3/22/09

Understanding the basics…
Mechanisms of Alkenes
Electrophilic Addition Reactions
•  Everyone knows that electrons are
negatively charged.
•  Everyone knows that electrons are
attracted to things with positive
charges.
•  Yet, the understanding of a “mechanism”
remains elusive to many students…
•  Let’s review the basics…
•  SO – electron flow is always from
Nucleophile to Electrophile.
•  Watch the direction of your arrows
–  from lone pairs to carbocation…
–  or anion to cation…
–  or anion to partial positive charge…
–  or alkene pi bond to cation or partial
positive charge…
•  Mechanisms are the most mind-boggling
part of organic chemistry.
•  Students, generally speaking, have spent
their time memorizing their way through
science courses.
•  Mechanisms require a student to
actually UNDERSTAND the
fundamentals of electron flow…
•  Electron flow is always from the
electron-rich to the electron-poor
species.
•  The electron-rich species is a Lewis
Base (must have a lone pair) and is called
the “nucleophile”.
•  The electron-poor species is a Lewis
Acid (must have empty orbital) and is
called the “electrophile”.
•  When working through a mechanism, the
goal is NOT to memorize the steps of a
mechanism OF A SPECIFIC MOLECULE–
when you do that, typically you become
too focused on the structures provided
in one example.
•  When that happens, you get confused
when the next mechanism problem has a
DIFFERENT structure.
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•  What you want to do is break down the

Dehydration of Alcohols
steps of the mechanism, into little parts
or steps. Identify this mechanism – Starts with
alcohol, ends with alkene…
•  These basic little steps can be
memorized. OH

•  By knowing the steps, you know how the H+

+ H2O

mechanism progresses, regardless of

the structure you are given to work
with.
•  SO – break them down…

Dehydration of Alcohols Dehydration of Alcohols

Steps Involved: Step 1: Convert –OH to H2O
–  Convert –OH to H2O
H H
–  Loss of H2O and Carbocation formation OH
H+
O

–  Removal of H+, resulting in formation of pi

bond to complete conversion to alkene

Dehydration of Alcohols Dehydration of Alcohols

Step 2: Loss of H2O (“spontaneous Step 3: Removal of H+, resulting in
dissociation”) to form carbocation formation of pi bond to complete
conversion to alkene
H H
O
+ H-O-H
+ H-O-H + H-O-H

H H

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Acid-Catalyzed Hydration Acid-Catalyzed Hydration

Steps Involved:
Identify this mechanism – Starts with –  Reaction of pi bond with H+ (acid cat.)
alkene, ends with alcohol… resulting in Carbocation formation
OH
–  Addition of H2O
H+, H2O –  Removal of extra proton (H+) to finish
formation of –OH.

Acid-Catalyzed Hydration Acid-Catalyzed Hydration

Step 1: Reaction of pi bond with H+ (acid Step 2: Addition of H2O
cat.) resulting in Carbocation formation
H H
O

H+ + H-O-H

H H
H

Acid-Catalyzed Hydration Addition of H-X

Step 3: Removal of extra proton (H+) to Identify this mechanism – Starts with
finish formation of –OH. alkene, ends with single halide…
X
H H + H-O-H OH
O H-X
+ H-O-H

H
H

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Addition of H-X Addition of H-X

Steps Involved:
–  Reaction of pi bond with H+ (of H-X),
concurrent separation of X-, and formation
of carbocation intermediate.
–  Attack of X- to finish formation of product.
Step 1: Reaction of pi bond with H+ (of H-
X), concurrent separation of X-, and
formation of carbocation intermediate.
H X H + X

Addition of H-X Addition of X2

Step 2: Attack of X- to finish formation
of product. Identify this mechanism – Starts with
alkene, ends with two halides…
X X
X2
H X H

Addition of X2 Addition of X2
Steps Involved: Step 1: Attack by pi bond on polarized X-
–  Attack by pi bond on polarized X-X with X with Halonium Ion formation
Halonium Ion formation
–  Attack of X- to pop open three-membered X X
+ X
ring and finish formation of product. X

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Addition of X2 Addition of X2
Step 2: Attack of X- to pop open three- Of course, you can “attack” the other end
membered ring and finish formation of of the halonium and open in the other
product. direction…
X
X
+ X
X
X X
X
X

Addition of X2 and H2O Addition of X2 and H2O

Identify this mechanism – Starts with Steps Involved:
alkene, ends with one alcohol and one –  Attack by pi bond on polarized X-X with
halide… Halonium Ion formation
OH
–  Attack by H2O to pop open three-
X2
X + HX membered ring.
H2O
–  Removal of extra proton (H+) by X- to
complete the formation of –OH.

Addition of X2 and H2O Addition of X2 and H2O

Step 1: Attack by pi bond on polarized X- Step 2: Attack by H2O to pop open three-
X with Halonium formation membered ring.
H H
O
X X
+ X
+ H-O-H + X
X
X
X

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Addition of X2 and H2O AND REMEMBER…

Step 3: Removal of extra proton (H+) by If you UNDERSTAND the basic steps to
X- to complete the formation of –OH. these mechanisms, it won’t matter what
H H H the double bond in the molecule looks
like...
O O

+ X + H-X

X X
Every alkene reacts the same way, every
time, regardless of what’s attached…

Finally…
Track the pieces you need to add or
subtract overall… See where you are
starting and where you are ending…
Don’t memorize a specific molecule but go
ahead and memorize the sequence of
steps involved… it won’t matter what
the alkene looks like if you approach it
this way…

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