Introduction to Pyrrolidone and Caprolactam Chemistry

This chapter provides an introduction to the structure, conformation, physical properties and reactivity of pyrrolidones and caprolactams. It begins with an overview of the nomenclature of lactams since there are several systems of nomenclature in practice, plus common names and various syncretisms. The chapter discusses the structures of pyrrolidone and caprolactam, starting with the X‐ray crystal structures of pyrrolidone, N‐methylpyrrolidone and caprolactam. The distinctive structural feature that dictates the physical and chemical properties of simple pyrrolidones and caprolactams is the cyclic amide moiety. The physical properties of lactams are dominated by the strong dipole moments and hydrogen bonding of their amide bonds. Pyrrolidones and caprolactams display reactivities comparable to other secondary and tertiary amides. Pyrrolidones and caprolactams display reactivities comparable to other secondary and tertiary amides. Like other amides, pyrrolidones and caprolactams are susceptible to hydrolysis, particularly at elevated temperature and extremes of pH.