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toxicity, environmental impact) criteria (see Chapter 6) have to be weighed against
each other, and the best methods and reagents for the desired transformation
should be worked out or developed, free of ideological indoctrination. This may or
may not point to the use of phosgene itself.
The aim of this topic is to present the state-of-the-art on phosgenation chemistry,
including all its phosgene equivalents and substitutes (some 70 are dealt with in this
topic), resulting in many novel reactions and processes for improved methods to
obtain ''phosgenation'' products (see Chapters 4 and 5).
A second concern of this topic is to show the modern trend of producing phos-
gene captively, and on demand, thereby minimizing storage (see Section 2.1.2), as
well as the efforts to combine safe equivalents with the sometimes superior prop-
erties of phosgene in so-called safety phosgenation, which involves no storage of
phosgene. The phosgene is generated on demand and immediately consumed, and
so the quantity actually present in the reaction system is minimized (see Sections
2.2.2.1 and 7.1.2).
A third, forward-looking concern of this topic is the presentation of examples of
processes that meet the requirements of ''green chemistry'', which are often syn-
theses using carbon dioxide, such as the production of dimethyl carbonate from
methanol (see Section 4.3.3.8). The other class of reactions in this branch of
chemistry are smart catalytic reactions, through which the generally high activation
energies of phosgenation reactions can be lowered, thus saving energy. Further
considerations on trend-setting will be mentioned in Chapter 9 - Outlook.
References
1 T. Ito, M. Tsubokawa (to Idemitsu
Petrochem Co.), JP 03065595, 1991;
Chem. Abstr. 1991, 115, 219647.
2 J. S. Tou, B. D. Vineyard, J. Org.
Chem. 1985, 50, 4982-4984.
3 T. R. Kelly, R. A. Silva, H. de Silva,
S. Jasmin, Y. Zhao, J. Am. Chem. Soc.
2000, 122, 6935-6949.
4 SIPRI, ''The Problem of Chemical and
Biological Warfare'', vol. 1, ''The Rise of
CB Weapons'', Almquist & Wiksell,
Stockholm, 1971, p. 125-141.
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