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Green Chemistry:
An Overview
Over the past few years, the chemistry community has been mobilized to develop new
chemistries that are less hazardous to human health and the environment. This new
approach has received extensive attention (1-16) and goes by many names including
Green Chemistry, Environmentally Benign Chemistry, Clean Chemistry, Atom
Economy and Benign By Design Chemistry. Under all of these different designations
there is a movement toward pursuing chemistry with the knowledge that the
consequences of chemistry do not stop with the properties of the target molecule or
the efficacy of a particular reagent. The impacts of the chemistry that we design as
chemists are felt by the people that come in contact with the substances we make and
use and by the environment in which they are contained.
For those of us who have been given the capacity to understand chemistry and
practice it as our livelihood, it is and should be expected that we will use this capacity
wisely. With knowledge comes the burden of responsibility. Chemists do not have
the luxury of ignorance and cannot turn a blind eye to the effects of the science in
which we are engaged. Because we are able to develop new chemistries that are more
benign, we are obligated to do so.
0097-6156/96/0626-0001$12.00/0
1996 American Chemical Society
In Green Chemistry; Anastas, P., et al.;
ACS Symposium Series; American Chemical Society: Washington, DC, 1996.
GREEN CHEMISTRY
This volume details how chemists from all over the world are using their
creativity and innovation to develop new synthetic methods, reaction conditions,
analytical tools, catalysts and processes under the new paradigm of Green Chemistry.
It is a challenge for the chemistry community to look at the excellent work that has
been and continues to be done and to ask the question, "Is the chemistry / am doing
the most benign that I can make it?".
One obvious but important point: nothing is benign. A l l substances and all
activity have some impact just by their being. What is being discussed when the term
benign by design or environmentally benign chemistry is used is simply an ideal.
Striving to make chemistry more benign wherever possible is merely a goal. Much
like the goal of "zero defects" that was espoused by the manufacturing sector, benign
chemistry is merely a statement of aiming for perfection.
Chemists working toward this goal have made dramatic advances in
technologies that not only address issues of environmental and health impacts but do
so in a manner that satisfies the efficacy, efficiency and economic criteria that are
crucial to having these technologies incorporated into widespread use. It is exactly
because many of these new approaches are economically beneficial that they become
market catalyzed. While most approaches to environmental protection historically
have been economically costly, the Green Chemistry approach is a way of alleviating
industry and society of those costs.
What is Green Chemistry?
While it has already been mentioned that nothing is truly environmentally benign,
there are substances that are known to be more toxic to humans and more harmful to
the environment than others. By using the extensive data available on human health
effects and ecological impacts for a wide variety of individual chemicals and chemical
classes, chemists can make informed choices as to which chemicals would be more
favorable to use in a particular synthesis or process. Simply stated, Green Chemistry
is the use of chemistry techniques and methodologies that reduce or ehminate the use
or generation of feedstocks, products, by-products, solvents, reagents, etc., that are
hazardous to human health or the environment.
Green Chemistry is a fundamental and important tool in accomplishing
pollution prevention. Pollution prevention is an approach to addressing environmental
issues that involves preventing waste from being formed so that it does not have to be
dealt with later by treatment or disposal. The Pollution Prevention Act of 1990 (17)
established this approach as the national policy of United States and the nation's
"central ethic" (18) in dealing with environmental problems.
There is no doubt that over the past 20 years, the chemistry community, and
in particular, the chemical industry, has made extensive efforts to reduce the risk
associated with the manufacture and use of various chemicals. There have been
innovative chemistries developed to treat chemical wastes and remediate hazardous
waste sites. New monitoring and analytical tools have been developed for detecting
contamination in air, water and soils. New handling procedures and containment
technologies have been developed to minimize exposure. While these areas are
laudable efforts in the reduction of risk, they are not pollution prevention or Green
An Overview
Chemistry, but rather are approaches to pollutant control. Many different ways to
accomplish pollution prevention have been demonstrated and include engineering
solutions, inventory control and "housekeeping" changes. Approaches such as these
are necessary and have been successful in preventing pollution, but they also are not
Green Chemistry. There is excellent chemistry that is not pollution prevention and
there are pollution prevention technologies that are not chemistry. Green Chemistry
is using chemistry for pollution prevention.
No one who understands chemistry, risk assessment and pollution prevention
would claim that assessing which substances or processes are more environmentally
benign is an easy task. To the contrary, the implications of changing from one
substance to another are often felt throughout the life-cycle of the product or process.
This difficulty for obtaining a quantifiable measurement of environmental impact has
been, however, too often used historically as a rationale for doing nothing. The fact
is that for many products and for many processes, clear determinations can be made.
Many synthetic transformations have clear advantages over others, and certain target
molecules are able to achieve the same level of efficacy of function while being
significantly less toxic.
It is important that chemists develop new Green Chemistry options even on an
incremental basis. While all elements of the lifecycle of a new chemical or process
may not be environmentally benign, it is nonetheless important to improve those
stages where improvements can be made. The next phase of an investigation can then
focus on the elements of the lifecycle that are still in need of improvement. Even
though a new Green Chemistry methodology does not solve at once every problem
associated with the lifecycle of a particular chemical or process, the advances that it
does make are nonetheless very important.
This volume highlights some of the many advances currently being made in
Green Chemistry that are everything from incremental to universal in their impact on
the problems that they are addressing. The work described is pioneering and highly
innovative, and will provide an information data set of proven Green Chemistry
methods and techniques that chemists in the future will need in order to be able to
design entire synthetic pathways and processes that are more environmentally benign.
Why is Green Chemistry Important?
In 1993,30 billion pounds of chemicals were released to air, land and water as tracked
by the Toxic Release Inventory of the U.S. Environmental Protection Agency (see
Figure 1). While this data covers releases from a variety of industrial sectors, it
includes only 365 of the approximately 70,000 chemicals available in commerce
today. Of the industrial sectors that are covered by the toxic release inventory, the
chemical manufacturing sector is understandably the largest releaser of chemicals to
the environment, releasing more than 4 times as many pounds to the environment as
the next highest sector (see Figure 2).
The current status of environmental protection in the United States is
constructed from a generation of statutes and regulations. The vast majority of these
regulations were written at a time where command and control approaches to
environmental protection was the order of the day. Many of these laws require
GREEN CHEMISTRY
rZI
Underground Injection
Surface Water
Land
20,000 - i
a: chemicals
b: primary metals
c: (multiple codes)
d: paper
e: petroleum
f: stone/clay
g: fabricated metals
h: electronics
i : plastics
j : transportation
equipment
1.
An Overview
GREEN CHEMISTRY
1.
An Overview
GREEN CHEMISTRY
reduction to eliminate the need for this substance in the generation of isocyanates.
Manzer (36-37) at DuPont has reported the development of a catalytic process that
again eliminates the use of phosgene from the isocyanate process. In this work the
amine is directly carbonylated through the use of carbon monoxide in a proprietary
system. The generation of isocyanates by this DuPont process has reportedly been
commercialized.
D-glucose
An Overview
GREEN CHEMISTRY
10
Product
Isolated Yield
Entry
An Overview
11
GREEN CHEMISTRY
12
The early studies carried out during this resurgence of interest in supercritical
fluids have been quite promising. The studies conducted by Tanko (55-58) at Virginia
Polytechnic Institute and State University on free-radical reactions in S C - C 0
provided a foundation for understanding how a classical reaction type would function
in this new solvent system. Using standard brornination reactions of alkylated
aromatics as the model system, Tanko demonstrated that the yields and selectivities
of free-radical halogenations in supercritical fluids were equal and in some cases
superior to those conducted in conventional solvent systems. As is the case in all
Green Chemistry alternatives, demonstrating technical efficacy is crucial in order to
evaluate the true advantages offered by the environmental and risk reduction benefits.
Polymerization reactions in supercritical fluids have been studied extensively
in the laboratory of DeSimone (59-61) at the University of North Carolina.
DeSimone had demonstrated the ability to synthesize a variety of polymer types with
several different monomelic systems. His methyl methacrylate polymer studies have
demonstrated that there are pronounced advantages to using supercritical fluids as a
solvent system compared to using conventional halogenated organic solvents.
The National Laboratory at Los Alamos has been actively engaged over the
past several years in research in the applications of S C - C 0 as a synthetic solvent.
The work of Tumas (61-66) and co-workers as detailed in a later chapter of this
volume profiles the performance of reactions such as polymerization of epoxides,
oxidation of olefins and asymmetric hydrogenations in supercritical systems. In each
of these cases the reactions proceeded without compromise when compared to
conventional solvent systems, and superior performance was reported in the
asymmetric hydrogenation reactions.
Although currently under extensive study, supercritical fluids are the only
example of an alternative solvent under investigation for Green Chemistry. Hatton
(67) at MIT has reported early results of the use of amphiphilic star polymers as
solvents in synthesis. In addition to their innocuous nature, due in part to their size,
they also have the advantage of rninirnizing the need for intensive separations that can
require additional solvent use.
Too numerous to list are the projects that are currently investigating the use of
aqueous solvent systems in place of organic solvents in chemical manufacturing.
While many of these show great promise and in some cases improved efficacy, the
environmental impact is one that needs to be carefully evaluated on a case-by-case
basis. It is possible that what was once an air pollution problem brought on by the use
of volatile organic compounds could become a more serious water pollution problem
if wastes are difficult to remove from the aqueous solvent system and are subsequently
lost as effluent. Even though the environmental concern associated with a
conventional process is eliminated by the use of an aqueous solvent system, the
alternative process cannot be considered a viable substitute until the total impacts of
the substitution is assessed.
Alternative Products and Target Molecules. The goal of designing safer chemicals
is both straightforward and extremely complex. It is well recognized that in many
cases the part of a molecule which provides its intended activity or function is separate
from the part of a molecule responsible for its hazardous properties or toxicity.
1.
An Overview
13
Therefore, the challenge is to reduce the toxicity of a molecule without sacrificing the
efficacy of function. This goal has been actively pursued in specific industrial sectors,
such as pharmaceutical and pesticide manufacture, where it is of obvious importance.
With some notable exceptions, this same goal has been generally ignored in most of
the other chemical sectors.
The following examples provide insight into how an understanding of the
mechanism of action of the toxicity of chemical coupled with the knowledge of the
structural requirements for the desired function can be used to design safer chemicals.
By utilizing the knowledge that synthetic chemists possess, it is possible to greatly
reducing the hazards associated with certain chemical products while maintaining their
performance and innovation that has become expected from the chemical industry.
The work conducted by DeVito (68) at the U.S. Environmental Protection
Agency on a large range of nitriles elucidated the nature of the hazard posed by the
release of cyanide, since the degree of toxicity can be directly correlated to the ability
of the nitrile to form an alpha radical. By blocking the alpha position such that radical
formation is not possible, the nitrile's toxicity can be decreased by several orders of
magnitude without adversely effecting the ability of the nitrile to carry out its function
as a cross-linking agent.
Another example of designing chemicals such that their function is maintained
without the toxicity is the work of DePompei (69) at Tremco, Inc., in designing
alternatives to isocyanates as sealants. This work utilizes acetoacetate esters which as
a class do not have the human health and environment concerns that are associated
with isocyanates in this use. Rather than modifying the molecular structure in order
to reduce the hazard, this work demonstrates the approach of reexamining the function
that needs to be performed and subsequently identifying or developing compounds
that can accomplish this function without the accompanying hazards.
Green Chemistry's approach to designing safer chemicals is simply another
option for chemists to employ in their overall evaluation and decision making process
on what to make and how to make it. A great deal of effort has been expended in
developing ways of handling hazardous chemicals in a safe manner such that the risk
of injury and adverse health effects is minimized. In many cases this approach to
minimizing risks is a costly one. Where appropriate, chemicals can be designed such
that their hazards are already minimized thereby obviating the need for expenditures
on handling and control procedures.
Universal Issues. While it is possible to classify the Green Chemistry research that
is currently being conducted into several categories, there are some subjects that do
not fit neatly into these categories because of their overarching nature. The work
being done in these areas is both innovative and significant and more importantly,
fundamental to the basic direction that Green Chemistry needs to follow in order to
be successful in all its endeavors.
At the foundation of the principles of Green Chemistry is that of Atom
Economy. This concept as elucidated and demonstrated by Trost (70) couples the
most important elements of the idea of environmentally benign synthesis and the
definition of synthetic elegance to provide a framework for how synthetic design
should be guided. The economical use of atoms in the construction of a synthetic
14
GREEN CHEMISTRY
1.
15
An Overview
Literature Cited
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
16
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.
57.
GREEN CHEMISTRY
McGhee, W.D.; Riley, D.P.; Christ, M.E.; Christ, K.M. Organometallics 1993,
12, pp. 1429-1433, and references cited therein.
Riley, D.P.; McGhee, W.D. U.S. Patent # 5,055,577, 1991.
Riley, D.P.; McGhee, W.D. U.S. Patent # 5,200,547, 1993.
McGhee, W.D.; Parnas, B.L.; Riley, D.P.; Talley, J.J U.S. Patent # 5,223,638,
1993.
McGhee, W.D.; Stern, M.K.; Waldman, T.E. U.S. Patent # 5,233,010, 1993.
McGhee, W.D.; Waldman, T.E. U.S. Patent # 5,189,205, 1993.
Manzer, L.E. In Benign By Design: Alternative Synthetic Pathways for
Pollution Prevention; Anastas, P.T.; Farris, C.A., Eds.; ACS Symposium
Series #577; American Chemical Society: Washington, D.C., 1994, pp. 144.
(DuPont) U.S. Patent # 4,537,726, 1985.
See Chapter in this book by Komiya, K., et.al.
Epling, G.A.; Wang, Q. In Benign By Design: Alternative Synthetic Pathways
for Pollution Prevention; Anastas, P.T.; Farris, C.A., Eds.; ACS Symposium
Series #577; American Chemical Society: Washington, D.C., 1994, pp. 64.
Kraus, G.A.; Kirihara, M.; Wu, Y. In Benign By Design: Alternative Synthetic
Pathways for Pollution Prevention; Anastas, P.T.; Farris, C.A., Eds.; ACS
Symposium Series #577; American Chemical Society: Washington, D.C.,
1994, pp. 76.
Kraus, G.A.; Kirihara, M. J. Org. Chem. 1992, 57, p. 3256.
See Chapter in this book by Tundo, P.; Selva, M.; Marques, C.A.
Tundo, P.; Selva, M. Chemtech 1995, pp. 31-35.
Tundo, P.; Trotta, F.; Moraglio, G. J. Chem. Soc., Perkin Trans.I1989, p.
1070.
Tundo, P.; Trotta, F.; Moraglio, G. J. Org. Chem 1987, 52, p. 1300.
Tundo, P.; Trotta, F.; Moraglio, G.; Ligorati, F. Ind. Eng. Chem. Res. 1988, 27,
p. 1565.
Loosen, P.; Tundo, P.; Selva, M. U.S. Patent # 5,278,533, 1994.
See Chapter in this book by Rivetti, F.; Delledonne, D.
Rivetti, F.; Romano, U. U.S. Patent # 5,206,409(ECS).
Rivetti, F.; Romano, U. U.S. Patent # 5,159,099(ECS).
Rivetti, F.; Romano, U.; DiMuzio, N. U.S. Patent # 4,318,862(ECS).
Delledonne, D.; Rivetti, F.; Romano, U. EP Pat. Appl. 463,678(ECS).
Delledonne, D.; Rivetti, F.; Romano, U. J. Organomet. Chem. 1995, 488, p.
C15.
Paquette, L. In Abstracts of Papers Presented at the 209th ACS National
Meeting; Pasto, D.J., Program Chairperson; Division of Organic Chemistry,
American Chemical Society: Washington, D.C., 1995, #125.
Tanko, J.M.; Blackert, J.F.; Sadeghipour, M. In Benign By Design: Alternative
Synthetic Pathways for Pollution Prevention; Anastas, P.T.; Farris, C.A., Eds.;
ACS Symposium Series #577; American Chemical Society: Washington, D.C.,
1994, p. 98.
Tanko, J.M.; Blackert; J.F. Science 1994, 263, p. 203.
Tanko, J.M.; Mas, R.H.; Suleman, N.K. J. Am. Chem Soc. 1990, 112, p. 5557.
58.
59.
60.
61.
62.
63.
64.
65.
66.
67.
68.
69.
70.
71.
72.
An Overview
17
Tanko, J.M.; Suleman, N.K.; Hulvey, G.A.; Park, A.; Powers, J.E. J. Am.
Chem. Soc. 1993, 115, p. 4520.
DeSimone, J.M.; Guan, Z.; Elsbernd, C.S. Science 1992, 257, p. 945.
DeSimone, Y.M.; Maury, E.E.; Lemert, R.E.; Combes, J.R. Polym. Mater. Sci.
Eng. 1993, 68, p. 41.
DeSimone, J.M.; Maury, E.E.; Menceloglu, Y.Z.; McClain, J.B.; Romack, T.
J.; Combes, J.R. Science 1994, 265, p. 356.
Burk, M.J.; Feng, S.; Gross, M.F.; Tumas, W. J. J. Am. Chem. Soc. 1995, 117,
p. 8277.
Morgenstern, D.A.; Tumas, W. J. Am. Chem. Soc. submitted.
Burk, M.J.; Harper, G.P.; Kalberg, C.S. J. Am. Chem. Soc. 1995, 117, p. 4423.
Burk, M.J. J. Am. Chem. Soc. 1991, 113, p. 8518.
Burk, M.J.; J.E., F., Nugent, W.A.; Harlow, R.L. J. Am. Chem. Soc. 1993, 115,
p. 10125.
Hurter, P.N.; Hatton, T.A. Langmuir 1992, 8, pp. 1291-1299.
Grogan, J., DeVito, S.C.; Pearlman, R.S.; Korzekwa, K.R.; Modeling Cyanide
Release From Nitriles: Prediction of Cytochrome P450 Mediated Acute Nitrile
Toxicity. Chem. Res. in Tex. 1992, 5, pp. 548-552.
DePompei, M.F. In Preprits of Papers Presented at the 208th ACS National
Meeting; Bellen, G.E., Chairman; Division of Environmental Chemistry,
American Chemical Society: Washington, D.C., 1994, 34(2), p. 393.
Trost, B.M. Science 1991, 2, pp. 1471-1477.
See Chapter in this book by Simmons, M.
Cusamano, J. Chemtech 1992, pp. 482-489.