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ORGANIC CHEMISTRY 1

CHM 257

Chapter 1:
Introduction to Organic Chemistry

NOR AKMALAZURA JANI


SUBTOPICS
Characteristic features of organic
compounds
- composition
- electronic structure
- bonding
- chemical formula
Electrophiles and nucleophiles
Lewis acids and Lewis bases
Isomerism
Functional groups and homologous series
ORGANIC CHEMISTRY
The branch of chemistry that deals with carbons
compounds.
Also contain element such as O, N, P, S and halogen (F,
Cl, Br, I)
Organic derived from living organisms
Study of compounds extracted from living organisms and
their natural products.
Examples: sugar, starch, urea, waxes, carbohydrates, fats
and etc
Human are composed of organic molecules proteins in
skin, lipid in cell membranes, glycogen in livers and the
DNA in the nuclei of cells.
Position of Carbon
Chemistry of carbon:

- Two stable isotops (13C and 12C)


- electron configuration: 1s2 2s2 2p2
- four valence electrons
- can form more compounds than any
other element
- can form four covalent bonds
- able to form single, double and triple
carbon-carbon bonds, and to link up with
each other in chains and ring structures
Chemical Bonds
An attraction between atoms or molecules that allows the
formation of chemical compounds, which contain two or more
atoms.
Atoms will transferred or shared electrons to achieve a noble-
gas configuration i.e. surrounded by eight valence electrons.
Type of chemical bonds:
i) Ionic bonding
- the electrostatic force that holds ions together in an
ionic compound.
- atoms attain noble-gas configuration by transferring
electrons from one atom to another.
- Atoms of the elements with low ionization energies tend to
form cation by losing valence electron(s) alkali metals and
alkaline earth metals
- Atoms of the elements with high electron affinities tend to
form anion by gaining valence electron(s) halogens and
oxygen
- common in inorganic compounds like NaCl, KI, etc
ii) Covalent bonding

- atoms attain noble-gas configuration by


sharing electrons
- common type of bonding in organic
compounds such as CH4, CH3OH, C6H6, etc
- type of covalent bonds:
i) single bond
ii) double bond
iii) triple bond
Lewis Structure
A representation of covalent bonding in which shared
electron pairs are shown either as lines or as pairs of dots
between two atoms, and lone pairs are shown as pairs of
dots an individual atoms.
Only valence electrons are shown.
Example: Methane (CH4)
Total number of valence electrons:
C=4e H H
H=1ex4=4e H C H or H C H
TOTAL = 8 e
H H
Example: Ethane (C2H6)
Total number of valence electrons:
C = 4 e x 2 = 8e H H H H
H=1ex6=6e or H C C H
H C C H
TOTAL = 14 e
H H H H
TYPES OF COVALENT BONDS
Single bond two atoms share a pair of electrons
single covalent bonds

H + O + H H O H or H O H
2e-8e-2e-

Double bond two atoms share two pairs of electrons

O C O or O C O
8e- 8e- 8e- double bonds
double bonds
Triple bond two atoms share three pairs of electrons
N N or N N
8e-8e-
triple bond triple bond
A lone pair (nonbonding electrons)
- valence-shell electrons that are not shared between two
atoms.
- oxygen atoms, nitrogen atoms and halogens (F, Cl, Br, I)
have nonbonding electrons in their stable compounds.
- examples:

lone pair lone pair lone pair


H H H
H C N H H C O H H C Cl lone pair
lone pair lone pair
H H H H
methylamine methanol chloromethane
ELECTRONEGATIVITY
Electronegativity: the ability of an atom to attract toward
itself the electrons in a chemical bond.

Electronegativity is used to estimate the degree of ionic


or covalent character in a chemical bond.

A non polar covalent bond is one in which the difference


in electronegativity between the bonded atoms is 0.4 or
less.
- example: bond between C and H is classified as
nonpolar covalent because the difference in
electronegativity between two atoms is 0.4 unit on the
Pauling scale.
A polar covalent bond is one in which the difference in
electronegativity between two atoms is between 0.5 and
1.8.
- example: bond between H-Cl (electronegativity between
two atoms is 0.9 unit)

CH3 CH3 CH3 NH2 CH3 OH CH3 Cl H3CNH3+ Cl-


ethane methylamine methanol chloromethane methylammonium chloride

nonpolar ionic
increasing polarity
The Electronegativities of Common Elements

Among the main group elements, electronegativity


increases moving from left to right in periodic table
and increase moving up a group.
Dipole Moments and Polar Molecules

electron poor electron rich


region region

H F

d+ d-

m=Qxr * Dipole moment a quantitative


measure of the polarity of a bond.
Q is the charge Shift of electron density
r is the distance between charges
1 D = 3.36 x 10-30 C m
Bond moments and resultant dipole moments in NH3 and NF3.
Which of the following molecules have a dipole moment?
H2O, CO2, SO2, and CF4
* Molecules that have dipole moments = polar molecules
* Molecules that do not have dipole moments = nonpolar molecules

O S

have dipole moments value


have dipole moments value
polar molecule
polar molecule

O C O C
Do not have dipole moment value F F
nonpolar molecule F
Do not have dipole moment value
nonpolar molecule
FORMAL CHARGE
An atoms formal charge is the difference between the
number of valence electrons in an isolated atom and the
number of electrons assigned to that atom in a Lewis
structure.

total number
formal charge on total number
of valence
electrons in -
an atom in a = electron
Lewis structure assigned to atom
the free atom

The sum of the formal charges of the atoms in a molecule or


ion must equal the charge on the molecule or ion.
Examples:
H C O H
formal charge = valence electrons electrons assigned to atom
formal charge of C = 4 5 = -1
formal charge on O = 6 5 = + 1

H
C O
H

formal charge of C = 4 4 = 0

formal charge on O = 6 6 = 0
Formal Charge and Lewis Structures
1. For neutral molecules, a Lewis structure in which there are
no formal charges is preferable to one in which formal
charges are present.
2. Lewis structures with large formal charges are less
plausible than those with small formal charges.
3. Among Lewis structures having similar distributions of
formal charges, the most plausible structure is the one in
which negative formal charges are placed on the more
electronegative atoms.

Which is the most likely Lewis structure for CH2O?

-1 +1 H 0 0
H C O H C O
H
Exercises:

1. Compute the formal charge for the nitrogen atom in


ammonia, NH3.

2. Compute the formal charge for the oxygen and hydrogen


atoms in hydronium ion, [H3O]+.
VALENCE BOND THEORY
A covalent bonds forms when two atoms approach each
other closely and a singly occupied orbital on one atom
overlaps a singly occupied orbital on the other atom.
The electrons are now paired in the overlapping orbitals
and are attracted to the nuclei of both atoms and bonding
the atoms together.
Example: H2 molecule

1s 1s H2 molecule
HYBRIDIZATION
Hybridization mixing of two or more atomic orbitals to
form a new set of hybrid orbitals.

1. Mix at least 2 nonequivalent atomic orbitals (e.g. s and p).


Hybrid orbitals have very different shape from original
atomic orbitals.
2. Number of hybrid orbitals is equal to number of pure
atomic orbitals used in the hybridization process.
3. Covalent bonds are formed by:
a. Overlap of hybrid orbitals with atomic orbitals
b. Overlap of hybrid orbitals with other hybrid orbitals
How to predict the hybridization of the central atom?
1. Draw the Lewis structure of the molecule.
2. Count the number of lone pairs AND the
number of atoms bonded to the central atom

# of Lone Pairs
+
# of Bonded Atoms Hybridization Examples

2 sp BeCl2

3 sp2 BF3

4 sp3 CH4, NH3, H2O

5 sp3d PCl5

6 sp3d2 SF6
Formation of sp3 Hybrid Orbitals
Formation of Covalent Bonds in CH4
sp3 Hybridization of Carbon
Example: Methane (CH4)
Electronic configuration: 1s22s22p2
Ground state

2s 2p

Promotion of
electron
2s 2p

sp3 hybridized
state
sp3 orbitals
sp3 hybrid orbitals
- when an s orbital combines with three p orbitals, it will
formed four hybrid orbitals and oriented at 109.5o angles to
each other.
- called sp3 hybrid orbitals (composed of one s orbital and
three p orbitals).
- the arrangement is called tetrahedral.
Hydridization of other atoms: Nitrogen and oxygen
- type of hybridization: sp3
- bond angle for N-H : 107.3o
- bond angle for O-H : 104.5o
Formation of sp2 Hybrid Orbitals
sp2 Hybridization of Carbon
Example: Ethene / ethylene (C2H4)
H H
C C
H H

Formation of p bond

Formation of s bond
Bonding in Ethylene, C2H4

Sigma bond (s) covalent bonds formed by orbitals overlapping


end to-end , with the electron density between the nuclei of the
bonding atoms
Pi bond (p) a covalent bond formed by sideways overlapping
orbitals with electron density concentrated above and below
plane of nuclei of the bonding atoms
Another View of p Bonding in Ethylene, C2H4
sp2 hybrid orbitals
- when an s orbital combines with two p orbitals, it
will formed three hybrid orbitals and oriented at 120o
angles to each other.
- called sp2 hybrid orbitals (composed of one s
orbital and two p orbitals).
- the 120o arrangement is called trigonal geometry.

121.7o

116.6o

Ethylene, close to 120o


Formation of sp Hybrid Orbitals
sp Hybridization of Carbon

Example: Acetylene (C2H2)

H C C H

Formation of s bond Formation of p bond


Bonding in Acetylene, C2H2
sp hybrid orbitals

- combine a s orbital and a p orbital on the same


atom
- hybrid orbitals give a bond angle of 180o
- linear bonding arrangement
- example: acetylene (contains carbon triple bond)

180o
CHEMICAL FORMULA
Four different ways of writing the structural formula of organic
compounds.
i) Condensed structural formula
- carbon-hydrogen and carbon-carbon single bonds
are not shown, but double or triple bonds are shown.
- each central atom is shown together with the atoms that
are bonded to it.
- the atoms bonded to a central atom are often listed after
the central atom. For example, CH3CH3.
- branches in the carbon chain are indicated in
parentheses. For example, CH3CH(CH3)CH2CH3
- if there are two or more identical groups, parentheses and a
subscript may be used to represent all the identical groups.
For example, CH3(CH2)4CH3
- lone pair are rarely shown.
ii) Expanded structural formula
- shows every atom and type of covalent bond in the
molecule.
Examples of expanded and condensed structural formula

ethane
H H
H C C H
H H CH3CH3
Expanded structural formula condensed structural formula

isobutane
H H H
H C C C H
H H
H C H
(CH3)3CH
H
Expanded structural formula condensed structural formula
Examples of expanded and condensed structural formula

hexane
H H H H H H
H C C C C C C H
H H H H H H CH3(CH2)4CH3

Expanded structural formula condensed structural formula

ethanol
H H
H C C O H
H H CH3CH2OH
Expanded structural formula condensed structural formula
Examples of expanded and condensed structural formula

2-butene

H H H
H C C C C H
CH3CHCHCH3 or CH3CH=CHCH3
H H H

Expanded structural formula condensed structural formula

acetic acid
H O
O
H C C O H
CH3COOH or CH3CO2H or CH3C OH
H
Expanded structural formula condensed structural formula
iii) Skeletal structures / line-angle formulas / stick figure
- do not show carbon and hydrogen atoms or C-H bonds
unless they are part of a functional group.
- single bonds are indicated with a single line, double bonds
with double lines and triple bonds with triple lines.
- the ends of the lines and corners between lines indicate
the presence of a carbon atom.
- examples:

CH3(CH2)4CH3
hexane
condensed structural formula skeletal structure

2-hexene CH3CH=CHCH2CH2CH3
condensed structural formula skeletal structure
CH3CH2CH(OH)CH2CH2CH3
3-hexanol OH
condensed structural formula skeletal structure

H2
C O
H2C C
O
2-cyclohexenone H2C CH
C
H
condensed structural formula skeletal structure

# structural formulae may be written as a combination


of expanded, condensed and/or skeletal structure
CH2CH3

N H
H
THREE-DIMENSION (3D) FORMULA
H
H
C H Cl C H
Cl
Cl Cl
The 3-dimensional line-wedge-dash structure and the expanded
structural formula of dichloromethane (CH2Cl2)

represents the covalent bond coming out of the plane of the paper

represents the bond behind the plane of the paper

represents the covalent bond lying in the plane of the paper


iv) Fisher projection
- drawing asymmetric carbon atoms.
- representation of a 3D molecule as a flat structure where a
tetrahedral carbon is represented as two crossed lines.
ELECTROPHILE AND NUCLEOPHILE
Reagents in organic reactions can be classified either
electrophiles or nucleophiles depending on whether they
attack regions of high electron density (-) or regions of
low electron density (+).
regions of low electron density (+) also known as
electron-deficient sites.
Electrophiles:
- a species (ion or molecule) which attacks by a negatively
charged carbon atom by accepting an electron pair.
- Lewis acid
-positive ions or molecule that have an electron-deficient
atom (+).
- known as electrophilic reagents
Nucleophile:
- a species (ion or molecule) that attacks a positively
charged carbon atom by donating an electron pair to
form a dative covalent bond.

- known as nucleophilic reagents

- Lewis bases

- negative ions or molecules that have at least one


lone pair of electrons.
Examples of nucleophiles and electrophiles
nucleophiles electrophiles
(donors of electron pairs) (acceptors of electron pairs)
OH, RO H+ (or H3O+), NO2+ (nitronium ion)

CI, Br, I Cl2, Br2

C (carbanion) C+ (carbocation)

R-OH RN2+

C C BF3

NH3, RNH2 AlCl3


H2O FeBr3, ZnCl2

Reducing agents Oxidising agents

-
CN Cl+, Br+, I+
Lewis acids and Lewis bases
An Lewis acids:
- a species which can form a dative covalent bond by
accepting an electron pair from a base.
- Examples: some metal compounds (AlCl3, TiCl4, FeCl3,
ZnCl2), some cations (Li+, Mg2+), some neutral proton donors
(H2O, HCl, HBr, HNO3, H2SO4, an alcohols such as CH3CH2OH,
C6H5OH, a carboxylic acids such as CH3CH2COOH)
A Lewis bases:
- a species that has an unshared electron-pair which can be
donated to form a dative covalent bond with an atom,
molecule or ion.
- examples: H2O, organic compounds that contain oxygen
and nitrogen such as amines, ketones, aldehydes, alcohols,
etc.
In the other word, a Lewis acid is an electron-pair acceptor
and Lewis base is an electron-pair donor.
Examples of Lewis acids and Lewis bases

-
H+ + OH


H O H

acid base
H H
+
H+ +

N H H N H
H H
acid base
ISOMERISM
Isomers: organic compounds that have same
molecular formula but different arrangements
of atoms.
Isomerism: the existence of two or more
organic compounds with the same molecular
formula but different arrangements of atoms.
Two types of isomerism:
i) constitutional isomerism / structural
isomerism
ii)stereoisomerism
CONSTITUTIONAL (STRUCTURAL)
ISOMERISM

Molecules that have same molecular formula


but have different structural formulae.

Subdivided into 3 different categories:


i) Chain isomerism
ii)Positional isomerism
iii)Functional group isomerism
Chain isomerism
Chain isomers are those which differ in the
structure of their carbon chains, differ in the
length of their straight chains or branch.
Example:
- alkane with molecular formula C4H10 has 2
chain isomers

CH3CH2CH2CH3 CH3CHCH3
butane CH3
(straight chain)
2-methylpropane
(branched chain)
- alcohols with the formula C4H9OH

CH3CH2CH2CH2OH CH3CHCH2OH
butanol CH3
(straight chain)
2-methyl-1-propanol
(branched chain)

Possess the same functional group, belong to the


same homologous series.
Different physical properties.
Similar chemical properties.
Positional isomerism
Have the same carbon skeleton and belong to the same
homologous series, but differ position of the functional
group.
Similar chemical properties because have the same
functional group.
Different physical properties.
Examples:
i) bromoalkanes with the molecular formula C3H7Br
H H H H H H
H C C C Br H C C C H
H H H H BrH
1-bromopropane 2-bromopropane
(boiling point: 70.8oC) (boiling point: 59.4oC)
ii) Alcohols with the molecular formula C3H7OH

H H H H H H
H C C C OH H C C C H
H H H H OH H
1-propanol 2-propanol

iii) Alkenes with the molecular formula C5H10

CH3CH2CH2CH CH2 CH3CH2CH CHCH3


1-pentene 2-pentene
Aromatic compounds.
- If two bromine atoms replace two hydrogen
atoms to form disubstituted benzene, three
isomers can be formed.
Br
Br
Br
Br
Br
Br
1,2-dibromobenzene 1,3-dibromobenzene 1,4-dibromobenzene
Functional Group Isomerism
Isomers which have the same molecular
formula but contain different functional
groups.

Same molecular formula but belong to


different homologous series.

Different chemical and physical properties.


Examples
Types of Molecular Functional group isomers
compounds formula
Alkene and C5H10
cycloalkane CH3CH2CH2CH CH2
1-pentene cyclopentane
Alcohol and C3H8O
CH3CH2CH2OH CH3OCH2CH3
ether
1-propanol methoxyethane

Aldehyde and C3H6O


ketone CH3CH2CHO CH3COCH3
propanal propanone
Carboxylic acid C3H6O2
and ester CH3CH2COOH CH3COOCH3 HCOOC2H5
propanoic acid methyl ethanoate ethyl methanoate
STEREOISOMERISM
Isomers with same structural formula but
they have different spatial arrangements of
their atoms or groups.

Divided into two categories:


i) cis-trans isomerism
ii)optical isomerism
cis-trans (geometrical) isomerism

Geometrical isomers: stereoisomers which have the same structural


formula but differ in the spatial arrangement of atoms around the
double bond or ring structure.
Occurs in compounds in which free rotation is prevented by the
presence of a carbon-carbon double bond or a cyclic structure which
hinders or obstructs the rotation of a C-C single bond in the ring.
Example:
- alkenes: 2-butene exists has two cis-trans isomers.

H3C CH3 H CH3


C C C C
H H H3C H
cis-2-butene (bp: 4o) trans-2-butene (bp: 1o)
(two methyl groups are on the (two methyl groups are on the
same side of the double bond) opposite side of the double bond)
Have same functional group, thus have same chemical
properties.
Have different physical properties as a result of the different
spatial arrangements of the groups.
For example:
- boiling point of cis-2-butene is 3.7oC but boiling point of trans-
2-butene is 0.9oC.
cis isomers have higher bp compared to trans isomer due to
more polarised nature.
trans isomer have higher melting points:
- more linear structure that enables them to form a more
densely-packed crystalline structure.
CH3 CH3 CH3 H
C C C C
H H H CH3
cis-2-butene trans-2-butene
bp: 3.7oC bp: 0.9oC
= 0.33 D =0D
Cannot occur if one of the carbons atoms in the double bond
or the ring structure has two identical atoms or groups.
Example:
- 1,2-dichloroethene shows cis-trans isomerism but 1,1-
dichloroethene and 1,1,2-trichloroethene do not show cis-
trans isomerism.

Cl Cl H Cl
C C C C
H H Cl H
cis-1,2-dichloroethene trans-1,2-dichloroethene

exhibit cis-trans isomerism


H Cl Cl Cl
C C C C
H Cl Cl H
1,2-dichloroethene 1,1,2-trichloroethene

do not exhibit cis-trans isomerism


Examples of cyclic compounds that show cis-trans
isomerism:
H H H CH3

CH3 CH3 CH3 H


cis-1,4-dimethylcyclohexane trans-1,4-dimethylcyclohexane

H H H CH3

CH3 CH3 CH3 H


cis-1,2-dimethylcyclohexane trans-1,2-dimethylcyclohexane

Cl H
Cl Cl
H Cl
H H
cis-1,3-dichlorocyclohexane trans-1,3-dichlorocyclohexane
Optical isomerism
Optical activity is the ability of certain crystals or solutions of
certain substances to rotate the plane of plane-polarised light.
The substances are said to be optically active.
Optical isomers: optically active substances which possess the
same structural formula but differ in their effect on plane-
polarised light.
Isomers which rotates the plane of polarisation to the right (in
clockwise direction) dextrorotatory isomer or the (+)isomer.
Isomer that rotates the plane of polarisation to left (anti-
clockwise direction) laevorotatory or the (-)isomer.

Dextrorotatory (+) laevorotatory (-)


CHIRALITY CENTRE AND ENANTIOMERS
An organic molecule will exhibit optical isomerism or optical
activity if it contains at least one chiral carbon atom.
Chiral carbon atom or asymmetric carbon atom (C*): carbon
atom attached to four different atoms or groups.
Two subdivisions of stereoisomers:
i) Enantiomers (mirror image)
ii) Diastreoisomers (non-mirror image)
Enantiomers / optical isomers:
- the existence of a pair of mirror image stereoisomers that
are not superimposable.
- have one or more chiral carbon atoms.
- have same structural formula but different spatial
arrangement of the atoms.
- optically active.
Diastreoisomers:
- stereoisomers that are not mirror image of each other.
- include cis-trans isomers.
Example: 2-butanol
CH3
*
H C OH chiral carbon

CH2CH3
C* = chiral carbon
2-butanol

mirror plane

CH3 CH3
H OH HO H
CH2CH3 CH2CH3

D-2-butanol L-2-butanol

2 enantiomersof 2-butanol
The maximum number of stereoisomers = 2n
(n = number of chiral carbons)
H H H H H
*
H C C C* C C H

H Cl Cl H H
2,3-dichloropentane

CH3 CH3 CH3 CH3

H Cl Cl H H Cl Cl H
H Cl Cl H Cl H H Cl

CH2CH3 CH2CH3 CH2CH3 CH2CH3


(i) (ii) (iii) (iv)

Enantiomers: - (i) and (ii)


- (iii) and (iv)
Diastreoisomers: - (i) and (iii)
- (i) and (iv)
- (ii) and (iii)
- (ii) and (iv)
In some cases, the number of stereoisomers is less than the
maximum.
For example, CH3CH(OH)CH(OH)CH3 has two chiral carbons
but have 3 stereoisomers.

CH3 CH3 CH3 CH3

H OH HO H H OH HO H
HO H H OH H OH HO H

CH3 CH3 CH3 CH3


(i) (ii) (iii) (iv)

Enantiomers: - (i) and (ii)


Diastreoisomers: - (i) and (iii)
- (ii) and (iii)
Structure (iii) is the same as structure (iv). It belongs to a
stereoisomers termed as meso compound.
Meso compound: an achiral compound with chirality centers
and has a plane of symmetry.
How to determine the meso compound?

- determine whether the compound has an internal plane of


symmetry.
- if the upper structure is mirror image with lower
structure, the compound is a meso compound.

CH3 CH3
H OH HO H
H OH HO H
CH3 CH3

(iii) (iv)

internal plane of symmetry


Write the expanded formula for each of these
molecules and mark the chiral carbon or
stereogenic centre in each of the molecule
with an asterisk (*):

a) 2-bromopentane
b) 1,2-dibromobutane
c) 4-ethyl-4-methyloctane
Isomerism
(same molecular
formula)

Constitutional isomerism Stereoisomerism


(different structural formula; (same structural formula;
different spatial different spatial
arrangement of atoms) arrangement of atoms)

Functional
Chain Positional cis-trans Optical
group
isomerism isomerism isomerism isomerism
isomerism
FUNCTIONAL GROUPS AND
HOMOLOGOUS SERIES
Functional groups:
- the atom or group of
atoms that gives the
organic compound its
characteristics properties.
Homologous series:
- A series of organic compounds with similar chemical properties,
in which each member differs from the previous one by the addition
of a -CH2- group.
- The general characteristics of a homologous series:
i) All the compounds in the homologous series have the
same functional group and have similar chemical
properties.
ii) each member differs from the next in the series by a
CH2- group.
iii) all the compounds in the series may be prepared by
similar methods.
iv) the physical properties of the compounds show a
progressive change with increasing relative molecular
mass.
v) all the compounds in the series contain the same elements and
can be represented by the same general formula.
Homologous series / classes of
compounds
Alkanes Carboxylic acids
Cycloalkanes Esters
Alkenes Acid anhydrides
Aromatic Acyl halides
Alcohols Amides
Alkynes Amines
Haloalkanes / alkyl halides
Aldehydes
Ketones
Ethers
HOMEWORK !
Class of compound General structure Functional group Name of functional group
Alkanes
Alkenes
Alkynes
Alkyl halides
Aromatic compounds
Alcohols
Phenols
Ethers
Aldehydes
Ketones
Carboxylic acids
Esters
Amides
Amines
Nitriles
Thiols