3.2 Organic Synthesis (Reaction Pathways) : Pupil Notes Learning Outcomes Questions & Answers

Revised Advanced Higher Unit 3- Organic Chemistry
3.2
Organic
Synthesis
(Reaction Pathways)
Pupil Notes
Learning Outcomes
Questions
& Answers
KHS Chemistry Nov 2013 page 1 Systematic Organic Chemistry - Synthesis

An Introduction to Organic Synthesis

Organic synthesis creates molecules by design
Synthesis can produce new molecules that are needed as drugs or materials
Different syntheses for established chemicals can be designed and tested to improve efficiency
Highly advanced synthesis is used to test new ideas and methods
In order to propose a synthesis you must be familiar with (Named) reactions
What they begin with (Reactant)

What they lead to (Product)
How they are accomplished (Reagent, Mechanism etc)
What the limitations are ( e.g. conditions, multiple products, isomeric products, solvents etc )
A synthesis combines a series of proposed steps to go from a defined set of reactants to a specified
product. You will be expected to devise synthetic routes with up to 3 steps from a given reactant to a final
product.
propane 2-bromopropane
propanone propan-2-ol

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Reaction are a series of animations that can be used in conjunction with these notes. They can

Pathways be found at http://www.new.chemistry-teaching-resources.com/Mechanisms.html

Functional Groups
The study of organic chemistry is made easier by knowledge of the various functional groups found in
molecules. Some of the main functional groups are shown in the table below.
Reactions learnt in the context of simple families can be applied to more complex molecules.

Intermolecular Attractions
Intermolecular attractions are largely determined by the extent of polarity within a molecule.
Non-polar molecules like butane rely on London Dispersion forces, while propanal and acetone will
have polar-polar attractions between molecules. Propanol will benefit from the stronger Hydrogen
bonds set up.
Boiling Points
Most organic molecules have a mainly hydrocarbon
portion to their structures, and as the hydrocarbon
chain increases in length the number of London
Dispersion forces will increase.
As a result, more energy is needed to move the

molecules further apart. Branched molecules tend to
be more compact and have fewer attractions so they
tend to have slightly lower Boiling Points than the
equivalent chain only molecule.
The elevated boiling points of the polar molecules reflect the extra energy needed to overcome the
stronger attractions between their molecules.
Solubility
The increasing influence of the hydrocarbon chain in polar molecules has an effect on solubility as well as
boiling points.


Solubility (in water) is also largely dependant on

the polarity of the molecule. To dissolve in water
a molecule would need to be able to establish
attractions similar in strength to the hydrogen
bonding that already exists between water
molecules.
Alcohols and acids are amongst the most soluble

because they also have hydrogen bonding between
their molecules.
However, in larger alcohols, the non-polar carbon

chain will begin to dominate the properties of the
molecule and solubility will be much less than for
the smaller alcohols.
Though only able to set up polar-polar attractions between

their own molecules, carbonyl compounds such as propanal
and propanone can be quite soluble due to their ability to get
involved in hydrogen bonding with water.
Again, solubility will be greatly decreased in longer chained

molecules as the 'hydrophobic' hydrocarbon tails begin to
dominate properties.


1. Which of the following has nucleophilic 6. Which of the following compounds is likely
properties? to be the most soluble in water?
A Na A
B Br +
C CH3+
D NH3

B
2. In the homologous series of amines, increase
in chain length from CH3NH2 to C4H9NH2 is
accompanied by

D
3. A compound, X, has the formula C6H12.
X must be
A a hydrocarbon
B an alkene
C a cycloalkane
7. Which of the following is most reactive as a
D hexene. nucleophile?
A Br2
4. In the homologous series of alkanols,
increase in chain length from CH3OH to B CH3I
C10H21OH is accompanied by C NH4+
A increased volatility and increased D NH3
solubility in water
B increased volatility and decreased 8. Hydrogen bonding occurs in
solubility in water A CH3I
C decreased volatility and decreased B CH3OH
solubility in water
C CH3OCH3
D decreased volatility and increased
D CH3CH2CHO.
solubility in water.
9. In the presence of bright light, hydrogen and
5. Which of the following is not caused by
chlorine react explosively. One step in the
hydrogen bonding?
reaction is shown below.
A The low density of ice compared to water
H2(g) + Cl(g) HCl(g) + H(g)
B The solubility of methoxymethane in
The enthalpy change for this step can be
water
represented as the bond enthalpy of
C The higher boiling point of methanol
A (HH) + (ClCl)
compared to ethane
B (HH) (ClCl)
D The higher melting point of hydrogen C (HH) + (HCl)
compared to helium D (HH) (HCl).

ALKANES ( & Cycloalkanes)

Just about everything you need to know about alkanes will have been covered in earlier courses.
Though alkanes can be made by the catalytic addition

of hydrogen to an alkene (hydrogenation), this would
never be an economical way of making an alkane.
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The conversion of unsaturated fatty acids into

saturated fatty acids in the 'hardening' of
vegetable oils is an example of catalytic
hydrogenation that you will have met
previously.
Alkanes tend to be extracted directly from the various fractions produced from the fractional
distillation of crude oil.
Other processes such as cracking ( to form alkenes) and reforming (to form ring
molecules such as benzene) also take place during the refining process. Neither of
these processes give us the specificity we would want in a Synthesis - too
many different molecules would be produced.
In the context of Organic Synthesis, the significant reaction

is the Radical Substitution of an alkane using halogens such
as bromine and chlorine.
This produces a polar molecule which can easily go on to

produce a carbonium ion as a reaction intermediate.

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Reaction Free Radical Though this reaction is due to become
Substitution
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part of the Higher course, I would still

expect aspects of the Mechanism to be
tested at Advanced Higher.
Initiation
UV radiation is
absorbed
half arrows are used to
Homolytic fission results in the
2 Cl
show the movements of
single electrons formation of two chlorine free
Cl : Cl radicals
Propagation
A series of reactions between a free radical and a molecule Because each step makes another free readical, the reaction
keep the reaction going. is a chain reaction.
Termination
Cl CH3 CH3Cl

Any collisions betwee two free radicals will stop a chain.
A mixture of haloalkanes will be produced but the first

stage can be represented by the equation:
CH4 + Cl2 CH3Cl + HCl
Substitution
ALKENES ( & Cycloalkenes, Alkynes)

Again, all of these reactions will have been met in earlier courses, so the emphasis shifts to Mechanisms
and how these reactions would fit into Synthesis Pathways. In particular, the significance of
halogenoalkanes (alkylhalides) cannot be overstressed.
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Synthesis of Alkene - Elimination

Though alkenes can be made by the cracking of alkanes (can be called dehydrogenation), this would
only be used on a specific alkane (e.g. propane) to produce a specific alkene (e.g.propene) when part of a
Synthesis. The other option would be to perform an Elimination reaction on either an alcohol (also called
dehydration) or on an alkylhalide (rarely called dehydrohalogenation !)
Dehydration
There is no requirement to know the mechanism of this reaction. The concentrated H2SO4 can be
considered as a dehydrating agent in this reaction.
Elimination
Again, there is no requirement to know the mechanism of this reaction. However, be aware that the
solvent used is crucial. Elimination when solvent is alcohol, substitution if solvent is water.

Reaction of Alkene - Radical Addition - Hydrogenation

Covered in Higher Chemistry and revised briefly in section on Alkanes (page 10).
Reaction of Alkene - Electrophilic Addition - Hydration

Also covered in Higher Chemistry and the production of an alcohol can be a significan step in Synthesis
as it opens up the route to the oxygen containing molecules - aldehydes, ketones, acids, esters etc.
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This is one of the main mechanisms that you will be expected to learn and a detailed description of the
mechanism can be found on the next page.
Reaction of Alkene - Electrophilic Addition - Hydrohalogenation

Also covered in Higher Chemistry and the production of an alkylhalide can be a significan step in
Synthesis as it opens up the route to a variety of other molecules - ethers, alcohols, amines, acids etc.
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This is one of the main mechanisms that you will be expected to learn and a detailed description of the
mechanism can be found on the next page.

Electrophilic Addition Electrophilic Addition

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(carbocation intermediate) (carbocation intermediate)
H H H H
| |
| |

H C = C H H C = C H
Though water is polar,
H the presence of H+ ions

makes this reaction easier
H O H
+ As the polar HBr + (catalyst).
molecule approaches,

electrons from the C=C
| electrons from the C=C
bond come out to form a H bond come out to form a

new bond with the H+ ion
Br new bond with the
Hydrogen atom.

The electrons of the HBr bond H H
| |
move onto the bromine to form a
bromide ion, Br.
H C C H
H H | H
| | H

:O
H C C H
H
| The carbocation is now attacked by

H :Br
a lone pair on the oxygen atom

The carbocation is then attacked by H H
| |
the lone pair of the bromide ion, a
neucleophile.
H C C H
H H | |
| |
H O H

H C C H |
| | H

H Br
A hydrogen ion is reformed (catalyst) and an alkanol is
A monohaloalkane is prduced and overall the reaction can be produced. Overall the reaction can be represented by the
represented by the equation: equation:
C2H4 + HBr C2H5Br C2H4 + H2O C2H5OH
Addition Addition, Hydration

Markovnikov Rule
In the previous two addition reactions, there were the possibilities of two isomeric products forming
depending on which of the carbon atoms in the C = C was attacked first by the electrophile ( H+ ).
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To understand (and therefore predict) which isomer is the more likely product, you need to learn about the
Inductive Effect. In essence, when a positive charge forms on a carbon (carbocation intermediate) it can
be stabilised by drawing in negative charge from any alkyl groups attached to the carbon.
The more alkyl groups attached, the greater the stability.
In forming two possible isomeric products, one of the carbocation intermediates will be more stable than
the other and that isomer will be the main product formed - sometimes, the only product formed.
Quick 'Rule of Thumb' - the hydrogen will always add to the carbon atom that
already has the most hydrogen atoms attached.

Reaction of Alkene - Electrophilic Addition - Bromination

Also covered in Higher Chemistry, the production of
an alkylhalide can be a significan step in Synthesis as
it opens up the route to a variety of other molecules
- ethers, alcohols, amines, acids etc.
Alkynes will have a similar addition reaction but will be able to react with 2 moles of halogen.
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Reaction Electrophilic Addition From the normal equation there is no obvious
(cyclic ion intermediate)
Pathways
sign that this addition is any different from the

previous additions.
H H However, it has a totally different mechanism
| |
and is also one of those you will be expected to

learn.
H C = C H
:Br
H
Br + As the non-polar Br
molecule approaches,
2
H C C H
| electrons from the C=C
bond induce polarity and H
Br then come out to form a

new bond with the nearer

Br

The electrons of the BrBr bond
Bromineatom.
The positive charge is shared between the 2 carbon atoms and
the bromine atom. The Bromide ion will then attack from the
move onto the further bromine to
other side. A TRANS arrangement.
form a bromide ion, Br.
Br H
H H | |
| | H C C H
H C C H | |
|
H Br

:Br: A dihaloalkane is prduced and overall the reaction can be
represented by the equation:
:
Unlike the previous mechanism, where the H+ ion was

effectively the electrophile, the bromine has lone pairs
C2H4 + Br2 C2H4Br2
of electrons. One of these will be attracted to the charge
on the carbocation. The bromine forms two bonds. Addition
10. Which of the following is a propagation step 15. When but-2-ene is shaken with an aqueous
in the chlorination of methane? solution of chlorine in potassium iodide, the
A Cl2 Cl + Cl structural formula(e) of the product(s) is/are
B CH3 + Cl CH3Cl A
C CH3 + Cl2 CH3Cl + Cl

D CH4 + Cl CH3Cl + H B
11. Which of the following does not occur in the
reaction between methane and chlorine?
C
A A chain reaction
B Homolytic fission
C Free radical formation D
D An addition reaction
12. Propene can be produced by heating

1-bromopropane with ethanolic potassium 16.
hydroxide.
This reaction is an example of
A reduction
B hydrolysis
C elimination
D condensation.
13. Part of a possible chain reaction mechanism

for chlorine reacting with methane is:
Cl2 2Cl The two steps in the reaction mechanism shown
can be described as
Cl + CH4 HCl + CH3
A ethene acting as a nucleophile and
CH3 + Cl2 CH3Cl + Cl Br acting as a nucleophile
Which of the following will not be a B ethene acting as a nucleophile and
termination step in this reaction? Br acting as an electrophile
A H + Cl HCl C ethene acting as an electrophile and
B Cl + Cl Cl2 Br acting as a nucleophile
C CH3 + CH3 C2H6 D ethene acting as an electrophile and
D CH3 + Cl CH3Cl Br acting as an electrophile.
14. The major product in the reaction of HCl 17. OH + CO2 HCO3
with 2-methylpent-2-ene, C2H4 + Br2 C2H4Br+ + Br
Which substances act as electrophiles in
the above reactions?
A OH and Br2
A 2-chloro-2-methylpentane
B 3-chloro-2-methylpentane B OH and

C2H4
C 2,3-dichloro-2-methylpentane C CO2 and Br2
D 4-chloro-4-methylpentane.
D CO2 and C2H4
HALOGENOALKANES ( Alkylhalides)
In Higher Chemistry the alkylhalides were not particularly important chemicals. In Advanced Higher,
however, the significance of halogenoalkanes (alkylhalides) cannot be overstressed. They can be a very
important step in many Synthesis Pathways.
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Introduction to Halogenoalkanes
Organic compounds containing halogen substituents are comparatively rare in the natural
world. Consequently, most have to be synthesised in laboratories. They are widely used in the
modern world.
For example, they are important in medicine, agriculture and in the manufacture of plastics. In
medicine, one of the first examples of their use was in 1847 by James Young Simpson of
Bathgate, who was the first to use chloroform (trichloromethane) as a general anaesthetic.
More recently, safer halogenoalkanes and halothanes have been devised for use as
anaesthetics.
In this course, the most significant feature of a

halogenoalkane is the production of a dipole and, in
particular, a positively charged carbon.
This carbon is now vulnerable to attack by a number of

different nucleophiles leading to:
Nucleophilic Substitution

The other significant feature in a halogenoalkane can be the number of alkyl groups attached
to the carbon with the halogen atom - whether it is a primary, secondary or tertiary alkylhalide.
H R R
| | |
RCX RCX RCX
| | |
H H R
primary alkylhalide secondary alkylhalide tertiary alkylhalide
One possible mechanism for nucleophilic substitution involves the formation of a carbonium ion after
the halogen atom leaves as a halide ion.
H R R
| | |
RC X RC X RC X
| | |
H H R
primary carbonium secondary carbonium tertiary carbonium
As in the explanation for the

Markovnikov Rule, the inductive
effect of the alkyl groups helps
stabilise the carbonium ion making
this mechanism more likely with
tertiary alkylhalides and less likely
with primary alkylhalides.
The other factor that can have a major effect, is the nature of the halogen present. Fluorine is
the most electronegative and will result in the most polar molecule.
However, the C F bond is also the strongest and will therefor be the hardest to break.
Overall, the most reactive halogenoalkanes are the iodo- and bromo-alkanes and they tend to
be used almost exclusively for nucleophilic substitution.
Nucleophilic substitution Nucleophilic substitution

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(Sn1) (Sn2)
R' R'
R C + Br

Nu C + Br
R'' The polar CHal bond breaks approaches the
The nucleophile
R R''
heterolytically. electon deficient carbon
R' Attrigonal
A carbocation is
produced which can
this stage the molecule is
planar and R'
The intermediate is a
trigonal bipyramid
| either side is equally likely.
be attacked by any
nucleophilic group
nucleophilic attack from shape
|
C Nu C Br
R R'' R R''
Nu Nu : As the nucleophiles' electron pair moves in, the electons of
the CBr bond move onto the bromine
If R , R' and R'' are all different (assymetric carbon), then Even if R , R' and R'' are all different (assymetric carbon),
a mixture of optical isomers will be produced. only one possible isomer can be produced.
Nucleophiles include: Nucleophiles include:
HO alcohols HO alcohols
: :
: :

(NaOH(aq) or other aqueous solutions) (NaOH(aq) or other aqueous solutions)
RO ethers RO ethers
: :
: :

(Alkoxide ions, from Na/alcohols) (Alkoxide ions, from Na/alcohols)
H3N: amines H3N: amines

(Ammonia) (Ammonia)
CN: nitriles CN: nitriles

(Alcoholic cyanides) (Alcoholic cyanides)
A variety of products can be made by this reaction but over- A variety of products can be made by this reaction but over-
all the reaction can be represented by the equation: all the reaction can be represented by the equation:
RHal + Nu RNu + Hal RHal + Nu RNu + Hal
Substitution Substitution
The first step is the rate determining step and, since it only The rate determining step involves both chemicalss so the
involves one substance, the reaction is first order reaction is second order
Sn1 or Sn2 ? Can depend on the polarity of the CHal bond. Can depend on the polarity of the solvent used. Can depend on the
size of the R , R' and R'' groups. No easy answer. Just need to be aware of the the two possibilities.

Summary of SN2 Mechanism
2 molecules involved in rate determining step

Transition state is trigonal bipyramidal - 5
groups arranged around carbon atom
No isomeric products though inversion of the
molecule will take place
Nucleophile has to attach from opposite side
to the departing halogen
Most likely for primary alkylhalide, least
likely for tertiary alkylhalide - steric
hindrance is 'best' explanation.
Steric Hindrance
Steric Hindrance refers to the effect that larger groups can have on the formation of a bond to a new
group.
with one methyl and two with three methyl groups

hydrogen atoms, there is and no hydrogen atoms,
still room for the there is no room for the
nucleophile to attach to the nucleophile to attach to the
carbonium ion carbonium ion

Summary of SN1 Mechanism

Only 1 molecule involved in rate determining step
Transition state is planar trigonal - 3 groups arranged
around carbonium ion
Isomeric products possible if alkylhalide was chiral

Nucleophile can attach from either side
Least likely for primary alkylhalide, most likely for tertiary

alkylhalide - inductive effect is 'best' explanation.
In reality, the departing halide ion is likely to be

attracted by the carbocation formed and may
remain in close proximity to the reaction
intermediate.
This may make it very difficult or impossible for

the incoming nucleophile to approach from that
When designing, for example, side.
a drug molecule, it is essential
that possible changes in the As a result, one of the possible isomers may
stereochemistry are factored not form or will be the minority product only.
into the planned Synthesis

Reaction of Alkylhalide - Nucleophilic Substitution - to Alcohol

The production of an alcohol can be a significant step in Synthesis as it opens up the route to the oxygen
containing molecules - aldehydes, ketones, acids, esters etc.
Traditionally, the 'easiest' reagent given for this reaction is NaOH(aq) and it is perfectly acceptable to
assume that the hydroxide ion is the attacking nucleophile:
In reality, just about any aqueous solution can be used as the attacking nucleophile is actually a water
molecule, but the final step requires the elimination of a H+ and the hydroxide ion can play an important
part here.
What is much more important is that careful attention is paid to the solvent used as hydroxides dissolved
in ethanol, e.g. NaOH(ethanol) , can lead to an Elimination reaction instead
Reaction of Alkylhalide - Nucleophilic Substitution - to Ether

Ethers are introduced in Advanced Higher and generally would be the final product in a Synthesis.
Traditionally, there would appear to be two different reagents given for this reaction but, in reality, it is
the same reagent both times. The key to this reaction is the production of an alkoxide ion ( R O )
which can be conveniently made by reacting an alkali metal, e.g. Na, with the equivalent alcohol
( R OH ).
Reagent: Na / alcohol or Na+ alkoxide - both will lead to formation of ether

Reaction of Alkylhalide - Nucleophilic Substitution - to Amines

The production of an amine group can be an important step in the synthesis of complex molecules but in
Advanced Higher it will usually be the final product.
Normally, it will be enough to know the reaction above but be aware that amines can themselves act as
the nucleophile which would lead to the production of secondary and tertiary amines.
Like ammonia, primary and secondary amines

can do hydrogen bonding which makes the
smaller molecules very soluble in water.
Tertiary amines have no hydrogen bonding.
Another effect of this hydrogen bonding

is that amines have higher than expected
boiling points.

Reaction of Alkylhalide - Nucleophilic Substitution - to Nitrile

The production of a nitrile group can be an important step in the synthesis of complex molecules. At one
level it can be a means of 'growing a chain' as it results in an extra carbon being added to a molecule.
Having produced a nitrile group, the next step is usually hydrolysis, which results in the production of an
acid (carboxyl) group.
Importance of Alkylhalides
As mentioned earlier, the importance of alkylhalides, and the nucleophilic substitution reaction in
particular, cannot be stressed enough and they will feature in many of the reaction pathways met at
Advanced Higher.
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18. Which of the following amines has the 24. The hydrolysis of the halogenoalkane
lowest boiling point? (CH3)3CBr was found to take place by an
A C4H9NH2 SN1 mechanism.
B C3H7NHCH3 The rate-determining step involved the

formation of
C C2H5NHC2H5
A
D C2H5N(CH3)2
19. Which of the following is the formula for a

tertiary halogenoalkane?

A CHBr3 B
B (CH3)3CBr
C (CH2Br)3CH
D BrCH2C(CH3)3

C
20. Which of the following molecules is likely
to produce the most stable carbocation
intermediate in a substitution reaction?
A CH3CH2I
B (CH3)3CCl
C CH3CH2Cl D
D CH3CHICH2CH3
21. Which of the following bases is the

strongest?

A C2H5NH2
B (C2H5)2NH 25. When 2-bromobutane is reacted with
potassium cyanide and the compound formed
C C6H5NH2
is hydrolysed with dilute acid, the final
D (C6H5)2NH product is
A butanoic acid
22.
C3H7Cl + C2H5O C3H7OC2H5 + Cl B pentanoic acid
The above reaction is C 2-methylbutanoic acid
A an elimination reaction D 2-methylpropanoic acid.
B a nucleophilic addition reaction
26. Which line in the table correctly describes
C a nucleophilic substitution reaction the types of reaction in the following
D an electrophilic substitution reaction. sequence?
C H
3
C H Br
8 3
C H OH
7 3
CH
7 3 6
23. 2-Bromobutane reacts with KOH in ethanol
to produce two unsaturated products.
Reaction 1 Reaction 2 Reaction 3
The type of reaction involved is A addition substitution elimination
A addition B addition addition condensation
B elimination
C substitution substitution dehydration
C oxidation
D substitution. D substitution addition condensation
ALCOHOLS
One of the most important reactions met in Higher Chemistry was the oxidation of alcohols and this
remains a very useful step in many Synthesis Pathways. The production of an alcohol from alkylhalide is
new but was covered in the previous section.
Absolutely new is the use of hydrides (H) to reduce aldehydes and ketones back to the corresponding
alcohol.
Oxidation & Reduction

In general, Oxidation - increase in the O:H ratio (more O or less H)
Reduction - decrease in the O:H ratio (less O or more H)

As it was at Higher Chemistry, acidified K2Cr2O7 ( orange to green ) remains the oxidising agent of
choice. There is no need to know how this reagent works.
Cr2O72- / H+
LiAlH4
Cr2O72- / H+
LiAlH4
Hydrides are compounds containing the H ion. Again, there is no need to know how this reagent works
but it is not a complicated reaction:
Comparison between Alcohols and Ethers

With alcohols and ethers being isomeric, ethanol C 2H 6O
there is much scope for 'confusion' but
the two families have distinctly different
properties and reactions so should be
easy to distinguish between them. dimethylether C 2H 6O
Unlike alcohols, ethers are unable to

do hydrogen bonding between their
molecules. They are only slightly
polar so tend to be very volatile,
very flammable liquids.
They can, however, set up hydrogen

bonds with water molecules so the
smaller members of the family can
be reasonably soluble.

ALDEHYDES
Again, Oxidation was covered in Higher chemistry

and Reduction in the previous section.
Worth mentioning again are the 3 oxidising agents that

can be used to distinguish an aldehyde from a ketone:
acidified dichromate - Cr2O72-(aq) Cr3+(aq) - orange to green
tollens reagent - Ag+(aq) Ag(s) - silver mirror test
benedict's - Cu2+(aq) Cu+(s) - blue to reddy-brown
A better way of identifying individual aldehydes and ketones is to

produce a solid derivative and determine accurately its Melting Point
which can be compared with DataBook values.
Nucleophilic Addition - Derivative Formation

Not a mechanism that you need to know in
any detail but worth appreciating that this
addition is totally different from 'normal'
(Electrophilic) addition to a C = C double
bond.
Though a C = O double bond is as 'electron

rich', it is also very polar and it is the
positively charged carbon atom that is
vulnerable to attack by nucleophiles like
ammonia and amines.
An example of a suitable amine chosen to form derivatives is 2,4-dinitrophenyl hydrazine

(Brady's reagent) which forms characteristic reddy brown crystals with known melting points
with most aldehydes and ketones.
H NO2 H NO2
O N N
+ H2N N
H3C C + H2O
C H H3C C
H2 NO2 C H NO2
H2
propanal 2,4-dinitrophenylhydrazine propanal 2,4-dintrophenylhydrazone

(melting point 152-155 C )
KETONES
Again, Oxidation was covered in Higher chemistry

A better way of identifying individual aldehydes and ketones is to

produce a solid derivative and determine accurately its Melting Point
which can be compared with DataBook values.
Nucleophilic Addition - Derivative Formation
Important Ketones
Due to their susceptibility to oxidation, aldehydes are fairly rare in the natural world wheras ketones are
found everywhere including many steroids and medicinal drugs.


27. A substance, X, is readily oxidised by 32. Which of the following is not a correct
acidified potassium dichromate solution to statement about ethoxyethane?
give a product which does not react with A It burns readily in air.
sodium carbonate, nor with Tollens reagent.
B It is isomeric with butan-2-ol.
Which of the following could represent the
structure of X? C It has a higher boiling point than
butan-2-ol.
A CH3CH2CH2OH
D It is a very good solvent for many organic
B CH3CH(OH)CH3 compounds.
C
33. Cinnamaldehyde, which can be extracted
from cinnamon, has the structure:

D
28. Which of the following compounds would

liberate one mole of hydrogen gas if one Cinnamaldehyde will not react with
mole of it reacts with two moles of sodium?
A sodium metal
A C2H5OH
B bromine solution
B HOCH2CH2OH
C lithium aluminium hydride
C CH3COOH
D acidified potassium dichromate.
D CH3CHO
34. Which of the following will not form a
29. Which of the following compounds would
derivative with 2,4-dinitrophenylhydrazine?
liberate one mole of hydrogen gas if one
mole of it reacts with excess sodium?
A
A C2H5OH
B CH3CHO
C CH3COOH
B
D HOCH2CH2OH
30. Which of the following reacts with ethanol

to form the ethoxide ion?
A Na(s) C
B Na2O(s)
C NaCl(aq)
D
D NaOH(aq)
31. Which of the following compounds could not

be oxidised by acidified K2Cr2O7solution?
A CH3CH2CHO
B CH3CH2COOH
C CH3CH2CH2OH
D CH3CH(OH)CH3
ACIDS & ESTERS
Oxidation and Esterification ( Condensation )

were covered in Higher chemistry
Also met in a previous section was the Hydrolysis

of a nitrile as an alternative method of synthesising
an acid.
The production of salts from organic acids (weak

acids) is covered in Unit 2.
The carboxyl group and derivatives of the carboxyl group

such as acid chlorides and amides can feature in a number of
condensation reactions leading to the formation of polymers such as
polyesters, polyamides and proteins.
Synthesis of Acids - Recap
Oxidation of a primary alcohol

CH3 K2Cr2O7 CH3 O
CH3CHCH2CH2CH2OH CH3CHCH2CH2COH
H+
4-methylpentan-1-ol 4-methylpentanoic acid
Oxidation of an aldehyde
O K2Cr2O7 O
CH3CH2CH2CH2CH2CH CH3CH2CH2CH2CH2COH
H+
hexanal hexanoic acid
Hydrolysis of a nitrile (after nucleophilic substitution of an alkylhalide) - grows the carbon chain
Na+ CN- H+ / H2O O

CH3CH2Br CH3CH2C N CH3CH2COH
bromoethane propanenitrile propanoic acid
Hydrolysis of an ester
O H+ / H2O O
CH3CH2C OCH2CH3 CH3CH2COH CH3CH2OH
ethylpropanoate propanoic acid

Uses of Acids (carboxyl group)

Acids are found everywhere in nature and have widespread applications in the production of drugs.
O O O O
H3C OH OH OH OH
OH
ethanoic acid butanoic acid hexanoic acid lactic acid
responsible for responsible for responsible for responsible for
the pungent smell the rancid odour the odour the taste of
of vinegar of sour butter of smelly feet sour milk
O
OH HO
O
O NH2
HO HO O
O
acetylsalicylic acid p-aminosalicylic acid isotretinoin
Aspirin: a widely used in the treatment of used in the treatment of
used analgesic tuberculosis acne
Reactions of Acids (formation of derivatives)

Carboxylic Acids, as you will have learnt in earlier courses and in Unit 2, are first and foremost our main
examples of weak acids and will do all the normal reactions of a dilute acid.
In organic chemistry, the main reaction of carboxylic acids remains esterification ( a condensation
reaction in which an acid and an alcohol join together with the elimination of a small stable molecule,
usually water). An ester can be considered as a derivative of an acid.
O c. H2SO4 O
C CH3CH2OH C HOH
H3C OH H3C OCH2CH3
ethylethanoate
O c. H2SO4 O
C CH3OH C HOH
OH OCH3
methylbenzoate

Another previously met reaction of carboxylic acids involves the formation of an amide ( a condensation
reaction in which an acid and an amine join together with the elimination of a small stable molecule,
usually water). An amide can also be considered as a derivative of an acid.
The amide link is much used in the manufacture of polymers,

whilst the same condensation reaction is used to join together
amino acids in the production of proteins, though in this context
it is more normally referred to as the peptide link.
Two less familiar condensation reactions lead to unfamiliar products - an acid chloride and an anhydride.
PCl3 or
+ PCl5 or + inorganic products
SOCl2
+ H2O
Unusually, the significance of these derivatives is less as products and more as alternative reactants. All
of these derivatives, including esters and amides, are themselves capable of doing the same condensation
reactions as the acid molecules themselves. However, they can be more reactive which can make them
the preferred option in many synthesis pathways as alternatives to acids - particularly the acid chlorides.
'small' molecule
produced by NH3 H2O ROH RCOOH HCl
condensation

Properties
The properties of acids are strongly influenced by the ability of the
molecules to set up hydrogen bonding. This can be seen clearly by
comparing molecules of similar size and mass.
Acids can often form two

hydrogen bonds which lock
two molecules together to
form a dimer.
The ability to hydrogen bond with water molecules ensures

that the smaller carboxylic acids are very soluble in water.
However, the solubility falls off quite quickly as the length

of the carbon chain increases.
35. A compound C3H8O does not react with 38. A white crystalline compound, soluble in
sodium and is not reduced by lithium water, was found to react with both dilute
aluminium hydride. It is likely to be an hydrochloric acid and sodium hydroxide
A acid solution.
B ether Which of the following might it have been?
C alcohol A C6H5OH
D aldehyde. B C6H5NH2
C C6H5COOH
36. Which of the following is least acidic? D H2NCH2COOH
A CH3OH 39. Which of the following esters gives a

secondary alcohol when hydrolysed?
B
A

C
B

D C

D

37. Two isomeric esters, X and Y, have the
molecular formula C4H8O2. Ester X on 40. Which of the following will react with dilute
hydrolysis with sodium hydroxide solution sodium hydroxide solution?
gives CH3CH2COONa, and ester Y on A CH3CHOHCH3
similar treatment gives CH3CH2OH. B CH3CH=CH2
Which line in the table shows the correct C CH3COOCH3

names of X and Y? D CH3CH2OCH3
41. Which of the following compounds would be

produced by passing ammonia gas into dilute
ethanoic acid?
A CH3CONH2
B CH3COONH4+
C NH2CH2COOH
D CH3CH2NH3+Cl

AROMATICS
Aromatics are an enormous group of chemicals based on the benzene ring. The ring
gives distinctive properties to any molecule that contains it.

Despite the unsaturated nature of a
Web
Reaction
benzene, it does not readily undergo

Pathways
addition reactions as this would destroy the

delocalised p cloud which is responsible for
the great stability of this ring structure.
Most functional groups are introduced into

the benzene ring by means of a substitution
reaction. Though the delocalised p cloud of
electrons will be disturbed during the
reaction, it will be re-established in the final
product molecule.
Elecrophilic Substitution
Though only four electrophilic substitution reactions need to be learnt in detail for Advanced Higher,
there are a wide variety of molecules that can be made in this way.

Electrophilic Substitution
This is the main reaction of benzene rings. Though they have even more electrons than the C = C bond
in alkenes, they resist addition because the loss of the delocalised ring is too destabilising.
Alkylation - using alkyl halides/AlCl3 Halogenation - using Halogens/AlCl3

The production of the electrophile requires the presence of The production of the electrophile is helped by the presence
AlCl3 . (The Al make use of its empty 4th orbital). of AlCl3 . The reaction would be very slow otherwise.
H An AlCl4 ion is
also formed
An AlCl4 ion is
also formed
H C Cl : AlCl3 Web Cl Cl : AlCl3
H
Reaction
Pathways

CH3
Cl electrons move from the
electrons move from the ring to form a new bond with
ring to form a new bond with the chlorine ion, Cl+.
the methyl ion.
H CH3 H Cl
The positive charge is shared The positive charge is shared
over the whole ring. over the whole ring.
Electrons move from the CH Electrons move from the CH
bond, a H+ ion is eliminated. bond, a H+ ion is eliminated.
CH3 Cl
Overall, an alkyl group takes the place Overall, a halogen atom takes the place
of a hydrogen atom, Substitution. of a hydrogen atom, Substitution.
The H+ ion reacts with the AlCl4 to reform The H+ ion reacts with the AlCl4 to reform
AlCl3 and a molecule of HCl. AlCl3 and a molecule of HCl.
Nitration - using H2SO4/HNO3 Sulphonation - using H2SO4/SO3

The production of the electrophile , NO2+ is a result of a The electrophile is a molecule of SO3. The 3 oxygen atoms
reaction between these two strong acids. are more electronegative; a large + forms on the sulphur.
2 H2SO4 + HNO3 2 HSO4 + NO2+ + H3O+

O
electrons move from the
+
S O
ring to form a new bond with

NO2 electrons move from the Othe sulphur trioxide, SO3.
ring to form a new bond with
Electrons also move in one of the SO
the nitro ion, NO2+.
bonds.

O
H NO2 H
S O
The positive charge is shared The positive charge is shared O
over the whole ring. over the whole ring.
Electrons move from the CH Electrons move from the CH
bond, a H+ ion is eliminated. bond, a H+ ion is eliminated.

OH
NO2 S O The H+ ion that is eliminated from

Overall, a nitro group takes the place of O the benzene ring attaches itself to the
a hydrogen atom, Substitution. oxygen ion.
Overall, a HSO3 group takes the place
of a hydrogen atom, Substitution.

Common Aromatics
Most of the aromatics you will come across are substituted benzene rings and can be named accordingly
with the substituent's name preceding benzene - chlorobenzene. Alternatively the label phenyl can be used
for the benzene ring followed by the substituent - phenylchloride.
Conjugated Systems
In general, you can assume that a functional group attached to a benzene ring will continue to behave as
normal. There are, however, two exceptions that you will be expected to be aware of.
Alcohols all possess a very polar O H bond, but have little to no ability to form H+ ions (acidity) due
to the instability of the alkoxide ion that would also have to form. Phenol is an exception. The molecular
orbital of the benzene ring can extend to form a conjugated system with the orbitals containing the lone
pairs on the oxygen. This draws electrons away from the oxygen to be shared between 7 atoms ( 1 oxygen
plus 6 carbons).
This allows phenol (also called carbolic acid) to be weakly acidic.

A similar conjugated system can be set up in aniline (aminobenzene
or phenylamine) with the lone pair of electrons on the nitrogen atom.
However, amines rely on the attraction of their lone pair for H+ ions
to give them their basic properties.
NH3 + H 2O NH4+ + OH

RNH2 + HCl RNH3+ + Cl
The formation of the conjugated system results in

electrons being drawn away from the amine group
which explains why aniline is a much weaker base
than would be expected.
The strengths of weak bases are measured on the pKb scale.

The smaller the number on this scale, the stronger the base is.
ammonia pKb 4.75

methylamine pKb 3.36
phenylamine pKb 9.38
Methylamine is a stronger base than ammonia because alkyl chains

are generally electron donating (the inductive effect met earlier) and so increase the electron density on
the nitrogen atom.

42. Chlorobenzene, nitrobenzene and 46. Which of the following molecules is planar?
ethylbenzene can all be formed from benzene A Hexane
by
B Cyclohexane
A electrophilic substitution
C Chlorobenzene
B electrophilic addition
D Methylbenzene (toluene)
C nucleophilic substitution
D nucleophilic addition. 47. Which of the following reactions is least
likely to take place?
43. Which of the following shows the above
compounds in order of increasing acid A
strength?
A X Y Z
B Y Z X C
C Z X Y
D X Z Y
D
44.
48. In which of the following pairs does an

aqueous solution of the first compound have a
What is the molecular formula for the above higher pH than an aqueous solution of the
structure? second?
A C17H11
B C17H14
C C17H17
D C17H20
45. Which of the following compounds is soluble

in water and reacts with both dilute
hydrochloric acid and sodium hydroxide
solution?
A C2H5NH2
B C6H5NH2
C C2H5NH3Cl
D HOOCCH2NH2
3.2. ORGANIC SYNTHESIS

Hydrocarbons & Haloalkanes
3.2.1 Bonding in alkanes can be described in terms of sp3 hybridisation
and sigma bonds.
3.2.2 Hybridisation is the process of mixing atomic orbitals in an atom

to generate a set of new atomic orbitals called hybrid orbitals.
3.2.3 A sigma () bond is a covalent bond formed by end on overlap of

two atomic orbitals lying along the axis of the bond
3.2.4 Alkanes undergo substitution reactions with chlorine and bromine

by a chain reaction mechanism.
3.2.5 The chain reaction includes the following steps

( i) initiation by homolytic fission to produce radicals
( ii) propagation
(iii) termination
3.2.6 Bonding in ethene can be described in terms of sp2 hybridisation,

sigma and pi bonds.
3.2.7 Alkenes can be prepared in the laboratory by

( i) dehydration of alcohols using aluminium oxide,
concentrated sulphuric acid or orthophosphoric acid
(ii) base-induced elimination of hydrogen halides from
monohalogenoalkanes.
3.2.8 Alkenes undergo:

( i) catalytic addition with hydrogen to form alkanes
( ii) addition with halogens to form dihalogenoalkanes
(iii) addition with hydrogen halides according to Markovnikovs
rule to form monohalogenoalkanes
( iv) acid-catalysed addition with water according to
Markovnikov's rule to form alcohols.
3.2.9 The mechanisms of the above reactions involve

( i) for halogenation cyclic ion intermedate
( ii) for hydrohalogenation carbocation intermediate
(iii) for acid catalysed hydration carbocation intermediate
3.2.10 Halogenoalkanes are named according to IUPAC rules.
3.2.11 Monohalogenoalkanes can be classified as primary, secondary or

tertiary.
3.2.12 Monohalogenoalkanes undergo nucleophilic substitution reactions.
3.2.13 Monohalogenoalkanes undergo elimination reactions to form

alkenes.

3.2.14 Monohalogenoalkanes react with:

( i) alkalis to form alcohols
( ii) alcoholic alkoxides to form ethers
(iii) ethanolic cyanide to form nitriles which can be hydrolysed to
carboxylic acids(chain length increased by one carbon atom)
( iv) ammonia to form amines via alkyl ammonium salts.
Alcohols and ethers

3.2.15 Alcohols exhibit hydrogen bonding and as a result have higher
boiling points than other organic compounds of comparable
relative formula mass and shape.
3.2.16 The lower alcohols are miscible with water but as their chain
length increases their solubility in water decreases.
3.2.17 Alcohols can be prepared from

( i) alkenes by hydration
(ii) halogenoalkanes by substitution.
3.2.18 In industry, alcohols (except methanol) can be manufactured by the

acid-catalysed hydration of alkenes.
3.2.19 Alcohols react with some reactive metals to form alkoxides .
3.2.20 Alcohols can be dehydrated to alkenes.
3.2.21 Alcohols undergo condensation reactions slowly with carboxylic

acids and more vigorously with acid chlorides to form esters.
3.2.22 Ethers have the general formula Rl-O-R2 where Rl and R2 are alkyl
groups.
3.2.23 Ethers are named according to IUPAC rules.
3.2.24 Due to the lack of hydrogen bonding, ethers have lower boiling
points than the corresponding isomeric alcohols.
3.2.25 Ether molecules can hydrogen bond with water molecules thus
explaining the solubility in water of some ethers of low relative
formula mass.
3.2.26 Ethers are highly flammable and on exposure to air may form
explosive peroxides.
3.2.27 Ethers can be prepared by the reaction of halogenoalkanes with

alkoxides.
3.2.28 Ethers are useful solvents for many organic compounds due to
( i) relative stability with respect to oxidation and reduction
(ii) polarity

Aldehydes, ketones & carboxylic acids

3.2.29 The following physical properties can be explained in terms of
dipole-dipole attractions and/or hydrogen bonding
( i) higher boiling points than corresponding alkanes
( ii) Iower boiling points than corresponding alcohols
(iii) miscibility of lower members with water
3.2.30 Tollens reagent or Benedicts solution can be used to distinguish

between aldehydes and ketones. Aldehydes reduce the complexed
silver(I) ion and the complexed copper(II) ion to silver and
copper(I), respectively.
3.2.31 Aldehydes and ketones can be reduced to primary and secondary

alcohols, respectively, by reaction with lithium aluminium hydride
in ether.
3.2.32 Aldehydes and ketones undergo

( i) addition reactions in which the carbon atom in the polar
carbonyl group submits to nucleophilic attack.
(ii) condensation reactions with derivatives of ammonia (XNH2)
which proceed by nucleophilic addition of XNH2 followed by
elimination of a water molecule.
3.2.33 The reaction with 2,4-dinitrophenylhydrazine to form a

2,4-dinitrophenylhydrazone is an example of a condensation
reaction.
3.2.34 The melting points of the resulting 2,4-dinitrophenylhydrazones are

used to identify carbonyl compounds.
3.2.35 Aldehydes are generally more reactive than ketones because the
presence of two alkyl groups in ketones hinders nucleophilic attack
and reduces the partial positive charge on the carbonyl carbon
atom.
3.2.36 In pure carboxylic acids hydrogen bonding produces dimers thus

explaining the relatively high boiling points. Dimerisation does not
occur in aqueous solution.
3.2.37 Carboxylic acid molecules also form hydrogen bonds with water
molecules thus explaining the appreciable solubility of the lower
carboxylic acids in water. As the chain length increases water
solubility decreases.
3.2.38 Carboxylic acids are weak acids. Their slight dissociation in water
can be explained by the stability of the carboxylate ion caused by
electron delocalisation.
3.2.39 Carboxylic acids can be prepared by:

( i) oxidising primary alcohols and aldehydes
( ii) hydrolysing nitriles, esters or amides

3.2.40 Reactions of carboxylic acids include:

( i) formation of salts by reactions with metals, carbonates and alkalis
( ii) condensation reactions with alcohols to form esters
(iii) reaction with ammonia or amines and subsequent heating of the
ammonium salt to form amides
( iv) reduction with lithium aluminium hydride to form primary
alcohols.
Amines
3.2.41 Amines are named according to IUPAC rules.
3.2.42 Amines are organic derivatives of ammonia and can be classified as

primary, secondary or tertiary.
3.2.43 Primary and secondary amines, but not tertiary amines, associate by
hydrogen bonding and as a result have higher boiling points than
isomeric tertiary amines and alkanes with comparable relative
formula masses.
3.2.44 Amine molecules can hydrogen bond with water molecules thus
explaining the appreciable solubility of the lower amines in water.
3.2.45 The nitrogen atom in amines has a lone pair of electrons which can
accept a proton from water, producing hydroxide ions. Amines are
weak bases.
3.2.46 Amines react with aqueous mineral or carboxylic acids to form salts.
Aromatics
3.2.47 Bonding in benzene can be described in terms of sp2 hybridisation,
sigma and pi bonds and electron delocalisation.
3.2.48 Benzene is the simplest aromatic hydrocarbon and its unexpected

stability can be attributed to the presence of delocalised electrons.
3.2.49 Most reactions of benzene involve attack of an electrophile on the

cloud of delocalised electrons, that is electrophilic substitution.
3.2.50 Benzene resists addition reactions but undergoes electrophilic

substitution reactions. These include:
( i) chlorination and bromination to produce chlorobenzene and
bromobenzene
( ii) nitration to produce nitrobenzene
(iii) sulphonation to produce benzene sulphonic acid
( iv) alkylation to produce alkylbenzenes.
3.2.51 The presence of delocalised electrons in the phenyl group can be

used to explain:
( i) the stronger acidic nature of phenol compared to aliphatic
alcohols
(ii) the weaker basic nature of the aromatic amine, aniline compared
with aliphatic amines.

Exam Practice
1.
2.

3.
4.

5.
6.

7.
8.

9.
10.

11.
12.

13.
14.

Multiple Choice Answers

Page 7:

1. D 2. B 3. A 4. C 5. D 6. C 7. D 8. B 9. D
Page 15:

10. C 11. D 12. C 13. A 14. A 15. D 16. A 17. C
Page 24:

18. D 19. B 20. B 21. B 22. C 23. B 24. A 25. C 26. C
Page 30:

27. B 28. B 29. D 30. A 31. B 32. C 33. A 34. B
Page 35:

35. B 36. A 37. B 38. D 39. C 40. C 41. B
Page 40:

42. A 43. B 44. B 45. D 46. C 47. B 48. A

Exam Practice Answers

1.
2.
3.

4.

5.
6.
7.

8.
10

11.
12

13.
14.

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Revised Advanced Higher Unit 3- Organic Chemistry

KHS Chemistry Nov 2013 page 2 Systematic Organic Chemistry - Synthesis

An Introduction to Organic Synthesis

In order to propose a synthesis you must be familiar with (Named) reactions

What they begin with (Reactant)

KHS Chemistry Nov 2013 page 3 Systematic Organic Chemistry - Synthesis

KHS Chemistry Nov 2013 page 4 Systematic Organic Chemistry - Synthesis

As a result, more energy is needed to move the

KHS Chemistry Nov 2013 page 5 Systematic Organic Chemistry - Synthesis

Solubility (in water) is also largely dependant on

Alcohols and acids are amongst the most soluble

However, in larger alcohols, the non-polar carbon

Though only able to set up polar-polar attractions between

Again, solubility will be greatly decreased in longer chained

KHS Chemistry Nov 2013 page 6 Systematic Organic Chemistry - Synthesis

KHS Chemistry Nov 2013 page 7 Systematic Organic Chemistry - Synthesis

ALKANES ( & Cycloalkanes)

Though alkanes can be made by the catalytic addition

The conversion of unsaturated fatty acids into

In the context of Organic Synthesis, the significant reaction

This produces a polar molecule which can easily go on to

KHS Chemistry Nov 2013 page 8 Systematic Organic Chemistry - Synthesis

part of the Higher course, I would still

Any collisions betwee two free radicals will stop a chain.

A mixture of haloalkanes will be produced but the first

CH4 + Cl2 CH3Cl + HCl

ALKENES ( & Cycloalkenes, Alkynes)

Synthesis of Alkene - Elimination

KHS Chemistry Nov 2013 page 10 Systematic Organic Chemistry - Synthesis

Reaction of Alkene - Radical Addition - Hydrogenation

Reaction of Alkene - Electrophilic Addition - Hydration

Reaction of Alkene - Electrophilic Addition - Hydrohalogenation

KHS Chemistry Nov 2013 page 11 Systematic Organic Chemistry - Synthesis

Electrophilic Addition Electrophilic Addition

(carbocation intermediate) (carbocation intermediate)

H the presence of H+ ions

C2H4 + HBr C2H5Br C2H4 + H2O C2H5OH

Addition Addition, Hydration

The more alkyl groups attached, the greater the stability.

KHS Chemistry Nov 2013 page 13 Systematic Organic Chemistry - Synthesis

Reaction of Alkene - Electrophilic Addition - Bromination

sign that this addition is any different from the

H H However, it has a totally different mechanism

Br then come out to form a

Unlike the previous mechanism, where the H+ ion was

C CH3 + Cl2 CH3Cl + Cl

12. Propene can be produced by heating

13. Part of a possible chain reaction mechanism

In this course, the most significant feature of a

This carbon is now vulnerable to attack by a number of

KHS Chemistry Nov 2013 page 16 Systematic Organic Chemistry - Synthesis

primary alkylhalide secondary alkylhalide tertiary alkylhalide

primary carbonium secondary carbonium tertiary carbonium

As in the explanation for the

Nucleophilic substitution Nucleophilic substitution

Nucleophiles include: Nucleophiles include:

H3N: amines H3N: amines

CN: nitriles CN: nitriles

RHal + Nu RNu + Hal RHal + Nu RNu + Hal