Ib PPT 10 HL PDF

20.

1 Types of organic reactions

Higher level
OBJECTIVES
Nucleophilic Substitution Reactions:
• SN1 represents a nucleophilic unimolecular substitution reaction and SN2 represents a nucleophilic bimolecular substitution reaction. SN1involves a
carbocation intermediate. SN2 involves a concerted reaction with a transition state.
• For tertiary halogenoalkanes the predominant mechanism is SN1and for primary halogenoalkanes it is SN2. Both mechanisms occur for secondary
halogenoalkanes.
• The rate determining step (slow step) in an SN1reaction depends only on the concentration of the halogenoalkane, rate = k[halogenoalkane]. For
SN2, rate = k[halogenoalkane][nucleophile]. SN2 is stereospecific with an inversion of configuration at the carbon.
•SN2 reactions are best conducted using aprotic, non-polar solvents and SN1reactions are best conducted using protic, polar solvents.
• Explanation of why hydroxide is a better nucleophile than water.
• Deduction of the mechanism of the nucleophilic substitution reactions of halogenoalkanes with aqueous sodium hydroxide in terms of SN1and SN2
mechanisms. Explanation of how the rate depends on the identity of the halogen (ie the leaving group), whether the halogenoalkane is primary,
secondary or tertiary and the choice of solvent.

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• Outline of the difference between protic and aprotic solvents
Electrophilic Addition Reactions:

• An electrophile is an electron-deficient species that can accept electron pairs from a nucleophile. Electrophiles are Lewis acids.
• Markovnikov’s rule can be applied to predict the major product in electrophilic addition reactions of unsymmetrical alkenes with hydrogen halides
and interhalogens. The formation of the major product can be explained in terms of the relative stability of possible carbocations in the reaction
mechanism.
•Deduction of the mechanism of the electrophilic addition reactions of alkenes with halogens/interhalogens and hydrogen halides.
Electrophilic Substitution Reactions:

• Benzene is the simplest aromatic hydrocarbon compound (or arene) and has a delocalized structure of π bonds around its ring. Each carbon to
carbon bond has a bond order of 1.5. Benzene is susceptible to attack by electrophiles.
• Deduction of the mechanism of the nitration (electrophilic substitution) reaction of benzene (using a mixture of concentrated nitric acid and
sulfuric acid).
Reduction Reactions:
• Carboxylic acids can be reduced to primary alcohols (via the aldehyde). Ketones can be reduced to secondary alcohols. Typical reducing agents are
lithium aluminium hydride (used to reduce carboxylic acids) and sodium borohydride.
• Writing reduction reactions of carbonyl containing compounds: aldehydes and ketones to primary and secondary alcohols and carboxylic acids to
aldehydes, using suitable reducing agents.
• Conversion of nitrobenzene to phenylamine via a two-stage reaction.
Higher level
Nucleophilic Substitution
Reactions
SN1 and SN2
Higher level
Solvents
Polar – have dipole moments due to different
electronegativities
Non-polar – similar electronegativities
Protic – polar solvents with O-H or N-H bonds allowing

hydrogen bonding and a source of protons eg. water,
ethanol
Aprotic – a polar or non-polar solvent that do not have
O-H or N-H bonds nor provide a source of protons eg.
acetone (propanone) (polar), ethanenitrile (polar),
benzene (non-polar), hexane (non-polar)
SUMMARY: 3 main types of solvents, non-polar, polar

protic, polar aprotic, no such thing as a non-polar protic
Substitution – Nucleophilic – reaction rate dependent on 2 (both reactants)
Higher level
SN2 reaction mechanism
SN2 reactions involve heterolytic fission and
nucleophilic substitution with mainly primary
halogenoalkanes.
An unstable transition state is created meaning the

reaction is bimolecular requiring two molecules:
rate = k[halogenoalkane][nucleophile]
Polar aprotic solvents are preferred which are

those unable to form hydrogen bonds, eg.
propanone, ethyl ethanoate. Otherwise the solvent
would bind to the nucleophile inhibiting its action.
Mechanism to be known
Higher level
Inversion at 180⁰ must be shown.
Substitution – Nucleophilic – reaction rate dependent on 1 (just concentration of carbocation)
Higher level
SN1 reactions involve heterolytic fission and nucleophilic substitution with
mainly tertiary halogenoalkanes.
Due to steric hindrance the halogen must be heterolytically removed to

create a carbocation before the nucleophile can attached.
This creates a more stable carbocation intermediate so the reaction is
unimolecular:
rate = k[halogenoalkane]
Polar protic solvents are preferred

which are able to form hydrogen
bonds which stabilize the
carbocation by ion-dipole interactions
eg. water, alcohol
Positive induction
Higher level
The positive induction is the stabilization of a
carbocation because the other alkyl groups can
unevenly share their electrons with the positive
centered carbon:
Higher level
Effect of leaving group
Higher level
As halogen-carbon bonds become less polar you
would expect nucleophilic attack to be less and
so rate to decrease down the group:
However we must also consider how much

energy it takes to break bonds:
And this is the deciding factor meaning rate

increases down the group:
Effect of mechanism
Higher level
In general SN1 tertiary reaction rates are faster
than SN2 primary due to the stability of the
formation of carbocations:
Higher level
Electrophilic Addition Reactions
Alkenes
Ethene and bromine
Higher level
Ethene and HBr
Higher level
Asymmetric alkenes
Higher level
Markovnikov’s rule: the hydrogen will attach to
the carbon that is already bonded to the greater
number of hydrogens.
Asymmetric alkenes
Higher level
b. Will be more stable due to positive induction:
Hence reaction b. prevails.

Propene and HBr
Higher level
Higher level
Electrophilic Substitution
Reactions
Benzene
Nitration of benzene
Higher level
Firstly sulfuric acid is stronger so protonates the nitric acid:
Area within red square is taken from IB exam markscheme

Nitration of benzene
Higher level
With heat, the electrophilic substitution by the nitronium ion
causes a momentary loss of symmetry of the electron structure of
benzene.
Red circles represent emphasis on IB exam markscheme

Higher level
Reduction Reactions
Alcohols
Nitrobenzene
Reduction of carbonyl compounds
Higher level
The oxidation of alcohols can be reversed by reduction as follows:
[+H-] [+H-]
Needs lithium aluminium hydride (LiAlH4) in dry ether.

[+H-]
Needs heat with sodium borohydride (NaBH4).

Mechanism to be known?
Reduction of nitrobenzene
Higher level
20.2 Synthetic routes
Higher level
OBJECTIVES
• The synthesis of an organic compound stems from a readily available starting material
via a series of discrete steps. Functional group interconversions are the basis of such
synthetic routes.
• Retro-synthesis of organic compounds.
• Deduction of multi-step synthetic routes given starting reagents and the product(s).
Synthetic routes
Higher level
A synthetic route is a series of discrete chemical steps to change a
reactant to a desired product. Efficient design has been the result
of retrosynthetic analysis where you think of the target molecule
and work backwards through precursors to the starting material.
Higher level
Cr2O72- H+
aldehyde Reflux Oxidation phenylamine (aniline)

Reduction M
LiAlH4 dry ether Cr2O72- H+ Reduction carboxylic acid

1⁰ Oxidation LiAlH4 dry ether
Cr2O72- H+ NaOH
2⁰ Oxidation
ketone alcohol Condensation
Reduction M phenylammonium ion
NaBH4
M
halogenoalkane
NaOH
1⁰ SN2, 3⁰ SN1
Substitution
H2O/H2SO4
Addition
ester
Sn conc. HCl
M M
dihalogenoalkane
Cl2 UV HCl
M nitrobenzene
Free radical Addition Cl2
M
Homolytic fission Addition
Ni H2 Conc. HNO3O/H2SO4
alkane Addition Addition
polymerization
alkene polymer benzene
Higher level
Problem 1: Produce ethanol from ethane.
20.3 Stereoisomerism
Higher level
OBJECTIVES
• Stereoisomers are subdivided into two classes—conformational isomers,
which interconvert by rotation about a σ bond and configurational isomers
that interconvert only by breaking and reforming a bond.
Configurational isomers are further subdivided into cis-trans and E/Z isomers
and optical isomers.
• Cis-trans isomers can occur in alkenes or cycloalkanes (or heteroanalogues)
and differ in the positions of atoms (or groups) relative to a reference plane.
According to IUPAC, E/Z isomers refer to alkenes of the form R1R2C=CR3R4
(R1 ≠ R2, R3 ≠ R4) where neither R1 nor R2 need be different from R3 or R4.
• A chiral carbon is a carbon joined to four different atoms or groups.
• An optically active compound can rotate the plane of polarized light as it
passes through a solution of the compound. Optical isomers are enantiomers.
Enantiomers are non-superimposeable mirror images of each other.
Diastereomers are not mirror images of each other.
• A racemic mixture (or racemate) is a mixture of two enantiomers in equal
amounts and is optically inactive.
• Construction of 3-D models (real or virtual) of a wide range of
stereoisomers.
• Explanation of stereoisomerism in non-cyclic alkenes and C3 and C4
cycloalkanes.
• Comparison between the physical and chemical properties of enantiomers.
• Description and explanation of optical isomers in simple organic molecules.
• Distinction between optical isomers using a polarimeter.
Isomers
Higher level
S
C
Higher level
Cis-trans isomers
Cis isomers are those
with the same groups on
the same side of the
double bond or cyclical
compounds.
Trans isomers have the
groups on the opposite
sides of the double bond.
Higher level
Example:
Higher level
E/Z isomers
For isomers with more than 2 different groups, the group with the
highest priority on the left hand side is determined and then the group
with the highest priority on the right hand side is determined.
E isomers have these two groups opposite. (entgegen in German)
Z isomers have these two groups on the same side. (above) (zusammen
in German)
Z is S in a mirror
Priority rules:
1. The atom with the highest atomic number has the highest priority.
2. If the atom is the same, apply this rule to the next bonded atom in
the chain.
Higher level
Example:
Different compounds - different properties.
Higher level
Optical isomers
Higher level
Optical isomers are those which
contain a chiral carbon, that is, it
contains four different groups.
These compounds are non-

superimposable on each other and
exist in pairs called enantiomers eg.
amino acids. Diastereomers
contain two or more chiral carbons
and are not mirror images.
Optical activity
Higher level
• isomers differ in their reaction to plane-polarised light
• plane polarised light vibrates in one direction only
• one isomer rotates light to the right, the other to the left (degree of
angle equal)
• rotation of light is measured using a polarimeter
• rotation is measured by observing the polarised light coming out
towards the observer
• If the light appears to have
turned to the right turned to the left

DEXTROROTATORY LAEVOROTATORY
d or + form l or - form
A racemate or racemic mixture is a 50-50 mixture of the two

enantiomers (dl) or (±). The opposite optical effects of each isomer
cancel each other out.
Polarimeter
Higher level
A B
C D
E
F
A Light source produces light vibrating in all directions
B Polarising filter only allows through light vibrating in one direction
C Plane polarised light passes through sample
D If substance is optically active it rotates the plane polarised light
E Analysing filter is turned so that light reaches a maximum
F Direction of rotation is measured coming towards the observer
If the light appears to have: turned to the right turned to the left
DEXTROROTATORY LAEVOROTATORY
Optical isomers – Other points
Higher level
• The formation of racemic mixtures is more likely in a
laboratory reaction than in a chemical process occurring
naturally in the body.
• If a compound can exist in more than one form, only one
of the optical isomers is usually effective.
• The separation of isomers will make manufacture more
expensive.
• A drug made up of both isomers will require a larger
dose and may cause problems if the other isomer is
‘poisonous’ like thalidomide, which is a teratogen –
causes birth defects.
TOK - problems for evolution?
Higher level
(which is different to natural selection!)
Only L-forms of amino acids are used in cells.

Aren’t proteins a violation of entropy and enthalpy anyway?
If there are no proteins, how did the DNA reproduce?
Which came first the chicken or the egg?

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20.

1 Types of organic reactions

Electrophilic Addition Reactions:

Electrophilic Substitution Reactions:

Protic – polar solvents with O-H or N-H bonds allowing

SUMMARY: 3 main types of solvents, non-polar, polar

An unstable transition state is created meaning the

Polar aprotic solvents are preferred which are

SN1 reaction mechanism

Due to steric hindrance the halogen must be heterolytically removed to

Polar protic solvents are preferred

However we must also consider how much

And this is the deciding factor meaning rate

Hence reaction b. prevails.

Area within red square is taken from IB exam markscheme

Red circles represent emphasis on IB exam markscheme

Needs lithium aluminium hydride (LiAlH4) in dry ether.

Needs heat with sodium borohydride (NaBH4).

aldehyde Reflux Oxidation phenylamine (aniline)

LiAlH4 dry ether Cr2O72- H+ Reduction carboxylic acid

These compounds are non-

turned to the right turned to the left

A racemate or racemic mixture is a 50-50 mixture of the two

Only L-forms of amino acids are used in cells.

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