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What are curly reaction mechanism arrows and what is their physical meaning?
How do we form bonds with pairs of electrons (lone pairs or bonding electron pairs)?
Lecture Outline: Part 2
Organic Reaction Mechanisms
2 electrons
Two atoms ‘equally’ shared
bonded by… by two atoms
…2 electrons
Reaction Mechanism ‘Curly’ Arrows
A—B A B:
A:B A B:
Br
+
H CH3 H
-
Br - H OH
OH -
Nucleophilic
Substitution on a
Saturated Carbon
H
Electron rich Nucleophile + -
CH3 C X
(Nu)
Atom X is more
in search of an H electronegative
electron poor saturated than C
Nu
carbon centre
AS Level
Nucleophilic Substitution: 1 12
H H
+ -
CH3 C Br CH3 C OH
H -
Br
H
OH-
Nucleophilic Substitution: 2
H H
+ -
CH3 C Br CH3 C CN
H -
Br
H
CN-
Nucleophilic Substitution: 3
H
+ -
CH3 C Br
-
Br
H H H
+
CH3 C NH2 CH3 C NH2
NH3
H H H
NH3
H NH3+Br -
Nothing is Black and White: 1
Stereochemistry
R R
Rate
Nu X Nu X
Equation
R' R'
"R "R
It is found that there are two possible stereochemical outcomes, each described
by a different rate equation, and different stereochemical outcomes.
1 R1
R Rate = k[R-Hal][Nu]
Nu Cl Nu Cl
3 R3
R
2 Bimolecular R2
R Process
Inversion
Rate of Configuration
Determinig
Step
http://chemistry.boisestate.edu/rbanks/organic/sn2.gif
Nucleophilic Addition to
Acid Chlorides
(R(Cl)C=O) Followed by
Elimination
-
Electron rich Nucleophile (Nu)
+ O
in search of an CH3 C Then
electron poor unsaturated Cl elimination
of Cl-
carbon centre Nu
AS Level
Nucleophilic Substitution: SN1
Carbocation
1
1 R
R Rate = k[R-Hal]
Cl Nu Nu
3
R
2 Unimolecular R3 2
R R
Process
Cl
Rate
Determining
State
1
R
1 R
One enantiomer Nu
Nu Racemisation
R 3 R3
2 2
R R
QUIZ
• Predict the product for the following reactions and make their reaction
mechanism
CH3CH2Br NaOMe
Br H2O
(CH3)2CHI HCN
Cl
NaOH
Nucleophilic
Addition to
Aldehydes/Ketones
(C=O)
-
Electron rich Nucleophile (Nu)
+ O
in search of an CH3 C
electron poor unsaturated CH3
carbon centre Nu
A2 Level
Nucleophilic Add’n to Aldehydes/Ketones 1
- H+ +
O + O H
+ O H
CH3 C CH3 C
CH3 CH3 CH3 C CH3
CN CN
Nucleophilic Add’n to Acid Chlorides 1
- O
- O
+
O CH3 C
CH3 C CH3 C Cl OH
Cl OH - H +
H + Cl
H2O
O
CH3 C
HCl OH
Nucleophilic Add’n to Acid Chlorides 1
- O
- O
+
O CH3 C
CH3 C CH3 C Cl +
NHR
Cl + - H
NHR
H Cl
RNH2
An amide O
CH3 C
HCl NHR
Electrophilic
Aromatic
Substitution
in search of an E
A2 Level
Electrophilic Aromatic Substitution 1
+
HNO3 + 2H2SO4 NO2 + 2HSO4- + H3O+
Electrophile
catalyst Nitronium Ion
+ NO2
O SO3H
-
NO2
H
+
NO2
H O SO3H
Electrophilic Aromatic Substitution 2
Lewis
C6H6 + (CH3)2CHCl acid C6H5CH(CH3)2 + HCl
+ -
AlCl3 Cl AlCl3
CH3 CH Cl CH3 CH -
Lewis Secondary + Cl AlCl3
CH3 Acid carbocation
CH3
catalyst
CH(CH3)2
+
HC CH3
+
H -
Cl AlCl3
CH3 + AlCl3
CH(CH3)2
+ HCl
Electrophilic Aromatic Substitution 3
Lewis
acid
C6H6 + RCOCl C6H5COR + HCl
O +
CH3C CH3C O -
Cl AlCl3 Acylium ion Cl AlCl3
+ O
CH3C O CH3
CH3C
C O
H
+
-
Cl AlCl3
H Cl
Not catalytic.
Why? AlCl3
Electrophilic
Addition to Alkene
AS Level
Electrophilic Addition to an Alkene: 1
H CH3
carbocation
C C
H H
CH3 H
CH3 C C CH3
+ +
H
H
H H
Br Br-
- C C CH3
CH3
Permanent dipole
Br H
Electrophilic Addition to an Alkene: 2
H H H H
carbocation
C C
CH3 C C CH3
CH3 CH3 +
H -
+ OSO3H
H H H
OSO3H CH3 C C CH3
-
H OSO3H
Electrophilic Addition to an Alkene: 3
H H
carbocation
C C
H H
CH3 H
CH3 C C H
+ +
Br
Br
H H
Br
- Br-
Br CH3 C C H
Induced Dipole
Br Br Br
Elimination of HX
from Alkanes to
form an alkene
H H
Lone Pair of Electrons on Base + +
CH3 C C H
(B:)in search of an +
AS Level
Elimination of HX: 1
H H H H
+ +
CH3 C C H C C
Br
+
H CH3 H
-
Br - H OH
OH -
acting as a base
this time….
Nothing is Black and White! 2
Nucleophilic
Substitution H H
CH3 C C Nu
-Nu
H H
Cl-
H H
+ + -
CH3 C C Cl
+
H H
- H H
B
C C Cl-
CH3 H
Elimination of HX
BH
Free Radical
Substitution of
Alkanes
Light Induced Radical CH3 Cl Cl
Formation and
Subsequent
Replacement Cl
H3C Cl
Reactions
AS Level
Reaction Mechanism ‘Curly’ Arrows
C—D C• D•
C:D C• D•
Light
Cl Cl Cl Cl
Radicals
Formed
Propagation reaction of the chlorine radicals with
methane, which generates methyl radicals
and HCl. Followed by the methyl radicals
reacting with diatomic chlorine, to afford
chloromethane and a chlorine radical.
Radicals
Consumed
Cl Cl H3C Cl Cl
Chlorine Radical
Reformed
Termination
Radicals
Consumed
CH3 Cl H3C Cl
Radicals
Not Reformed
Further Free Radical Chlorination Reactions
H - -
CH3 C X + O + O
CH3 C CH3 C Then
H CH3 Cl elimination
of Cl-
Nu Nu Nu
Electrophilic Electrophilic
Substitution Addition
Summary of the
H CH3
Chemistry Looked at
E C C
CH3 H
E
Free Radical Substitution Elimination of HX
H H
CH3 Cl Cl + +
CH3 C C H
+
X H
-
H3C Cl Cl B
Chemistry at Birmingham
www.chem.bham.ac.uk
Identify polarity to
Initiate: Cleave bond identify electrophilc
homolytically centre