Experiment

Experiment 2

Green Chemistry Experiments

Solvent-free AldolAldol
Solvent-free Condensation between
Condensation
3,4-dimethoxybenzaldehyde
between and
3,4-dimethoxybenzaldehyde
1-indanone
and 1-indanone

Chemical Concepts
Chemical Concepts
Carbonyl chemistry, base catalyzed aldol reaction, melting point,
Carbonyl chemistry, base catalyzed aldol reaction, melting point,
recrystallisation
recrystallization
Green Chemistry Concepts
Green Chemistry Concepts
Concepts:
Concepts: solvent
solvent free
free reaction,
reaction, solid-solid
solid-solid reaction
reaction at
at room
room
temperature,
temperature, high atom economy, and ease of separation andwaste
high atom economy, and ease of separation and waste
prevention.
prevention.
Green chemistry principles
Green chemistry principles
Atom
Atom economy,
economy, safer
safer solvents
solvents and and auxiliaries,
auxiliaries, use
use ofof selective
selective
catalyst, safer chemistry.
catalyst, safer chemistry.
The Aldol
The Aldol condensation
condensation isisone oneofofthethe
fewfew reactions
reactions andand perhaps
perhaps the
the
most powerful and useful reaction, used to form new carbon-carbon-
most powerful and useful reaction, used to form new carbon
carbon
bonds. Itbonds. It is used
is widely widely in used in synthetic
synthetic chemistry.chemistry. Many
Many biological
biological systems
systems utilize the utilize the aldol condensation
aldol condensation or one of itsorvariations
one of itsto
variations
build up the tocarbon
build skeletons
up the carbonof many skeletons
complex of many complex
naturally occurring
naturally
compounds. occurring compounds.
Under the
Under theinfluence
influence of aofdilute
a dilute
base or base or acid,
dilute dilutetwoacid, two
molecules
molecules of an aldehyde or ketone may combine together
of an aldehyde or ketone may combine together to form a b hydroxy to form
aaldehyde
β hydroxy oraldehyde
b-hydroxy or β-hydroxy
ketone. The ketone. The reaction
reaction is called
is called aldol
aldol condensation. In every case the product results
condensation. In every case the product results from addition from addition
of one
of one molecule
molecule of aldehyde
of aldehyde (or ketone) (ortoketone)
second to second in
molecule molecule in
such a way
such a way that
that a-carbon α-carbon
of the of theattached
first becomes first becomes attachedcarbon
to the carbonyl to theof
carbonyl carbon of the second.
the second.

9
 (b)(b) This
This reactantis ismixed
reactant mixedwith
withaa catalyst
catalyst

Green Chemistry Experiments

(c)(c) 
A Acarbonyl
carbonylcompound
compoundthatthatcontains
containsα-hydrogen
a-hydrogenisis added
added
slowly
slowly totothis
thismixture.
mixture.
In this experiment, aldol condensation reaction of
3,4-dimethoxybenzaldehyde
In this experiment, and 1-indanone
aldol is done. reaction of
condensation
3,4-dimethoxybenzaldehyde and 1-indanone is done.

Conventional method
Conventional method of of preparation
preparation
The reaction
The reaction isis carried
carried out
out inin absolute
absolute ethanol
ethanol according
according toto the
the
method of Waltanasin and Murphy. Powdered
method of Waltanasin and Murphy. Powdered reactants are reactants are
dissolved in absolute ethanol and powdered sodium hydroxideis
dissolved in absolute ethanol and powdered sodium hydroxide
added. The
added. The reaction
reaction mixture
mixture isis stirred
stirred overnight
overnightduring
duringwhich
whichtime
time
products separate from the reaction mixture as solids.
products separate from the reaction mixture as solids. 1M aqueous 1M aqueous
HCl is
HCl is added
added to to the
the slurry
slurry toto quench
quench the
the reaction
reaction and
and this
this leads
leads
to further precipitate. The precipitation is filtered off and
to further precipitation. The precipitation is filtered off and where where
necessary, recrystallized
necessary, recrystallised inin appropriate
appropriate solvent.
solvent.

Green Method of preparation

Green Method of preparation
Some solvent-free aldol condensation reactions between acetophenone
Some solvent-free
derivatives aldol condensation
and benzaldehyde are known. In reactions
many ofbetween
these
acetophenone derivatives and benzaldehyde are
reactions one of the reagents is a liquid at room temperature known. In manyandof
these reactions one of the reagents is a liquid at room
in all cases aldehydes without α-hydrogen are used to ensure that temperature
and in
only all cases
a single aldehydes
aldol condensationwithout a-hydrogen
process is possible.are In
used
the to ensure
reaction
that only a single aldol condensation process
between 3,4-dimethoxybenzaldehyde and 1-indanone, also a singleis possible. In the
condensation product is expected as the aldehyde bears no also
reaction between 3,4-dimethoxybenzaldehyde and 1-indanone, α-
a single condensation
hydrogen and cannotproduct act as isa expected as the aldehyde
carbon nucleophile. bears
Another
no a-hydrogen
advantage is thatandbothcannot act are
reactants as asolid
carbon nucleophile.
at room Another
temperature yet
react under solvent-free conditions at room temperature. This yet
advantage is that both reactants are solid at room temperature is
react under
done simplysolvent-free
by grinding conditions
the solidat room temperature.
reagents together This
withissolid
done
simply by
NaOH. grinding remarkably
Moreover, the solid reagents
a hightogether
degree with solid NaOH.
of conversion is 11
Moreover, remarkably a high degree of conversion is achieved and
 aachieved
single majorand product
a single results.
major product results.
It produces onlyIt aproduces only a
small quantity

Green Chemistry Experiments

small quantity of aqueous acidic waste. Although
of aqueous acidic waste. Although such reactions are frequently such reactions
are frequently
referred referred
to as solid statetoreactions.
as solid state
It hasreactions.
been notedIt has been
that noted
in many
that in
cases many cases
mixture of themixture of the solid
solid reactants reactants
results resultssoin that
in melting melting
the
so that actually
reaction the reaction actually
occurs in theoccurs
liquid in the solvent-free
albeit liquid albeitstate.
solvent-free
state.
The aldol condensation if affected without dehydration has an
atomThe aldol condensation
economy if affected
of 100% and requires without
only dehydration
a catalytic amount of hasacid
an
atom economy of 100% and requires only a catalytic
or base and even with dehydration; the atom economy remains very amount of
acid
high. or base and even with dehydration; the atom economy remains
very high.
Chemicals and equipment
Chemicals and equipment
Sodium hydroxide
Sodium hydroxide
3,4-dimethoxybenzaldehyde
1-indanone
3,4-dimethoxybenzaldehyde
1-indanone
10% aqueous HCl
pH
10%paper
aqueous HCl
pH ethanol
90% paper
Glass
90% rodethanol
Glass glass
Watch rod
Mortar
Watch andglasspestle
Mortar and
Filtration flaskpestle
Vacuum
Filtrationpump
flask
Vacuum
Test tube pump
Filter
Test paper
tube
Filter paper
Procedure
Proceduregrind 0.25 g of 3,4-dimethoxybenzaldehyde and 0.20 g
Separately
ofSeparately
1-indanone in a 0.25
grind pestle
g& ofmortar. Mix them together in and
3,4-dimethoxybenzaldehyde a test0.20
tubeg
and crush the two
of 1-indanone in solids together
a pestle with aMix
& mortar. glass rod until
them theyinbecome
together a test
brown
tube and oil crush
(mix carefully to avoid
the two solids breaking
together withthe tube).
a glass rodAdd
until0.05 g
they
ofbecome
finely ground solid NaOH to the reaction mixture
brown oil (mix carefully to avoid breaking the tube). Add and continue
mixing
0.05 g until it becomes
of finely ground solid,
solid and
NaOH allow the reaction
to the mixture mixture
to stand andfor
15continue
minutes. Add about 2 ml of 10% aqueous HCl solution.
mixing until it becomes solid, and allow the mixture to Check
the pH for
stand of solution
15 minutes.to make
Add sure
aboutit2ismlacidic,
of 10%filter, washHCl
aqueous withsolution.
1 ml of
water
Checkand thedry
pH to of
yield 94% ofto
solution themake
compound.
sure itRecrystallise fromwash
is acidic, filter, 90%
ethanol.
with 1 ml of water and dry to yield 94% of the compound.
This remarkably
Recrystallise from 90% simple yet effective methodology is further
ethanol.
enhanced by the stability
This remarkably simple yet of the powdered
effectiveintermediate
methodology formed after
is further
grinding. The solid material obtained at this stage
enhanced by the stability of the powdered intermediate formed may be stored,
prior
after togrinding.
work up,The for solid
a lengthy period
material of time.atNo
obtained thisdeterioration
stage may be in
product
stored, quality
prior to was noted
work up,after
forstoring
a lengthyof solid reaction
period mixture,
of time. No
without protection
deterioration from either
in product lightwas
quality or atmospheric
noted after oxygen
storing orofwater
solid
for 1 month.
reaction This advantage
mixture, withoutmakes this methodology
protection from either attractive
light or in
industrial application.
atmospheric oxygen or water for 1 month. This advantage makes
12 this methodology attractive in industrial application.
Green Chemistry Experiments

REFERENCES
REFERENCES
Raston,
Raston, C.L. C.L.
and and
Scott,Scott, J.L. Green
J.L. Green Chemistry,
Chemistry, 2000,
2000, 2, 49. 2, 49. Wattansin,S. and
Murphy, W.S.and
Wattansin,S. Synthesis,
Murphy,1980,W.S. 647.
Synthesis, 1980, 647.

14
Success
Success isis aa journey,
journey, not destination.
not a destination.

Green Chemistry Experiments

The
The doing is often more important than
is often more important than
the
the outcome.
outcome.
.... Arthur Ashe
.... Arthur Ashe

Too Much of Anything is

Harmful..... even Heating
It can cause an

EXPLOSION
Too Much of Anything is
Harmful..... even Heating
It can cause an
EXPLOSION
15