Vous êtes sur la page 1sur 159

DEPARTMENT OF

PHARMACY
ORGANIC CHEMISTRY
Submitted by: Sumaira
( Roll No. 93)

Submitted To:
Topics
1.Chemical bond
2.Hybridization
3.Conjugation
4.Resonance
5. Hyperconjugation
6.Aromaticity
7.Inductive Effect
8.Electromeric
Effect
9.Hydrogen
Topicsbonding
10.Steric effect
11.Effect of structure on
reactivity of compound
12.tautornnerism
13.stereoisomerism
14.Optical isomerism
15.Geometrical isomerism
16.Resolution of racemic
solution
Topics
17.Conformational analysis
18. Subsitution reaction
19.Nucleophilic and electrophilic
reaction in aliphatic and aromatic
compound
1.Chemical Bond
Definition:
A chemical bond can be defined as the force of
attraction between two atoms, molecules or ions in
which join together by donate of electrons or
metual sharing of electrons
Types of bond
There are three types of bond which are given
below
1- ionic or electrovalent bond
2- COVALENT BOND
3- COORDINATE
1- Ionic or electrovalent bond
Ionic or electrovalent bond are formed by transfer of
valance electron from one atom to another atom
Example;
The formation of sodium chloride example of ionic bond ii
this way here sodium atom having one electron in the
valance shell while chlorine atom having seven electron in
the valance shell then sodium lose the electron and
appear the partial positive charge whenever this lose
electron to gain the chlorine and appear the negative
charge . These oppositely charged ions are held together
by electrostatic force of attraction . This type of bond called
ionic bond
2- Covalent Bond
When a atoms are combine together by the
metual sharing of electrons is called covalent
bond
Example;

Here the two electrons are shared and give to


each hydrogen atom the configuration of
helium. This type of bond is termed covalent
bond and indicate by a line. Covalent bonds are
3- Coordinate
Bond
Coordinate bond is also formed by mutual sharing of
electrons but in this case the two electrons that are
shared come from the same atom. A coordinate bond
unites two atoms, one of which has a spare pair of
electron and the other is short of a pair of electrons.
The first atom donor atom contributes and pair lone
pair of electrons and the second atom acceptor atom
accept it. After the formation of the lone pair of
electrons is held in common. The coordinate bond is
represent by an arrow, pointing away from the donor
atom. An excellent illustration of the coordinate bond
is found in the boron hydride-ammonia complex.
2- Hybridization
Definition
Hybridization can be defined as the mixing of two
or more then two atomic orbitals having different
shape of size and energy but after the mixing
together and a formed equal shapes of size and
energy of atomic orbitals is known as hybridization .
There are three types of hybridization which are
given below;
Sp3 hybridization
Sp2 hybridization
Sp hybridization
Sp-3 or
tetrahedral
hybridization

One S and three P orbitals called sp hybridization.


Shape of methane molecule, CH4
In the methane molecule are formed by sp
hybridization in which one of the electron from a 2s
orbital is promoted to a vacant 2p orbital. The one
2s and the three 2p orbitals are mixed hybridized
to form four identical sp orbitals. The four new
orbitals are called sp hybrid orbitals and the
process is known as sp hybridization each sp
orbital containing one electron. The sp orbitals are
directed towards four corners of a regular
tetrahedron with the carbon atom located at the
centre. In methane molecule each of the four sp
hybrid orbitals then overlap with 1s orbital of four
hydrogen atoms to form four sigma bond C-H
bonds
Sp2 - trigonal
hybridization
One s and two p orbitals of carbon atom
mix to give a set of three sp hybrid orbitals
which pointing at angles of 120 and each of
them contains one electron . the lobes of sp
hybridized orbitals are directed towards the
coners of an equilateral triangle. That is why sp
hybridization is called trigonal hybridization. The
unhybridized orbital is always prependicular to
the plane containing three sp hybrid orbitals. All
compound with C=C bonds have sp -hybridized
carbon atoms. Each sp hybrid orbital has 33
percent s- character and 66 percent p-
Shape of ethylene molecule, C2H4
A molecule of ethylene has two electron pairs shared between two
carbon atoms. A bond of this type is known as carbon-carbon double
bond.each carbon atom in the molecule of ethylene is attached to
three other atoms by the overlaping of its three hybrid orbitals. These
hybrid orbitals are formed by mixing of one 2s and two 2p orbitals are
equivalent and each one of them has one electron.
Two sp hybridized carbon atoms use one sp orbital each to form a
sigma bond between them. The rest of the molecule is formed by the
overlapping of the of the remaining two sp orbitals on each carbon
atom 1s orbital of the two hydrogen atoms. The structure of ethylene
is still not compelet as there are two unhybridized p orbitals,
eachcarbon. These two orbitals overlap each other sideway producing
a new type of bond called pi bond and the electron involved in the
formation of this bond are known as pi electrons. In the molecular
orbital of ethylene having six atoms i.e two carbon and four
hydrogens should lie in one plane with a bond angle of 120. the pi
3- Conjugation
Definition;
The word "conjugation" is derived from a Latin
word that means "to link together". In organic
chemistry terms, it is used to describe the situation
that occurs when systems (e.g.double bonds) are
"linked together".
An "isolated" (pi) system exists only between a single pair of
adjacent atoms (e.g.C=C)
An "extended" (pi) system exists over a longer series of atoms
(e.g.C=C-C=CorC=C-C=Oetc.).
An extended (pi) system results in a extension of the chemical
reactitvity.
The fundamental requirement for the existence of a conjugated
system is revealed if one considers the p orbitals involved in the
bonding within the system.Aconjugatedsystem requires that
there is a continuous array of "p" orbitals that can align to produce
a bonding overlap along the whole system.
If a position in the chain does not provide a "p" orbital or if
4- Resonance
Definition ;

These two structure are differ only in


the position of electrons neither 1 nor
2 is a correct representation of
benzene these two structure of
benzene lies somewhere between
these two structure . This phenomenon
in which two or more structure can be
written for a compound which involve
identical positions of atoms is called
The resonance concept is extremely useful in organic chemistry
and will come up a number of time. The following are some
important rules governing resonance.
1- resonance occurs whenever a molecule can be represented by
two or more structures differing only in the arrangement of
electrons, without shifting any atoms resonance only involves the
delocalization of electrons.
2-Resonance structure are not exist in actual molecule structure.
3- Resonance structure are interconvertible by one or a serise of
short electron shift. for example
5-Hyperconjugation
6-Aromaticity
Aromaticity mean;
Although the name aromatic was originated from the
characteristic odor or aroma of benzene-like compounds, chemists now
have a completely different method of deciding whether a compound is aromatic or
not. Based on the analysis of a number of compounds with unusual resonance
stabilization energies, the following characteristics have been accepted as criteria
for aromaticity. 1. The molecule must be cyclic, planar with uninterrupted cloud of
electrons above and below the plane of the ring. 2. It should have 4n+2
electrons. Here every atom in the ring must have a p orbital and the delocalization
should result in an uninterrupted cyclic cloud of electrons above and below the
plain of the ring. The German Chemist Erich Hckel was the first one to recognize
that an aromatic compound must have an odd number of pairs of electrons, which
can mathematically be written as 4n+2 (n = 0,1,2,3 etc). Molecules which obey
these rules are aromatic and those which follow these rules partially fall in the
category of anti-aromatic and non aromatic compounds. The p orbital array (A) and
delocalization (B) in benzene can be pictorially represented as shown below (Figure
4). Figure 4. A B We will now go through examples starting from cyclopropene to
higher conjugated ring systems and look for the property of aromaticity.
Molecular orbital description of
aromaticity and antiaromaticity
Molecular orbital description of aromaticity and
antiaromaticity Our current understanding on the structure
of benzene is based on molecular orbital theory. As
mentioned earlier, all the six sp2 carbon atoms are arranged
in such a way that each uses two of its hybridized orbitals to
bond to adjacent carbon atoms and the third one to bond to
the 1s orbital of hydrogen. The un-hybridized p orbital
associated with each carbon atom contain one electron and
lie perpendicular to the plane of the ring. According to
molecular orbital theory, these six p orbitals combine to form
six molecular orbitals, three of which are bonding and three,
anti-bonding. Six electrons occupy the bonding orbitals,
which are lower in energy compared to the un-hybridized p
orbitals (atomic orbitals). The relative energies of atomic
orbitals and molecular orbitals are shown in Figure 5. A more
comprehensive picture of
7-Inductive Effect
DEFINITION;
When a covalent bond is formed between two atoms
having different electronegativities there is induce a
permenent dipole in such a bond . This induction of dipole
due to polarization is referred to as the inductive effect.
Actually this polarization is due to drift of the shared pair
of electron towards the more electronegative atom
resulting in the origin of small fractional charges on the
consituent atoms i.e partial positve and partial negative .
When a carbon is bonded to a hydrogen C-H or another C-
C by a covalent bond such as in alkanes , the sharing of
electron pair is symmetrical between them, because
there is no significant difference in the electronegativity
values of the two bonded atoms .
Example

Types of inductive effect


The inductive effect are two types which is depend
on the atom or group is electron repelling donor
group or electron withdrawing acceptor group
respectively.
1-Groups showing -I-Effect
The I-effect of the group having hetero atoms such
as oxygen ,nitrogen ,halogen etc is due to the
greater electronegativity of these groups as
compared to carbon . These groups thus case I-
effect due to their electron attracting nature.
Groups showing + I-Effect
The + I- effect of these groups is due to electron
donating nature of alkyl groups. Deutrium
causes + I-effect greater than hydrogen probably
because of larger atomic radious which makes it
more electropositive than hydrogen . The highly
subsituted the alkyl group stronger is its + I-
effect . Thus decreasing order of +I effect of
some alkyl group s relative to hydrogen when
attached to a saturated carbon chain follow the
order;
Tert-butyl > Isopropyl > n-prop > Ethyl > Methyl
Characteristics Of Inductive Effect
Inductive effect involve only the tendency of
displacement of sigma electrons and it occurs in
polar single covalent bond .
It is permanent effect which cannot reversed.
The inductive effect decrease progressively with
increasing distance between atom the carbon
atom and other atom or group causing this effect .
The electrons shifting slightly without leaving their
orbitals. Only little distortion of the orbital occur
which leads to polarization.
8-Hydrogen Bonding
Definition
;Ahydrogen bondis the electrostatic attraction

between two polar groups that occurs when


ahydrogen(H) atom covalently bound to a highly
electronegative atom such as nitrogen (N), oxygen
(O), or fluorine (F) experiences the electrostatic
field of another highly electronegative atom nearby.
Electromeric effect
(1) The phenomenon of movement ofelectrons from one atom to another in
multibondedatomsat the demand of attacking reagent is calledelectromeric effect. It is
denoted as E-effect and represented by a curved arrow ( ) showing the shifting of
electron pair.

(2) (i)When the transfer ofelectrons take place towards the attacking reagent, the
effect is called +Eeffect. The addition of acids to alkenes.

Since, CH3group iselectrondonating, theelectrons are transferred in the direction


shown.

The attacking reagent is attached to that atom on whichelectrons have been transferred.

(ii) When the transfer ofelectrons takes place away from the attacking reagent, the
effect is calledE effect. Example, The addition of cyanide ion tocarbonyl compounds.

(3)Direction of the shift ofelectron pair:The direction of the


shift ofelectron paircan be decided on the basis of following
points.
(i) When the groups linked to a multiple bond are similar, the
shift can occur in either direction.

(ii) When the dissimilar groups are linked on the two ends of
the double bond, the shift is decided by the direction of inductive
effect.

In the case ofcarbonyl group, the shift is always towards


oxygen,i.e.,moreelectronegative atom.

In cases where inductive effect andelectromeric effect


simultaneously operate, usually electrometric effect predominates.
10-Steric Effect
Definition Steric effectsare theeffectsseen in
molecules that come from the fact that atoms occupy
space. When atoms are put close to each other, this costs
energy. The electrons near the atoms want to stay away .

Steric effectsarise from a fact that eachatom


within amoleculeoccupies a certain amount of space. If
atoms are brought too close together, there is an
associated cost inenergydue to overlapping
electron clouds(Pauli orExchange interaction, orBorn
repulsion), and this may affect the molecule's preferred
shape (conformation) andreactivity.rom each other.
Distinction from electronic effect
The structure, properties, and reactivity of a molecule
is dependent on straightforward bonding interactions
includingcovalent bonds,ionic bonds,hydrogen bonds
and lesser forms of bonding. This bonding supplies a
basic molecular skeleton that is modified by repulsive
forces. These repulsive forces include the steric
interactions described above. Basic bonding and steric
are at times insufficient to explain many structures,
properties, and reactivity. Thussteric effectsare often
contrasted and complemented byelectronic effects
implying the influence of effects such as induction,
conjunction, orbital symmetry, electrostatic
interactions, and spin state. There are more esoteric
electronic effects but these are among the most
important when considering structure and chemical
reactivity.
12-
Tautomerism
Definition; Tautomerism may
be defined as the phenomenon
in which a single compound
exists in two readily
interconvertible structures that
differ markedly in the relative
position of at least one atomic
nucleus, generally hydrogen.
The two different structures are
known as tautomers of each
Aldehydes and ketones are somewhatlycanthropic
chemical species. Take acetone. It behaves as a
garden-variety polar aprotic solvent, which makes it
a useful medium for SN2 reactions; it reacts readily
with nucleophiles like enolates, Grignards, and
amines; and is several pKa units less acidic than
alcohols (~20 vs. 16). This chemical behavior
reflects the fact that it spends the vast majority of
its time as a ketone, with an electrophilic carbonyl
carbon. Its nice and stable. You use it to wash
glassware with, or as paint thinner.
Although theketoform is most stable
for aldehydes and ketones in most
situations, there are several factors that
will shift the equilibrium toward
theenolform.The same factors that
stabilize alkenes or alcohols will also stabilize
the enol form. There are two strong factors
and three subtle factors.
1. Aromaticity.Phenols can theoretically exist in their keto
forms, but the enol form is greatly favored due to aromatic
stabilization.
2.Hydrogen Bonding.Nearby hydrogen bond acceptors
stabilize the enol form.When a Lewis basic group is nearby,
the enol form is stabilized by internal hydrogen bonding.
3. Solvent. Solvent can also play an important role in the relative
stability of the enol form. For example, in benzene, the enol form
of 2,4-pentanedione predominates in a 94:6 ratio over the keto
form, whereas the numbers almost reverse completely in water.
Whats going on? In a polar protic solvent like water, the lone
pairs will be involved in hydrogen bonding with the solvent,
making them less available to hydrogen bond with the enol form.
4. Conjugation. systems are a little like Cheerios in
milk: given the choice, they want to connect together
than hang out in isolation. So in the molecule depicted,
the more favorable tautomer will be the one on the left,
where the double bond is a connected by conjugation to
the phenyl.
5. Substitution. In the absence of steric factors,
increasing substitution at carbon will stabilize the enol
form.Enols are alkenes too so any factors that stabilize
alkenes, will stabilize enols as well. All else being equal,
double bonds increase in thermodynamic stability as
substitution is increased. So in the above example, the
enol on the left should be the more stable one. As you
might suspect, all things being equal sounds like a big
caveat. It is all else is rarely equal. But thats a topic
for another day or, more likely, another course.

11- Nomenculature of organic


compound
Resolution of racemic
mixture
The separation of aracemateinto its
components, the pure enantiomers, is called a
chiralresolution. There are various methods,
including crystallization, chromatography, and
the use of enzymes.
Conformational analysis
Definition;
The different spatial arrangments that a
molecule can adopt due to rotation about
bonds are calledconformationsand
henceconformationalisomers orconformers.
The study of the energy changes that occur
during these rotations is
calledconformational analysis.