AL-Kitab organic chemistry

University
college of
ALKANE
Pharmacy

Lec:
2
 Alkanes or Paraffin
• All C atoms are tetrahedral and sp3 hybridized (only C-C
single bonds)
• General formula = CnH2n+2 (CH4, C2H6, C3H8, C4H10, etc.)
• Can have linear or branched alkanes CH3

C5H12 3° 1° H3C C CH2 CH3

2° H
• Same molecular formula, different structure: structural isomers
• Branches are called substituents ( Give examples)
• Primary (1°) carbon atom: bound to one other C atom
• Secondary (2°) C atom: bound to 2 other C atoms
• Tertiary (3°) C atom: ” 3 ”
• Quaternary (4°) C atom: ” 4 ” 9
.A group of organic
compounds having
similar structures and
similar chemical
properties in which the
successive compounds
differ by CH2 group is
called a homologous
series………. .
 Names of Linear Alkanes and Alkyl Substituents

# of
Alkane Alkyl substituents
C atoms
1 CH4 Methane -CH3 Methyl
2 CH3CH3 Ethane -CH2CH3 Ethyl
3 CH3CH2CH3 Propane -CH2CH2CH3 Propyl
4 CH3CH2CH2CH3 Butane etc.
5 Pentane Note: alkyl substituent
is an alkane missing
6 Hexane one hydrogen.

7 Heptane
Root: number of C atoms
8 Octane
Suffix: functional group
9 Nonane (-ane for alkanes)
(-yl for alkyl groups)
10 Decane 10
 Linear Alkanes:
1 - 4 C atoms: gas at room temp
5 - 17C atoms: liquid at room temp
>17 C atoms: solid at room temp

Fractional
Distillation of
Crude Oil

11
Kelter, Carr, Scott, Chemistry A World of Choices 1999, page 429
Naming
Alkanes
IUPAC Rules

Alkane

12
 Naming Alkanes

1. Name the main chain. Find the longest continuous

chain of carbons in the molecule, and use the name
of that chain as the parent name:

13
 Naming Alkanes

2. Number the carbon atoms in the main chain.

Beginning at the end nearer the first branch point,
number each carbon atom in the parent chain:

14
 Naming Alkanes

3. Identify and number the branching substituent.

Assign a number to each branching substituent group
on the parent chain according to its point of attachment:

15
 Naming Alkanes

3. Identify and number the branching substituent.

Assign a number to each branching substituent group
on the parent chain according to its point of attachment:

16
Naming
Alkanes

17
18
Naming
Alkanes

19
 Naming
Practice
Expanded Structure Line Structure
H H H H
H C C C C H
H H H

H C H
H

20
Isomers: Compounds with the same molecular
formula but different chemical structures.

22
 Branched alkane
• Branching and cycloalkane decrease boiling
point

• Branching and cycloalkane increase melting

point
 Home work1
• molecule with the formula C3H8 is
(a) hexane (b) propane

• (c) decane (d) butane

(e) ethane
 Home work 2
• Select the correct IUPAC name for:

•
(a) 5-methyl-5-ethyloctane(b) 5-methyl-5-
propylheptane(c) 4-ethyl-4-methyloctane(d) 3-
methyl-3-propyloctane(e) 3-methyl-3-
propylheptane
 Home work 3
• Select the correct IUPAC name for:

(a) 1,1,3-trimethylpentane(b) 1-ethyl-1,3-

dimethylbutane(c) 2,4-dimethylhexane(d) 3,5-
dimethylhexane(e) 3,5,5-trimethylpentane
 Home work4
•
What is the expected product formed from
the reaction between 2-butene and Cl2
• (a) 1-chlorobutane
(b) 2-chlorobutane
(c) 2,3-dichlorobutane
(d) 2,2-dichlorobutane
(e) 3,3-dichlorobutane
 Home work 5

Select the IUPAC name for:

(CH3)2CHCH(𝐶𝐻3 )CH(Br)CH(CH3)2
(a) 3-bromo-2,4,5-tri methyl hexane
(b) 3- bromo-1,4,4-pentamethyl butane
(c) 3-bromo-1,1-dimethylhexane
(d) non of these
 Home work 6
• Which of the following is 2,2,3-methyl butane?
• a 𝐶𝐻3 C(𝐶𝐻3 )2 CH(𝐶𝐻3 )𝐶𝐻3
• b 𝐶𝐻3 CH(𝐶𝐻3 )CH(𝐶𝐻3 )𝐶𝐻3
• c 𝐶𝐻3 C(𝐶𝐻3 )2 CH(𝐶𝐻3 )𝐶𝐻2 𝐶𝐻3
• d 𝐶𝐻3 𝐶(𝐶𝐻3 )2 𝐶𝐻2 𝐶𝐻3
Alkanes, syntheses:

1- Hydrogenation of alkene(discussed later )

𝐻2 +Pt,Pd orNi
𝐶𝑛 𝐻2𝑛 → 𝐶𝑛 𝐻2𝑛+2
Alkene → Alkane
2-Reduction of an alkyl halide
a) hydrolysis of a Grignard reagent
b) with an active metal and an acid

3- Corey-House synthesis
(coupling of an alkyl halide with lithium dialkylcopper)
2-Reduction of an alkyl halide
a) hydrolysis of a Grignard reagent (two steps)
i) R—X + Mg  RMgX (Grignard reagent)
ii) RMgX + H2O  RH + Mg(OH)X

CH3CH2CH2-Br + Mg  CH3CH2CH2-MgBr
n-propyl bromide n-propyl magnesium bromide

CH3CH2CH2-MgBr + H2O  CH3CH2CH3 + Mg(OH)Br

propane
b) with an active metal and an acid
R—X + metal/acid  RH
active metals = Sn, Zn, Fe, etc.
acid = HCl, etc. (H+)

CH3CH2CHCH3 + Sn/HCl  CH3CH2CH2CH3 + SnCl2

Cl
sec-butyl chloride n-butane

CH3 CH3
CH3CCH3 + Zn/H+  CH3CHCH3 + ZnBr2
Br
tert-butyl bromide isobutane
3-Corey-House synthesis

R-X + Li  R-Li
Rli+ CuX  R2CuLi +LiX

R2CuLi + R´-X  R—R´ (alkane)

(R´-X should be 1o or methyl)

This synthesis is important because it affords a synthesis of
a larger alkane from two smaller alkyl halides.
 CH3 CH3
CH3CH-Br + Li  CH3CH-Li
isopropyl bromide

CH3 CH3
(CH3CH)2-Li + CuX  ( CH3CH)2-CuLi + Lix

CH3 CH3
(CH3CH)2-CuLi + CH3CH2CH2-Br  CH3CH-CH2CH2CH3
Diisoprpyl lithium cupper 2-methylpentane
(isohexane)

Note: the R´X should be a 1o or methyl halide for the best yields of the final product.
ALKYL HALIDES

Li
Mg
Sn,HCl
H2O CuI

R’X

ALKANES
Reactions of alkanes:
alkane + H2SO4  no reaction (NR)
alkane + NaOH  NR
alkane + Na  NR
alkane + KMnO4  NR
alkane + H2,Ni  NR
alkane + Br2  NR
alkane + H2O  NR
(Alkanes are typically non-reactive. They don’t react with acids, bases, active
metals, oxidizing agents, reducing agents, halogens, etc.)
Alkane, reactions:

1. Halogenation

2. Combustion (oxidation)

3. Pyrolysis (cracking)
1. Halogenation

R-H + X2, heat or hv  R-X + HX

a) heat or light required for reaction.

b) X2: Cl2 > Br2  I2
c) yields mixtures 
d) H: 3o > 2o > 1o > CH4
e) bromine is more selective
 Substitution Reactions of Alkanes
(Free radical chain mechanism)
• Primarily where halogen atoms replace hydrogen atoms. The cleavage of the
chlorine molecule leads to the formation of two highly reactive chlorine free
radicals (chlorine atoms). A free radical is an atom or group that has a single
unshared electron.
• CH4 + Cl2 
hv
CH3Cl + HCl
CH3Cl + Cl2 
hv
CH2Cl2 + HCl
CH2Cl2 + Cl2 
hv
CHCl3 + HCl
CHCl3 + Cl2 
hv
CCl4 + HCl
 Chain reaction mechanism
• The mechanism of substitution reaction
include three steps
• initiation step

• a propagation step

• a termination step
 • Combustion(exothermic reaction)
• alkanes used as fuel source

CnH2n+2 + (xs) O2, flame  n CO2 + (n+1) H2O + heat

gasoline, diesel, heating oil…
Incomplete Combustion with insufficient O2 produces CO

3. Pyrolyis (cracking)

alkane, 400-600oC  smaller alkanes + alkenes + H2

 Cycloalkanes
• Alkanes with closed ring(s) of C atoms
• General formula: CnH2n (C3H6, C4H8, C5H10, etc.)
• Naming: use cyclo- prefix before alkane name

cyclopropane cyclobutane cyclopentane cyclohexane

n=3 n=4 n=5 n=6
C3H6 C4H8 C5H10 C6H12
Naming substituted cycloalkanes:
• 1 substituent: no numbering necessary
• 2 or more substituents: highest alpha priority on C #1
CH3

methylcyclopentane
 Home work1
• -which of the following statements concerning the
reaction of methane with bromine is/are correct?
• 1) It is an addition reaction.
• (2) It is a substitution reaction.
• (3) A similar reaction will occur if propane is used
instead of
• (1) only
• (2) only
• (1) and (3) only
• (2) and (3) only
 Home work2
• Which name is acceptable for the following compound?

•
• (A) 5-chloro-2-methylcyclohexane
• (B) 4-chloro-2-methylcyclohexane
• (C) 1-chloro-3-methylcyclohexane
• (D) 2-chloro-5-methylcyclohexane
•
•
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