Lecture 2

Thursday, January 5, 2017 3:35 PM

Mechanism of radical chlorination:

Initiation:

Propagation:

Analogous bromination is also possible using NBS (N-bromosuccinimide).

N-bromosuccinimide or
NBS

Again, the reaction proceeds through the allylic radical intermediate. As you can see hydrogen atoms from both position 3
and position 6 can be abstracted and we get both allylic radicals. In this case their reaction with the Br leads to the formation
of the same product. In cases where the structure of the starting material is less symmetrical we can get a complex mixture
of products.
For example: In the following reaction we can get two different allylic radical intermediates which are of roughly similar
stabilities. They are both secondary allylic radicals. Furthermore, both radicals have an additional resonance structure. As a
result of all of that we can get 4 different bromide products. Write the structure of the 4 possible products. In this case the
for products are formed roughly in the same amounts.

NBS

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That's why allylic radical substitution is useful only for systems where two allylic positions are the same and both resonance structures
of the allylic radical are the same . In other words only with very simple and highly symmetrical systems.

Allylic anions:

resonance and inductive effects!

Allylic anions are more stable than the analogous alkyl anions. As a result allylic positions are more acidic than simple alkanes.
It is easier to deprotonate the allylic position than it is to deprotonate the alkane. The stability of the allylic anions comes
from the fact that the two electrons of the anion can be delocalized across the 3 atom fragments by conjugation with the
double bond. That is reflected in the shown resonance structure. An additional stabilization of the allylic anion, relative to the
simple alkyl anion, comes from the fact that the anion is next to the carbon that is sp2 hybridized and not sp3 hybridized (see
in red). Remember sp2 carbon atoms are more electronegative than the sp3 carbons.
Dienes
Dienes are molecules that have two double bonds. When two double bonds are found in the same molecule they can have
a profound effect on each other's stability and activity. What effect they will have on each other depends on their relative
position in the molecule. Based on the relative position double bonds have in the diene dienes can be divided into:

Isolated dienes: at least one sp3 atom between the double bonds

Conjugated dienes: double bonds next to each other.

Cumulated dienes or allenes: share the same carbon.

Stability of the dienes follows the following trend. Isolated dienes behave and have the stability that is
directly related to the stability and reactivity of simple alkenes. Dienes are more stable and allenes are
less stable than simple alkenes.

56 kcal/mol is the energy we get from the hydrogenation of the conjugated diene. That energy comes from
breaking two double bonds in the diene, breaking 2 H-H bonds and making 4 C-H bonds. 60 kcal/mol we get
from the isolated diene come from the same calculation, we break 2 double bonds and 2 H-H bonds and make
same 4 C-H bonds. Everything is the same except the two double bonds we are breaking. So, the extra 4
kcal/mol we get is because two double bonds we are breaking are easier to break. With allene, the two double
bonds are even easier to break and we get more energy out (70 kcal/mol)
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The 1 MO suggests that a bond between C2&C3 has a partial double

bond character. That is consistent with the fact that the C2-C3 bond is
shorter than the regular C-C bond. Another manifestation of the partial
double bond character is the fact that the conjugated dienes can exist in
two conformations s-trans and s-cis and more importantly that there is
an activation barrier for the conversion of one to the other. The
activation barrier is about 6 kcal/mol and is associated with the breaking
of the bond between C2&C3.
Finally, it is worth mentioning that the s-trans isomers are in general
more stable than the s-cis isomers.

Allenes - structure
In allenes the central carbon is sp hybridized and the terminal ones are sp2
hybridized. If you think about the central carbon, it has two p orbitals that are
perpendicular to each other. Those atomic orbitals are used to make bond with
the neighboring carbons. So, the bonds in an allene are perpendicular to each
other. Also, the substituents at the terminal carbons are in the planes that are
perpendicular to each other. So hydrogen atoms on carbon 1 are in the plane of
the paper, and hydrogen atoms on carbon 3 are in a plane that is perpendicular to
the plane of the board.

Remember, it all starts with the fact that the middle carbon is sp hybridized and as
a result the two bonds it forms have to be perpendicular to each other.

One of the consequences of the fact that the substituents on the terminal carbons are perpendicular to each other is
that the compounds 1 and 2 are enantiomers. They are mirror images of each other but are not superimposable.
Interestingly these molecules do not have a chiral center, but have a chiral axis. Allenes will be chiral as long as each
terminal carbon has two different substituents. That is sufficient for the existence of enantiomers.

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Diene synthesis: Dienes are commonly made through elimination reactions. Either from alcohols under
acidic reaction, through E1. Or from halides in the presence of a base through E2 reaction. E1 under
acidic conditions tends to be reversible and the regioselectivity (are we going to remove protons Ha or
Hb from the carbocation) of the reaction is under thermodynamic control. We form a more stable
conjugated diene.

E2 reactions are usually irreversible and are under kinetic control. Again, under kinetic control we get
the conjugated diene as the major products.

Reactions of conjugated dienes

Protonation always to the terminal position as that way we get a more stable allylic cation. In this case the reaction of
the allylic cation forms only one product.

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However, in the following reaction, from one allylic cation we can get two products (1,2-addition
product and 1,4-addition product). It turns out that the product distribution varies with temperature.

Furthermore, if we expose the 1,2-addition product to HBr (small amount) we get again the mixture of products.

Reaction diagram:

reversible reactions: thermodynamic control -

more stable product dominates

Irreversible reactions: kinetic control - faster to

form dominates

The reaction of the 1,2-addition product with HBr tells us that at 25 C, reaction is reversible. Product can go back to the
cation and then over to another isomer of the product. When a reaction is reversible, the distribution of the products is
determined by the thermodynamic stability of the products (thermodynamic control). More stable product will be the
major product.

If a reaction is not reversible, the product distribution will depend on which product is formed faster (which product is
easier to make), and we say that the reaction is under kinetic control.

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