Professional Documents
Culture Documents
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
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)
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
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
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
CH 3(CH2)4CH3
n-Hexane
H3C
H3 C
H3 C
CHCH2CH3
Isopentane
H3C
CH(CH2)2 CH3
Isohcxanc
1.
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
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 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
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
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
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.
CH3CHO
VDW, DD
MW = 44
bp = 21 C
CH3CH2OH
VDW, DD, HB
MW = 46
C
bp = 79
CH 3CH2CH2 CH 2CH 3
bp = 36 C
CH3CH2CH2CH2CH3
bp = 36 C
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
mp = - 95 C
(CH3)4 C
mp = - 17 C
Increasing symmetry
Increasing melting point
Solubility
Key
11
1.8 Preparatio
1. Hydrogenation of alkenes ( reduction of alkene ).
Pt, Pd, or Ni
H2
Alkene
Alkane
CnH2n
CnH2n + 2
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
Zn
H+
RH
Zn++ +
X-
Example:
CH3CH2CHCH3
Zn , H+
CH3CH2CHCH3
H
Br
sec-Butyl bromide
n-Butane
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
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
H = heat of combustion
Example:
flame
C5 H12 + 8O2
5CO2 + 6H2O
kcal
3. Pyrolysis (cracking).
alkane
400-600o ; with or
without catalysts
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
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%
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%
2X.
(1)
X2
(2)
X. + RH
HX + R.
(3)
R. + X2
RX + X.
Chain-initiating step
Chain-propagating steps
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
no tertiary hydrogen.
one tertiary hydrogen.
two tertiary hydrogens.
no secondary hydrogen.
two secondary hydrogens.
half the number of secondary hydrogens as primary hydrogens.
16
c)
d)
e)
f)
g)
h)
i)
j)
k)
3,3-dimethylpcntane
2-methylheptane
2-methylhexane
n-heptane
n-pentane
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)
n-butyl bromide
sec-butyl bromide
ethyl chloride
l-butene
2-butene
17