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Brown's Chemistry Clinic
GCE-AS-A2-IB ADVANCED LEVEL ORGANIC CHEMISTRY
A summary of organic REACTION
MECHANISMS
INTRODUCTION page with links to detailed Parts Ia-IV
revision-information notes
Revision notes include full diagrams
and explanation of the mechanisms and the 'molecular' equation and
reaction conditions and other con-current reaction pathways and products
are also explained.
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download!!! © Dr W P Brown Alphabetical
list of organic terminology *
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PLEASE
NOTE:
-
Whatever their abstract nature
(and 'truthfulness'!) a study of mechanisms is
important to understand how organic chemical reactions take
place and why molecules react in a particular way. It also
allows predictions of what might happen to an organic molecule
with a particular reagent. They also explains why, in many
cases, there is more than one organic product of the reaction or
an unexpected product is formed.
-
I
thank Jim Clark at
http://www.chemguide.co.uk
for his patience, advice and email discussions of issues involved
in the representation of organic reaction mechanisms.
-
Many of the
graphic images are quite compressed in design. This is quite
deliberate, so that they will fit on screen plus text lines in
future quizzes.
-
The image
numbers 1, 2, 3 etc. are NOT meant to be sequential, its just
the order they were drawn!
-
Unless
otherwise stated R or R' = H, alkyl (e.g. -CH2CH3)
or aryl (e.g. C6H5),
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ALLOW TIME for the many © Dr W P Brown
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Main molecule index - each page has a mechanism sub-index
Part Ia
Alkane mechanisms * Part Ib Alkene
mechanisms
Part II
Halogenoalkane mechanisms (haloalkanes, alkyl halides)
Part III
Alcohols, Carbonyl compounds-Aldehydes/Ketones
and Acid Chloride mechanisms
Part IV
Aromatic Hydrocarbons - arene mechanisms
IMPORTANT
DEFINITIONS and ORGANIC TERMINOLOGY
An
alphabetical list of some terms used in organic reactions
-
abstraction:
When one reacting species removes an atom/ion from another molecule,
radical or ion.
-
acylation:
The introduction of a R-C=O group into a molecule (R = alkyl
or aryl). (see
mechanisms Part IV)
-
acylonium ion:
A type of carbocation formed in the electrophilic substitution
alkylation of aromatic compounds
-
activated
complex: An unstable
or 'transient state' formed when two reactant particles collide with
sufficient kinetic energy in a reaction mechanism step. The
activated complex breaks down to give the products. (see
mechanisms Part II)
activation
energy Ea: The
minimum energy reacting particles must possess in order to form an
'activated complex' or transition state before forming the products.
Its the top of the hump on a reaction progress energy profile
diagram. (see
mechanisms Part II)
addition:
The adding of one molecule to another with no other product, but not
necessarily in a single reaction step.
-
alkoxy
group: An alkyl-oxygen part of a molecule e.g. CH3CH2-O-
is an ethoxy group.
-
alkyl
group: A saturated section of a molecule derived from an alkane e.g.
-
arrows,
use of in mechanisms: A half-arrow head means a single
electron shift and a
full arrow head shows an electron pair shift and used in the
context of making or breaking bonds. Examples: 1. to 2. show single
electron shifts and 4. to 6. show bond pair shifts.
-
The bonding pair of
electrons of the chlorine molecule is split between the two
chlorine atoms/radicals on homolytic bond fission in the
initiation of a free radical chain reaction. (for 1.
and 2. see
mechanisms Part Ia)
-
One electron from each radical pairs up to form a C-Cl covalent
bond in a free radical chain termination step.
-
A bond pair from the alkene is donated to a proton on the
oxonium ion, H3O+, forming a C-H bond and
simultaneously the H-O bond pair moves completely on to the
oxygen to form a lone pair of non-bonding electrons.
(see mechanisms Part Ib)
-
A hydroxide ion, OH-, donates a lone pair of
non-bonding electrons to a carbon atom to form a C-OH bond and
simultaneously the C-Cl bond pair shifts to become a lone pair
of electrons on the chlorine atom as a chloride ion is formed.
(see mechanisms Part
II)
-
The cyanide ion, -CN, donates a lone pair of
electrons to form a C-N bond and simultaneously one of the C=O
bond pairs moves completely on to the oxygen to form a lone pair
of non-bonding electrons and giving the oxygen atom an overall
single positive charge. (see
mechanisms Part III)
-
The C-H bond pair shifts to complete the
∏
electrons of the benzene ring and simultaneously a
hydrogensulphate ion donates a lone pair and forms an H-O bond
in forming a sulphuric acid molecule. (see
mechanisms Part IV)

aryl
group: A section of a
molecule derived from aromatic compounds like benzene or
methylbenzene
-
attacking ...
: A somewhat dramatic term
applied to the 'active' part of a reagent that directly interacts
with the organic 'substrate' molecule in question. You can use
phrases like 'nucleophilic attack'
or 'electrophilic attack'.
-
e.g. the
nucleophile OH- 'attacking' the positive carbon
of the polarised
Cδ+-Clδ-
bond in a nucleophilic substitution of halogenoalkane
-
or the
positive part of the polarised
Hδ+-Brδ-
electrophile attacking the ∏ electrons of an alkene
double bond in an electrophilic addition reaction.
-
'bimolecular'
mechanism/kinetics : see
e.g. SN2
-
bond
fission: This
means breaking a bond between two atoms to give two 'fragments'
(atoms, ions or molecules), but there are two modes of fission,
depending on what happens to the original bonding pair of electrons.
This is illustrated by the breaking of a C-Br (or C:Br)
bond.
-
Heterolytic bond fission: The bonding
pair of electrons (: below) leaves with one of the
fragments and usually leads to ion formation. This follows from
the bond polarity, Cδ+-Clδ-
due the difference in electronegativity (Cl > C).
-
Homolytic bond fission: The bonding
pair of electrons is 'split' between the two fragments with an
unpaired electron and usually leads to the formation of free
radicals initiated by heat or uv light.
-
bromonium ion:
A form of carbocation produced in the 1st step of the electrophilic
addition of bromine to an alkene. It involves a C-Br-C bonded
triangle which carries the positive charge. The addition of chlorine
proceeds in the same way via a chloronium ion. (see
mechanisms Part Ib)
-
carbocation
(carbonium ion): A
positive ion derived from an organic molecule where the charge is
usually carried by a carbon atom e.g. the ethyl carbocation is CH3CH2+ ,
and note that the three bonds from the carbon carrying the
positive charge are in a trigonal planar configuration (2 x C-H
and a C-C in this case). (see
mechanisms Part Ib)
-
chain
reaction
: Here the term is often
used in the context of highly reactive free radicals, where in a
reaction step, one radical brings about a chemical change and forms
another reactive radical to continue the reaction. (see
mechanisms Part Ia)
-
E1:
Shorthand for an elimination reaction in which the rate determining step
involves just one of the reactant molecule or intermediate (X) and the
rate is independent any other reactant or intermediate. (see
mechanisms Part II)
-
E2:
Shorthand for a nucleophilic substitution reaction in which the rate
determining step is a bimolecular collision of two reactant
molecules or intermediates (X and Y) and the rate is
independent any other reactant or intermediate. (see
mechanisms Part II)
-
electron
shift:
see use of arrows in mechanisms
-
electronegativity: The electron
attracting power of an atom in a covalent bond situation.
-
One of the
most common scales used is the Pauling electronegativity
and a selection of values is listed.
-
e.g.
Na 0.9,
Al 1.5, C 2.1, H 2.1, P 2.1,
S 2.5, Br 2.8, Cl 3.0, N 3.0, O
3.5, F 4.0
The
concept is important when considering polar bonds, which
arise when there is a significant electronegativity difference
between two atoms in a bond. The bigger the difference, the more
polar the bond. Polar bonds can determine how a molecule reacts
in terms of which part of the structure of a molecule changes,
how reagents react and what reagents the molecule will react
with. The more electronegative atom carries the
d-
charge e.g. ...
-
The Cδ+
in the polar bond Cδ-Clδ-
in halogenoalkanes are susceptible to nucleophilic
attack by electron pair donors. (see
mechanisms Part II)
-
The Cδ+
in the polar bond >Cδ+=Oδ-
in aldehydes/ketones/acyl chlorides etc. are susceptible
to nucleophilic attack by electron pair donors.
(see mechanisms Part
III)
-
The
polarised hydrogen bromide molecule, Hδ+-Brδ-,
acts as an electrophile by proton donation in which the
proton (H atom) of the HBr acts as a H+
ion and accepts a pair of electrons to form an C-H bond.
(see mechanisms Part Ib)
-
electrophile: A 'reagent' atom, ion or molecules that can
accept a pair of electrons (Lewis acids) from an 'electron rich'
part of a molecule like the
∏
electrons of an alkene or arene. They acts as Lewis acids, electron
pair acceptors when interacting with molecules such as alkenes and
arenes. (see alkene
mechanisms or aromatic
mechanisms)
-
e.g.
Br2,
CH3CH2+, Br+, SO3,
H-OSO2OH, Hδ+-Brδ-
-
electrophilic
attack: The
interaction of an electrophile reagent (electron pair acceptor)
interacting with an electron pair donor prior to forming the
products of that mechanism step e.g. 'attacks' on ....
-
electrophilic
addition: An electrophilic
reagent adds to a molecule to give the product (without any elimination).
-
electrophilic
substitution: An
electrophilic reagent replaces an atom or group of atoms in another
molecule.
-
e.g. the
nitration of benzene. C6H6 + HNO3
==> C6H5NO2
+ H2O
-
where a H in
the benzene ring replaced by NO2 via the electron
pair accepting electrophile, the NO2+
ion.
-
elimination
reaction: A small molecules is eliminated from a larger molecule,
often by combining two fragments from adjacent atoms e.g.
-
free radical:
An atom or fragment of a molecule with an unpaired electron, often
shown by a dot. (see alkane
mechanisms)
-
functional
group: (see
summary of functional groups)
-
heterolytic
bond fission: see
bond fission
-
homolytic
bond fission: see
bond fission
-
hydrolysis:
A reaction, usually in aqueous media, between one molecule and
water/acid/alkali which leads to the formation of at least two
products e.g.
-
the tertiary
halogenoalkane 2-chloro-2-methylpropane, reacts with water to
form 2-methylpropan-2-ol and hydrochloric acid. (see
halogenoalkane
mechanisms)
-
The ester
methyl ethanoate forms sodium ethanoate and methanol when
refluxed with aqueous sodium hydroxide.
Aliphatic
acid/acyl chlorides readily hydrolyse back to the parent
carboxylic acid with water. (see
mechanisms Part III)
-
initiation
step: The name of the 1st step in
a reaction mechanism sequence. The term is usually applied to the 1st step in
free radical chain reactions, when the initial radicals are formed. (see
alkane mechanisms)
-
e.g. in the
chlorination of methane the 1st step is: Cl2
==hv==>
2.Cl when a uv
photon splits the chlorine molecule
-
or an
organic peroxide splitting on heated to give two alkoxy radicals
: RO-OR ==> 2RO.
-
isomeric
products: This means
two or more products from the same reaction which have the same
molecular formula but different molecular structure (positional
isomerism/isomerizm). [see
detailed notes on ISOMERISM]
-
Lewis acid:
An atom, ion or molecule that can accept a pair of electrons to form
a bond. Electrophiles
are Lewis acids.
-
Lewis base:
An atom, ion or molecule that can donate a pair of electrons to form
a bond. Nucleophiles are Lewis
bases.
-
Markownikoff Rule
(Markownikov/Markovnikov): This is a rule that predicts the
orientation of electrophilic addition of an electrophile like Hδ+Brδ-
or
Iδ+Clδ+
(in general lets call it Wδ+-Xδ-)
to a non-symmetrical alkene and it can be expressed in
several ways (see alkene
mechanisms) e.g.
-
The negative
part of the addendum, Wδ+-Xδ-,
attaches itself to the carbon atom of the double bond which
initially has the least hydrogen atoms bonded it to it.
-
So for an
non-symmetrical alkene like propene, you would expect the
majority reaction to be ...
-
CH3CH=CH2
+ W-X
==> CH3CHX-CH2W
(much less of CH3CHW-CH2X,
as you cannot assume zero probability of forming the
other isomeric product!)
-
mechanism:
A detailed step by step representation of how a reaction actually
takes place and is far more complicated that the 'usual'
stoichiometric equation! (lots of examples of
organic mechanisms)
-
molecularity
: This can mean several
things unfortunately and is frankly confusing at times.
-
The number
of species involved in a chemical change or reaction step. Since
most reactions occur via one or more steps involving bimolecular
collisions, so the molecularity is often 2.
-
Some
reactions, whose rate depends on just one reactant are described
as 'unimolecular' or if the reaction depends on two reactant
concentrations it may be described as 'bimolecular'. The use of
the 'molecularity' here has more to do with kinetic studies of
reactions (e.g. the nucleophilic substitutions of
halogenoalkanes, see SN1
and SN2).
-
non-polar
bond: A bond where the to atoms
have similar electronegativities and the bonding pair of electrons is 'equally
shared'.
-
non-symmetrical/unsymmetrical
alkene: An alkene in
which the groups attached to each carbon of the double bond are NOT
identical. (see alkene
mechanisms) e.g.
-
propene
CH3-CH=CH2, methylpropene (CH3)2C=CH2
or but-1-ene CH2=CH-CH2-CH3
-
If an
unsymmetrical reagent e.g. HX is added, two isomeric
products
can be formed.
-
e.g. CH3-CH2-CH2X
or CH3-CHX-CH3 from propene.
-
nucleophile: An 'reagent' electron
pair donor (Lewis base) that will 'attack' an electron deficient
part of a molecule e.g. the 'positive' of polarised bonds Wδ+Xδ-,
in halogenoalkanes C-X, or aldehydes/ketones >C=O or
acyl (acid) chlorides RCOCl
-
e.g.
hydroxide ion :OH-, ammonia :NH3,
ethanol CH3CH2OH, water H2O:,
cyanide ion :CN-
-
nucleophilic
addition: An
nucleophilic reagent adds to a molecule (without any elimination).
(see
aldehyde/ketone mechanisms)
e.g.
-
nucleophilic
addition-elimination:
A nucleophilic reagent adds to another molecule and then a small
molecule is eliminated to give the final product.
-
e.g.
ethanoyl chloride reacts with methanol to make methyl ethanoate
and hydrogen chloride is eliminated in the process. The electron
pair (on the oxygen) donating nucleophile is methanol. (see
mechanisms Part III)
-
CH3COCl
+ CH3OH ==> CH3COOCH3 +
HCl
-
nucleophilic
attack: The
interaction of a nucleophile reagent (electron pair donor)
interacting with an electron pair acceptor prior to forming the
products of that mechanism step e.g. 'attacks' on ...
-
or
or
Halogenoalkanes - 3 examples
-
or
Aldehydes and ketones - 2 examples
-
or
Acyl chlorides - 2 examples
-
nucleophilic
substitution: A nucleophilic
reagent replaces an atom or group of atoms in another molecule.
-
polar bond:
A covalent bond in which the two atoms have different
electronegativities leading to an unequal sharing of the bonding
pair(s) of electrons.
-
primary
(prim or 1o): A
structural term in organic chemistry to indicate no or just one
alkyl/aryl group are attached to the
carbon
or
nitrogen
atom of the functional group e.g.
-
bromomethane
CH3Br
and 1-chloropropane CH3CH2CH2Cl
are primary halogenoalkanes
-
methylamine CH3NH2
and propylamine CH3CH2CH2NH2
are primary aliphatic amines
-
methanol
CH3OH
and butan-1-ol CH3CH2CH2CH2OH
are primary alcohols
-
CH3+
and CH3CH2CH2+
are primary carbocations
-
see also
secondary
and tertiary for comparison
-
propagation
step: Type of
mechanism step in free radical chain reactions, where a radical
reacts with a substrate molecule, but also/only produces another
reactive free radical which continues the reaction .e.g.
-
CH3.
+ Cl2
==> CH3Cl + .Cl
(which produces the product in the chlorination of methane AND a
reactive chlorine radical)
-
RO-CH2-CH2.
+ CH2=CH2
==> RO-CH2-CH2-CH2-CH2.
(in the free radical
polymerization of alkenes, a peroxide radical adds to an alkene
(1st reactant on left) and this radical adds to another alkene
molecule (right product) which is itself a radical and continue
reaction building up the polymer chain until terminated!)
-
protonation:
Adding a proton, H+, to a species e.g.
-
quaternary
(quat or 4o): The term used
to describe the alkylammonium salts formed when
nitrogen
is bonded to four alkyl groups i.e. all four hydrogens on the
ammonium ion are replaced by alkyl groups.
-
secondary
(sec or 2o): A
structural term in organic chemistry to indicate two alkyl/aryl groups are
attached to the
carbon
or
nitrogen
atom of the functional group e.g.
-
2-chloropropane CH3CHClCH3
is a secondary halogenoalkane
-
diethylamine (CH3CH2)2NH
is a secondary aliphatic amine
-
CH3CH+CH3
is a secondary carbocation
-
butan-2-ol CH3CH2CHOHCH3
is a secondary alcohol
-
see also
primary
and tertiary for comparison
-
shift of
electrons:
see use of arrows in mechanisms
-
SN1:
Shorthand for a nucleophilic substitution reaction in which the rate
determining step is the formation of carbocation from just one of
the reactant molecules or intermediates (X) and the rate is
independent any other reactant or intermediate.
-
SN2:
Shorthand for a nucleophilic substitution reaction in which the rate
determining step is a bimolecular collision of two reactant
molecules (X and Y) and the rate is independent any
other reactant or intermediate.
-
stereospecific/stereospecificity:
means the change reactants ==> products is dependent in
some way on the spatial orientation of at least one of the
reactants or intermediates, e.g. in the key-lock mechanism of
enzymes, the 'key into lock' interaction, i.e. the stereospecificity
of enzymes, partly depends on the spatial orientation of the
enzyme's protein structure and the shape of the substrate molecule,
particularly from the point of view of bond formation or the
inter-molecular force of hydrogen bonding.
-
steric
hindrance: This means
a reaction is inhibited because of some spatial/orientation
limitation, e.g. bulky groups attached to an atom/bond that
theoretically is susceptible to attack by a particular reagent.
-
substitution:
When one atom or group of atoms is replaced by another atom or group
of atoms. (see mechanism index for
lots of examples)
-
symmetrical
alkene: An alkene in
which the groups attached to each carbon of the double bond are
identical. (see alkene
mechanisms) e.g.
-
ethene H2C=CH2
or but-2-ene CH3-CH=CH-CH3
-
If an
unsymmetrical reagent e.g. HX is added, only one
product is formed.
-
e.g. CH3-CH2X
or CH3-CH2-CHX-CH3 from
ethene or but-2-ene.
-
termination
step
: A step in a free radical chain reaction in which two radicals
combine to bring that particular 'chain' to a halt.
-
tertiary
(tert or 3o): A
structural term in organic chemistry to indicate three alkyl or aryl
groups are attached to the
carbon
or
nitrogen
atom of the functional group e.g.
-
2-chloro-2-methylpropane (CH3)3CCl
is a tertiary halogenoalkane
-
trimethylamine (CH3)3N:
is a tertiary aliphatic amine
-
2-methylpropan-2-ol (CH3)3COH
is a tertiary alcohol
-
(CH3)2C+CH2CH3
is a tertiary carbocation
-
see also
primary
and secondary for comparison
-
transition
state: see
activated complex above
-
'unimolecular'
mechanism/kinetics :
see SN1
-
unsymmetrical
alkene: structure and
addition to, see non-symmetrical alkene
GENERAL
REVISION
NOTES

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