Chapter 6

An Overview of Organic Reactions

With thanks to Mark Nitz and Kris Quinlan

H H Pheromone of the
Silkworm Moth
H
Male moths can detect
10-13 mol/L in air!
topics H

• Degree of unsaturation OH
• Cis/trans, E/Z isomers
• Electrophilic addition / carbocation stability
• Carbocation rearrangements 1
 OH

O
OH

HO

O
*
* 25 million
n tons/year

Cl OH

Cl
O
Cl O

2
 Calculating the Degrees of Unsaturation of a
Molecule

A degree of unsaturation
refers to a double bonds or a
ring in a system

H2
CH2 CH3 C CH2
H3C CH2 H3C C
H
Degrees of 0 1 1
Unsaturation
C4H10 C4H8 C6H12

Degrees of Unsaturation can be calculated from the Molecular

Formula 3
 Degree of unsaturation

deg unsat = 0 deg unsat = 1

H H
4
C2H4
H H

H H
2 6
C3H6
H CH3

3 8 C6H12

CnH2n+2 CnH2n
4
 Degree of unsaturation

deg unsat = 2 CH3

4 6
deg unsat = 4

CnH2n-6
2 2

6 10

CnH2n-2
5
 Calculating Degree(s) of Unsaturation:

1) Look at number of carbons in the formula.

2) Write out the formula of the LINEAR ALKANE with

same number of carbons.

3) Calculate: [(# of H in alkane) – (# of H in compound)]/2

CH3

1) 2) n-heptane is C7H16 3) (1/2)(16 – 8) = 4

C7H8

6
 What to do about –X, -O-, N

Degree(s) of Unsaturation:

Halogens (-X): replace each halogen with H and do the same

calculation.

Oxygen (-O-): remove all oxygens from formula and do the

same calculation

Nitrogen (N): remove N and one H (for each nitrogen) and do same
calculation.

O
Br/H -O - NH
1) C9H8NOBr C9H9NO C9H9N C9H8
Br

N
2) nonane is C9H20 3) (1/2)(20 – 8) = 6
H
C9H8NOBr

7
 Examples: calc deg unsat of

furan C4H8O O
H
O O N

tetrahydrofuran
C4H4O C8H7N O
(THF)
C4H4O2

H H
H

OH

8
Cannot Rotate a Double bond without
Breaking it!

Cis and Trans

cis-2-Butene trans-2-Butene 9
Naming Tri and Tetra substituted double bonds?
Use E and Z
Assign priorities to groups on each end of
double bond (use Cahn-Ingold-Prelog rules)

High priority groups on

same side “Z”

High priority groups on

opposite sides “E”

10
Naming

CH2CH3 H CH3 CH2CH3

C C C C

H CH3 CH2Cl H

Note: Disubstituted alkenes can be named with cis/trans OR E/Z.

(Z)-4-Chloro-1-fluoro-2,4-dimethyl-2-hexene

11
Stability of Substituted Alkenes

R R

C C tetra
R R

R R

C C tri
R H
Decreasing stability

R R

C C
di
H H

R H
Why?
C C mono
H H

R = substituent group
12
 Stability of Substituted Alkenes
cis-2-butene is less stable than trans-2-butene

acid K=3
H3C CH3 catalyst H3C H
G = - 2.8 kJ/mol
H H H CH3
Measure concentrations of
cis-2-butene trans-2-butene each species at equilibrium

steric strain

cis-2-butene trans-2-butene
13
Alkene stabilities can be measured 3
different ways

• Equilibrium Constant between isomers via a

chemical transformation
• Heats of Combustion
• Heats of Hydrogenation

14
 Heat of Combustion

H3C CH3
+ 6 O2 4 CO2 + 4 H2O

H3C

+ 6 O2 4 CO2 + 4 H2O
CH3
Different starting material diastereomers, same products
Measure heat (enthalpy) for each reaction 15
 H3C CH3

? H3C

CH3
H = -2685.5 kJ/mol
H = -2682.2 kJ/mol
4 CO2 + 4 H2O

? = 3.3 kJ/mol

16
 Example: Heat of Hydrogenation

H H
H 3C CH3
+ H2 H 3C CH3
H H

H3 C H H

+ H2 H3C CH3
CH3
H H

Different starting material diastereomers, same products

Measure and compare H for each reaction.

17
 Example: Heat of Hydrogenation

H3C CH3

? H3C

CH3
H = -120 kJ/mol

H = -116 kJ/mol

H H

H3C CH3 ? = 4 kJ/mol

H H

18
 Examples: Heats of Hydrogenation

H R
R H
H H
R H R H
R H R H
R R R R
R R

alkane

More substituted double bonds are more stable

19
 Why are more substituted  bonds more stable ?

antibonding C-C
p orbital bonding C-H
(unfilled) orbital
(filled)

p-orbital p-orbital

Hyperconjugation

 bond in ethylene 20
 Addition of HX to an Alkene
Electrophilic Addition

X is usually Cl, Br, I or OH

21
 Markovnikov’s Rule

X
In the addition of HX to an alkene, the H attaches to the
carbon with fewer alkyl substituents and the X attaches to
the carbon with more alkyl substituents

22
23
Explanation for the specificity of the addition is the
stability of the intermediate in the reaction

The product from the lower energy

reaction pathway predominates 24
 Carbocation stability

tertiary secondary primary methyl

3o 2o 1o

The addition of HX goes through the most stable

carbocation

25
 Why are more substituted
carbocations more stable?

H
H
H Hyperconjugation- C-H  bond overlaps
with empty p-orbital on carbocation
H +

Inductive effects: Alkyl substituents donate electron density

more readily than H substituents

R H H H
+ + + +
R > R > R > H

R R H H
26
How does intermediate stability relate to the
pathway of the reaction?

• Hammond Postulate

“Transition state structures resemble the structures

of the nearest stable species”

Links transition state energy to the energy of the intermediate

27
The Hammond Postulate
Two cases:
1) For an endergonic reaction step, the transition state will more
closely resemble the product(s).
2) For an exergonic reaction step, the transition state will more
closely resemble the reactant(s).

28
The Hammond Postulate

So a more stable intermediate results in a lower energy transition

state and therefore a faster reaction
29
 H H
+ _
H3 C Br

CH3 H

H3C H
_
Br + H
H3C H

A more stable
H3C H
intermediate usually
results from a lower
H Br energy transition state
H3C H

30
31
32
Carbocation Rearrangements

33
1,2-Hydride shift mechanism

34
1,2-Alkyl shift

35
example

36
 When to look for carbocation rearrangements

When a less stable carbocation can rearrange to a more stable

carbocation by a 1,2 hydride shift or alkyl shift in a single step.
H H
H H
H
The most important cases are: + HCl
ether

2o  3o
Cl H H
H
2o  benzylic or allylic H

Cl

Primary carbocations (1o) will rearrange to 2o or 3o, BUT 1o carbocations

are rare. You will not encounter them until chm247 (Ch 16).

If a reaction is given with products, you should be able to draw the

mechanism with rearrangements that result in the given product.
 What you should know

Calculate degree of unsaturation of a molecule

Recognizing and naming E and Z alkenes

Alkene stability

HX addition to alkenes, Markovknikov’s rule

Carbocation stability

The Hammond postulate and what it means

Carbocation rearrangements via 1,2-alkyl shifts and hydride shifts