DR.

JOAZAIZULFAZLI JAMALIS
Department of Chemistry Faculty of Science Universiti Teknologi Malaysia
joazaizul@kimia.fs.utm.my
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Hydrocarbons
Aliphatic
Alkane Alkene Alkyne
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Aromatic (Arenes) Benzene & derivatives

Alkanes
all bonds are single bonds (C-C and C-H, bonds) Known as saturated hydrocarbons Categorized as acyclic or cyclic General formula for acyclic alkanes: CnH2n+2 General formula for cyclic alkanes: CnH2n
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 Acyclic alkanes contain only linear and branched chains of carbons atoms.

 Cyclic alkanes are also known as cycloalkanes.

Alkanes Homolog
Number of Carbon Atoms

Methane Ethane Propane Butane Pentane Hexane Heptane Octane Nonane Decane

1 2 3 4 5 6 7 8 9 10

Cycloalkanes Homolog
Number of Carbon Atoms

Cyclopropane Cyclobutane Cyclopentane Cyclohexane Cycloheptane

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3 4 5 6 7

Types of Carbons and Hydrogens

C - primary (1), secondary (2), tertiary (3) &
quaternary (4)

H - primary (1), secondary (2) & tertiary (3)

1o

H 1 1o H Co H o 1 o 1 2 Ho o H H 3 1 2o H C C C C Ho 1 1o H Ho Ho H o o
o

TRY THIS !!!

H H H H C H H C H
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C C

H H C H H H C H H

Alkyl Groups
- removing one hydrogen atom from the alkane
- substituent groups

- The symbol is R.
Alkane
CH3-H methane CH3CH2-H ethane

Alkyl group
CH3methyl CH3CH2ethyl

Abbreviation

MeEt-

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Propyl (remove 1 H from propane)

CH3CH2CH2

CH3CH2CH3 propane
Isopropyl (remove 2 H from propane)

CH3CHCH3
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n- Butyl (remove 1 H from butane)

CH3CH2CH2CH2

CH3CH2CH2CH3
n-butane

sec-Butyl (remove 2 H from butane)

CH3CH2CHCH3
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isobutyl (remove 1 H from isobutane)

CH3 H3C C CH2 H

CH3 CH3CHCH3
isobutane

tert-butyl or t-butyl (remove 3 H from isobutane)

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CH3 H3C C CH3

IUPAC NAMES
International Union of Pure and Applied Chemistry

Rule 1: Determine the main chain

1. Find the longest continuous chain of carbon atoms, and name it. 2. Use the chain with greater number of substituents as the main chain. 3. Substituents can be an alkyl groups, hydroxyl groups (-OH), halogen (-Cl,-Br,-I,-F), phenyl groups etc.

CH3CH2CH2CH2CHCH2CH2CH3 CH3
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CH3CH2CH2CH2CHCH2CH3 CH2CH2CH3
3 2 1

4. Determine the chain with the greater number of substituents

CH3 CH3CHCH2 CH-CHCH2CH3 CH3 CH-CH3 CH3

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Rule 2 & 3: Numbering the Main Chain and naming the alkyl groups

1. Number the longest chain, start with the end of the chain nearest to a substituent
2. Substituted carbons always get the lowest possible number

CH3CHCH2CH2CH3 CH3
2-methylpentane (IUPAC)
isohexane (common name) 17

CH3 2 CH3 CHCH3 6 3 7 5 4 CH3CH2CHCHCHCH2CH3 CH3

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3-ethyl-2,4,5-trimethylheptane

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Rule 4: Organizing multiple groups

when two or more substituents are present, list them in alphabetical order. when two or more of the same alkyl groups (or other substituent) are present, use the prefixes di-, tri-, tetra-, hexa- etc. follow the alphabet of the alkyl groups, NOT the prefixes di-, tri-, tetra- (IGNORE alphabet of the prefixes)

CH3 1 3 2 CH3CHCHCH2CHCH2CH3 4 6 5 7 CH3

19 5-ethyl-2,3-dimethylheptane

CH2CH3

CH2CH3 CH3 1 2 10 7 4 6 9 5 3 CH3CH2CCH2CH2CHCHCH2CH2CH3 8 CH2CH3 CH2CH3

3,3,6-triethyl-7-methyldecane

CH3CH2CHCH2CHCH2CH2CH3 CH3 CH2CH3

5-ethyl-3-methyloctane
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 When both directions lead to the same lowest number for one of the substituents, choose the direction that gives the lowest possible number to the remaining substituents.

CH3 4 2 CH3CCH2CHCH3 CH3 CH3

2,2,4-trimethylpentane NOT 2,4,4-trimethylpentane
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CH3 CH2CH3 3 4 1 6 CH3CH2CHCHCH2CHCH2CH3 CH3

6-ethyl-3,4-dimethyloctane NOT 3-ethyl-5,6-dimethyloctane
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[6,3,4]

[3,5,6]

 If the same number is obtained in both directions, follow the alphabet of the substituent.

CH3 CH2CH3 5 CH3CH2CHCHCHCH2CH3 4 3 1 CH3

3-ethyl-4,5-dimethylheptane

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Cl CH3CHCHCH3 Br

2-bromo-3-chlorobutane NOT 3-bromo-2-chlorobutane

CH2CH3 CH3CH2CHCH2CHCH2CH3 CH3

3-ethyl-5-methylheptane NOT 5-ethyl-3-methylheptane 24

Certain common names are still used in the IUPAC system Eg.

CH3 CH3CH
Isopropyl

CH3 CH3CHCH2
Isobutyl
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CH3CH2CH2CH2CHCH2CH2CH3 CHCH3 1 2 CH3

25 4-isopropyloctane or 4-(1-methylethyl)octane

CH3CH2CH2CH2CHCH2CH2CH2CH2CH3 1 2 3 CH2CHCH3 CH3

5-isobutyldecane or 5-(2-methylpropyl)decane
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Cycloalkanes
Rings of carbon atoms (CH2 groups) Formula: CnH2n Nonpolar, insoluble in water Compact shape Melting and boiling points similar to branched alkanes with same number

of carbons
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Nomenclature of Cycloalkane
no number is needed for a single substituent on a ring

H3C

Cl

methylcycloheptane
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chlorocyclohexane

CH3
methylcyclopentane May be cycloalkyl attachment to chain.

CH2CH2CH2CH2CH3

1-cyclobutylpentane 29

 if more than one substituent, arrange in alphabetical order give number to the carbon of the ring choose the best combination of numbers

CH3CH2CH2 H3 C

1 4 3 2 2 3 1 4

CH2CH3

4-ethyl-2-methyl-1-propylcyclohexane NOT 1-ethyl-3-methyl-4-propylcyclohexane NOT 5-ethyl-1-methyl-2-propylcyclohexane

[4,2,1]=7 [1,3,4]=8 30 [5,1,2]=8

H3C

CH3 CH3

1,1,3-trimethylcyclopentane NOT 1,3,3-trimethylcyclopentane NOT 1,1,4-trimethylcyclopentane

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Complex Substituents
If the branch has a branch, number the carbons from the point of attachment. Name the branch off the branch using a locator number. Parentheses are used around the complex branch name.

2 3

1-methyl-3-(1,2-dimethylpropyl)cyclohexane
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Isomerism
Molecules which have the same molecular formula, but differ in the arrangement of their atoms, are called isomers.

Constitutional (or structural) isomers differ in their bonding sequence.

Stereoisomers differ only in the arrangement of the atoms in space (in alkene).
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C4H10

Structural Isomers
CH3

CH3CH2CH2CH3

and

CH3CHCH3

C2H6O
H3C O CH3 and CH3CH2OH
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Geometric Isomerism in Cycloalkanes

The lack of free rotation of single-bonded carbons in a ring produces a kind of isomerism called geometric isomerism.
H CH3

CH3 H
trans 1,2-dimethylcyclopropane

CH3 CH3
cis 1,2-dimethylcyclopropane
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Source of alkanes
1. Natural gas methane (60%-80%) ethane, propane and butane 2. Petroleum gasoline kerosene diesel fuel
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C5H12-C12H26 C12H26-C16H34 C15H32-C18H38

Physical Properties of Alkanes

1. Alkanes from C1 to C4 are gasses C5 to C17 are liquids >C18 are wax-like solids 2. Alkanes are nonpolar compounds. Their characteristic known as like dissolves like rule. Nonpolar compounds are soluble in other nonpolar solvents. Alkanes are soluble in organic solvents.
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3. Boiling Points (bp)

a. Alkanes have low bps compared to more polar compounds of comparable size
CH3CH2CH3
O

CH3CH

CH3CH2OH

MW= 44 BP= -42oC

Van der Wall forces (weak)

MW =44 BP=21oC
dipole-dipole attraction

MW = 46 BP=79oC
hydrogen bonding (strong)

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b. Boiling points(b.p) increases as the numbers of carbons increases because of increased surface area CH3CH2CH2CH3 b.p = 0oC

CH3CH2CH2CH2CH3

b.p = 36oC

CH3CH2CH2CH2CH2CH3
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b.p = 69oC

c. The b.p of isomers decrease with branching because of decreased surface area
branched alkanes are more compact, less surface contact between molecules, less van der Waals attractions.

CH3CH2CH2CH2CH3
b.p = 36C

CH3CH2CHCH3 CH3
b.p = 28C

CH3 CH3CCH3 CH3

40 b.p =10C

Synthesis of Alkanes
1. Hydrogenation of Alkenes

Alkene + H2 Alkane
Catalyst required, usually Pt, Pd, or Ni.

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2.

Reduction of alkyl halide

Zn CH3COOH or LiAlH4
Zn CH3COOH

Sources of H: Zn / CH3COOH, LiAlH4, NaBH4

H Cl

H H

CH3CH2CH2CH2Br

LiAlH4

CH3CH2CH2CH3

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3.

Reduction of alkyl halide via Grignard Reagent

add an organometallic reagent to water

this will reduce an alkyl halide to an alkane

Grignard Reagent react with water molecule:

R MgX

H O H
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R H

Mg(OH)X

Reactions of Alkanes
1. Combustion
2 CH3CH2CH2CH3 + 13 O2 heat 8 CO2 + 10 H2O

2. Cracking and hydrocracking (industrial)

long chain alkane
catalyst

shorter chain alkane

3. Halogenation
CH4 + Cl2 heat or light CH3Cl + CH2Cl2 + CHCl3 +CCl4
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Mechanism of Halogenation
Step 1 (Initial Step) Homolytic cleavage of the chlorine molecule

Cl

Cl

hv or heat

2 Cl

Step 2 (Propagation Step) i) Chlorin radical attack alkane molecule to form alkyl radical

R
ii)

Cl

HCl

+ R

Alkyl radical will attack chlorine molecule to produce chlorine radical

Cl

Cl

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Cl + Cl

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Step 3 (Termination Step) Free radicals will combine or transfer its electrons to form a molecule

R Cl R

+ +

R
Cl

R Cl R

R Cl Cl

+ Cl

Halogenation will give mixtures of products because there are more than one atom of hydrogen that will be substituted.
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Try This !!!

Propose the mechanism for the following reaction. Which compound is the major product. Explain your answer.

CH3CH2CH3 + Cl2

heat or uv light

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