Organic Chemistry

Chapter 24

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Common Elements in Organic Compounds

24.1
 Some General
Characteristics of Organic
Molecules
The Structures of Organic Molecules
• Organic molecules exhibit three different types of
hybridization at the carbon center:
– sp3 hybridized carbons for tetrahedral geometries;
– sp2 hybridized carbons for trigonal planar geometries; and
– sp hybridized carbons for linear geometries.

Prentice Hall © 2003 Chapter 25

 Some General
Characteristics of Organic
Molecules
The Structures of Organic Molecules

Prentice Hall © 2003 Chapter 25

 Some General
Characteristics of Organic
Molecules
The Stabilities of Organic Molecules
• Carbon forms very strong bonds between H, O, N, and
halogens.
• Carbon also forms strong bonds with itself.
• Therefore, C can form stable long chain or ring
structures.
• Bond strength increases from single to double to triple
bond.
• Bond length decreases in the same direction.
Prentice Hall © 2003 Chapter 25
 Some General
Characteristics of Organic
Molecules
The Stabilities of Organic Molecules
• Carbon and hydrogen have very similar
electronegativities, so the C-H bond is essentially non-
polar.
• Therefore, compounds containing C-C and C-H bonds
are thermodynamically stable and kinetically inert.
• Adding functional groups (e.g., C-O-H) introduces
reactivity into organic molecules.

Prentice Hall © 2003 Chapter 25

 Some General
Characteristics of Organic
Molecules
Solubility and Acid-Base Properties of Organic
Substances
• Compounds with only C-C or C-H bonds are nonpolar
and are soluble in nonpolar solvents and not very soluble
in water.
• Water soluble organic molecules have polar functional groups.
• Surfactants have long nonpolar portions of the molecule with a
small ionic or polar tip.
• The most important organic acids are carboxylic acids with the
-COOH functional group.
Prentice Hall © 2003 Chapter 25
 Some General
Characteristics of Organic
Molecules
Solubility and Acid-Base Properties of Organic
Substances
• Basic organic molecules are usually amines, -NH2, -NHR, or -NR2
functional groups.

Prentice Hall © 2003 Chapter 25

 Introduction to
Hydrocarbons
• Hydrocarbons are compounds with only C and H.
• There are four classes:
– alkanes (all bonds and no bonds);
– alkenes (a mixture of and bonds, but no triple bonds);
– alkynes (must contain triple bonds); and
– aromatics (have planar, ring structures with alternating single
and double bonds).
• Saturated compounds have only bonds.
• Unsaturated compounds have both and bonds.
Prentice Hall © 2003 Chapter 25
Classification of Hydrocarbons

24.1
Prentice Hall © 2003 Chapter 25
 Alkanes

Alkanes have the general formula CnH2n+2 where n = 1,2,3,…

• only single covalent bonds
• saturated hydrocarbons because they contain the
maximum number of hydrogen atoms that can bond with the
number of carbon atoms in the molecule

CH4 C2H6 C3H8

methane ethane propane

24.2
 Alkanes

Prentice Hall © 2003 Chapter 25

 Alkanes

• The name of alkanes varied according to the number of C

atoms present in the chain.
• Since the only intermolecular forces available to alkanes
are London dispersion forces, the boiling points increase
smoothly as the molar mass increases.
• Methane to butane are gases at normal pressures.
• Pentane to decane are liquids at normal pressures.
• Each carbon in an alkane has 4 single bonds.

Prentice Hall © 2003 Chapter 25

 Alkanes

• In this table each member differs by one CH2 unit. This

is called a homologous series.
Structures of Alkanes
• VSEPR theory predicts each C atom is tetrahedral.
• Therefore, each C atom has sp3 hybridized orbitals.
• It is easy to rotate about the C-C bond in alkanes.

Prentice Hall © 2003 Chapter 25

 Alkanes
Structural Isomers
• Straight chain hydrocarbons have each C atom joined in a
continuous chain.
• In a straight chain hydrocarbon no one C atom may be
attached to more than two other C atoms.
• Straight chain hydrocarbons are not linear. Each C atom
is tetrahedral, so the chains are bent.
• Branched chain hydrocarbons are possible for four or
more C atoms, which give rise to structural isomers.
• Structural isomers have different physical properties.
Prentice Hall © 2003 Chapter 25
Structural isomers are molecules that have the same molecular
formula but different structures
24.2
 How many structural isomers does pentane, C5H12, have?

H H H H H

H C C C C C H

H H H H H
H CH3 H
n-pentane
H C C C H
H CH3 H H H CH3 H
H C C C C H
2,2-dimethylpropane
H H H H
2-methylbutane
24.2
 Alkanes
Structural Isomers

Prentice Hall © 2003 Chapter 25

 Alkanes
Nomenclature of Alkanes
• All organic molecule names have three parts:
− Prefix, which tells the nature of the substituents;
− Base, which gives the number of carbons; and the
− Suffix, which gives the family (alkanes, etc.).
• Rules for naming compounds are given by the
International Union for Pure and Applied Chemistry
(IUPAC).

Prentice Hall © 2003 Chapter 25

 Alkanes
Nomenclature of Alkanes
• To name alkanes:
– Find the longest chain and use it as the name of the compound.
– Number the carbon atoms starting with the end closest to the
substituent.
– Name and give the location of each substituent.
• When two or more substituents are present list them in
alphabetical order.

Prentice Hall © 2003 Chapter 25

 Alkane Nomenclature

1. The parent name of the hydrocarbon is that given to the

longest continuous chain of carbon atoms in the molecule.
CH3

CH3 CH2 CH2 CH CH2 CH2 CH3 4-methylheptane

1 2 3 4 5 6 7

2. An alkane less one hydrogen

atom is an alkyl group.

CH4 methane

CH3 methyl
24.2
Alkane Nomenclature

24.2
 Alkane Nomenclature

3. When one or more hydrogen atoms are replaced by other

groups, the name of the compound must indicate the
locations of carbon atoms where replacements are made.
Number in the direction that gives the smaller numbers for
the locations of the branches.
CH3

CH3 CH CH2 CH2 CH3

1 2 3 4 5

2-methylpentane CH3

CH3 CH2 CH2 CH CH3

1 2 3 4 5

4-methylpentane
24.2
 Alkane Nomenclature

4. Use prefixes di-, tri-, tetra-, when there is more than one
alkyl branch of the same kind.
CH3 CH3

CH3 CH CH CH2 CH2 CH3

1 2 3 4 5 6

2,3-dimethylhexane

CH3

CH3 CH C CH2 CH2 CH3

1 2 3 4 5 6
CH3

3,3-dimethylhexane
24.2
 Alkane Nomenclature

5. Use previous rules for other types of substituents.

Br NO2

CH3 CH CH CH3
1 2 3 4
2-bromo-3-nitrobutane

Br NO2

CH2 CH2 CH CH3

1 2 3 4

1-bromo-3-nitrobutane

24.2
What is the IUPAC name of the following compound?
CH3 C2H5

CH3 CH CH2 CH CH2 CH2 CH2 CH3

1 2 3 4 5 6 7 8

2-methyl-4-ethyloctane

What is the structure of 2-propyl-4-methylhexane?

C2H5 CH3

CH3 CH CH2 CH CH2 CH3

1 2 3 4 5 6

24.2
 Alkanes
Cycloalkanes
• Alkanes that form rings are called cycloalkanes.
• Cyclopropane and cyclobutanes are strained because the
C-C-C bond angles in the ring are less than 109.5
required for the tetrahedral geometry.
• Because of the strain in the ring, cyclopropane is very
reactive.

Prentice Hall © 2003 Chapter 25

 Alkanes
Cycloalkanes

Prentice Hall © 2003 Chapter 25

 Cycloalkanes

Alkanes whose carbon atoms are joined in rings are called

cycloalkanes. They have the general formula CnH2n where n =
3,4,…

24.2
Cycloalkanes

24.2
 Alkanes
Reactions of Alkanes
• The C-C and C-H bonds are very strong. Therefore,
alkanes are very unreactive.
• At room temperature alkanes do not react with acids,
bases, or strong oxidizing agents.
• Alkanes do combust in air (making them good fuels):
2C2H6(g) + 7O2(g) 4CO2(g) + 6H2O(l) H = -2855 kJ

Prentice Hall © 2003 Chapter 25

 Alkane Reactions
Combustion
CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l) DH0 = -890.4 kJ

Halogenation
light
CH4 (g) + Cl2 (g) CH3Cl (g) + HCl (g)

Cl2 + energy Cl• + Cl•

H H

Cl• + H C H •C H + HCl

H H
H H

H C • + Cl Cl H C Cl + Cl•

H H 24.2
 Unsaturated
Hydrocarbons
Alkenes
• Alkenes contain C, H atoms and single and double bonds.
• The simplest alkenes are H2C=CH2 (ethene) and
CH3CH=CH2 (propene):
– their trivial names are ethylene and propylene.
• Alkenes are named in the same way as alkanes with the
suffix -ene replacing the -ane in alkanes.
• The location of the double bond is indicated by a number.

Prentice Hall © 2003 Chapter 25

 Unsaturated
Hydrocarbons
Alkenes
• Geometrical isomers are possible since there is no
rotation about a C=C bond.
• Note the overlap between orbitals is above and below the
plane of the bonds.
– As the C-C bond begins to rotate (moving from cis to trans) the
overlap decreases.

Prentice Hall © 2003 Chapter 25

 Unsaturated
Hydrocarbons
Alkenes
– At 90 the bond breaks completely.
– Therefore, there is no rotation about a bond.
– Therefore, cis and trans isomers do not readily interconvert.

Prentice Hall © 2003 Chapter 25

 Alkenes

Alkenes have the general formula CnH2n where n = 2,3,…

• contain at least one carbon-carbon double bond
• also called olefins
CH2 CH CH2 CH3 CH3 CH CH CH3

1-butene 2-butene

Cl Cl Cl H
C C C C
H H H Cl
cis-dichloroethylene trans-dichloroethylene

24.2
 Alkene Reactions
Cracking
Pt
C2H6 (g) catalyst
CH2 CH2 (g) + H2 (g)

Addition Reactions
CH2 CH2 (g) + HBr (g) CH3 CH2Br (g)

CH2 CH2 (g) + Br2 (g) CH2Br CH2Br (g)

24.2
A polymer is a high molar mass molecular compound made up
of many repeating chemical units.

Naturally occurring polymers

•Proteins
•Nucleic acids
•Cellulose
•Rubber
Synthetic polymers
•Nylon
•Dacron
•Lucite
25.1
The simple repeating unit of a polymer is the monomer.

Homopolymer is a polymer made up of only one type of

monomer
( CF2 CF2 )n ( CH2 CH2 )n ( CH2 CH )n

Teflon Polyethylene Cl
PVC

25.2
Copolymer is a polymer made up of two or more monomers

( CH CH2 CH2 CH CH CH2 )n

Styrene-butadiene rubber

25.2
 Stereoisomers of Polymers

R groups on same
side of chain
Isotactic

R groups alternate
from side to side
Syndiotactic

R groups disposed
at random
Atactic
 Unsaturated
Hydrocarbons
Alkynes
• Alkynes are hydrocarbons with one or more C C bond.
Therefore, alkynes have one and two bonds between
two C atoms.
• Ethyne (acetylene) is a reactive alkyne: HC CH.
• When acetylene is burned in the presence of oxygen
(oxyacetylene torch) the temperature is about 3200 K.
• Alkynes are named in the same way as alkenes with the
suffix -yne replacing the -ene for alkenes.

Prentice Hall © 2003 Chapter 25

 Alkynes

Alkynes have the general formula CnH2n-2 where n = 2,3,4,…

• contain at least one carbon-carbon triple bond

CH C CH2 CH3 CH3 C C CH3

1-butyne 2-butyne

Production of acetylene
CaC2 (s) + 2H2O (l) C2H2 (g) + Ca(OH)2 (aq)

24.2
 Alkyne Reactions

Hydrogenation
CH CH (g) + H2 (g) CH2 CH2 (g)

Addition Reactions
CH CH (g) + HBr (g) CH2 CHBr (g)
CH CH (g) + Br2 (g) CHBr CHBr (g)
CH CH (g) + 2Br2 (g) CHBr2 CHBr2 (g)

24.2
 Unsaturated
Hydrocarbons
Addition Reactions of Alkenes and
Alkynes
• The most dominant reaction for alkenes and alkynes
involves the addition of something to the two atoms
which form the double bond:
H2C CH2 + Br2 H2C CH2
Br Br
• Note that the C-C bond has been replaced by two C-Br
bonds.

Prentice Hall © 2003 Chapter 25

 Unsaturated
Hydrocarbons
Addition Reactions of Alkenes and
Alkynes
• A common addition reaction is hydrogenation:
CH3CH=CHCH3 + H2 CH3CH2CH2CH3
• Hydrogenation requires high temperatures and pressures
as well as the presence of a catalyst.
• It is possible to cause hydrogen halides and water to add
across bonds:
CH2=CH2 + HBr CH3CH2Br
CH2=CH2 + H2O CH3CH2OH
Prentice Hall © 2003 Chapter 25
 Unsaturated
Hydrocarbons
Mechanism of Addition Reactions
• Consider the reaction between 2-butene and HBr:
CH3CH CHCH3 + HBr CH3HC CHCH3
H Br
• Careful kinetics experiments show the rate law to be
[CH3CH CHCH 3 ]
Rate k[CH3CH CHCH 3 ][HBr ]
t
• Therefore, both 2-butene and HBr must be involved in
the rate determining step.
Prentice Hall © 2003 Chapter 25
 Unsaturated
Hydrocarbons
Mechanism of Addition Reactions
• From the kinetics data, we can propose the following
mechanism:
− The -electrons in the alkene attack the d+ H atom of
the HBr to leave a positive charge on one carbon (slow
step):

CH3CH CHCH3 + HBr CH3HC CHCH3

H Br-
Prentice Hall © 2003 Chapter 25
 Unsaturated
Hydrocarbons
Mechanism of Addition Reactions
− Then the pair of electrons on bromide attacks the
carbon with a positive charge to give the product.

CH3HC CHCH3 CH3HC CHCH3

H H Br
Br-

Prentice Hall © 2003 Chapter 25

 Unsaturated
Hydrocarbons
Aromatic Hydrocarbons
• Aromatic structures are formally related to benzene.
• The delocalized electrons are usually represented as a
circle in the center of the ring.
• Benzene is a planar symmetrical molecule.
• Benzene is not reactive because of the stability associated
with the delocalized electrons.
• Most aromatic rings are given common names.

Prentice Hall © 2003 Chapter 25

 Unsaturated
Hydrocarbons
Aromatic Hydrocarbons
• Even though they contain bonds, aromatic
hydrocarbons undergo substitution more readily than
addition.
• Example: if benzene is treated with nitric acid in the
presence of sulfuric acid (catalyst), nitrobenzene is
produced.

Prentice Hall © 2003 Chapter 25

 Aromatic Hydrocarbons
H H

H C H H C H
C C C C

C C C C
H C H H C H

H H

24.3
 Aromatic Compound Nomenclature

ethylbenzene aminobenzene
CH2CH3 Cl NH2 NO2

chlorobenzene nitrobenzene

Br Br
1
6 2 Br

5 3 Br
4
1,2-dibromobenzene 1,3-dibromobenzene
24.3
 Aromatic Compound Reactions

Substitution reaction

H Br
H H H H
FeBr3
+ Br2 + HBr
catalyst
H H H H
H H

H CH2CH3
H H H H
AlCl3
+ CH3CH2Cl + HCl
catalyst
H H H H
H H
24.3
Polycyclic Aromatic Hydrocarbons

24.3
 Functional Groups:
Alcohols and Ethers
• To get reactivity out of an organic molecule, functional
groups have to be added.
• Functional groups control how a molecule functions.
• More complicated functional groups contain elements
other than C or H (heteroatoms).
• Functional group containing molecules can either be
saturated (alcohols, ethers, amines etc.) or unsaturated
(carboxylic acids, esters, amides, etc.).
• We usually use R to represent alkyl groups.
Prentice Hall © 2003 Chapter 25
 Functional Groups:
Alcohols and Ethers
Alcohols (R OH)
• Alcohols are derived from hydrocarbons and contain -OH
groups.
• The names are derived from the hydrocarbon name with -
ol replacing the -ane suffix. Example: ethane becomes
ethanol.
• Since the O-H bond is polar, alcohols are more water
soluble than alkanes.
• CH3OH, methanol, is used as a gasoline additive and a
fuel.
Prentice Hall © 2003 Chapter 25
 Functional Groups:
Alcohols and Ethers

Prentice Hall © 2003 Chapter 25

 Functional Groups:
Alcohols and Ethers
Alcohols (R OH)
• Methanol is produced by the reaction of CO with
hydrogen under high pressure (200 - 300 atm) and high
temperature (400 C):
CO(g) + 2H2(g) CH3OH(g)
• Ethanol is produced by fermenting carbohydrates.
• Ethanol is the alcohol found in alcoholic beverages.
• Polyhydroxy alcohols (polyols) contain more than one
OH group per molecule (e.g. ethylene glycol used as
antifreeze).
Prentice Hall © 2003 Chapter 25
 Functional Groups:
Alcohols and Ethers
Alcohols (R OH)
• Aromatic alcohols can also be formed (e.g. phenol).
• Note that aromatic alcohols are weak acids.
• The only biochemically important alcohol is cholesterol.
Ethers (R O R′)
• Compounds in which two hydrocarbons linked by an
oxygen are called ethers.
• Ethers are commonly used as solvents.

Prentice Hall © 2003 Chapter 25

 Functional Group Chemistry

Alcohols contain the hydroxyl functional group and have the

general formula R-OH.

24.4
Biological production of ethanol
enzyme
C6H12O6 (aq) 2CH3CH2OH (aq) + 2CO2 (g)

Commercial production of ethanol

H2SO4
CH2 CH2 (g) + H2O (g) CH3CH2OH (g)

Metabolic oxidation of ethanol

alcohol dehydrogenase
CH3CH2OH CH3CHO + H2

24.4
 Functional Group Chemistry

Ethers have the general formula R-O-R’.

Condensation Reaction
H2SO4
CH3OH + HOCH3 catalyst
CH3OCH3 + H2O

24.4
 Compounds with a
Carbonyl Group
Aldehydes and Ketones
• The carbonyl functional group is C=O.
• Aldehydes must have at least one H atom attached to the
carbonyl group: O
R H
• Ketones must have two C atoms attached to the carbonyl
group: O

R R'
• Aldehydes and ketones are prepared from the oxidation
of alcohols.
Prentice Hall © 2003 Chapter 25
 Functional Group Chemistry

O
Aldehydes and ketones contain the carbonyl ( C )
functional group.
O
• aldehydes have the general formula R C H
O
• ketones have the general formula R C R’

O O O
H C H H C CH3 H3C C CH3
formaldehyde acetaldehyde acetone

24.4
 Compounds with a
Carbonyl Group
Carboxylic Acids
• Carboxylic acids contain a carbonyl group with an -OH
attached.
• The carboxyl functional group is -COOH: O

R OH
• Carboxylic acids are weak acids.
• Typical carboxylic acids are spinach, vinegar, cleaners,
vitamin C, aspirin, and citrus fruits.
• Carboxylic acids are also used to make polymers for
fibers, paints, and films.
Prentice Hall © 2003 Chapter 25
 Compounds with a
Carbonyl Group
Carboxylic Acids

Prentice Hall © 2003 Chapter 25

 Compounds with a
Carbonyl Group
Carboxylic Acids
• Trivial names of carboxylic acids reflect their origins
(e.g. formic acid was first extracted from ants, the Latin
formica means “ant”).
• Carboxylic acids can be prepared by oxidizing alcohols
which contain a -CH2OH group.
• Acetic acid can be prepared by reacting methanol with
CO in the presence of a Rh catalyst. This sort of reaction
is called carbonylation.

Prentice Hall © 2003 Chapter 25

 Functional Group Chemistry
Carboxylic acids contain the carboxyl ( -COOH ) functional
group.

24.4
 Compounds with a
Carbonyl Group
Esters
• Some common esters are: benzocaine (in sun burn
lotions), ethyl acetate (nail polish remover), vegetable
oils, polyester thread, and aspirin.
• Esters contain -COOR groups: O

R OR'
• Esters can be prepared by reacting a carboxylic acid with
an alcohol and eliminating water:
O O
+ HO CH CH + H2O
C 2 3 C
H3C OH H3C OCH2CH3
Prentice Hall © 2003 Chapter 25
 Compounds with a
Carbonyl Group
Esters
• Esters are named first using the alcohol part and then the
acid part (in the above example: ethyl from ethanol and
acetate from acetic acid).
• In the presence of base, ester hydrolyze (molecule split
into acid and alcohol).
• Saponification is the hydrolysis of an ester in the
presence of a base.
• Esters tend to have characteristic odors and are used as
food flavorings and scents.
Prentice Hall © 2003 Chapter 25
 Functional Group Chemistry

Esters have the general formula R’COOR, where R is a

hydrocarbon group.

O
CH3COOH + HOCH2CH3 CH3 C O CH2CH3 + H2O
ethyl acetate

24.4
 Compounds with a
Carbonyl Group
Amines and Amides
• Amines are organic bases.
• Just as alcohols can be thought of organic forms of water,
amines can be thought of organic forms of ammonia.
• Amides are composites of carbonyl and amine
functionalities: O
C
R N R'
H

Prentice Hall © 2003 Chapter 25

 Functional Group Chemistry

Amines are organic bases with the general formula R3N.

CH3NH2 + H2O RNH3+ + OH-

CH3CH2NH2 + HCl CH3CH2NH3+Cl-

24.4
24.4
 Chirality in Organic
Chemistry
• A molecule that exists as a pair of nonsuperimposable
mirror images is called chiral.
• Organic compounds that contain one carbon atom that is
attached to four different atoms or groups are chiral.
• The carbon atom attached to the four different moieties is
called a stereogenic carbon.

Prentice Hall © 2003 Chapter 25

achiral chiral
24.2
 Chirality in Organic
Chemistry
• Consider *CHBr(CH3)(CH2CH2CH3). The *C is
attached to: (i) H, (ii) Br, (iii) CH3, and (iv) CH2CH2CH3:

Prentice Hall © 2003 Chapter 25

 Chirality in Organic
Chemistry
• Chiral molecules exist as a pair of enantiomers.
• The enantiomers are nonsuperimposable mirror images.
• Organic chemists label enantiomers as R and S.
• If two enantiomers are placed in a solution in equal
amounts, then the mixture is called racemic.
• If one molecule contains two stereogenic centers, one R
and one S, then the molecule shows no optical activity.
• Many pharmaceuticals are chiral molecules.
Prentice Hall © 2003 Chapter 25
S-ibuprofen: