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CHM 257
Chapter 1:
Introduction to Organic Chemistry
H + O + H H O H or H O H
2e-8e-2e-
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:
nonpolar ionic
increasing polarity
The Electronegativities of Common Elements
H F
d+ d-
O S
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
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.
-1 +1 H 0 0
H C O H C O
H
Exercises:
1s 1s H2 molecule
HYBRIDIZATION
Hybridization mixing of two or more atomic orbitals to
form a new set of hybrid orbitals.
# of Lone Pairs
+
# of Bonded Atoms Hybridization Examples
2 sp BeCl2
3 sp2 BF3
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
121.7o
116.6o
H C C H
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
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
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
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
- Lewis bases
C (carbanion) C+ (carbocation)
R-OH RN2+
C C BF3
-
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
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)
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
Cl Cl H Cl
C C C C
H H Cl H
cis-1,2-dichloroethene trans-1,2-dichloroethene
H H H CH3
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.
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
H Cl Cl H H Cl Cl H
H Cl Cl H Cl H H Cl
H OH HO H H OH HO H
HO H H OH H OH HO H
CH3 CH3
H OH HO H
H OH HO H
CH3 CH3
(iii) (iv)
a) 2-bromopentane
b) 1,2-dibromobutane
c) 4-ethyl-4-methyloctane
Isomerism
(same molecular
formula)
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