Chapter 18 — Further Reading

Textbooks

• Clayden, Greeves, and Warren. Organic Chemistry, 2nd ed. (Oxford University Press, 2012). Chapter 39 ("Radical Reactions"). Comprehensive treatment.

• McMurry, John. Organic Chemistry, 9th or later ed. (Cengage). Chapter 6 has radical halogenation; Chapter 31 (later editions) covers radicals in more depth.

• Carey and Sundberg. Advanced Organic Chemistry, Part B. Chapter 11 covers radical reactions in advanced detail.

• March's Advanced Organic Chemistry, 7th ed. (Wiley, 2013). Chapter 14 covers free radicals.

• Curran, D. P. (1988). The Design and Application of Free Radical Chain Reactions in Organic Synthesis. Synthesis. The classic synthesis review for radical chemistry.

Primary literature: radical halogenation

• Goldfinger, P., et al. (1948). Mechanism studies of radical chlorination. Various papers in Helvetica.

• Russell, G. A. (1957). Selectivity in radical bromination. Journal of the American Chemical Society 79, 4344-4353.

Primary literature: peroxide effect

• Kharasch, M. S., and Mayo, F. R. (1933). The peroxide effect in HBr addition. Journal of the American Chemical Society 55(6), 2468-2496. The original discovery.

• Walling, C. (1957). Free Radicals in Solution. Wiley. Walling's classic monograph.

Primary literature: NBS

• Wohl, A. (1919). N-bromosuccinimide synthesis. Berichte der Deutschen Chemischen Gesellschaft.

• Ziegler, K. (1942). NBS for allylic bromination. Justus Liebigs Annalen 551, 80-119. The Ziegler-Wohl procedure.

Primary literature: photoredox

• Yoon, T. P., et al. (2010). Photoredox catalysis review. Nature Chemistry 2, 527-532. The modern field.

• Nicewicz, D. A., and MacMillan, D. W. C. (2008). Asymmetric photoredox. Science 322(5898), 77-80.

Lipid peroxidation and antioxidants

• Halliwell, B., and Gutteridge, J. M. C. (2015). Free Radicals in Biology and Medicine, 5th ed. (Oxford University Press). The standard reference.

• Burton, G. W., and Ingold, K. U. (1989). "Vitamin E as in vitro and in vivo antioxidant." Annals of the New York Academy of Sciences 570(1), 7-22. Foundational paper on vitamin E antioxidant chemistry.

• Niki, E. (multiple papers). Vitamin E and lipid peroxidation kinetics.

Polymer chemistry

• Odian, G. (2004). Principles of Polymerization, 4th ed. (Wiley-Interscience). The standard polymer textbook.

• Matyjaszewski, K., and Davis, T. P. (eds.) (2002). Handbook of Radical Polymerization. Wiley. ATRP and other CRP methods.

• Moad, G., and Solomon, D. H. (2006). The Chemistry of Radical Polymerization. Elsevier.

Industrial radical polymerization

• Weissermel, K., and Arpe, H.-J. (2003). Industrial Organic Chemistry. Polymer chapters cover LDPE, PVC, PS, PMMA, etc.

Computational tools

• Avogadro (https://avogadro.cc/). Build radicals; compute spin density.

• PubChem — look up: AIBN (CID 6685), benzoyl peroxide (CID 7187), NBS (CID 12932), α-tocopherol (CID 14985).

Online resources

• Master Organic Chemistry, "Radical Reactions" series. Free undergraduate-level explanations.

• Khan Academy: Organic Chemistry — Free Radicals. Free videos.

For practice problems

• Klein, David. Organic Chemistry as a Second Language, 4th ed. (Wiley). Chapter on radical chemistry.

• Karty, Joel. Organic Chemistry: Principles and Mechanisms, 2nd ed. (W. W. Norton, 2018). Chapter on radicals.

Mathematically inclined readers

• Fischer, H. (1992). Mathematical kinetics of chain reactions. Chemical Reviews 92(7), 1545-1576.

• Beckwith, A. L. J., and Easton, C. J. (1981). Theoretical treatment of radical reactions.

Notes on this chapter's pedagogy

Chapter 18 introduces a parallel mechanism toolkit (radicals + chains) alongside the ionic chemistry of Chs 10-17. The unifying theme: stability of intermediates determines selectivity, but in radical chemistry the intermediate is a radical (not a carbocation).

The chapter develops: 1. Radical structure, stability, and homolysis. 2. The chain mechanism (initiation/propagation/termination). 3. Specific applications: halogenation, anti-Markovnikov HBr, NBS bromination. 4. Industrial: radical polymerization (LDPE, etc.). 5. Biological: lipid peroxidation, antioxidant defense. 6. Modern: photoredox catalysis (forward connection to Ch 40).

Chapter 19 turns to conjugation — molecules with alternating double bonds — and the Diels-Alder reaction, one of the most useful pericyclic reactions in organic chemistry.