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Higher
level
10.1 Fundamentals of organic chemistry
OBJECTIVES
• A homologous series is a series of compounds of the same family, with the same general
formula, which differ from each other by a common structural unit.
• Structural formulas can be represented in full and condensed format.
• Structural isomers are compounds with the same molecular formula but different
arrangements of atoms.
• Functional groups are the reactive parts of molecules.
• Saturated compounds contain single bonds only and unsaturated compounds contain double
or triple bonds.
• Benzene is an aromatic, unsaturated hydrocarbon.
• Explanation of the trends in boiling points of members of a homologous
• Identification of different classes: alkanes, alkenes, alkynes, halogenoalkanes, alcohols, ethers,
aldehydes, ketones, esters, carboxylic acids, amines, amides, nitriles and arenes.
• Identification of typical functional groups in molecules eg phenyl, hydroxyl, carbonyl, carboxyl,
carboxamide, aldehyde, ester, ether, amine, nitrile, alkyl, alkenyl and alkynyl.
• Construction of 3-D models (real or virtual) of organic molecules.
• Application of IUPAC rules in the nomenclature of straight-chain and branched-chain isomers.
• Identification of primary, secondary and tertiary carbon atoms in halogenoalkanes and
alcohols and primary, secondary and tertiary nitrogen atoms in amines.
• Discussion of the structure of benzene using physical and chemical evidence.
Father of Organic Chemistry
Friedrich Wöhler
Terminology
Hydrocarbon
compounds that contain mostly hydrogen and carbon
Homologous series
compounds with the same general formula
Molecular formula
shows the number of atoms only
Structural formula
shows how the atoms are arranged
Empirical formula
shows lowest whole number ratio of atoms
Examples
Homologous series = CnH(2n+2)
Molecular formula = C4H10
Structural formula =
STRAIGHT CHAIN
CH3CH2CH2CH3
BRANCHED CHAIN
CH3CH2(CH2)CH3
Functional groups
Atoms or groups of atoms attached to a
hydrocarbon
They are usually the reactive groups on a stable
carbon chain so form the important part of the
molecule
Examples:
• alcohols
• aldehydes
• ketones
• carboxylic acids
• halides (halogenoalkanes)
Class name
alkane
Formula
CnH2n+2
Functional group
name alkyl
Functional group
none
Alkanes
Suffix
-ane
Alkanes
Name Number of Condensed
carbons Structural Formula
Methane 1 CH4
Ethane 2 CH3CH3
Propane 3 CH3CH2CH3
Butane 4 CH3CH2CH2CH3
Pentane 5 CH3CH2CH2CH2CH3
Hexane 6 CH3CH2CH2CH2CH2CH3
Alkyl Groups
Branches on carbon chains
H
C H CH3 methyl
H
H H
C C H CH2CH3 ethyl
H H
IUPAC Naming Summary
1. Count the C’s in the longest chain.
2. Name each attached group.
3 Count the longest carbon chain to give the
first attached group the smallest number.
4. Name and locate each group.
Naming Branched Alkanes
CH3 methyl branch
CH3CH2CH2CHCH2CH3
6 5 4 3 2 1 Count
3-methylhexane
Alkenes
Suffix
-ene
Alkenes
Name Number of Condensed
carbons Structural Formula
Ethene 2 CH2CH2
Propene 3 CH2CHCH3
Butene 4 CH2CHCH2CH3
Pentene 5 CH2CHCH2CH2CH3
Hexene 6 CH2CHCH2CH2CH2CH3
Naming Branched Alkanes
• select the longest chain of C atoms containing the double
bond and number the chain from this end
• place the ending ENE on the basic name
• use a number to indicate the lower number carbon of the
C=C
• as in alkanes, prefix with substituents
• side chain positions are based on the number allocated to
the first C of the C=C
pent-1-ene pent-2-ene
Branching
3-methybut-1-ene
Class name
alkyne
Formula
CnH2n-2
Functional group
name alkynyl group
Functional group
Alkynes
Suffix
-yne
Alkynes
Name Number of Condensed
carbons Structural Formula
Ethyne 2 CHCH
Propyne 3 CHCCH3
Butyne 4 CHCCH2CH3
Pentyne 5 CHCCH2CH2CH3
Hexyne 6 CHCCH2CH2CH2CH3
Saturated vs unsaturated
Saturated hydrocarbons are hydrocarbons
that contain no double or triple bonds
(alkanes).
Unsaturated hydrocarbons are alkenes and
alkynes.
Class name
halogenoalkane
Formula
CnH2n+1X
Functional group
name X = F, Cl, Br, I
Functional group
Halogenoalkanes Suffix
none
Prefix
flouro-, chloro-,
bromo-, iodo-
Halides and naming
Different positions for the halogen and branching of the carbon chain
1-chlorobutane 2-chlorobutane
2-chloro-2-methylpropane 1-chloro-2-methylpropane
Halides
The number of carbons that are joined to the carbon
with the halogen group determine if it is a 1⁰, 2⁰,
or 3⁰ halide.
Alcohols
Suffix
-ol
Naming Alcohols
Full structure Skeletal Formula
formula Name
Ethanol
Propan-1-ol
Propan-2-ol
Full structure Skeletal Formula
formula Name
Butan-1-ol
Pentan-1-ol
Butan-2-ol
Pentan-3-ol
Alcohols
• The number of carbons that are joined to the
carbon with the alcohol group determine if it
is a 1⁰, 2⁰, or 3⁰ alcohol.
Class name
ether
Formula
ROR’
Functional group
name ether
Functional group
Ethers
Suffix
none
Midfix
-oxy-
Naming Ethers
methoxy methane
2-ethoxy-2-methylpropane
Class name
aldehyde
Formula
RCHO
Functional group
name aldehyde
Functional group
Aldehydes
Suffix
-al
Naming Aldehydes
CARBONYL COMPOUNDS - NOMENCLATURE
CH3CHO ethanal
CH3CH2CHO propanal
CH3CH2CH2CHO butanal
CH3CH2CH2CH2CHO pentanal
Class name
ketone
Formula
RC(O)R’
Functional group
name carbonyl
Functional group
Ketones
Suffix
-one
Naming Ketones
CH3COCH3 propanone
CH3CH2COCH3 butanone
CH3COCH2CH2CH3 pentan-2-one
CH3CH2COCH2CH3 pentan-3-one
Class name
ester
Formula
RCOOR’
Functional group
name ester
Functional group
Esters
Suffix
-oate
Naming Esters
•The first part is from the alcohol group (of a
carboxylic acid), the second part is from the
acid (of a carboxylic acid).
•Add oate
e.g. methyl ethanoate CH3COOCH3
Carboxylic acids
Suffix
-oic acid
Carboxylic acids
Carboxylic acids form a homologous series
C3H7COOH (CH3)2CHCOOH
NAMING CARBOXYLIC ACIDS
Naming Carboxylic acids
• select the longest chain of C atoms containing the COOH
group;
• remove the e and add oic acid after the basic name
• number the chain starting from the end nearer the COOH
group
• as in alkanes, prefix with alkyl substituents
• side chain positions are based on the C in COOH being 1
Amines
Suffix
-amine
Naming Amines
Nomenclature Named after the groups surrounding the nitrogen +
amine
C2H5NH2 ethylamine
(CH3)2NH dimethylamine
(CH3)3N trimethylamine
Amides
Suffix
-amide
Naming Amides
• Solids named from the corresponding acid
• Remove oic acid, add amide
Nitriles
Suffix
-nitrile
Naming Nitriles
CH3CH2CH2C≡N butanenitrile
ethanenitrile
Class name
arene
Formula
CnH2n-6
Functional group
name phenyl
Functional group
Arenes
Suffix
none
Benzene
or or
Bromobenzene 1,2-diphenylethyne
Physical Characteristics of the
functional groups
• Explain volatility between functional groups
(H-bonding and Van der Waals)
• Explain solubility
Effects of lengthening chain and branching
10.2 Functional group chemistry
OBJECTIVES
Alkanes: Alcohols:
• Alkanes have low reactivity and undergo free-radical • Alcohols undergo nucleophilic substitution reactions with
substitution reactions. acids (also called esterification or condensation) and some
• Writing equations for the complete and incomplete undergo oxidation reactions.
combustion of hydrocarbons. • Writing equations for the complete combustion of
• Explanation of the reaction of methane and ethane with alcohols.
halogens in terms of a free-radical substitution mechanism • Writing equations for the oxidation reactions of primary
involving photochemical homolytic fission. and secondary alcohols (using acidified potassium
dichromate(VI) or potassium manganate(VII) as oxidizing
Alkenes: agents). Explanation of distillation and reflux in the isolation
of the aldehyde and carboxylic acid products.
• Alkenes are more reactive than alkanes and undergo
addition reactions. Bromine water can be used to • Writing the equation for the condensation reaction of an
distinguish between alkenes and alkanes. alcohol with a carboxylic acid, in the presence of a catalyst
(eg concentrated sulfuric acid) to form an ester.
• Writing equations for the reactions of alkenes with
hydrogen and halogens and of symmetrical alkenes with
hydrogen halides and water. Halogenoalkanes:
• Outline of the addition polymerization of alkenes. • Halogenoalkanes are more reactive than alkanes. They
• Relationship between the structure of the monomer to can undergo (nucleophilic) substitution reactions. A
the polymer and repeating unit. nucleophile is an electron-rich species containing a lone
pair that it donates to an electron-deficient carbon.
• Writing the equation for the substitution reactions of
Benzene:
halogenoalkanes with aqueous sodium hydroxide.
• Benzene does not readily undergo addition reactions but
does undergo electrophilic substitution reactions
Polymers:
• Addition polymers consist of a wide range of monomers
and form the basis of the plastics industry.
.
Writing conventions
Double barbed arrow to indicate
movement of an electron pair.
Dash is going
behind the page
Wedge is coming
out of the page
Alkane reactions
Combustion
Photochemical substitution
(halogenation)
Alkanes – chemical properties
Carbon in general:
CATENATION is the ability to form bonds between atoms of the same
element.
Carbon forms chains and rings, with single, double and triple covalent
bonds, because it is able to FORM STRONG COVALENT BONDS WITH
OTHER CARBON ATOMS
In particular alkanes:
- fairly unreactive; (old family name, paraffin, meant little reactivity)
- have relatively strong, almost NON-POLAR, SINGLE covalent bonds
-they have no real sites that will encourage substances to attack them
Alkanes – chemical properties
Carbon forms a vast number of carbon compounds because of the
strength of the C-C covalent bond. Other Group IV elements can do
it but their chemistry is limited due to the weaker bond strength.
The larger the atoms, the weaker the bond. Shielding due to filled inner
orbitals and greater distance from the nucleus means that the shared
electron pair is held less strongly.
Alkanes – combustion reactions
complete CH4(g) + 2O2(g) 🡪 CO2(g) + 2H2O(l)
combustion
UNEQUAL SPLITTING
produces IONS
known as HETEROLYSIS or
HETEROLYTIC FISSION
EQUAL SPLITTING
produces RADICALS
known as HOMOLYSIS or
HOMOLYTIC FISSION
• If several bonds are present the weakest bond is usually broken first
• Energy to break bonds can come from a variety of energy sources - heat / light
• In the reaction between methane and chlorine either can be used, however...
• In the laboratory a source of UV light (or sunlight) is favoured.
Alkanes – free radical mechanism
(substitution reactions)
Homolytic fission
substitution reaction where electrons are shared when a
bond is broken
Free radical
atom or molecule with one free unpaired electron
Mechanism to be known
Methane + Cl2
Initiation Cl2 ——> 2Cl• RADICALS CREATED
The Cl-Cl bond is broken in preference to the others as it is the weakest and requires requires
less energy to separate the atoms.
Mechanism to be known
Methane + Cl2
1. Initiation
2. Propagation
Must start
and end with
a radical.
3. Termination
Mechanism to be known
Methane + Br2
Homolytic fission
making 2 free radicals
Bromomethane
UV
CH4 + Br2 → CH3Br + HBr
(Hydrogen bromide is a colourless gas) ie. Brown to clear
Alkene reactions
Addition
Polymerization
Properties of alkenes
Alkene
Alkane
Bromine
Water
Addition of halogen to alkene
Addition of water to alkene
Polymerization
Combustion
Oxidation
Esterification
Complete combustion of alcohols
• This is an extreme form of oxidation
• Like all organic compounds they give CO2 & H2O – in excess
O2(g)
• They burn more cleanly than their equivalent alkanes – O in
the compound is available for combustion products so less CO
made in limited O2 conditions (incomplete combustion).
Alcohols with longer chains have greater molar enthalpies,
but may not be able to burn cleanly.
it is essential to distil off the aldehyde before it gets oxidised to the acid
Practical details
• the alcohol is dripped into a warm solution of acidified KMnO 4 or K2Cr2O7
• K2Cr2O7 is reduced from orange Cr(VI) to green Cr(III)
• aldehydes have low boiling points - no hydrogen bonding - they distil off immediately
• if it didn’t distil off it would be oxidised to the equivalent carboxylic acid
• to oxidise an alcohol straight to the acid, reflux the mixture
Aldehyde has a lower boiling point so Aldehyde condenses back into the
distils off before being oxidised further mixture and gets oxidised to the acid
Oxidation of secondary alcohols
Secondary alcohols are easily oxidised to ketones
Nucleophic substitution
Terminology
Nucleophile
Reactants with a non-bonding electron pair that are attracted to a
positive carbon (a form of electrophile – loves negative)
Heterolytic fission
Formation of a carbocation and a negative ion, due to carbon losing
it’s shared electron
Electrophilic substitution
Electrophilic substitutions
Just know
electrophiles
will substitute.
Specific
reactions do
not need to be
memorized.
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 S N1and
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.
• Outline of the difference between protic and aprotic solvents
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
Higher level
Inversion at 180⁰ must be shown.
SN1 reaction mechanism
Higher level
SN1 reactions involve heterolytic fission and nucleophilic substitution with
mainly tertiary halogenoalkanes.
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:
Mechanism to be known
SN1 reaction mechanism
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:
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
Mechanism to be known
Ethene and bromine
Higher level
Mechanism to be known
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.
Higher level
Higher level
Electrophilic Substitution
Reactions
Benzene
Mechanism to be known
Nitration of benzene
Higher level
Firstly sulfuric acid is stronger so protonates the nitric acid:
Alcohols
Nitrobenzene
Reduction of carbonyl compounds
Higher level
The oxidation of alcohols can be reversed by reduction as follows:
- -
[+H ] [+H ]
-
[+H ]
Higher level
Reduction of nitrobenzene
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
2⁰ Oxidation
ketone alcohol Condensation
Reduction M phenylammonium ion
NaBH4
M
NaOH ester
1⁰ SN2, 3⁰ SN1 H2O/H2SO4
halogenoalkane Substitution Addition
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.
C
S
Isomers
Higher level
Higher level
Cis-trans isomers
Cis isomers are those
with the same groups on
the same side of the
double bond or cyclical
compounds.
Higher level
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.
Example:
Higher level
Higher level
Different compounds - different properties.
Optical isomers
Higher level
Optical isomers are those which
contain a chiral carbon, that is, it
contains four different groups.
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
C D
E
F
If the light appears to have: turned to the right turned to the left
DEXTROROTATORY LAEVOROTATORY
Higher level
Optical isomers – Other points
• 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!)