Unsaturated By :

2 Double
HeghiBond
Rado Gama P.
Dewangga
Harjuno
 Alkenes and Alkynes: Structure
and Physical Properties

An unsaturated hydrocarbon is a hydrocarbon containing at least one

double or triple bond.

An alkene is a hydrocarbon containing double bonds. The general

formula of an alkene is CnH2n.

2
 The term "unsaturated" is used to designate a compound which contains
double or triple bonds and therefore not every carbon is bonded to a
different atom

Ethene, C2H4, is an example of an unsaturated

hydrocarbon.
3
Respectively. Saturated and unsaturated
compounds need not consist only of a
carbon atom chain. They can form
straight chain, branched chain, or ring
arrangements. They can have functional
groups, as well. It is in this sense that
fatty acids are classified as saturated or
unsaturated. The amount of unsaturation
of a fatty acid can be determined by
finding its iodine number.

4
In a chain of carbons, such as a fatty acid, a double or triple bond will
cause a kink in the chain. These kinks have macro-structural
implications. Unsaturated fats tend to be liquid at room temperature,
rather than solid, as the kinks in the chain prevent the molecules from
packing closely together to form a solid. These fats are called oils and
are present in fish and plants.
 Specific Structural
Formations

-cis
In other unsaturated hydrocarbons, the double bond between two carbons
prevents rotation of the atoms about the bond, locking them into specific
structural formations. When attached atoms occupy similar positions on each
carbon, they are referred to as "cis”.
 Specific Structural
Formations

-trans
And when they are on opposite sides, they are called "trans". Most natural
hydrocarbons exist in the cis state, but artificially manufactured hydrocarbons
are trans.
Properties

The body lacks the enzymes to properly break down the trans
configuration. This is why trans fats are viewed as dangerous and
unhealthy, as they tend to build up. Unsaturated compounds of the
two formations are classified as geometric isomers of one another.
– All bond angles about the carbon-carbon double bond are 120 degree. All
atoms bonded to the double bonded carbon atoms lie in the same plane.
– Carbon-carbon triple bond angles are 180o. Thus, all atoms bonded to the triple
bonded carbons are in a straight line.
– Like alkanes, both alkenes and alkynes are nonpolar and have relatively low
melting points and boiling points. Alkynes generally have slightly higher boiling
points than alkenes.
 Example

Unsaturated alcohols, aldehydes,

Unsaturated hydrocarbons ketones, carboxylic acids and
esters

Alkenes Ascorbic acid

polyenes, terpenes acetylformoin, bombycol,
retinol

Abscisic acid
Alkynes anthrone, cyclohexenone

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Calculating Degrees of Unsaturation
(DoU)
Degree of Unsaturation (DoU) is also known as Double Bond
Equivalent. If the molecular formula is given, plug in the numbers
into this formula:
DoU =
2𝐶 + 2 + 𝑁 − 𝑥 − 𝐻
2
 C is the number of carbons
 N is the number of nitrogens
 X is the number of halogens (F, Cl, Br, I)
 H is the number of hydrogens
What is the Degree of Unsaturation for Benzene?

SOLUTION
The molecular formula for benzene is C6H6. Thus,
DoU= 4, where C=6, N=0,X=0, and H=6. 1 DoB can equal 1 ring or 1 double bond.
This corresponds to benzene containing 1 ring and 3 double bonds.

However, when given the molecular formula C6H6, benzene is only one of many
possible structures (isomers). The following structures all have DoB of 4 and have
the same molecular formula as benzene.
Functionalization of Unsaturated Fatty Compounds Across the
C,C Double Bond
Lipid Chemistry

Oils and fats of vegetable and animal origin are historically as well as
currently the most important renewable feedstock of the chemical
industry. Classic and well-established oleochemical transformations occur
preferentially at the ester functionality of triglycerides [1] such as
hydrolysis to free fatty acids and glycerol [2] and transesterification to
fatty acid methyl esters.

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Figure 1. Unsaturated fatty compounds as starting
materials for synthesis: oleic acid (1a), linoleic acid (2a),
linolenic acid (3a), erucic acid (4a), ricinoleic acid (5a),
petroselinic acid (6a), 5-eicosenoic acid (7a), calendic
acid (8a), α-eleostearic acid (9a), punicic acid (10a),
santalbic acid (11a), vernolic acid (12a), 10-undecenoic
acid (13a), and the respective methyl esters (1b-13b)
and alcohols (1c-13c).
 –

Lewis Acid-Induced
Electrophilic Addition
Reactions
2.1. Ethylaluminium Sesquichloride Induced
Alkylations with Alkyl Chloroformates

The alkylation of long-chain unsaturated fatty

compounds is of great importance because
alkyl-branched oleochemicals have interesting
properties [17]. They are used for many
applications such as lubricants, cosmetics,
softeners, defoamers and wood-protecting
agents.
The Lewis acid-induced hydro-alkylation reaction using alkyl
chloroformates has thus been developed as a new method for the
alkylation of alkenes in general and of unsaturated fatty compounds in
particular [11,12]. The reaction of, for example, oleic acid 1a and
isopropyl chloroformate in the presence of ethylaluminium
sesquichloride (Et3Al2Cl3) gave approximately a 1:1 mixture of the
regioisomers 9- and 10-isopropyloctadecanoic acid 14 (Fig. 2).
2.2. Alkylaluminium Chloride-Induced Friedel-
Crafts Acylations

The ethylaluminium dichloride (EtAlCl2)-

induced Friedel-Crafts acylation is an
interesting and versatile method for the
functionalization of unsaturated fatty
compounds yielding the respective β,γ-
unsaturated ketones with high selectivity
The EtAlCl2-induced acylation of oleic acid 1a, among others,
with acyl chlorides 15 gave the (E)-configured β,γ-unsaturated
oxocarboxylic acids 16 with high selectivity (Fig. 4). The
acylation products are substrates for a number of interesting
follow-up reactions, for example 16g for Nazarov cyclizations
 –

Additions of
Aldehydes and
Ketones
3.3. Synthesis of Homoallylic Alcohols

ω-Hydroxycarboxylic acids, including alkyl-

branched acids such as 21, are of interest as
polyester components. They are obtained
with high selectivity by the ene addition of
formaldehyde to unsaturated fatty acids such
as 1a (Fig. 9)
Figure 9. Me2AlCl-induced reaction of paraformaldehyde and
oleic acid 1a to give homoallyl alcohol 21 and the respective
regioisomer (E)-10-hydroxymethyl-8-octadecenoic acid. The
corresponding reaction of 10-undecenoic acid 13a yields
homoallylic alcohol 22 ([E]:[Z] = 4:1)
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