Ch5 Organic Chemistry

CHAPTER 5: ORGANIC
CHEMISTRY
5.1 Alkanes
5.2 Alkenes
5.3 Aromatic Hydrocarbons
5.4 Alcohols
5.5 Haloalkanes (Alkyl Halides)
5.6 Carbonyl Compounds
5.7 Carboxylic Acids
What Is Organic Chemistry?

Organic chemistry is a branch of chemistry that focuses
on compounds that contain carbon
except CO, CO2, carbonates, and carbides
Even though organic compounds only contain a few
elements, the unique ways carbon atoms can attach
together to form molecules leads to millions of different
organic compounds
2
Tro: Chemistry: A Molecular Approach, 2/e
Whats So Special About Carbon?
Carbon atoms can do some unique things that other atoms cannot
Carbon can bond to as many as four other atoms
Bonds to carbon are very strong and nonreactive
Carbon atoms can attach together in long chains
Carbon atoms can attach together to form rings
Carbon atoms can form single, double, or triple bonds
3
Whats Special About

Organic Compounds?
Organic compounds tend to be molecular
Mainly composed of just six nonmetallic elements
C, H, O, N, S, and P
Compounds found in all three states

solids, liquids, and gases
solids tend to have low melting points
Solubility in water varies depending on which of the other

elements are attached to C and how many there are
CH3OH is miscible with water; C10H21OH is insoluble
4
Carbon Bonding
Carbon forms four bonds
When C has four single bonds, the
shape is tetrahedral
When C has one triple + one single
or two double bonds, the shape is
linear
When C has two single + one
double bond, the shape is trigonal
planar
5
Hydrocarbons
Hydrocarbons contain only C and H
aliphatic or aromatic
Insoluble in water
no polar bonds to attract water molecules
Aliphatic hydrocarbons
saturated or unsaturated aliphatics
saturated = alkanes, unsaturated = alkenes or alkynes
may be chains or rings

chains may be straight or branched
Aromatic hydrocarbons
6
alkanes
7
Alkanes
Saturated hydrocarbons (Aliphatic)
Hydrocarbons Contain only C and H atoms.

Saturated Only single bonds.
Aliphatic Fat like.
Can be acyclic (no rings) or cyclic
(cycloalkanes).
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Table 5.1 Numerical Roots for Carbon Chains and Branches

PREFIX + ROOT + SUFFIX
Roots
Number of C
atoms
meth-
eth-
prop-
but-
pent-
hex-
hept-
oct-
non-
dec-
10
Physical Properties of nAlkanes
12
Physical Properties of Alkanes

Alkanes
Solubility Like dissolves like
Alkanes are nonpolar, hydrophobic
They are soluble in nonpolar solvents and
insoluble in water.
Ways of depicting an alkane.
Formulas
Molecular formulas : shows what kinds
of atoms are in the molecule, but not how
they are bonded together
Structural formulas shows the bonding
pattern in the molecule
15
Alkanes
Methane, CH4
H C H
H
Ethane, CH3CH3
H H
H C C H
H H
Alkanes
Propane, CH3CH2CH3
H H H
H C C C H
H H H
Butane, CH3CH2CH2CH3
H H H H
H C C C C H
H H H H
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Condensed Structural Formulas

Elements listed in order
central atom with attached atoms
Follow normal bonding patterns
shows position of multiple bonds
() used to indicate more than one identical group
attached to same previous central atom
unless () group listed first in which case
attached to next central atom
18
Example Write the structural and condensed formula for the

straight chain alkane C8H18
Connect the C atoms in a row
Carbon backbone
Add H to complete four bonds on

each C.
middle C gets 2 Hs
end C gets 3 Hs
The condensed formula has the H

attached to each C written directly
after it
19
Alkanes
Pentane, CH3CH2CH2CH2CH3
Hexane, CH3CH2CH2CH2CH2CH3
Heptane, CH3CH2CH2CH2CH2CH2CH3
Octane, CH3CH2CH2CH2CH2CH2CH2CH3
Nonane, CH3CH2CH2CH2CH2CH2CH2CH2CH3
Decane, CH3CH2CH2CH2CH2CH2CH2CH2CH2CH3
Carbon Skeleton Formulas

Each angle, and beginning and end, represents a C atom
H omitted on C
included on functional groups
Multiple bonds indicated
double line is double bond, triple line is triple bond
21
Isomerism
Isomerism The phenomenon whereby certain
chemical compounds have structures that are
different although the compounds possess the
same elemental composition.
Isomers Two or more chemical substances
having the same elementary composition and
molecular weight but differing in structure.
Structural isomers are isomers are also called
Constitutional isomers
Isomerism
Consider C4H10
H H H H
H C C C C H
H H H H
H
C
H C C C H
Normal Butane
These structures are constitutional isomers
H H H
Isobutane
Rotation about a Bond Is Not Isomerism
24
Possible Structural Isomers of Alkanes
Example 20.1: Write the structural formula and carbon skeleton

formula for the 5 structural isomers of C6H14
fill in the H to
give each
carbon four
bonds
26
Alkyl Groups
Names and Formulas of Alkyl Groups:
Formula
Name
Formula
Name
CH3-
methyl
CH3CH2CH2CH2-
butyl
CH3CH2-
ethyl
(CH3)2CHCH2-
isobutyl
CH3CH2CH2-
propyl
CH3CH2CH(CH3)-
sec-butyl
(CH3)2CH-
isopropyl
(CH3)3C-
tert-butyl
Alkanes
Primary (1o)
carbon

Formula
Name
Formula
Name
CH3-
methyl
CH3CH2CH2CH2-
butyl
CH3CH2-
ethyl
(CH3)2CHCH2-
isobutyl
CH3CH2CH2-
propyl
CH3CH2CH(CH3)-
sec-butyl
(CH3)2CH-
isopropyl
(CH3)3C-
tert-butyl
Alkanes
Secondary (2o)
carbon

Formula
Name
Formula
Name
CH3-
methyl
CH3CH2CH2CH2-
butyl
CH3CH2-
ethyl
(CH3)2CHCH2-
isobutyl
CH3CH2CH2-
propyl
CH3CH2CH(CH3)-
sec-butyl
(CH3)2CH-
isopropyl
(CH3)3C-
tert-butyl
Alkanes
Tertiary (3o)
carbon

Formula
Name
Formula
Name
CH3-
methyl
CH3CH2CH2CH2-
butyl
CH3CH2-
ethyl
(CH3)2CHCH2-
isobutyl
CH3CH2CH2-
propyl
CH3CH2CH(CH3)-
sec-butyl
(CH3)2CH-
isopropyl
(CH3)3C-
tert-butyl
IUPAC Rules for Naming Alkanes

Select the longest continuous chain of carbon atoms
as the parent compound.
Number the carbon atoms in the parent carbon chain
starting from the end closest to the first carbon atom
that has an alkyl or other group.
Name the alkyl group and designate the position on
the parent carbon chain by a number.
When the same alkyl group branch chain occurs
more than once, indicate this repetition by a prefix
(di-, tri-, tetra-, and so forth).
When several different alkyl groups are attached to
the parent compound, list them in alphabetical order.
Example 1
5
CH3
CH2
CH2
CH
CH3
CH3
CH3
parent alkane
alkyl group
3-methylpentane
4
3
2
1
CH2 CH2 CH CH3
CH3
3-methylpentane
parent alkane
alkyl group
Example 1
5
CH3
CH2
CH2
CH
CH3
CH3
parent alkane
alkyl group
3-methylpentane

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Example 1
5
CH3
CH2
CH2
CH
CH3
CH3
parent alkane
alkyl group
2-methylpentane

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Example 2
1
CH3
CH
CH
CH3
CH3 CH3
2,3-dimethylbutane
CH3
CH2
CH3
C CH3
CH3
2,2-dimethylbutane
Example 2
1
CH3
CH
CH
CH3
CH3 CH3
2,3-dimethylbutane
CH3
CH2
CH3
C CH3
CH3
2,2-dimethylbutane
Example 2
1
CH3
CH
CH
CH3
CH3 CH3
2,3-dimethylbutane
CH3
CH2
CH3
C CH3
CH3
2,2-dimethylbutane
Example 2
1
CH3
CH
CH
CH3
CH3 CH3
2,3-dimethylbutane
CH3
CH2
CH3
C CH3
CH3
2,2-dimethylbutane
Example 3
CH3
CH
CH3
CH2
CH3
CH
4
CH
CH3
CH
2
CH3
2,3,4,6-tetramethylheptane
CH3
Example 3
CH3
CH
CH3
CH2
CH3
CH
4
CH
CH3
CH
2
CH3
CH3
Note: Number the chain so that the substituents get

the lowest possible numbers.
Example 3
CH3
CH
CH3
CH2
CH3
CH
4
CH
CH3
CH
2
CH3
CH3
Note: Number the chain so that the substituents get

the lowest possible numbers.
Example 4
2
CH3
CH2
CH3
CH
CH2
CH2
5
3-methylhexane
CH3
6
Examples
2
CH3
CH2
CH3
CH
CH2
CH2
5
CH3
6
3-methylhexane
Caution: Be careful to choose the longest chain as

the parent alkane.
Examples
2
CH3
CH2
CH3
CH
CH2
CH2
5
CH3
6
3-methylhexane
Caution: Be careful to choose the longest chain as

the parent alkane.
Examples
CH2 CH3
CH3 CH2 CH2 CH2 C
CH CH CH3
CH3 Cl
CH3
3-chloro-4-ethyl-2,4-dimethyloctane
Examples
CH2 CH3
CH3 CH2 CH2 CH2 C
CH CH CH3
CH3 Cl
CH3
Example 4
CH2 CH3
CH3 CH2 CH2 CH2 C
CH CH CH3
CH3 Cl
CH3
Note: Substituents are listed in alphabetical order.
Draw the Compounds

3-ethylpentane
2,2,4-trimethylpentane
Draw the Compounds

3-ethylpentane
1
CH3
CH2
CH2
CH2
CH2
CH3
CH3
Draw the Compounds

3-ethylpentane
1
CH3
CH2
CH
CH2
CH2
CH3
CH3
Draw the Compounds

3-ethylpentane
1
CH3
CH2
CH
CH2
CH2
CH3
CH3
1
CH3
CH3
CH2
CH3
CH2
CH2
CH3
CH3
Draw the Compounds

3-ethylpentane
1
CH3
CH2
CH
CH2
CH2
CH3
CH3
1
CH3
CH3
C
CH3
CH2
CH2
CH3
CH3
Naming of Cycloalkanes
CH2
H2C CH2
H2C
H2C
CH2
CH
CH3
CH2
CH2
=
CH3
CH2
=
H2C CH2
Cyclopropane
H2C
H2C
CH2
CH
CH3
CH2
CH2
=
CH3
Cycloalkanes
CH2
=
H2C CH2
Cyclopropane
H2C
H2C
CH2
CH
CH2
CH2
CH3
Methylcyclohexane
=
CH3
Cycloalkanes
CH2
=
H2C CH2
Cyclopropane
H2C
H2C
CH2
CH
CH2
CH2
CH3
Methylcyclohexane
=
CH3
CH2
H2C
CH CH2CH2CH2CH2CH2CH3
CH2
1-Cyclobutylhexane
(CH2)5CH3
Hexylcyclobutane
Cycloalkanes
H2C
H2C
CH2
CH2
CH
CH
CH2
CH3
CH3
5
4
1-Ethyl-2-methylcyclohexane
2
3
Name the Following Compounds
Name the Following Compounds
Methylcyclopropane
1,2Dimethylcyclopentane
1,1-Dimethylcyclohexane
3-Cyclopropylpentane
Geometric Isomerism in Cycloalkanes

Geometric isomers have the same molecular
formula but a different orientation in space that
cannot be overcome by rotation around a bond.
1,2-Dimethylcyclopentane:

H3C
CH3
1,2-dimethylcyclopentane
H
H3C
H
CH3
cis-1,2-dimethylcyclopentane
H
H3C
CH3
H
trans-1,2-dimethylcyclopentane

Geometric isomers have the same molecular
formula and the same order of attachment but a
different orientation in space that cannot be
overcome by rotation around a bond.
H3C
CH3
1,2-dimethylcyclopentane
H
H3C
H
CH3
cis-1,2-dimethylcyclopentane
H
H3C
CH3
H
trans-1,2-dimethylcyclopentane

Name the following compounds:
CH3
H
C
H
C
H3C
C
H
H3C
H3C
CH3
C CH3
H
H

Name the following compounds:
CH3
H
C
H
C
H3C
H3C
H3C
trans-1,2-dimethylcyclopropane
CH3
C CH3
H
cis-1-tert-butyl-4-methylcyclohexane

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Reactions of Hydrocarbons
All hydrocarbons undergo combustion
Combustion of butane
2 CH3CH2CH2CH3(g) + 13 O2(g) 8 CO2(g) + 10 H2O(g)
66
Alkane Reactions
Substitution Reaction
replace H with a halogen atom
initiated by addition of energy in the form of heat or
ultraviolet light
to start breaking bonds
generally get multiple products with multiple

substitutions through chain reactions
67
Chlorination of Methane
Methane reacts with chlorine in the presence of heat or
light to produce a mixture of products through a sequence
of substitution reactions in which the H atoms are
successively replaced by Cl atoms.
CH4 + Cl2
heat or light
CH3Cl + HCl
Cl2
CH2Cl2 + HCl
CH3Cl , chloromethane
CH2Cl2 , dichloromethane
CHCl3 , trichloromethane
CCl4 , tetracloromethane
Cl2
CHCl3 + HCl
Cl2
CCl4 + HCl
Free Radical Substitution

The breaking of a covalent bond so that each atom retains
one of the shared electrons will produce two free radicals.
Free radicals are very reactive. They are intermediates in
reaction mechanism.
The substitution reactions of alkanes follow the free
radical mechanism, which involved three major steps:
1. Initiation: Initial production of free radicals
2. Propagation: Free radicals attack molecules to produce
another free radical
3. Termination: Two free radicals combine to form a
molecule
Mechanism of Free Radical substitution

1. Chlorination of methane starts with the production of Cl free radicals (Cl
atoms)
Cl2 hv
Cl + Cl
2. The Cl free radical attacks the CH4 molecule to give a methyl free radical,
CH3 and HCl.
CH4 + Cl
CH3 + HCl
The methyl free radical reacts with Cl2 to give chloromethane.

CH3 + Cl2
CH3Cl + Cl
Subsequent reactions produce various alkyl free radicals which lead to the
formation of the other substitution products.
3. Reaction stops when free radicals combine
CH3 + Cl
CH3Cl
CH3 + CH3
CH3CH3 (by product)
Unsaturated Hydrocarbons
Unsaturated hydrocarbons have one or more C=C double bonds
or CC triple bonds
Unsaturated aliphatic hydrocarbons that contain C=C are called
alkenes
the general formula of a monounsaturated chain alkene is
CnH2n
Unsaturated aliphatic hydrocarbons that contain CC are called
alkynes
the general formula of an alkyne with one triple bond is
CnH2n2
71
Alkenes
Also known as olefins
Aliphatic, unsaturated
C=C double bonds
Formula for one double bond = CnH2n
subtract 2 H from alkane for each double bond
Trigonal shape around C
flat
Polyunsaturated = many double bonds
72
Naming Alkenes and Alkynes

Change suffix on main name from -ane to -ene for
base name of alkene, or to -yne for the base name
of the alkyne
Number chain from end closest to multiple bond
Number in front of main name indicates first
carbon of multiple bond
73
Alkenes
ethene = ethylene
propene = propylene
C C
H
H
C C
CH3
produced by ripening fruit

used to make polyethylene
used to make polypropylene

74
75
Nomenclature of Alkenes
Find the longest carbon chain.
Number the carbons such that the functional
group, here the double bond, gets the lowest
possible number.
Substituents are cited before the parent longest
chain, along with a number indicating its position
at the chain.
3
4
1
2
2-butene
High electron density
3
4
Electrostatic map shows

high electron density
at double bond
1
2
Low electron density
7
H3C
H3C
CH3
H
5-methyl-3-heptene
6 5

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2
1
5
6 H3C
CH3
CH3
2-methyl-3-hexene
3
2

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Name the Alkene

1. Find the longest, continuous C chain that contains the
double bond and use it to determine the base name
Because the longest chain with the double bond has

6 C the base name is hexene
80
Name the Alkene
2.
Identify the substituent branches
there are 2 substituents

one is a 1 C chain, called methyl
the other one is a 2 C chain, called ethyl
81
Name the Alkene

3.
number the chain and substituents

a) determine the end closest to the double bond
if double bond equidistant from both ends, number from
end closest to the substituents
b) then assign numbers to each substituent based on
the number of the main chain C it is attached to
Name the Alkene

4. Write the name in the following order
a.
substituent number of first alphabetical substituent

substituent name of first alphabetical substituent
use prefixes to indicate multiple identical substituents
b. repeat for other substituents
c. number of first C in double bond name of main chain
3ethyl 4methyl 2hexene
4
83
Practice Name the following
3
2
3,4-dimethyl-3-hexene
84
Physical Properties of Alkenes
85
Geometric Isomerism
Because the rotation around a double bond is highly restricted,
you will have different molecules if groups have different spatial
orientation about the double bond
This is often called cistrans isomerism
When groups on the doubly bonded carbons are cis, they are on
the same side of the double bond
When groups on the doubly bonded carbons are trans, they are
on opposite sides
86
cis/trans Isomers
cis
trans
All substituents are

on one side
of bond
All substituents are

on different sides
of bond
Cis-Trans Isomerism
The cis and trans
isomers are different
molecules with
different properties.
88
cis/trans Isomers
3
5
2
1
cis-2-pentene
5
4
2
1
2
1
cis/trans Isomers
2
4
3
6
5
7
6
7
4
5
trans-3-heptene
2
3
1
7
4
5
2
3
cis/trans Isomers
The main chain determines cis/trans in the name
6
H3C
3
2
CH3
CH3
H3C
2
3
4
5
6
cis-3-methyl-2-hexene
trans-3-methyl-2-hexene
This compound is cis

but the two methyl
groups are
trans to each other.
This compound is trans

but the two methyl
groups are
cis to each other.
NOTE: For more than two substituents, the cis/trans system

cannot be used
Reactions of Alkenes
Alkenes are relatively more reactive than alkanes.
The electron-rich double bond is the active site or the
functional group of the molecule .
Organic Functional Groups

Class
Functional
Group
Example
CH3
Alkene
C
H3C
CH2
Limonene
Addition Reactions
An addition reaction is a reaction in which an unsaturated
molecule becomes saturated by the addition of a molecule
across a multiple bond.
Addition reaction to a double bond:
C
+ X
Types of Addition Reactions

1. Catalytic Hydrogenation:
Alkenes and hydrogen react in the presence of a catalyst
to form alkanes.
C2H4 + H2 Ni C2H6
2(a) Addition of Halogen in inert solvent
Halogens dissolved in an inert solvent such as
carbon tetrachloride, react readily with alkenes at
room temperature and even in the dark.
CH3 CH
propene
CH2 + Br2
bromine
inert solvent
CH3CHBrCH2Br
1,2-dibromopropane
Note: For some alkenes, heat or light may be required.
Addition Reactions
2(b) Addition of Halogen in water
Chlorine or bromine dissolved water reacts with alkene
to produce halohydrin as the major product.
CH3 CH
propene
CH2 + Br2
water
bromine
CH3CH(OH)CH2Br + CH3CHBrCH2Br
bromohydrin
(major product)
1,2-dibromopropane
(minor product)
Note: In both reactions 2(a) and 2(b), the red-brown colour of the bromine
solution will disappeared.
In reaction 2(b), bromine water contains HBr and HOBr.
Br2(aq) + H2O(l) HBr(aq) + HOBr(aq)
Addition Reactions
3. Addition of Halogen halides
Addition reaction of alkenes with hydrogen halides (HX)
form haloalkanes (alkyl halides)
Relative reactivity of HX towards alkenes increases in the
order of HF < HCl < HBr < HI
CH2
CH2 + HBr
ethene
hydrogen
bromide
CH3CH2Br
bromoethane
Addition of HBr to Alkenes
H2C C
CH2 CH3 HBr(aq)

CH3
CH3
C
H
CH2 CH3
H2C C Br
CH3
H
CH3
HBr(aq)
Br
C
H H
Predicting Major and Minor Addition Products:

When an HX molecule is added to an unsymmetrical alkene, two
possible products can be formed:
CH3CH CH2 + HBr
propene
CH3CHBrCH3
2-bromopropane
+ CH3CH2CH2Br
1-bromopropane
(major product)
(minor product)
The Markovnikovs rule

When an HX molecule is added to an unsymmetrical alkene,
the X atom attaches itself to the C atom (of the double bond)
which is more alkylated (having less H atoms), while the H atom
bonds to the adjacent C atom with larger number of H atoms
(already bonded to it).
Electrophile and Nucleophile

An electrophile is a species (ion or molecule) which attacks
electron-rich site of organic molecules such as double bonds.
Electrophiles are Lewis acids (either positive ions or molecules
with electron-deficient atom)
Examples: HCl , H3O+
A nucleophile is a species (ion or molecule) which attacks electronpoor carbon atom of organic molecule, by donating electron-pair to
the atom.
Nucleophiles are Lewis bases, containing lone pair of electrons
Examples:
H2O
CH3NH2
Cl
HO
Reaction Mechanism: Electrophilic Addition
electrophile
HBr + H2O
Br + H3O
Hydrogen bromide is a strong acid and forms

hydronium ions, H3O+, and bromide, Br, when
dissolved in water.
H3O+ is positively charged, thus it is electron deficient.
It is electrophilic (electron-loving)
Reaction mechanism: Electrophilic attack

The hydronium ion reacts with the C=C bond,
producing an electrophilic carbocation
H3C H2C
C CH2 + O H
H3C
H
H3C H2C
C CH2 + H2O
H3C
H
Carbocation
Note: Another carbocation CH3CH2CH(CH3)CH2 is also formed,

but it is less stable.
Reaction mechanism:
Br is rich in electrons. It is nucleophilic.
Br seeks for the electron-poor carbocation.
The two species, electrophile and nucleophile, combine
and form a new compound, 2-bromo-2-methylpropane
CH2 CH3
+ Br
H2C C
CH3
H
CH2 CH3
H2C
H
Br
CH3
2-bromo-2-methylpropane
(Major product)
Note: Reaction of Br with the other carbocation CH3CH2CH(CH3)CH2 will

produce the minor product, 1-bromo-2-methylpropane. This is the minor
product as predicted by the Markovnikovs rule.
Electrophilic Addition: Summary of Mechanism

Step 1 reaches a carbocation intermediate.
One new bond is formed.
Step 2 completes the reaction by forming a second
bond. Again, it is the interplay between positively
charged (electrophilic) and negatively charged
(nucleophilic) species.
Overall Mechanism of Electrophilic Addition

Summarizing our reaction, we realize it is a 2-step mechanism

HBr + H2O
H3C
H2C
C
H3C
CH2 + O H
H
CH2 CH3
+ Br
H2C C
CH3
H
Br + H3O
H3C H2C
C CH2 + H2O
H3C
H
STEP 1
CH2 CH3
H2C
H
Br
CH3
STEP 2
Addition Reactions
4. Addition with acidified water (H3O+) : Hydration of alkenes
Addition of H and OH groups from a water molecule to a
double bond will produce an alcohol. The reaction is
facilitated by using an acid as a catalyst.
CH3CH
CH2 + H2O
H2SO4
CH3CH(OH)CH3
2-propanol
Hydration of alkenes using concentrated H2SO4 followed by

hydrolysis, would give the same results.
Unsaturation Tests for Alkenes

Alkenes or unsaturated organic compounds may be identified
using simple lab tests
1. Br2 in inert solvent or dilute bromine water are yellow brown
in colour. The solution is decolorised when added to an alkene
(See: Addition reactions with halogens)
2. Reaction with cold, dilute, alkaline KMnO4 (Baeyers test)
Alkenes are oxidised readily by the Baeyers reagent. The
purple colour of the KMnO4 solution disappears, and a brown
precipitate of Mn(IV) oxide appears. The organic product is a
diol.
CH3(CH2)6CHCH2
1-nonene
KMnO4 (aq), OH
CH3(CH2)6CH(OH)CH2OH
a diol
Unsaturation Tests for Alkenes

3. Reaction of Alkenes with hot, acidified KMnO4
Vigorous oxidation of alkenes results in the cleavage of
the double bonds producing ketones, carboxylic acids or
CO2
CH3CH
CHCH2 CH3
KMnO4/H+
CH3COOH + CH3CH2COOH
carboxylic acids
In this reaction, the KMnO4 solution is decolourised.

By identifying the products, the position of the double bond in
the alkene can be determined.
Alkynes
Aliphatic, unsaturated
CC triple bond
Formula for one triple bond = CnH2n2
subtract 4 H from alkane for each triple bond
Linear shape
Internal alkynes have both triple bond carbons
attached to C
Terminal alkynes have one carbon attached to H
109
Alkynes
both used in welding torches
110
111
Name the Alkyne

1. Find the longest, continuous C chain that contains the
triple bond and use it to determine the base name
Because the longest chain with the triple bond has

7 C the base name is heptyne
112
Name the Alkyne
2. Identify the substituent branches
there are 2 substituents

one is a 1 C chain, called methyl
the other one is called isopropyl
113
Name the Alkyne

3. number the chain and substituents
a. determine the end closest to the triple bond
if triple bond equidistant from both ends, number from
end closest to the substituents
b. then assign numbers to each substituent based on the
number of the main chain C it is attached to.
114
Name the Alkyne

4. write the name in the following order
a) substituent number of first alphabetical substituent
substituent name of first alphabetical substituent
use prefixes to indicate multiple identical substituents
b) repeat for other substituents
c) number of first C in triple bond name of main chain
4isopropyl6methyl 2heptyne
115
Practice Name the Following
4
5
3,3-dimethyl-1-pentyne
116
Examples of Naming Alkynes
117
Examples of Naming Alkenes
118
Alkyne Reactions:
Alkynes undergo many reactions similar to alkenes:
Hydrogenation = adding H2
alkene or alkyne + H2 alkane
generally requires a catalyst
Halogenation = adding X2
Hydrohalogenation = adding HX
HX is polar
when adding a polar reagent to a double or triple
bond, the positive part attaches to the carbon with
the most Hs
119
Alkynes: Reactions
Alkynes are electron-rich molecules, thus also
electrophilic addition takes place.

HBr
H3C
H3C C C CH3
H3C
2-butyne
vinyl-carbocation
Alkynes: Reactions
H
H3C
H3C
+
Br
CH3
H3C
Br
After the addition of the nucleophile we obtain an alkene

that still can be attacked by an electrophile.
Alkynes: Reactions
H
CH3
H3C
Br
HBr
Formation of a second carbocation
H3C
CH3
Br
Alkynes: Reactions
H3C
CH3
Br
H3C
H
Br
CH3
Br
H
H3C
CH3
Br
Br
Both nucleophiles end up on the same carbon.
Aromatic Compounds
An aromatic compound is a compound that contains a
benzene ring in its molecule.
Aromatic hydrocarbons are also called arenes
The Structure of benzene (C6H6)
Derivatives of benzene: Other compounds have the benzene ring with

other groups substituted for some of the Hydrogens
Aromatic Hydrocarbons
Aromatic hydrocarbons contain a ring structure that
seems to have C=C, but doesnt behave that way
The most prevalent example is benzene.
C6H6
Other compounds have the benzene ring with other groups
substituted for some of the Hydrogens
125
Naming Monosubstituted Benzene Derivatives

halogen substituent
Names of a common derivatives
126
Naming Benzene as a Substituent

When the benzene ring is not the base name, it is called a phenyl
group
127
Naming Disubstituted Benzene Derivatives

Number the ring starting at attachment for first substituent,
then move toward second
order substituents alphabetically
use di if both substituents are the same
128
Practice Name the Following
1-chloro-4-fluorobenzene
1,3-dibromobenzene
or meta-dibromobenzene
or m-dibromobenzene
129
Polycyclic Aromatic Hydrocarbons

Contain multiple benzene rings fused together
fusing = sharing a common bond
130
Alcohols
Aliphatic, hydroxy compounds
Contain hydroxy functional groups (OH)
General formula = CnH2n + 1OH (n 1)
Considered as derivatives of alkanes with H atoms replaced
by OH groups.
RH
alkane
ROH
alcohol
131
Functional Groups
Other organic compounds are hydrocarbons in which
functional groups have been substituted for hydrogens
A functional group is a group of atoms that show a
characteristic influence on the properties of the molecule
generally, the reactions that a compound will perform are
determined by what functional groups it has
because the kind of hydrocarbon chain is irrelevant to the
reactions, it may be indicated by the general symbol R
CH3OH
R group
functional group
132
133
Alcohols
ROH
Ethanol = CH3CH2OH
grain alcohol = fermentation of sugars in
grains
alcoholic beverages
proof number = 2x percentage of alcohol
gasohol
Isopropyl alcohol = (CH3)2CHOH
2-propanol
rubbing alcohol
poisonous
Methanol = CH3OH
wood alcohol = thermolysis of wood
paint solvent
poisonous
134
Naming Alcohols
Identify main chain containing OH group
Number main chain C atoms from end closest to
the OH group
Give base name ol ending and place number of C
on chain where OH is attached in front
Name all substituents present and write the lowest
possible numbers
List substituents in alphabetical order
135
Naming Alcohols
Give the IUPAC name of the alcohol:
CH3CH2CH2CH2CHCH2OH
C
CH2CH2CH3

Education, Inc.
Naming Alcohols
Determine longest chain with OH
Blue chain is longer; however,
Red chain contains OH
1
CH3CH2CH2CH2CHCH2OH
C
CH2CH2CH3
6

Education, Inc.
Naming Alcohols
Determine longest chain with OH
Blue chain is longer; however,
Red chain contains OH
6
CH3CH2CH2CH2CHCH2OH
C
CH2CH2CH3
1
Name:
2-propyl-1-hexanol
Notice that
numbering starts
at alcohol group
Classification of alcohols
Based on the number of alkyl groups (R) bonded to the C
atom that carries the -OH group, alcohols are classified into
three types:
Primary, Secondary, and Tertiary
R CH2 OH
10
CH OH
R'
20
OH
R C
R
30
Reactions of Alcohols
Nucleophilic substitution:
1. Reaction with H X
CH3OH
+ HCl CH3Cl + H2O
Cl acts as a nucleophile, replacing OH group
2. Reaction with PCl3

CH3 CH2OH
PCl3
CH3 CH2Cl
Note: Conversion of an alcohol to a haloalkane can also be done

by using PCl5 or SOCl2 (thionyl chloride) instead of PCl3
140
HI
+ H2O
HO
iodocyclohexane
cyclohexanol
OH
HCl
Cl
1-propanol
+ H2O
1-chloropropane
**Substitution reactions may be used to convert an

alcohol to a haloalkane
Elimination Reaction (Dehydration)

Elimination of water, dehydration, is commonly obtained
using sulfuric acid (H2SO4) as a catalyst.
H3C
OH
CH3
H2SO4
H3CHC CHCH3 + H2O
**Dehydration can be used to convert alcohols to alkenes
Elimination (Dehydration)
The ease of dehydration follows the order:

R
OH
R
>
OH
R
>
OH
H
Elimination reaction
Saytzeffs rule: For elimination reaction that
produces more than one alkenes, the alkene with
more than one alkyl substituents in the double bond is
the predominant product.
OH
1-pentene (minor product)
2-pentanol
2-pentene (major product)
Reactions of Alcohols
3. Oxidation: Dehydrogenation
2 H
2 H
CH3CH2OH CH3CHO CH3COOH

Typical oxidizing agents are:
1. Acidified potassium dichromate (K2Cr2O7)
or chromic acid H2CrO4
2. Acidified potassium permanganate (KMnO4)
145
Oxidation of Alcohols
Remember, we distinguish three types of alcohols:
R
R
R CH2 OH
CH OH
R'
10
20
OH
30
Dehydrogenation (oxidation) is possible for

10 and 20 leading to aldehydes and ketones,
respectively. 30 resists oxidation
10 alc.
R
H
aldehyde
20 alc.
R
R'
ketone
Oxidation of Alcohols
Aldehydes can be further oxidized to carboxylic acids.
O
R
O
R
H
aldehyde
OH
acid
Oxidation of alcohols
H2CrO4
OH
cyclopentanol
OH
O
cyclopentanone
H2CrO4
butanol
O
butanal
OH
O
butanoic acid
H2CrO4
Reaction of alcohols with very active metals

2 CH3OH
+ 2 K 2 CH3OK+ + H2
potassium
methoxide
2 CH3CH2OH
+ 2 Na 2 CH3CH2ONa+ + H2
sodium ethoxide
Tests to Distinguish Classes of Alcohols

Two simple lab tests can be used to distinguish between
Primary, secondary and tertiary alcohols:
1. Lucas test:
The alcohols is shaken with a solution of ZnCl2 in
concentrated HCl. (Lucas reagent)
For a 30 alcohol , the solution turns cloudy almost
immediately.
For a 20 alcohol , cloudiness* observed in about 5 minutes.
10 alcohol shows no cloudiness.
*Cloudiness is due to the formation of alkyl halide
Lucas Reagent Test

OH
Cl
ZnCl2 / HCl
2-2-butanol
2-chloro-2-methylbutane
(Cloudiness appears immediately)
(a 30 alcohol)
ZnCl2 / HCl
OH
2-pentanol
(a 20 alcohol)
Cl
2-chloropentane
(cloudiness appears in a few minutes)
No reaction
OH
155
0

2. Oxidation test:
Only 10 and 20 alcohols are oxidised by hot acidified
KMnO4 or hot acidified K2Cr2O7 solution.
10 and 20 alcohols decolourise the KMnO4 solution,
whereas the colour of the K2Cr2O7 solution changes from
orange to green.
No reaction for 30 alcohols.

3. Iodoform test
Ethanol and 20 alcohols with methyl alcohol group
H
CH3C
(methyl alcohol group)
OH
reacts with iodine in aqueous NaOH to produce pale yellow
solid of iodoform (CHI3).
CH3CH2OH
I2 / NaOH
CHI3
Triiodomethane (iodoform)
yellow precipitate
Haloalkanes
Also called alkyl halides
General formula = CnH2n + 1X (n 1), or R X
X = F, Cl, Br or I
Functional Group:
CX
Nomenclature
Name as derivative of alkane:
replacing the H atom(s) by halogen atom(s)
Positions of halogen atoms are indicated by the
number assigned to the C atom to which it is attached
CH3CH2Br
IUPAC name:
Common name:
(CH3)3CI
bromoethane
ethyl bromide
2-iodo-2-methylpropane
tert-butyl iodide
Nomenclature
Name the compounds:
a)
CH3CH2CH (CH3)CH2CHCH3
Cl
2-chloro-4-methylhexane
b)
Br
CH3
1-bromo-3-methylcyclopentane
Reactions of Haloalkanes
The C X bonds in haloalkanes are polar bonds
The C atom is electron-poor, it attracts nucleophiles
+
CX
Reactions of haloalkanes include:
1.
2.
3.
Elimination
Nucleophilic substitution
Grignard reactions
Reactions of haloalkanes
Elimination Reaction: Dehydrohalogenation
adjecent H and X atoms are removed to produce a double
bond (an alkene)
RCH CH2
RCH
CH2 + HX
H
X
alkene
Example: When bromoethane is heated with a solution of
NaOH in ethanol under reflux, elimination of HBr occurs
and ethene is produced.
HCH CH2 Ethanolic NaOH HCH CH2 + HBr
H
Br
ethene
Reactions of haloalkanes
Dehydrohalogenation of alkyl halides follows the Saytzeffs rule. When
more than one alkenes can be formed, the alkene with double bond
containing more alkyl substituents is the predominant product.
Example: Dehydrohalogenation of 2-iodobutane by refluxing with
alcoholic KOH produces:
2-butene
H H CH3CH
CHCH3
(major product)
CH3CCCH
H
CH3CH2CH
2-iodobutane
CH2
1-butene
(minor product)
Nucleophilic Substitution Reactions
The reaction of alkyl halides with hydroxide ion in
aqueous solution is a nucleophilic substitution
reaction. The OH acts as a nucleophile, relpacing the
halogen atom to form an alcohol
H
CH3 C Cl + OH
H
Chloroethane
heat
CH3 C OH
H
ethanol
Grignard Reactions
When an alkyl halide reacts with a metal such as Mg, an
organometallic compound, called the grignard reagent , is
produced.
R X + Mg ether R Mg X
a Grignard reagent
The reaction must be carried out in the absence of water.

Diethyl ether is often used as the solvent.
The Grignard reagent is a very strong Lewis base. The alkyl
portion of the molecule can act as a nucleophile. It reacts rapidly
with molecules having acidic H atom including water, producing
an alkane.
CH3CH2 MgBr + H OH
ethylmagnesium bromide
water
CH3CH3 + BrMgOH
ethane
Grignard reagent is primarily used in the synthesis of alcohols. It

reacts with aldehyde or ketone to produce alcohols of the desired
structures. (See: Reactions of Aldehyde and Ketone)
Aldehydes and Ketones

Contain the carbonyl group
Aldehydes = at least 1 side H
Ketones = both sides R groups
Many aldehydes and ketones have
pleasant tastes and aromas

Formaldehyde : H2C=O
pungent gas
formalin = a preservative
wood smoke, carcinogenic
Acetone : CH3C(=O)CH3
nail-polish remover
163
Aldehyde Odors and Flavors

butanal = butter
vanillin = vanilla
benzaldehyde = almonds
cinnamaldehyde = cinnamon
164
Ketone Odors and Flavors

acetophenone = pistachio
carvone = spearmint
ionone = raspberries
muscone = musk
165
Naming Aldehydes and Ketones

Main chain contains C=O group
Number the main chain from end closest to C=O
For aldehydes, give base name al ending
always on C1
For ketones, give base name one ending and according to number
of C on chain where C=O attached
166
Reactions of Aldehydes and Ketones

The carbonyl group in aldehydes and ketones has a constant
polarity.
+
C=O
The O atom attracts electrophiles; the C atom attracts nucleophiles
169
Addition of HCN to C=O

polar molecule HCN adds across the C=O,
with the positive part (H) attaching to O;
the nucleophile CN attaching to C atom
2-hydroxypropanenitrile
168
Reduction Reactions of Aldehydes and Ketones

Aldehydes and ketones are generally synthesized by the
oxidation of alcohols
Therefore, reduction of an aldehyde or ketone results in an
alcohol.
Common reducing agents are H2 with a Ni catalyst, NaBH4, and
LiAlH4
Catalytic hydrogenation reactions:
RCHO
H2/Ni or LiAlH4
RCH2OH (a 10 alcohol)
O
R C R
OH
H2/Ni or
LiAlH4
R C R
169
(a 20 alcohol)
Oxidation of Aldehydes
Aldehydes are easily oxidised using mild oxidising agents
Ketones would not oxidise even using strong oxidising agents
A. Tollens reagent (Silver mirror test)

Tollens reagent is a solution of silver nitrate in ammonium
hydroxide containing the silver complex Ag(NH3)2 +,
An aldehyde is oxidised by Ag(NH3)2 + , which is reduced to
metallic Ag. Ketones give no reaction.
RCHO + 2Ag(NH3)2+ + OH
RCOO + 2Ag + 2NH4+ + 2NH3
173
Oxidation of Aldehydes
B. Fehlings reagent test for aldehydes
Fehlings reagent consists of a basic solution of Cu(II)
complex with a deep blue colour.
It oxidises aldehyde, and is itself reduced to a brick-red
deposit of Cu(I) oxide. Ketones give no reaction.
RCHO + 2Cu2+(complex) + 5OH
*Aldehydes
RCOO + Cu2O
+ 3H2O
also decolourise acidified solution of KMnO4
173
C. Iodoform test for ethanal, CH3CHO, and methyl Ketones

A methyl ketone has a CH3 group attached to the carbonyl carbon.
O
R C CH3
R = H or any alkyl group
The reagent consists of an aqueous solution of I2 in NaOH or

KOH. On reacting with ethanal, a yellow precipitate of
triiodomethane (iodoform) appears.
CH3CHO + 3 I2 + NaOH
CH3COONa + CH3I + 3HI
Note: ethanol, CH3CH2OH or a sec. alcohol with the group CH3CH

also give positive iodoform tests.
OH
174
Reactions of Aldehydes and Ketones

Reaction of Grignard Reagents (RMgX)
a) With methanal gives a 10 alcohol
RMgX + HCHO ether R CH2OMgX
H2O/H+
RCH2OH
H2O/H+
R CHOH
(a 10 alcohol)
b) With other aldehydes give 20 alcohol

RMgX + RCHO ether R CHOMgX
R
(a 20 alcohol)
With ketones gives 30 alcohol

O
OMgX
RMgX + R C R
R
ether
OH
RCR
R
(a 30 alcohol)
175
H2O/H+
RCR
Carboxylic Acids
CnH2n + 1COOH (n 0)
RCOOH
Sour tasting
Weak acids
Citric acid
found in citrus fruit
Ethanoic acid = acetic acid, CH3COOH

vinegar
Methanoic acid = formic acid, HCOOH

insect bites and stings
174
Synthesis of Carboxylic Acids

Made by the oxidation of aldehydes and alcohols
175
Naming Carboxylic Acids

Carboxylic acid group always on end of main chain
has highest naming precedence of functional groups
C of group always C1
position not indicated in name
Change ending to oic acid
176
Examples of Naming Carboxylic Acids
177
Practice Name the following

hexanoic acid
(aka caproic acid, which causes
foot odor)
2-hydroxy-3-methylbutanoic acid
178
Reactions of Carboxylic Acids

Neutralisation: Reactions with bases to form salts of the acids and
water.
RCOOH + NaOH
RCOONa + H2O
Reactions with Reactive Metals : forming salts of the acids and H2 gas
2CH3COOH + 2Na
2CH3COONa + H2
Reactions with hydroegn carbonates: forming salts of the acids, CO2 and H2O
RCOOH + NaHCO3
RCOONa + CO2 + H2O
183
Reductions of Carboxylic Acids

Carboxylic acids are reduced by very strong reducing agents such as lithium
aluminum hydride in ether, producing primary alcohols.
RCOOH
LiAlH4/ether
RCH2OH + H2O
Esterification
When a carboxylic acid is heated with an alcohol in the presence of
concentrated sulphuric acid as catalyst, an ester is produced.
RCOOH + ROH
conc. H2SO4
RCOOR + H2O
Example:
CH3CH2COOH + CH3OH
propanoic acid
conc. H2SO4
methanol
CH3CH2COOCH3 + H2O
methylpropanoate
184
Esters
RCOOR
Sweet odor
Made by reacting carboxylic acid with an alcohol in the
presence of conc. sulphuric acid as catalyst
RCOOH + ROH conc. H2SO4
RCOOR + H2O
181
Naming Esters
Carboxylic acid group always on end of main chain
unless carboxylic acid group present
C of ester group on C1
position not indicated in name
Begin name with alkyl group attached to O
Name main chain with oate ending
182
Hydrolysis of Esters
Hydrolysis of esters is the reverse of esterification
Acid Hydrolysis of an ester in the presence of dilute HCl or dilute
sulphuric acid produces an alcohol and a carboxylic acid
If an alkali is used instead of an acid, the carboxylic acid formed will
be converted to the salt
CH3CH2COOCH3 + H2O
H+/reflux
methylpropanoate
CH3CH2COOCH3 + NaOH
methylpropanoate
CH3CH2COOH + CH3OH
propanoic acid
reflux
methanol
CH3CH2COONa + CH3OH
sodium propanoate
methanol

Ch5 Organic Chemistry

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Ch5 Organic Chemistry

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CHAPTER 5: ORGANIC

What Is Organic Chemistry?

Whats So Special About Carbon?

Whats Special About

Compounds found in all three states

Solubility in water varies depending on which of the other

may be chains or rings

Hydrocarbons Contain only C and H atoms.

Copyright 2010 Pearson

Table 5.1 Numerical Roots for Carbon Chains and Branches

Physical Properties of nAlkanes

Physical Properties of Alkanes

Ways of depicting an alkane.

Condensed Structural Formulas

Example Write the structural and condensed formula for the

Add H to complete four bonds on

The condensed formula has the H

Carbon Skeleton Formulas

Rotation about a Bond Is Not Isomerism

Possible Structural Isomers of Alkanes

Example 20.1: Write the structural formula and carbon skeleton

Names and Formulas of Alkyl Groups:

Names and Formulas of Alkyl Groups:

Names and Formulas of Alkyl Groups:

IUPAC Rules for Naming Alkanes

Copyright 2010 Pearson

Copyright 2010 Pearson

Note: Number the chain so that the substituents get

Note: Number the chain so that the substituents get

Caution: Be careful to choose the longest chain as

Caution: Be careful to choose the longest chain as

CH3 CH2 CH2 CH2 C

CH3 CH2 CH2 CH2 C

CH3 CH2 CH2 CH2 C

Note: Substituents are listed in alphabetical order.

Draw the Compounds

Draw the Compounds

Draw the Compounds

Draw the Compounds

Draw the Compounds

Name the Following Compounds

Name the Following Compounds

Geometric Isomerism in Cycloalkanes

Geometric Isomerism in Cycloalkanes

Geometric Isomerism in Cycloalkanes

Geometric Isomerism in Cycloalkanes

Geometric Isomerism in Cycloalkanes

Copyright 2010 Pearson

generally get multiple products with multiple

Free Radical Substitution

Mechanism of Free Radical substitution

The methyl free radical reacts with Cl2 to give chloromethane.

CH3CH3 (by product)

Naming Alkenes and Alkynes

produced by ripening fruit

used to make polypropylene

Tro: Chemistry: A Molecular Approach, 2/e

High electron density

Electrostatic map shows

Low electron density

Copyright 2010 Pearson

Copyright 2010 Pearson

Name the Alkene