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Dina akhotmah-232 1
Chemistry of polyfunction
1. Types of carbon atom

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Classification of multiple bonds of polyunsaturated compounds

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Organic chemistry, solomons, 10th edition, page 599
Many hydrocarbons are known that contain more than one double or triple bond:
a) Hydrocarbons with two double bonds is called an alkadiene (or dienes)
b) three double bonds is called an alkatriene (or trienes) , and so on…
c) A hydrocarbon with two triple bonds is called an alkadiyne
d) a hydrocarbon with a double and triple bond is called an alkenyne
The following examples explain how specific compounds are named.

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Allylic substitution and allyl radical
Reference organic chemistry, solomons, chapter 13, page 585-

 when propene for example reacts with chlorine or bromine at low


temperatures, an addition reaction of halogen to the double bond is
take place

However, when propene for example reacts with chlorine or bromine at very high
temperatures or low concentration of the halogen, the reaction that occurs is a
substitution

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Why allyl product is formed?

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The resonance description of the allyl radical
The allyl compound break either
• hemolytic producing free radical
• Heterolytic producing cation or anion
All these product resonate witch explain its stability, high reactivity and the possibility
to form two products.
For an example:

Why B is the
major product?
Think back to
Zaitsev’s rule
the more
substituted an
alkene is, the
more stable it is

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H
C C H 2 B r
C
H
H
C C H A
3
C d ire c t p ro d u c t
H N B S , h eat
C C l4
H H C C H 2
C

B r
B
a lly lic re a rra n g m e n t p ro d u c t

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Organic Chemistry, solomons, 10th edition , page 602

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Conjugated alkadienes are thermodynamically more stable than isomeric isolated
alkadienes, these stability can be seen in an analysis of the heat of hydrogenation.
For an example,

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Electrophilic Attack on Conjugated Dienes 1,4 Addition
Conjugated dienes undergo both 1,2 and 1,4 addition through an allylic
intermediate. for example, 1,3-butadiene react with one molar equivalent of
hydrogen chloride to give two products , 3-chloro-1-butene and
1-chloro-2-butadiene. Why ?

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The addition of HX undergo by allylic intermediate, the mechanism will give
better understanding for this result

Reaction Mechanism

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1.2 addition 1.4 addition

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(Page 625)

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Preparation of conjugated diene

Dienes can be prepared by elimination reactions of unsaturated alcohols


and alkyl halides.
The outcome of eliminations typically favors the more stable product,
Since conjugated dienes are more stable than isolated dienes, the
formation of the conjugated diene is usually favored over the isolated
diene unless the structure prevents the formation of the conjugated
system.

O H R B r
H H
H 2S O 4 K O H
heat heat
R c o n ju g a te d d ie n e s R
H H

What would the products of the following sequences be? Why?


a) 1-butene reacted with N-bromosuccinimide (NBS) then treated with KOH / heat
b) cyclohexene reacted with Br2 / CH2Cl2 then with KOH / heat

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a
) H H B
r
H
2C C
C C
H3 N BS K
O H
,h
eat
h
eat,C
Cl4 -H
Br
H
1
-bu
te
ne m
ores
tab
led
ie
ne

b
)
B
r

B
r
2/
CCl
4 KOH
,h
ea
t K
OH,
hea
t
-H
Br -HBr
B
r B
r

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Class exercises

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Preparation of isoprene


H C C H
O  s tro n g b a s e O H H O H
H /P d
C + C C H H 3 C C C C H 2
H 2 C C C C H 2
H C  +
C H
3 3 H
C H 3 A l2 O 3 C H 3
-H 2O

H
H 2 C C
C C H 2
p o ly m e riz a tio n
C H 3
is o p r e n e

Chemical structure of cis polyisoprene


the main constituent of natural rubber

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Terpenes
Terpenes is made of isoprene unit (2-methyl-1,3-butadiene) linked in a head-to-tail
fashion. (isoprene is a building block of terpenes).
For example, Monoterpenes are consists of two isoprene units , They are volatile natural
products found in higher plants as essential oils and are widely used in perfumery and
flavouring industries. For example, Lemon oil and Myrcene

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Solomon's, page 616
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What Is the Diels-Alder Reaction?

Heat
200oC

• The reaction occurs via a concerted mechanism, meaning that it


takes place all at once, with no isolatable intermediates.

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Diels-alder reaction is favoured by presence of :
a) Electron-releasing groups in the diene (e.g. -R, -OR)
b) Electron-withdrawing groups in the dienophile, for example Maleic anhydride

The easiest way to predict


Diels-Alder products is to
number the six carbons
that make up the
cyclohexene ring.
Note: this is not a
nomenclature numbering

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The Diels-Alder is Stereospecific
The Diels-Alder is a stereospecific reaction, because the stereochemistry of the dienophile is
maintained in the cyclohexene product: a trans dienophile yields in the trans product, and a cis
dienophile yields the cis product.
What Can and Can’t Undergo Diels-Alder?
Only conjugated dienes in the s-cis conformation can undergo Diels-Alder reactions.
If a diene is not conjugated, or can’t be in the cis conformation, then it can’t undergo a Diels-
Alder reaction.
Dienes that are located in rings can’t rotate, and so are stuck in either an s-cis or s-trans
conformation. But acyclic dienes can rotate into the s-cis conformation, as long as their substituents
aren’t too big/bulky to prevent easy rotation.

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Retro Diels-Alder
The Diels-Alder reaction is reversible. Going from cyclohexene to a diene and
dienophile is called a retro Diels-Alder reaction. It’s also a very common to be asked
“what starting materials produced this Diels-Alder product?” The best strategy for
determining retro Diels-Alder questions is also to number the cyclohexene ring. Below are
some examples.

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Multiple Choice Quiz
For a diene to undergo Diels-Alder reaction it
must:
a) be substituted with electron-withdawing groups.
b) be able to adopt an s-trans conformation
c) be substituted with electron-donating groups
d) be able to adopt the s-cis conformation
. What is the major product of the following reaction:

None of the Above

More questions and information's on chemheler.com

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