Substituent

This article is about the term in chemistry. For other meanings, see Substitution (disambiguation).

In organic chemistry, a substituent is one or a group of atoms that replaces (one or more) atoms, thereby becoming a moiety in the resultant (new) molecule.[1] (In organic chemistry and biochemistry, the terms substituent and functional group, as well as side chain and pendant group, are used almost interchangeably to describe those branches from the parent structure,[2] though certain distinctions are made in polymer chemistry.[3] In polymers, side chains extend from the backbone structure. In proteins, side chains are attached to the alpha carbon atoms of the amino acid backbone.)

The suffix -yl is used when naming organic compounds that contain a single bond replacing one hydrogen; -ylidene and -ylidyne are used with double bonds and triple bonds, respectively. In addition, when naming hydrocarbons that contain a substituent, positional numbers are used to indicate which carbon atom the substituent attaches to when such information is needed to distinguish between isomers. Substituents can be a combination of the inductive effect and the mesomeric effect. Such effects are also described as electron-rich and electron withdrawing. Additional steric effects result from the volume occupied by a substituent.

The phrases most-substituted and least-substituted are frequently used to describe or compare molecules that are products of a chemical reaction. In this terminology, methane is used as a reference of comparison. Using methane as a reference, for each hydrogen atom that is replaced or "substituted" by something else, the molecule can be said to be more highly substituted. For example:

  • Markovnikov's rule predicts that the hydrogen atom is added to the carbon of the alkene functional group which has the greater number of hydrogen atoms (fewer alkyl substituents).
  • Zaitsev's rule predicts that the major reaction product is the alkene with the more highly substituted (more stable) double bond.
  1. ^ "Definition of SUBSTITUENT". www.merriam-webster.com. Retrieved 4 June 2022.
  2. ^ D.R. Bloch (2006). Organic Chemistry Demystified. Mcgraw-hill. ISBN 978-0-07-145920-4.
  3. ^ Jenkins, A. D.; Kratochvíl, P.; Stepto, R. F. T.; Suter, U. W. (1996). "PAC, 1996, 68, 2287. Glossary of basic terms in polymer science (IUPAC Recommendations 1996)". Pure and Applied Chemistry. 68 (12): 2287–2311. doi:10.1351/pac199668122287. This distinguishes a pendant group as neither oligomeric nor polymeric, whereas a pendant chain must be oligomeric or polymeric.