Created by Group 5 Class A

Muhammad Nabiel A. P. 110117284

Vincent Chandra K. 110119108
Ni Putu Ardhiani K. P. 110119227
Arif Maulana Aziz 110119390
Dina Qurrotu Aini 110119448

Organic Chemistry Lab

Faculty Of Pharmacy
University Of Surabaya
ABSTRACT
• Knoevenagel's conductive reactions are: reactions between aldehydes and
compounds that have hα from the activation group (such as C = O or C≡N),
usually using ammonia or amine catalysts. From the reaction between
benzaldehyde and malonic acid with NH3 catalyst, then heated, will
produce as much as 85% cinnamic acid.

• The knoevenagel reaction is originally applied to condensation of the

carbonyl (-co) groups on base-catalyzed aldehydes and ketones with
reactive methylene groups, with the release of water molecules. Currently
more commonly used malonic acid derivatives, such as diethyl monoethyl-
malonic, ethyl cyanacetate, etc. A variety of amines can be used as
catalysts, and the most effective is piperidine (hexahydropyridine): a mixture
of piperidine with pyridine, or simply pyridine, is also often used.
Abstract

 The main use of the base is as a proton donor of the reactive methylene group: if
B represents a base, reaction (i) produces a carbanion, which combines with the
positively charged carbonyl group carbon atom (reaction ii): the reaction
product accepts the proton back from the piperidinium ion , and with the
release of water molecules followed by monocarboxylation of malonic acid the
yield acid is formed. (Mann & Sanders, 1974)
 Apart from going through the Knoevenagel reaction, cinnamic acid synthesis
can also be done through the Perkin reaction. The condensation of the aromatic
aldehyde with acid anhydride in the presence of the sodium or potassium salt of
the acid associated with the anhydride to form αβ unsaturated acids, known as
the Perkin reaction. Benzaldehyde when heated with acetic anhydride and
potassium acetate produces cinnamic acid. It is interesting to note that
although cis-trans isomerism due to the presence of double bonds is theoretically
possible to form in cinnamic acid, the Perkin reaction gives only the trans form,
m.p. 133 ° C, its cis form, m.p. 68 ° (allosinamic acid) is unstable and very easily
changes to its trans form. (Vogel, 1956)
Objectives

Be able to explain the Understand the formation of Gain good crystals

Knoevenagel condensation carbanion intermediates
reaction
Tools & Materials
Tools
• Erlenmeyer flask
• Maat glass
• Separating funnel
• Buchner funnel & suction flask
Materials
• 5 ml Benzaldehyde
• 3.2 g (30 mmole) Malonic acid
• 5 ml Pyridine
• 10 drops Piperidine
• 8.0 g K2CO3 (potassium
Carbonate)
• 2 N Hydrochloric Acid
Procedure

Weigh the potassium carbonate into a 100 ml erlenmeyer flask and add 20 ml
water and the benzaldehyde. Swirl the mixture vigorously, pour it into a test
tube and allow the two phases to separate over 30 min when the upper layer of
benzaldehyde should be clear. Meanwhile weigh the propanedioic acid into a
second 100 ml conical flask and dissolve it in the pyridine with gentle warming on
a hot water bath. From the test-tube remove 2 ml of the upper layer carefully
using a graduated pipet and add it to the solution of propanodioic acid in
pyridine. Heat the resultant mixture on the water bath and add a catalytic
quantity of piperidine (10 drops). Reaction is indicated by evolution of bubbles of
carbon dioxide as the decarboxylation proceeds. Continue heating until the rate
of appearance of bubbles become very slow (30min). Make the volume up to 50
ml with 2 M hydrochloric acid and the filter of the resultant solid with suction
between washing. Tip the crystals into a preweighed 100 ml. (Harwood & Moody,
1989)
WORK SCHEME
Mechanism Of Reaction
DISCUSSION & CONCLUSION
From this experiment, benzaldehyde and malonic acid were used as the main ingredients.
Benzaldehyde is unstable and easily oxidized to benzoate acid through the Cannazaro reaction
mechanism, so K2CO3 is used. This substance works by binding benzoate acid to potassium
benzoate. After being shaken and left in a separating funnel, two phases will be formed, above pure
benzaldehyde and lower than potassium benzoate. Then malonic acid is added with pyridine.
Pyridine is an amine that can be used as a catalyst. Then the results of the separation are taken a
little and then added to the mixture of malonic acid and pyridine. Then it is heated in a water bath
and CO2 bubbles will form as a result of decarboxylation. Then add piperidine and wait for the CO2
bubbles to disappear. Piperidine also functions as a catalyst, besides that piperidine also helps
decarboxylation so that later results are formed that have a double bond faster. After that, added 50
mL of HCl 2N ad. HCl functions as a strong acid which is better at binding bases (pyridine and
piperidine) to form pyridinium and piperidinium salts. This is necessary because cinnamic acid is
acidic, so if left in the presence of pyridine and piperidine it will react to form cinnamic salts. The
result is filtered with a Buechner funnel and a suction flask and then dried in the oven.
  Fessenden RJ & Fessenden JS, 1994, Organic Chemistry, 5th
edition, Brooks/Cole Publishing Company Pasific Grove,
California, 722-723.
 Harwood LM & Moody Cj, 1989, Experimental Organic
Chemistry, Principes and Practice, Blackwell Scientific
Publication, USA, 558-559.
 Mc Murry J, 2000, Organic Chemistry, 5th Edition, Brooks /
References Cole Publishing Company Pasific Grove, USA, 973.
 Vogel AI, 1956, A Text-book of Practical Organic Chemistry
including Qualitative Organic Analysis, 3rd edition, Longman
Group Inc., New York, 706-707.
 Mann FG & Saunders BC, 1974, Practical Organic Chemistry,
4th edition New Impression, Longman Inc., New York, 279-280.