The History of Free Radical Chemistry

Abstract

Suggestions of free radicals before 1900 were realized with the discovery first of the triphenylmethyl radical, and then unstabilized aliphatic radicals in the twentieth century. The finding of new types of radicals and the development of their chemistry are outlined. Many individuals participated in the advance of free‐radical chemistry, and some of the most prominent original contributors are recognized where possible. The article provides an overview of the development of many fundamentals of free radicals, while the definitive articles in this encyclopedia on the various topics provided by leaders in their study articles describe the current state of knowledge.

Radicals in Action: A Festival of Radical Transformations

“…), then became a curiosity at the turn of the 20th century with Gomberg’s triphenylmethyl radical . Their possible implication as reaction intermediates had to wait until the 1930s . While this development had an enormous impact on the rise of polymers with their incalculable and dramatic effect on the improvement of the quality of life, the influence of radical reactions on the synthesis of small molecules remained strangely subdued until the early 1970s.…”

“…2 Their possible implication as reaction intermediates had to wait until the 1930s. 3 While this development had an enormous impact on the rise of polymers with their incalculable and dramatic effect on the improvement of the quality of life, the influence of radical reactions on the synthesis of small molecules remained strangely subdued until the early 1970s. The rather sudden availability of reliable kinetic data from laser flash photolysis experiments and the emergence of powerful methods based mostly on organotin chemistry ushered an explosive growth in the application of radicals in synthesis.…”