P11-13 Isomerisms Functional Groups and Reaction

Lecture Presentation
Mechanism
ISOMERS Reaction of
Organic
Compounds
TYPE OF REACTION
Cahyaning Rini U., S.Si., M.Sc.
Some molecules with the alcohol functional group
Figure 15.20 Some common aldehydes and ketones.
Methanal (formaldehyde) Used

to make resins in plywood,
dishware, countertops; Benzaldehyde Artificial
biological preservative almond flavoring
Ethanal (acetaldehyde) 2-Propanone (acetone) 2-Butanone

Narcotic product of ethanol Solvent for fat, rubber, plastic, (methyl ethyl ketone)
metabolism; used to make varnish, lacquer; chemical Important solvent
perfumes, flavors, plastics, feedstock
other chemicals
Figure 15.22 Some molecules with the carboxylic acid functional
group.
Methanoic acid (formic acid) Butanoic acid (butyric acid)

An irritating component of ant and Odor of rancid butter; suspected
bee stings component of monkey sex
attractant
Benzoic acid
Calorimetric standard; used in
preserving food, dyeing fabric, Octadecanoic acid (stearic acid)
curing tobacco Found in animal fats; used in making
candles and soaps
Figure 15.23 Some lipid molecules with the ester functional
group.
Cetyl palmitate
The most common
lipid in whale
blubber
Tristearin Typical dietary fat

used as an energy store in
animals
Lecithin Phospholipid found in all cell
membranes
Figure 15.18 Some biomolecules with the amine functional group.
Lysine (1° amine) Adenine (1° amine)

amino acid found component of
in proteins nucleic acids
Epinephrine
(adrenaline; 2° Cocaine (3°
amine) amine)
neurotransmitter brain stimulant;
in brain; widely abused
hormone drug
released during
stress
Figure 15.24 Some molecules with the amide functional group.
Acetaminophen
Active ingredient in nonaspirin
pain relievers; used to make dyes
and photographic chemicals
Lysergic acid diethylamide (LSD-25)

N,N-Dimethylmethanamide A potent hallucinogen
(dimethylformamide)
Major organic solvent; used in
production of synthetic fibers
Identify of Compounds—Functional Groups
Pharmaceuticals Are Organic Compounds

Open the package of any prescription medication, and you will find
an insert that includes a description and chemical structure.
ISOMERISM
TYPE ISOMERISM
STRUCTURAL ISOMERISM - INTRODUCTION
COMPOUNDS HAVE THE SAME MOLECULAR FORMULA
BUT DIFFERENT STRUCTURAL FORMULA
Chain different arrangements of the carbon skeleton

similar chemical properties
slightly different physical properties
more branching = lower boiling point
Positional same carbon skeleton

same functional group
functional group is in
a different position
similar chemical
Functional Group properties - slightlygroup
different functional
different
different physical
chemical properties
properties
different physical properties
• Sometimes more than one type of isomerism occurs in the same molecule.
• The more carbon atoms there are, the greater the number of possible isomers
STRUCTURAL ISOMERISM - CHAIN
caused by different arrangements of the carbon skeleton

similar chemical properties
slightly different physical properties
more branching = lower boiling point
There are two structural isomers of C4H10. One is a straight chain molecule where all
the carbon atoms are in a single row. The other is a branched molecule where three
carbon atoms are in a row and one carbon atom sticks out of the main chain.
BUTANE 2-METHYLPROPANE
straight chain branched
C4H10
STRUCTURAL ISOMERISM - CHAIN
DIFFERENCES BETWEEN CHAIN ISOMERS
Chemical Isomers show similar chemical properties because

the same functional group is present.
Physical Properties such as density and boiling point show trends according
to the of the degree of branching
Boiling Point “straight” chain isomers have higher values than branched ones
the greater the degree of branching the lower the boiling point
branching decreases the effectiveness of intermolecular forces
less energy has to be put in to separate the molecules
- 0.5°C - 11.7°C greater branching

straight chain branched = lower boiling point
STRUCTURAL ISOMERISM - POSITIONAL
molecule has the same carbon skeleton
molecule has the same same functional group... BUT
the functional group is in a different position
have similar chemical properties / different physical
properties
Example 1 POSITION OF A DOUBLE BOND IN ALKENES
1 2 2 3
PENT-1-ENE PENT-2-ENE
double bond between double bond between
carbons 1 and 2 carbons 2 and 3
There are no other isomers with five C’s in the longest chain but there are three
other structural isomers with a chain of four carbons plus one in a branch.
properties
Example 2 POSITION OF A HALOGEN IN A HALOALKANE
1 2 BUT 2
1-CHLOROBUTANE 2-CHLOROBUTANE is NOT

halogen on carbon 1 halogen on carbon 2 3-CHLOROBUTANE
Moving the chlorine along the chain makes new isomers; the position is measured from
the end nearest the functional group... the third example is 2- NOT 3-chlorobutane.
There are 2 more structural isomers of C4H9Cl but they have a longest chain of 3
properties
Example 3 RELATIVE POSITIONS ON A BENZENE RING
1,2-DICHLOROBENZENE 1,3-DICHLOROBENZENE 1,4-DICHLOROBENZENE

ortho dichlorobenzene meta dichlorobenzene para dichlorobenzene
STRUCTURAL ISOMERISM – FUNCTIONAL GROUP
molecules have same molecular formula
molecules have different functional groups
molecules have different chemical properties
molecules have different physical properties
ALCOHOLS and ETHERS
ALDEHYDES and KETONES
ACIDS and ESTERS

ALCOHOLS and ETHERS
Name ETHANOL METHOXYMETHANE
Classification ALCOHOL ETHER
Functional Group R-OH R-O-R
Physical properties polar O-H bond gives rise No hydrogen bonding

to hydrogen bonding. low boiling point
get higher boiling point insoluble in water
and solubility in water
Chemical properties Lewis base Inert

Wide range of reactions
ALDEHYDES and KETONES
Name PROPANAL PROPANONE
Classification ALDEHYDE KETONE
Functional Group R-CHO R-CO-R
Physical properties polar C=O bond gives polar C=O bond gives
dipole-dipole interaction dipole-dipole interaction
Chemical properties easily oxidised to acids of undergo oxidation under

same number of carbons extreme conditions only
reduced to 1° alcohols reduced to 2° alcohols

CARBOXYLIC ACIDS and ESTERS
Name PROPANOIC ACID METHYL ETHANOATE
Classification CARBOXYLIC ACID ESTER

Functional Group R-COOH R-COOR
Physical properties O-H bond gives rise No hydrogen bonding
to hydrogen bonding. insoluble in water
get higher boiling
point
and solubility in
water
Chemical properties acidic fairly unreactive
react with alcohols hydrolysed to acids
STEREOISOMERISM
Molecules have the SAME MOLECULAR FORMULA but the atoms are
joined to each other in a DIFFERENT SPACIAL ARRANGEMENT - they
occupy a different position in 3-dimensional space.
There are two types...
• GEOMETRICAL ISOMERISM
• OPTICAL ISOMERISM
GEOMETRICAL ISOMERISM IN ALKENES
Introduction
• an example of stereoisomerism
• found in some, but not all, alkenes
• occurs due to the RESTRICTED ROTATION OF C=C bonds
• get two forms...
Introduction
• an example of stereoisomerism
• found in some, but not all, alkenes
• occurs due to the RESTRICTED ROTATION OF C=C bonds
• get two forms...
CIS (Z) TRANS (E)

Groups/atoms are on the Groups/atoms are on OPPOSITE
SAME SIDE of the double bond SIDES across the double bond
GEOMETRICAL ISOMERISM
RESTRICTED ROTATION OF C=C BONDS
Single covalent bonds can easily rotate. What appears to be a different structure is
not. It looks like it but, due to the way structures are written out, they are the same.
ALL THESE STRUCTURES ARE THE SAME BECAUSE C-C BONDS HAVE ‘FREE’ ROTATION
Animation doesn’t
work in old
versions of
Powerpoint
RESTRICTED ROTATION OF C=C BONDS
C=C bonds have restricted rotation so the groups on either end of the bond are
‘frozen’ in one position; it isn’t easy to flip between the two.
Animation doesn’t
work in old
versions of
Powerpoint
This produces two possibilities. The two structures cannot interchange easily
so the atoms in the two molecules occupy different positions in space.
E/Z or CIS-TRANS
E/Z Z (zusammen) higher priority groups / atoms on

the SAME side of C=C bond
E (entgegen) higher priority groups / atoms on

OPPOSITE sides of C=C bond
E/Z or CIS-TRANS


To determine priority, the Cahn, Ingold and Prelog convention is used.
eg C2H5 > CH3 > H and I > Br > Cl > F > C > H
E/Z or CIS-TRANS


E/Z or CIS-TRANS


E Z Z E
E/Z or CIS-TRANS
CIS / Should only be used when there are two H’s and two
TRANS non-hydrogen groups attached to each carbon.
cis non-hydrogen groups / atoms on the

SAME side of C=C bond
trans non-hydrogen groups / atoms on

E/Z or CIS-TRANS


E/Z or CIS-TRANS


cis trans cis trans

GEOMETRY ISOMERS
Isomerism in butene
There are 3 structural isomers of C4H8 that are alkenes*. Of these ONLY
ONE exhibits geometrical isomerism.
but-1-ene cis but-2-ene trans but-2-ene 2-methylpropene

(Z) but-2-ene (E) but-2-ene
* YOU CAN GET ALKANES WITH FORMULA C H 4 8 IF THE CARBON ATOMS ARE IN A RING
How to tell if it exists
Two different Two different

atoms/groups
attached
atoms/groups
attached  GEOMETRICAL ISOMERISM
Two similar Two similar

atoms/groups
attached
atoms/groups
attached  Once you get two similar
atoms/groups attached to
one end of a C=C, you
Two similar Two different cannot have geometrical
atoms/groups
attached
atoms/groups
attached  isomerism
Two different Two different

atoms/groups
attached
atoms/groups
attached  GEOMETRICAL ISOMERISM
OPTICAL ISOMERISM
Occurrence another form of stereoisomerism
occurs when compounds have non-superimposable mirror images
Isomers the two different forms are known as optical isomers or enantiomers
they occur when molecules have a chiral centre
a chiral centre contains an asymmetric carbon atom
an asymmetric carbon has four different atoms (or groups)
arranged tetrahedrally around it.
OPTICAL ISOMERISM
Occurrence another form of stereoisomerism
occurs when compounds have non-superimposable mirror images
Isomers the two different forms are known as optical isomers or enantiomers
they occur when molecules have a chiral centre
a chiral centre contains an asymmetric carbon atom
an asymmetric carbon has four different atoms (or groups)
arranged tetrahedrally around it.
CHIRAL CENTRES
There are four different colours 2-chlorobutane exhibits optical isomerism

arranged tetrahedrally about because the second carbon atom has
the carbon atom four different atoms/groups attached
OPTICAL ISOMERISM
SPOTTING CHIRAL CENTRES
Look at each carbon atom in the chain and see what is attached to it. For a chiral centre
you need an asymmetric carbon with four different atoms/groups) arranged tetrahedrally around
it.
IF A CARBON HAS MORE THAN ONE OF ANY ATOM/GROUP ATTACHED, IT CAN’T BE CHIRAL
C 3 H’s around it NOT chiral

CH3CH2CH2CH2Cl C 2 H’s around it NOT
1-chlorobutane C 2 H’s around it chiral 
NOT
chiral
OPTICAL ISOMERISM
it.

CH3CH2CH2CH2Cl C 2 H’s around it NOT chiral
1-chlorobutane C 2 H’s around it NOT chiral 
CH3CH2CHClCH3 C 3 H’s around it NOT chiral

2-chlorobutane C H, CH3, Cl,C2H5 around it CHIRAL 
OPTICAL ISOMERISM
it.

CH3CH2CH2CH2Cl C 2 H’s around it NOT
1-chlorobutane C 2 H’s around it chiral 
NOT
chiral
NOT chiral
CH3CH2CHClCH3 C 3 H’s around
it C 2 H’s around NOT
2-chlorobutane it chiral 
C H, CH3, CHIRAL
Cl,C2H5 around it NOT chiral
(CH3)2CHCH2Cl
1-chloro-2-methylpropanane
it 2 CH3’s around it
C
C 2 H’s around it chiral
NOT 
NOT chiral
(CH3)3CCl C 3 H’s around it NOT chiral

2-chloro-2-methylpropanane
C 3 CH3’s around it NOT
chiral

OPTICAL ISOMERISM
Spatial differences between isomers
• two forms exist which are NON-SUPERIMPOSABLE MIRROR IMAGES of each other
• non-superimposable means you you can’t stack one form exactly on top of the other
OPTICAL ISOMERS - DIFFERENCE
• isomers differ in their reaction to plane-polarised light
• plane polarised light vibrates in one direction only
• one isomer rotates light to the right, the other to the left
• rotation of light is measured using a polarimeter
• rotation is measured by observing the polarised light coming out towards the observer
• If the light appears to have turned to the right turned to the left
DEXTROROTATORY LAEVOROTATORY
d or + form l or - form
• If the light appears to have turned to the right turned to the left
DEXTROROTATORY LAEVOROTATORY
d or + form l or - form
Racemate a 50-50 mixture of the two enantiomers (dl) or (±) is a racemic mixture.
The opposite optical effects of each isomer cancel each other out
Examples Optical activity is common in biochemistry and pharmaceuticals

• Most amino acids exhibit optical activity
• many drugs must be made of one optical isomer to be effective
- need smaller doses (safer and cost effective)
- get reduced side effects
- improved pharmacological activity

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Lecture Presentation

Methanal (formaldehyde) Used

Ethanal (acetaldehyde) 2-Propanone (acetone) 2-Butanone

Methanoic acid (formic acid) Butanoic acid (butyric acid)

Tristearin Typical dietary fat

Lysine (1° amine) Adenine (1° amine)

Lysergic acid diethylamide (LSD-25)

Pharmaceuticals Are Organic Compounds

Chain different arrangements of the carbon skeleton

Positional same carbon skeleton

caused by different arrangements of the carbon skeleton

Chemical Isomers show similar chemical properties because

- 0.5°C - 11.7°C greater branching

Example 1 POSITION OF A DOUBLE BOND IN ALKENES

Example 2 POSITION OF A HALOGEN IN A HALOALKANE

1-CHLOROBUTANE 2-CHLOROBUTANE is NOT

Example 3 RELATIVE POSITIONS ON A BENZENE RING

1,2-DICHLOROBENZENE 1,3-DICHLOROBENZENE 1,4-DICHLOROBENZENE

ALCOHOLS and ETHERS

ALDEHYDES and KETONES

ACIDS and ESTERS

ALCOHOLS and ETHERS

Name ETHANOL METHOXYMETHANE

Classification ALCOHOL ETHER

Functional Group R-OH R-O-R

Physical properties polar O-H bond gives rise No hydrogen bonding

Chemical properties Lewis base Inert

ALDEHYDES and KETONES

Name PROPANAL PROPANONE

Classification ALDEHYDE KETONE

Functional Group R-CHO R-CO-R

Chemical properties easily oxidised to acids of undergo oxidation under

reduced to 1° alcohols reduced to 2° alcohols

CARBOXYLIC ACIDS and ESTERS

Name PROPANOIC ACID METHYL ETHANOATE

Classification CARBOXYLIC ACID ESTER

There are two types...

CIS (Z) TRANS (E)

RESTRICTED ROTATION OF C=C BONDS

RESTRICTED ROTATION OF C=C BONDS

E/Z Z (zusammen) higher priority groups / atoms on

E (entgegen) higher priority groups / atoms on

E/Z Z (zusammen) higher priority groups / atoms on

E (entgegen) higher priority groups / atoms on

To determine priority, the Cahn, Ingold and Prelog convention is used.

E/Z Z (zusammen) higher priority groups / atoms on

E (entgegen) higher priority groups / atoms on

To determine priority, the Cahn, Ingold and Prelog convention is used.

E/Z Z (zusammen) higher priority groups / atoms on

E (entgegen) higher priority groups / atoms on

To determine priority, the Cahn, Ingold and Prelog convention is used.

cis non-hydrogen groups / atoms on the

trans non-hydrogen groups / atoms on

cis non-hydrogen groups / atoms on the

trans non-hydrogen groups / atoms on

cis non-hydrogen groups / atoms on the

trans non-hydrogen groups / atoms on

cis trans cis trans

but-1-ene cis but-2-ene trans but-2-ene 2-methylpropene