BENZOFURAN

Introduction

 Benzofuran is the heterocyclic compound consisting of fused benzene and

furan rings.
 This colorless liquid is a component of coal tar.
 Benzofuran is the "parent" of many related compounds with more complex
structures.
 For example, psoralen is a benzofuran derivative that occurs in several
plants.
 Several heterocyclic compounds are found in many medications and have
formed an essential base for medicinal chemistry research.
 This is mainly due to heterocyclic compounds’ versatility and distinctive
physicochemical features .
 Among these discovered heterocyclic compounds is benzofuran , known as a
natural compound originating from plants such as Asteraceae, Rutaceae,
Liliaceae, and Cyperaceae .
 Benzofurans can also emerge from non-natural sources through the
dehydrogenation of 2-ethylphenol .
 Structurally, benzofuran is characterized by a distinctive motif consisting of
fused benzene and furan rings,
Chemical structure of benzofuran
Structure
Production

 Benzofuran is extracted from coal tar. It is also obtained by dehydrogenation

of 2-ethylphenol.
Laboratory methods

 Benzofurans can be prepared by various methods in

the laboratory. examples
O-alkylation of salicylaldehyde with chloroacetic acid followed by dehydration
(cyclisation) of the resulting ether and decarboxylation.
Perkin rearrangement, where a coumarin
is reacted with a hydroxide
Diels–Alder reaction of nitro vinyl furans with various
dienophiles
Cyclo-isomerization of alkyne ortho-substituted
phenols
Mechanism for synthesis of benzofuran
 Synthesis of Benzofurans

• A convenient metal-free cyclization of ortho-hydroxystilbenes into 2-

arylbenzofurans and 2-arylnaphthofurans is mediated by hypervalent
iodine reagents. Using stoichiometric (diacetoxyiodo)benzene in
acetonitrile, desired products can be isolated in good yields.
 An iodine(III)-catalyzed oxidative cyclization of 2-
hydroxystilbenes using 10 mol%
(diacetoxyiodo)benzene [PhI(OAc)2] as catalyst in
the presence of m-chloroperbenzoic acid provides
2-arylbenzofurans in good to excellent yields.
Substituted benzofurans were synthesized from their corresponding
substituted 1-allyl-2-allyloxybenzenes using ruthenium-catalyzed C-
and O-allyl isomerization followed by ring-closing metathesis.
An effective, Ru-catalyzed cycloisomerization of
benzannulated homo- and bis-homopropargylic alcohols
affords benzofurans and isochromenes chemo- and
regioselectively (5-, and 6-endo cyclizations). The presence of
an amine/ammonium base-acid pair is crucial for the catalytic
cycle.
Reactions of calcium carbide with salicylaldehyde p-tosylhydrazones or
2-hydroxyacetophenone p-tosylhydrazones provide methyl-substituted
benzofuran rings in good yields in the presence of cuprous chloride as
catalyst. The advantages of this method are the use of a readily
available and easy-to-handle acetylene source and a simple workup
procedure.
Regioselectivity in electrophilic aromatic substitution of
benzofuran and indole
 In electrophilic substitution of aromatic systems sigma complexes are
typically formed as reaction intermediates. Let's look at the sigma complexes
formed in the reaction of benzofuran and indole with an electrophile (NO2+ )
at the 2 and 3 positions and compare their stability.