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A free review of chemical reactions in organic chemistry provided by Examville
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Unit One Part 6:analysing chemical reactions
at last...chemical reactions!
Unit One
Part6Balanced reactions (pg69-70)Reaction types (pg71-72)Reagents (pg72-77)
NUCLEOPHILEelectron richhigh electron
density
ELECTROPHILEelectron poorlow electron
density
Chemistry...
...it’s that simple
this slide sums up the majority of
chemical reactions (even the funkier ones
follow these principles)
NUCLEOPHILEelectron richhigh electron
density
ELECTROPHILEelectron poorlow electron
density
Chemistry...
...it’s that simple
...so that was a quick lecture...
lets look at a simple reaction...
lets just show its that simple (we do have 50 minutes to
kill after all)
OHH3C
H3CH3C + HCl
ZnCl2 (aq)
the Lucas test
water solubleH-bond
water solubleion-dipole
water insolubletwo layers
ClH3C
H3CH3C + H2O
the Lucas test is simple...you’ll do it lab this week...two water soluble compounds
react...
OHH3C
H3CH3C + HCl
ZnCl2 (aq)
the Lucas test
water solubleH-bond
water solubleion-dipole
water insolubletwo layers
ClH3C
H3CH3C + H2O
to give an insoluble compound. Why
insoluble? (no longer able to H-bond)
ZnCl2 (aq)Cl
H3C
H3CH3C + H2OOH
H3C
H3CH3C + HCl
the Lucas test
} }reactants products
stoichiometry
1 11 1 ::: simple definitions
ZnCl2 (aq)Cl
H3C
H3CH3C + H2OOH
H3C
H3CH3C + HCl
the Lucas test
} }reactants products
stoichiometry
1 11 1 :::
ratio of compounds in
reaction
...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...
NOatoms (or electrons)
created or destroyed
we only move them (or change
the bonds)
unfortunately, chemists are lazy...
a quick word of warning...organic chemists are a little lazy and often
miss side products off their reaction schemes!
OMeH2SO4
OMe
HO3S
depiction of a standard reaction
...so, here is a standard reaction as shown in many text
books...
OMeH2SO4
OMe
HO3S
depiction of a standard reaction
...problem is, it doesn’t show
everything...so lets have a closer look...
so what bonds are broken?
OMe
depiction of a standard reaction
obviously lost OH
OMe
HO3SHO SO3H
redraw sulfuric acid and it becomes
clear that we will loose an OH...
OMe
depiction of a standard reaction
obviously lost OH
OMe
HO3SHO SO3H
...we can’t just add it to the aryl ring or one C would have too many
electrons...
OMe OMe
HO3SH
HO SO3H
depiction of a standard reaction
remember we don’t always draw H
depiction of a standard reaction
which means we ‘forgot’ to add HOH
OMe OMe
HO3SHO
HH
HO SO3H
...overall we have lost H from
aromatic and OH from acid...or water
depiction of a standard reaction
which means we ‘forgot’ to add HOH
OMe OMe
HO3SHO
HH
HO SO3H
depiction of a standard reaction
O OMe
MeOH
HO
HO
Br
O OMe
MeO
O
O
depiction of a standard reaction
all the bonds broken & formed
O OMe
MeO
HO
HO
Br
O OMe
MeO
O
O
H
...break O–H bonds...
depiction of a standard reaction
all the bonds broken & formed
O OMe
MeO
HO
HO
Br
O OMe
MeO
O
O
H
...break C–Br bond...
depiction of a standard reaction
...and the ‘mystery’ product
O OMe
MeO
HO
HO
Br
O OMe
MeO
O
O
H Br
H
...form C–O bond AND H–Br
depiction of a standard reaction
don’t forget the stoichiometry
1 13 3
O OMe
MeO
HO
HO
Br
O OMe
MeO
O
O
H Br
H
what is happening in a reaction?
it is the movement of electrons
Lewis structures
OHH3C
H3CH3C + Cl + H Cl
H3C
H3CH3C + H
OH
as each bond is two electrons we have just moved electrons...
here is the Lucas reaction again...
C
C
C
CH
HH
HHH
HH
HO H
Cl
HC
C
C
CH
HH
HHH
HH
H
O HH
Cl
Lewis structures
OHH3C
H3CH3C + Cl + H Cl
H3C
H3CH3C + H
OH
as each bond is two electrons we have just moved electrons...
...and here is the Lewis structures
C
C
C
CH
HH
HHH
HH
HO H
Cl
HC
C
C
CH
HH
HHH
HH
H
O HH
Cl
Lewis structures
OHH3C
H3CH3C + Cl + H Cl
H3C
H3CH3C + H
OH
as each bond is two electrons we have just moved electrons...
...we take O with its complete octet of
electrons and share two of them with H
to...
C
C
C
CH
HH
HHH
HH
HO H
Cl
HC
C
C
CH
HH
HHH
HH
H
O HH
Cl
Lewis structures
OHH3C
H3CH3C + Cl + H Cl
H3C
H3CH3C + H
OH
as each bond is two electrons we have just moved electrons...
...form water...
C
C
C
CH
HH
HHH
HH
HO H
Cl
HC
C
C
CH
HH
HHH
HH
H
O HH
Cl
Lewis structures
OHH3C
H3CH3C + Cl + H Cl
H3C
H3CH3C + H
OH
as each bond is two electrons we have just moved electrons...
...then we share the electrons of the chloride octet to make sure the original C is still an a
happy octet...
C
C
C
CH
HH
HHH
HH
HO H
Cl
HC
C
C
CH
HH
HHH
HH
H
O HH
Cl
Lewis structures
OHH3C
H3CH3C + Cl + H Cl
H3C
H3CH3C + H
OH
as each bond is two electrons we have just moved electrons...
so just swapped electrons around...
what types of reaction are there?
3basic reactions
substitution reactions
A B + C A C + Bdoes what it says...the reagent swaps with a
functional group in our molecule...
CH3NH2Br
OH
NHCH3
OH
H Br
substitution reactions
here’s an example from the synthesis of prozac® where an amine substitutes / displaces /
exchanges with a bromide...
fluoxetineProzac®
F3C
Cl
NHCH3
ONa
NaCl
O
F3CNHCH3
substitution reactions
here is another example finishing the synthesis of prozac®; an alkoxide (alcohol derivative) substitutes a
chloride...
addition reactions
A + Y A Ytwo molecules add
together or combine...all atoms in both starting
materials are found in the product
CH3 H Br BrH
CH3
addition reactions
here hydrogen bromide adds across an alkene to give us a
new bromide
CH3 H Br BrH
CH3
addition reactions
at some point you’ll have to learn why it adds the bromide
to the more hindered end of the alkene...but that’s someone
else’s job!
Ph
OH3C MgBrCH3 Ph
CH3H3C O MgBr
addition reactions
here a Grignard reagent is adding to a ketone to
give (eventually) an alcohol
elimination reactions
A X A + X
elimination is the opposite of addition...we rip a bit of
the molecule off.
CH3OH
H
CH3HO
H
elimination reactions
this example shows the elimination of
water (dehydration) to form an alkene
H3C
CH3H3C
H
Br
H3C
CH3H3C H Br
elimination reactions
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?
nucleophileselectron rich molecules
donate2electrons
nucleophiles are electron rich compounds that
donate two electrons to form a new bond...examples include...
anionsH O ≡ OH
3 lone pairs
Br Br≡4 lone pairs
H3CPr C
H
H1 lone pair
≡
anionsH O ≡ OH
3 lone pairs
Br Br≡4 lone pairs
H3CPr C
H
H1 lone pair
≡
negatively charged compounds that possess a lone pair of electrons that
can form a new bond
HO H H
OH
anionsnucleophilic reaction
HO H H
OH
anionsnucleophilic reaction
hydroxide donates a pair of electrons to form a new bond to
proton
HO H H
OH
anionsnucleophilic reaction
note: both sides of equation have same
charge (both are neutral overall)
HO H H
OH
anionsnucleophilic reaction
this is a good sign that you’ve got the reaction right!
note: both sides of equation have same
charge (both are neutral overall)
lone pairs
HO
Hwater
HN
HH
ammoniaH3C
SCH3
dimethyl sulfide (DMS)
lone pairs as nucleophile
lone pairs on neutral molecules are also good
nucleophiles...
HN
HH
H
Cl
lone pairsnucleophilic reaction
HN
HH
H Cl
HN
HH
H
Cl
lone pairsnucleophilic reaction
HN
HH
H Cl
ammonia donates a pair of electrons to form a new bond to hydrogen chloride
HN
HH
H
Cl
lone pairsnucleophilic reaction
HN
HH
H Cl
can’t have two bonds to H (4 electrons) so break H–
Cl bond with electrons flowing towards most
electronegative element
HN
HH
H
Cl
lone pairsnucleophilic reaction
HN
HH
H Cloverall its been a substitution
HN
HH
H
Cl
lone pairsnucleophilic reaction
HN
HH
H Cl
note: overall both sides are neutral (have same
charge)
bondsC Y
δ+δ–
nucleophilic site
Y=Li, MgHB
HHH
HC
HC
H
Hhigh electron density
nucleophile
RR = electron
donating group
reactive σ bond
bonds can also be a source of electrons...and these cause confussion!
electrophileselectron poor molecules
accept2electrons
the other kind of reagents are...electrophiles are electron
poor compounds that accept two electrons to form a new bond...
examples include...
H ≡ H
proton
empty 1s orbitalno electrons!
simplest electrophile...it has no electrons and
desperately wants some!
HO
H
HHO
HH
protonelectrophilic reagent
HO
H
HHO
HH
protonelectrophilic reagent
nucleophilic water donates two electrons to
proton, which accepts them to form new bond
Group 13F B
FF
empty 2p orbital
Cl AlClCl
empty 3p orbital
F BF
F
only have 6 valence electrons...need 8 to obey
octet rule so happily accept a pair of electrons
bondsC Yδ+ δ–
electrophilic site
Y = Cl, Br, N, O C Y Y = O,
NRδ+ δ–
electrophilic site
bonds can be electrophiles if they are polarised and have a δ+
centre
H3C CH3
O OH
HHO
H H3C CH3
O
bondselectrophilic reagent
is it that easy?
nucleophile + electrophile product
yup, this equation sums up the majority of reactions...
yes!
...and no...
OH3C
H3CH3C
H
δ+ δ–Cl
H3C
H3CH3C
δ+ δ–
polarity in these two compounds looks the
same...so do they behave in the same way??
OH3C
H3CH3C
H
δ+ δ–Cl
H3C
H3CH3C
δ+ δ–
of course not!this is chemistry after all...
OH3C
H3CH3C
H
δ+ δ–
nucleophile
C ClH3C
H3CH3C
δ+ δ–
electrophile
alcohol uses lone pair to act as a
nucleophile
OH3C
H3CH3C
H
δ+ δ–
nucleophile
C ClH3C
H3CH3C
δ+ δ–
electrophilechloride is an electrophile
...you will learn to to identify which is which...
so what actually happens in a reaction?
H3C O
CH3H3C
H + H ClH3C Cl
CH3H3C +
HO
H
what order are the bonds made and broken?
so here’s the Lucas test again...overall
it’s a substitution of hydroxyl for chlorine
H3C O
CH3H3C
H + H ClH3C Cl
CH3H3C +
HO
H
what order are the bonds made and broken?
OH
H3C
CH3H3C
HO
HH3C
CH3H3C
H
additionstepstep
one
CH3CCH3
CH3O H H CH3C
CH3
CH3O HH
OH
H3C
CH3H3C
HO
HH3C
CH3H3C
H
additionstepstep
one
CH3CCH3
CH3O H H CH3C
CH3
CH3O HH
nucleophilic alcohol donates 2 electrons to a proton from H–Cl in an addition reaction
OH
H3C
CH3H3C
HO
HH3C
CH3H3C
H
additionstepstep
one
CH3CCH3
CH3O H H CH3C
CH3
CH3O HH
note: octet rule is obeyed and the
charge is the same on both sides
(positive)
C
C
C
CH
HH
HHH
HH
HO HH
C
C
C
CH
HH
HHH
HH
H
O HH
CH3
CH3H3C
HOH
OH
H3C
CH3H3C
H
eliminationsteptwo
C
C
C
CH
HH
HHH
HH
HO HH
C
C
C
CH
HH
HHH
HH
H
O HH
CH3
CH3H3C
HOH
OH
H3C
CH3H3C
H
eliminationsteptwo
elimination of water...molecule splits in two...electrons go with most electronegative
atom
C
C
C
CH
HH
HHH
HH
HO HH
C
C
C
CH
HH
HHH
HH
H
O HH
CH3
CH3H3C
HOH
OH
H3C
CH3H3C
H
eliminationsteptwo
charge is the sameon both sides (positive)...we now have a reactive
intermediate(charged species with 6
electrons)
C
C
C
CH
HH
HHH
HH
HCl C
C
C
CH
HH
HHH
HH
HCl
ClH3C
CH3H3C
CH3
CH3H3CCl
additionstepstep
three
C
C
C
CH
HH
HHH
HH
HCl C
C
C
CH
HH
HHH
HH
HCl
ClH3C
CH3H3C
CH3
CH3H3CCl
additionstepstep
three
finally, second addition step to complete octet
C
C
C
CH
HH
HHH
HH
HCl C
C
C
CH
HH
HHH
HH
HCl
ClH3C
CH3H3C
CH3
CH3H3CCl
additionstepstep
three
nucleophile donates two electrons to electrophile
that accepts them to form new bond
C
C
C
CH
HH
HHH
HH
HCl C
C
C
CH
HH
HHH
HH
HCl
ClH3C
CH3H3C
CH3
CH3H3CCl
additionstepstep
three
note: the charge is the same on both
sides (neutral)
3steps
1substitutionreaction
another representation...
we can follow the change of energy during a reaction...in a
reaction profile
ener
gy
reaction progress
OH + HCl
O + ClH
H
+ ClH2O
Cl + H2O
reaction profile
ener
gy
reaction progress
OH + HCl
O + ClH
H
+ ClH2O
Cl + H2O
reaction profile
each hill represents one step in our
reaction
ener
gy
reaction progress
OH + HCl
O + ClH
H
+ ClH2O
Cl + H2O
reaction profile
each dip represents an
intermediate we can see
ener
gy
reaction progress
OH + HCl
O + ClH
H
+ ClH2O
Cl + H2O
reaction profile
higher the hill, the harder the step
ener
gy
reaction progress
OH + HCl
O + ClH
H
+ ClH2O
Cl + H2O
reaction profile
the lower in energy any stage the more
stable it is
ener
gy
reaction progress
HOCH3Br
CH3OHBr
just one hill, so just one step
ener
gy
reaction progress
HOCH3Br
CH3OHBr
no dip so no intermediates
ener
gy
reaction progress
HOCH3Br
CH3OHBr
HO + CH3Br CH3OH + Br
direct substitution
would look like this
HBr
HH
H
HHHO Brδ– δ–
+ + BrH
NuH
H
transition state
12
12SLOW
RDSHO
ener
gy
reaction progress
HOCH3Br
CH3OHBr
once again, you will learn more about this but not
from me! Why don’t I get to teach the cool stuff?
what have....we learnt?
Picture: © Pittsburgh Supercomputing Center
•analyse reactions•classify reagents•react ion t ypes