ORGANIC CHEMISTRY

PRESENTATION
PRESENTED BY
KEERTHANA R-(21S012)
NANDIRA DEVI R-(21S017)
NISHVANTH KUMAR K R-(21S018)
PRAVEEN RAAJ K R-(21S019)
REACTIVE METHYLENE
COMPOUNDS
PRESENTED BY
NISHVANTH KUMAR K R –(21S018)
REACTIVE METHYLENE COMPOUNDS

 The class of compounds which contain a methylene group

 (-[𝐶𝐻]_2-) directly bonded to two electron withdrawing groups such as –
[𝐶𝑂𝐶𝐻]_3, - [𝐶𝑂𝑂𝐶]_2 𝐻_5, -𝐶𝑁, are called Active Methylene Compounds. This is
so because the [−𝐶H]_2− group in them is acidic and reactive. Ethyl
acetoacetate(Acetoacetic ester) and Diethyl malonate( Malonic ester) belong to
this class.

Ethyl acetoacetate( Acetoacetic ester)

Diethyl malonate( Malonic ester)
When a methylene group is present between two strongly
electronegative (electron attracting) groups such as >C=O
or -C≡N, the hydrogen atoms of methylene group (called
𝛼-hydrogen, being present on carbon atom next to functional groups
on either side) become reactive or acidic. Such compounds exist in
keto-enol equilibrium.
If the compound is symmetrical the hydrogen atom of the
methylene group migrates to either of the keto groups but if
the compound is unsymmetrical only one form is present
exclusively or predominantly and the migration of the
hydrogen atom depends upon the inductive effect of the alkyl
or other groups present on either side of > 〖𝐶𝐻〗 _(2 )group
JOHANNES WISLICENUS

 German Research Chemist , best known for the acetoacetic

ester and malonic ester synthesis, and for the synthetic
production of lactic acid.
 Wislicenus elucidated the structure of acetoacetic ester by
replacing hydrogen with sodium.
 The ethyl sodioacetoacetate combined with an alkyl iodide
gave high yields of a substituted acetoacetic ester that could
accept another sodium atom and exchange it for a second alkyl
group.
INTRODUCTION

 Diethyl Malonate, also known as DEM, is the diethyl ester of Malonic acid. It

occurs naturally in grapes and strawberries as a colorless liquid with an apple-
like odor, and is used in perfumes.

 It is also used to synthesize other compounds such as barbiturates, artificial

flavorings, vitamin B1, and vitamin B6.
STRUCTURE

 Malonic acid is a rather simple Dicarboxylic acids, with two the carboxyl

groups close together. In forming diethyl Malonate from Malonic acid,
the hydroxyl group (-OH) on both of the carboxyl groups is replaced by an
ethoxy group (; -OCH2CH3).

 The methylene group (-CH2-) in the middle of the Malonic part of the diethyl
Malonate molecule is neighbored by two carbonyl groups (-C(=O)-).
PHYSICAL PROPERTIES

 Colourless

 Pleasant smelling liquid

 Sparingly soluble in water

 Soluble in ether and alcohol Diethyl Malonate/ Malonic Ester

 B.P=199◦C
Is diethyl Malonate acidic?

Diethyl Malonate is useful because it: has a relatively acidic a-proton, pKa =
13, so the enolate is readily formed with ethoxide.

Is diethyl Malonate volatile?

Diethyl Malonate is a volatile diester that occurs naturally in fruits such as

grapes, strawberries, guava, melon, pineapple, and blackberries.