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ORGANIC CHEMISTRY
Chapter 1
COURSE TITLE:
ORGANIC CHEMISTRY
COURSE
CODE:ASC 0303
CREDIT:
2 + 1 (120 hrs)
DURATION:
14 weeks
Activities
Lecture
Revision
Prelab report
Laboratory
Group discussion
Tutorial presentation
Test 1 preparation
Hours
2 hrs x 14
2 hrs x 14
1 hr x 7
3 hrs x 7
2 hrs x 7
2 hrs x 7
28
28
7
21
14
14
2.5
Test 1
1.5
Test 2 preparation
2.5
Test 2
TOTAL
1.5
120
Wk
Topics
1. Introduction Part 1
1. Introduction Part 2
Wk Tutorial
1
1,2
4. Arenes
5. Haloalkanes
10
11
12
9. Amines
13
14
1st test
7
4,5
6,7
2nd Test
11
13
9,10,11
Learning Outcomes
a. Identify types of bonds for carbon atoms
b. Define functional group and homologous series
c. Identify functional groups of the following homologous series:
i.
ii. Haloalkanes
iii. Alcohols and phenols
iv. Aldehydes and ketones
v. Carboxylic acids and their derivatives (acyl chlorides, amides, anhydrides, nitrile and esters)
vi. Amines
Learning Outcomes
g. Define isomerism, constitutional and stereoisomerism
h. Explain three types of constitutional isomerisim
i.
ii.
iii.
i.
j.
Chain isomers
Positional isomers
Functional group isomers
Double bonds
Cyclic compounds (single bond)
Organic Chemistry
sub-discipline within chemistry involving the scientific
study of:
structure,
properties,
composition,
reactions, and
preparation (by synthesis or by other means)
of carbon-based compounds, and their derivatives.
Hydrocarbons
contain only two elements, which are C and H.
Hydrocarbons that contain a delocalized ring of -bonds such as
benzene ring are called aromatic hydrocarbons.
Those without delocalized systems (contain only -bonds) are
called aliphatic hydrocarbons.
Saturated contains only single bonds
Unsaturated contain at least one double or triple bond
Hydrocarbons
Aliphatic
hydrocarbo
ns
Alkanes
Cycloalkan
es
Alkenes
Alkynes
Aromatic
hydocarbo
ns
Hybridisation
Example
Single
H
H
CC
CH
CX
sp
one -bond
3
methane (CH4)
H
C Cl
chloroethane
(CH3CH2Cl)
Double
H
C
sp
one -bond
and one bond
2
C=C
C=O
ethane (CH2CH2)
H3C
H
C
C
CH3
but-2-ene
(CH3CHCHCH3)
PUSAT ASASI SAINS
H C
CC
CN
sp
one -bond and
two -bonds
ethyne (CHCH)
sp2
-bonds and
delocalized electrons
benzene (C6H6)
Aromatics
Alternate
C-C &
C=C
Bonding in Benzene
Each carbon atom uses the sp2 hybrids to form sigma bonds with
two other carbons and one hydrogen atom
The px and py orbital are hybridized to form sp2 hybridization. pz
electron on each carbon atom overlapping with those on both
sides of it.
electrons are no longer held between just two carbon atoms, but
are spread over the whole ring (delocalised).
Functional Groups
A functional group is an atom or group of atoms within a molecule
that shows a characteristic set of physical and chemical properties
of the compound. Functional groups are important for three
reason; they are
the units by which we divide organic compounds into classes
the basis for naming organic compounds (parent chain)
the sites of characteristic chemical reactions
OH
Functional Groups
Multiple carbon-carbon bonds
Alkanes have a C-C
single bond
Alkenes have a C=C
double bond
Alkynes have a CC
triple bond
Arenes or Aromatics
have special bonds that
are represented as
alternating single and
double C-C bonds in a
six-membered ring
Functional Groups
Carbon singly bonded to an electronegative atom
Functional Groups
Carbon-Oxygen double bond (Carbonyl)
Functional Groups
Priority as parent chain in nomenclature
Functional
Group
Highest priority
Prefix
(substituent)
Suffix
(parent)
-carboxylic
carboxylic acid carboxyacid
-oic acid
ester
(R)-oxycarbonyl-oate
acyl halide
halocarbonyl-oyl halide
-carboxamide
amide
carbamoyl-amide
nitrile
cyano-nitrile
-al
aldehyde
formyl-carbaldehyde
ketone
oxo-one
alcohol
hydroxyl-ol
amine
amino-amine
alkene
alkenyl
-ene
alkyne
alkynyl
-yne
Everything below from here ends in -ane
alkane
alkyl
-ane
ether
alkoxy
-ane
haloalkane
halo-ane
nitro
nitro-
-ane
Example
ethanoic acid
methyl ethanoate
ethanoyl chloride
ethanamide
ethanonitrile
ethanal
2-propanone
methanol
methylamine
butene
butyne
butane
methoxy methane
bromoethane
nitromethane
Homologous Series
group of organic chemical compounds, usually listed in order of
increasing size,
have a similar structure (and hence also similar properties) and
structures differ only by the number of CH2 units in the main carbon
chain.
CnH2n+2
where the letter n represents the number of carbon atoms in each
molecule of the compound
Homologous Series
Name of Series
Alkanes
CnH2n+2
Alkenes
CnH2n
Alkynes
CnH2n-2
Haloalkanes
Alcohols (primary)
CnH2n+1X
CnH2n+1O or CnH2nOH
CnH2nO
Carboxylic Acids
CnH2nO2
Acyl Halides
CnH2nOX
Amines
CnH2n+1NH2 or CnH2n+3N
Amides
CnH2n-1ONH2 or CnH2n+1ON
Nitriles
CnH2n-3N
Homologous Series
Name based on number of carbon in the longest or parent
hydrocarbon chain
Number of Carbon
Prefix
Meth-
Eth-
Prop-
But-
Pent-
Hex-
Hept-
Oct-
Non-
10
Dec-
11
Undec-
12
Dodec-
Homologous Series
EXAMPLE 1.1: Homologous series for alkanes
Name
Formula
Methane
CH4
Ethane
CH3CH3
Propane
CH3CH2CH3
Butane
CH3CH2CH2CH3
Pentane
CH3CH2CH2CH2CH3
Hexane
CH3CH2CH2CH2CH2CH3
Heptane
CH3CH2CH2CH2CH2CH2CH3
Octane
CH3CH2CH2CH2CH2CH2CH2CH3
Nonane
CH3CH2CH2CH2CH2CH2CH2CH2CH3
10
Decane
CH3CH2CH2CH2CH2CH2CH2CH2CH2CH3
11
Undecane
CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3
12
Dodecane
CH3CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH3
No. of Carbon
Homologous Series
Organic compounds that are part of the same homologous series
generally have similar chemical properties as each other,
presence of the same functional group in the molecules of all
compounds
there may still be trends through the group
Physical properties of organic compounds that are part of the
same homologous series follow trends through the series.
depends on its size, (it's position within the series)
E.g. boiling points
Chemical Formulas
The formulas for compounds can be expressed as an empirical
formula and as a molecular(true) formula.
An empirical formula represents the simplest whole number
ratio of the atoms in a compound.
The molecular formula is the true or actual ratio of the atoms in
a compound.
Empirical
Molecular Formula
Formula
(true)
CH
C 2H2
acetylene
CH
C 6H6
benzene
CO2
CH2O
PUSAT ASASI SAINS
CO2
Name
carbon dioxide
C5H10O5
ribose
Structural Formula
Expanded Structural Formula
otherwise known as Lewis Structures
used to represent organic compounds and show which atoms are
connected each other.
Basically, a line is drawn between atoms to show a bond, or the
bond can be symbolized with a pair of dots.
Lone pairs of electrons are always shown as pairs of dots.
Structural Formula
Condensed Structural Formula
written without showing all the individual bonds.
In a condensed structure, each central atom is shown together
with the atoms that are bonded to it.
Expanded
Condensed
Structural Formula
Structural Formula
Skeletal Formula
In a skeletal formula, all the hydrogen atoms are removed from
carbon chains, leaving just a carbon skeleton with functional
groups attached to it.
The normal structural formula and the skeletal formula look like
this:
Butane
CH3
butan-2-ol
CH3-CH2-CH2-
CH3-CH-CH2-CH3
Structural Formula
EXAMPLE 1.2: A hexane molecule can be represented in several
ways. Show the expanded, condensed and skeletal
structure of hexane. (molecular formula: C6H14)
SOLUTION:
Expanded
Skeletal
Condensed
Structural Formula
EXAMPLE 1.3: Show the empirical formula, expanded, condensed
and skeletal formula for ethanoic acid. The
molecular formula of acetic acid is: C2H4O2
SOLUTION:
Skeletal Structure:
3D Models
Condensed Structure:
CH3COOH
Structural Formula
EXERCISE 1.1: Represent the succinic acid molecule,
HOOCCH2CH2COOH, through empirical, molecular,
structural, and skeletal formulas
Molecular formula:
C4H6O4
Empirical formula:
C2H3O2
Expanded formulas:
Skeletal
formula:
O
Isomerism
Isomers are molecules that have the same molecular formula, but
have a different arrangement of the atoms in space. That excludes
any different arrangements which are simply due to the molecule
rotating as a whole.
Not isomers
F
Isomers
F
PUSAT ASASI SAINS
Isomerism
Chain
Position
Functional Group
cis- ; transZ- ; E-
R-; SD-; L-
Meso
eclipsed
staggered
Constitutional Isomers
Compounds that have the same molecular formula and
different connectivity
Chain
Different arrangement of hydrocarbon chain
Position
Different positions of atoms other than C and H on the
hydrocarbon chain
Functional Group
Different position of functional groups on the hydrocarbon
chain
Constitutional Isomers
EXAMPLE 1.4: Constitutional isomers (chain) of pentane
n-pentane
isopentane or 2methylbutane
neopentane or 2,2dimethylpropane
Constitutional Isomers
EXAMPLE 1.5: Constitutional isomers of butanol (chain and
position)
OH
OH
butan-1-ol
butan-2-ol
OH
OH
2-methylpropan-1-ol
2-methylpropan-2-ol
Constitutional Isomers
EXAMPLE 1.6: Constitutional isomers (functional group) of between
aldehyde and ketone
O
H
butanal (C4H8O)
butan-2-one (C4H8O)
(aldehyde)
(ketone)
Constitutional Isomers
EXAMPLE 1.6: Draw the constitutional isomers of butane (C4H8):
SOLUTION
The constitutional isomers of butene are but-1-ene, but-2-ene, 2methylprop-1-ene, cyclobutane and 1-methylcyclopropane
Constitutional Isomers
EXERCISE 1.2: Draw six possible constitutional isomers of C6H12 :
SOLUTION
Stereoisomers: Conformational
Involves rotation about the -bonds
All conformational isomers are the exact same molecule
differ only in terms of the angle about one or more sigma bonds.
Stereoisomers: Conformational
A convenient way of visualizing the conformational isomers of a
molecule is by using the Newman projection
CH3
H3C
CH2
CH2
CH3
CH3
Condensed structure
Sawhorse projection
Newman projection
Stereoisomers: Conformational
In ethane, (C2H6), the central carbon-carbon bond rotates freely.
the hydrogen atoms on the adjacent carbon atoms can be either
alternating (staggered) or all lined up (eclipsed)
H
H
H
staggered
H
H
H
H
eclipsed
Stereoisomers: Conformational
On larger molecule, more conformational isomers are possible:
A
Anti
conformation
Eclipsed
conformation
Gauche
conformation
Fully-eclipsed
conformation
Stereoisomers: Conformational
Anti has the lowest energy conformation while fully eclipsed is the
least stable of all
D
D
B
C
A
60
120
180
Degrees of Rotation
240
300
360
Stereoisomers: Geometric
Geometric isomers occur where there is a restricted rotation
somewhere in a molecule.
The common example is the double bond.
double bond comprised of two p orbitals that form a -bond surrounding the
single -bond, it cannot be rotated.
other atoms connected to the two double-bonded carbon atoms can move,
they can be in different position in space.
This create stereoisomers of the molecule. Other types of bond that cannot be
rotated is the -bonds that formed a ring (cyclic) structures.
Stereoisomers: Geometric
Example: but-2-ene molecule.
Two possible isomers
CH3 atoms are locked on opposite sides of the double bond.
trans isomer (from latin meaning "across" - as in transatlantic).
CH3 atoms are locked on the same side of the double bond.
cis isomer (from latin meaning "on this side").
H3C
CH3
trans- but-2-ene
H3C
H
cis- but-2-ene
CH3
Stereoisomers: Geometric
Branched cycloalkanes also have the cis-trans isomers
CH3
CH3 CH3
cis- 1,2-dimethylcyclopentane
H3C
trans- 1,2-dimethylcyclohexane
restricted rotation
two different groups on the left-hand end of the bond and two
different groups on the right-hand end. It doesn't matter whether
the left-hand groups are the same as the right-hand ones or not.
Stereoisomers: Geometric
EXERCISE 1.3: Draw the cis-trans isomers of the following
compounds:
pent-2-ene
1,2-dichlorobutane
SOLUTION
i)
trans-pent-2-ene
cis-pent-2-ene
ii)
Cl
Cl
trans-1,2-dichlorobutane
PUSAT ASASI SAINS
Cl
Cl
cis-1,2-dichlorobutane
Stereoisomers: Geometric
The E-Z notation
when there are more than two different atoms connected to the
carbon-carbon double bond, problem arise on deciding which
atoms to look at when determining the geometrical isomerism
H
Cl
Br
Cl
Cl
trans -1,2-dichloroethene
?-1-bromo-2-chloro-1-fluoroethene
Stereoisomers: Geometric
For the 1-bromo-2-chloro-1-fluoroethene,
priority needs to be determined between (F and Br)
and (Cl and H) atoms.
Br takes priority before F and Cl takes priority before H.
In this case the two priority atoms are on the same side
of the double bond, and therefore given the notation Z(a German word zusammen which means together).
Therefore, the correct IUPAC name for the molecule is
(Z)-1-bromo-2-chloro-1-fluoroethene.
Br 1
Cl 1
F2
H2
Stereoisomers: Geometric
The rule for determining priorities are known as Cahn-IngoldPrelog (CIP) rules. The following rules applies when in CIP:
Rule 1
First, examine at the atoms directly attached to the stereocenter
(or the double bond) of the compound.
A substituent with a higher atomic number takes precedence over a
substituent with a lower atomic number. Hydrogen is the lowest possible
priority substituent, because it has the lowest atomic number.
Stereoisomers: Geometric
Rule 2
If there are two substituents with equal rank, proceed along the
two substituent chains until there is a point of difference.
First, determine which of the chains has the first connection to an atom with
the highest priority (the highest atomic number).That chain has the higher
priority.
If the chains are similar, proceed down the chain, until a point of difference.
Stereoisomers: Geometric
Rule 3
If a chain is connected to the same kind of atom twice or three
times, check to see if the atom it is connected to has a greater
atomic number than any of the atoms that the competing chain is
connected to.
If none of the atoms connected to the competing chain(s) at the same point has a
greater atomic number: the chain bonded to the same atom multiple times has the
greater priority
If however, one of the atoms connected to the competing chain has a higher atomic
number: that chain has the higher priority.
Stereoisomers: Geometric
EXAMPLE 1.7: Determine whether the following compound, 2-bromo-3chloro-4-ethylhept-3-ene should use the E- or Z- notation:
Br
CH3
H3C
Cl
CH3
Stereoisomers: Geometric
Br
CH3
H3C
Cl
CH3
SOLUTION
1.On the left side of the C=C, Cl takes priority over C-H
2.On the right side, the first immediate atoms is similar (C-H), the second atoms are C-C
at the top and C-H at the bottom. So C-C takes priority.
3.Since the priority atoms are on the opposite side of the C=C, the correct notation is E4.The full IUPAC name of the molecule is:
(3E)-2-bromo-3-chloro-4-ethylhept-3-ene
NOTE: 3E means the C=C is between carbon number 3 and 4.
Stereoisomers: Optical
Optical isomerism is one form of stereoisomerism. Optical isomers
are named like this because of their effect on plane polarised light
Stereoisomers: Optical
Only chiral molecule has optical isomer. Consider two
compounds A and B:
F
H3C
F
CH3
Br C
Cl
Cl
(A)
(B)
CH3
Stereoisomers: Optical
EXERCISE 1.4: Determine whether the following structures are
chiral or achiral molecules:
O
Cl
achir
al
chiral
CH3 Br
CH3
H2N
H3C
OH
achir
al
H
CH3 Cl
chiral
Stereoisomers: Optical
Enantiomer
Simple substances which show optical isomerism exist as two
isomers known as enantiomers.
rotate the plane of polarization in a clockwise and anti-clockwise
direction.
Two enantiomers are non-superimposable mirror images of
one another (chiral)
Stereoisomers: Optical
Optical isomers have basically the same properties (melting
points, boiling points, etc.)
There are drugs, called enantiopure drugs that have different
effects based on whether the drug is a racemic mixture or purely
one enantiomer.
For example, D-ethambutol treats tuberculosis, while Lethambutol causes blindness.
Optical activity is the interaction of these enantiomers with planepolarized light
Stereoisomers: Optical
R and S Configurations
The absolute configuration for an enantiomer can be notated by
determining whether it rotate clockwise (to the right) or anticlockwise (to the left).
These are noted as R- (in Latin: rectus) and S- (in Latin: sinister)
respectively.
Other notations can also be used (usually for the more complex
molecules in spectroscopy) such as:
(+)-, D- or d- (dextrorotary) for the rotation to the right, and
(-)-, L- or l- (levorotary) for rotation to the left.
Stereoisomers: Optical
Example: 3D projection of 2-bromobutane
Br
Br
CH2CH3
H3C
(2R)-2-bromobutane
H3CH2C
CH3
(2S)-2-bromobutane
Stereoisomers: Optical
Determination of R- and S- notation
1.
2.
3.
Reposition the molecule so that the lowest priority (4) group is at the
back as if you were looking along the C-(4) bond
1
4
2
3
3
2
(R)
(S)
4. Assess whether the increasing order of priority follow clockwise (to the
right) which means R or anti-clockwise (to the left) which means S.
PUSAT ASASI SAINS
Stereoisomers: Optical
EXERCISE 1.5: Determine whether the following Lactic acid is R or
S enantiomer:
OH
COOH
H3C
SOLUTION
R enantiomer
Stereoisomers: Optical
EXERCISE 1.6: Draw the R and S enantiomer of 3-chlorohexane
using the 3D projection:
Cl
H5 C 2 C
C 3H 7
SOLUTION
Cl
Cl
C
C2 H 5
H 7C3
(3R)-3-chlorohexane
PUSAT ASASI SAINS
H5 C2
H
C3H 7
(3S)-3-chlorohexane
Stereoisomers: Optical
Larger molecules have the possibility of having two or more chiral
centers.
To determine whether two molecules are enantiomer to each other
needs further evaluation rather than just looking at the one chiral
center.
A pair of isomers that have more than one chiral center can be
diastereomers.
Diastereomers are stereoisomers that are not mirror images
of one another and are non-superimposable on one another.
Diastereomerism occurs when two or more stereoisomers of a
compound have different configurations at one or more (but not
all) of the equivalent (related) chiral centers.
Stereoisomers: Optical
CH3
CH3
CH3
CH3
Br
Br
Br
Br
Cl
Cl
Cl
H H
Cl
CH3
Mirror image
Enantiomers
CH3
CH3
CH3
Non-mirror image
Diastereomers
Stereoisomers: Optical
If a molecule with two chiral centers produces a mirror image
within the molecule, it is called a meso compound.
Meso compound is optically inactive.
CH3
CH3
CH3
H
Br
Br
Br
CH3
Enantiomers
H
Br
CH3
CH3
Br
Br
Br
Br
CH3
CH3
Meso
Stereoisomers: Optical
EXERCISE 1.7 : Draw the possible geometric and optical isomers of
1-bromo-1,3-dichlorobut-2-ene:
H3C
Cl
Br
Cl
Stereoisomers: Optical
SOLUTION
H3C
Br
H3C
Cl
Br
Cl
Cl
(2Z)-1-bromo-1,3-dichlorobut-2-ene
(2E)-1-bromo-1,3-dichlorobut-2-ene
Br
Br
C
Cl
ClH 4C3
(1S)-1-bromo-1,3-dichlorobut-2-ene
Cl
Cl
H
C3H4Cl
(1R)-1-bromo-1,3-dichlorobut-2-ene
To be continued
PUSAT ASASI SAINS