Organic Compounds

Alkanes
Alkenes
Alcohols
Halogenoalkanes
Carbonyl Compounds
Carboxylic acids and Derivatives
Benzene Chemistry
Phenols
Alkanes
3
Alkanes
Contains carbon and hydrogen only
(hydrocarbons)
Contains no double bonds; no other atoms can be
added to carbon (saturated)
Chemically unreactive due to strong CC and CH
bonds ( bonds)
Do not react with acids, bases, or strong oxidizing
and reducing agents
Used as fuels - hydrocarbons with small
molecules make good because they are volatile,
flow easily and are easily ignited
4
Hydrocarbons
Preparation of Alkanes
Petroleum as a source of hydrocarbons by
fractional distillation and cracking
Crude petroleum is a complex mixture of
gaseous, liquid and solid hydrocarbons
such as alkanes , cycloalkanes, aromatics
(benzene) and some alkenes as well as
some compounds of oxygen, nitrogen and
sulphur

6
http://www.bbc.co.uk/schools/gcsebitesize/science/aqa_pre_2011/rocks/fuelsrev3.shtml
Fraction Size
Boiling-Point
Range (
0
C)
Uses
Gas C
1
to C
5
-160 to 30
Gaseous fuel,
production of H
2

Gasoline C
5
to C
7
25 to 75 Motor fuel
Naphtha C
6
to C
10
75 to 190
cracked to make
more petrol and
alkenes
Kerosene, fuel-
oil
C
12
to C
18
180 to 400
Diesel fuel,
furnace fuel,
cracking
Lubricants C
16
and up 350 and up Lubricants
Paraffins C
20
and up
Low-melting
solids
Candles, matches
Asphalt C
36
and up Gummy residues Surfacing roads
Reactions of Alkanes
1.Combustion
Alkanes undergo combustion in air; good fuels
2C
2
H
6(g)
+ 7O
2(g)
4CO
2(g)
+ 6H
2
O
(l)

0
H = 2855 kJ/mol
Complete combustion occurs in excess O
2
and produces
CO
2
and H
2
O
Incomplete produces a combination of CO and Carbon in
addition to water and carbon dioxide
Carbon dioxide contributes to global warming; Carbon
monoxide is toxic
9
Combustion Analysis
Avogadros Law
Equal volumes of all gases, under the same
conditions of temperature and pressure,
contain equal numbers of molecules

Gay-Lussacs Law
When gases react, they do so in volumes that
bear a simple ratio to one another and to the
volume of the product
Combustion Analysis (Method)
Fixed volume of hydrocarbon mixed with a fixed
volume of oxygen and the mixture ignited
The change in volume is determined
The new volume is due to steam (H
2
O), CO
2
and
excess O
2
The mixture cooled to room temperature (H
2
O
(l)
)
The mixture passed through sodium hydroxide
solution (CO
2
)
Remaining volume due to excess O
2
HW: Combustion Analysis
30 mL of a hydrocarbon is mixed with 180 mL of
O
2
and the mixture ignited. The resulting
mixture was cooled to room temperature and
the new volume determined to be 120 mL. After
passing the mixture through sodium hydroxide
the volume was reduced by 75%. Determine the
molecular formula of this compound.
12
Reactions of Alkanes (Cont'd)
2. Free Radical Substitution Reactions
In the presence of light alkanes undergo
substitution reactions with halogens
R-H + Cl
2
R-Cl + H-Cl
In substitution reactions, one atom of a
molecule is removed and replaced or
substituted by another atom or group of atoms
Mechanism of substitution reaction for alkanes
involves free radicals
13
Free Radical Substitution of Alkanes
14
For reaction to occur
between alkane and
chlorine, C-H and Cl-Cl
bonds must break

The C-H bond is stronger
than Cl-Cl bond,
therefore, the reaction
proceeds by first
breaking the Cl-Cl bond
Free Radical Substitution: Mechanism
Step 1: Initiation

15
UV light provides enough energy to break the halogen bond

Cl-Cl bond is broken via homolytic fission to produce radicals

Reactivity of halogens increases in the order of Br < Cl < F
Free Radical Substitution: Mechanism
16
The chlorine radical abstracts a hydrogen atom
from the alkane forming hydrogen chloride and
a free radical of the alkane
The alkyl free radical goes on to react with a
molecule of chlorine and regenerate another
chlorine free radical, and so on...
Free Radical Substitution of Alkanes
17
Two radicals combine to form neutral molecule
These steps stop the reaction (no new radicals formed to
propagate the reaction)
Step 3: Termination
Free Radical Substitution of Alkanes
Once initiated, the reaction can keep itself
going and is referred to as a chain reaction
The reaction gives a mixture of halogenated
products (halogenoalkanes/alkylhalides)
because more than one hydrogen can be
substituted
18
Reactions of Alkanes (Cont'd)
3. Cracking of Alkanes
Cracking is the name given to breaking up large
hydrocarbon molecules into smaller, more useful
molecules
Cracking can be achieved by:
using high pressures and temperatures without
a catalyst (thermal cracking) or
lower temperatures and pressures in the
presence of a catalyst (catalytic cracking)
19
http://www.chemguide.co.uk/organicprops/alkanes/cracking.html
Cracking of Alkanes (Cont'd)
Hydrocarbons are broken up in a random
manner to produce mixtures of smaller
hydrocarbons (eg. alkanes and alkenes)
20
Cracking of Alkanes (Cont'd)
21
Thermal cracking
High temperatures (typically in
the range 450 to 750
0
C) and
pressures (up to about 70
atmospheres) are used

Gives mixtures of products
containing high proportions of
hydrocarbons with double bonds
(alkenes)

Catalytic cracking
Modern cracking uses zeolites
(alumino silicates) as the catalyst

Zeolites are chosen to give high
percentages of hydrocarbons with
between 5 and 10 carbon atoms -
particularly useful for gasoline

produces high proportions of
branched alkanes and aromatic
hydrocarbons like benzene

http://www.chemguide.co.uk/organicprops/alkanes/cracking.html
Checkpoint: Alkanes
Q2.
a) Do you expect methane to react
with bromine in the dark?
b) Write a mechanism to show how
methane would react with bromine.
22
Review: Empirical and
Molecular Formulae
1. Define the following: a) Empirical Formula b) Molecular
Formulae c) Structural formula

2. 14.4 g of an alkane, when analyzed, is found to contain 12 g
carbon. What is its molecular formula?

3. A compound containing 85.71% C and 14.29% H has a
relative molecular mass of 56. Find its molecular formula.

4. 0.00382 mol of a hydrocarbon X was burnt in oxygen and
1.68 g of carbon dioxide was formed and 0.756 g of water
was formed.
a) Calculate the empirical formula of hydrocarbon X
b) Suggest a molecular formula for hydrocarbon X



Alkenes
24
Alkenes
Alkenes are hydrocarbons containing a C=C double
bond

Alkenes are called unsaturated molecules because
atoms can be added if double bond breaks; carbon
atoms are not bonded to the maximum number of
atoms they can be

Alkenes are extremely reactive and important
compounds in chemical industry and are converted
into useful compounds e.g. plastics and alcohols
25
Alkenes
26
Alkene contains at least one
double bond which forms
through one bond and one
bond

Pi electrons are loosely held and
readily react with electrophiles
or free radical

Alkenes are more reactive
compared to alkanes

Usually undergo addition
reactions in which the pi bond is
broken and two new groups are
attached to give a saturated
compound

Alkenes undergo Electrophilic Addition reactions
Key:
E
+
= electrophile
N
-
= nucleophile
Double bonds and electrophiles
The double bond of an alkene is an area of high electron
density, and therefore an area of high negative charge

The negative charge of the double bond may be attacked by
electron-deficient species (electrophiles), which will accept
a lone pair of electrons

These species have either a full positive charge or slight
positive charge on one or more of their atoms. They are
called electrophiles, meaning electron loving

Alkenes undergo addition reactions when attacked by
electrophiles. This is called electrophilic addition
Reactions of Alkenes
1. Reaction with bromine liquid (Br
2 (l)
)
Alkenes are unsaturated molecules

Bromine adds across the C=C double bond

Test used to distinguish between alkenes and alkanes;
Alkenes decolourise bromine liquid (in CCl
4
); red-brown
colour disappears

Product: dihalogenoalkane

Conditions: room temperature

http://www.chemguide.co.uk/mechanisms/eladd/symbr2.html
1. Reactions of alkenes with bromine
As Br
2
approaches the alkene it
becomes polarised by the pi
electron cloud; a dipole is
induced in the Br
2
molecule
What is the name of the
product that is formed?
The double bond attacks
the electrophilic end of
the molecule to form a
bromonium ion
A carbon in the bromonium
ion intermediate is now
attacked from the back by
the bromide ion

-

Examples:
C C
H H
H H Br Br
Br
2
Br
Br
CCl
4
CH
3
CH=CH
2
Cl
2
CCl
4
CH
3
CH
Cl
CH
2
Cl
C C
Br
H H
Br
H H
inert solvent (CCl
4
)
ethene
1,2-dibromoethane
* the red-brown colour of the bromine solution will fade and the
solution becomes colourless.
cyclohexene
1,2-dibromocyclohexane
propene
1,2-dichloropropane
Reactions of Alkenes
2. Reaction with aqueous bromine (Br
2 (aq)
)
Aqueous bromine contains Br
2
and H
2
O

The major product of the test is not 1,2-dibromoethane
(CH
2
BrCH
2
Br) but 2-bromoethan-1-ol (CH
2
BrCH
2
OH)

CH
2
=CH
2
+ Br
2
+ H
2
O CH
2
BrCH
2
OH + HBr

Bromine water used to test for unsaturation eg. alkenes




Reaction with aqueous bromine (Br
2 (aq)
)
Water is present in such a large amount (greater than Br
-
),
a water molecule (which has a lone pair) adds to one of
the carbon atoms, followed by the loss of a H
+
ion.
The major product of the test is not 1,2-dibromoethane
(CH
2
BrCH
2
Br) but 2-bromoethan-1-ol (CH
2
BrCH
2
OH).
Ethene is a symmetrical alkene it
gives the same carbocation
regardless which carbon of the
double bond, bromine attaches to
What if the alkene is
unsymmetrical? Which carbon does
bromine add to?
Reactions of Alkenes
3. Reaction with hydrogen halides (eg. HBr

)
Alkenes react with hydrogen halides (in gaseous state or in
aqueous solution) to form addition products

The hydrogen and halogen atoms add across the double bond
to form haloalkanes (alkyl halides)





Reactivity of hydrogen halides : HF < HCl < HBr < HI



Reaction of Ethene with HBr
Addition to unsymmetrical alkenes eg. prop-1-ene
When an electrophile (e.g. HBr)
attacks an alkene with three or
more carbon atoms (e.g.
propene), a mix of products is
formed. This is because these
alkenes are unsymmetrical
The major product can be predicted using Markovnikovs rule.
This states that when a substance HX reacts with an alkene, the major product is the
one in which the hydrogen atom is bonded to the carbon atom which bears the
greatest number of hydrogen atoms.
minor product:
1-bromopropane
major product:
2-bromopropane
+ HBr
Unequal amounts of each
product are formed due to
the relative stabilities of the
carbocation intermediates.
A chain of carbon atoms can be represented by R when
drawing organic structures. This is an alkyl group (general
formula C
n
H
2n+1
).
Primary (1) carbocations have
one alkyl group attached to the
positively-charged carbon.
Secondary (2) carbocations have
two alkyl groups attached to the
positively-charged carbon.
Tertiary (3) carbocations have
three alkyl groups attached to the
positively-charged carbon.
Structure of carbocations
The stability of carbocations increases as the number of alkyl groups
on the positively-charged carbon atom increases.
The stability increases because alkyl groups contain a greater
electron density than hydrogen atoms. This density is attracted
towards, and reduces, the positive charge on the carbon atom,
which has a stabilizing effect.
Stability of carbocations
increasing stability
tertiary primary secondary
ADDITION OF HYDROGEN HALIDES TO
UNSYMMETRICAL ALKENES AND
MARKOVNIKOVS RULE
CH
3
CH=CH
2
HCl
CH
3
CHCH
2
H Cl
CH
3
CHCH
2
Cl H
1-chloropropane
2-chloropropane
(major product)
according to Markovnikov's
rules
1
2 3
Propene
MECHANISM:
Step 1: Formation of carbocation
C C
H H
H CH
3
H Cl
C C
H H
H C
H
H
H
H
C C
H H
H C H
H
H H
or
less stable carbocation
(1
o
carbocation)
more stable carbocation
(2
o
carbocation)
Cl
-
- 2
o
carbocation is more stable than 1
o
carbocation.
- 2
o
carbocation tends to persist longer, making it more likely to combine with
Cl
-
ion to form 2-chloromethane (basis of Markovnikov's rule).
C C
H H
H C H
H
H H
Cl
-
Step 2: Rapid reaction with a negative ion
C C
H H
H C H
H
H H Cl
2-chloromethane (major product)
When HBr is added to an alkene in the absence of peroxides it
obey Markovnikovs rule

When HBr (not HCl or HI) reacts with unsymmetrical alkene in
the presence of peroxides or oxygen, HBr adds in the opposite
direction to that predicted by Markovnikovs rule

The product between propene and HBr under these conditions
is 1-bromopropane and not 2-bromopropane.
How would you get the anti-markovnikov product as
the major product?
CH
3
CH=CH
2
HBr CH
3
CH
2
CH
2
Br
peroxide
1-bromopropane
(major product)
anti-Markovnikov's orientation
Reactions of Alkenes
4. Reaction with concentrated H
2
SO
4

Hydration of alkenes to produce alcohols

What are conditions for the rxn to proceed?

Alkenes react with concentrated sulphuric acid in the
cold to produce alkyl hydrogensulphates

Follow by addition of hot water to form alcohol

For unsymmetrical alkenes, follow Markovnikovs rule



http://www.chemguide.co.uk/organicprops/alkenes/h2so4.html
4. Reaction of alkene with conc. H
2
SO
4

5. Hydrogenation of Alkenes
Hydrogen can be added to the carboncarbon double bond using a
nickel catalyst in a process called hydrogenation.
C
2
H
4
+ H
2
C
2
H
6

Vegetable oils are unsaturated and
may be hydrogenated to make
margarine, which has a higher
melting point.
As well as a nickel catalyst, this
requires a temperature of 200
C and a pressure of 1000 kPa.
Hydrogenation of alkenes
What are the conditions under which alkenes
are hydrogenated?

What is meant by hardening of fats?

Give one benefit of hydrogenating fats?

What are trans fats? How do they arise?

In some parts of the world trans fats have
been banned in restaurants. Why is this?

6. Oxidation of Alkenes
a) Reaction between alkenes and cold, acidified
KMnO
4

Solution changes from purple to colourless

Used as a test for alkenes
6. Oxidation of Alkenes
b) Reaction between alkenes and hot, acidified KMnO
4

















The double bond of the alkene is broken
Products may be carboxylic acids, ketones or CO
2
depends on
the alkene
C C
R
R
R'
H
C C H
R' R
OH
R
OH
KMnO
4
/H
+
C O
R
R
C O
H
R'
C O
R
R
C O
OH
R'
ketone acid
ketone
aldehyde
Example:
KMnO
4
/H
+
C
O
O
C
HO
4-methyl-4-octene
2-pentanone
butanoic acid
Under vigorous
conditions:
Diol is oxidized
further (C=C is
broken)

Aldehydes are
quickly oxidized to
carboxylic acids
For example, milder oxidation of an alkene produces
methanal and propanone. What is the structure of
the alkene?
DETERMINATION OF THE POSITION OF THE DOUBLE BOND
C
O
methanal
H
H C
O
CH
3
CH
3
propanone
C
H
H C CH
3
CH
3
C C CH
3
CH
3
H
H
remove the oxygen atoms from the carbonyl compounds and
joining the carbon atoms with a double bond.
2-methylpropene
Example:
An alkene with the molecular formula C
6
H
12
is oxidised with hot
KMnO
4
solution. The carboxylic acids, butanoic acid
(CH
3
CH
2
CH
2
COOH) and ethanoic acid (CH
3
COOH), are produced.
Identify the structural formula of the alkene.
C C
H
R
H
R'
CH
3
CH
2
CH
2
COOH and CH
3
COOH
C
O
OH
R
C
O
OH
R'
CH
3
CH
2
CH
2
CH=CHCH
3
KMnO
4
/H
+
i) cleavage of the double bond gives a mixture of carboxylic acids
ii) location of the double bond is done by taking away the oxygen atoms from the
carboxylic acids and then joining the carbon atoms by the double bond.
RCOOH and R'COOH RCH=CHR'
butanoic acid
ethanoic acid
2-hexene
Electrophiles: true or false?
Checkpoint: Structure of Carbocations
Checkpoint
1. Show the mechanism for the reaction
between cyclohexene and bromine.
What is the name of the product formed?

2. Write a mechanism to show how prop-1-ene
would react with
a) bromine water
b) concentrated sulphuric acid
Name the major and minor products in each
case.
Alcohols
Classification: CH
3
, 1
o
, 2
o
, 3
o





IUPAC Nomenclature:
parent = longest continuous carbon chain containing
the OH group.
alkane drop -e, add ol
Prefix: locant for OH (lower number for OH)
Alcohol: Physical Properties
hydrogen bonding due to OH group
relatively higher mp/bp
water insoluble (except for alcohols of three
carbons or less)
CH
3
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
-OH
hydrophobic end hydrophilic end

1. Oxidation of Alcohols
Oxidizing agents: KMnO
4
/H
+
(warm), K
2
Cr
2
O
7
/H
+
(warm)
Primary alcohols:




1. Oxidation of Alcohols
Oxidizing agents: KMnO
4
/H
+
(warm), K
2
Cr
2
O
7
/H
+
(warm)
Secondary alcohols:
Alcohol is oxidized to ketone
Ketone is not further oxidized




Tertiary alcohols:
No oxidation occurs
Very vigorous, extreme conditions for cleavage of 3
0
alcohol

Breathalyser Test
Breathalyser - device contains orange crystals of potassium
dichromate lightly soaked in dilute sulphuric acid

The suspected drunk driver is asked to exhale into the device

Alcohol in bloodstream means alcohol in breath

The alcohol vapour is oxidised by the crystals which are at the
same time reduced to the green Cr
3+
ion.

The intensity of the green colour is calibrated to alcohol
concentration in the blood which is shown as a digital readout.

2. Ester formation
Esters are alkyl salts of acids
Nomenclature: first part of the name comes from alcohol
(alkyl); second part comes from acid used (-oate)

3. Iodoform reaction
Used as qualitative tests for the presence of CH
3
(OH) or
CH
3
(C=O) group
Add iodine and NaOH to ethanol a yellow ppt (CH
3
I) is
obtained
Secondary alcohols containing the CH
3
(OH) group, a methyl
ketone and ethanol all react with iodine in alkaline solution to
form the yellow ppt


3. Iodoform reaction
Draw the structures for the compounds below and state
whether they would give a positive or negative test with the
iodoform reaction

1. propan-1-ol


2. butan-1-ol


3. butan-2-ol

4. Reaction with sodium metal

2C
2
H
5
OH + 2Na 2C
2
H
5
O
-
Na
+
+ H
2

sodium ethoxide
5. Reaction with concentrated sulphuric acid

C
2
H
5
OH C
2
H
4
+ H
2
O

With excess acid at 170 C, the corresponding alkene
is formed
6. Reaction with hydrogen halides (H-X)

Alcohols react with hydrogen halides to form the
corresponding alkylhalides

ROH + HX RX + H
2
O
alkylhalide

** Reaction with PBr
3
and PI
3
to form alkyl bromides and
alkyl iodides respectively (heating under reflux)
ROH + PBr
3
3RBr + H
3
PO
3

ROH + PI
3
3RI + H
3
PO
3

6. Reaction with hydrogen halides (contd)
Formation of alkylchlorides
3
0
alcohols react rapidly with concentrated hydrochloric
acid to form 3
0
alkylhalides; for 1
0
and 2
0
alcohols rxn
rates are too slow to be important

For 1
0
and 2
0
alcohols use PCl
5
(or PCl
3
)
eg. CH
3
CH
2
OH + PCl
5
CH
3
CH
2
Cl + POCl
3
+ HCl

Solid PCl
5
reacts violently with alcohols at room
temperature, producing clouds of hydrogen chloride gas
(white fumes); used as a test for -OH groups

SOCl
2
(in pyridine) may be used
http://www.chemguide.co.uk/organicprops/alcohols/halogen.html
Distinguishing between 1
0
, 2
0
and 3
0

alcohols
Reagent 1
o
alcohols 2
o
alcohols 3
o
alcohols
Acidified
potassium
dichromate
(K
2
Cr
2
O
7
/ H
+
)
Changes from
orange to green
Changes from
orange to green
Remains orange
Tollens Reagent
(or Fehlings
Reagent)
Silver mirror with
Tollens reagent or
brick-red ppt with
Fehlings reagent)
NO reaction with
either Tollens or
Fehlings reagent
NO reaction with
either Tollens or
Fehlings reagent
Lucas Reagent
(ZnCl
2
in conc.
HCl)
No visible reaction
Solution turns
cloudy in 3-5
minutes
Solution turns
cloudy immediately
Halogenoalkanes
(or Alkylhalides)

66
67
Halogenoalkanes
Alkyl halides are organic molecules containing a
halogen atom bonded to an sp
3
hybridized carbon
atom.






Aryl halides have the halogen atom attached directly
to the aromatic ring

68
Halogenoalkanes
Weak polar molecules
Exhibit dipole-dipole interactions due to polar CX
bond
www.chem.uky.edu/courses/che230/JH/Chapter%207%20Lecture.ppt

The Polar Carbon-Halogen Bond
69
The CX bond is polar,
making the carbon atom
electron deficient

The carbon bearing the
halogen is electrophilic
and susceptible to attack
by nucleophiles

Halogenoalkanes undergo
substitution reactions
when the electrophilic
carbon is attacked
70
Reactions of Halogenoalkanes
71
The electron deficient carbon is attacked by a nucleophile and the
halogen leaves as a halide ion
Nucleophilic Substitution Reactions of Alkylhalides
72
In a nucleophilic substitution reaction of RX:
the CX bond is heterolytically cleaved
the leaving group departs with the electron pair in that
bond, forming the halide ion, X:
the more stable the leaving group X:, the better able it
is to accept an electron pair
The Leaving Group
Leaving Group
73
1. Hydrolysis of Alkylhalides
Hydrolysis is achieved by heating the alkylhalide under
reflux with aqueous hydroxide
RX + OH
-
(aq)
-
ROH + X
-
Alcohols are formed
Primary and secondary alkyl halides undergo
alkaline hydrolysis to the alcohol
Tertiary alkyl halides are so reactive that they can be
hydrolysed by water to the alcohol; alkali not necessary
Aryl halides do not undergo hydrolysis except under
very severe conditions
http://www.chemguide.co.uk/mechanisms/nucsub/hydroxide.html

74
Alkaline Hydrolysis (Mechanism)
Mechanism can occur via:
(a) A stepwise mechanism (S
N
1)
or
(b) A concerted mechanism (S
N
2)

Primary Alkylhalides undergo S
N
2 mechanism
S= substitution; N = nucleophilic; 2 = bimolecular rate
determining step (i.e. 2 species involved in the rds)

Tertiary Alkylhalides undergo S
N
1 mechanism
1 = unimolecular rds(1 species involved in forming the
intermediate)

Secondary Alkylhalides can undergo either S
N
1 or S
N
2
75
S
N
2 Mechanism
Bond making and bond breaking are occurring at the
same time (concerted reaction mechanism)
Bimolecular Reaction: TWO species (alkylhalide
and nucleophile) are involved in the rate determining
step (RDS)
Rate = k[Nu
-
][alkylhalide]
76
S
N
2 Mechanism (contd)
Nucleophile attacks the electrophilic carbon from the
side that is opposite to the halogen (least hindrance)

This backside attack can result in inversion of
configuration if the halide leaving group is attached to a
stereocenter
What is a stereocenter?
77
S
N
1 Mechanism
Bond breaking occurs before bond making (step-
wise mechanism)
Unimolecular Reaction: One species
(alkylhalide) is involved in the rate determining
step (RDS)
Rate = k[alkylhalide]
78
S
N
1 Mechanism (cont'd)
Carbocation (planar) is formed as an intermediate
Nucleophile can, therefore, attack from either side
of the carbocation (no preference for either side)
What is the configuration of the product(s) formed
if the final product has a stereocenter?
79
S
N
1 Mechanism



Alkyl groups are electron donating groups and will stabilize the
positive charge on the carbocation (positive inductive effect)
The greater the number of alkyl groups attached to the carbon
bearing the positive charge, the more stable the carbocation will be
80
Summary: S
N
1 vs. S
N
2



81
2. Elimination Reactions of Alkylhalides
The alkylhalide is heated under reflux with a
concentrated solution of sodium or potassium
hydroxide in ethanol
Elimination of X and H from adjacent carbons to
produce an alkene
http://www.chemguide.co.uk/mechanisms/elim/elim.html#top

82
2. Elimination Mechanism for Alkylhalides
Concerted Mechanism

Both bonds (C-H and C-X) are breaking at the same time

83
2. Elimination Mechanism for Alkylhalides
Step-wise Mechanism

First: C-X bond breaks to form a carbocation

Second: C-H bond of the carbocation breaks to form an alkene

Homework
State all the possible products that could be
formed when the following halogenoalkanes
undergo elimination:

(a) 1-bromobutane

(b) 2-bromobutane

(c) 2-bromo-2-methylpropane
84
85
3. Reaction with Ammonia
R-X + NH
3 (alc)
R-NH
2
+ H-X
Alkylhalide and concentrated solution of ammonia in
ethanol are heated in a sealed tube
No reflux; ammonia gas would escape up condenser
The amines formed can react with more ammonia
A mixture of primary, secondary and tertiary amines
is obtained
The main product can be manipulated by controlling
the amounts of alkylhalide or ammonia used
http://www.chemguide.co.uk/organicprops/haloalkanes/nh3.html

86
3. Reaction with Amine (cont'd)
CH
3
I + NH
3
H-I + CH
3
NH
2

1
0
amine

CH
3
NH
2
+ CH
3
I H-I + (CH
3
)
2
NH
2
0
amine

(CH
3
)
2
NH+ CH
3
I H-I+ (CH
3
)
3
N
3
0
amine

(CH
3
)
3
N + CH
3
I (CH
3
)
4
N
+
I
-

4
0
ammonium salt

* In excess alcoholic ammonia, primary amine is the main product
**In excess alkyl halide, 4
0
ammonium salt is the main product
87
4. Reaction with CN
-
RX + CN
-
X
-
+ RCN
The halogenoalkane is heated under reflux with a
solution of sodium or potassium cyanide in ethanol
Alcohol dissolves the organic compound while the water
dissolves the sodium cyanide
Nucleophilic substitution mechanism where the halogen
is replaced by the CN
-
group
Product formed is a NITRILE
This method can be used to increase the carbon chain by
one carbon atom
Nitriles can be hydrolysed to carboxylic acids by heating
under reflux (under acidic or basic conditions)
Homework
Theoretically methane can be converted into
ethanoic acid via the following steps:

Step I CH
4
CH
3
Cl
Step II CH
3
Cl CH
3
CN
Step III CH
3
CN CH
3
COOH
State the reagents and conditions for each of
the steps.


88
Homework
For each of the following alkyl halides:
State what type of alkylhalides they are and
Indicate whether they would undergo S
N
1
or S
N
2 mechanism
(a) 2-chloro-2-methylpropane
(b) chloroethane
(c) 2-chloropropane
89

Carbonyl Compounds

90
Carbonyl Compounds
Refer to Aldehydes and Ketones
Contain C=O functional group

91
http://www.chemistryrules.me.uk/candrands/carbonyls.htm

Aldehyde
Ketone
Carbonyl Compounds
The carbon-oxygen double
bond is polar
Oxygen is more electronegative
than carbon, so electron density
is higher on the oxygen side of
the bond and lower on the
carbon side
Carbon is electron deficient;
susceptible to attack from
nucleophiles
The carbon-oxygen dipole can
be illustrated by two resonance
forms of a carbonyl group
Carbonyl Group
93
Oxygen is more electronegative
than carbon, and thus draws
electron density away from
carbon to increase the bond's
polarity

Carbonyl carbon is electrophilic;
carbonyl carbon is susceptible to
attack by nucleophiles eg. CN
-
,
H
2
O

Electronegative oxygen can react
with an electrophile eg. H
+


Homework
Rank the following according to increasing
boiling points. Explain your reasoning.
1. Alkanes
2. Aldehydes and ketones
3. Alcohols

95
Identification of Aldehydes and Ketones
2,4-Dinitrophenylhydrazine (DNPH, Bradys reagent)
can be used to qualitatively detect the carbonyl
functionality





Bradys reagent is prepared by dissolving 2,4-DNPH in a
solution containing methanol and some concentrated
sulfuric acid

Structure of 2,4-DNPH
96
A positive test with 2,4-DNPH is signaled by a yellow,
orange or red precipitate (dinitrophenylhydrazone )
Dinitrophenylhydrazone is a condensation product





Identification of of Aldehydes and Ketones
http://www.knockhardy.org.uk/sci_htm_files/08ald.pdf
97






If the carbonyl compound is aliphatic, then the
precipitate will have a more yellow color
If aromatic, then the precipitate will be red

Identification of of Aldehydes and Ketones
http://www.chemguide.co.uk/organicprops/carbonyls/addelim.html

Distinguishing between Aldehydes and
Ketones
Use a mild oxidizing agent to distinguish between
aldehydes and ketones:
Tollen's Reagent
Ammoniacal silver nitrate containing [Ag(NH
3
)
2
]
+
Ag
+
(aq)
+ e
-
Ag(s)
Fehling's Reagent
Contains Cu
2+
ions
Cu
2+
is reduced to a red ppt, Copper (I) oxide (Cu
2
O)
98
99 **2,4-DNPH -2,4-dinitrophenylhydrazine
Distinguishing between Aldehydes and Ketones
Reagent Aldehyde Ketone
2,4-DNPH (Bradys reagent)
Yellow or light
orange ppt
Yellow or light
orange ppt
Tollens reagent
Silver mirror on
inside of test-tube
No visible change

Fehlings reagent


Brick-red ppt


No ppt formed

Reactions of Carbonyl Compounds
100
1. Nucleophilic Addition reactions
Carbonyl carbon is attacked by the
nucleophile
The negatively charged oxygen now
has the capacity to act as a
nucleophile

2. Condensation reactions (Addition-
elimination reactions
Addition reaction is followed by the loss
of a small molecule such as H
2
O
Carbonyl Reactions (Oxidation)
1. KMnO
4
/H
+
Aldehyde: oxidised to carboxylic acids
Ketone: resistant to oxidation

2. Tollens reagent / Fehlings reagent
Aldehyde: Silver mirror with Tollens reagent;
brick-red ppt seen with Fehlings reagent
Ketone: No Reaction

101
Carbonyl Reactions (Reduction)
3. LiAlH
4
(in dry ether)
Aldehyde: reduced to the primary alcohol
Ketone: reduced to the secondary alcohol

4. H
2
/Pt
Aldehyde: reduced to the primary alcohol
Ketone: reduced to the secondary alcohol



102
Carbonyl Reactions
5. Hydrogen cyanide (NaCN/HCl)
Nucleophilic addition reaction
H and CN
-
cyanide adds across the carbon-oxygen double bond to
form Cyanohydrin (or hydroxynitrile)
Source of CN
-
can be KCN or NaCN (HCN is rarely used; too toxic to
work with)




103
Carbonyl Reactions
5. Reaction with NaCN/HCl (continued)





104
Cyanohydrin (or hydroxynitrile) contain both an OH group
and a CN group
Mechanism of Nucleophilic
Addition to Carbonyl Group
Example: HCN + propanone
Step 1: nucleophilic attack by the cyanide ion
on the partially positive carbon atom (CN
-

adds to carbon; pi bond breaks)

105
Mechanism of Nucleophilic
Addition
Step 2: a negative ion is formed which
abstracts a hydrogen ion from a hydrogen
cyanide molecule to form a cyanohydrin

106
Mechanism of Nucleophilic
Addition to Carbonyl Group
Example: HCN + ethanal
In the first stage, there is a nucleophilic attack
by the cyanide ion on the slightly positive
carbon atom

107
Mechanism of Nucleophilic
Addition


108
The negative ion formed then abstracts a hydrogen
ion from a hydrogen cyanide molecule to form a
cyanohydrin
Carbonyl Reactions
6. Haloform / Iodoform Reaction
This reaction is used to test for the presence of :
secondary alcohol with adjacent methyl group
methyl ketone
Reagents:
I
2
and NaOH
Observations for positive reaction:
fine yellow crystals (iodoform) with characteristic hospital
smell
109
110
111


112
Carboxylic Acids and
their Derivatives
113
Benzene Chemistry
Benzene Chemistry
114
Benzene - Kekule Structure
Molecular formula :
C
6
H
6
Carbons are arranged
in a hexagon with
alternating double and
single bonds between
them
Each carbon atom has
a hydrogen attached to
it
Benzene Chemistry
115
Problems with Kekule Structure of Benzene
Physical Properties C-C Bond length
X-ray diffraction studies show bond only one bond
length for C-C bonds (0.139 nm)


Chemistry
Benzene has double bonds but it does not
undergo addition reactions like alkenes
Benzene undergoes substitution reactions by
replacement of hydrogen
C-C 0.154 nm
C=C 0.134 nm





Benzene Chemistry
116
Problems with Kekule Structure of Benzene
Stability



Benzene Chemistry
117
Problems with Kekule Structure of Benzene
Stability (cont'd)
increase in stability of benzene is
known as the delocalisation energy or
resonance energy of benzene
real benzene is about 150 kJ mol
-1
more stable than the Kekul structure



Benzene Chemistry
118
So what does Benzene really look like...
The p electron on each
carbon atom is
overlapping with those on
both sides of it
Extensive sideways
overlap produces a
system of delocalised pi
electrons which are
spread out over the
whole carbon ring
Six delocalised electrons

http://www.chemguide.co.uk/basicorg/bonding/benzene1.html
Benzene Chemistry
119
Relating the orbital model to properties of
benzene
Shape
planar regular hexagon(bond angle 120)
because all the bonds are identical
no alternating double and single bonds
planar to allow p orbitals to overlap sideways to
give the delocalised pi system
Energetic Stability
hhhhh
Stability
120
Phenols