CHM185 Chemistry for

Engineering Students Revision

Organic Chemistry
Dr J Wilkie:
STRUCTURE AND BONDING (tick when completed)
-Simple representation of structure, line formulae
- Atomic and molecular orbitals shape and phase
- Covalent bonds
- Hybridisation,

bonds , bonding and antibonding orbitals

STEREOCHEMISTRY
- Isomers constitutional isomers, E/Z isomerism, stereoisomers, enantiomers,
diastereoisomers.
- Dotted line/wedge notation
- Chirality
- R and S descriptors
- Conformaion, staggered and eclipsed, axial and equatorial
- Newman projections

REACTIONS AND MECHANISMS

-

Curly Arrow/ Arrow pushing representations

Electrophiles, nucleophiles and radicals
Polarisation and electron distribution
Substitution reactions, SN1 and SN2
Eliminations E1 and E2
Carbon metal bond formation (Grignard Reagents)
Reactions with carbonyl compounds

ALKENES
- Geometrical Isomerism, cis and trans, Z/E-Descriptors
- Additions reactions (Hydration , reactions with halogens and hydrogen halides
, Hydroboration , Hydrogenation and Epoxidation
- Dienes: Addition reactions and Diels Alder reactions

ALKYNES
- Addition reactions
- Acidity

STRUCTURE AND BONDING

Hydrogen Atomic Orbitals
Each orbital contains a maximum of two electrons. These two electrons must
have opposite values for the spin, generally indicated by an up arrow or a down
arrow. When filled, the first shell (one 1s orbital) holds two electrons, the second
shell (one 2s and three 2p orbitals) holds eight electrons and the thirds shell (one
3s, three 3p orbitals, and five 3d orbitals) holds eighteen electrons.
- The Aufbau principle (aufbau means building up in german, extra points)
explains the order in which electrons fill the various orbitals in an atom. Filling
begins with the orbitals in the LOWEST ENERGY, or MOST STABLE shells, and
continues through the higher-energy shells, until the appropriate number of
shells is filled for each atom. Thus, the 1s orbitals fill first, then the 2s, followed
by the 2p and then the 3s.

Hunds rule says that each degenerate orbital 2p x, 2py and 2pz, must FIRST
RECEIVE ONE ELECTRON BEFORE ANY OF THE ORBITALS CAN RECEIVE A SECOND
ELECTRON

- Orbitals are described by quantum numbers these must be unique for each
orbital
An atomic orbital is defined by a unique set of three quantum numbers (n, l
and ml). A fourth quantum number ms gives information about the spin of an
electron in an orbital and specifies how many electrons can occupy that orbital.
>> Principal Quantum Number (n): n = 1,2,3

- This specifies the energy of an electron and the SIZE of the orbital. The
principal quantum number may have any positive integral value between 1 and
infinity. All orbitals that have the same value of n are said to be in the same
SHELL (level).
>> The Orbital, or Angular Momentum Quantum number (l)
- The quantum number l is called the orbital quantum number. For a given value
of the principal quantum number, the allowed values of l are positive integers
lying between 0 and (n-1). Therefore is n=3, the permitted values of l are
0,1 and 2. Each value of l corresponds to a particular type of atomic orbital. The
value of l provides information about the shape of the orbital and the angular
momentum of the electron within the orbital
n=1 l=0
n=2 l= 0,1
n=3 l = 0,1,2
n=4 l = 0,1,2,3,
>> The Magnetic Quantum Number (ml): ml = -l,.,0,.,+l
- The magnetic quantum number m1 relates to the directionality of an orbital and
has values which are integers between +l and l. If l=1, the allowed values m1
are -1, 0 and +1.
>> The Electron Spin Quantum Number (ms): ms = + or
- This specifies the orientation of the spin axis of an electron, up or down arrows.
No two electrons can have a set of identical quantum numbers. Each orbital
can accommodate two electrons, one of each and opposite spins.
Deriving quantum numbers and shit.
1) Derive possible sets of quantum numbers for n=2, and explain the
significance of these sets of numbers
- Let n=2
i) Remember that a value of n defines an energy or principal level.
ii) Possible values of l lie in the range of 0 to (n-1). Therefore for n=2, l = 0 and 1
iii) This means that the n=2 level gives rise to two sub levels, one with l=0 and
one with l=1
iv) Now determine the possible values of the quantum number m l. We know
values of ml lie in the range l0+l
The sub level l=0 has associated with it ONE value of m l
ml = 0 for l=0
The sub level l=1 has associated with it THREE values of m l
ml = -1, 0 or +1 for l=1
The possible sets of quantum numbers for n=2 are
N
2
2
2

L
0
1
1

ml
0
-1
0

2
1
+1
Total of 4 orbitals in second energy level, it can accommodate 8 electrons. 2 in
the 2s orbital and 6 in the 2p orbitals
- The physical meaning of these sets is that for the level n=2, there will be two
types or orbital (because there are two values of l). For l=1, there will be three
orbitals all of similar type but with different directionalities.

COMBINING ORBIALS TO MAKE BONDS

Orbitals can overlap in phase or out of phase. During bonding, wave functions
with the same sign overlap in an IN-PHASE OVERLAP, and wave functions with
opposite signs overlap in an OUT-OF-PHASE OVERLAP
In-phase overlap is a constructive, or bonding overlap of atomic orbitals. In this
overlap, the wave functions reinforce one another. This reinforcement increases
the probability of finding the electrons in the regions between the two nuclei. The
molecular orbital that results from an in-phase overlap is a BONDING
MOLECULAR ORBITAL.

This is a
representation of the 1s orbitals of two hydrogen atoms forming a bonding
molecular orbital. In a bonding molecular orbital two or more in-phase orbitals
overlap to form a bond
An out-of-phase overlap forms and ANTIBONDING MOLECULAR ORBITAL. With
an out-of phase overlap, a node develops between the two nuclei. For each
bonding molecular orbital that forms, an antibonding molecular orbital
also forms.

This is an OUTOF-PHASE overlap of the 1s orbitals of two hydrogen atoms forming an

ANTIBONDING MOLECULAR ORBITAL.
- Usually, an antibonding molecular orbital contains no electrons because it
DESTABILISES the bond. Generally, molecules in the lowest energy state have
empty antibonding orbitals.
- To illustrate this concept, we will look at the bond between two hydrogen atoms
in a H2 molecule. The 1s ATOMIC orbital of EACH HYDROGEN combines and
generates the two hydrogen-hydrogen MOLECULAR ORBITALS one bonding and
one antibonding.

The two molecular orbitals of a H2 molecule are generated by combining two 1s

atomic orbitals. One of the molecular orbitals is BONDING and is LOWER IN
ENERGY. The other is antibonding and is higher in energy. The arrows represent
the electrons involved in forming the bonding molecular orbital. Electrons prefer
to occupy the orbital with the LOWEST POSSIBLE energy state, both electrons
reside in the bonding molecular orbital of a hydrogen molecule.

HYBRIDISATION OF ATOMIC ORBITALS

HYBRID ORBITALS are spatially directed orbitals which may be used to produce
LOCALISED BONDS in a valence bond scheme, they are the individual orbitals
formed from hybridisation. The three types of orbital hybridisation are sp, sp 2,
sp3.

i) sp in sp hybridisation TWO orbitals are involved, one s and one p

ii) sp2 in sp2 hybridisation THREE orbitals are involved, one s and two p orbitals

iii) sp3 in sp3 hybridisation FOUR orbitals are involved, one s and three p orbitals
- Because hybridisation blends all the characteristics of the s and p orbitals, the
name of the new orbital indicates what PROPORTION of each orbital is like an s
orbital and what portion is like a p orbital. With sp 2 hybridisation each hybrid
orbital bears 33.3% of the s orbitals characteristics and 66.6% of the p orbitals
characteristics.
Another consideration with hybridisation is the shape of the hybridised orbitals.
The FOUR hybrid sp3 orbitals have a shape that is a combination of the s and p

orbital shapes, as illustrated below

- Similar to p orbitals, each sp 3 orbital (there are four of them) has two lobes, but
unlike the p orbitals they are of UNEQUAL size. This means that for each orbital
there is a greater electron density on one side of the nucleus than on the other.
This unsymmetrical electron density allows for greater overlap and the formation
of STRONGER BONDS than is possible with an unhybridised orbital.

PI AND SIGMA BONDS

- Using the illustrations above let us consider the hybridisation in ethane. Ethene
requires 3 hybrid orbitals (3 C-H bonds) so we combine 3 atomic orbitals (1 x s, 2
x p) so sp2 hybridisation.

What happens to the sp2-orbitals on the C atom? They overlap END-ON forming a
SIGMA BOND
And the p orbitals? They overlap SIDE-ON giving a PI BOND

A Double Bond consists of one SIGMA BOND and one PI BOND

Essentially
C bonded to 4tings(NOT C) = sp 3
C bonded to 3tings(NOT C) = sp 2
C bonded to 2tings(NOT C) = sp

LONE PAIRS
- Let us look at the oxygen atom in a carbonyl group
Carbon has hybridisation of sp2
Oxygen has:
1 x sigma bond hybrid
1 x pi bond p orbital
2 lone pairs hybrids.
Total of 3 hybrid orbitals on the oxygen, must be
sp2
What about the oxygen in furan?
- It also has two lone pairs
In furan the oxygen has:
2 x sigma bonds 2 hybrids
0 x pi bonds 0
2 x lone pairs 1 hybrid and 1 p-orbital
3 hybrids therefore must be a sp2 oxygen

Why are the different?

We can draw ALTERNATIVE BONDING PATTERNS that involve one of the lone pairs
in a pi bond

HYBRIDISATION RULES
1) sigma bonds are formed from HYBRID orbitals
2) pi bonds are formed from p-orbitals
3) lone pairs that can form pi bonds in alternative structures are in p and hybrid
orbitals
4) lone pairs that cannot form pi bonds in any alternative structure are in hybrid
orbitals
RESONANCE
- Alternative ways of drawing molecules that still satisfy the octet rule. The real
structure is an average of all the possible resonance structures. Some structures
may contribute more than others if they are MORE STABLE
RULES FOR RESONANCE STRUCTURES
-Only pi bonds and LONE PAIRS can move
-You CANNOT break sigma bonds
- The connectivity must not change.

ALKYLHALIDES: SUBSTITUTION AND ELIMINATION

REACTIONS
Alkylhalides:
- What are they?
-

Summary
Atomic Orbitals
- Determined for the hydrogen atom
-Level 1 has only 1 s-orbital
-Level 2 has 1 x s and 3 x p orbitals
Hybridisation
- Same number of hybrids out as atomic orbitals in
- Always use an s-orbital and however many o-orbitals
required
- sigma bonds ALWAYS hybrid, pi ALWAYS p-orbitals, lone
pairs either
Hybridisation and shape
- sp3 is TETRAHEDRAL
-sp2 is TRIGONAL PLANAR
- sp is LINEAR

How are they formed?

- Chemical reactions
- Reactivity of different alkylhalides
Reactions of alkylhalides
- SN2substitutions
-SN1 substitutions
- Factors that decide which substitution mechanism
- E2 elimination
- Factors that decide between elimination and substitution
- E1 elimination
- Factors that decide between elimination mechanisms

The general formula for an alkylhalide, otherwise known as a halogenoalkane,

is RX where R is an alkyl group and X is F, Cl, Br or I; the halogens.
Halogens have seven valence electrons. The halogens have very high
electronegativities and are very reactive, especially with the alkali metals.
FORMATION OF ALKYLHALIDES
Radical Halogenation.
- Simple nucleophillic substitution reaction involving the halogen anion acting as
a nucleophile

Addition to alkenes both symmetrical and unsymmetrical

Reactions of alkyhalides
- The halide ion is a good leaving group so it is easily substituted by nucleophiles.

Direct substitution in a single step: SN2

mechanism
- In an SN2 reaction, a new bond is formed between the nucleophile and the
carbon atom, while the carbon-halogen bond is broken. We call the chlorine the
leaving group. The species being attacked by the nucleophile is the electrophile.
- The term SN2 stands for Substitution Nucleophillic 2nd Order (also called
bimolecular). According to the SN2 mechanism, there is a single TRANSITION
STATE because bond-breaking and bond making occur SIMULTANEOUSLY for this
to occur, the nucleophile must approach from the backside of the carbon-leaving
group bond:

- Note that there is NO INTERMEDIATE in an S N2 reaction, just a TRANSITION

STATE. A transition state has no lifespan and is just the highest ENERGY POINT on
the reaction profile as starting materials transition into products
Rate Equation for SN2 reactions:

rate = k[R-X] [Nuc]

As you can see from the rate equation, rate depends on the CONCENTRATION
of both the nucleophile and the akylhalide. It is a BIMOLECULAR REACTION, one
which two reactant take part in the transition state of the SLOW RATEDETERMINING STEP of the reaction. Note: [ ] means concentration,
remember?

SUBSTITUTION IN TWO STEPS: SN1 MECHANISM

SN1 indicates a substitution, nucleophilic, unimolecular reaction, described by
the expression Rate = k [R Leaving Group]. This implies that the rate
determining step of the mechanism depends on the decomposition of a single
molecular species
SN1 is a multi-step process with the following characteristics: The carbonhalogen bond is broken first, and there is a SLOW loss of the leaving group

forming a HIGH ENERGY carbocation intermediate. Then there is a rapid of a

nucleophile on the electrophilic carbocation to form a new bond.

STEREOCHEMISTRY OF SN1 REACTIONS (do you know what stereochemistry

means yet?)
In an SN1 reaction, the nucleophile attacks the PLANAR carbocation. Since there
is an EQUAL PROBABILITY of attack on each face of the plane there will be a
LOSS OF STEREOCHEMISTRY at the reactive centre as both products will be
observed.

Because the mechanism goes through a carbocation, the leaving group must
be attached to either a tertiary or secondary carbon to stabilise the intermediate.
A methyl or primary leaving group will NOT form a carbocation

DECIDING
SN2 AND
- SN1
involves formation of a carbocation intermediate
- Stabalising the intermediate favours an Sn1 mechanism

BETWEEN
SN1
mechanism

WHY ARE TERTIARY CARBOCATIONS MORE STABLE?

- Alkyl groups are ELECTRON DONATING by induction. They push electrons away from
themselves. This means the alkyl group becomes slightly positive and the carbon they are
attached to becomes slightly negative. The alkyl group has a positive inductive effect:

- This spreads the positive charge over the entire molecule, rather than keeping
it on one atom. If the carbocation is primary there will only be one electrondonating alkyl group. If it is secondary, there will be two, tertiary there will be
three. The more electron donating groups present, the more stable the ion will
be.
LEAVING GROUPS

Halide X
F
Cl
Br
I
- Reactions are easier if we

C-X Bond strength

118
81
67
54
are breaking a C-I bond

pKa of HX
+3
-7
-9
-10

OH is a very bad leaving group, how can we make it leave?

We can

ask it politely, or simply change the CONDITIONS. We

can protonate the alcohol to make the leaving group water, so that we can then
substitute the OH for our choice of halogen

ELIMINATION REACTIONS
E2 REACTIONS
- The term E2 stands for elimination bimolecular. E2 eliminations, in contrast to
E1 mechanisms are PROMOTED BY A STRONG BASE. The base is VITAL to the
reaction; it is directly involved in the RATE-DETERMINING step. The reaction is
BIMOLECULAR because TWO MOLECULES must come together for the reaction to

occur. The mechanism of an E2 elimination is shown below:

E2 mecanism:
- Remember the base attacks the NEIGHBOROUGHING C-H bond and removes
the H at the SAME TIME the alkene double bond starts to form and the SAME
TIME the X group starts to leave. THREE ARROWS.
Rate = k[R-X][Base]
Stereochemistry Of Elimination reactions

- Elimination is antiperiplanar.
It is the staggered arrangement,
aligning two sigma bond that become the pi bond.
E1 REACTION MECHANISM

- E1 indicates an elimination unimolecular reaction, where rate = k[R-X]. This

implies that the rate determining step depends on the decomposition of a single
molecular species. Overall it is a multistep process with two critical steps:
1) The loss of a leaving group LG to generate a carbocation intermediate
2) The loss of a proton, H+ from the carbocation to form the pi bond

How Various Components Affect The Reaction Pathway

1) Reactivity order:
3 > 2 > 1
- In an e1 reaction the rate determining step is the loss of the leaving group to
form the intermediate carbocation. The more stable the carbocation is, the easier
it is to form, and the faster the e1 reaction will be
2) Leaving group
- The only event in the rate determining step of the e1 reaction is the breaking of
the C-LG bond. Therefore, there is a very strong dependence on the nature of the
leaving group. In the acid catalysed reactions of alcohols, the OH is protonated
to give an OXONIUM ION (any oxygen cation with three bonds), providing the
much better leaving group of water
3) Base
Since the base is NOT involved in the rate determining step, the nature of the
base is unimportant in an E1 reaction. However, the more reactive the base, THE
MORE LIKELY AN E2 REACTION BECOMES.
E1 or E2?
- E1 reactions usually favour the more STABLE alkene as the MAJOR product. E1
favours producing E over Z isomers.
The E1 pathway is most common with:
- GOOD LEAVING GROUPS
- MORE STABLE CARBOCATIONS

- VERY WEAK BASES

CHOOSING BETWEEM E2, SN2, AND E1/SN1

- How do we choose between elimination and substitution mechanisms and how
can we predict which is most likely?
Order Of Preference
E2

Requirements
i) strong base
ii) Moderate or better LEAVING GROUP
III) Antiperiplanar H-C-C-LG
S N2
i) NOT TERTIARY
ii) Good leaving group
iii) Good nucleophile
iv) Polar solvent
E1/SN1
i) STABLE carbocation
ii) Moderate or better leaving group
iii) Polar solvent
iv) hydrogen (for E1). Hydrogen bond
adjacent to the carbon bearing the
leaving group
Because E1 and SN1 share the same rate determining step and both involve
the production of a carbocation intermediate, it is generally understood than

reactions undergo both SN1 and E1 reactions simultaneously

GRINGARD REAGENTS
A Grignard reagent has the formula RMgX where X is a halogen and R is an alky
or aryl(based on a benzene ring) group.
- A typical gringard reagent might be CH 3CH2MgBr
The Preparation Of A Grignard reagent
Grignard reagents are made by adding the AKLHALIDE or halegenoalkane to
SMALL BITS OF MAGNESIUM in a flask containing ethoxyethane.
Bromoethane + Magnesium

Ehylmagnesium Bromide

- Everything must be kept perfectly dry and in ANHYDROUS CONDITIONS

because Gringard reagents react with water to produce alkanes

Grignard reagents are very STONG BASES. One of their most common uses is in
their reaction wih aldehydes and ketones to form ALCOHOLS.

ISOMERISM AND STEREOCHEMISTRY

Isomers
Isomers are molecules with the SAME FORMULA but different structures. It is
important to realise isomers can have different chemical, physical and biological
properties.

Constitutional Isomers
Constitutional isomers have different atoms connected to different things, they
have the same structural formula though. They are also called STRUCTURAL
ISOMERS.
Example Compare ethers(where two hydrocarbon groups are linked by an
oxygen atom, ROR)with alcohols

- They have DIFFERENT CHEMICAL PROPERTIES

i.e. alcohol can be oxidised (e.g. carboxylic acids) but ethers cannot be oxidised.
- They have DIFFERENT PHYSICAL PROPERIES
i.e. ethers are non-polar solvent and alcohols are polar solvents
- They can have the same functional groups but in DIFFERENT PLACES. This
would mean that they would have similar chemical properties. Like undergo the
same reaction but the rate may be different. Sometimes the reaction may even
be different.

Stereoisomers
- Stereoisomers have the same STRUCTURAL FORMULA AND CONNECTIVITIES,
but the structures CANNOT BE SUPERIMPOSED UPON ONE ANOTHER
They have the SAME CHEMICAL PROPERTIES They undergo the same
reactions mostly with identical rates. But they have DIFFERENT PHYSICAL
PROPERTIES for instance they have different MELTING AND BOILING POINTS,
fluidity etc.
Geometric Isomers
Geometric isomers result most commonly from carbon-carbon double bonds.
The important property is the INABILITY OF THE CARBON ATOMS TO ROTATE
RELATIVE TO ONE ANOTHER ABOUT THE DOUBLE BOND. The molecules have
identical connectivitys so they cannot be described as structural isomers
- These isomers used to be called cis and trans isomers but not anymore. We
now use E and Z notation:
E Entgegen = opposite
Z Zusammen = together
HOW TO DECIDE E AND Z
You assign properties based on atomic number and consider each end of the
double bond separately
1) Take each end of the double bond separately
2) Consider the FIRST atom in each chain
3) Chain which has the highest atomic number is the highest priority
4) If highest priority is on the SAME SIDE of the double bond then it is Z. If it is on
the OPPOSITE SIDE OF THE DOUBLE BOND then it is E

Atoms With Four Different Bonds Can Be Chiral

- The centre carbon is termed the STEREOGENIC CENTRE. The bonds are
arranged so that It cannot be superimposed on its own mirror image.
- A pair of mirror images are called ENANTIOMERS
Stereogenic Centers
- These have CHIRAL centres or STEREOCENTERS. Any molecule with a
stereogenic centre will be chiral.
- A stereogenic centre cannot be:
-sp- or sp-2hybridised (MUST be sp3)
-an atom with 2 identical subsitutents
Properties of Enantiomers
ENANTIOMERS HAVE THE SAME CHEMICAL AND PHYSICAL PROPERTIES!!
The only way to distinguish them is the fact THAT THEY ROTATE POLARISED
LIGHT IN DIFFERENT DIRECTIONS. And the fact that they interact with other
chiral molecules differently.

ASSIGNING CHIRALITY
In order to assign the configuration as R or S, identify each of the chirality
centers (most commonly an sp3C with 4 different groups attached
Then at each chirality centre
Assign the priority (high=1 to low=4) to each group attached to the chirality
center based on atomic number.
Reposition the molecule so the LOWEST PRIORITY GROUP is away from you
Determine the relative direction of the priority order of the three higher priority
groups ( 1 to 2 to 3)
If this is CLOCKWISE then it is the R-STEREOISOMER (Latin; rectus = right
handed)
If this is ANTICLOCKWISE then is the S-STEREOISOMER (Latin; sinister = left
handed)

MULTIPILE STEREOGENIC CENTERS

- Compounds with more than two stereocentres have more than two
stereoisomers. In general n number of stereocentres gives 2n stereoisomers
DIASTEREOISOMERS
- These are stereoisomers that are not enantiomers . They are not exact mirror
images. Anything that gives us a stereogenic centre with no mirror image must
be a diastereoisomer.

MESO COMPOUNDS
If we can make an enantiomer superimposable on its own mirror image by
rotating it then it is NOT an enantiomer. A compound like this is called a meso
compound. /
- Because it is superimposable upon its mirror image, it is NOT optically active,
even though it has two (or more) stereogenic carbon atoms
Another to detect a meso compound is to look for a plane of symmetry within
the molecule. This is particularly easy with Fischer projections. If the bottom half
is a mirror image of the top half, then we have a meso compound.

CONFORMATION
Although single bonds can rotate freely, not all positions are equally preferred.

The simple alkane ethane is a good example of conformational analysis. Here

there is just one carbon-carbon bond and the rotational structures may fall
between two extremes, STAGGERED AND ECLIPSED
Eclipsed groups at the front LIE DIRECTLY IN LINE WITH THOSE AT THE BACK
Staggered groups at the front LIE IN LINE WITH THE GAPS AT THE BACK
The table below shows the conformations of the ethane molecule. The first view
shows the molecule form the side. The hydorgens are located in the surrounding
space by WEDGE(in front of the plane) and HATCHED(behind the plane) BONDS.
If we rotate this structure so that carbon 1 is brought down and closer to the
viewer the sawhorse projection is presented. Finally, the Newman projection is
when carbon 1 is directly infront of carbon 2.

As a result of bond-electron repulsion, the eclipsed conformation is LESS

STABLE than the staggered conformation. The most severe bond repulsion in the
eclipsed conformation (depicted by the red arrows) and far more severe than the
roughly equal bond repulsions in the staggered conformation. The staggered
conformation is also a lower energy form, and lowest energy is always favoured.

SOMETIMES THE ECLIPSED CONFORMATION CAN BE MORE STABLE

Ethylene glycol
- In the case of ethylene glycol, intramoleculer HYDROGEN BONDING is possible
in the eclipsed form but not the staggered. This makes the molecule slightly
more stable, by about 30 KJ mol-1, this is enough to make the eclipsed
conformation MORE FAVOURABLE.

- With cyclic molecules, EQUATORIAL is more stable than ANXIAL. Things that are
in the axial position are more crowded.
ALKENES AND ALKYNES: Addition Reactions
Alkenes
Alkenes are unsaturated hydrocarbons. They contain:
- Only Hydrogen and carbon
- At least one carbon-carbon double bond
- Sigma bonds and Pi bonds

- No lone pairs!
- sp3 and sp2 hybridised carbons
The general formula for alkenes is CnH2n
Geometric Isomers
- These are alkenes, they form on the basis of limited rotation around a carboncarbon double bond.

FORMATION OF ALKENES
1) Elimination from alkylhalides

2) CRACKING OF LONG-CHAIN ALKANES

- We break up long chain alkanes to give a mixture of short chain alkanes and
alkenes. Remember from A-level there is thermal and catalytic cracking

THE WITTIG REACTION

This reaction is best for making complex alkenes
- The wittig (W.ell I.snt T.his T.errifically I.nconvinient to learn G.) reaction can
be used to increase the size of the carbon skeleton
The reaction uses an ylid (aka ylide or phosphoranwe)
-Relies on the strength of P-O bonds

Example
- The mechanism of the Wittig reaction is not fully established, but a simple
version is given below. The initial step is the nucleophilic addition of NEGATIVELY
CHARGED carbon of YLIDE onto the carbonyl carbon to give a betaine, which can
cyclise to give an oxaphosphetane as an intermediate. The oxaphosphetane is
decomposed to give an alkene and a phosphine oxide.
- The driving force of the Witting reaction is the FORMATION OF THE HIGHYLY
STABLE DOUBLE BOND BETWEEN PHOSPHORUS AND OXYGEN IN PHOSPHINE
OXIDE

- Replaces the carbonyl with an alkene

REACTIONS OF ALKENES
- Alkenes are ten million quantillion times more useful than alkanes. They are
more reactive and the double bond is a site of extreme electron density.
- We can extend the carbon skeleton using the Wittig reaction above.

Addition To Alkanes
This is an electrophilic mechanism and proceeds via a carbocation intermediate
i) Adds positive component first
ii) Generates the MOST STABLE carbocation as the intermediate
TO DETERMINE THE MECHANISM
1) Identify the + end of the REAGENT
2) This is then attacked by the -electrons of the double bond
3) To generate the most substituted carbocation
4) The resulting anion (negatively charged ion) forms a bond to the
carbocation
SOME SPECIFIC EXAMPLES

1. Alkenes Alkyl Halides

e.g. using Br2: The overall transformation C=C into X-C-C-X
Reagent: Br2

Step 1: The - electrons of the double bond act as a NUCLEOPHILE and are
attracted to the bromine molecule (because of the INDUCED DIPOLE between BrBr). This forms a BROMONIUM INTERMEDIATE

Step 2: Attack of the nucleophilic bromide form the side AWAY from the
bromonium centre of the cyclic molecule in an SN2 like fashion opens up the
bromonium ion to
give overall trans
addition.

e.g. using HBr

-As with all alkenes, unsymetrrical alkenes like propenes react with hydrogen
bromide in the cold.

- This shows MARKOVNIKOVS RULE This states that when a compound HX is

added to an unsymmetrical alkene, the hydrogen becomes attached to the
carbon on the double bond that HAS THE MOST HYDROGENS ATTACHED TO IT
ALREADY. In this case the hydrogen becomes attached to the CH 2 group because
the CH2 group has more hydrogens than the CH group.
The mechanism

2. ALKENES ALCOHOLS
e.g. H2O in dilute acid (Essentially H3O+) This is a REVERSIBLE reaction.

http://www.ochem4free.info/YQcr3l7Abrssp/01-Atoms.pdf
http://www.angelo.edu/faculty/kboudrea/general/quantum_numbers/Quantum_Nu
mbers.htm
http://www.smallscalechemistry.colostate.edu/PowerfulPictures/Orbitals.pdf
http://www.personal.psu.edu/the1/e2.htm
http://www.chem.ucalgary.ca/courses/350/Carey5th/Ch05/ch5-5.html e2
http://www.lasalle.edu/~price/Electrophilic%20Addition%20Reactions.pdf
electrophilic addition
http://www.chem.ucalgary.ca/courses/350/Carey5th/Ch14/ch14-4-6.html
oxymercurication mechanism
http://www.chem.ucalgary.ca/courses/350/Carey5th/Ch15/ch15-3-3.html alkenes
to diols
http://www.youtube.com/watch?v=WwTCf-bv1SQ epoxination of alkenes