Professional Documents
Culture Documents
CH 1012 Alkenes 2020
CH 1012 Alkenes 2020
CH 1012 Alkenes 2020
1
Alkenes (Olefins)
• Alkenes contain carbon—carbon double bonds.
2
➢ Bond dissociation energies of the C—C bonds in ethane (a
bond only) and ethylene (one and one bond) can be used to
estimate the strength of the component of the double bond.
3
Cis-Trans Isomerism in Alkenes
Monosubstituted
Tetrasubstituted Trisubstituted Disubstituted
5
Introduction to Addition Reactions
➢The characteristic reaction of alkenes is addition—the …… bond
is broken and ……………………………. bonds are formed.
7
Five important Addition Reactions of Alkenes
8
Reactions of Alkenes
For example, H for the addition of HBr to ethylene is –14 kcal/mol,
as illustrated below.
10
Hydrohalogenation
11
Hydrohalogenation
➢ In the representative energy diagram below, each step has its own
energy barrier with a transition state energy maximum.
➢Since step 1 has a higher energy transition state, it is rate-determining.
H for step 1 is positive because more bonds are broken than formed,
whereas H for step 2 is negative because only bond making occurs.
12
Hydrohalogenation
Hydrohalogenation follows Markovnikov’s Rule
• With an unsymmetrical alkene, HX can add to the double bond to
give two constitutional isomers, but only one is actually formed:
14
Hydrohalogenation
What would be the major product of the reaction? Write the stepwise mechanism
15
Reactions of Alkenes
16
Hydration of alkene
17
Reactions of Alkenes
18
Halogenation
➢ Initial addition of the electrophile Cl+ from (Cl2) occurs from either side of
the planar double bond to form a bridged chloronium ion.
20
Halogenation
➢ In the second step, nucleophilic attack of Cl¯ must occur from the
……………………… of the bridged halogen atom.
➢ Since the nucleophile attacks from below and the leaving group
departs from above, the two Cl atoms in the product are oriented
trans to each other.
21
Halogenation
22
Reactions of Alkenes
23
Halohydrin Formation
25
Halohydrin Formation
26
Reactions of Alkenes
, THF
27
➢ With unsymmetrical alkenes, the larger boron atom bonds to the
…………. substituted carbon atom (less sterically hindered, more
accessible carbon atom)
28
➢ Oxidation replaces the C—B bond with a C—O bond, forming a new OH
group with retention of configuration.
29
30
Reactions of Alkenes
(6) Oxymercuration-Demercuration
➢ A useful laboratory procedure for synthesizing alcohols from alkenes that
avoids rearrangement
➢ Two-step reaction and both steps carried out in the same vessel.
➢ Step 1: Oxymercuration: Mercuric acetate and water add to the double bond
to form (hydroxyalkyl)mercury compound.
31
What are the products of the following reactions of alkenes?
32
Reactions of Alkenes
33
Oxidation of Alkenes
(1) Epoxidation of Alkenes
➢ Epoxidation is the ………………………….. atom to an alkene to
form an epoxide.
➢ Epoxidation is typically carried out with a ……………………...
34
Oxidation of Alkenes
(2) Dihydroxylation of Alkenes
35
Anti dihydroxylation
36
Syn dihydroxylation
cold
37
➢ Each reagent adds two oxygen atoms in a syn fashion.
38
Oxidative Cleavage of Alkenes
➢ Oxidative cleavage of an alkene breaks both the and bonds of the
double bond to form two carbonyl compounds.
39
What is the product of the following reaction?
40