Applications of ultrasound in organic synthesis.

 Ultrasound refers to sound waves having frequencies higher than those to which the human ear
can respond (μ, > 16 KHz). High frequency ultrasound waves are used in medical equipment. The
ultrasound frequencies of interest for chemical reactions (about 20-100 KHz) are much lower than
those used for medical applications, but the power used is higher.

 The ultrasound is generated with the help of an instrument having an ultrasonic transducer, a
device by which electrical or mechanical energy can be converted into sound energy. The most
commonly used are the electromechanical transducers which convert energy into sound - they are
mostly made of quartz and are commonly based on the piezoelectric effect. When equal and
opposite electrical charges are applied to opposite faces of a crystal of quartz, expansion or
contraction occurs. Application of rapidly reversing charges sets up a vibration that emits
ultrasonic waves called the piezoelectric effect.

 The use of ultrasound in chemical reactions in solution provides specific activation based on a
physical phenomenon: acoustic cavitation. Cavitation is a process in which mechanical activation
destroys the attractive forces of molecules in the liquid phase. Applying ultrasound, compression
of the liquid is followed by rarefaction (expansion), in which a sudden pressure drop forms small,
oscillating bubbles of gaseous substances. These bubbles expand with each cycle of the applied
ultrasonic energy until they reach an unstable size; they can then collide and/or violently collapse.

 In case the internal forces are great enough to ensure collapse of these bubbles, very high local
temperature (around 5000°C) and pressure (over 1000 bar) may be created. It is this very high
temperature' and pressure that initiate chemical reactions. The term 'sonochemistry' is used to
describe the effect of ultrasound waves on chemical reactivity

Some examples of ultrasound assisted green synthesis

1. Esterification
This is generally carried out in presence of a catalyst like sulphuric acid, p-toluenesulphonic acid,
tosylchloride, polyphosphoric acid, dicyclohexylcarbodiimide etc. The reaction takes longer time
and yields are low. A simple procedure for the esterification of a variety of carboxylic acids with
different alcohols at ambient temperature using ultrasound has been reported (Scheme 1).

2. Substitution Reactions
Halides can be converted into cyanides. Thus, the reaction of benzyl bromide in toluene with potassium
cyanide, catalysed by alumina, on sonication gives the substitution product, viz. benzyl cyanide in 76%
yield. In the absence of ultrasound alkylation is the preferred pathway (Scheme 2). The difference is
because ultrasound forces cyanide into the surface of alumina, enhancing cyanide nucleophilicity and
reducing the Lewis acid character.
 Scheme 2

3. Diels-Alder Reaction
Sonication facilitates Diels-Alder reaction. Therefore, the addition of dimethyl acetylene
dicarboxylate to furan in water at 22-45 °C gives quantitative yield of the adduct (Scheme 3)

Scheme 3

4. The Cannizarro reaction

The Cannizarro reaction under heterogenous conditions catalysed by barium hydroxide is considerably
accelerated (Scheme 4) by sonication. The yields are 100% after 10 min, whereas no reaction is
observed during this period with the use of ultrasound

Scheme 4