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Chapter 1

Aliphatic Hydrocarbons
Alkanes
By:
Bin hayan

1.1 An Introduction
Alkanes are aliphatic hydrocarbons having only C C and C H bonds .
Because their carbon atoms can be joined together in chains or rings, they can
be categorized as acyclic or cyclic.
Acyclic alkanes have the molecular formula CnH2n +2 , (where n = an
integer) and contain only linear and branched chains of carbon atoms.
They are also called saturated hydrocarbons because they have the
maximum number of hydrogen atoms per carbon.
Cycloalkanes contain carbons joined in one or more rings. Because their
general formula is C n H2n , they have two fewer H atoms than an acyclic
alkane with the same number of carbons.
Simple cycloalkanes are named by adding the prefix cyclo- to the name of the
acyclic alkane having the same number of carbons.
Table 1.1 Acyclic and cyclo alkanes
Number
of C
atoms

Names
of
Acyclic
alkanes

Condensed
Structures

Names of
Cycloalkanes

Propane

CH3 CH2 CH3

Cyclopropane

butane

CH3( CH2)2CH3

Cyclobutane

pentane

CH3(CH2)3CH3

cyclopentane

hexane

CH3(CH3)4CH3

cyclohexane

heptane

CH3(CH3)5CH3

cycloheptane

octane

CH3(CH3)6CH3

cyclooctane

Structures
(Shapes)

Table 1.2 Summary: Straight-Chain Alkanes


Number
of
C atoms

Molecular
formula

Name
(n- alkane )

Number
of C
atoms

Molecular
formula

Name
(n- alkane )

CH4

Methane

13

C13H28

Tridecane

C2H6

Ethane

14

C14H30

Tetradecane

C3H8

Propane

15

C15H32

Pentadecane

C4H10

Butane

16

C16H34

Hexadecane

C5H12

Pentane

17

C17H36

Heptadecane

C6H14

Hexane

18

C18H38

Octadecane

C7H16

Heptane

19

C19H40

Nonadecane

C8H18

Octane

20

C20H42

Eicosane

C9H20

Nonane

10

C10H22

Decane

11

C11H24

Undecane

12

C12H26

Dodecane

1.2 Alkyl groups


Carbon substituents bonded to a long carbon chain are called alkyl groups.
An alkyl group is formed by removing one hydrogen from an alkane.
Alkyl substituents are named by replacing the ane ending of the alkane with
yl The letter R is used to indicate any alkyl group.
The general formula for an alkyl group is CnH2n + 1 .
Table 1.3 Some names of alkyl groups
R(any alkyl group)

Name

CH3-

Methyl

CH3CH2

Ethyl

CH3CH2 CH2

n-Propyl

CH3CH2 CH2CH2

n-Butyl

Among the alkyl groups we again encounter the problem of isomerism. There is
only one methyl chloride or ethyl chloride, and correspondingly only one
methyl group or ethyl group. We can see, however, that there are two propyl
chlorides. I and II, and hence that there must be two propyl groups. These
groups:

I
n-Propyl chloride

Cl

Cl

II
Isopropyl chloride

Both contain the propane chain, but differ in the point of attachment of the
chlorine; they are called n-propyl and isopropyl: We can distinguish the two:

CH3CH2CH2

CH3CHCH3

n-Propyl

Isopropyl

chlorides by the names n-propyl chloride and isopropyl chloride; we distinguish


the two propyl bromides, iodides, alcohols, and so on in the same way.
We find that there are four butyl groups, two derived from the straight chain
n-butane, and two derived from the branched-chain isobutane. These are given
the designations n- (normal), sec- (secondary), iso-, and tert- (tertiary), as
shown below. Again the difference between n-butyl and sec-butyl and between
isobutyl and tert-butyl lies in the point of attachment of the alkyl group to the
rest of the molecule.

CH3CH2 CH2CH2

CH3CH2CHCH3

n-Butyl

sec-Butyl

CH3

CH3
CHCH2
CH3

CH3

CH3

CH3
Isobutyl

tert-Butyl

The prefix n- is used to designate any alkyl group in which all carbons form a
single continuous chain and in which the point of attachment is the very end
carbon. For example:

CH3CH2CH2CH2CH2Cl

CH3(CH2)4CH2Cl

n-Pentyl chloride

n-Hexyl chloride

The prefix iso- is used to designate any alkyl group (of six carbons or less)
that has a single one-carbon branch on the next-to-Iast carbon of a chain and has
the point of attachment at the opposite end of the chain. For example:

CH3

CH3

CH(CH2)2CH2C1

CHCH2CH2 C1
CH3

CH3
Isopentyl chloride

Isohcxyl chloride

If the branching occurs at any other position, or if the point of attachment is at


any other position, this name does not apply.

1.3 Common names of alkanes


As we have seen, the prefixes n-, iso-, and neo- are adequate to differentiate the
various butanes and pentanes, but beyond this point an impracticable number of
prefixes would be required. However, the prefix n- has been retained for any
alkane, no matter how large, in which all carbons form a continuous chain with
no branching:

CH3CH2 CH 2CH 2CH3


n-Pentane

CH 3(CH2)4CH3
n-Hexane

An isoalkane is a compound of six carbons or less in which all carbons except


one form a continuous chain and that one carbon is attached to the next-to-end
carbon

H3C

H3 C
H3 C

CHCH2CH3
Isopentane

H3C

CH(CH2)2 CH3
Isohcxanc

1.4 IUPAC names of alkanes


The IUPAC is ( International Union of Pure and Applied Chemistry).

1.

The rules of the IUPAC system are:


Select as the parent structure the longest continuous chain, and then consider the
compound to have been derived from this structure by the replacement of
hydrogen by various alkyl groups. Isobutane (I) can be considered to arise

CH3CHCH3

CH3CH2CH2CHCH3

CH3
I
Methylpropane
(Isobutane)
2.
3.

4.

CH3CH2CHCH2CH3

CH3

CH3

II
2-Methylpentane

III
3-Methylpentane

Where necessary, as in the isomeric methyl pentanes (II and III), indicate by a
number the carbon to which the alkyl group is attached.
In numbering the parent carbon chain, start at whichever end results in the use of
the lowest numbers; thus II is called 2-methylpentane rather than 4methylpentane.
If the same alkyl group occurs more than once as a side chain, indicate this by
the prefix di-. tri-, tetra-, etc., to show how many of these alkyl groups there
are, and indicate by various numbers the positions of each group,as in2,2,4trimethylpentane.
CH3
CH2

CH3
CH3 CHCH2CCH3
CH3

CH3CH2CH2CH CH C CH2 CH3


CH CH3 CH2

CH3
H3 C

IV
2.2,4-trimethylpentane

5.

CH3

CH3

V
4-Methyl-3,3-diethyI-5-isopropyloctane

If there are several different alkyl groups attached to the parent chain, name
them in order of increasing size or in alphabetical order; as in
4-methyl-3,3-diethyl-5-isopropyhctane (V).

1.5 Classes of carbon atoms and hydrogen atoms


A primary
(1) carbon atom is attached to only one other carbon atom.
A secondary (2) is attached to two others.
A tertiary
(3) is attached to three others.
A quaternary (4) is attached to four others.
For example:

1 2 2 1
H H H H

1 3 1
H H H

1 3 2 1
H H H H

H C C C C H

H C C C H

H C C C C H

H H H H

CH3CH3
CH3CH2 C

H H

H C H

H C H

H
1

CH3

CH3
4

Each hydrogen atom is similarly classified, being given the same designation of
primary, secondary, or tertiary as the carbon atom to which it is attached,
except quaternary (there is no a quaternary hydrogen atom).
1.6 Isomers
We have seen that carbon forms four covalent bonds and hydrogen forms only
one covalent bond. This means that there is only one possible structure for
alkanes with molecular formulas CH4 (methane) , C2H6 (ethane), and C3H8
(propane).
As the number of carbons in an alkane increases beyond three, the number of
possible structures increases. There are two possible structures for an alkane
with molecular formula C4H10 (butane and isobutane).

CH3
CH3CH2 CH2CH3
Butane

CH3CHCH3
Isobutane

Compounds such as butane and isobutane that have the same molecular
formula but differ in the order in which the atoms are connected are called
constitutional isomers.
There are three alkanes with molecular formula C5H12 , Pentane is the straight
chain alkane, Isopentane and The third isomer is called neopentane.

CH3
CH3 CH2CH2CH2CH3
Pentane

CH3CHCH2CH3
Isopentane

CH3
CH3 CCH3
CH3
Neopentane

There are five constitutional isomers with molecular formula C6H14. The name
three of them (hexane, isohexane, and neohexane).
CH3
CH3 CH2CH2CH2CH2 CH3
Hexane

CH3

CH3CHCH2 CH2CH3
Isohexane
2-methylpentane

CH3CCH2 CH3
CH3
Neohexane
2,2-dimethylbutane

CH3
CH3CH2CHCH2 CH3
3-methylpentane

CH3CH

CHCH3

CH3 CH3
2,3-dimethylbutane

There are nine alkanes with molecular formula C7H16. We can name only two of
them (heptane and isoheptane), Notice that neoheptane cannot be used as a
name because three different heptanes have a carbon that is bonded to four other
carbons and a name must specify only one compound.

CH3
CH3CH2CH2CH2CH2CH2CH3
Heptane

CH3

CH3CH

CH3CHCH2CH2CH2CH3
Isoheptane
2-methylhexane

CHCH2CH3

CH3 CH3
2,3-dimethylpentane

CH3 CH 2CHCH 2CH2CH3


3-methylhexane

CH3CHCH2CHCH3
CH3 CH3
2,4-dimethylpentane

CH3

CH3
CH3CCH2CH2CH3

CH3CH2CCH2CH3

CH3CH2CHCH2CH3

CH3
2,2-dimethylpentane

CH3
3,3-dimethylpentane

CH2CH3
3-ethylpentane

CH3 CH3
CH3C

CHCH3

CH3
2,2,3-trimethylbutane

Table 1.4 Summary: constitutional isomers


Number of
Molecular
Name
C atoms
formula
(n-alkane)

Number of
constitutional isomers

CH4

Methane

C2H6

Ethane

C3H8

Propane

C4H10

Butane

C5H12

Pentane

C6H14

Hexane

C7H16

Heptane

C8H18

Octane

18

C9H20

Nonane

35

10

C10H22

Decane

75

20

C20H42

Eicosane

366,319

1.7 Physical properties


An alkane molecule is held together entirely by covalent bonds. These
bonds either join two atoms of the same kind and hence are non-polar, or
join two atoms that differ very little in electronegativity and hence are only
slightly polar.
As a result an alkane molecule is either non-polar or very weakly polar.
Alkanes contain only nonpolar C C and C H bonds.

the forces holding non-polar molecules together (van der Waals forces)
are weak and of very short range; they act only between the portions of
different molecules that are in close contact, that is, between the surfaces
of molecules.

Table 1.5 summarizes how these intermolecular forces affect the physical
properties of alkanes.

Table 1.5 Physical Properties of Alkanes


Property
Observation
Boiling point Alkanes have low bps compared to more polar compounds of comparable size.
CH3CH2CH3
VDW
MW = 44
bp = -42 C

CH3CHO
VDW, DD
MW = 44
bp = 21 C

CH3CH2OH
VDW, DD, HB
MW = 46
C
bp = 79

Increasing strength of intermolecular forces


Increasing boiling point

bp increases as the number of carbons increases because of increased surface area.


CH3 CH 2CH2CH3
bp = 0 C

CH 3CH2CH2 CH 2CH 3
bp = 36 C

CH 3CH2CH2 CH 2CH 2CH3


bp = 69 C

Increasing surface area


Increasing boiling point

The bp of isomers decreases with branching because of decreased surface area.


(CH3 )4C
bp = 10 C

(CH3)2 CHCH 2CH3


bp = 30 C

CH3CH2CH2CH2CH3
bp = 36 C

Increasing surface area


Increasing boiling point

Melting point

Alkanes have low mps compared to more polar compounds of comparable size.

CH3CH2CH3
VDW
mp = - 190 C

CH3CHO
VDW, DD
mp = - 121 C

Increasing strength of intermolecular forces


Increasing melting point

mp increases as the number of carbons increases because of increased surface area.


CH 3CH2CH2CH3
mp = - 138 C

CH3 CH 2CH 2CH2CH2 CH 3

mp = - 95 C

Increasing surface area


Increasing melting point

mp increases with increased symmetry.


CH 3CH2CH(CH3)2
mp = - 160 C

(CH3)4 C
mp = - 17 C

Increasing symmetry
Increasing melting point

Solubility
Key

Alkanes are soluble in organic solvents.


Alkanes are insoluble in water.
bp = boiling point; mp = melting point; VDW = van der Waals; DD = dipoledipole;
HB = hydrogen bonding; MW = molecular weight

11

1.8 Preparatio
1. Hydrogenation of alkenes ( reduction of alkene ).

Pt, Pd, or Ni

H2

Alkene

Alkane

CnH2n

CnH2n + 2

2. Reduction of alkyl halides.


a. Hydrolysis of Grignard reagent.
RX

ether

Mg

H 2O

RMgX

RH

Grignard
reagent

Alkane

Example:
Mg

CH3CH2CHCH3

H2O

CH3CH2CHCH3

ether

Br

CH3CH2CHCH3
H

MgBr
Sec-Butylmagncsium
bromide

Sec-ButyI bromide

n-Butane

b. Reduction by metal and acid.


RX

Zn

H+

RH

Zn++ +

X-

Example:

CH3CH2CHCH3

Zn , H+

CH3CH2CHCH3
H

Br
sec-Butyl bromide

n-Butane

3. Coupling of alkyl halides with organometallic compounds.

RX
May be
1o, 2 o, 3o

Li

RLi
Alkyl
lithium

CuX

R2CuLi
Lithium
dialkylcopper

R'X
Should be 1o

R'

11

Examples:
Li

CH3CH2Cl

CH3CH2Li

Ethyl
chloride

CuBr

(CH3CH2)2CuLi

Ethyllithium

Lithium
diethylcopper

CH3(CH2)7CH3
n-Nonane

CH3(CH2)5CH2Br
n-Heptyl bromide
CH3
Li

CH3CCH3

CuBr

CH3

(t-C4H9)2CuLi

CH3CCH2CH2CH2CH2CH3

CH3
tert-Butyl chloride

CH3CH2CH2CH2CH2Br
n-Pentyl bromide

CH3
2,2-Dimethylheptane

For good yields, R'X should be a primary halide; the alkyl group R in the
organometallic may be primary, secondary, or tertiary. For example:
CH3Br
Methyl
bromide

Li

CH3Li
Methyllithium

CuI

(CH3)2CuLi
Lithium
dimethylcopper

CH3(CH2)7CH3
n-Nonane

CH3(CH2)6CH2I
n-Octyl iodide

For good yields, R'X should be a primary halide; the alkyl group R in the
organometallic may be primary, secondary, or tertiary. For example:
Cl
CH3CH2CHCH3
sec-Butyl
chloride

Li

CuI

(CH3 CH2CH

)2CuLi

CH3
CH3CH2CH2 CH2CH2Br
n-Pentyl bromide

CH3
CH3 CH2CH(CH2)4CH3
3-Methyloctane

12

1.9 Reactions
1. Halogenation. Discussed in Sec. 1.10

X2

250-400 o or light

HX

Usually a
mixture
Reactivity

X2: Cl2 > Br2


H: 3o > 2o > 1o > CH3

Example:
CH3
H3 C

CH3

CH3
CH3

Cl 2
250-400o

CH3CHCH2Cl

and

Isobutyl chloride

H
Isobutane

H3C

CH3

Cl
tert-Butyl chloride

2. Combustion.
flame

CnH2n+2 + excess O2

nCO2 + (n+ 1)H2O

H = heat of combustion

Example:
flame

C5 H12 + 8O2

5CO2 + 6H2O

kcal

3. Pyrolysis (cracking).

alkane

400-600o ; with or
without catalysts

H2 + smaller alkanes + alkenes

1.10 Halogenation.
Under the influence of ultraviolet light, or at 250-400 oC, chlorine or bromine
converts alkanes into chloroalkanes (alkyl chlorides) or bromoalkanes (alkyl
bromides); an equivalent amount of hydrogen chloride or hydrogen bromide is
formed at the same time.
Depending upon which hydrogen atom is replaced, any of a number of isomeric
products can be formed from a single alkane. Ethane can yield only one
haloethane ; propane, n-butane, and isobutane can yield two isomers each; npentane can yield three isomers, and isopentane, four isomers.

13

Experiment has shown that on halogenation an alkane yields a mixture of all


possible isomeric products, indicating that all hydrogen atoms are susceptible to
replacement. For example, for chlorination :
CH3CH3

Cl 2
light, 25o

CH3CH2Cl
Chloroethane
Ethyl chloride

ethane

Cl
CH3CH2CH3

Cl2
light, 25o

CH3 CH2CH2Cl

Propane

and

CH3CHCH3

1-Chloropropane
n.Propylchloride
45%

2-Chloropropane
Isopropyl chloride
55%
Cl

Cl2

CH3CH2CH2CH3

light, 25o

n-butane

1-Chlorobutane
n-Butylchloride
28%

CH3
CH3CHCH3

and

CH3CH2CH2 CH2Cl

2-Chlorobutane
sec- butyl chloride
72%

CH3
Cl2

Isobutane

CH3

CH3 CHCH2Cl

light, 25 o

CH3 CH2CHCH3

and

1-Chloro-2-methylpropane
Isobutyl Chloride
64%

CH3CCH3
Cl
2-Chloro-2-methylpropane
tert-Butyl chloride
36%

Bromination gives the corresponding bromides but in different proportions:


CH3CH3
Ethane

Br2
light, 127o

CH3CH2Br
ethyl bromide
Br

CH3 CH2CH3
Propane

Br2
light, 127o

CH3CH2CH2Br
n-propyl bromide
3%

and

CH3 CHCH3
Isopropyl bromid
97%

14
Br
Br2

CH3 CH2CH2CH3
n-Butane

CH3CH2CH2CH2 Br
n-Butyl bromide
2%

light, 127o

CH3

CH3CH2CHCH3
Sec-butyl bromide
98%

and

CH3
Br2

CH3CHCH3
Isobutane

CH 3

CH3CHCH2Br
trace
1%

light, 127o

and

CH3CCH3
Br
over 99%

1.11 Mechanism of halogenation


250-400o
or UV light

2X.

(1)

X2

(2)

X. + RH

HX + R.

(3)

R. + X2

RX + X.

Chain-initiating step

Chain-propagating steps

then (2), (3), (2), (3), etc., until finally a chain.

A halogen atom abstracts hydrogen from the alkane (RH) to form an alkyl
radical(R.). The radical in turn abstracts a halogen atom from a halogen molecule
to yield the alkyl halide (RX).
Which alkyl halide is obtained depends upon which alkyl radical is formed.
CH4
Metane

CH3CH3
Ethane

CH3CH2CH3
Propane

X.

CH3.
Methyl radical

X.

CH3CH2.
Ethyl radical

X2

X2

CH3X
Methyl halide

CH3CH2X
Ethyl halide

abstraction of 1H

CH3CH2CH2.
n-Propyl radical

X2

abstraction of 2H

CH3CH.CH3
Isopropyl radical

X2

X.

CH3CH2CH2X
n-Propyl halide
X
CH3CHCH3
Isopropyl halide

15

PROBLEMS
1. Give the structural formula of:
a)
b)
c)
d)
e)
f)
g)
h)

2,2,3,3-tetramethylpentane
2,3-dimethyIbutane
3,4,4,5-tetramethylheptane
3,4-dimethyI-4-ethylheptane
2,4-dimethyl-4-ethylheptane
2,5-dimethylhexane
2-methyI-3-ethylpentane
2,2,4-trimethylpentane

2. Draw out the structural formula and give the IUPAC name of:
a)
b)
c)
d)
e)
f)
g)
h)
i)

(CH3 )2CHCH2CH2CH3
CH3CH2 C(CH3)2 CH2CH3
(C2 H5)2 C(CH3)CH2 CH3
CH3CH2 CH(CH3)CH(CH3)CH(CH3)2
(CH3)3CCH2C(CH3)3
(CH3 )2CHCH2CH2CH(C2H5)2
(CH3 )2CHCH(CH3)CH2C(C2H5 )CH3
(CH3)2 CHC(C2H5 )2CH2CH2CH3
CH3CH2CHCH2 CHCH2CH3
CH3

CH2CH2 CH 3

CH3

CH3

j) CH3CH2CHCH2 CHCHCH3
CH 2CH2CH3

3. Pick out a compound in Problem 1 or 2 that has:


a)
b)
c)
d)
e)
f)

no tertiary hydrogen.
one tertiary hydrogen.
two tertiary hydrogens.
no secondary hydrogen.
two secondary hydrogens.
half the number of secondary hydrogens as primary hydrogens.

4. Pick out a compound (if any) in Problem 1 or 2 that contains:


a) one isopropyl group.
b) two isopropyl groups.

16

c)
d)
e)
f)
g)
h)
i)
j)
k)

one isobutyl group.


two isobutyl groups.
one sec-butyl group.
two sec-butyl groups.
one tert-butyl group.
two tert-butyl groups.
an isopropyl group and a sec-butyl group.
a tert-butyl group and an isobutyl group.
a methyl, an ethyl, a n-propyl, and a sec-butyl group.

5. list the following hydrocarbons in order of decreasing boiling points


a)
b)
c)
d)
e)

3,3-dimethylpcntane
2-methylheptane
2-methylhexane
n-heptane
n-pentane

6. Arrange the following compounds in order of increasing boiling point.


1.
2.
3.
4.

CH3(CH2 )5CH2
CH3
CH3(CH2 )5CH3
CH3CH2 CH2CH2CH(CH3)2
(CH3)3 CCH(CH3 )2

7. Write balanced equations, naming all organic products, for the following reactions
a)
b)
c)
d)
e)
f)

isobutyl bromide + Mg/ether


tert-butyl bromide + Mg/ether
product of (a) + H2O
product of (b) + H2O
sec -butyl chloride + Li, then Cul
product of (e) + ethyl bromide

8. Write equations for the preparation of n-butane from:


a)
b)
c)
d)
e)

n-butyl bromide
sec-butyl bromide
ethyl chloride
l-butene
2-butene

17

From the books:

Robert Thornton Morrison Robert Neilson Boyd.


Organic Chemistry by Janice Gorzynski Smith third edition