Unit One Part 6:

analysing chemical reactions

at last...chemical
reactions!
Part 6
Unit One

Balanced reactions (pg69-70)

Reaction types (pg71-72)
Reagents (pg72-77)
Chemistry...

NUCLEOPHILE ELECTROPHILE
electron rich electron poor
high electron low electron
density density

this slide sums up

the majority of
chemical reactions
(even the funkier ones
follow these

...it’s that simple

principles)
Chemistry...

NUCLEOPHILE ELECTROPHILE
electron rich electron poor
high electron low electron
density density

...so that was a

quick lecture...

...it’s that simple

 lets look at a simple
reaction...

lets just show its

that simple (we do
have 50 minutes to
kill after all)
 the Lucas test
H3C H3C
ZnCl2 (aq)
H3C OH + HCl H3C Cl + H2O
H3C H3C

the Lucas test is

simple...you’ll do it lab
this week...two water
soluble compounds
react...

water soluble water soluble water insoluble

H-bond ion-dipole two layers
 the Lucas test
H3C H3C
ZnCl2 (aq)
H3C OH + HCl H3C Cl + H2O
H3C H3C

to give an insoluble
compound. Why
insoluble? (no longer
able to H-bond)

water soluble water soluble water insoluble

H-bond ion-dipole two layers
 the Lucas test
H3C H3C
ZnCl2 (aq)
H3C OH + HCl H3C Cl + H2O
H3C H3C
}
}
reactants products
stoichiometry
1 : 1 :
simple
definitions
1 : 1
 the Lucas test
H3C H3C
ZnCl2 (aq)
H3C OH + HCl H3C Cl + H2O
H3C H3C
ratio of
}
}
compounds in
reaction

reactants products
stoichiometry
1 : 1 : 1 : 1
...simply count atoms (or electrons)...

sorting out the

stoichiometry is
easy...just make sure you
have the same number of
atoms on both sides of
the equation and
remember...
NO
atoms (or electrons)

we only move
them (or change
the bonds)

created or destroyed
unfortunately,
chemists are lazy...

a quick word of
warning...organic chemists
are a little lazy and often
miss side products off their
reaction schemes!
depiction of a standard reaction

OMe OMe
H2SO4
HO3S

...so, here is a
standard reaction as
shown in many text
books...
depiction of a standard reaction

OMe OMe
H2SO4
HO3S

...problem is, it
doesn’t show
everything...so lets
have a closer look...
so what bonds are
broken?
depiction of a standard reaction
redraw sulfuric acid
and it becomes
clear that we will
loose an OH...

OMe OMe
HO SO3H
HO3S

obviously lost OH
depiction of a standard reaction

OMe OMe
HO SO3H
HO3S

...we can’t just add it to

the aryl ring or one C
would have too many
electrons...

obviously lost OH
 depiction of a standard reaction

OMe OMe
HO SO3H
H HO3S

remember we don’t always draw H

 depiction of a standard reaction

OMe OMe
HO SO3H O
H H
H HO3S
...overall we have
lost H from
aromatic and OH
from acid...or water

which means we ‘forgot’ to add HOH

 depiction of a standard reaction

OMe OMe
HO SO3H O
H H
H HO3S

which means we ‘forgot’ to add HOH

 depiction of a standard reaction

OH
HO Me Br O
O Me
HO
O OMe
O
O OMe
 depiction of a standard reaction

H
O
HO Me Br O
O Me
HO
O OMe ...break
O O–H bonds...
O OMe

all the bonds broken & formed

 depiction of a standard reaction

H
O
HO Me Br O
O Me
HO
O OMe
O
O ...break
OMe C–Br bond...

all the bonds broken & formed

 depiction of a standard reaction
...form C–O bond
AND H–Br
H
O
HO Me Br O
H Br
O Me
HO
O OMe
O
O OMe

...and the ‘mystery’ product

 depiction of a standard reaction

H
O
HO Me Br O
H Br
O Me
HO
O OMe
O
O OMe

1 3 1 3

don’t forget the stoichiometry

what is happening
in a reaction?
it is the movement
of electrons
 Lewis structures

here is the Lucas

reaction again...

H3C H3C
H3C OH + + H3C Cl + O
Cl H H H
H3C H3C

as each bond is two electrons

we have just moved electrons...
 Lewis structures
H H
H C H H C H
H H H
Cl
H C C O H H C C Cl O H
HH H HH
C H C H
H H

H3C H3C
H3C OH + + H3C Cl + O
Cl H H H
...and here is the
H3C H3C
Lewis structures

as each bond is two electrons

we have just moved electrons...
 Lewis structures
...we take O with its
complete octet of
electrons and share
H two of them with H H
to...
H C H H C H
H H H
Cl
H C C O H H C C Cl O H
HH H HH
C H C H
H H

H3C H3C
H3C OH + + H3C Cl + O
Cl H H H
H3C H3C

as each bond is two electrons

we have just moved electrons...
 Lewis structures
H H
...form water...
H C H H C H
H H H
Cl
H C C O H H C C Cl O H
HH H HH
C H C H
H H

H3C H3C
H3C OH + + H3C Cl + O
Cl H H H
H3C H3C

as each bond is two electrons

we have just moved electrons...
 Lewis structures
...then we share the
electrons of the chloride
octet to make sure the
original C is still an a
happy octet...
H H
H C H H C H
H H H
Cl
H C C O H H C C Cl O H
HH H HH
C H C H
H H

H3C H3C
H3C OH + + H3C Cl + O
Cl H H H
H3C H3C

as each bond is two electrons

we have just moved electrons...
 Lewis structures
H H
H C H H C H
H H H
Cl
H C C O H H C C Cl O H
HH H HH
C H C H
H H

H3C H3C
H3C OH + + H3C Cl + O
Cl H H H
so just swapped
H3C H3Caround...
electrons

as each bond is two electrons

we have just moved electrons...
what types of
reaction are there?
3
basic
reactions
substitution
reactions

A B + C A C + B
does what it says...the
reagent swaps with a
functional group in our
molecule...
substitution
reactions

OH OH

Br CH3NH2 NHCH3 H Br

here’s an example from the

synthesis of prozac® where an
amine substitutes / displaces /
exchanges with a bromide...
substitution
reactions

Na O
Cl O
NHCH3 NaCl
NHCH3 F3C
F3C

fluoxetine
here is another example finishing
Prozac®the
synthesis of prozac®; an alkoxide
(alcohol derivative) substitutes a
chloride...
 A + Y A Y
two molecules add
together or combine...all
atoms in both starting

addition
materials are found in the
product

reactions
 CH3
CH3
H Br Br
H

here hydrogen
bromide adds across
an alkene to give us a

addition
new bromide

reactions
 at some point you’ll have to
learn why it adds the bromide
to the more hindered end of the CH3
CH alkene...but
3 that’s someone
H Br
else’s job! Br
H

addition
reactions
 O H3C O MgBr
H3C MgBr CH3
CH3
Ph Ph

here a Grignard reagent

is adding to a ketone to
give (eventually) an

addition
alcohol

reactions
elimination
reactions

A X A + X

elimination is the opposite

of addition...we rip a bit of
the molecule off.
elimination
reactions

OH
CH3 CH3
O
H H
H

this example shows

the elimination of
water (dehydration) to
form an alkene
elimination
reactions

CH3 Br
H3C CH3
H3C
H3C H Br
H3C
H
or the elimination of
hydrogen bromide
(hydrobromic acid) to
form an alkene
 what reagents are
involved in these
reactions?

now we know what reactions

we can perform...what
reagents can we use?
nucleophiles

2
electron rich molecules

nucleophiles are electron

rich compounds that
donate two electrons to
form a new bond...
examples include...

donateelectrons
anions
H O ≡ H O Br ≡ Br

3 lone pairs 4 lone pairs

H3C
≡ Pr C
H
1 lone pair
anions
H O ≡ H O Br ≡ Br
negatively charged
compounds that possess a
3 lonethat
lone pair of electrons pairs 4 lone pairs
can form a new bond
H

H3C
≡ Pr C
H
1 lone pair
anions
nucleophilic reaction

O H O
H H H
anions
nucleophilic reaction
hydroxide donates a
pair of electrons to
form a new bond to
proton

O H O
H H H
anions
nucleophilic reaction

O H O
H H H
note: both sides of
equation have same
charge (both are
neutral overall)
anions
nucleophilic reaction

O H O
H H H
note: both sides of
equation have same
charge (both are this is a good sign that you’ve
neutral overall) got the reaction right!
lone pairs
lone pairs as
nucleophile

O N S
H H H H H3C CH3
H
water ammonia dimethyl sulfide
(DMS)
lone pairs on neutral
molecules are also good
nucleophiles...
lone pairs
nucleophilic reaction

H
N H Cl N Cl
H H H H
H H
lone pairs
nucleophilic reaction
ammonia donates a
pair of electrons to
form a new bond to
hydrogen chloride

H
N H Cl N Cl
H H H H
H H
lone pairs
nucleophilic reaction
can’t have two bonds to H
(4 electrons) so break H–
Cl bond with electrons
flowing towards most
electronegative element

H
N H Cl N Cl
H H H H
H H
lone pairs
nucleophilic reaction

H
overall its been a
N H Cl
substitution N Cl
H H H H
H H
lone pairs
nucleophilic reaction

H
N H Cl N Cl
H H H H
H H
note: overall both sides
are neutral (have same
charge)
bonds bonds can also be a
source of electrons...and
these cause confussion!

δ– δ+ H
C Y
Y=Li, Mg B
H H
nucleophilic H
site
reactive
σ bond

H H
C C
H H R
high electron density R = electron
nucleophile donating group
electrophiles

2
electron poor molecules

the other kind of reagents

are...electrophiles are electron
poor compounds that accept two
electrons to form a new bond...
examples include...

acceptelectrons
proton
H ≡ H

empty 1s orbital
no electrons!
simplest electrophile...it
has no electrons and
desperately wants some!
proton
electrophilic reagent

H H
H
O H O
H H
proton
electrophilic reagent

H H
H
O H O
H H
nucleophilic water
donates two electrons to
proton, which accepts
them to form new bond
Group 13
F
F Cl
F B Cl Al F B
F Cl F
empty 2p empty 3p
orbital orbitalonly have 6 valence
electrons...need 8 to obey
octet rule so happily accept a
pair of electrons
bonds
δ+ δ– Y = Cl, δ+ δ–
C Y Y = O,
Br, N, O C Y NR

electrophilic electrophilic
site site
bonds can be
electrophiles if they are
polarised and have a δ+
centre
bonds
electrophilic reagent

H H
O
O H O O
H H3C CH3
H3C CH3
is it that easy?
nucleophile + electrophile product

yup, this equation sums up

the majority of reactions...
yes!
...and no...
 H3C δ+ δ– H3C δ+ δ–
H3C O H3C Cl
H3C H H3C

polarity in these two

compounds looks the
same...so do they behave in
the same way??
 H3C δ+ δ– H3C δ+ δ–
H3C O H3C Cl
H3C H H3C

of course not!
this is chemistry after all...
 H3C δ+ δ– H3C δ+ δ–
H3C O H3C C Cl
alcohol uses lone
H3C H H3C pair to act as a
nucleophile
nucleophile electrophile
 H3C δ+ δ– H3C δ+ δ–
H3C O H3C C Cl
H
chloride isC
3 an
electrophile
H H3C
nucleophile electrophile
 ...you will learn to to
identify which is which...
 so what actually
happens in a reaction?
H3C O H3C Cl H
H + H Cl + O
H3C H3C
CH3 CH3 H
so here’s the Lucas
test again...overall
it’s a substitution of
hydroxyl for chlorine

what order are the

bonds made and broken?
H3C O H3C Cl H
H + H Cl + O
H3C H3C
CH3 CH3 H

what order are the

bonds made and broken?
 H
H3C O H3C O
H H H
H3C H3C
CH3 CH3

CH3 CH3 H
H3C C O H H H3C C O H
CH3 CH3

addition
step

step
one
 H
H3C O H3C O
H H H
H3C H3C
CH3 CH3

nucleophilic alcohol
CH3 donates 2 electrons
CH3 H to
a proton from H–Cl in
H3C C O H H anHaddition
3C Creaction O H
CH3 CH3

addition
step

step
one
 H
H3C O H3C O
H H H
H3C H3C
CH3 CH3
note: octet rule is
obeyed and the
charge is the same
CH3 on both sides CH3 H
(positive)
H3C C O H H H3C C O H
CH3 CH3

addition
step

step
one
 H CH3 H
H3C O
H O
H3C H3C CH3
CH3 H

H H
H C H H C H
H H H H
H C C O H H C C O H
HH HH
C H C H
H H

step
two elimination
 H CH3 H
H3C O
H O
H3C H3C CH3
CH3 H

H H
elimination of
H C H H water...molecule
C H splits in
H H H two...electrons go with
H
most electronegative
H C C O H H C C atom O H
HH HH
C H C H
H H

step
two elimination
 H CH3 H
H3C O
H O
H3C H3C CH3
CH3 H

charge is the same

H on both sides (positive)... H
we now have a reactive
H C H intermediate H C H
H H H H
(charged species with 6
H C C O H electrons) H C C O H
HH HH
C H C H
H H

step
two elimination
 CH3 H3C Cl
Cl H3C
H3C CH3 CH3

H H
H C H H C H
H H
H C C Cl H C C Cl
HH HH
C H C H
H H

addition
step

step
three
 CH3 H3C Cl
Cl H3C
H3C CH3 CH3

H H
H C H H C
finally,Hsecond H
H
addition step to
H C C Cl H C octet
complete C Cl
HH HH
C H C H
H H

addition
step

step
three
 CH3 H3C Cl
Cl H3C
H3C CH3 CH3

H H
H C H H C H
H H
H C C Cl H C C Cl
HH HH
C H C H
H H two
nucleophile donates
electrons to electrophile

addition
step

that accepts them to

step form new bond

three
 CH3 H3C Cl
Cl H3C
H3C CH3 CH3

H H
H C H H C H
H H
H C C Cl H C C Cl
HH note: the charge is HH
C H the same on both C H
sides (neutral)
H H

addition
step

step
three
3
steps

1
substitution
reaction
another
representation...

we can follow the change of

energy during a reaction...in a
reaction profile
reaction profile
energy

Cl
+
H2O

H
O + Cl
H

OH + HCl
reaction
progress Cl + H2O
reaction profile
each hill represents
one step in our
reaction
energy

Cl
+
H2O

H
O + Cl
H

OH + HCl
reaction
progress Cl + H2O
reaction profile
each dip
represents an
intermediate we
can see
energy

Cl
+
H2O

H
O + Cl
H

OH + HCl
reaction
progress Cl + H2O
reaction profile
higher the hill, the
harder the step
energy

Cl
+
H2O

H
O + Cl
H

OH + HCl
reaction
progress Cl + H2O
reaction profile
the lower in energy
any stage the more
stable it is
energy

Cl
+
H2O

H
O + Cl
H

OH + HCl
reaction
progress Cl + H2O
just one hill, so
just one step

energy

HO
CH3Br

Br
reaction CH3OH
progress
 no dip so no
intermediates
energy

HO
CH3Br

Br
reaction CH3OH
progress
 direct

energy
substitution
would look like
this HO
CH3Br

Br
reaction CH3OH
progress

HO + CH3Br CH3OH + Br
 once again, you will learn

energy
more about this but not
from me! Why don’t I get
HO
to teach the cool stuff? CH3Br

Br
reaction CH3OH
progress

H 1 H 1 H
SLOW 2 δ– 2 δ–
HO + Br HO Br Nu + Br
H RDS H
H H H H
transition state
 what have
....we learnt?

• analyse reactions
• classify reagents
•r e a c t i o n t y p e s
Picture: © Pittsburgh Supercomputing Center