materials such as reaction solvents, work-up, and purification materials.

Eoverall (or Em):

Ratio of mass of total waste generated from all sources to mass of target product collected for a given reaction or synthesis plan.

f ∗ :

Fractional kernel waste contribution from target bond forming reactions.

f(sac) :

Molecular weight fraction of reagents that absolutely do not end up in the final target molecule structure.

f(nb) :

Fraction of number of reaction stages that do not form target bonds.

Hypsicity index:

A parameter that tracks the oxidation numbers of atoms in target bond forming reactions over the course of a synthesis plan relative to their values in the target molecule.

I :

Number of input materials in a synthesis plan.

Kernel mass of waste:

Mass of all reagents used in a synthesis reaction or plan minus the mass of target product collected.

Kernel reaction mass efficiency:

The ratio of the mass of target product collected to the sum of the stoichiometric masses of all reagents used in a chemical reaction or synthesis plan.

μ1, First molecular weight moment:

Parameter that describes the degree of building up going on from the reagent molecules toward the target molecule over the course of a synthesis plan.

Mass intensity:

Ratio of mass of all materials used to mass of target product collected in a given chemical reaction or synthesis plan.

Material recovery parameter:

A parameter that describes the mass consumption of all solvents and auxiliary materials used in carrying out a given chemical reaction that may be potentially recoverable by recycling.

M :

Number of reaction steps in a synthesis plan.

N :

Number of reaction stages in a synthesis plan.

Radial hexagon:

A diagram that depicts the overall atom economy, overall reaction yield along the longest branch, overall kernel reaction mass efficiency, molecular weight fraction of reagents in whole or in part that end up in the target molecule, fraction of the kernel waste contribution from target bond forming reactions, and the degree of convergence for a given synthesis plan as a hexagon for easy visualization of the synthesis performance.

Radial pentagon:

A diagram that depicts the reaction yield, atom economy, stoichiometric factor, material recovery parameter, and overall reaction mass efficiency for a given chemical reaction as a pentagon for easy visualization of the reaction performance.

Raw material cost:

Sum of the costs of all reagents in a synthesis plan calculated using the basis scale in moles of the target product, assuming balanced chemical equations for all reactions in the plan and taking account of excess reagent consumption.

Reaction step:

Refers to interval between a given isolated intermediate and the next consecutive isolated intermediate in a synthesis plan.

Reaction yield:

Ratio of moles of target product to moles of limiting reagent for a given balanced chemical equation.

Sacrificial reactions:

Nonproductive reactions in a synthesis plan that do not form target bonds appearing in the target product structure.

Side product of a reaction:

A product formed in a reaction between reagents, usually undesired, that arises from a competing reaction pathway other than the one that produces the intended target product and its associated by-products.

Stoichiometric factor (SF):

A parameter that describes the total amount of excess reagents used in a given chemical reaction relative to the amounts prescribed by its stoichiometrically balanced chemical equation.

Stoichiometric coefficient:

An integer appearing before the chemical formula for a reagent in a balanced chemical equation.

Synthesis tree:

A diagram that describes all features of a synthesis plan, including number of steps, number of stages, number of branches, number of intermediates, number of reagents used, and molecular weights of all chemical species.

Target bond map:

A chemical structure drawing of the target product of a synthesis plan showing the target bonds made, the step numbers of each target bond, and the set of atoms that correlate directly with the corresponding reagents that ended up in the target molecule.

Target bond forming reactions:

Productive reactions in a synthesis plan that result in the formation of bonds that appear in the structure of the target molecule.

Total (overall) mass of waste:

The sum of all masses of materials used in synthesis plan minus the mass of the target product collected.

Total (overall) reaction mass efficiency:

The ratio of the mass of target product collected to the sum of the masses of all reagents, solvents, and auxiliaries used in a given reaction or synthesis plan.

|UD| :

A parameter that tracks the “oxidation length” traversed over the course of a synthesis plan equal to the sum of all the “ups” and “downs” in a hypsicity profile or bar graph beginning with the zeroth reaction stage.

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  1. Department of Chemistry, York University, 4700 Keele Street, Toronto, ON, M3J 1P3, Canada

    John Andraos

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    Robert A. Meyers

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Andraos, J. (2012). Green Chemistry Metrics : Material Efficiency and Strategic Synthesis Design. In: Meyers, R.A. (eds) Encyclopedia of Sustainability Science and Technology. Springer, New York, NY. https://doi.org/10.1007/978-1-4419-0851-3_224

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