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4.2 Naming Complex Substituents

Sep 30, 2025

Overview

This lecture covers how to systematically and commonly name complex substituents in organic chemistry, extending basic alkane nomenclature to branched and larger substituent groups.

Review of Simple Substituents

  • Simple substituents are groups like methyl, ethyl, propyl, and butyl, attached by a single carbon chain.
  • When naming alkanes, identify and number the longest continuous carbon chain as the parent chain.

Introduction to Complex Substituents

  • Complex substituents are substituents that have their own branches (i.e., not straight-chain groups).
  • Two naming methods exist: common names (for some small substituents) and systematic IUPAC naming (always applicable).

Systematic Naming of Complex Substituents

  • Number the substituent’s longest chain starting at the carbon attached to the parent chain (always carbon 1).
  • Name the substituent as an alkyl group using "-yl" and indicate branches as substituents on that group.
  • List numbers and names of substituents on the main substituent, e.g., (1,2-dimethylpropyl).
  • Enclose systematic complex substituent names in parentheses in the full compound name.
  • Alphabetize complex substituents by the first letter inside the parentheses, including prefixes if present.

Common Names for Branched Substituents

  • Three-carbon substituents: propyl (straight) and isopropyl (branched).
  • Four-carbon substituents: butyl (straight), sec-butyl (attached via a secondary carbon), isobutyl (branched with a Y shape), tert-butyl (attached via a tertiary carbon).
  • Sec- and tert-butyl are hyphenated and alphabetized by "B," while iso groups are not hyphenated and are alphabetized by "I."
  • For five or more carbons, use only the systematic method.

Alphabetization and Parentheses Rules

  • Systematic complex substituents in parentheses are alphabetized by the first letter inside, including prefixes such as di-, tri-.
  • Common names are not placed in parentheses and are alphabetized as usual.

Examples and Practice

  • When naming entire molecules, always choose the longest parent chain and assign the lowest numbers to substituents.
  • When multiple naming options exist (e.g., common vs systematic), either may be used if IUPAC allows.
  • Order of substituent names can change based on which naming system is used, affecting alphabetical listing.

Key Terms & Definitions

  • Substituent — An atom or group attached to the main carbon chain.
  • Complex substituent — A substituent with its own branching.
  • Systematic name — IUPAC-approved approach for naming compounds using standardized rules.
  • Common name — Traditional, often shorter or widely used names for certain groups (e.g., isopropyl, tert-butyl).
  • Parent chain — The longest continuous carbon chain in a molecule.
  • Isopropyl — A branched three-carbon group attached by the middle carbon.
  • Sec-butyl — Four-carbon group attached by a secondary carbon.
  • Isobutyl — Four-carbon group with a Y-shaped branch at the end.
  • Tert-butyl — Four-carbon group attached by a tertiary carbon.

Action Items / Next Steps

  • Practice identifying and naming complex substituents both systematically and by common names.
  • Memorize common names for three- and four-carbon branched substituents.
  • Review how to apply alphabetical order and parentheses in naming compounds.