MEDICAL UNIVERSITY - PLEVEN

FACULTY OF MEDICINE
DISTANCE LEARNING CENTRE

DEPARTMENT OF „CHEMISTRY & BIOCHEMISTRY“

LECTURE № 25

FOR E-LEARNING IN „CHEMISTRY“

FOR MEDICAL STUDENTS

TITLE: HYDROCARBONS AND HALOGEN DERIVATIVES

PREPARED BY Prof. A. Stoyanova, PhD

PLEVEN, 2020
 HYDROCARBONS AND HALOGEN DERIVATIVES. FUNDAMENTAL TYPES OF
ORGANIC REACTIONS
I. Organic chemistry
The term organic was first used about 1777 to describe compounds occurring in or
derived from living organisms. Such substances as starch, alcohol and urea were
classified as organic, for starch is produced by living plants, alcohol is a product of
fermentation caused by microorganisms and urea is contained in urine. In 1828, however,
the German chemist Friedrich Wohler synthesized urea from materials obtained from
inanimate sources, and the original meaning of organic was no longer applicable. Organic
compounds, in the modern sense, are compounds of carbon that contain either carbon-
carbon bonds, or carbon-hydrogen bonds or both. Thousands of carbon compounds not
found in or derived from living organism have been produced by chemists and about five
million organic compounds have been characterized.
That so many organic compounds exist is due primarily to the ability of carbon atoms
to combine with other carbon atoms, forming chains of different length and rings of
different sizes. As pointed out previously, carbon forms covalent bonds in compounds, with
all of its valence electrons usually used in the bonding. It exhibits sp3, sp2 or sp
hybridization of its atomic orbitals. Carbon thereby displays a coordination number of 4, 3
or 2 with a tetrahedral, trigonal planar or linear geometry. Examples are C 2H6 (ethane),
C2H4 (ethylene), or C2H2 (acetylene) respectively.
Other than carbon, the elements most frequently found in organic compounds are
hydrogen, oxygen, nitrogen, sulfur, halogens, phosphorus, and some of the metals.

II. Classification of organic compounds

II.1. Basic classification
Organic compounds can be divided into two major groups. They are open chain or
acyclic compounds and cyclic compounds. In the former type, the carbon atoms in the
compounds are linked one after the other so that a chain is formed, while in the latter they
are arrange in the ring form. The open chain compounds are also known as aliphatic
compounds.
Cyclic compounds are further divided into carbocyclic or homocyclic compounds and
heterocyclic compounds. Carbocyclic compounds consist of rings made up of only carbon
atoms. The number of carbon atoms in the ring may differ. It can be 3, 4, 5, 6 etc. The
remaining valences of the carbon atoms in the ring may be joined with other atoms or
groups. When this ring contains three double bonds, which are alternately placed, an
important group of carbocyclic compounds is obtained. They are known as aromatic
compounds. Heterocyclic compounds contain rings composed of one or more atoms other
than carbon atom. Such atoms are known as hetero atoms. Usually nitrogen, oxygen and
sulphur function as hetero atoms.
The above classification of organic compounds can be summarized as follows:

Page 2 of 16 pages
 Organic compounds

Open chain or acyclic Cyclic compounds

compounds (Aliphatic)

Homo cyclic compounds Heterocyclic compounds

Alicyclic compounds Aromatic compounds

II.2. Functional groups

On the basis of properties organic compounds can be separated into families or
series. A particular family contains a large number of compounds and these compounds
have a characteristic group possesses certain properties. The presence of such groups in
a molecule gives it the properties which are characteristic of the group. Therefore the
study of organic chemistry is essentially the study of a number of characteristic groups.
These characteristic groups are known as functional groups. A functional group is an
aggregate of one or more atoms in a molecule whose presence confers upon the molecule
a unique chemical property, characteristic listing of the common functional groups with the
appropriate prefix and suffix used to designate each one.

Table II.2.1. Functional groups as prefixes and suffixes

Group Prefix Suffix
-COOH carboxy- -oic acid
-carboxylic acid
-SO3H sulfo- -sulfonic acid
-COOR alkoxycarbonyl- -carboxylate
-COCl chloroformyl- -oyl chloride
-carbonyl chloride
-CONH2 carbamoyl- -amide
-carboxamide
-CN cyano- -nitril
-carbonitril
-CHO formyl- -al
oxo- -carbox aldehyde
-carbaldehyde
C=O oxo- (IUPAC) -one
keto- (common)
-OH hydroxy- -ol

Page 3 of 16 pages
 -SH mercapto- -thiol
-NH2 amino- -amine
-C  C- - -yne
-C = C- - -ene
-Cl chloro- -

II.3. Homologous series

If we examine the molecular formulae of various compounds in each family, we can
find that each member differs from the one just before or after it by one CH2 group. A set
of such compounds in which the members differ by a CH2 group is known homologous
series. The individual member is known as a homologue. A homologous series can be
represented by a general formula. The individual members can be prepared by similar
methods and they show same chemical properties and graded physical properties.
As example for homologous series paraffins, alcohols, aldehydes, acids and amines
could be cited:

Name of the series General formula Examples

Alkanes CnH2n+2 CH4, C2H6, C3H8 etc.
Alkens CnH2n C2H4, C3H6, C4H8 etc.
Alkynes CnH2n - 2 C2H2, C3H4, C4H6 etc.
Alcohols CnH2n+1OH CH3OH, C2H5OH, C3H7OH etc.
Aldehydes CnH2n+1CHO CH3CHO, C2H5CHO, C3H7CHO etc.
Acids CnH2n+1COOH CH3COOH, C2H5COOH, C3H7COOH etc.
Amines CnH2n+1NH2 CH3NH2, C2H5NH2, C3H7NH2 etc.
n= a whole number

III. Nomenclature of organic compounds

There are different systems by which organic compounds can be named; of which
one is known as trivial system and another IUPAC system. In trivial system the compound
is named on the basis of its origin. In the second system of naming, the rules are
recommended by the commission on the Nomenclature of Organic chemistry of the
International Union of Pure and Applied Chemistry.
By using these systems, we can name some simple organic compounds of different
families.

III.1. Hydrocarbons
In the trivial system, the straight chain compounds are always designated as normal
CH3
CH
CH3
compounds. If the compound contains the grouping , it is known as the iso-
compound.
The names of saturated hydrocarbons end in -ane. The first four hydrocarbons have
special names; from fifth onwards - Greek numerals are used to indicate the number of
carbon atoms in the molecule:
CH4 - methane CH3 - methyl
C2H6 - ethane C2H5 - ethyl
C3H8 - propane C3H7 - propyl
C4H10 - butane C4H9 - butyl
Page 4 of 16 pages
C5H12 - pentane C5H11 - pentyl
C6H14 - hexane C6H13 - hexyl
In the IUPAC system, the name of saturated hydrocarbon ends in -ane as in the
trivial system. If the hydrocarbon contains a substituent group, then the naming is done as
follows: Chose the longest chain, containing the substituent and the compound is named
as a derivative of this hydrocarbon. The carbon chain is numbered from one end to the
other. The direction of numbering is so chosen as to give the lowest number possible to
the substituent carrying carbon atom. Now the name of the substituent with the number of
its position is prefixed to the name of the hydrocarbon.
1 2 3
CH3 CH CH3
CH3
e.g. 2-methyl propane
4 3 2 1
CH3 CH2 CH CH3
CH3
2-methyl butane
The name of the unsaturated hydrocarbons of the alkene series ends in -ylene
according to the common naming system and in -ene according to IUPAC system
common name IUPAC name
e.g. C2H4 ethylene ethene
C3H6 propylene propene
The name of the alkyne series ends in -yne.
Thus C2H2 is ethyne (acetylene).

III.2. Other compounds

The simpler alcohols are known by their trivial names. In the IUPAC system the class
suffix is -ol.
CH3OH - methyl alcohol, methanol
C2H5OH - ethyl alcohol, ethanol

One method of naming aldehyde is to name them after acids that they form on
oxidation. According to IUPAC system class suffix is -al which is added to the name of the
hydrocarbon from which they are derived.
HCHO - formaldehyde, methanal
CH3CHO - acetaldehyde, ethanal

The trivial names of some carboxylic acids are

HCOOH - formic acid
CH3COOH - acetic acid
According to IUPAC system, the suffix of the monocarboxylic acids is -oic which is
added to the name of the alkane corresponding to the longest chain containing the
carboxy group, e.g.
HCOOH - methanoic acid
CH3COOH - ethanoic acid
More details about the nomenclature of organic compounds must be left to other
texts. However, in spite of the advantages of the IUPAC nomenclature, in biochemistry the
trivial names of biomolecules are preferred and almost always used for simplicity and
shorter communications.
Page 5 of 16 pages
 IV.Hydrocarbons
IV.1. Classification and characteristic
One large class of organic compounds, whose molecules contain atoms only of
carbon and hydrogen are the hydrocarbons. The hydrocarbons are the simplest organic
compounds and they are the basic building blocks from which all other organic compounds
can be formed. Many hydrocarbons are found in plants, animals and their fossils, other
hydrocarbons have been prepared in the laboratory. Several types of hydrocarbons have
been characterized.

1. Alkanes and cycloalkanes

Saturated hydrocarbons contain only single covalent bonds. All of the carbon atoms
in a saturated hydrocarbon have sp3 hybridization and are bonded to four other carbon or
hydrogen atoms. Saturated hydrocarbons of one series have the general molecular
formula CnH2n+2, where n is an integer and are called alkanes, or paraffins (from the Latin
for having little affinity, or being not very active).
With the exception of methane each of the alkanes contains a chain of carbon atoms.
All of the carbon atoms are sp3 hybridized and bonded either to other carbon atoms or to
hydrogen atoms by single bonds. A carbon atom, bonded to only one other carbon atom is
a primary carbon (I); this, bonded to two other carbon atoms is called secondary carbon
(II); and a carbon atom, carbon (III) and a carbon atom bonded to four other carbon atoms
is quaternary (IV). For example:
H H H H H
I III II II I
H C C C C C H
H H H H
I
H C H
H 2-methyl pentane
A substituent that contains one hydrogen atom less than the corresponding alkane is
called an alkyl group. The name of an alkyl group is obtained by dropping the suffix -ane of
the alkane name and adding -yl. For example, methane becomes CH3- methyl and ethane
becomes C2H5- ethyl.
The members of a second series of saturated hydrocarbons have the general
molecular formula CnH2n, where n is an integer and are called cycloalkanes. As the name
implies, the molecules of these substances are cyclic (possessing rings).
Structural isomerism and conformation isomerism are characteristic for alkanes and
cycloalkanes.
The reactions of alkanes and cycloalcanes all involve the breaking of C - H or C - C
single bonds - substitution reactions, pyrolisis, cracking and combustion processes.

2. Alkenes and cycloalkenes

Hydrocarbon molecules that contain a double bond are members of another series
called alkenes. The two carbon atoms linked by a double bond are bound together by two
bonds, one  bond and one  bond. The alkenes have the general molecular formula
CnH2n.

Page 6 of 16 pages
 The carbon atoms involved in single bonds in alkenes have sp3 hybridization, and
those in double bonds have sp2 hybridization. Thus, the geometry around the carbon
atoms at the double bonds is trigonal planar.
Except of structural isomerism, geometrical or cis-trans isomerism is characteristic for
alkenes.
Alkenes are much more reactive than alkanes. A  bond, being relatively weaker
bond, is disrupted much more easily than a  bond. Thus the reaction characteristic of
alkenes is a type in which the  bond is broken and replaced by two  bonds. Such a
reaction is called an addition reaction.
The cycloalkenes are similar to the cycloalkanes, but they have two carbon atoms
linked by a double bond and possess reaction characteristic of the alkenes.
3. Polyenes
Unsaturated hydrocarbons, in which there are more than one double bonds, are
called polyenes. Polyenes in which the double bonds are separated by single bonds are
called conjugated polyenes. Polyenes in which two or more single bonds separate the
double bonds are called unconjugated polyenes. The polyenes with two double bonds are
dienes, with three double bonds trienes, etc.

4.Alkynes
Hydrocarbon molecules with a triple bond are called alkynes; they make up another
series of unsaturated hydrocarbons. Two carbon atoms joined by a triple bond are bound
together by one  bond and two  bonds. The alkynes have the general molecular formula
CnH2n - 2.
Chemically, the alkynes are similar to the alkenes, except having two  bonds, they
react even more readily, adding twice as much reagent in addition reactions.

5. Aromatic hydrocarbons
Benzene, C6H6, is the simplest member of a large family of hydrocarbons, called
aromatic hydrocarbons that contain ring structures. The benzene molecule contains a
hexagonal ring of sp2 hybridized carbon atoms with the unhybridized p orbital of each one
perpendicular to the ring. Three valence electrons in the sp2 hybrid orbitals of each carbon
atom and the valence electron of each hydrogen atom form the framework of sigma bonds
in the benzene molecule. The unhybridized carbon p orbitals, each with one electron
combine to form  bonds. The electrons in the  bonds are delocalized around the ring.
Since the  electrons are delocalized, benzene does not have alkene character. Each
bond between two carbon atoms in neither a single nor a double bond, but is equivalent to
the others.
H o
H
C C
H
H 120
H
C o
H
C 120 0.140 nm
H

H H
C C 0.108nm
H H H

The property which makes aromatic rings especially stable is referred to as

aromaticity or aromatic character. In order to preserve this structure, the molecule
undergoes mainly substitution reactions, in which one or more hydrogens on the aromatic
ring are replaced with other atoms or groups of atoms.

Page 7 of 16 pages
 IV.2. Representatives with medico-biological importance
1. Alkanes and cycloalkanes
Alkanes - the first 10 members of the homologous series.
The most abundant sources of alkanes are natural gas and petroleum deposits,
formed over a period of millions of years by the decay of organic matter in the absence of
oxygen.
With the exception of the alkanes that are readily available from petroleum, alkanes are
synthesized in the laboratory and in industry by the hydrogenation of alkenes.

Cycloalkanes:
CH2
H2 C H2 C CH2 H2 C CH2
H2 C CH 2
H2 C CH2 H2 C CH2
H2 C CH2 H2 C CH 2 CH2 CH2
cyclopropane cyclobutane cyclopentane cyclohexane

2. Alkenes and cycloalkenes

Alkenes - CH2=CH2 - ethene (ethylene); CH2=CH-CH3 - propene (propylene)

CH2 HC CH
HC CH2

H2C CH2
HC CH2
CH2 CH2
Cycloalkenes - cyclohexene cyclopentene

3. Dienes
H2C=CH-CH=CH2 - butadiene (1,3-butadiene)

H2 C C CH CH2
CH3
- isoprene (2-methyl-1,3-butadiene)

4. Alkynes
HC  CH - ethyne (acetylene) HC C-CH3 propyne

5. Aromatic hydrocarbons
CH3
CH3 CH CH2 CH3 CH3

CH3
CH3
CH3
benzene toluene styrene o-xylene m-xylene p-xylene

Page 8 of 16 pages
 CH

CH2

biphenyl diphenylmethane triphenylmethane

naphthalene anthracene phenanthrene 3,4-benzpyrene

6. Biological importance
The heavier liquid alkanes have properties more like the naturally occurring body oils.
When applied to the skin, mixtures such as mineral oil act as softeners by replacing the
natural skin oils lost in repeated contact with water. Petroleum jelly, a mixture of high
molecular weight liquid and solid alkanes, is used as both a skin softener and protective
film.
There are also many other examples showing the usefulness of hydrocarbons but,
the medal has also its reverse side. Especially, hydrocarbons, containing multiple benzene
rings are obtained in the production of coal tar. Their harmful effects to humans became
evident, when workers in European coal tar factories developed skin cancer. A later study
of the chemical components of coal tar determined that several aromatic fused-ring
compounds could cause cancer in mice. Chemicals that cause cancer in animals are
known as carcinogens. All the carcinogenic hydrocarbons in coal tar have a similar
arrangement of fused benzene rings. These compounds are formed in the partial
combustion of many large organic molecules. One of the most active carcinogens, 3,4-
benzpyrene, is discharged in very large quantities into the atmosphere from industrial
nations. It is also one of the major carcinogens found in cigarette smoke. Only a few
milligrams of 3,4-benzpyrene is enough to produce cancer in experimental animals.

V.Halogen derivatives of hydrocarbons

V.1.Characteristic and classification
The halogen derivatives of hydrocarbons are regarded as formed through
substitution of hydrogen atoms with halogen atoms. Halogen derivatives are classified
according to the following criteria:
a) type of the halogen atoms - fluorine, chlorine, iodine and mixed derivatives;
b) number of halogen atoms in the molecule - mono-, di- and polyhalogen
derivatives;

Page 9 of 16 pages
 c) type of the hydrocarbon radical - derivatives of saturated, unsaturated and
aromatic hydrocarbons. Aromatic halogen compounds are of two types; one in which the
halogen is substituted in the benzene nucleus and the other in which the halogen is
present in the side chain.
The names of the derivatives are formed in the following way: the halogen element is
stated first, numbers show the places of the halogen atoms and the prefixes di-, tri- etc.
give the number of atoms of a definite kind. The prefix mono- is usually omitted and if this
does not bring to ambiguity the numbers are also omitted.
Halogen derivatives are reactive substances and take part in a variety of reactions
because of the high polarity of the C - X bond.
In substitution reactions, the halogen derivatives of hydrocarbons react with polar
and ionic compounds. Halogen atoms can be replaced by various atomic groups. New
classes of organic compounds are obtained.
Elimination reactions generally involve the loss of atoms or atomic groups from a
molecule. New compounds are formed. They have double or triple bond or a ring.

V.2. Representatives with medico-biological importance

CHCl3 - trichloromethane (chloroform) and CCl4 - tetrachloromethane are colorless
liquids used as solvents. Trichloromethane (chloroform) is used in anesthesiology but it is
toxic and its application in this field is already restricted. Tetrachloromethane does not
burn and is used to extinguish small fires.
CHI3 - triiodomethane (iodoform). It is in form of yellow crystals smelling of iodine. It
decomposes slowly in the air and liberates iodine which kills microorganisms. It is used for
wound treatment.
Hexachlorocyclohexane (hexachlorane) is used
widely in agriculture and in household as insecticide. Nine CHCl
stereo-isomers of hexachlorocyclohexane are known. Only Cl HC CH Cl
one of them is a strong insecticide; the others are inactive.
The commercially available hexachlorane preparations are Cl HC CHCl
CHCl
mixtures of isomers and their quality is determined by the
content of the active isomer.
Dichlorodiphenyltrichloroethane (DDT) was a Cl
synthetic product that proved to be a highly effective
Cl C Cl
insecticide, causing death both on contact and by
ingestion. It also had very low toxicity to mammals. DDT is Cl C Cl
odorless and tasteless and it is chemically very stable - a
H
property that to be its greatest drawback.

CCl2F2 - difluoro-dichloro-methane and other completely halogenated (fluorine-

chlorine) derivatives of hydrocarbons are easily liquefied. They are used in household and
they are components of aerosol preparations (they create the pressure in “spray”-type
packings).
There are serious grounds to think that Freon is ecologically dangerous air pollutant.
It is proved that Freon presence in the high atmosphere layers is the cause of destruction
of its ozone layer, which retains some of the solar radiation. Because of the “ozone holes”,
rays of high energy, dangerous to living organisms, reach Earth’s surface. In some
countries the use of Freon in sprays is already prohibited.

Page 10 of 16 pages
Fundamental types of organic reactions
• Addition reactions
• Substitution reactions
• Elimination reactions
• Rearrangement reactions

Addition reactions
Addition reactions occur when two starting materials add together to form only one
product with no atoms left over. In an addition all parts of the adding reagent appear in the
product - two molecules become one.
A + B → A-B
CH2 CH2 + Br2 CH2 CH2
Br Br
1,2-dibromoethane

Br
CH3 C CH CH3 + H Br CH3 C CH2 CH3
CH3 CH3
2-methyl-2-butene 2-bromo-2-methylbutane* Markovnikov's Rule

Substitution reactions
Substitution reactions occur when two starting materials exchange groups to form
two new products.
The atoms and atomic groups of the initial molecules are replaced by other atoms or
atomic groups.
A-В + C-D → A-C + B-D
h
CH4 + Cl Cl CH3Cl + HCl
methane chloromethane

H Br
FeBr3
+ Br - Br + HBr

benzene bromobenzene

CH3-C O + C2H5 O-H CH3- C O + HCl

Cl O C2H5

Elimination reactions
Elimination reactions are the opposite of addition reactions. A single reactant is split
into two products.

A-B → A + B

Page 11 of 16 pages
Elimination reactions give a method for preparing compounds with double and triple
bonds.
H H H H
H2SO4
H C C OH 170 oC
C C + H2O
H H H H
ethanol ethene
Addition and elimination reactions are exactly opposite. A  bond is formed in elimination
reactions, whereas a  bond is broken in addition reactions.
elimination

- XY
H H H H
C C
H C C H
H H
X Y + XY
addition

Rearrangement reactions
Rearrangement reactions occur when the original molecule forms a product with a
different arrangement of atoms and bonds. A molecule undergoes reorganization of its
constituent parts.
Heating the alkene with a strong acid causes the formation of another isomeric
alkene. The position of the double bond, methyl group and hydrogen has shifted:

H H H+ H3C CH3
H3C C C C C
C H H3C CH3
H3C
CH3 2,3-dimethyl-2-butene
3,3-dimethyl-1-butene

vinyl alcohol acetaldehyde

Basic concepts of organic reactions mechanisms

An overall description of how a reaction occurs is called a reaction mechanism. A
mechanism describes in detail exactly what takes place at each stage of a chemical
transformation - which bonds are broken and in what order, which bonds are formed and in
what order.
Bonds can be broken symmetrically (one electron remains with each product
fragment) - homolytic cleavage
A : B → A· + ·B
radicals
or

Page 12 of 16 pages
unsymmetrically (bonding electrons remain with one product fragment) - heterolytic
cleavage
A : B → A+ + :B-
ions

Just as there are two ways in which a bond can break, there are two ways in which a
covalent two-electron bond can form.

Free Radical Reactions

The term free radical refers to any atom or group of atoms with an odd number of
electrons. Even though a free radical does not have a “+” or “-“ charge, such a species is
highly reactive. A classic example a reaction that involve a free radical is halogenation of
alkanes in the presence of light (hv) .

Cl. + . Cl
h
Initiation
Cl : Cl (step 1)

Propagation
CH4 + . Cl .CH3 + HCl (step 2)

H3C. + Cl2 H3C .. Cl + . Cl (step 3)

Termination
H3C. + . Cl CH3Cl (step 4)
H3C. + .CH3 C2H6 (step 5)
Cl. + . Cl Cl2 (step 6)

Polar Reactions
Polar reactions occur between oppositely charged species, cations and anions, or
between an electron deficient and an electron rich species. In referring to the electron-rich
and electron-poor species involved in polar reactions, the terms nucleophile and
electrophile are used.
A nucleophile is a substance that has a negatively polarized, electron-rich, atom and
can form a bond by donating a pair of electrons to a positively polarized, electron poor
atom.
Nucleophiles can be either neutral or negatively charged. Typical nucleophiles are:
H2O, :NH3, :OH−, :OR−, :C≡N−, :SH−

An electrophile has a positively charged, electron poor atom and can form a bond by
accepting a pair of electrons from a nuc leophile. Electrophiles are Lewis acids because
thy accept electrons.

Electrophiles can be either neutral or positively charged.

Typical electrophiles are:

Page 13 of 16 pages
hydronium ion (H3O+), boron trifluoride (BF3), aluminum chloride (AlCl3), carbocation

R C R
R .

*Neutral compounds can often react either as nucleophiles or as electrophiles, depending

on the circumstances.

Mechanism of electrophilic addition reaction to alkenes

Bromination of ethene
The bromine is a very "polarisable" molecule and the approaching pi bond in the ethene
induces a dipole in the bromine molecule.
The induced polar bond in bromine molecule is cleaved to form bromide cation and
bromide anion.
The bromide cation attaches itself to the molecule of ethene - a reactive carbocation is
formed.
The carbocation reacts rapidly with the bromide anion and the end product – 1,2-
dibromoethane is formed.
+
CH2 CH2 CH2 CH2 CH2 CH2
+
Br Br Br- Br Br
induced 1,2-dibromoethane
_
dipole
Br 

Electrophilic addition reaction with hydrogen bromide

+
CH2 CH2 CH2 CH2 CH2 CH2
+ H Br- H Br
H
_
bromoethane
Br 

Electrophilic substitution reactions

Electrophilic substitution happens in many of the reactions of compounds containing
benzene rings - the arenes.
Because of the delocalised -electrons benzene molecule is highly attractive to
electrophiles.
In most of benzene's reactions, the electrophile is a positive ion, and these reactions all
follow a general pattern.
Bromination of benzene mechanism
FeBr3 + Br:) Br [FeBr4]- + Br+
sp2 3
Br
Br+ sp
Br
+ Br+ + H Br:
+ HBr
6 е- -complex
6 е-
4 e-
Page 14 of 16 pages
Nucleophilic addition to aldehydes and ketones
The mechanism for the addition of HCN
In the first stage, there is a nucleophilic attack by the cyanide ion on the slightly positive
carbon atom.

_
 O H_ CN OH
+ O
CH3 C
_
CH3 C H CH3 C_ H + CN
H CN CN
CN

The negative ion formed then picks up a hydrogen ion from somewhere - from a HCN
molecule, or the H3O+ ions present in the slightly acidic solution.
H H
CH3 C O + H_ CN CH3 C_ OH
ethanal CN
acetaldehyde cyanohydrin

Nucleophilic substitution in primary halogenoalkanes

Common nucleophiles are hydroxide ions OH-, cyanide ions CN-, water H2O and ammonia
NH3.
Nucleophilic substitution in bromoethane
The Nu- ion approaches the + carbon from the side away from the bromine atom. The
large bromine atom hinders attack from its side and, being -, would repel the incoming Nu-
anyway.
CH3 CH3 H CH3
Nu C+ Br Nu C Nu C
Br Br
H  
_
H +
H H H
transition state

This reaction is known as an SN2 reaction.

• S - for substitution
• N - for nucleophilic
• 2 - the initial stage of the reaction involves two species - the bromoethane and the
Nu- ion

Page 15 of 16 pages
Nucleophilic substitution in tertiary halogenoalkanes SN1 reaction
This mechanism involves an initial ionization of the halogenoalkane to give a carbocation
and a bromide ion.

CH3 CH3
slow
CH3 C Br_ CH3 C + + Br
+ 
CH3 CH3

This reaction is possible because tertiary carbocations are relatively stable compared with
secondary or primary ones.
The reaction is slow (rate determining).
In the second stage, the carbocation formed reacts with a nucleophile Nu -.
CH3 CH3
fast
CH3 C + + Nu CH3 C Nu
CH3 CH3

The slow step of the reaction only involves one species - the halogenoalkane.
It is known as an SN1 reaction.

Mechanism of elimination reactions producing alkenes from simple halogenoalkanes

2-bromopropane is heated with a concentrated solution of sodium or potassium hydroxide
in ethanol.
In elimination reactions, the hydroxide ion acts as a base - removing a hydrogen as a
hydrogen ion from the carbon atom next door to the one holding the bromine. The resulting
re-arrangement of the electrons expels the bromine as a bromide ion and produces
propene.
OH
H H 2O
H C CH _ CH 3 H C CH _ CH + 3

H Br H Br

General scheme:

Nu
H
C C C C + Nu H + X
X

Page 16 of 16 pages