Green Chemistry Theory and Practice

by Anastas, Paul; Warner, John

• ISBN13: 9780198502340
• ISBN10: 0198502346
• Format: Hardcover
• Copyright: 1998-12-10
• Publisher: Oxford University Press

Summary

This book provides the first introductory treatment of the design, development, and evaluation processes central to Green Chemistry. A comprehensive textbook, it takes a broad view of the subject and integrates a wide variety of approaches. Topics include alternative feedstocks, environmentally benign syntheses, the design of safer chemical products, new reaction conditions, alternative solvents and catalyst development, and the use of biosynthesis and biomimetic principles. It introduces new evaluation processes that encompass the complete health and environmental impact of a synthesis, from the choice of starting materials to the final product. Throughout, the text provides specific examples which compare the new methods with classical ones.

Table of Contents

Introduction	1	(10)
The current status of chemistry and the environment	1	(1)
Evolution of the environmental movement	2	(7)
Public awareness	2	(4)
`Dilution is the solution to pollution'	6	(1)
Waste treatment and abatement through command and control	6	(1)
Pollution prevention	7	(1)
Green chemistry	8	(1)
The role of chemists	9	(2)
What is green chemistry?	11	(10)
Definition	11	(1)
Why is this new area of chemistry getting so much attention?	12	(1)
Why should chemists pursue the goals of green chemistry?	13	(3)
The root of innovation	16	(1)
Limitations/obstacles	16	(5)
Tools of green chemistry	21	(8)
Alternative feedstocks/starting materials	21	(3)
Alternative reagents	24	(1)
Alternative solvents	24	(1)
Alternative product/target molecule	25	(1)
Process analytical chemistry	26	(1)
Alternative catalysts	27	(2)
Principles of green chemistry	29	(28)
It is better to prevent waste than to treat or clean up waste after it is formed	29	(4)
Synthetic methods should be designed to maximize the incorporation of all materials used in the process into the final product	33	(1)
Rearrangements	34	(1)
Addition	34	(1)
Substitution	34	(1)
Elimination	34	(1)
Wherever practicable, synthetic methodologies should be designed to use and generate substances that possess little or no toxicity to human health and the environment	34	(2)
Chemical products should be designed to preserve efficacy of function while reducing toxicity	36	(2)
What is designing safer chemicals?	36	(1)
Why is this now possible?	37	(1)
The use of auxiliary substances (e.g. solvents, separation agents) should be made unnecessary wherever possible and innocuous when used	38	(4)
The general use of auxiliary substances	38	(1)
Concerns for solvents	38	(1)
Environment	39	(1)
Supercritical fluids	40	(1)
Solventless	41	(1)
Aqueous	41	(1)
Immobilized	41	(1)
Energy requirements should be recognized for their environmental and economic impacts and should be minimized	42	(3)
Energy usage by the chemical industry	42	(1)
How energy is used	43	(1)
The need to accelerate reactions with heat	43	(1)
The need to control reactivity through cooling	43	(1)
Separation energy requirements	44	(1)
Microwaves	44	(1)
Sonic	44	(1)
Optimizing the reaction should mean minimizing the energy requirements	44	(1)
A raw material or feedstock should be renewable rather than depleting, wherever technically and economically practicable	45	(3)
What are renewable vs. depleting feedstocks?	45	(1)
Sustainability	46	(1)
Direct environmental effects	46	(1)
Indirect environmental effects	46	(1)
Limited supply creates economic pressure	47	(1)
The political effects of petroleum	47	(1)
Concerns about biological feedstocks	48	(1)
Unnecessary derivatization (blocking group, protection/deprotection, temporary modification of physical/chemical processes) should be avoided whenever possible	48	(2)
The prevalence of this practice in chemistry	48	(1)
Blocking/protecting groups	49	(1)
Making salts, etc. for ease of processing	49	(1)
Adding a functional group only to replace it	49	(1)
Catalytic reagents (as selective as possible) are superior to stoichiometric reagents	50	(1)
Chemical products should be designed so that at the end of their function they do not persist in the environment and break down into innocuous degradation products	51	(2)
The current situation	51	(1)
Persistence in the environment	52	(1)
Analytical methodologies need to be further developed to allow for real-time, in-process monitoring, and control prior to the formation of hazardous substances	53	(1)
Substances and the form of a substance used in a chemical process should be chosen so as to minimize the potential for chemical accidents, including releases, explosions, and fires	54	(3)
Evaluating the effects of chemistry	57	(10)
How does a chemist evaluate a chemical product or process for its effect on human health and the environment?	57	(10)
Toxicity to humans	58	(3)
Toxicity to wildlife	61	(2)
Effects on the local environment	63	(1)
Global environmental effects	63	(4)
Evaluating to feedstocks and starting materials	67	(4)
Origins of the feedstock/starting materials	67	(1)
A renewable or a depleting resource	68	(1)
Hazardous or innocuous feedstock	69	(1)
Downstream implications of the choice of feedstock	69	(2)
Evaluating reaction types	71	(14)
What are the different general types of chemical transformation?	71	(10)
Rearrangements	72	(1)
Addition reactions	73	(2)
Substitution reactions	75	(2)
Elimination reactions	77	(1)
Pericyclic reactions	78	(2)
Oxidation/reduction reactions	80	(1)
What is the intrinsic nature of the various reaction types?	81	(4)
Do they require additional chemicals?	81	(1)
Do they necessarily generate waste?	82	(3)
Evaluation of methods to design after chemicals	85	(8)
Mechanism of action analysis	86	(2)
Structure activity relationships	88	(1)
Avoidance of toxic functional groups	89	(1)
Minimizing bioavailability	89	(1)
Minimizing auxiliary substances	90	(3)
Examples of green chemistry	93	(22)
Examples of green starting materials	93	(4)
Polysaccharide polymers	93	(1)
Commodity chemicals from glucose	94	(1)
Biomass conversion to chemical products	95	(2)
Examples of green reactions	97	(3)
Atom economy and homogeneous catalysis	97	(1)
Halide-free syntheses of aromatic amines	97	(1)
A green alternative to the Strecker synthesis	98	(2)
Examples of green reagents	100	(3)
Non-phosgene isocyanate synthesis	100	(1)
Selective methylations using dimethylcarbonate	101	(1)
Solid-state polymerization of amorphous polymers using diphenylcarbonate	102	(1)
Green oxidative transition metal complexes	103	(1)
Liquid oxidation reactor	103	(1)
Examples of green solvents and reaction conditions	103	(6)
Supercritical fluids	104	(1)
Aqueous reaction conditions	105	(2)
Immobilized solvents	107	(1)
Irradiative reaction conditions	108	(1)
Examples of green chemical products	109	(6)
Design of alternative nitriles	110	(1)
Rohm and Haas Sea-Nine(tm) product	111	(1)
Rohm and Haas CONFIRM(tm) insecticide	111	(1)
Donlar's polyaspartic acids	112	(1)
Polaroid's complexed developers	112	(3)
Future trends in green chemistry	115	(6)
Oxidation reagents and catalysts	115	(1)
Biomimetic, multifunctional reagents	116	(1)
Combinatorial green chemistry	117	(1)
Chemistry that both prevents problems and solves current pollution problems	117	(1)
Proliferation of solventless reactions	118	(1)
Energy focus	118	(1)
Non-covalent derivatization	119	(2)
Exercises	121	(4)
References	125	(6)
Index	131