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INTRODUCTION TO ORGANIC CHEMISTRY

organic chemistry is the most important branch of chemistry - but of


course it would be nothing without the many other areas of chemistry -
in fact all branches of chemistry should not be viewed in isolation,
even though they may often be taught in isolation
organic chemistry is all around us, life is based on organic chemistry,
the clothes we wear, the drugs we take, the cars we drive and the fuel
that propels them, wood, paper, plastics and paints

organic chemistry is the study of compounds containing carbon


the ability of carbon to form as many as 4 strong bonds to many other
atoms, e.g., carbon, hydrogen, oxygen, nitrogen, halogens, sulphur,
phosphorus ensures a virtual infinite number of possible compounds

the constituent atoms and their exact combination determines the


chemical and physical properties of compounds and hence their
suitability for applications

the organic chemistry for this first semester will consist of the following
topics
general introduction - structure and bonding, examples of
organic compounds, nomenclature, examples of organic reactions,
an introduction to reaction mechanisms

Alkanes - physical properties, synthesis, chemical properties

Alkenes - physical properties, synthesis, chemical properties

Alkynes - physical properties, synthesis, chemical properties

all examined as part of module 06510

recommended texts
Organic Chemistry by Solomons and Fryhle (8th edition) 2004
Organic Chemistry by Maitland Jones (3rd edition) 2004
Organic Chemistry by Clayden, Greeves, Warren, Wothers 2001
TYPICAL ORGANIC COMPOUNDS
STRUCTURES AND NOMENCLATURE
hydrocarbons - contain carbon and hydrogen only
alkanes - fully saturated, all single bonds, chain and cyclic
there are many different ways to draw chemical structures, often it does
not matter which is used, but sometimes a full structure will be required
if reaction mechanisms are being considered, for example
the nomenclature of organic compounds follows the IUPAC system -
International Union of Pure and Applied Chemistry
first important IUPAC rule - names are based on the number of
carbon atoms present in the longest possible chain
H H H H H H
H C H H C C H H C C C H
H H H H H H butane
methane ethane propane
CH3 CH2 CH2CH 2CH3 CH3 (CH2)4CH 3
pentane hexane hept, oct, non, dec, undec, dodec,
what about branched chain systems?
take the longest chain - C5 - hence pentane,
number the chain so that the substituents have
the lowest possible numbers - hence
2,3-dimethylpentane not 3,4-
note the commas and hyphens - very important
look carefully, you might think a pentane? but no
the longest chain is six - hence hexane - what is the
substituent? ethyl, at the 3- position - hence
3-ethylhexane not 3-propylpentane!!!
same rules as above, then list substituents
alphabetically (ignore prefixes such as di and
tri; i.e., dimethyl comes after ethyl) - hence
4-ethyl-2-methylhexane
H3C
C2H5
same rules
for cyclics

Cl
1-ethyl-3-methylcyclohexane
4-chloro-2-ethyl-1-methylcyclohexane
hydrocarbon sub-units with trivial names retained by IUPAC
H3C CH trivial names persist in many cases beacuse they
CH3
are convenient, but often difficult to deal with - in
some cases the trivial names are common and
1-methylethyl or have been retained under the IUPAC system
isopropyl
CH3
H3C CH2 CH H3C CH CH2 H3C C
CH3 CH3 CH3
1-methylpropyl or 2-methylpropyl or 1,1-dimethylethyl or
sec-butyl isobutyl tert-butyl

CH3
H3C C CH2 this is the only five-carbon unit with a
trivial name allowed by IUPAC
CH3

2,2-dimethylpropyl or
neopentyl

the hydrogen atoms of an alkane are classified according to their


position - primary (1°), secondary (2°), tertiary (3°)

3° hydrogen atom 2° hydrogen atoms

H3C CH CH2 CH3 as we shall see later, the 'removal'


CH3
of a hydrogen atom leaves a
sub-unit that is classified 1°, 2° or 3°
as appropriate - of great significance
in organic reactions
1° hydrogen atoms

other common sub-units


X
CH2
H X H CH2 X
X
H CH2
H H H H
vinyl allyl benzyl propargyl

the above sub-units are also of significance in organic reactions


alkenes - unsaturated, C=C double bond, chain and cyclic
the nomenclature of alkenes follows the IUPAC system and is very
similar to that of alkanes - really very easy with experience
H H H CH3 H CH2 CH3
note the same
H H H H prefix as for
H H alkanes
ethene propene but-1-ene
1-butene (USA)
note from butene we get
possible isomers, but-1-ene
and but-2-ene, and because
the π-bond restricts rotation
but-1-ene trans-but-2-ene cis-but-2-ene there are two isomers of
but-2-ene (cis and trans)

CH3 CH=CHCH2CH2 CH3


definitely trans
general formula, obvious why
cis or trans not defined
trans-hex-2-ene not trans-hex-4-ene
lowest possible number for double bond is chosen
note that the numbering is usually based on the position of the
double bond - not substituents, hence
H H CH3
trans-5,5-dimethylhex-2-ene
C C CH3
H3 C H CH3 not trans-2,2-dimethylhex-4-ene
H
but not for alcohols!!!, which we have not even mentioned yet,
perhaps you know what they are!!!
OH
HO

4-methylpent-3-en-2-ol 2-methylcyclohex-2-en-1-ol
not 2-methylpent-2-en-4-ol not 2-methylcyclohex-1-en-3-ol
speaking of cyclics!
very similar to acyclic alkenes,
but where the numbering is set
by the double bond at position 1
cyclohexene 3-methylcyclohexene there is no need to include it
alkynes - unsaturated, C≡C triple bond, chain and cyclic (rare)
the nomenclature of alkynes follows the IUPAC system and is very
similar to that of alkanes and alkenes - really very easy with experience

H C C H CH3 C C H CH3 C C CH2 CH2 CH3


ethyne propyne hex-2-yne
not hex-4-yne
H C C CH2 CH2 OH as for alkenes, with alcohols the OH takes
preference for the numbering
but-3-yn-1-ol
H H a double bond takes preference
over a triple bond for numbering
H H H pent-1-en-4-yne
H not pent-4-en-1-yne
rules on branching just the same as for alkenes

aromatic systems - benzene rings


benzene is a simple aromatic system and extremely common, naming is
very easy!

most substituted benzenes are named easily as


a benzene derivative - but some are not!!
benzene
Br OH NO2 CH3 CN

bromobenzene phenol nitrobenzene toluene ethylbenzene benzonitrile


not hydroxybenzene not methylbenzene not cyanobenzene

NO2
substituents are listed alphabetically -
as seen for other systems
Br 1-bromo-3-nitrobenzene

CN
OH
some suffixes have higher priorities than others
which forces the lower one to become a prefix
2-hydroxybenzonitrile
not 2-cyanophenol
Representative Organic Compounds
haloalkanes or alkyl halides
Cl
I Cl Br

2-iodobutane 2-chloro-3-methylbutane (2-chloroethyl)benzene benzyl


2° 2° 1° bromide
1° - but a
note the primary (1°), secondary (2°), tertiary (3°) bit special
designations, they give rise to different chemical reactivity
aryl halides

Cl chemically, aryl halides are much


Br
less reactive than alkyl halides
chlorobenzene 2-bromonaphthalene

alcohols
OH OH
OH
CH3CH 2OH
ethanol 2-methylbutan-2-ol cyclohexanol benzyl alcohol
1° 3° 2° 1° - but a
bit special
phenols
the aromatic analogues of alcohols,
OH but their chemical properties are
phenol often different to those of alcohols

amines
NH2 H2N
Et
Et Et
propylamine NH2 N
1° isopropylamine triethylamine 2-amino-2-methylbutane
1° not 2° 3° 1° not 3°

H
N notice the way 1°, 2° and 3° amines
N are made up, and how they differ
H from 1°, 2° and 3° alcohols and
diisopropylamine pyrrolidine alkyl halides for example
2° 2°
ethers
O
O
O
ethoxyethane
(ether) 2-methoxy-2-methylpropane tetrahydrofuran
(MTBE) (THF)
Representative Organic Compounds
aldehydes and ketones (carbonyl compounds)
essentially the same class of compound but given different names!!
O O O O

H H H
methanal propanone pentanal hexan-2-one
(acetone)
O notice the difference between aldehydes and ketones -
a bit like primary and secondary
cyclohexanone
carboxylic acids and their derivatives
combine the carbonyl group of aldehydes and ketones with another
group on the same carbon - the other group can be hydroxyl (acids),
chloro (acid chlorides), acetyl (acid anhydrides), ether (esters),
amino (amides) - examples are shown below

O O O O O O
H O(CH2)3CH3 NH2
O Cl O
ethanoic acid ethanoyl chloride ethanoic anhydride butyl ethanoate ethanamide
(acetic acid) (acetyl chloride) (acetic anhydride) (butyl acetate) (acetamide)
1° amide
O O
O H

O N Me
O
benzoic acid Me
phenyl cyclohexanecarboxylate N,N-dimethylbenzamide
3° amide
OEt O
Ph O
N
O Et
ethyl benzoate H O
N-phenylethanamide ethyl acetate
2° amide (ethyl ethanoate)

nitriles (cyanides)

H3C C N C N C N
ethanenitrile benzenecarbonitrile cyclohexanecarbonitrile
(acetonitrile) (benzonitrile)
Orbital Hybridisation - models for bonding in organic compounds
Carbons in methane, ethane, cyclohexane for example
methane has the formula CH4 , but what does this tell us about the
structure? - not much is the answer, but you may know that the
carbon atom is at the centre of a tetrahedron
experimental evidence shows methane and other analogues to have a
tetrahedral arrangement of atoms - all four bonds are equivalent with
each hydrogen as far from the next as possible - tetrahedral

how do we account for the tetrahedral shape given the ground state
electron configuration of carbon?

2p 2p
2sp3
2s 2s

1s 1s 1s
ground state excited state hybridised state

the ground state configuration would seemingly only give two bonds!
the excited state does allow four bonds, but not all would be equivalent!
but if the three 2p orbitals are hybridised with the 2s orbital then four new,
equivalent orbitals (2sp3 ) are generated which arrange as far apart as
possible (minimum energy) in a tetrahedral arrangement which allows
the formation of four equivalent bonds with angles of 109.5°

the bonds are called sigma bonds


if all four 2sp3 atomic orbitals overlap with 1s atomic orbitals of
hydrogen atoms, then methane is formed
if one 2sp3 atomic orbital overlaps with one from another carbon atom
and the remaining six overlap with 1s atomic orbitals of hydrogen atoms,
then ethane is formed - other combinations are obvious
it is appropriate at this point to look at atomic orbitals and molecular
orbitals, how they are defined and what shapes they are
note that this concept is only a model - orbitals and hybridisation
should not be considered real! - but the model does provide an
excellent explanation for reality!
Atomic Orbitals
ψ2 represents the probability of finding an electron at a certain location
plots of ψ2 generate the shapes of atomic orbitals such as s, p, d and f
hence atomic orbitals result from quantum mechanics and represent
a region of space where the probability of finding an electron is large
electrons have the property of waves and can be positive and negative
or zero in value - the positives and negatives as shown in orbitals does
not indicate charge! and does not indicate a greater or a lesser
probability of finding an electron

examples of atomic orbitals


both the 1s and the 2s orbitals are spherical and the 2s orbital has a nodal
surface where ψ2 = 0 and the inner portion is negative
the 2p orbitals are dumb-bell shaped with two almost-touching spheres,
one is positive and one is negative, ψ2 = 0 at the nodal plane

nodal plane
(–)
(–) (+) (–) (+)
(+) 2sp2 and 2sp
nodal
are similar
surface 2s 2p 2sp3

4 +

1s 109.5°
3
4x2sp
methane

when two atomic orbitals combine they do so to produce two molecular


orbitals - combination with like signs (constructive) produces a bonding
molecular orbital, which is larger and so ψ2 is larger - combination with
opposite signs (destructive) produces an antibonding molecular orbital,
which is small, so ψ2 is small, and there is a nodal plane where ψ2 = 0
Orbital Hybridisation - models for bonding in organic compounds
Carbons with C=C, C=O, C=N for example
we have just seen how we can account for the structure of alkanes
through hybridisation, but how do we account for the structure of
alkenes, carbonyls and imines for example
experimental evidence shows that these compounds at the bonding in
question are planar, so how do we account for this given the ground
state electron configuration of carbon?

2p 2p

2sp2
2s 2s

1s 1s 1s
ground state excited state hybridised state

the ground state configuration would seemingly only give two bonds!
the excited state does allow four bonds, but not to the required shape
a similar hybridisation 'occurs' to that seen for alkanes, but one of the
2p orbitals is left out and only two hybridise with the 2s orbital to give
three 2sp2 orbitals
the three 2sp2 orbitals arrange in a trigonal planar manner (maximum
distance apart, minimum energy) with angles of 120° between - like
those found in methane, these bonds are called sigma bonds
the remaining 2p orbital is perpendicular to the planar framework, and
overlaps with another p orbital, from one of the three attached units,
to form a pi (π) bond - hence creating a double bond

p orbital

sp2 orbital

two sp2 4
hybridised 1s
carbons
120° planar

ethene
Orbital Hybridisation - models for bonding in organic compounds
Carbons with C≡C, C≡N, C=C=C for example
we have just seen how we can account for the structure of tetrahedral
and planar organic units, but how do we account for those structures, for
example, alkynes, nitriles, allenes that are linear?

2p 2p

2sp
2s 2s

1s 1s 1s
ground state excited state hybridised state

the ground state configuration would seemingly only give two bonds!
the excited state does allow four bonds, but not to the required shape
a similar hybridisation 'occurs' to that seen for alkanes and alkenes,
for example, but here two 2p orbitals are left out and only one hybridises
with the 2s orbital to give two 2sp orbitals

the two 2sp orbitals arrange in a linear manner (maximum


distance apart, minimum energy) with angles of 180° between - like
those found in methane, these bonds are called sigma bonds

the remaining two 2p orbitals are perpendicular to the linear framework, and
overlap with other p orbitals, from the two attached units to form two pi (π)
bonds; where one unit provides both p orbitals a triple bond is formed, where
a p orbital is provided by each unit two double bonds are formed

p orbital
sp orbital
p orbital
180° linear
two sp
hybridised
carbons 2
ethyne
1s
Some Important Implications of Hybridisation
bond lengths and bond angles

H H
118°
H H H H
180° C C C
121° 109.5°
1.20 Å 1.34 Å 1.54 Å
C 1.09 Å C C 1.10 Å
1.06 Å H H H H
H H
ethyne ethene
ethane
note the trend for carbon-carbon bond length

alkyne < alkene < alkane


sp < sp2 < sp3

the greater the s character the more overlap is possible, hence


the shorter the bond and the stronger the bond
the same trend is true for carbon-hydrogen bond length but not so great

the bond angles in ethene are not all 120° as would be expected
because the π electrons push the H-C-H angle smaller to 118°
H
a similar situation arises for the carbonyl group 118° C O
H

in ammonia, the nitrogen is sp3 hybridised which


N
gives a tetrahedral shape, but two electrons are
H H
paired (lone pair) which takes up more space than a
107° H
bonded pair hence the slightly smaller bond angles

O similarly, the oxygen of water is sp3 hybrdised which


H gives a tetrahedral shape, but here two lone pairs
H
105° leads to even smaller bond angles
Conformational Analysis of Alkanes
the study of bond rotations - the carbon-carbon single bond can rotate
freely - but there are energy barriers to overcome which allows the
possibility of different conformers of different stabilities, but usually too
similar to allow isolation - hence conformers NOT isomers
stability here means favourability
to illustrate we need ways of representing 3-D molecules in 2 dimensions, and
there are 2 common systems
staggered eclipsed
H H H
H
sawhorse H
H H H
H H
H H
H
H H HH
Newman H
H H projections H H
H H
one of the above conformers is the most stable, and the other the least stable
I hope that you can see clearly that the staggered conformer is the most stable,
the eclipsed conformer has protons in closest proximity causing the maximum
repulsive forces - hence the least stable

HH
H
H H
H

energy

H H
H H H H

H H H H
H H

rotation
ethane is used in the above example, but of course with larger systems,
such as butane, and systems with other functional groups (e.g., -OH, -Br),
the conformation situation is much more complex
Conformational Analysis of Butane - a larger carbon chain
the more carbons in the chain then the conformational possibilities become
more numerous and more complex, do not have staggered and eclipsed,
now have anti, eclipsed and gauche

H3C CH3
H
H CH3 H H H CH3
H
H eclipsed (IV) CH3
H H H H
CH3 H
eclipsed (II) eclipsed (VI)

energy

CH3 CH3
CH3 H3C H H CH3 CH3
H H H H
H H H H
H H H H H H
CH3 gauche (III) gauche (V) CH3
anti (I) anti (I)

rotation

the anti (I) conformation does not have torsional strain because all groups are
staggered and the methyl groups are far apart - the gauche conformations are
similar, but have the methyl groups closer together - thus higher in energy,
less stable and hence less favourable
the eclipsed conformers are much less favourable since the groups are all in
line (eclipsed), and the eclipsed (IV) conformer least favourable because the
larger methyl groups are in line with each other

the energy difference between the various conformers is larger than for ethane,
but still far too small to enable isolation of conformers at normal temperatures
Relative Stabilities of Cycloalkanes
cycloalkanes do not all have the same relative stability - obvious, but
why is this? and how do we measure relative stability?
heat of combustion is the energy released on complete oxidation and is a
negative number - the lower the negative number the less energy evolved -
hence the more stable (in relative terms)
but the larger the compound the more energy will be released - so we
need the heat of combustion per CH2 group for effective comparison

H H
H cyclopropane - is it stable? hopefully you
can see that it is relatively unstable
H H
H

reasons? - two issues angle strain and torsional strain


the bond angles for sp 3 should be 109° but here they are 60°, a large
difference and hence unstable through angle strain
the protons on adjacent carbons are eclipsed and so repulsive forces are
at a maximum and hence unstable through torsional strain

H H H
H H H H
H H
H
H H
H H
H H H H

cyclobutane cyclopentane

cyclobutane has bond angles of 88° hence unstable, but the favoured bent
conformer has little torsional strain - the planar conformer has bond angles
of 90° (better for angle), but protons would be eclipsed hence very unstable
planar cyclopentane would not have angle strain (108°), and so you
might think the planar conformer to be the most stable, but the
torsional strain would be enormous - hence the most stable
conformer is the bent form because of less torsional strain
cyclohexane is not planar, the most stable conformer is the chair which
ensures that bond angles are 109° and that all protons are staggered
torsional
H H H H strain
H H H H H
H H H
H H H H
H H H
H
H H H H
cyclohexane - chair cyclohexane - boat
the boat form of cyclohexane also has no angle strain but does have
torsional strain as arrowed above, hence the boat form is less stable
than the chair - the boat form can twist to remove some of the
torsional strain - twisted boat, more stable than the boat but
less stable than the chair - in fact the chair conformer is so stable
relatively that 99% of the molecules exist in the chair conformation at
any given time

Heats of Combustion of Cycloalkanes

cycloalkane (CH2)n heat of combustion heat of combustion ring strain


–1
(kcal mol ) per CH2 group (kcal mol ) (kcal mol–1)
–1

hexane 944.5 157.4 -


cyclopropane 499.8 166.6 27.6
cyclobutane 655.9 164.0 26.3
cyclopentane 793.5 158.7 6.5
cyclohexane 944.5 157.4 0
cycloheptane 1108.2 158.3 6.4
cyclooctane 1269.2 158.6 10.0
cyclononane 1429.5 158.8 12.9
cyclodecane 1586.0 158.6 12.0
cyclopentadecane 2362.5 157.5 1.5

ring strain is the difference from the expected heat of combustion based on
157.4 kcal mol–1 (for unstrained hexane) to the actual heat of combustion
it is clear from the table above that small rings have much ring strain as
described earlier, cyclohexane has no ring strain (dicussed above)
larger rings then begin to develop ring strain because of the steric interactions
between protons across the ring (torsional strain), but there is minimal
angle strain - angle strain may be present when certain conformers are
adopted to minimise the torsional strain!
the very large rings have virtually no ring strain because conformers can be
adopted that have ~no angle strain and ~no torsional strain
Further Discussion of Ring Systems
there are two distinct positions for the attachment of substituents in the
chair cyclohexane -these are called axial and equatorial
a cyclohexane ring in the more stable chair conformer can flip between
two forms, groups that were axial become equatorial and groups that
were equatorial become axial

cyclohexane - chair
axial
axial
5 6 4 5 6
ring flip equatorial
equatorial 1

4 3 2 2 1
3

both are of equal stability because both are identical in structure

methylcyclohexane - chair
axial methyl equatorial methyl
H CH3 H H
H H ring flip H H
H H H H
H H H CH3
H H H H
H H H H
1,3-diaxial interactions methyl group is well away from the
cross-ring protons and hence is more
stable by 7.5 kJ mol–1
and constitutes 95% of molecules

obviously unsymmetrical now so both are not the same - the axial methyl
has 1,3-diaxial interactions giving steric strain, so much so that 95% of the
molecules exist with equatorial methyl at a given time
smaller substituents give less pronounced effects, but larger substituents, such
as tert-butyl have 99.99% of molecules in equatorial form at a given time
Basic Introduction to Stereochemistry
ISOMERS are different compounds that have the same molecular formula
CONSTITUTIONAL ISOMERS are isomers that differ because the constituent
atoms are connected in a different order - different connectivity

Br
Br
pentane 2-methylbutane 1-bromobutane 2-bromobutane

CH3 CH2 OH CH3 OCH3


ethanol dimethyl ether cyclobutane but-1-ene
the lower pairs are also known as functional group isomers

STEREOISOMERS have the same atomic connectivities, but their arrangement


in space is different - interconversion is not possible without bond breakage,
followed by rearrangement and then reformation of the bond
the most simple cases of stereoisomers are found in alkenes and
cycloalkanes, often called cis-trans isomers or diastereomers
Cl Cl Cl H

H H H Cl
cis-1,2-dichloroethene trans-1,2-dichloroethene

cis-trans isomers can arise here because of the complete restriction of


rotation about the carbon-carbon double bond due to the pi system
similarly, the framework of a ring system restricts the complete rotation of
a carbon-carbon bond thus fixing two substituents either on one side of
the ring (cis) or on opposite sides of the ring (trans)

both methyl groups fixed on both methyl groups fixed on


the same side of the ring opposite sides of the ring
H H H3 C H

H3 C CH3 H CH3
cis-1,2-dimethylcyclohexane trans-1,2-dimethylcyclohexane
of course, the same is true for the other positions (1,3 and 1,4) on the ring
a more subtle form of stereoisomerism involves chirality or handedness
certain molecules can exist as object and image and are called enantiomers
an exact 50:50 mixture is called a racemic mixture
most notably, these molecules have a tetrahedral carbon that have FOUR
different groups attached, for example butan-2-ol exists as (R) and (S)
enantiomers which cannot be superimposed on each other and are
therefore mirror images
the bold wedge indicates a bond coming out of the paper
the dashed wedge indicates a bond going into the paper
mirror
CH3 CH3 OH OH
HO C H H C OH

CH2 CH2 (R ) (S)


CH3 CH3 do not worry about how (R) and (S)
(R ) (S) are determined at this stage

the (R) and (S) enantiomers are different compounds and cannot be
interconverted without breaking a bond and reforming the bond in
the alternative position in space
certain cyclic systems exhibit both cis-trans isomerism and chirality
cis-1,2-dimethylcyclohexane trans-1,2-dimethylcyclohexane
mirror
H H
H3 C H H CH3
H3 C CH3
H CH3 H3 C H
has two carbons with four has two carbons with four different
different groups attached, but groups attached, not plane of
there is a plane of symmetry symmetry, and hence two enantiomers
so only one compound
such cases are called meso
more normally a system with two chrial centres would give four stereoisomers
two pairs of enantiomers with the other relationships being diasteromers
enantiomers are stereoisomers that are mirror images of each other
diastereomers are stereoisomers that are not mirror images of each other

an extensive course on stereoisomerism is presented in year 2


An Introduction to Chemical Reactions

organic reactions involve the breaking of covalent bonds and


the making of new covalent bonds
important points that determine reactivity include bond polarity,
the nature of the bonded units, stability of starting materials,
intermediates and products
in illustrating reaction pathways and mechanisms we use a
recognised system of arrows
these arrows show the movement of electrons both within
compounds and between compounds in the reaction pot
a single barbed arrow for the movement of one electron
a double barbed arrow for the movement of a pair of electrons

a covalent bond may break in two fundamentally different ways -


homolytically and heterolytically
where two bonded units have little polarity there is no preference
for both electrons to go either way - hence one electron goes to
each unit to produce two radicals
homolytic fission
A B A + B

if there is a difference in electronegativity then both electrons


are likely to go to the most electronegative unit giving an anion,
the other unit would be a cation

heterolytic fission
A B A + B
heterolytic fission
A B A + B

even in highly polarised systems heterolysis rarely occurs without


some assistance from a reagent or sometimes solvent, e.g.,

δ+ δ−
A B Z A + B
Z

δ+ δ−
A B Z A + B
Z
the above show how reaction mechanisms should be presented
Types of Chemical Reactions
virtually all organic reactions fall into four categories

substitution, additions, eliminations, rearrangements

often the overall result may be substitution, but the reaction


mechanism may be one of addition, followed by elimination
most organic reactions can be said to be acid-base reactions,
how are acids and bases defined? under the Bronsted-Lowry theory,
acids are substances that can donate (lose) a proton, bases are
substances that can accept (remove) a proton
since not all organic reactions involve protons, a more general
theory was developed by Lewis
a Lewis acid is a substance that can accept a pair of electrons
a Lewis base is a substance that can donate a pair of electrons
another way of looking at organic chemistry is often more
appropriate and useful which is to view reacting species as
either electrophiles or nucleophiles
electrophiles are electron defficient - seek electrons - also acids
nucleophiles are electron rich - seek nuclei - also bases
Cl
Cl Al NH3

Cl nucleophile
electrophile lewis base
lewis acid
H2O
a substitution reaction H3C Cl + NaOH H3C OH + NaCl

H H H H
CCl4
an addition reaction C C + Br Br H C C H
H H Br Br
Me
Me C OK
H H H H
Me
an elimination reaction H C C H C C
H Br H H

Me H H Me Me
H
a rearrangement reaction Me C C C H Me C C Me
Me
Physical Properties of Alkanes

alkanes are non-polar, so they are virtually insoluble in water, but soluble
in a wide range of organic solvents
alkanes are less dense than water, hence petroleum floats on water
alkanes are non-polar, hence only weak van der Waals intermolecular
forces of attaction operate (through induced temporary dipoles)
hence low melting points and boiling points
van der Waals intermolecular forces of attraction increase with increasing
relative molecular mass (because of increased temporary dipoles) and
contact area tends to increase with increasing size
hence melting points and boiling points increase with increasing mass
generally true, but a few subtle points to mention
Boiling Points
unbranched alkanes show a regular increase in bp with increasing mass
increased van der Waals forces of attraction (see above) but also
increased surface area is very important
branched alkanes tend to have lower boiling points than unbranched
isomers because of reduced area of contact.

bp = 68 °C bp = 63 °C bp = 49 °C

Melting Points
unbranched alkanes show an odd-even effect in their mps, those with
an even number of carbons pack better and hence have higher mp than
expected in comparison with odd-numbered alkanes
the effect of branching on mp is difficult to predict, but one branch on a
long chain tends to lower mp because the steric effect reduces packing,
however, extensive branching produces a more symmetrical structure
which enhances packing and causes an increase in mp, the mp is high
for cyclic systems for the same reason (symmetrical structure)

mp = 101 °C note the high mp, yet low bp (see above)


bp = 107 °C
mp = –57 °C
bp = 126 °C
mp = 13.5 °C
bp = 149 °C high mp, high bp low mp, high bp
The Variation of Boiling Point of Alkanes with Size

300

250

200

150

100

50

boiling
point (°C) 0

-50 open chain alkanes

cyclic alkanes
-100

-150

-200
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
number of carbon atoms in striaght chain or ring
The Variation of Melting Point of Alkanes with Size

50

-50

melting
point (°C)
-100

full trend

odd carbons
-150
even carbons

-200
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
number of carbon atoms in striaght chain
Synthesis of Alkanes and Alkyl Chains
many are sourced from the refinement of crude oil and are commercially
available - hence preparations not important for simple examples, but
of course more complex examples must be synthesised
hydrogenation of alkenes (reduction)

metal catalyst
C C + H H C C
solvent
H H

the alkene in a solvent, usually ethanol, with a finely-divided metal catalyst,


usually as a 5 to 10% Pt, Pd or Ni on powdered carbon or alumina
is stirred in a hydrogen atmosphere
hydrogenation of alkynes (reduction)
similarly alkynes can be hydrogenated to alkanes

2x H H
metal catalyst
C C + H H C C
solvent
H H

the above are useful synthetic routes because alkenes and alkynes are
more readily synthesised from a wide range of functional groups than are
alkanes directly (rare)
examples
Pt, ethanol
(a)
25 °C

F F
PtO2 , ethanol
(b) Br C C C3H7 Br C5H11
25 °C

in many cases the choice of catalyst is important, for example, Pt tends to


reduce aromatic rings, and in (b) above Pd would reduce out the Br - hence
PtO2 is an excellent choice for (b) but is a bit expensive! Nickel is cheaper,
and is used in industry for most systems, but high pressure is required.
alkanes can also be prepared through the reduction of alkyl halides, the
decarboxylation of carboxylic acids, the reduction of aldehydes and ketones,
and through organometallic coupling reactions

you will really need to appreciate a wider range of functional groups and
have experience of organic synthesis to appreciate fully the significance
of the synthesis of alkanes
Chemical Properties of Alkanes

alkanes are the most simple organic compounds, they contain only
carbon and hydrogen (hydrocarbons) in a fully-saturated structure
can be sub-divided into two distinct types:-
open-chain - general formula Cn H2n+2
cyclic - general formula CnH 2n

non-polar, no obvious sites for reactivity, and in fact they are relatively
unreactive - known as parafins, which means 'little reactivity'!!
but alkanes do react, violently with oxygen! - quite a useful reaction really!
alkanes also react with fluorine, chlorine and bromine
since C-C and C-H bond are little polarised when the bonds break they
do so with an electron going to each unit - homolytic fission

chlorination of methane
H H
H C H + Cl Cl H C Cl + H Cl
H H
methane chloromethane
the reaction will also produce polychlorinated products, CH2 Cl2 ,
CHCl3 and CCl4 to give a mixture

occurs by a mechanism that involves radical intermediates

UV light at 20 °C initiation
Cl Cl Cl + Cl ΔH = +58 kcal mol–1
or 250 °C in dark

requires 58 kcal mol–1 (quite a lot) of energy

can be done at 150 °C in the presence of PbEt 4


150 °C in dark
PbEt4 Pb + 4Et

Et Cl Cl Et Cl + Cl

why does initiation not involve H3C H H3C + H ?

needs 104 kcal mol–1 which is too much energy


the next steps of the reaction are propagation

H3C H Cl H3C + H Cl ΔH = +1 kcal mol–1

propagation

H3C Cl Cl H3C Cl + Cl ΔH = –25.5 kcal mol–1

breaking the bonds takes 104 + 58 = 162 kcal mol–1


forming the bonds gives 103 + 83.5 = 186.5 kcal mol–1
overall exothermic reaction = –24.5 kcal mol –1
even though the reaction is exothermic overall, bonds must be broken
before new ones are formed - hence energy is required for the process
to occur - activation energy - the potential enegy diagram is shown below

PE

reaction coordinate

termination can occur in three ways, no bonds are broken, so no


activation energy is involved and they are highly exothermic

H3C Cl H3C Cl ΔH = –83.5 kcal mol–1

termination
H3C CH3 H3C CH3 ΔH = –88 kcal mol–1

Cl Cl Cl Cl ΔH = –58 kcal mol–1


other important aspects of halogenation of alkanes

oxygen inhibits the reaction because it mops up radicals

removes methyl
H3C O O H3C O O radicals

what about other halogens?

relative rates violent F 2 > Cl2 > Br2 > I2 no reaction why?

on initiation grounds we would expect the reverse because the


I-I bond is much weaker than the F-F bond - but as we saw earlier,
it is the activation energy of propagation that is important -
F = 1.2, Cl = 3.8, Br = 18.6, I = 33.5 (kcal mol–1)
what about other alkanes?
the alkane is involved in the propagation step and so the lower
the bond dissociation energy (BDE) then the faster the reaction

104 H3C 98 H3C 94.5 H3C 91


H3C H H C H H C H H3C C H
H H3C H3C

the reason for the BDE is that tertiary (3°) radicals are more stable
than 2°, which are more stable than 1° because of the inductive effects
of the attached alkyl groups which make up for the low electron density
H3C H3C H3C
H3C H C H C H3C C
H H3C H3C
methyl (1°) ethyl (1°) isopropyl (2°) tert-butyl (3°)

least stable - slowest reaction most stable - fastest reaction

hence halogenation occurs more readily at a tertiary site, but in the case
of chlorination which is relatively fast mixtures of products are still
obtained - however, bromination is slower and more selective - hence -
H3C Br2 H3C
H3C C H H3C C Br >99% selectivity
127 °C light
H3C H3C
more on radicals
experimental evidence shows that the carbon of a radical is
sp2 hybridised - hence a planar structure with one electron
in the p orbital
such a structure has important implications in reactions where
stereoselectivity is an issue
allyl and benzyl radicals
radicals are electron defficient and anything that supplies electron
density or spreads the electron defficiency over more atoms will
stabilise the radical - we have already seen how inductive effects
can stabilise radicals - 3° radical are more stable
however, in some systems mesomeric effects can operate that can
spread the charge over more atoms creating cannonical structures -
structures that are not real but which contribute to the real structure -
such a situation stabilises the radical - the more cannonical forms that
can be drawn the greater the stability - but in many cases not all
cannonical forms contribute equally
H
H note the
H arrow H H the true structure is
H
a resonance hybrid
H H H H of both contributors
this structure is not this is also not the
the true structure true structure

H 1
/2 where the radical electron is
H H shared by two atoms and the
1
/2
two pi electrons are spread over
H
two bonds - stabilised structure
H

so at first glance you may think the allyl radical is primary (1°) - and it is -
but it is allylic - special and relatively stable
H H H H H H H H H H

δ
H H
similarly, the benzyl radical is not
simply primary (1°) but stabilised true
by resonance - more stable than δ δ
structure
allyl because of more contributors
δ
other chemical properties of alkanes

autoxidation
a process that generates peroxyl radicals from allylic and benzylic alkanes
in the case of polyunsaturated fats in the body, the peroxyl radicals can
cause tissue damage - radical traps (vitamin E) prevent this

H HH H H HH H
+ H Z
R C R' R C R'

H H H

Z
H HH H H HH H
O O O O
R C R' R C R'
H H

autoxidation is exploited in the synthesis of both propanone and


phenol from cumene

Me H Me Me H
Me H Me O
O
H H
+

cumene
only one 3° H OH
also benzylic
Me
O +
Me

cracking and reforming


the breaking of C-C bonds on large alkanes to form smaller units
C-C BDE = ~85 kcal mol–1 C-H BDE = ~100 kcal mol–1

combustion
the reaction of alkanes with oxygen involves a complex series of
radical chain reactions
Physical Properties of Alkenes

not much different to alkanes really, they are slightly more polar and so they
are a bit more soluble in water, but still classed as insoluble in water -
soluble in organic solvents
alkenes are less dense than water, hence petroleum floats on water
alkenes are non-polar, hence only weak van der Waals intermolecular
forces of attaction operate (through induced temporary dipoles)
hence low melting points and boiling points
Relative Stabilities of Alkenes
sounds obvious, but some alkenes are more stable than others, so
where more than one alkene is possible in a chemical reaction a
distribution of products is often obtained that depends upon stability -
normally the most stable alkene will predominate, however, there are
exceptions where a lesser stable alkene predominates

enthalpy of hydrogenation can be used as a measure of stability, but


only if each alkene gives the same product
Et H
Pt
+ H2 butane ΔH = –30.3 kcal mol–1
H H
Me Me
Pt
+ H2 butane ΔH = –28.6 kcal mol–1
H H

Me H
Pt
+ H2 butane ΔH = –27.6 kcal mol–1
H Me

the strain cause by the crowding of the two Me groups of the cis alkene
makes it less stable than the trans alkene, however, both are more stable
than but-1-ene because they are more substituted

hydrogenation of 2-methylpropene does not give


the same product as the above (butane), so for H Me
relative comparision here we must use the
enthalpies of combustion because this does
H Me
give the same products, and we find that
2-methylpropene is the most stable of the four alkenes
in summary, the more substituted the alkene, the more stable it is -
Zaitsev's Rule - but there are exceptions
Synthesis of Alkenes

we need to generate an unsaturated system - a C=C double bond -


hence we usually prepare alkenes by elimination reactions - where
for example H2 O, HCl, HBr, Br2 is eliminated
Dehydration of Alcohols
mechanism - acid-catalysed elimination

H
H3C H H H3C O H
O H C O
C O H H H H
H C
C
H H H H H
H water leaves as a stable,
neutral molecule to provide
a carbocation - in this case
protonation of the alcohol
a secondary one (2°) -
generates a good leaving group
more stable than 1°
H3C
H H H3C H C
H O
O H C H H
H H H H H
regenerated alkene
water then acts as a base by
abstracting a neighbouring
proton to generate an alkene
conditions - vary according to the alcohol
primary are the slowest and so require stronger acids and higher temperatures -
why? - because the carbocation intermediate is primary (1°) and hence least stable -
hence use concentrated sulphuric acid at 180 °C
secondary (as above) react via a more stable 2° carbocation and so less
concentrated sulphuric acid can be used - often phosphoric acid (milder) is used
at 165 °C because it causes less side products and charring
tertiary, allylic and benzylic alcohols dehydrate under very mild conditions,
in fact preventing elimination is sometimes difficult!! - so 20% sulphuric acid
can be used - reason? - these carbocations are more stable and in the case
of allylic and benzylic the product is stabilised by conjugated diene structure

a mild dehydrating
H agent - e.g., P2O 5
H3C H
(phosphorus
OH
pentoxide) 25 °C
2° benzylic alcohol H H

particularly stable alkene due


to extended conjugation
many alcohols give more than one alkene on dehydration - to explain why we
need to look at the mechanism of the reaction
we have seen that carbocations are involved in the reaction mechanism, and we
know that 1° are less stable than 2° which are less stable than 3° and sometimes
less stable carbocations can rearrange to generate more stable carbocations,
which results in unexpected alkene products
CH3CH 2CH2CH2OH might expect CH3CH 2CH=CH2 but NO
mechanism, as you will recall, produces a carbocation, in this case a
primary (1°) one, but a 2° is much more stable and so rearrangement occurs

H
H H H
hydride shift
H3C C C C H H3C C C C H
H H H
H H H

H2O H2O H2O

CH3CH 2 H H3C H H3C CH3

H H H CH3 H H
minor product -
major product as a mixture of cis and trans
can come through
isomers - trans predominates
two routes
in this case a 2° carbocation rearranges to a 3° for increased stability
H3C
H methanide shift H3C H
H3C C C C H H3C C C C H
H C H H H
H H C H
H H
H2O H
H CH3 H2O
H3C CH3

H CH3 minor product


despite a H3C CH3
H3C H 80%
6:1 proton
20% advantage major product despite only one
possible proton to give the product
the shift to form the more stable carbocation usually occurs completely so
virtually no product results from the less stable carbocation, when it comes
to the loss of a proton to generate the alkene product, the position is less
certain and a mixture of products results

in general, the more substituted alkene is the more stable and hence
the predominant product - Zaitsev's rule
other methods of alkene formation
1 an interesting method of alkene formation that avoids any rearrangement is
called the Tschugaev method
RCH2CH2OH RCH=CH2 in high yield

Na – CH3SH
– S C O
RCH2CH2O
H H
CS2
H
CH3I R O
RCH2CH2 C S
H C
S S
S
CH3
2 dehydrohalogenation
RCH=CH2
covered in detail in
RCH2CH2Br EtO semester two
RCH2CH2OEt

1° RBr ether is main product


2° RBr alkene is main product
ethoxide is a base and a nucleophile - as a base it abstracts a beta proton
and the bromo is expelled to give an alkene

3 partial reduction of alkynes


a H3C H
Na / NH3 (liquid)
H3C C C CH3 trans-but-2-ene
H CH3
called a dissolving metal reduction - the Hs approach from opposite sides (anti)
which gives the more stable trans isomer
b
H2 / Pd-on-CaCO3 H3C CH3
H3C C C CH3 cis-but-2-ene
quinoline
H H
the palladium catalyst is poisoned with quinoline to prevent further
hydrogenation to butane
the reaction occurs at the surface of the metal where the hydrogen is
absorbed - the alkyne approaches and the hydrogen adds from the
same side (syn) which gives a cis alkene

4 debromination of a vicinal dibromide


Br
Zn dust

Br
Chemical Properties of Alkenes

what makes alkenes reactive? afterall they are simply hydrocarbons


and what type of reaction do they undergo
well, the π electrons of the double bond are available for bond formation -
hence species that are electron defficient (electrophiles) react with alkenes
which behave as nucleophiles
overall electrophiles react and the net result is addition across the double bond -
hence electrophilic addition
examples of electrophiles

H–Cl, H–Br, H–I, H–OSO3H, H–OH, Cl–Cl, Br–Br

H H H Br
H–Br
H H
H H H H
in this simple case both carbon atoms are the same and hence the
structure of the product is obvious - but what happens with propene?

H3C H H3C H H3C Br


H–Br
H H H H
H H Br H H H
a 100% b not formed
to explain such reactivity we need to consider the mechanism of the reaction

H3C H H3C H H3C


slow
H H H H
H H RDS
H H H
δ+ δ− Br 1° - less stable
H Br not formed

the carbocation is sp2 hybridised fast


so planar and hence Br– can add
from either side equally H3C H
H H
Br H

such an addition occurs according to Markovnikov's rule - which states that


the hydrogen adds to the carbon with the most hydrogens already present,
the rule aids memory, but remember the reaction occurs through the most
stable carbocation (3° most stable, 1° least stable)
free energy diagram

δ+ δ+
CH3CH CH2 H δ+
CH3CHCH3
free δ−
energy Br

CH3CHCH3

Br

CH3CH CH2
H–Br

CH3CHBrCH3

reaction coordinate

the energy from starting materials to the transition state (TS1) is the activation
energy, the transition state as drawn is from H+ reacting not actually HBr - this
is the rate determining step - the intermediate carbocation is stabilised by
solvation and the transition state (TS2) represents a half way house between
the carbocation and the product which lies at lowest energy

δ+ δ−
CH3CH CH2 H Br actual transition state if H–Br reacting species

the whole energy profile for the route via the 1° carbocation is much higher and
so does not occur - in some systems a lower energy profile may be possible by
a rearrangement of the carbon skeleton to generate a more stable carbocation -
see previous notes on preparation of alkenes

3° CH 2° CH 1° H 1° H
3 3

H3C CH3 H3C H H3C H H H

3 inductive effects only 1 inductive special 1° case


help diminish the effect - more with no inductive
positive charge positive charge effects most unstable
hence most stable less stable

see also the account of radical stability


more on carbocations - see also account of radical stability
experimental evidence shows that the carbon of a carbocation is
sp2 hybridised - hence a planar structure with an empty p orbital
such a structure has important implications in reactions where
stereoselectivity is an issue
allyl and benzyl carbocations
carbocations are electron defficient and anything that supplies
electron density or spreads the electron defficiency over more
atoms will stabilise the carbocation - we have already seen how
inductive effects can stabilise carbocations - 3° are more stable
however, in some systems mesomeric effects can operate that can
spread the charge over more atoms creating cannonical structures -
structures that are not real but which contribute to the real structure -
such a situation stabilises the carbocation - the more cannonical forms
that can be drawn the greater the stability - but in many cases
not all cannonical forms contribute equally
H
H note the
H arrow H H the true structure is
H
a resonance hybrid
H H H H of both contributors
this structure is not this is also not the
the true structure true structure

H 1
/2 where the positive charge is
H H shared by two atoms and the
1
/2
two pi electrons are spread over
H
two bonds - stabilised structure
H

so at first glance you may think the allyl carbocation is primary (1°) -
and it is - but it is allylic - special and relatively stable
H H H H H H H H H H

δ
H H
similarly, the benzyl carbocation is
not simply primary (1°) but stabilised true
by resonance - more stable than δ δ structure
allyl because of more contributors
δ
Addition of Halogens to Alkenes

rate F 2 > Cl2 > Br2 >> I2


violent unreactive
why do halogens react? afterall they are non-polar! - well the
halogen becomes polarised as it approaches the alkene -
occurs fastest in a polar solvent - yields are very high 95%+

H3C H H3C Br
Br–Br
H H
H H Br H

so which carbon does the first Br end up on and which carbon


does the second Br end up on?? - does not really matter because
the product would be the same anyway - but to prove we need to
consider the reaction mechanism
the mechanism is really very similar to that for H–Br addition - but
a full carbocartion is not formed - a cyclic bromonium ion is formed -
restricted rotation allows a stereospecific reaction

a bromonium ion
Br
H3C H H3C Br
slow fast
H H
RDS
H H H3C H H H Br H
δ+ Br
Br note - we do not always
δ− Br show all the lone pairs!!

the Br– adds to the more substituted carbon because there is some
carbocation character and the greater positive charge is more stable
on 2° than 1° - hence Markovnikov's rule is followed

the Br– adds from the opposite side of the molecule to the first
Br due to steric hindrance and polar repulsion - anti addition

the fact that the Br– adds from the opposite side of the molecule to the first Br
makes no difference to the product above because there is free rotation - but
in cyclohexene this stereospecific reaction give trans-1,2-dibromocyclohexane

H
Br–Br
Br trans-1,2-dibromocyclohexane
(as a racemic mixture)
Br
H
stereochemistry is covered fully in year 2
Halohydrin Formation - and Analogues

if halogenation is carried out with a large excess of another nucleophile present -


(other than Br–) then the major product may incorporate that nucleophilic species
for example, if bromination is carried out in aqueous solution a large excess of
water will be present and react at the second step of the mechanism

H3C Br H3C Br
H3C H Br–Br
H H H H
H
H H O HO H Br H
H a b
compound b is formed through the mechanisim given previously - but compound a
dominates because water is present in vast excess - the mechanism is identical for
the first step, but in the second step a protonated halohydrin is formed - a third step
removes the proton to give compound a

a bromonium ion
Br
H3C H H3C Br
slow fast
H H
RDS
H H H3C H H H O H
δ+ Br H
H
H
O H
δ− Br
H O
H
H3C Br fast
a bromohydrin H H
(1-bromopropan-2-ol)
HO H
a
H3C Br
other analogues are common, for example, if sodium
chloride is present in the aqueous solution we could H H
get a sizable quantity of compound c as well as a and b,
the product distribution depends on concentration Cl H
c
H3C Br
similarly, if the reaction was carried out in methanol as
H H
the solvent, compound d would be the major product,
although a little compound b would still be formed MeO H
d
Some other Important Reactions involving Alkenes
preparation of alcohols - Markovnikov addition

H3C H H3C H H3C H


slow fast
H H H
RDS
H H H H HO3SO H
cold
H OSO3H OSO3H
H–O–H
heat
H3C H

propan-2-ol H H
HO H
on a large industrial scale sulphuric or phosphoric acid is used to catalyse the
addition of water across the double bond to generate alcohols - but the big
problem is the rearrangement of some carbocations
H3C
H3C H3C H3C
H
H3C H slow H3C H
H O H H
H H RDS
H H
2° carbocation - a 3° would be
more stable - and a 3° can be
generated by a methyl migration
H H
O H fast
H
O
O H fast H
H3C H3C
CH3 H CH3 H
H3C H3C
H H
H H H H
fast
H 3° carbocation
O
H3C
overall acid-catalysed addition of water CH3 H
H3C
H
H H
hydrogenation of alkenes
a very important reaction - see also preparation of alkanes and alkyl chains

H2 reaction is hetergeneous - occurs


at the metal surface and is a syn
catalyst addition - note mechanism is
H H not electrophilic addition!
preparation of alcohols - anti-Markovnikov addition

borane adds across a double bond as BH3 -


actually exists as diborane (B2H6) or more O
commonly is used as the adduct with tetrahydrofuran (THF)

note that boron is electron defficient H B H


H
the mechanism of addition across a C=C double bond involves a cyclic,
four-centre transition state and involves syn addition

H3C H H3C H H3C H


δ+

H H H H H H
H B H H B H H B H
δ−
H H H
the BH3 approaches the positive charge four-centre transition state -
with the methyl away lies on the more syn addition - leads to a
for steric reasons substituted carbon trans product - where possible
more stable

H3C H H3C H
H2O2
H H H H
H OH OH H B H
two more alkenes
propan-1-ol apparent H
can react here to
anti-Markovnikov addition
give R3B

in a cyclic alkene the stereospecificity can be shown

(i) BH3•THF
anti-Markovnikov product and
(ii) H2O 2, HO – trans stereochemistry
OH
of course, the other enantiomer of trans-2-methylcyclopentanol is equally produced -
but chiral hydroborating agents allow the formation of just one enantiomer -
invaluable in the synthesis of enantiomerically pure liquid crystals and drugs -
covered fully in advanced final year organic modules

hydroboration was discovered by Herbert Brown about 40 years ago - he was


a physical chemist who noticed that the grease on his glass taps hardened -
he found that it was borane gas saturating the double bonds in the grease - he
was awarded the Nobel Prize for chemistry in 1979
preparation of diols from alkenes
syn hydroxylation

H3C H H3C H H3C H


cold HO
H H H H
H2O
H H O O O O
H H
O O Mn
Mn O O propane-1,2-diol
O O

often the KMnO4 oxidises the diol by breaking the C-C bond O O
to give two carboxylic acids - osmium tetroxide is a much Os
better reagent but it is toxic and expensive!! O O

again need a cyclic system to illustrate stereochemistry

OH
(i) OsO4 cis-cyclohexane-1,2-diol -
shows stereospecificity
(ii) NaHSO3
OH

anti hydroxylation - via epoxides (oxiranes)


O
H3C H O H3C H
O H H H
+
H H MCPB O
Cl

the epoxide can be opened up by base (HO–) or by see text


water - the latter method requires prior protonation
of the cyclo-oxygen - but in each case the nucleophile H3C OH
approaches from the back of the epoxide to give H H
anti addition and gives a trans product where possible
HO H
mechanism will be covered in later courses

OH
(i) MCPB trans-cyclohexane-1,2-diol -
shows stereospecificity
(ii) see text
OH

epoxides are invaluable intermediates in organic synthesis - they can be opened


up by many nucleophiles to give a wide range of products
breakage of the C–C bond
ozonolysis
ozone is produced when oxygen is subjected to an electrical discharge

R1 R3 R1 O R3 R1 R3
O3
O + O
R 2
R 4 R 2 R4
R2 R4 O O
using oxidising conditions (H2O2)
gives ketones and/or carboxylic acids
using reducing conditions (zinc)
gives ketones and/or aldehydes

traditionally a useful procedure for determining the structure of complex alkenes -


breakage into two units makes procedure more simple - working backwards
reveals the original alkene structure

H3C CH2CH 3
reducing
conditions O + O
H3C CH2CH 3 H3C H

H3C H H3C CH2CH 3


oxidising
conditions O + O
H3C O H

(i) O3 O note that for cycloakenes only


O one product will result, but
(ii) H2O 2 there will be two carbonyls
H
O

hot permanganate (KMnO4)

compare with syn hydroxylation

H3C CH2CH 3 H3C CH2CH 3


KMnO4, HO–
O + O
H3C H heat O H
H3C

an identical result to
oxidative ozonolysis
Polymerisation of Alkenes

cationic polymerisation
H

H H2C CH H C CH H2C CH
R H R R

note the most stable carbocation H H H


is always formed and so on and so on
H C C C CH
H R H R

cationic polymerisation is not commonly used, but the conditions are used
in a dimerisation reaction that produces isooctane (high grade petrol)
60% H2SO4 at 70 °C

H3C H3C H
H3C H
C C H H3C C C C
H3C H H3C H3C H

H
H
CH2 H2O
H3C C C H
a
C CH3
20% H3C H3C H CH2
H3C H3C C C C
CH3
H
H3C
H3C H H
C
H H2O
b H3C C C C
80% CH3
H3C H
surprisingly, b is favoured despite it being the less substituted alkene - but it is
less sterically hindered and there are 9 protons to 2 protons and they are easier
for H2O to abstract

H2
Ni in any case hydrogenation of the mixture
gives the same product isooctane or
H3C H H 2,2,4-trimethylpentane (highest grade petrol)
H3C C C C CH3
H3C H CH3
radical polymerisation
very important in the commercial preparation of many polymers
reaction is initiated by a compound that easily generates free radicals,
for example benzoyl peroxide - Rad = Ph
O O
light
O Rad or C Rad + CO2
Rad O mild Rad O

O heat

H H H H
Rad H2C CH Rad C CH H2C CH H C C C CH
R H R R H R H R
and so on and so on
note the most stable radical is
always formed - see earlier notes

examples of alkenes that provide common polymers


H H H CH3 H Cl H CN H Ph

H H H H H H H H H H
poly(ethylene) poly(propylene) poly(vinylchloride) poly(acrylonitrile) poly(styrene)
polythene PVC orlon or acrilan
H CO2CH3 H O2CCH3 F F

H CH3 H H F F
poly(methyl methacrylate) poly(vinyl acetate) poly(tetrafluoroethylene)
perspex PTFE or teflon
all the above alkenes generate important polymers that have a variety of
different properties and are used in various plastics applications

anionic polymerisation
not often used - only applicable to alkenes with strong electron-withdrawing groups -
one particular use is in superglue - formation of poly(methyl α-cyanoacrylate)

H CO2CH3 H CO2CH3 H CO2CH3


A A
H CN H CN H CN

the two strong electron withdrawing


groups stabilise the carbanion

traces of moisture allow polymerisation - skin is very easily bonded!!!


Radical Reactions of Alkenes
in addition to free radical polymerisation of alkenes, alkenes also react
with H-Br and Br-Br through free radical mechanisms to give different
products to those in the absence of free radicals
addition of H-Br
in 1933 Kharasch and Mayo found that in the presence of free radicals, H-Br
added to an alkene in an anti-Markovnikov manner
light or
R O O R R O H Br R OH + Br
heat
note that H• is not formed - very unstable

H CH3 H CH3

Br Br H Br
H H H H

in this mechanism it is the Br that adds


first to generate the most stable radical H CH3
and then in effect the H adds last to Br H + Br
give the anti-Markovnikov product
H H

substitution with Br-Br


normally the reaction between Br-Br and alkenes is one of addition - but
in presence of peroxides - and if there is an allylic hydrogen present in the
alkene - then substitution occurs - not addition

need to use either:- (i) Br-Br (or Cl-Cl) at very high temperature (500 °C) or (ii) a specialist
reagent such as N-bromosuccinimide (NBS) or the chloro analogue
O O
best method
Br Br Br or NBS N Br N + Br

O O

H H H H + H-Br
H H
H C H Br H C
H C Br
Br X
H H H H
H H
resonance stabilised
radical - very stable a substitution
product - an
see earlier notes allyl bromide
Physical Properties of Alkynes

not much different to alkanes and alkenes, they are slightly more polar -
are a bit more soluble in water, but are still classed as insoluble in water -
soluble in organic solvents
alkynes are less dense than water, hence petroleum floats on water
alkynes are non-polar, hence only weak van der Waals intermolecular
forces of attaction operate (through induced temporary dipoles)
hence low melting points and boiling points
a very important physical property of terminal alkynes is their
acidity - and of course this affects chemical properties
terminal alkynes are only relatively acidic - much more acidic than the
protons in alkenes and alkanes but much less acidic than the protons
of carboxylic acids - the lower the pKa the stronger the acid

O R H H
R C R O R C C H H2 N H C C R C H
O H H H H H
pKa 4.8 15.9 25 38 44 50

bond length bond dissociation energy


alkynes have
C C 1.20 Å 198 Kcal mol–1
shorter and
stronger carbon
C C 1.33 Å 163 Kcal mol–1 carbon bonds
than alkenes
C C 1.54 Å 88 Kcal mol–1 and alkanes

the sp hybridised acetylenic carbon holds the bonding electrons more


tightly so it is more difficult to break the C-H bond homolytically - but
it is easier to break heterolytically, with both electrons from the bond
going to the acetylenic carbon

H
N
R C C H H
R C C
maybe acidic but H
still requires a very very important in
strong base, e.g.,
C (CH2)2 CH3 organic synthesis
sodium amide or H
n-butyllithium
Synthesis of Alkynes

we need to generate an unsaturated system - a C≡C triple bond -


hence we usually prepare alkenes by elimination reactions - where
for example H2 O, HCl, HBr, Br2 is eliminated

R H H H
Br Br NH2
R R' R R'
H R' Br Br

O H
Cl Cl
C
PCl5 NH2 C
CH3 CH3

in organic synthesis the best synthesis of alkynes is from other alkynes -


by exploiting the acidic proton of terminal alkynes - additionally
palladium-catalysed cross-coupling reactions are very useful - see
chemical properties section for others

(i) nBuLi, THF


C5H11 C C H C5H11 C C ZnCl
(ii) ZnCl2, THF
F
Pd(PPh3)4
I Br
a one-pot reaction
F
a reaction developed an important intermediate
by Hird (1987) C5H11 C C Br
in liquid crystal synthesis

ethyne (acetylene) can be made from calcium carbide

CaC2 + H2O H C C H + CaO


Chemical Properties of Alkynes

the chemical properties of alkynes are somewhat similar to those of alkenes -


they are unsaturated systems and hence they undergo addition reactions - but
pi electrons are held more tightly (sp) hence less reactive than alkenes so it is
difficult to prevent further addition - but it can be done
H3C H
HBr
CH3 C C H follows Markovnikov's
rule
Br H
H3C Cl H3C H
Cl-Cl
CH3 C C H +
Cl H Cl Cl
the chlorination and bromination is anti addition only a little
and hence gives the trans product

the preparation of bromoalkenes from alkynes is made easy using


a more specialist reagent (acetyl bromide) that generates H-Br in situ

O
H3C C
Br H
Br
C5H11 C C H 82% yield
alumina
C5H11 H

hydration of the triple bond occurs in the presence of mercury salts - in


some systems concentrated sulphuric acid alone is sufficient - to give enols
which do not really exist as such and tautomerise to give ketones

HO H O
HgSO4 rapid
C5H11 C C H
H2O C5H11 CH3
tautomerisation
C5H11 H

follows Markovnikov's rule

ethyne is used to make many polymerisable alkenes of great importance

H H polymerisation
HCN acrilan
H C C H
CuCN
H CN
acrylonitrile
H H polymerisation
HCl poly(vinyl chloride)
H C C H (PVC)
H Cl
reactions that exploit the acidity of alkynes

H
NH2 Na
H C C H H C C Cδ+ I H C C CH3 84% yield
liquid NH3 H δ−
H
nBu
nBuLi in THF can also
H
be used as the base
I C C C CH3
H
CH3

79% yield CH3CH 2 C C CH3

acetylenic anions will attack a wide range of electrophiles

carbonyl compounds - for example aldehydes

O δ−
H3C C C H H3C C C
H3C C δ+
H
nBu

H3C H3C

H3C C C C OH H3C C C C O

H H
87% yield

carbon dioxide

nBuLi, THF
RO C C H RO C C

O C O

solid carbon dioxide


H
a propiolate acid - used in the
O
synthesis of twist-grain-boundary
95% yield
liquid crystals - discovered by RO C C C
Goodby (1987) O H
Revision Exercises - Questions to Expect in the Examination
1. Acid-catalysed dehydration of 3,3-dimethylbutan-2-ol gives a mixture of
2,3-dimethylbut-2-ene (66%), 2,3-dimethylbut-1-ene (31%) and 3,3-dimethylbut-1-ene (3%). Use
reaction mechanisms to explain.
(8 marks)
2. Comment on the relative stabilities of cyclopropane, cyclobutane, cyclopentane, and cyclohexane.
(5 marks)
3. When the bromination of propene is carried out using bromine in water,
1,2-dibromopropane is only the minor product. Use reaction mechanisms to explain, and hence give the
structure and the IUPAC name of the major product.
(5 marks)
4. Propose a mechanism to account for the following reaction. As usual, you should show the structure(s) of
all intermediates and use curly arrows to indicate the flow of electrons in each step.
Cl

+ HCl

(6 marks)
5. (i) Draw the structure of compound X, and give the mechanism for its formation.
(ii) Give all necessary reagents at Y.
OH
CH3 85% phosphoric acid Y
X CH3
OH 150 °C
(6 marks)
6. Draw the structure of compound X, and give the mechanism for its formation.

+ HBr X
(4 marks)
7. When 4-penten-1ol is treated with bromine in a large volume of water, the expected bromohydrin is not
formed, and the product is a cyclic bromo ether. Use reaction mechanisms to explain.
(6 marks)
8. When 2-methylpropane is treated with bromine in the presence of light at 127 °C a single product is
formed. Give the mechanism of this bromination reaction, and explain why a single product is formed.
(5 marks)
9. Why are terminal alkynes described as being acidic. Give an example of a base capable of removing the
terminal proton of a terminal alkyne, and show curly arrows to illustrate the movement of electrons.
(4 marks)
10. Show the mechanism of the reaction of cyclohexene with bromine at 500 °C (or
N-bromosuccinimide).
(4 marks)
11. Draw the structure of compound X, and give the reaction mechanism.

H HBr
X
peroxides
(ROOR)
(5 marks)
Revision Exercises - Questions to Expect in the Examination

(a) Give the IUPAC names for each of the following compounds (A-D).

H H H
H
CH3 CH3 H H
A H H
B C D
(5 marks)

(b) Draw structure E and indicate the hybridisation state of each carbon.

CN

CH3 C C CO2H E

(4 marks)

(c) By use of mechanisms, distinguish between homolytic and heterolytic bond fission.
(3 marks)

(d) Give the mechanism for the photochlorination of methylbenzene (toluene) to (chloromethyl)benzene.
Name the type of intermediate involved in the reaction and explain clearly why it is relatively stable.
(6 marks)

(e) Explain briefly why alkanes fail to react with iodine.


(2 marks)

(f) Place ethane, ethene and ethyne in order of increasing carbon-carbon bond length and give a brief reason
for your answer.
(2 marks)

(g) Explain briefly why compound F has a relatively high melting point and a relatively low boiling point.

H3 C H3 C CH3

C C F
H3 C
H3 C CH3
(3 marks)
Revision Exercises - Questions to Expect in the Examination

(a) Give reaction mechanisms and brief explanations to account for the two products (B and C) obtained
from the dehydration of alcohol A. Explain briefly why alkene B is the major product.

H3 C H3 C H H3 CCH2 H
conc. H2SO 4
H3 C C CH2 OH C C + C C
heat
H3 C H3 C CH3 H3 C H

A B C

(9 marks)

(b) Give reagents or products (a-g) as necessary to complete the following equations.

Na / NH 3
H3 C C C CH3 a

(i) Na, (ii) CS2


CH2 CH2 OH b
(iii) CH3 I, (iv) heat

H3 C H
HBr
C C c
polar solvent
H H

H3 CCH2 H d CH3 CH2 CH2 CH2 OH


C C
e
H H
CH3 CH2 CH(OH)CH3

f g
CH3 (CH2)2 C C H CH3 (CH2)2 C C CH3 (CH2)2 C C CH3

(9 marks)

(c) When propene is reacted with bromine water, two bromine-containing products are formed. With the aid
of mechanisms explain the formation of the two products and hence draw their structures.
(5 marks)

(d) Explain briefly why pent-1-yne is a stronger acid than pent-1-ene


(2 marks)
2. Answer all of the following parts. (06161 JANUARY 2001)

(a) Give a mechanism for the photochlorination of methylbenzene (toluene) to (chloromethyl)benzene.


Name the type of intermediate involved in the reaction and comment on its relative stability.
(7 marks)

(b) Give reaction mechanisms and brief explanations to account for the two products (B and C) obtained
from the reaction of alkene A with HBr. Give IUPAC names for products B and C, and state, with a
brief explanation, which is the major product.

H3 C H3 C H H3 C H
HBr
H3 C C CH CH2 H3 C C C CH3 + H3 C C C CH3
polar solvent
H3 C H3 C Br Br CH3
A B C

(10 marks)

(c) Give products (D-F) and reagents (a and b) to complete the following schemes.

H3 CCH2 H
KMnO4 H2 SO4 , H2 O
E C C D
NaOH
H H
Br2 in H 2O

a b
CH3 (CH2)2 C C H CH3 (CH2)2 C C CH3 (CH2)2 C C CH3

(6 marks)

(d) Give the structure of the product when cyclohexene reacts with either bromine at 500 °C or
with N-bromosuccinimide (NBS).
(2 marks)
06510 December 2003

2. Answer all of the following parts.

(a) Give IUPAC names for each of the following compounds (A-C).

CH3CH2 CH3
A B C
(3 marks)

(b) Draw the structures of (i) cis-1,2-dimethylcyclopentane, (ii) cis-but-2-ene, (iii) pent-1-yne.
(3 marks)

(c) For the reaction of methane with chlorine (see below), name (i) the type of mechanism, (ii) the type of
bond fission involved, and (iii) the general type of reactive intermediate involved.

UV light
CH4 + Cl2 CH3Cl + HCl
(3 marks)

(d) Draw the structure of the major product E. Give suitable reagents for a and b to complete the
reactions shown below.

HBr
E (major product)
acetic acid

D
a b
CH 3(CH 2)2 C C H CH 3(CH 2)2 C C CH 3(CH 2)2 C C CH3

(4 marks)

(e) Cyclohexylmethanol (F) dehydrates in the presence of 85% phosphoric acid to give
compound G as the major product (see below). Illustrate the mechanism of the
reaction and explain why compound G is the major product.

OH 85% phosphoric acid


G

F
(10 marks)

(f) Give the structure of the product when cyclohexene reacts with either bromine at
500 °C or with N-bromosuccinimide (NBS).
(2 marks)
06510 December 2004

2. Answer all of the following parts.

(a) Give IUPAC names for each of the following compounds (A-C).

CH3CH3
A B C
(3 marks)

(b) Draw the structures of (i) trans-1,2-dimethylcyclopentane, (ii) butan-2-ol, (iii) pent-2-yne.
(3 marks)

(c) For the reaction of methane with chlorine (see below), name (i) the type of mechanism, (ii) the type of
bond fission involved, and (iii) the general type of reactive intermediate involved.

UV light
CH4 + Cl2 CH3Cl + HCl
(3 marks)

(d) Draw the structures of the major organic products D-G, and give suitable reagents a and b to complete
the reactions shown below.

H2SO4, H2O
D
cold KMnO4
E
NaOH
H3CCH2 H
(i) BH3•THF
C C F
(ii) H2O2, NaOH
H H
Br2 in H2O
G

a b
CH3(CH2)2 C C H CH3(CH2)2 C C CH3(CH2)2 C C CH3

(6 marks)

(e) Cyclohexylethene (H) reacts with hydrogen bromide in acetic acid to give an alkyl bromide (I) as the
major product. Illustrate the mechanism of the reaction, draw the structure of product I and explain
why it is the major product.

HBr in acetic acid


I

H
(10 marks)