carboxylic derivatives

• Carboxylic Anhydrides


  Compounds derived from carboxylic acids, with the functional group of two carbonyl groups bonded to the same oxygen

  
• Esters


  Compounds derived from carboxylic acids, with the functional group of a carbonyl group bonded to an -OR group (R may be alkyl or aryl)

  
• Amides


  Compounds derived from carboxylic acids, with the functional group of a carbonyl group bonded to a nitrogen atom

  
• Anhydrides


  • May be symmetrical (from two identical acyl groups) or mixed (from two different acyl groups)
  • To name, drop the word "acid" from the name of the carboxylic acid and add the word "anhydride"
• Esters


  • Both IUPAC and common names are derived from the names of the parent carboxylic acids
  • Name the alkyl or aryl group bonded to oxygen first, followed by the name of the acid; replace the suffix -ic acid by -ate
  • A cyclic ester is called a lactone

  
• Amides


  • To name, drop the suffix -oic acid from the IUPAC name of the parent acid, or -ic acid from its common name, and add -amide
  • If the amide nitrogen is also bonded to an alkyl or aryl group, name the group and show its location on nitrogen by N- ; two alkyl or aryl groups by N,N-di-
  • A cyclic amide is called a lactam
• Fischer Esterification


  A carboxylic acid is reacted with an alcohol in the presence of an acid catalyst, such as concentrated sulfuric acid
• Preparation of Amides


  1. Treat an amine with an anhydride

  2. Heat an ammonium salt formed from a carboxylic acid and amine to eliminate water and form an amide
• Hydrolysis of Anhydrides


  Carboxylic anhydrides, particularly the low-molecular-weight ones, react readily with water (hydrolyze) to give two carboxylic acids

  
• Hydrolysis of Esters


  1. Esters hydrolyze only very slowly in boiling water, but hydrolysis becomes considerably more rapid when the ester is heated in aqueous acid or base

  2. Hydrolysis in aqueous acid is the reverse of Fischer esterification

  3. Hydrolysis in aqueous base is called saponification
• Hydrolysis of Amides


  1. Amides require more vigorous conditions for hydrolysis in both acid and base than do esters

  2. Hydrolysis in hot aqueous acid gives a carboxylic acid and an ammonium ion

  3. Hydrolysis in aqueous base gives a carboxylic acid salt and ammonia or an amine
• Reaction with Alcohols


  Anhydrides react with alcohols and phenols to give an ester and a carboxylic acid

  
• Reaction with Amines


  1. Anhydrides react with ammonia and with 1° and 2° amines to form amides

  2. Esters react with ammonia and with 1° and 2° amines to form amides
• Phosphoric Anhydrides


  The functional group is two phosphoryl (P=O) groups bonded to the same oxygen atom
• Phosphoric Esters


  • Phosphoric acid forms mono-, di-, and triphosphoric esters
  • In more complex phosphoric esters, it is common to name the organic molecule and then indicate the presence of the phosphoric ester by either the word "phosphate" or the prefix phospho-

  
• Step-Growth Polymers


  Formed by reaction between two molecules, each of which contains two functional groups, with each new bond created in a separate step
• Step-Growth Polymers


  • Polyamides
  • Polyesters
  • Polycarbonates
• Polyamides


  • Nylon-66 was the first purely synthetic fiber, synthesized from two six-carbon monomers
  • The polyaromatic amide known as Kevlar is made from an aromatic dicarboxylic acid and an aromatic diamine
• Polyesters


  • The first synthetic polyester involved polymerization of a diester and diol
• Polycarbonates


  • Lexan, the most familiar polycarbonate, is formed by reaction between the disodium salt of bisphenol A (BPA) and phosgene