Chemistry 1102

Charlie Bond
MCS Rm 4.16/4.27
Charles.Bond@uwa.edu.au

What is Organic Chemistry?

Organic Reactions I II
Alkanes (Ch 3)
Conformational Analysis (Ch 3)
Stereochemistry I II III (Ch 6)
Alkyl Halides I II (Ch 7)
Alcohols and Ether I II (Ch 8)
1

Reaction Mechanisms
To write mechanisms for organic chemistry, we show the flow of electrons
from electron-rich species to electron-poor species with curly arrows.
Placement of the curly arrow is important!
It originates at the electron pair and terminates
at the electron-poor atom

a curly arrow represents the

movement of two electrons

Example:
bond making
Write reaction mechanism between hydroxide ion and proton:

O H

Reaction Mechanisms
Example: bond breaking
chlorine
had gained
one
Cl gains
an electron
electron and becames
and becomes
negatively
charged

Cl

curly arrow is directed from

single bond to electronegative
atom

Cl

negatively charged

carbone
lostone
one
C loses
electron and becomes
electroncharged
and
positively

becomes positively
charged

Lone pairs: nonbonding electrons can also be used in bond-making process.

Write the reaction between water and a proton:

H
O
H

H
H O H
an oxonium
cation

Reaction Mechanisms
CARBON
-

has valency of four

carbon can also bond to just three other atoms by donating a pair of
electrons to one of the atoms originally bonded (breaking the bond)
-

tetravalent carbon

curly arrow is directed from

single bond to electronegative
atom

CARBOCATION
CARBOCATION

carbone lost one

electron
becomes
Carbonand
loses
positively charged

one electron and

becomes +ve

C
CARBOANION

CARBANION

H
4

NITROGEN
-

has valency of three

has three bonding electrons and a lone pair

however it can also bond to four atoms by donating its lone pair, in
which case it will than carry a positive charge.
-

Write reaction between ammonia and proton:

H N H
H
trivalent nitrogen

H
H N H
H

What shape is ammonia?

What shape is an
ammonium ion?

an ammonium
cation

OXYGEN
-

has two bonding electrons and two lone pairs

it can bond to two other atoms and it is usually divalent

it can also bond to one atom in a negatively charged form, or to three

atoms in positively charged form.
-

O
divalent oxygen

an oxide anion

H
O

H
O
6

an oxonium cation

BOND POLARITY
because different atomic nuclei electronegativity. This leads to charge
imbalance, with one of the atoms taking more than its share of electrons.
-

an atom that is more electronegative than carbon will polarize the bond,
this is indicated by putting partial charge + and - above the atoms. It
can also be represented by putting an arrowhead on the bond in the
direction of electron excess.
-

+
H3C

Br

H3C

Br

bromine is more
electronegative than carbon
polarity in C-O and C-N bonds

+
C O

+
C N

+
C O

Nucleophiles, Electrophiles and Leaving Groups

Reagents are classified as nucleophiles or electrophiles.
Nucleophiles are electron rich, nucleus-seeking reagents and typically
have a negative charge (anions) or a lone pair.

charged nucleophiles (anions)

Br

R O

C N

uncharged nucleophiles (lone pair)

H2O

R NH2

R SH
8

Electrophiles are electron-deficient, electron-seeking reagents, and

typically have positive charge (cations) or are polarisable molecules that
can develop an electron-deficient centre.

charged electrophiles (cations)

O N O

uncharged electrophiles (polarisation)

+
C Br

+
C O

Many reactions will involve both nucleophiles and electrophiles. The electronrich species is always regarded as the attacking agent.

Nu

Nu

E
9

Leaving group is the terminology used for ions or neutral molecules that
are displaced from a reactant as part of a mechanistic sequence.
Frequently this displacement is the consequence of a Nu- attacking an
E+ (E+ carries a suitable leaving group).

Nu
nucleophile

+
C

Nu C

L
leaving group

electrophile

Good leaving groups are those that form stable ions or molecules after they
leave molecule.

10

Tips for Writing Mechanisms

While you are learning:

Draw structures in full

Identify what has changed from reactant(s) to product(s)

Identify Nu: and E+

Show all lone pair electrons on atoms involved in reaction

Connect Nu: and E+ with curly arrow (colour is a good idea)

Do any atoms violate the octet rule? If so some bonds

must be broken in the same step.

Is the mechanism balanced (charge and atom)?

Curly arrows always move in the same direction never

11
meet head on.

Problem:
Order the following reagents into the nucleophiles and electrophiles:

H3C O
1

CH3
H3C C
CH3

H
2

NH2
Br

H3C

Br
6

4
5

H3C SH
7

H2O

O N O

12

Resonance

For many molecules and ions, no single

Lewis structure provides a truly
accurate representation
CH3

O
C
O

and

CH3

O
C
O

13

Resonance

Examples
Nitriteion
(equivalent
contributing
structures)

O
N

O
N

O
Ethanoateion
(equivalent
contributing CH3 C
structures)
O

O
O
CH3 C
O
14

Q. Write the mechanism for the reaction of aqueous HCl

with water

15

Reaction Mechanisms
Q. Write the mechanism for the reaction of:
1. hydroxide with CH3Cl

2. fluoride with Me3O+

16

Resonance

Draw the resonance structures of the

carbonate ion CO32-

17