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4.3 IUPAC Nomenclature of Bicyclic Compounds

Sep 30, 2025

Overview

This lecture explains the rules for naming bicyclic compounds in organic chemistry, covering bridged, fused, and spiro systems, including how to number and name substituents.

Types of Bicyclic Compounds

  • Bicyclic compounds contain two rings within their structure.
  • The three main types are bridged bicyclics, fused bicyclics, and spiro bicyclics.

Naming Bridged and Fused Bicyclic Compounds

  • Identify the total number of carbons for the parent name (e.g., bicyclooctane for 8 carbons).
  • Find the two bridgehead carbons, present in all rings.
  • Count carbons between bridgeheads on all paths (do not count the bridgeheads themselves).
  • Write these numbers in descending order inside brackets: [x.y.z].
  • For fused bicyclics, one path directly connects bridgeheads (this count is zero).
  • Number the ring by starting at a bridgehead, through the longest path first.
  • Number substituents to give the lowest possible locator number.

Naming Spiro Bicyclic Compounds

  • Spiro compounds share a single "spirocarbon" connecting two rings.
  • Name starts with "spiro" instead of "bicyclo".
  • Count the number of carbons in each ring (excluding the spirocarbon).
  • Place the counts in ascending order inside brackets: [smaller.larger].
  • For numbering, do not start with the spirocarbon; start on the smaller ring for lower numbers.
  • Number to give substituents the lowest possible locator number.

Functional Group Priority in Nomenclature

  • Only the highest-priority functional group is named as a suffix in the parent chain.
  • Other functional groups are named as substituents (prefixes).
  • Priority order (e.g., carboxylic acid > anhydride > ester, etc.) should be learned for applying correct suffixes and prefixes.

Key Terms & Definitions

  • Bicyclic compound — a molecule containing two connected rings.
  • Bridgehead carbons — carbons shared by both rings in a bridged or fused system.
  • Spirocarbon — single carbon atom where two rings are joined in a spiro compound.
  • Fused bicyclic — two rings sharing two adjacent carbons (directly bonded bridgeheads).
  • Bridged bicyclic — two rings sharing two non-adjacent carbons (bridgeheads), separated by bridges of varying length.

Action Items / Next Steps

  • Study the functional group priority list for nomenclature.
  • Review and practice naming bicyclic structures with and without substituents.
  • Prepare for upcoming lessons on conformational structures of alkanes.