Organic Molecules React in

Predictable Ways

Functional Groups – atoms or groups of atoms

that determine the reactive, structural, or other
functional characteristics of a molecule.

Understanding Functional Groups is

the secret to learning organic chemistry!
As the periodic table is to inorganic chemistry, functional groups are
to organic chemistry.

Four Important Functional Groups

Alcohol group (Hydroxyl group) Ether group

.. ..
C
..O H
C
..O C

Carboxylic acid group Ester group

.. ..
O O
..
..
..

..
..

..
C
..O H C
..O C

1
 Amazing Diversity of Organic Compounds
Consider the number of compounds with the formula C4H8O

These are structural isomers– (from Ch.20) compounds with the same
chemical formulas, but different ways of connecting the atoms.

Alcohols
CH3OH Methyl alcohol (Methanol)

C2H5OH Ethyl alcohol (Ethanol) CH3CH2OH

C3H7OH Propyl alcohol (Propanol)

H3C CH2 CH2 OH H3C CH OH

n-Propyl alcohol
CH3
H3C CH2 CH2 CH2 OH 2-Propyl alcohol
n-Butyl alcohol

2
Some Molecules with Alcohol Functional Groups

Ketones
O
Dimethyl ketone
H3C C CH3
(Acetone)

O
Ethyl methyl ketone
H3C CH2 C CH3

Diethyl ketone
O

H3C CH2 C CH2 CH3

3
 Aldehydes
O
Formaldehyde
(Methanal) H C H

O Acetaldehyde
(Ethanal)
H3C C H
O
CH
CH C C H
Benzaldehyde
CH CH
CH

Carboxylic Acids
O
Formic acid
H C O H
O Acetic acid

H3C C O H
Propionic acid O
H3C CH2 C O H
O
Butanoic acid
H3C CH2 CH2 C O H

4
 Esters: the Flavoring in Fruits
Benzyl acetate C9H10O2 –oil of jasmine O
CH3-C-O-CH2-
Isoamyl acetate C7H14O2–ripe apples
O CH3
CH3-C-O-CH2-CH2-CH-CH3
Ethyl 2-methylbutanoate C7H14O2–ripe apples
CH3 O
CH3-CH2-CH-C-O-CH2-CH3
Isoamyl acetate C7H14O2–bananas
O CH3
CH3-C-O-CH2-CH2-CH-CH3
Ethyl butyrate C6H12O2–pineapple O
CH3-CH2-CH2-C-O-CH2-CH3
Ethyl formate C3H6O2–rum O
H-C-O-CH2-CH3

Esters–II
Amyl butyrate C9H18O2–apricot O
CH3-CH2-CH2-C-O-CH2-CH2-CH2-CH2-CH3

Ethyl formate C3H6O2–lemonade O

H-C-CH2-CH3
n-Octyl acetate C10H20O2–oranges
O
CH3-C-O-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH3
Methyl salicylate C8H8O3–oil of wintergreen
O
C-O-CH3

OH

5
 Amines

Amines–I ..
N
NH3 Ammonia H H
H
CH3NH2 Methyl amine ..
N
(CH3)2NH Dimethyl amine H CH3
H
(CH3)3N Trimethyl amine
.. ..
N N
CH3 CH3 H CH3
CH3 CH3

6
 Amines–II

CH3-CH2-NH2 Ethyl amine

CH3-CH2-CH2-NH2 n-Propyl amine

CH3-CH2-CH2-CH2-NH2 n-Butyl amine

CH
CH C NH2
Phenyl amine
CH CH
CH

Some Biomolecules with the Amine

Functional Group

7
Structure
of a
Cationic
Detergent

Some Molecules with the Amide

Functional Group

8
 Important Functional Groups in Organic Compounds
(see Table 22.4)
Functional Group Compound Type Suffix or Prefix of Example Systematic Name
name (Common Name)
H H
C C alkene -ene C C ethene
H H (ethelene)

C C
alkyne -yne H C C H ethyne
H (acetylene)
.. ..
alcohol -ol methanol
C ..O H H C
..O H
H H (methyl alcohol)
H
C O C ether ether H C O C H dimethyl ether
H
.. H H
C ..X haloalkane halo- chloromethane
..

H C Cl
H H (methyl chloride)
.. amine -amine
H .. ethylamine
C N H C C N H

H H H

Important Functional Groups in Organic Compounds (cont)

Functional Group Compound Type Suffix or Prefix of Example Systematic Name

Name (Common Name)
..
..

..
..

O H O

C H aldehyde -al H C C H ethanal

..
..

H O H
(acetaldehyde)
..
..

O
H
C C C ketone -one H C C C H 2-propane
(acetone)
..
..

..
..

O H O
..O ..O
H H
C
.. H carboxylic acid -oic acid H C C
.. H ethanoic acid
(acedic acid)
..
..

O
H H O H
..
..
..

ester -oate ....O methyl ethanoate

..
C O C H C C C H
(methyl acetate
..
..

O
..
..
..

H H O H
C N
amide -amide
H C C
..N ethanamide
H (acetamide)
H
nitrile -nitrile H H ethanenitrile
..

C N
H C C N (acetonitrile,
..

methyl cyanide)
H

9
 Organic Molecules React in
Predictable Ways

Functional Groups – atoms or groups of atoms

that determine the reactive, structural, or other
functional characteristics of a molecule.

Understanding Functional Groups is

the secret to learning organic chemistry!

Types of Organic Reactions

1) Addition Reactions: These reactions occur when an unsaturated
compound containing a double or triple bond becomes
saturated by adding a compound. This reaction occurs
for C=O, C=C and C=C bonds.
X Y
General form: R-CH=CH-R + X-Y R-C-C-R
H H
Examples:
CH3-CH=CH-CH3 + H2 CH3-CH2-CH2-CH3

Br Br
H-CH=CH-CH2-CH3 + Br2 H-C-C-CH2-CH3
H H
H Cl
H2C=CH2 + HCl H-C-C-H
H H

10
 Types of Organic Reactions–II
2) Elimination Reactions: These are the opposite of addition reactions.
A saturated reactant becomes an unsaturated
compound, and another molecule is formed.
X Y
General form: R-CH-CH2 R-CH=CH2 + X-Y

Examples: OH H H2SO4
CH3-CH-CH2 CH3-CH=CH2 + H2O

OH Cr2O72- O
CH3-CH2-CH-CH3 CH3-CH2-C-CH3 + H2O
H2SO4
Cl H
CH3-CH-CH-CH2-CH3 CH3-CH=CH-CH2-CH3 + HCl

Types of Organic Reactions–III

3) Substitution Reactions: These reaction occur when an atom (or
group) from an added reagent substitutes
for one in the organic reactant.
General form: R-C-X + Y R-C-Y + X

Examples: CH3-OH + HBr CH3-Br + H2O

O CH3
CH3-C-Cl + CH3-CH-CH2-CH2-OH HCl + O CH3
CH3-C-O-CH2-CH2-CH-CH3

CH3-CH2-CH2-Br + NaOH CH3-CH2-CH2-OH + NaBr

CH3-CH2-CH2-Br + CH3-CH2-ONa NaBr +

CH3-CH2-CH2-O-CH2-CH3

11
 Recognizing the Type of Organic Reaction
Problem: State whether each of the following reactions is an addition,
elimination, or substitution reaction:
a) CH3-CH2-OH + CH3-OH CH3-CH2-O-CH3 + H2O
b) CH3-CH2-CH=CH-CH3 + H2 CH3-CH2-CH2-CH2-CH3
c) CH3-CH2-CH2-CH2-Cl CH3-CH2-CH=CH2 + HCl
Solution: a) Substitution–the C-OH in both reactant molecules is
converted into C-O bonds in the product molecule, so the same
number of atoms are bonded to carbon.

b) Addition–two C-H bonds form in the product, so more atoms are

bonded to carbon.

c) Elimination–two bonds in the reactant (C-H,C-Cl) are not in the

product, so fewer atoms are bonded to carbon in the product.

Redox Processes in Organic Reactions

Oxidation numbers are not relied upon as much in organic reactions.
Instead, organic chemists note the movement of electron density
around the carbon atom by counting the number of bonds to more
electronegative atoms (normally oxygen) or to less electronegative
atoms (normally H).
An oxidation-reduction (redox) reaction involves both oxidation and
reduction, but organic chemists normally focus on the organic
reactant only. Therefore:
When a C atom in the organic reactant forms more bonds to O or
fewer bonds to H, the reaction is an oxidation.

When a C atom in the organic reactant forms fewer bonds to O or

more bonds to H, the the reaction is a reduction.

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 Organic Oxidation and Reduction Reactions
An example of an organic reaction that involves oxidation-reduction
is the reaction that occurs with ethanol and acidic potassium dichromate
to yield acetic acid: O
K2Cr2O7 (acid)
CH3-CH2-OH CH3-C-OH
In ethanol, C-2 has 2 bonds to hydrogen and 1 bond to oxygen,
whereas in the product (acetic acid) C-2 has 3 bonds to oxygen and
no bonds to hydrogen. Thus, in this reaction the ethanol is oxidized to
form acetic acid, so this reaction is an oxidation.

Another example is the addition of hydrogen to the double bond in

propylene to form propane:
Pd
CH3-CH=CH2 + H2 CH3-CH2-CH3
Note that C-2 and C-3 of the product have more bonds to hydrogen than
in the reactant, so this reaction is a reduction.

Some Examples
Problem: Determine the reaction type and predict the products of the
following chemical reactions:
Cr2O7-2
(a) CH3-CH2-CH2-OH H2SO4

(b) CH3-CH2-Br + KOH

Solution:
O
(a) Elimination (oxidation): CH3-CH2-C-OH Propanoic acid

(b) Substitution: CH3-CH2-OH + KBr Ethyl alcohol

13
Important Polymer Linkage Groups
• Linkage -COO- -CONH- -C-O-C-

• Name Ester Amide Ether

• Precursors Acid + Acid + Alcohol +

• Alcohol Amine Alcohol

• Polymer
• Type
• Polyesters Polyamides Cellulose
• Proteins Starch

Image to come.

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 Benzoyl Peroxide
O

O
O

Heat
A “free radical” is a
O molecule with an
unpaired electron.

O.
2

Polymerization of Ethylene–I
O
Benzoyl peroxide Ethylene
radical
+ H2C CH2
O.

CH2
O CH2
.
Adduct

15
 Polymerization of Ethylene–II
O
CH2 + 2 H2C CH2
O CH2
.

O
CH2 CH2 CH2
O CH2 CH2 CH2
.

Poly(Vinyl Chloride) (PVC) and Teflon

H H H H H H H H H H
C C C C C C C C C C
H Cl H Cl H Cl H Cl H Cl n
Vinyl chloride PVC

F F F F F F F F F F
C C C C C C C C C C
F F F F F F F F F F n

Tetrafluoroethylene Teflon

16
 Styrene Polystyrene
H H
C C
H

H H H H H H H H H
C C C C C C C C C
H H H H H n

Condensation Polymers
O Polyamides–Nylon-66
OH
HO
Adipic acid
+
O NH2
H2N
Hexamethylenediamine

O H
N
N
O H n

17
Structures and Applications of Some Major Addition
Polymers (Based upon the Ethylene Molecule)–I

Monomer Polymer Applications

H H
C C Polyethylene Plastic bags, bottles, toys
H H

F F
C C Polytetrafluoroethylene Cooking utensils
F F (e.g. Teflon)

H H
C C Polypropylene Carpeting (indoor-outdoor),
H CH3 bottles

H H
C C Poly(vinyl chloride) Plastic wrap, garden hose,
H Cl indoor plumbing

Structures and Applications of Some Major Addition

Polymers (Based upon the Ethylene Molecule)–II

Monomer Polymer Applications

H H
C C Polystyrene Insulation, furniture
H Phenyl
H H
C C Polyacrylonitrile Yarns, fabrics, wigs,
H C N (e.g. Orlon, Acrilon)
..

H H
C C O Poly(vinyl acetate) Adhesives, paints, textile
H O C CH coatings, computer disks
H Cl
C C Poly(vinylidene chloride) Food wrap (e.g. Saran)
H Cl
H CH3 Poly(methyl methacrylate) Glass substitute (e.g.
C C Lucite, Plexiglas),
H C O CH3
O bowling balls, paint

18
Two Molecules with the Same Functional
Group at Both Ends of Each Molecule–
Two Different Monomers

Nylon-66 Adipic acid and

Hexamethylenediamine

Kevlar Terephthalic acid and

Phenylenediamine

Polyesters Terephthalic acid and

Ethylene glycol

19
 O
Kevlar

HO C H2N
+
C OH NH2
Terphthalic Acid Phenylenediamine
O

HO C H

N
+ H2O
C

O
NH2
E TC

Polyesters ( PET )
Polyethylene Terphthalate
O H H

C OH HO C C OH
+
H H
HO C Ethylene Glycol
Terphthalic acid
O
O
CH2
C
O CH2
+ H2O
O
C
n
O

20
 O Polyurethane
C H Glycerol
Toluene diisocyanate
N H C O H

H3C N C O + H C O H

H C O H
O H
C
N H
O H O H
H3C N C O C C C O H
Polymer H H H

21