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Alkanes are rarely prepared from other types of compounds because of economic

reasons. However, ignoring financial considerations, alkanes can be prepared from the
following compounds:
1. Unsaturated compounds via catalytic reduction

2. Alkyl halides via coupling (Wurtz reaction)

3. Alkyl halides via Grignard reagent

4. Alkyl halides via reduction

Although organic chemists refer to the above diagrams as equations, they are not balanced. In
addition, not every product formed is shown. These diagrams are reallyreaction schemes.

General Method of Preparation of Alkanes


(Paraffins):
Alkanes can be prepared by the following methods:
1. From unsaturated Hydrocarbons
2. From Haloalkanes

By Wurtz Reaction

By reduction

3.
4.
5.

By the Reduction of Aldehydes and Ketones


From Grignards Reagent
From salts of Carboxylic acids

By Kolbes electrolytic method

By Heating Na-salt of Carboxylic acid

6.

From Metal Carbides

1.
From unsaturated Hydrocarbons
Alkanes can be prepared by the catalytic hydrogenation of unsaturated hydrocarbons in
the presence of catalyst Ni or pt at 200C to 300C.

2.

From Haloalkanes

By Wurtz Reaction:

When alkyl halides are heated with sodium metal in the presence of dry ether, alkanes
are obtained (generally having double number of C-atoms than in alkyl halides). This
reaction is known as Wurtz reaction and used for the preparation of symmetrical
alkanes.

By Reduction of alkyl halides (RX)

Haloalkanes (R-X) when heated with reducing agents like; LiAlH 4/ether, Pd/H2, Pt/H2,
Zn/conc. HCl, alkanes are produced.
R-X
R-H + HX
3.

By the Reduction of Aldehydes and Ketones


Aldehydes and ketones can be reduced into alkanes in the presence of reducing
agents: amalgated zinc and conc. HCl.

4.

From Grignards Reagent


Hydrolysis of Grignards reagent in the presence of ether gives alkanes.
dry ether
RMgX + H2O > R-H + Mg(OH)X
alkyl magnesium halide
(alkane) (Hydroxy magnesium halide)
5.

From salts of Carboxylic acid


By Kolbes electrolytic method

Electrolysis of aqueous conc. solution of sodium or potassium salt of carboxylic acid


gives alkanes.
>>RCOONa-Sodium salt
>>RCOOKPotassium salt
RCOONa> RCOO- + Na+
anion

cation

During electrolysis;
Electrode reaction occurs as
At anode:
RCOO- - e > RCOO > R-R + 2CO2
unstable
alkane
At cathode:
Na+ + OH- > NaOH

By Heating Na-salt of Carboxylic acid

When Na-salt of carboxylic acid is heated with soda lime (NaOH & CaO), alkane is
obtained having one carbon less than salt by removal of a molecule of CO2. This reaction
is also known as decarboxylation.
RCOONa + NaOH
R-H + Na2CO3
Eg:

Sodium ethanoate
(methane)
This is the principle reaction for laboratory preparation of methane gas.

6.

From Metal Carbides


Metal carbide like aluminium carbide (Al4C3) and beryllium carbide (Be2C) reacts
with pure water to produce methane.
Al4C3 + 12H2O -> 4Al(OH)3 + 3CH4

Related Notes:
Read more: http://notes.tyrocity.com/preparation-of-alkanes/#ixzz3dKqaLmok
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Cracking

This page describes what cracking is, and the differences between catalytic cracking and thermal cracking used in the
petrochemical industry.

Introduction
Cracking is the name given to breaking up large hydrocarbon molecules into smaller and more useful bits. This is
achieved by using high pressures and temperatures without a catalyst, or lower temperatures and pressures in the
presence of a catalyst. The source of the large hydrocarbon molecules is often the naphtha fraction or the gas oil
fraction from the fractional distillation of crude oil (petroleum). These fractions are obtained from the distillation
process as liquids, but are re-vaporized before cracking.
There is not any single unique reaction happening in the cracker. The hydrocarbon molecules are broken up in a fairly
random way to produce mixtures of smaller hydrocarbons, some of which have carbon-carbon double bonds. One
possible reaction involving the hydrocarbon C15H32 might be:

Or, showing more clearly what happens to the various atoms and bonds:

This is only one way in which this particular molecule might break up. The ethene and propene are important
materials for making plastics or producing other organic chemicals. The octane is one of the molecules found in petrol
(gasoline).

Catalytic cracking
Modern cracking uses zeolites as the catalyst. These are complex aluminosilicates, and are large lattices of
aluminium, silicon and oxygen atoms carrying a negative charge. They are, of course, associated with positive ions
such as sodium ions. You may have come across a zeolite if you know about ion exchange resins used in water
softeners. The alkane is brought into contact with the catalyst at a temperature of about 500C and moderately low
pressures.
The zeolites used in catalytic cracking are chosen to give high percentages of hydrocarbons with between 5 and 10
carbon atoms - particularly useful for petrol (gasoline). It also produces high proportions of branched alkanes and
aromatic hydrocarbons like benzene. The zeolite catalyst has sites which can remove a hydrogen from an alkane
together with the two electrons which bound it to the carbon. That leaves the carbon atom with a positive charge. Ions
like this are called carbonium ions (or carbocations). Reorganization of these leads to the various products of the
reaction.

Thermal cracking
In thermal cracking, high temperatures (typically in the range of 450C to 750C) and pressures (up to about 70
atmospheres) are used to break the large hydrocarbons into smaller ones. Thermal cracking gives mixtures of
products containing high proportions of hydrocarbons with double bonds - alkenes. Thermal cracking does not go via
ionic intermediates like catalytic cracking. Instead, carbon-carbon bonds are broken so that each carbon atom ends
up with a single electron. In other words, free radicals are formed.

Reactions of the free radicals lead to the various products.

Contributors

General methods of preparation of


alkanes
A.

From Alkenes. Hydrogenation (reduction) of alkenes.

The addition of hydrogen to alkenes is known as a hydrogenation or


reduction. In this reaction a molecule of hydrogen is added to the alkene
molecule at the site of unsaturation i.e. where the double bond is. This is
achieved under mild conditions when a catalyst is used to bring about this
change.

Suitable catalysts for this reaction are : (a) Raney Nickel,


Pt on C

(b) Pd on C

or (c)

The conditions to be used can be moderate temperatures and pressures


although catalytic hydrogenations often occur at room temperature and
pressure. (Any increase in pressure is bound to bring about the expected
reaction in better yields Le Chatelier).

This is by far the most important way of generating alkanes and is in many ways
the easiest reaction to carry out.

B.
From Carboxylic Acids and their salts - by decarboxylation reactions
i.e. removal of CO2

(i)

Using Sodalime.

When a carboxylic acid, or its salt (sodium, potassium or calcium salts are
commonly used) is heated strongly with sodalime (which is essentially sodium
hydroxide mixed with calcium oxide to give a non-deliquescent solid), the
carboxylic acid looses CO2 and gives the alkane :

or by way of a generalized representation of this reaction :

where R represents any alkyl (or even aryl) group, and NaOH here specifically
refers to sodalime. (Some authors prefer to use Ca(OH)2 as the reagent in
sodalime then giving CaCO3 as the inorganic product)

This reaction gives the required alkane albeit in low yields. The problem being that it is
physically difficult to get an infinitely intimate mixture of solids for reaction to proceed
efficiently when the heating commences.

(ii)

By Electrolysis. (The Kolbe Process)

The electrolysis of aqueous solutions of carboxylic acid salts similarly gives a


decarboxylation of the anion (at the anode) and two alkyl residues (i.e. groups) combine
together to give an alkane.

or in general :

The limitation with this technique is that it only produces alkanes that have an even number
of carbons. If alkanes with an odd number of carbon atoms are needed, mixtures of
carboxylate salts will have to be used. Such procedures would however also make it possible
for other, perhaps undesirable, products to be formed. The nature of the alkanes is very much
dependent on the chance collisions of the various alkyl radicals present close to the anode
where the decarboxylation processes take place.

C.

From Haloalkanes.

(i)
By reduction of haloalkanes - using an active
(atomic?) form of hydrogen.
Haloalkanes can easily be made to give the alkanes if these are exposed to an
environment where hydrogen atoms are generated. Such conditions are found
for example when sodium/mercury or aluminium/mercury amalgams are in
contact with ethanol. Similarly, a zinc/copper couple with ethanol gives the same
result, as would nickel/aluminium + NaOH or zinc/mercury + HCl.

General reaction :

Sources
C2H5OH; Cu/Zn + C2H5OH;

of H

Na/Hg

Ni/Al + NaOH;

(ii)

C2H5OH ; Al/Hg

Zn/Hg + HCl.

Halogen removal via Grignard reaction.

In this reaction, the haloalkane is first made to give the Grignard reagent as an
intermediate and this is then hydrolysed (with water!) to give the alkane. This is
not the best use of Grignard chemistry but it does give the alkane as a product if
one so wishes.

or

(iii)
Reaction

Dehalogenation using metallic sodium. The Wurtz

In this procedure, where the haloalkane is heated with metallic sodium in an inert solvent
such as ether, the haloalkane loses its halogen and two radicals then come together to give an
alkane with a longer carbon chain. (In fact, the chain doubles in length).

for which the generalized reaction would be :

In this reaction, same as for one of the decarboxylation reactions, only even
numbered alkanes can be made. If the alkanes with an odd number of carbons
have to be produced, mixed haloalkanes must be used. However, this will again
then give rise to a number of products where the different alkyl groups come
together to give the final alkane. Hence, a mixture of RX and RX yields RR, RR
and RR as the alkanes.

D.

From Alcohols.

Aggressive reduction of alcohols by very strong reducing agents, will


remove the alcohol functionality (i.e. the OH group) replacing it with an H
atom. A Reducing agent that is good enough for this transformation is red
P + conc. HI(aq) heated under pressure.

Reaction represented in a general way would be :

E.
From Carbonyl compounds i.e. aldehydes and ketones By strong
reducing agents.

Using the same conditions for reduction of alcohols also gives alkanes from the
carbonyl compounds such as aldehydes (RCHO) and ketones (RCOR).

i.e.

Special synthetic methods for


methane.
a.

From Aluminium carbide.

The reaction of aluminium carbide with water gives methane and aluminium
hydroxide as the only products.

b.

Fischer Tropsch Process (Ind)

Industrial synthesis of methane can be achieved using CO and hydrogen (both


easily obtained from water and carbon) using Nickel as catalyst and the reaction
can be carried out at a modest 300oC.

General methods of
preparation of
alkanes
(i) Decarboxylation :
(a) Decarboxylation means
removal of CO2 from
molecules having - COOH
gp.
(b) Saturated
monocarboxylic acid salt of
sodium potassium on dry
distillation with soda lime
gives alkane.
RCOONa

R-H

or RCOONa +
NaOH
R-H +
Na2CO3
(c) The alkane formed
always contains one carbon
atom less than the original
acid.
(d) The yield is good in case
of lower members but poor
for higher members.
(e) Soda lime is prepared by
soaking quick lime CaO in
caustic soda solution and
then drying the products. It
is generally written as
NaOH + CaO. Its reaction is
milder than caustic soda.
Otherwise the reaction will
occur violently. Also CaO
used alongwith NaOH
keeps it dry (NaOH is
hygroscopic) to aid fusion.
(f) The decarboxylation of
sodium formate yields H2.
HCOONa + NaOH

Acids and Bases


Many students start organic chemistry thinking they know all about acids and
bases, but then quickly discover that they can't really use the principles
involved.
For example, many students are typically not comfortable when they are
asked to identify the most acidic protons or the most basic site in a molecule.
Yet this is critical since an acid will typically react at the most basic site first
and a base will remove the most acidic proton first.
Remember that acidity and basicity are the based on the same chemical
reaction, just looking at it from opposite sides, so they are opposites.
When evaluating acidity / basicity, look at the atom bearing the proton /
electron pair first. Then you may also need to consider resonance, inductive
(remote electronegativity effects), the orbitals involved and the charge on that
atom.

Acidity
Here are some general guidelines of principles to look for the help you
address the issue of acidity:
First, consider the general equation of a simple acid reaction:

The more stable the conjugate base, A-, is then the more the equilibrium
favours the product side.....
The more the equilibrium favours products, the more H+ there is....
The more H+ there is then the stronger H-A is as an acid....
So looking for factors that stabilise the conjugate base, A-, gives us a
"tool" for assessing acidity.
Key factors that affect the stability of the conjugate base, A-,

HF > H2O > NH3 > CH4

Electronegativity but only when comparing atoms within


the same row of the periodic table, the more
electronegative the anionic atom in the conjugate base, the
better it is at accepting the negative charge.

HI > HBr > HCl > HF

Size. When comparing atoms within the same group of


the periodic table, the larger the atom the weaker the HX bond and the easier it is to accommodate negative
charge (lower charge density)
Resonance. In the carboxylate ion, RCO2- the negative
charge is delocalised across 2 electronegative atoms which
makes it more stable than being localised on a specific
atom as in the alkoxide, RO-.

RCO2H > ROH

Basicity
A convinient way to look at basicity is based on electron pair availability.... the
more available the electrons, the more readily they can be donated to form a
new bond to the proton and, and therefore the stronger base.
Key factors that affect electron pair availability in a base, B

CH3- > NH2- > HO- > F-

F- > Cl- > Br- > I-

Electronegativity but only when comparing atoms within


the same row of the periodic table, the more
electronegative the atom donating the electrons is, the less
willing it is to share those electrons with a proton, so the
weaker the base.
Size. When comparing atoms within the same group of
the periodic table, the larger the atom the weaker the HX bond and the lower the electron density making it a
weaker base.
Resonance. In the carboxylate ion, RCO2- the negative
charge is delocalised across 2 electronegative atoms which
makes it the electrons less available than when they
localised on a specific atom as in the alkoxide, RO-

RO- > RCO2-

efinitions
There are three theories used to describe acids and bases :

Arrenhius

Acids

Bases

Ionise to give H+ in H2O

Ionise to give HO- in H2O

Bronsted-Lowry

A proton donor

A proton acceptor

Lewis

An electron pair acceptor

An electron pair donor

Now, some terminology:

Look at this equation and see how it fits the Bronsted-Lowry and Lewis
definitions.

Acidity
Here are some general guidelines of principles to look for that can help you
address the issue of acidity:
First, consider the simplified general equation of a simple acid reaction:

The more stable the conjugate base, A-, is then the more the equilibrium
favours the product side (Ka > 1), i.e. more dissociation of H-A
More dissociation of H-A then the stronger H-A is as an acid, or
The more the equilibrium favours products, the more H+ there is....
The more H+ there is then the stronger H-A is as an acid....
So looking for factors that stabilise the conjugate base, A-, gives
us a "tool" for assessing acidity.
The larger Ka implies more dissociation of HA and so the stronger the
acid.

The larger Ka is, the more negative the pKa so the lower the pKa, the
stronger the acid.
Key factors that affect the stability of the conjugate base, A-,

HF > H2O > NH3 > CH4

Electronegativity. When comparing atoms within the


same row of the periodic table, the more electronegative
the anionic atom in the conjugate base, the better it is at
accepting the negative charge.

HI > HBr > HCl > HF

Size. When comparing atoms within the same group of


the periodic table, the easier it is for the conjugate base to
accommodate negative charge (lower charge density). The
size of the group also weakens the bond H-X (note this
trend should be applied with care since it only works within
a group).

RCO2H > ROH

Resonance. In the carboxylate ion, RCO2- the negative


charge is delocalised across 2 electronegative oxygen
atoms which makes it more stable than being localised on
a specific atom as in the alkoxide, RO-.

General acidity trend of common organic acids (this is a very useful


sequence to remember and to be able to rationalise):

Basicity
A convenient way to look at basicity is based on electron pair availability.... the
more available the electrons, the more readily they can be donated to form a
new bond to the proton and, and therefore the stronger base.
Key factors that affect electron pair availability in a base, B
CH3- > NH2- > HO- > F-

Electronegativity. When comparing atoms within the

same row of the periodic table, the more electronegative


the atom donating the electrons is, the less willing it is to
share those electrons with a proton, so the weaker the
base.

F- > Cl- > Br- > I-

Size. When comparing atoms within the same group of the


periodic table, the larger the atom the weaker the H-X bond
and the lower the electron density making it a weaker base.

RO- > RCO2-

Resonance. In the carboxylate ion, RCO2- the negative


charge is delocalised across 2 electronegative atoms which
makes it the electrons less available than when they
localised on a specific atom as in the alkoxide, RO-.

General acidity trend of some common organic bases:


Note that organic chemists tend to think about bases by looking at the pKa's
of their conjugate acids, i.e. think about B- by looking at the acidity of BH. The
implications are that the higher the pKa of the related conjugate acid, BH, the
stronger the baseb B-.

Study Tip: Note that acidity and basicity are just the reverse of each other.
AND
Therefore, both are affected by the same factors, just in opposite ways.

Walkthrough of Acid Base Reactions (2): Basicity


by JA MES

in OR G AN IC CH E MIS TRY 1 , OR G AN IC RE AC TIO N S , UN DE RS TAN DI N G EL EC TR ON FLOW

I started writing about acid-base reactions. We


looked at this list of stabilities of anions going across the
topmost row of the periodic table.
Last time

Fluoride ion
is the most stable in this series because its the most
electronegative; carbon is the least stable because its the
least electronegative.
Because of this, we were able to say that H-F was the
most acidic, because it had the most stable conjugate
base.
And H-CH3 (methane)was the least acidic, because it had
the least stable conjugate base.

Lets look at the flip side of this reaction. Instead of starting


with HF, H2O, H3N, and CH4 and asking how likely they
are to donate a proton to a common base (water in our
example) , imagine we start with the anions [ F-, HO-,
H2N- and H3C- ] and have them take a proton away from
a common acid (such as water).
Which reactions would be most favorable? Which would
be least favorable?

The same principle applies. The less stable the anion,


the more likely the reaction will be to proceed to
completion.
So in this case, the reaction of F- with H2O would be
the least favored, because F- is the most stable. And the
reaction of H3C- with H2O would be the most favored,
becuse H3C- is the least stable.

[A clarification: these are equilibrium reactions. So what I


mean by favored here is the extent to which the
equilibrium would favor the products on the right]
Notice the role that each of these anions plays in these
reactions: it is accepting a proton from water, so in other
words it is acting as a base.
Therefore, our whole discussion of the stability of
anions, for lack of a better term, goes by another name
youre familiar with: basicity.
In other words:
the more stable a lone pair of electrons is, the less
basic it will be.

the less stable a lone pair of electrons is, the more


basic it will be.

Lets tie these two posts together with a common thread:


For any group of acids, H-X (where X can literally be
anything), the strongest acid will have the most
stable conjugate base. Since stability is inversely
correlated with basicity, another way of putting it is:

The stronger the acid, the weaker the conjugate


base.

Todays post is about how the opposite is also


true: The weaker the acid, the stronger the conjugate
base.

Next time, well apply this framework to other stability


trends weve discussed previously.

P.S. One last note: a common misconception students


have is that weak acids are strong bases. Not
true! Methane (CH4) is a weak acid, but it cant act as a
base it doesnt have a lone pair.
The proper way to say it is that weak acids have strong
conjugate bases. So the conjugate base of CH4, CH3(-)
is an extremely strong base.
Next Post: Walkthrough of Acid-Base Reactions (3) Acidity Trends

Related Posts:
Making Grignard reagents
What are Grignard reagents?

A Grignard reagent has a formula RMgX where X is a halogen, and


R is an alkyl or aryl (based on a benzene ring) group. For the
purposes of this page, we shall take R to be an alkyl group.
A typical Grignard reagent might be CH3CH2MgBr.
The preparation of a Grignard reagent
Grignard reagents are made by adding the halogenoalkane to small
bits of magnesium in a flask containing ethoxyethane (commonly
called diethyl ether or just "ether"). The flask is fitted with a reflux
condenser, and the mixture is warmed over a water bath for 20 - 30
minutes.

Everything must be perfectly dry because Grignard reagents react


with water (see below).

Warning! Ethoxyethane (ether) is very dangerous to work with. It is an


anaesthetic, and is extremely flammable. Under no circumstances should
you try to carry out this reaction without properly qualified guidance.
(I was challenged by a reader because I had previously used the word
"inflammable" rather than "flammable" in this paragraph. In fact, confusingly,
the two words mean exactly the same thing. However, by switching to
"flammable", I have removed any possible confusion.)

Any reactions using the Grignard reagent are carried out with the
mixture produced from this reaction. You can't separate it out in any
way.

Reactions of Grignard reagents


Grignard reagents and water
Grignard reagents react with water to produce alkanes. This is the
reason that everything has to be very dry during the preparation
above.
For example:

The inorganic product, Mg(OH)Br, is referred to as a "basic


bromide". You can think of it as a sort of half-way stage between
magnesium bromide and magnesium hydroxide.
Grignard reagents and carbon dioxide
Grignard reagents react with carbon dioxide in two stages. In the
first, you get an addition of the Grignard reagent to the carbon
dioxide.
Dry carbon dioxide is bubbled through a solution of the Grignard
reagent in ethoxyethane, made as described above.
For example:

The product is then hydrolysed (reacted with water) in the presence


of a dilute acid. Typically, you would add dilute sulphuric acid or

dilute hydrochloric acid to the solution formed by the reaction with


the CO2.
A carboxylic acid is produced with one more carbon than the
original Grignard reagent.
The usually quoted equation is (without the red bits):

Almost all sources quote the formation of a basic halide such as


Mg(OH)Br as the other product of the reaction. That's actually
misleading because these compounds react with dilute acids. What
you end up with would be a mixture of ordinary hydrated
magnesium ions, halide ions and sulphate or chloride ions depending on which dilute acid you added.

Note: What you need to learn about this depends on what your examiners
want. The only way to find that out is to look at old exam papers and mark
schemes. If you are a UK A level student and haven't got copies of these,
find out how to get hold of them by going to the syllabuses page to find your
Exam Board's web address.

Grignard reagents and carbonyl compounds


What are carbonyl compounds?
Carbonyl compounds contain the C=O double bond. The simplest
ones have the form:

R and R' can be the same or different, and can be an alkyl group or
hydrogen.

Note: Other carbonyl compounds also react with Grignard reagents, but
these are all that are required for UK A level purposes.

If one (or both) of the R groups are hydrogens, the compounds are
called aldehydes. For example:

If both of the R groups are alkyl groups, the compounds are


called ketones. Examples include:

The general reaction between Grignard reagents and carbonyl


compounds
The reactions between the various sorts of carbonyl compounds
and Grignard reagents can look quite complicated, but in fact they
all react in the same way - all that changes are the groups attached
to the carbon-oxygen double bond.
It is much easier to understand what is going on by looking closely
at the general case (using "R" groups rather than specific groups) and then slotting in the various real groups as and when you need
to.
The reactions are essentially identical to the reaction with carbon
dioxide - all that differs is the nature of the organic product.
In the first stage, the Grignard reagent adds across the carbonoxygen double bond:

Dilute acid is then added to this to hydrolyse it. (I am using the


normally accepted equation ignoring the fact that the Mg(OH)Br will
react further with the acid.)

An alcohol is formed. One of the key uses of Grignard reagents is


the ability to make complicated alcohols easily.
What sort of alcohol you get depends on the carbonyl compound

you started with - in other words, what R and R' are.


The reaction between Grignard reagents and methanal
In methanal, both R groups are hydrogen. Methanal is the simplest
possible aldehyde.

Assuming that you are starting with CH3CH2MgBr and using the
general equation above, the alcohol you get always has the form:

Since both R groups are hydrogen atoms, the final product will be:

A primary alcohol is formed. A primary alcohol has only one alkyl


group attached to the carbon atom with the -OH group on it.
You could obviously get a different primary alcohol if you started
from a different Grignard reagent.
The reaction between Grignard reagents and other aldehydes
The next biggest aldehyde is ethanal. One of the R groups is
hydrogen and the other CH3.

Again, think about how that relates to the general case. The alcohol
formed is:

So this time the final product has one CH3 group and one hydrogen
attached:

A secondary alcohol has two alkyl groups (the same or different)


attached to the carbon with the -OH group on it.
You could change the nature of the final secondary alcohol by
either:

changing the nature of the Grignard reagent - which would


change the CH3CH2 group into some other alkyl group;

changing the nature of the aldehyde - which would change


the CH3 group into some other alkyl group.

The reaction between Grignard reagents and ketones


Ketones have two alkyl groups attached to the carbon-oxygen
double bond. The simplest one is propanone.

This time when you replace the R groups in the general formula for
the alcohol produced you get a tertiary alcohol.

A tertiary alcohol has three alkyl groups attached to the carbon with
the -OH attached. The alkyl groups can be any combination of
same or different.
You could ring the changes on the product by

changing the nature of the Grignard reagent - which would


change the CH3CH2 group into some other alkyl group;

changing the nature of the ketone - which would change the


CH3 groups into whatever other alkyl groups you choose to
have in the original ketone.

Why do Grignard reagents react with carbonyl compounds?


The mechanisms for these reactions aren't required by any UK A
level syllabuses, but you might need to know a little about the
nature of Grignard reagents.
The bond between the carbon atom and the magnesium is polar.
Carbon is more electronegative than magnesium, and so the
bonding pair of electrons is pulled towards the carbon.

That leaves the carbon atom with a slight negative charge.

Note: If you aren't sure about electronegativity, you can read about it in an
organic context by following this link.
Use the BACK button on your browser to return to this page.

The carbon-oxygen double bond is also highly polar with a


significant amount of positive charge on the carbon atom. The
nature of this bond is described in detail elsewhere on this site.

Note: If you are interested, you could follow this link to thebonding in a
carbonyl group. Reading the last couple of paragraphs on that page would be
enough in the present context.
Use the BACK button on your browser to return to this page.

The Grignard reagent can therefore serve as


a nucleophilebecause of the attraction between the slight
negativeness of the carbon atom in the Grignard reagent and the

positiveness of the carbon in the carbonyl compound.


A nucleophile is a species that attacks positive (or slightly positive)
centres in other molecules or ions.

Note: I have included this because one of the UK A level syllabuses says
that candidates should "recall that Grignard reagents act as nucleophiles".
That is all you need to know! The mechanism is more complex than this
suggests at first sight, and isn't required. You won't find these mechanisms
anywhere on this site.

eagent Friday: Grignard


Reagents
by JAMES
in ALCOHOLS , ALDEHYDES , ALKYL HALIDES , KETONES , ORGANIC
CHEMISTRY 2 , ORGANIC REAGENTS
In a blatant plug for the Reagent Guide and the Reagents App for iPhone, each Friday I
profile a different reagent that is commonly encountered in Org 1/ Org 2.
NOTE I said that the Reagents app wouldnt be free forever. Todays the last day to
pick up the Reagents app for free from the App Store! Get it before the price goes
up.

Todays reagent is one that most students have experience in making at some point or
another.Grignard reagents are formed by the reaction of magnesium metal with alkyl or

alkenyl halides. Theyre extremely good nucleophiles, reacting with electrophiles such as
carbonyl compounds (aldehydes, ketones, esters, carbon dioxide, etc) and epoxides.
Theyre also very strong bases and will react with acidic hydrogens (such as alcohols,
water, and carboxylic acids).
Similar to or the same as: very similar to organolithium reagents.
Examples:
Grignard reagents are made through the addition of magnesium metal to alkyl or alkenyl
halides. The halide can be Cl, Br, or I (not F). Its slightly easier to make Grignards from the
iodides and bromides, however. Note whats happening here the magnesium is inserting
itself between the carbon and the halide. This halide the X referred to when we refer to
Grignard reagents as RMgX.

One of the most common uses of


Grignard reagents is in their reaction with aldehydes and ketones to form alcohols. In the
first step, the Grignard forms the carbon-carbon bond. This results in an alkoxide (the
conjugate base of an alcohol). To form the alcohol, its necessary to add acid at the end of
the reaction (in whats called the workup step). This is shown here as H3O+ (the X is
just the counter-ion, a spectator here)

Th
e reaction behaves similarly with ketones. Again, theres nothing special about the Cl here
it all depends on how you made the Grignard in the first place.

Grignard
reagents will also add to esters. What makes these reactions a little more complicated is
that they add twice. The net result (after addition of acid) is a tertiary alcohol. This is also
the case for acid halides (acyl halides) and anhydrides. One notable exception is carboxylic
acids (more on that below).

An
other important reaction of Grignard reagents is that they will add to epoxides to form
carbon-carbon bonds. One thing to keep in mind here is that the tendency is for them to add
to theless substituted end of the epoxide that is, the less sterically hindered end. You can
think of this reaction as being essentially similar to an SN2 reaction. After addition of acid,
an alcohol is obtained.

Grignard reagents also add to carbon dioxide (CO2) to form carboxylates, in a reaction
similar to their reactions with ketones and aldehydes. The carboxylates are converted to
carboxylic acids after addition of acid (such as our trusty H3O(+) ).

Finally, since Grignard reagents are essentially the conjugate bases of alkanes, theyre also
extremely strong bases. This means that sometimes acid-base reactions can compete with
their nucleophilic addition reactions. One common situation where this crops up is when
Grignard reagents are added to carboxylic acids. Its easy to forget that carboxylic acids
are acids. This means that instead of adding to the carbonyl, they react with the proton
instead and form the carboxylate salt.

This can also be used to convert alkyl halides to alkanes. First you treat it with magnesium,
and then you treat the Grignard with a strong acid. This gives you the alkane. You can also
use this to introduce deuterium (D) into molecules! The first step is to make the Grignard

reagent. The second is to treat that Grignard with a deuterated acid such as D2O. This
gives you the deuterated alkane!
So how does it work? The key to the Grignard reagent is actually very simple. When you
think about the relative electronegativities of carbon (2.5) and magnesium (1.1), the bond
between carbon and magnesium is polarized toward carbon. That means that carbon is
more electron rich than magnesium and is actually nucleophilic! Heres a closer look.

In the reaction of Grignards with aldehydes, the carbon attacks the carbonyl carbon and
performs a 1,2-addition to give an alkoxide. In the second step, acid is added to give you
the alcohol.
There are so many other elements to the Grignard but a limited amount of space. So Ill
leave it there. If you want more details youll have to check out the Reagent Guide!
P.S. You can read about the chemistry of Grignard reagents and more than 80 other
reagents in undergraduate organic chemistry in the Organic Chemistry Reagent
Guide, available here as a downloadable PDF. The Reagents App is also available for
iPhone, click on the icon below!

Clemmensen Reduction

The Clemmensen Reduction allows the deoxygenation of aldehydes or ketones, to produce the
corresponding hydrocarbon.
The substrate must be stable to strong acid. The Clemmensen Reduction is complementary to the WolffKishner Reduction, which is run under strongly basic conditions. Acid-labile molecules should be reduced
by the Wolff-Kishner protocol.

Mechanism of the Clemmensen Reduction


The reduction takes place at the surface of the zinc catalyst. In this reaction, alcohols are not postulated
as intermediates, because subjection of the corresponding alcohols to these same reaction conditions
does not lead to alkanes. The following proposal employs the intermediacy of zinc carbenoids to
rationalize the mechanism of the Clemmensen Reduction:

Clemmensen reduction is a chemical reaction described as a reduction of ketones (or aldehydes)


to alkanes using zinc amalgam and hydrochloric acid.[1][2][3] This reaction is named after Erik Christian
Clemmensen, a Danish chemist.[4]

The Clemmensen reduction is particularly effective at reducing aryl-alkyl ketones,[5][6] such as those
formed in a Friedel-Crafts acylation. With aliphatic or cyclic ketones, zincmetal reduction is much
more effective.[7]

The substrate must be unreactive to the strongly acidic conditions of the Clemmensen reduction.
Acid sensitive substrates should be reacted in the Wolff-Kishner reduction, which utilizes strongly
basic conditions; a further, milder method is the Mozingo reduction. The oxygen atom is lost in the
form of one molecule of water.