By: Rey
Organic Chemistry Cambridge As-Level Summary
Organic Molecules Representation
Empirical formula – e.g. C2H5 for Butane
Molecular formula – e.g. Butane (C4H10)
Structural formula – e.g. CH3CH2HC=CH2 for Butene
Displayed formula – e.g.
as Butene
Skeletal formula – e.g.
as Butene
Functional groups
Def. - a group of atoms in a molecule responsible for their characteristic reactions.
Alkenes – (CnH2n), C=C bond, e.g. Ethene C2H4
Arenes – (C6H5), e.g. Benzene
Halogenoalkanes – (CnH2n+1X) where X is halogens, -X bond, e.g. Chloromethane CH3Cl
Alcohols – (CnH2n+1OH), -OH bond, e.g. Propanol
Aldehydes – (CnH2n+1CHO), e.g. Propanal
Ketones – (CnH2n+1COCmH2m+1), e.g. Propanone
Carboxylic acids – (CnH2n+1COOH), e.g. Propanoic acid
Esters – (CnH2n+1COOCmH2m+1), e.g. ethyl propanoate
Amines – (CnH2n+1NH2), -NH2 bond, e.g. methylamine
Nitriles – (CnH2n+1CN), e.g. ethanenitrile
Isomerism
Structural isomerism – same molecular formula but different structural formulae
1. Position isomerism – position of functional group is different between isomers. For C3H6Br2:
2. Functional group isomerism – different functional group present in molecules of same molecular formula.
C3H8O can be written as alcohol and ether:
3. Chain isomerism – carbon skeleton positioned differently between isomers. C4H10 could be written as:
Stereoisomerism – same molecular formula but arranged differently in space
1. Cis-trans isomerism – most common in C=C bond, position of atoms connected to C=C atoms are at the same
side for cis- and across each other for trans-. For Br2HCHC=CHCH3, can be written as:
2. Optical isomerism – molecules that is a mirror image of each other such that they do not superimposed. Carbon
atom with four different groups connected is called the chiral centre. CH3CHOHCO2H can be written as:
Organic reactions – mechanisms
Homolytic fission – both atoms at each end of bond leave with one electron becoming free radicals.
1. Initiation step – input of energy to break covalent bond forming two free radicals
2. Propagation step – free radicals attack reactant molecules forming more free radicals
3. Termination step – two free radicals reacting together to form a molecule; no more free radicals formed.
Heterolytic fission – more electronegative takes both electron of the covalent bond.
Curly arrows are used to show the movement of a pair of electrons.
Types of organic reaction
1. Addition – two reactants into one product, e.g.
2. Substitution – replacement of one atom or more by another, e.g.
3. Elimination – one reactant into two products, e.g.
4. Hydrolysis – breakdown of molecule by water, e.g.
5. Oxidation – loss of electron from a species, addition of O atom e.g.
6. Reduction – gain of electron from a species, addition of H atom e.g.
Terminology enrichment
Electrophile – acceptor of a pair of electrons
Nucleophile – donator of a pair of electrons
Carbocation – alkyl ion that could either be primary, secondary, or tertiary
Positive inductive effect – pushing of electrons effect done by alkyl groups to adjacent groups. This is why the
primary carbocation is least stable and tertiary carbocation most stable.
Alkanes
A saturated hydrocarbon
Reaction of Alkanes
Combustion – if complete, C and H are oxidised fully to become CO2 and water respectively.
If incomplete,
Free radicals substitution – homolytic fission started with sunlight as energy input.
Alkenes
An unsaturated hydrocarbon
Reaction of Alkenes
Addition
Addition of hydrogen – Ni catalyst at 140 0C, producing alkane.
Addition of steam – conc. Phosphoric acid catalyst at 330 0C and pressure 6MPa, producing alcohol.
Addition of hydrogen halides – bubbling alkene to hydrogen halide solution at room temperature, producing
haloalkane. Markov Nikov principle is used here, to get the major product.
Addition of halogens – coloured solution of halogens turned colourless, producing haloalkane. Electrophilic
addition reaction.
……
Oxidation
Oxidation by cold dilute acidified manganate(VII) solution – producing diol.
Oxidation by hot conc. acidified manganate(VII) solution – producing either ketones, aldehydes, carboxylic
acid or carbon dioxide, depending on what is bonded to the carbon atom in C=C bond.
Polymerisation
Addition polymerisation – small reactive molecules that form polymers are called monomers.
Halogenoalkane
Nucleophilic substitution reactions
Reaction is carried out under reflux
Fastest reaction is with iodoalkanes and slowest with fluoroalkanes due to difference in bond energy of C-X
1. With aqueous alkali, OH- - alcohol is formed, hydroxide ion is a nucleophile.
2. With cyanide ions (in ethanol), CN- - potassium cyanide solution in ethanol is used, nitrile is produced.
3. With ammonia (in ethanol), NH3 – amine is formed, excess of ammonia.
This is a primary amine. A secondary amine like (CH3CH2)2NH would be
formed if ammonia is not in excess, such that the primary amine acts as a
nucleophile and attacks the halogenoalkane.
