Chemical properties

of alkanes and cycloalkanes

1. Inert to most common chemical

reagents, including:
• Strong acids
• Strong alkalis
• Oxidising agents (under normal
laboratory conditions)
• Halogens (in the dark)
2. Combustible
Two common reactions of alkanes

1. Oxidation
- combustion (burning) of alkanes
2. Radical halogenation of alkanes

Reaction type: Radical Substitution

• Relative reactivity
of alkanes: 3 o > 2o > 1o > methyl
• Halogen reactivity: F2 > Cl2 > Br2 > I2
Step 1 (Initiation)

heat or light

Step 2a (Propagation)

Step 2b (Propagation)
Step 3 (Termination)
Preparation of Alkenes:
Elimination Reactions

6
DEHYDROHALOGENATION

7
7
DEHYDRATION

8
8
How many alkene products from dehydration?

9
 Diverse Reactions of Alkenes

� Alkenes react with many electrophiles

to give useful products by addition
(often through special reagents)
10
Addition vs. Elimination Reactions

11
 add H-OH add H-H

add HO-X add HO-OH

add X-X

add :CH2
add H-X

12
 Electrophilic Addition Reactions of Alkenes

Name of Reaction Reagent Product

HX, Ether
Hydrohalogenation alkyl halide
X = Cl, Br
Acid-catalyzed
H2O, H2SO4 alcohols
Hydration
H2/Pd
Hydrogenation alkanes
25OC, 3 atm
X2, CH2Cl2
Halogenation X2=Cl2. Br2 dihalides

Polymerization polymer13
Electrophilic Addition of HX to Alkenes

• General reaction mechanism:

electrophilic addition
• Attack of electrophile (such as HBr) on
π bond of alkene produces carbocation
and bromide ion
• Carbocation is itself an electrophile,
reacting with nucleophilic bromide ion

14
15
16
Example of Markovnikov’s Rule

0%

100 %

17
 HALOGENATION: Addition of Halogens

Acid-catalyzed Hydration

18
 HYDRATION

Oxymercuration

Hydroboration/oxidation

19
Products of hydration?

20
Major Products?

21
Which alkene?

22
Catalytic Hydrogenation

Syn Addition

23
Major Products?

24
Solid Fats from Liquid Oils

Partial hydrogenation can cause double bonds

to flip from cis to trans producing what are
called as "trans fat" - considered a
cardiovascular health risk. 25
Addition of Radicals to Alkenes: Polymers

26
Free Radical Polymerization

27
28
29
Alkynes

McMurry Organic Chemistry 6th edition

Chapter 6 (c) 2003 30
Preparation of acetylene

McMurry Organic Chemistry 6th edition

Chapter 6 (c) 2003 31
PREPARATION OF ALKYNES
Dehydrohalogenation of vicinal dihalides

32
REACTIONS OF ALKYNES

33
C. Hydration

34
D. REDUCTION

35
 ALKYL HALIDES
Nucleophilic Substitution Reaction

Reaction with alcoholic Silver nitrate

Sodium iodide in Acetone Test

37
 SUMMARY OF SUBSTITUTION AND
ELIMINATION REACTIONS
� Alkyl halides undergo different reactions in competition,
depending on the reacting molecule and the conditions.
� Based on patterns, likely outcomes can be predicted.

SN 1 SN2 E1 E2
Does Highly Does not Occurs
RCH2X not favored with occur with strong
occur good sterically
nucleophiles hindered
RS-, I-,CN-, base such
NH3, Br- as t-
butoxide
 SUMMARY OF SUBSTITUTION AND ELIMINATION REACTIONS

SN1 SN 2 E1 E2
Can occur Competes Can occur Favored
with with E2 with with strong
R2CHX
benzylic and Weakly benzylic and bases :
allylic basic allylic CH3CH2O-,
halides; nucleophil halides; OH-, NH2-
Weakly e; polar Weakly
basic aprotic basic
nucleophile; solvent nucleophile;
protic protic
solvents solvents
ethanol and ethanol and
acetic acid acetic acid
SUMMARY OF SUBSTITUTION AND ELIMINATION REACTIONS

SN1 SN2 E1 E2
Favored in Does Occurs in Favored
R3C-X hydroxylic not competition when
solvents; occur with SN1 bases are
Reaction used :
under OH- or
neutral RO-
conditions
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43
END

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