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ARYNES (BENZYNES)
BY:
DR. FARHAT SAGHIR
introduction
 Benzynes or Arynes are highly reactive uncharged chemical species derived from an aromatic
ring by removal of two hydrogens or groups from adjacent carbon atoms. Thus they are 1,2-
didehydrobenzenes or 1,2-didehydroarenes.
 Benzynes or arynes are commonly described as having a strained triple bond. However they
possess some diradical character as well.
Structure
 Structure of benzynes can be represented by following resonance contributing
structures…
 The alkyne representation is the most widely accepted. However the cumulene and the
diradical structures are also significant resonance contributors. The alkyne structure
calls for sp-hybridized carbon atoms at the two bond termini of the triple bond. The
rest of the ring skeleton consists of sp2 -hybridized carbon atoms. Thus, the aromatic
character of the ring is still retained in the benzyne.
 Geometric constraints on the triple bond result in a reduced overlap of in-plane p-
orbitals and thus a weaker triple bond than in an unstrained alkyne.
 In a chemical reaction, benzynes behave as electrophiles.
GENERATION (Formation):
 Benzynes may be generated in a chemical reaction in following ways…
 a) From aryl halides: Aryl halides can be treated with a strong base to remove an aromatic proton
and generate benzyne via elimination.
b) From o-amino benzoic acid (anthranilic
acid):
 This method involves diazotization of o-amino benzoic acids. After diazotization, loss of nitrogen
and carbon dioxide generates benzyne.
c) From 1-amino benzotriazole:
 This method involves oxidative decomposition of 1-amino benzotriazole. The oxidized
intermediate decomposes with elimination of two molecules nitrogen.
d) From o-dihalo aromatic precursors:
 o-dihalo aromatic compounds generate benzyne when treated with lithium amalgam (Li/Hg) or
alkyl lithium (R–Li).
Reactions:
 Benzynes or arynes are very reactive reaction intermediates and show
electrophilic character. They undergo nucleophilic addition, pericyclic and
radical reactions. Following are the important reactions of benzynes…
a) Nucleophilic additions:
 Benzynes react with nearly all nucleophiles especially nitrogen bearing nucleophiles and
carbanions to give addition product.
 For example…
b) Pericyclic cycloaddition reactions:
 They can be of various types such as…
i. [4+2]-cycloadditions:
 Benzynes can undergo [4+2]-cycloaddition reactions. For example, Diels-Alder reaction
between benzyne and butadiene occurs as follows…
Cycloaddition between benzyne and furan
ii. [2+2]-cycloadditions:
 Benzynes undergo [2+2]-cycloaddition reactions with a wide range of olefins especially with
olefins bearing electron-donating substituents.
 For example, benzynes react with a ketene acetal to give benzocyclobutanones.
c) σ-bond insertion reactions:
 Benzynes can undergo carbon-carbon σ-bond insertion reactions.
 For example…
d) Metal catalyzed reactions:
 Metal catalyzed aryne chemistry is highly underdeveloped and involves complex reactions. An
example is the palladium catalyzed [2+2+2]-cyclization of aryne and diyne in total synthesis of
taiwanin-C (an antiviral drug).

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ARYNES (BENZYNES) PharmD ppt by dr farhat sagir

  • 2. introduction  Benzynes or Arynes are highly reactive uncharged chemical species derived from an aromatic ring by removal of two hydrogens or groups from adjacent carbon atoms. Thus they are 1,2- didehydrobenzenes or 1,2-didehydroarenes.  Benzynes or arynes are commonly described as having a strained triple bond. However they possess some diradical character as well.
  • 3. Structure  Structure of benzynes can be represented by following resonance contributing structures…
  • 4.  The alkyne representation is the most widely accepted. However the cumulene and the diradical structures are also significant resonance contributors. The alkyne structure calls for sp-hybridized carbon atoms at the two bond termini of the triple bond. The rest of the ring skeleton consists of sp2 -hybridized carbon atoms. Thus, the aromatic character of the ring is still retained in the benzyne.  Geometric constraints on the triple bond result in a reduced overlap of in-plane p- orbitals and thus a weaker triple bond than in an unstrained alkyne.  In a chemical reaction, benzynes behave as electrophiles.
  • 5. GENERATION (Formation):  Benzynes may be generated in a chemical reaction in following ways…  a) From aryl halides: Aryl halides can be treated with a strong base to remove an aromatic proton and generate benzyne via elimination.
  • 6. b) From o-amino benzoic acid (anthranilic acid):  This method involves diazotization of o-amino benzoic acids. After diazotization, loss of nitrogen and carbon dioxide generates benzyne.
  • 7. c) From 1-amino benzotriazole:  This method involves oxidative decomposition of 1-amino benzotriazole. The oxidized intermediate decomposes with elimination of two molecules nitrogen.
  • 8. d) From o-dihalo aromatic precursors:  o-dihalo aromatic compounds generate benzyne when treated with lithium amalgam (Li/Hg) or alkyl lithium (R–Li).
  • 9. Reactions:  Benzynes or arynes are very reactive reaction intermediates and show electrophilic character. They undergo nucleophilic addition, pericyclic and radical reactions. Following are the important reactions of benzynes…
  • 10. a) Nucleophilic additions:  Benzynes react with nearly all nucleophiles especially nitrogen bearing nucleophiles and carbanions to give addition product.  For example…
  • 11. b) Pericyclic cycloaddition reactions:  They can be of various types such as… i. [4+2]-cycloadditions:  Benzynes can undergo [4+2]-cycloaddition reactions. For example, Diels-Alder reaction between benzyne and butadiene occurs as follows…
  • 13. ii. [2+2]-cycloadditions:  Benzynes undergo [2+2]-cycloaddition reactions with a wide range of olefins especially with olefins bearing electron-donating substituents.  For example, benzynes react with a ketene acetal to give benzocyclobutanones.
  • 14. c) σ-bond insertion reactions:  Benzynes can undergo carbon-carbon σ-bond insertion reactions.  For example…
  • 15. d) Metal catalyzed reactions:  Metal catalyzed aryne chemistry is highly underdeveloped and involves complex reactions. An example is the palladium catalyzed [2+2+2]-cyclization of aryne and diyne in total synthesis of taiwanin-C (an antiviral drug).