Huckel’s rule: Aromatic vs anti-aromatic vs non-aromatic (Part 1)

Historically, benzene and its first derivatives had pleasant aromas and
were called aromatic compounds. In modern days though, the term
‘aromatic’ has a different meaning. In simple terms an aromatic compound
can be defined as a cyclic compound, containing a certain number
of conjugated double bonds, and being especially stable due to resonance. 
So what exactly is conjugation? The most common definition that one hears
is that conjugation is the presence of alternating single and double bonds.
However, this definition is too specific and not general enough. Let’s
consider the structure of furan. 

Furan is a conjugated molecule despite not having alternate single and

double bonds! Therefore, a better definition of conjugation will be: The
presence of side-to-side overlap of p-orbitals at every atom in a ring. P
orbital must be available for side-to-side overlap to occur due to its unique
dumb-bell shape. There is no way we can have a side-way overlap of s-
orbital because it is spherical regardless of its orientation. Furthermore it
must be sideway overlap and not head-on overlap. The former produces pi
bond while the latter produces sigma bond.
The hybridization of the oxygen atom in furan is sp2. Refer to this
link:http://aceyourchemistry.blogspot.sg/2014/03/basicity-of-pyridine-
and-pyrrole.html 
The oxygen atom possesses two lone pairs of electrons. One pair sits in a
sp2 hybrid orbital while the other resides in a p-orbital. This means that all
the 5 atoms (4 carbon atoms and 1 oxygen atom) have lone pairs in their p-
orbitals and hence conjugation can take place. 
 
For a molecule to be classified as aromatic, the presence of conjugation is
just one of the 4 considerations. An aromatic molecule must be: 1) Flat,
2) Cyclic, 3) Completely conjugated and 4) The number of  π electrons
must obey Huckel’s rule of 4n+2. In my next article, I shall continue with
the discussion on what aromaticity is.
Huckel’s rule: Aromatic vs anti-aromatic vs non-aromatic (Part 2)

Huckel’s rule: Aromatic vs anti-aromatic vs non-aromatic (Part 2)

Let’s continue from where we left off.  A molecule may be classified as (i)
aromatic, (ii) anti-aromatic and (iii) non-aromatic. 
An aromatic molecule is: 1) Flat, 2) Cyclic, 3) Completely conjugated and
4) The number of π electrons must obey Huckel’s rule of 4n+2,where n
is an integer.
An anti-aromatic molecule is: 1) Flat, 2) Cyclic, 3) Completely conjugated
and 4) The number of π electrons follows the formula of 4n, where n is
an integer.  Take note of point 4 which summarizes the key difference
between an aromatic and an anti-aromatic molecule.
A non-aromatic molecule is: 1) NOT flat, 2) NOT cyclic, 3) NOTcompletely
conjugated. Some examples include the typical alkane and/or alkene such
as butane or hexane. 
In 1866, Kekule bravely proposed (bravo!) that benzene had a cyclic
structure with three alternating C=C double and three C=C single bond.
While his proposed structure is reasonably close to accurate, in reality
benzene has much more stability than predicted by the simple resonance
delocalized structure. For example, the same reactions that work with a
normal cycloalkene simply do not work with benzene. Nevertheless, there
is no doubt that conjugation/resonance effect contributes an important
role in the extra stability of benzene. However, if having these identical
resonance structures were the sole cause of this pronounced stability,
then ALL structures with conjugated systems of alternating single and
double bonds should show analogous enhanced stability. This is
apparently not the case. In fact, the term ‘annulene’ has been coined to
categorize cyclic hydrocarbons with alternating single and double bonds.
An annulene can be named as [n] annulene where n is the number of
carbon atoms in the molecule. Some of the examples are shown below. 
  

As mentioned in the previous post 

http://aceyourchemistry.blogspot.sg/2014/03/huckels-rule-aromatic-vs-
anti-aromatic.html ,
conjugation may be defined as the sideway overlap of p-orbitals of all the
atoms in a ring. For maximum conjugation, the orbitals must 1) be of the
same type i.e. the overlap of 2p-2p is more effective than 2p-3p (this
explains why halogen is a deactivator of the ring while OH and NH2 are ring
activators despite all three of them being ortho/para-directing) and2) the
alignment of the orbitals must be in the correct orientation. To achieve
point 2, having a planar ring system is essential. This explains why being a
planar, cyclic molecule is a key characteristic of both aromatic and anti-
aromatic molecule. However in reality, it is almost impossible to determine
whether a molecule is flat/planar (or completely conjugated) by simply
looking at its displayed structure. In other words, we can’t tell if a molecule
is flat without building a 3D-model. In fact, molecules may undergo
distortion to relieve possible angle strain and this distortion has the
potential to disrupt the alignment of the p-orbitals and henceforth, its
conjugation. In any case should we confronted with such a question, we
should always assume that the molecule is flat. This is because there are
other ways to determine if a molecule is aromatic or anti-aromatic such as
using the Huckel’s rule. This shall be discussed in my next article. 
 
August Kekule (1829 – 1896)
Huckel’s rule: Aromatic vs anti-aromatic vs non-aromatic (Part 3)

In 1931, a German chemist and physicist Erich Huckel proposed a theory to

help determine if a cyclic molecule possesses aromatic properties.
According to him, if a cyclic, planar molecule contains 4n+2 π electrons,
then it is considered aromatic. This rule would come to be known as
Huckel’s rule. 
As mentioned in my previous post
[http://aceyourchemistry.blogspot.sg/2014/03/huckels-rule-aromatic-vs-
anti-aromatic.html], an aromatic molecule must be: 1) Flat, 2) Cyclic, 3)
Completely conjugated and 4) The number of π electrons must obey
Huckel’s rule of 4n+2. However, I had also mentioned that in reality, it is
almost impossible to determine whether a molecule is flat/planar (or
completely conjugated) by simply looking at its displayed structure. Refer
to this link: [http://aceyourchemistry.blogspot.sg/2014/03/huckels-rule-
aromatic-vs-anti-aromatic_16.html]. Hence, the Huckel’s rule is an effective
tool to determine if a molecule is aromatic.
However, the toughest part of Huckel’s rule is to figure out which electrons
in the molecule are actually π electrons. This can be achieved easily by
checking the individual atom’s hybridization i.e. if it is sp 2hybridized. One
of key requirements for aromaticity is that all the atoms must be
sp2 hybridized (almost always). This is because if an atom is sp hybridized
while the rest are sp2 hybridized, the π electron cloud is going to be
orthogonal to the empty p-orbital. Correspondingly, the extent of
conjugation will be adversely affected as well. Refer to this link:
[http://aceyourchemistry.blogspot.sg/2014/03/huckels-rule-aromatic-vs-
anti-aromatic_2044.html]for a more detailed discussion on this. 
A simple and relaxed method to determine if an atom is sp2 hybridized is to
see if an atom has 3 attached atoms and holds zero lone pair of electrons
(such as the carbon atoms in alkene). For furan though, a different rule of
thumb has to be adopted. Rule of thumb: An atom is sp2 hybridized if (1)
the atom has at least 1 lone pair of electrons and (2) the atom is
attached to another sp2 hybridized atom. Both these conditions must
be fulfilled before our ‘hero ‘atom can be classified as sp 2 hybridized.
As illustrated by the example on furan, although the oxygen atom holds 2
lone pairs of electrons, only one of them sits in an unhybridized p-orbital.
For lone pairs of electrons to be classified as π electrons, they must lie in
the p-orbitals.
Now, it is easy to understand why benzene is an aromatic molecule.  It is
cyclic and it contains 6π electrons (in accordance with Huckel’s rule of
4n+2, where n = 1). As mentioned previously, it is almost impossible to tell
if a molecule is planar based on its displayed structure. For Huckel’s rule,
the letter n holds no special meaning. It is through experimental
observations that scientists realize for some reasons, aromatic compounds
tend to have 2, 6, 10, 14 π electrons etc. By backward induction, Erich
Huckel then came up with a general formula to represent this
phenomenon. 
  
Besides applying Huckel’s rule on homocyclic molecule such as benzene
and heterocyclic molecule such as furan, it can also be applied on ions. As
long as the molecule has 4n+2 π electrons, it does not matter if it is neutral.
An example is the cyclopentadienyl ion. 

The carbon atom that contains the lone pair of electrons has a negative
charge attached to it. That negative charge simply means that our ‘hero’
carbon atom has just gained 1 lone pair and hence it has been assigned a
formal charge of -1. Although our ‘hero’ carbon atom has 3 attached atoms
and has 1 lone pair, it is NOT sp3 hybridized. This is because it is attached to
2 sp2 hybridized carbon atoms. Since our ‘hero’ carbon atom has a lone pair
and it is directly attached to at least 1 sp2 hybridized atom, it is also
sp2 hybridized. Once the hybridization has been determined, it is quite easy
to see that the lone pair on our ‘hero’ carbon atom actually lies in the
unhybridized p-orbital. Since all the 5 carbon atoms are sp 2 hybridized and
it contains 6π electrons (2 π electrons per C=C bond. 2x2 = 4. 4+2 lone pair
on our ‘hero’ atom = 6 π), cyclopentadienyl ion has aromatic character.  
However, is it possible to achieve a planar cyclic molecule with only 2π
electrons? I will leave that question for my next article.
Huckel’s rule: Aromatic vs anti-aromatic vs non-aromatic (Part 4)

Question from the previous post: Is it possible to achieve a planar cyclic

molecule with only 2π electrons?
Answer: The formula for Huckel’s rule is 4n+2 π electrons, where n is an
integer. When n=1, we get 6π electrons as represented by an aromatic
benzene ring. However, what happens if we let n be 0? Does such a
structure even exist? Indeed, it does. That ‘chosen one’ is cyclopropenyl
cation. 

Let’s recall the 4 conditions required for aromaticity. An aromatic molecule

has to be: 1) Flat, 2) Cyclic, 3) Completely conjugated and 4)The number
of π electrons must obey Huckel’s rule of 4n+2, where n is an integer.
Our ‘hero’ carbon atom bearing the positive charge is a sp2hybridized
carbocation. Although it does not possess any lone pair, it does have an
empty unhybridized p-orbital which is able to accommodate the 2π
electrons from the C=C system. Furthermore, the alignment of this
particular p-orbital is aligned properly with the other two p-orbitals. 
Special mention: This structure reminds me of the vinyl cation. 

The carbon atom on the left is sp2 hybridized while our ‘hero’ atom bearing
the positive charge is sp hybridized. With reference to the diagram above,
the ‘black’ p-orbital and the ‘red’ p-orbital of the ‘right’ carbon atom are
orthogonal to each other. The ‘red’ p-orbital is an empty orbital, though.
Since the π electron cloud is perpendicular or orthogonal to the ‘red’ empty
p-orbital, the extent of conjugation is adversely affected due to the poor
alignment of the p-orbitals. Hence, conjugation is not an important
stabilizing feature in vinyl cation as compared to hyperconjugation. I will
leave the discussion on hyperconjugation to another day. Stay tuned!

Erich Huckel (1896 – 1980)

Basicity of Pyridine and Pyrrole

Based on the pKb values, pyridine is a stronger base than pyrrole as it

has a lower pKb value. The lower the pKb value, the more basic is the
substance. So, what exactly is basicity? The basicity of a substance
depends on the availability of the lone pair of electrons for donation. For
example, let compare ammonia with a primary amine. 

The primary amine is definitely more basic than ammonia. This is

because the primary amine has an alkyl group attached to it. Since the
alkyl groups are electron donating by nature, their electron releasing
inductive effect will increase the availability of electrons on the nitrogen
atom for donation. Surprisingly though, tertiary amine is less basic than
secondary amine despite the former having three electron donating alkyl
groups as compared to the latter’s two. 
This is because although the electron releasing inductive effect is
greater for the tertiary amine, the presence of three ‘bulky’ alkyl groups
actually hinders the tertiary amine’s ability to donate its lone pair of
electrons! In other words, the steric factor is more dominant than the
electronic factor for this particular example. 
Alright, let’s go back to our initial discussion. Since pyridine has a lower
pKb value, it suggests that pyridine is a stronger base. In this example,
we can’t use the steric factor or the inductive factor to compare their
basicity. Instead, we have to look at the hybridization of the respectively
nitrogen atoms.

The nitrogen atoms in both compounds are sp2 hybridized.

Rule of thumb: An atom is sp2 hybridized if (1) the atom has at least
1 lone pair of electrons and (2) the atom is attached to another
sp2 hybridized atom. Both these conditions must be fulfilled before
our nitrogen atom can be classified as sp2 hybridized. In both pyrrole and
pyridine, the nitrogen atom has a lone pair (condition 1 is satisfied) and it
is seated next to a sp2 carbon atom (condition 2 is satisfied) and hence
the nitrogen atom is sp2hybridized. Recall that a sp2 hybridized atom has
3 hybridized sp2orbitals and 1 un-hybridized p orbital. For pyridine, the
lone pair resides in a sp2 hybrid orbital as the C=N already contains 2
pi electrons in the p-orbital. Since the lone pair is in the sp2 hybrid orbital,
conjugation does not occur which means that this particular lone pair is
available for donation.
For pyrrole however, the lone pair of electrons on the nitrogen atom
resides in the p-orbital. As a result, the lone pair gets delocalized into
the pi electron cloud of the neighbouring atoms, making it less available
for donation. Hence, this explains whypyridine is a stronger base than
pyrrole!
Hyperconjugation Explained

Carbocations are most stable when they are more substituted. Alkyl groups
are weakly electron donating via the inductive effect and that is the
mechanism by which they stabilize the carbocations. This is because by
reducing or delocalizing these charges, the ions are conferred with greater
stability. That is the reason why we rarely see methyl carbocation in our
organic reaction and primary carbocation is not much better. However, we
do see secondary and tertiary carbocations constantly in organic chemistry
and these are the staples of first order substitution (SN1) and elimination
(E1). 
Let’s take a closer look at what is so special about those R groups that
allows them to donate electrons into the carbocation centres. Let’s consider
the methyl and ethyl carbocations. Although we don’t see them frequently
in organic chemistry simply because they are very unreasonably unstable,
they are the simplest examples that will allow us to demonstrate how
hyper-conjugation works. A brief history. The term ‘hyper-conjugation’ was
first coined by Robert S Mulliken in 1939 in the course of his work on UV
spectroscopy of conjugated molecules. A Nobel Prize laureate, he was
primarily responsible for the early development of molecular orbital
theory. (Oh no, so he is the culprit!) Alright, back to our story. The key
difference between the methyl and ethyl carbocations is that the latter has
a neighbouring C-H sigma bonding orbital and this sigma bonding orbital is
filled with electrons. 

However, these electrons have free run over the entire volume that is
defined by the molecular orbital. Occasionally, these electrons may find
their way into the vacant p-orbital of the sp2 hybridized carbocation. After
all, an orbital is defined as a volume around a nucleus in which there is a
99% chance of finding an electron. Since the frequency of such a ‘slip up’
happening is rather rare (~1%), alkyl groups are only weakly electron
donating. An alternative view is that hyper-conjugation is more like a
dipole effect and a donation of electron density, rather than having the
electrons actually moves between the atoms. As such, the degree of ‘orbital
overlap’ is fairly weak. However should such a ‘slip up’ occurs, the positive
charge on the carbocation will be slightly attenuated. That is why having
additional alkyl groups around the carbocation centre makes it more stable
as it increases the probability of having such a ‘slip up’ and hence more
likely to be formed.
Special Note:
1) Only electrons that are beta to the positively charged carbon
can stabilize a carbocation by hyper-conjugation.  
2) For hyper-conjugation and resonance to occur, the orbitals must
be aligned in the correct orientation to maximize the degree of
orbital  overlap.  Hyper-conjugation is all about the donation of
electron density. In resonance, the electrons actually move between
the atoms and hence the stabilization due to resonance must
be greater than that of hyper-conjugation.
3) Hyper-conjugation involves a sigma orbital component, usually a C-C or
a C-H bond whereas resonance typically involves p-orbitals. 

Robert S Mulliken (1896 – 1986)

Friedel-Craft Alkylation and its limitations

The Friedel-Craft alkylation is a convenient way to introduce alkyl groups

onto the benzene ring. It is a typical electrophilic substitution reaction in
which the intermediate is a carbocation. However, the reaction suffers from
a series of limitations which makes it a poor candidate to achieve the
desired outcomes. 
For your information, Fridel-Craft alkylation was named after a French
chemist Charles Friedel and his partner, an American chemist James Craft,
in 1877. This reaction allows the formation of alkyl benzene from alkyl
halide (R-X) but is plagued with unwanted side reactions that reduced its
efficacy. 
Let’s list out some of the limitations of Friedel-Craft Alkylation:
1.        The reaction only works with benzene or activated
benzene   derivatives. In other words, it will not work if the aromatic ring
has   a deactivating group attached to it i.e. nitrobenzene,
benzaldehyde   etc.
2.        The reaction only works with alkyl halides (chloride, bromide
oriodide). It does not work for vinyl halide or aryl halide. 

3.        Carbocation rearrangement may occur via hydride shift or

alkyl shift.  Hydride shift usually happens in electrophilic
additionof alkenes while alkyl shift typically occurs for SN1 and E1of
alkyl halides, which involves the loss of a leaving group to generate
acarbocation. 
4.        Poly-alkylation of the aromatic ring may occur. For instance,
alkyl benzene is more reactive than the initial benzene ring. This is because
alkyl groups are electron donating substituents and therefore they are able
to activate the ring. As a result, the alkyl substituted aromatic ring is more
susceptible to electrophilic attack than what we began with. Therefore, this
reaction may be considered as ‘synthetically challenged’.
However, limitation 3 and 4 can be circumvented in certain cases. One
method is to use an excess of benzene or benzene derivatives to ensure
mono-substitution. However, this approach is not always practical due to
the availability of that particular benzene derivative. Fortunately, our
beloved Charles Friedel and James Craft had left us a very important
synthesis tool to circumvent the limitation of Friedel-Craft alkylation.
Thank goodness! And that is…  Friedel- Craft acylation, followed by a
carbonyl reduction i.e. Clemmensen reduction. However, I will leave
that discussion for another day. 

Charles Friedel (left) and James Craft

The Friedel-Craft alkylation is a convenient way to introduce alkyl groups
onto the benzene ring. It is a typical electrophilic substitution reaction in
which the intermediate is a carbocation. However, the reaction suffers from
a series of limitations which makes it a poor candidate to achieve the
desired outcomes. 
For your information, Fridel-Craft alkylation was named after a French
chemist Charles Friedel and his partner, an American chemist James Craft,
in 1877. This reaction allows the formation of alkyl benzene from alkyl
halide (R-X) but is plagued with unwanted side reactions that reduced its
efficacy. 
Let’s list out some of the limitations of Friedel-Craft Alkylation:
1.        The reaction only works with benzene or activated
benzene   derivatives. In other words, it will not work if the aromatic ring
has   a deactivating group attached to it i.e. nitrobenzene,
benzaldehyde   etc.
2.        The reaction only works with alkyl halides (chloride, bromide
oriodide). It does not work for vinyl halide or aryl halide. 

3.        Carbocation rearrangement may occur via hydride shift or

alkyl shift.  Hydride shift usually happens in electrophilic
additionof alkenes while alkyl shift typically occurs for SN1 and E1of
alkyl halides, which involves the loss of a leaving group to generate
acarbocation. 
4.        Poly-alkylation of the aromatic ring may occur. For instance,
alkyl benzene is more reactive than the initial benzene ring. This is because
alkyl groups are electron donating substituents and therefore they are able
to activate the ring. As a result, the alkyl substituted aromatic ring is more
susceptible to electrophilic attack than what we began with. Therefore, this
reaction may be considered as ‘synthetically challenged’.
However, limitation 3 and 4 can be circumvented in certain cases. One
method is to use an excess of benzene or benzene derivatives to ensure
mono-substitution. However, this approach is not always practical due to
the availability of that particular benzene derivative. Fortunately, our
beloved Charles Friedel and James Craft had left us a very important
synthesis tool to circumvent the limitation of Friedel-Craft alkylation.
Thank goodness! And that is…  Friedel- Craft acylation, followed by a
carbonyl reduction i.e. Clemmensen reduction. However, I will leave
that discussion for another day. 

Charles Friedel (left) and James Craft

Mechanism for the nitration of benzene

There are 2 different ways of drawing the mechanism for the nitration of
benzene. Under the H2 Chemistry syllabus, students will typically illustrate
the mechanism of the generation of electrophile via a chemical equation. In
fact, students are told that nitric acid serves as a base (a Bronsted Lowry
base, to be precise) while sulphuric acid serves as a Bronsted Lowry acid.
Very often, students get confused over this seemingly inaccurate statement.
Aren’t both of them acids? To explain this phenomenon, we have no choice
but to show THE mechanism.  If you look at the mechanism shown under
the H3 subtitle, you will notice that nitric acid gets protonated by sulphuric
acid. Under the Bronsted- Lowry acid-base theory, a substance is
considered as a Bronsted- Lowry base if it accepts a proton. In this
example, it is the nitric acid. Meanwhile, sulphuric acid is known as a
Bronsted-Lowry acid because it is a proton donor. Please bear in mind that
the Bronsted-Lowry theory is just one of the many theories used to
describe what an acid or a base is. In fact, we shall be acquainted with 2
more theories, namely the Arrhenius theory and the Lewis theory. Out of
these 3 theories, the Arrhenius theory has the narrowest definition while
the Lewis theory is the broadest of the 3 theories since it includes all the
possible acids and bases ascribed by the other 2 theories. (Think about why
this is the case)
Now, let’s go back to our story. The protonated nitric acid is not very stable
and it will split itself up to form a water molecule and the nitronium ion
which happens to be our electrophile.  Subsequently, the water molecule
gets protonated by a second molecule of the sulphuric acid. This makes
perfectly sense because there is no way the water molecule will REMAIN as
a water molecule especiallyif we have 2 strong mineral acids. 
When we draw our carbocation intermediate, please make sure that the ‘U’
shape is in the correct orientation with respect to the carbon atom carrying
the concerned electrophile.  To understand why this is important, please
refer to the resonance structures that have been drawn for you i.e. sigma
complexes. The positive charge gets delocalized over 3 carbon atoms in a
‘U’ shape manner. Meanwhile the HSO4- will abstract a proton from the
unstable carbocation to form nitrobenzene, thus regaining its initial
aromatic character. Do note that our sulphuric acid has been regenerated
as well because it is serving not only as an acid but a catalyst as well. 
Why does ethanoyl chloride react vigorously with water while benzoyl chloride reacts slowly with water?

Before answering this question, let’s refresh our knowledge on the

reactivity of different organic chlorides: acyl chloride (also known as acid
chloride. It obtains its name from the chemical reaction known as
‘Friedel-Craft acylation’), alkyl chloride and aryl chloride. 

Under the topic of ‘Halogen Derivatives’, we learnt that alkyl chlorides

undergo nucleophilic substitution more readily than aryl chlorides. Notice
I used the phrase ’more readily’… Does that mean that aryl chlorides
can undergo nucleophilic substitution as well? Yes, indeed they can but
only under extreme industrial conditions. Since we are only interested in
producing compounds under normal laboratory conditions, it is not wrong
to proclaim that aryl chlorides cannotundergo any form of hydrolysis or
nucleophilic substitution as indicated in our A Level H2 Chemistry
syllabus. The reason for this ‘lack of reactivity’ for aryl chloride is
because the p-orbitals (containing the lone pairs of electrons) of chlorine
can overlap with the pi-electron system of the aromatic ring. The
electrons get delocalised over the entire ring system to create resonance
effect. The resonance effect is possible because the 3p orbital from the
chlorine atom is well-aligned with the 2p orbital of the carbon atom.  
Side note: For maximum resonance effect, 2 conditions must be fulfilled.
Condition 1: The p-orbitals must be aligned in the correct direction. In
other words, resonance is not possible if we have 2 orbitals that are
orthogonal to each other. An example is: 
In the vinyl cation, the positive charge cannot be delocalized by the pi
electrons because the empty p orbital on the carbon is orthogonal to the
electrons in the pi bond. 
Condition 2: For maximum orbital overlap (which is basically what
resonance is all about), the orbitals must be of the same size. This
explains why Cl is weakly electron donating for chlorobenzene while OH
is strongly electron donating for phenol.  I will leave that discussion on
another occasion then.  Back to the above discussion… Thanks to the
resonance effect, the C-Cl bond has a certain degree of double bond
character and will be much tougher to cleave.

Let’s return to the topic question. Both ethanoyl chloride and benzoyl
chloride may be classified as carboxylic acid derivatives. For carboxylic
acid derivatives, the representative reaction is nucleophilic substitution.
Notice the trend: These carboxylic acid derivatives (acyl chloride) are
also known as organic chlorides whose main reaction is also nucleophilic
substitution! As far as nucleophilic substitution is concerned, the rate of
hydrolysis is dependent on 2 factors i.e. 1) how electron deficient is the
alpha carbon?  In this case, the alpha carbon refers to the carbon atom
in the C-Cl bond and 2) the strength of the C-Cl bond. Since both
ethanoyl chloride and benziyl chloride are both alkyl chlorides, factor 2 is
not a consideration at all. In fact, factor 1 is the only crucial factor we
need to consider.

As illustrated in the above diagram, the delta positive charge for benzoyl
chloride is delocalised over the entire aromatic ring system. Since the
electrophilicity of our alpha carbon has been reduced due to the
delocalization effect, its ‘attractiveness’ to potential nucleophiles has also
been reduced as well. This explains why benzoyl chloride is less reactive
than ethanoyl chloride!
Blog author is now listed as one of the expert Chemistry tutors in Singapore by 'Domain of Singapore Tutoring
Experts'

I am so pleased and honoured that I have been listed as

one of the expert Chemistry tutors in Singapore by
'Domain of Singapore Tutoring Experts'. A big thank you
to:
1) Domain of Singapore Tutoring Experts for
acknowledging my    
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2) My current students as well as those whom I had the
opportunity
    to share my knowledge with. I am able to improve
myself 
    because of your questions. So please keep those
questions   
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and confidence in 
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