Organic Chemistry

ngl in organic chem it’s more useful to learn the concepts and understand the mechanism then
memorise separately
the reactions from each chapter & some explanations/details to know regarding them (which
kinda? helps with memorisation) are in the summary the concepts/other things to know are
within each specific chapter
personally just find it easier learn that way ;-;

Chapter 8 – Introduction to Organic Chemistry

 Basic Introduction
o In Organic Chem we study carbon-containing molecules (organic compounds)
 Note that hydrocarbons are only a subset of organic compounds!
 hydrocarbon: only C and H
o Types of carbon chains
 Aliphatic – Open carbon chains (may have branches/double or triple
bonds)
 Alicyclic – compounds with closed rings of carbon atoms
 Aromatic – Compounds containing an aromatic system (commonly
benzene)
o Homologous Series (not important)
 Contain the same functional group, each successive member increases
by a -CH2- unit
 They:
 Have a general molecular formula (because arithmetic
progression)
 Show a regular trend in physical properties
 Can usually be prepared with similar methods (since its mostly
the functional group that matters)
 Have similar chemical properties
 Functional Groups
o A group of atoms that defines the physical properties & chemistry of that
compound
o note that there are many other functional groups, these are what’s covered in
the A-level syllabus
o Alpha α & Beta β positions
 α-carbon refers to the C directly next to
the functional group (carbons WITHIN
a FG don’t count towards α/β)
 α-hydrogen refers to the H bonded to Cα
 β-carbon refers to the 2nd carbon from
the functional group
o Substituents & Degree of substitution
  A substituent is an atom/group of atoms that takes the place of the
hydrogen atom in a hydrocarbon chain
 Usually alkyl (alkanes) or aryl (benzene ring)
 About this: when the term “R” / “R-group” is used, it literally just
means “Rest of the molecule”, referring to adjacent carbons that are
not part of another functional group (i.e. mostly alkyl groups)
 the specific identify of the R group will generally not radically change
the reactions of a compound: e.g -CH2CH3 is quite similar to -
CH2CH2CH3
 Degree of substitution: Primary, Secondary, Tertiary
 Primary 1º: one alkyl/aryl substituent
 Primary 2º: two alkyl/aryl substituents
 Tertiary 3º: three alkyl/aryl substituents
 NOTE that what they are bonded to differs!
 in Alcohols/Halogenoalkanes, the substituents are bonded to Cα
 In amines/carbocations/carbon radicals, the substituents are
bonded to the N/C+/C. atom directly!

 Types of Formulae
o Empirical & Molecular Formula: same as before
 almost never used in Organic Chem unless it’s some stoichiometry
question
o Structural formula: shows how atoms are joined together in a minimal way
that isn’t unambiguous: CH3CH(OH)CO2H lactic acid
 get used to reading this & converting it to structural formula
 To understand this, read from left to right and construct formula from
there
 If something is like 1-iodobutane CH3(CH2)3I, the CH2 is in a long
straight chain
 If something is like (CH3)2CHCH2Br, the 2 CH3 groups are bonded to

the same carbon:

o Displayed (full structural formula)
 detailed structure showing ALL bonds and their relative placing

 Rings of atoms are often still represented by their skeletal formula:

o Skeletal formula
 The best (and fastest) way to draw
organic molecules; super easy to read too
 Hydrogen atoms connected to carbon are
removed
 Carbon-carbon bonds & functional
groups remain
o Stereochemical formula
 shows 3D spatial arrangement of bonds,
usually around a stereochemical centre
(see Isomerism)
 Normal (straight) lines indicate in the plane of the paper
 Solid wedges (the black thingy) indicate pointing out of the plane of
the paper – towards you
 dashed/hashed lines (the linelineline thingy) indicate bonds pointing
away from you
 Drawing skeletal formulae
o With the carbon chain, go in a zig-zag manner (to allow for the
tetrahedral/trigonal planar geometry)
o Note that triple bonds will have linear geometry:

o Every joint/end point is a C atom i.e. when you put your pen down on the
paper, that point is already a C atom
o Filling in implicit hydrogens: all carbon atoms must have 4 bonds unless
stated otherwise (with -ve charges to fufil octet, or to indicate hydrogen loss)
o When drawing double bonds, try to draw other bonds as far apart from the
double bond

o Direction doesn’t really matter with normal zig-zags

o Thou shall NOT draw a carbon with >4 bonds/electron domains

o If you are drawing displayed formula, you HAVE to put in the hydrogens
instead of just C-C-C-C-C
 Nomenclature
o Background
 many compounds have “common names” derived from their source:
e.g. when large numbers of dead ants are collected and distilled, the
acid obtained is formic acid from the Latin word for ant, formica
  However, what about lab-synthesised chemicals? What about a logical
system of naming compound that doesn’t require an infinitely long list
of (ultimately) meaningless names??
 our besties over at IUPAC have the solution just for you!
Nomenclature
there is a really long long list of rules & exceptions that is continually
updated as you have to account for all possibilities, but this is what you
need for the As: (in order of where it is in the name) SSPUFthis mnemonic makes
zero sense difhjdbd

[Numbering is present throughout]

Stereoisomerism – Substituents – Parent Chain – Unsaturation – Functional Groups
o Numbering
 All about giving the smallest value of “locant numbers”
 Same FG – Double – Triple bond rules:

 If there is no FG, number the chain so that the substituent has the
lowest number
 If there is >1 substituent, number the chain so that there is the smallest
set of numbers:

this monstrosity is 2-bromo-3-chloro-1,1,1-trifluoroethane

 Applying numbers to the name
 generally goes in front of the respective component
 Numbers are separated by commas, letters-numbers are
separated by dashes
  For double/triple bonds, the lower number is taken e.g. hex-2-
ene

 Multiple identical substituents must all be numbered: 2,3-

dibromo-4,4-dichlorohexane
 Multiple different substituents are arranged by alphabetical
order of their name (not including the “di”) e.g. 2-chloro-3-
ethyl-2,4-difluoro-4-methylnonane
 Stereoisomerism follows the carbon numbering conventions for
carbons (2R, 4S) /double bonds (cis-but-2-ene)
o Stereoisomerism
 Cis-trans (H2), E/Z (H3), R/S (H3)
 e.g cis-pent-2-ene
o Substituents
 If there are multiple substituents of the same type, add the prefix
indicating their number
di: 2 | tri: 3 | tetra: 4 | penta: 5 | hexa: 6
 Substituents are ordered in terms of alphabetical order
 List of substituent names:

In naming, halogens are not used as functional groups but treated as

substituents even if they are the FG e.g. 1-iodobutane CH3(CH2)3I
Hydrocarbons are “-yl”
Alkenes are called “enyl”, triple bonded C is “ynyl”
 There are multiple way to represent alkyl substituents: either by
structural formula, skeletal formula of an abbreviated name e.g. Tert-
butyl (CH3)3C- is t-Bu
 Branched alkyl substituents:
  It may be wise to just name the substituent separately from the
parent chain

o Parent
 Choosing the parent chain: (in order of priority)
 Contains the functional group (note that the length of carbon
chain INCLUDES the carbon in the functional group) e.g.
butanoic acid has 4 carbons
 Contains more double bonds
 Contains more triple bonds
 Contains the most number of carbons
 If the carbon atoms are joined in a ring, “cyclo-” is added in front (e.g
cyclohexane)
 Naming the number of carbons in the parent chain:
o Unsaturation
 Unsaturation refers to double/triple bonds as there are fewer than the
maximum number of H atoms possible for that number of carbons
 No unsaturation: “-an-” (eg methane)
 Double bonds: “en” (pronounced een)
 Triple bonds: “-yn-“ (pronounced ine)
 Double bonds are placed first e.g. Pentadeca-8,10,14-trien-4,6-diyn-3-
ol
o Functional Group
 The primary functional group follows a priority list:

 Any other functional groups of lower priority become substituents

o [FYI] Nomenclature of connected rings

 IUPAC name for this thing is naphthalene

 For connected rings, the larger ring/longer carbon chain substituent
comes first, the other takes the -yl substituent e.g. 1-
cyclopentylcyclohexane
  If the rings share a carbon e.g. spiro[4,5]decane: “dec” – 10 carbons
total
 spiro carbon is the sole C atom joining the 2 rings

 The basis mechanics/patterns of organic reactions, organised in pairs

o Substitution: Standalone but simple

o Addition/Elimination
 Addition: Breaking a π bond to form 2 new σ bonds
 Elimination: Opposite of addition, removal of a molecule (new π bond
formed)

o Condensation/Hydrolysis
 Condensation: Two molecules combine, small molecule such as H2O
eliminated (condensation is NOT Elimination!!)
 Esters/Amides are formed as a result
 Concept of “half & half” – half of each molecule contributes to
the H2O/small molecule
  Mechanism for this is Addition - Elimination (H3); but these
add & elim processes ARE the steps from above
 Hydrolysis: Generally opposite of condensation, H2O thrown in
 Often catalysed by dilute acid/base

o Oxidation/Reduction
 This is where the “perfectly ionic Lewis structure” way to discern
oxidation states comes in handy
 Oxidation – oxidation state of the functional group increases (e.g. -1 in
ethanol to +3 in ethanoic acid)
 Reduction – oxidation state of the functional group decreases
 In general however:
 oxidation = O atoms added/H atoms removed
 reduction = O atoms removed/H atoms added
o Writing balanced redox reactions in organic chem: Simplified EOHC (use [O]
for oxygen atoms added, [H] for hydrogen atoms added)
 E: balance your elements
 Just like redox EOHC, you’ll be using H2O
 For oxidation: add H2O to balance the H followed by [O] to
balance O
 H: For reduction: add H2O to balance the O followed by [H] to
balance the remaining H
  This time H isn’t balanced with H+ that’s all
 Mechanisms
o Arrow-pushing
 Involves formation/breaking of covalent bonds
 Curly arrows are used to represent electron flow
 The tail represents the electron source
 The head represents where the electrons are going to
 Single electrons have a partial head
 An electron pair has a full head

o Homolytic Fission (“homo-”: same)

 A bonding pair of electrons is given equally to each atom
 Generally occurs where there is little to no EN difference
 Free radicals (species with unpaired electrons) are formed
 Radicals are highly reactive; will readily form bonds

o Heterolytic Fission (“hetero-”: different)

 Both bonding electrons are given to one atom (usually the more EN
one)
 Results in the formation of ions
 Carbocations are species with a positively charged carbon ion
C+ (6 valence electrons)
  Carbanions are species with a negatively charged carbon ion C-
(octet)
 E.g Grignard Reagent: electrons are pushed to more
electronegative C (remember metals want to lose electrons to
obtain octet)

o Arrow pushing in bond forming

 Reaction Mechanisms – Polar molecules
o Heterolytic fission & bond formation occurs
o Electrons move from electron-rich to electron-poor sites
o Nucleophiles & Electrophiles
 “philos” means loving in Greek -> hence the “phile
suffix
 Nucleophiles: Nucleus-loving; electron-rich
 Donates an electron pair to form a covalent bond
 Comes from either a lone pair of electrons/negatively charged
species e.g. HO:- or double bonds (H2C=CH2)
 Lewis Bases
 Electrophiles: Electron-loving
 Accepts an electron pair to form a covalent bond
 Has a positively charged centre (e.g. +CH3)
 Induced/permanent partial positive charge (e.g. H in HBr: Hδ+-
Brδ-)
 Are Lewis acids
 Note that beyond this point acid-base behaviour refers to the Bronsted-
Lowry definition, if not the entirety of organic chem is acid-base
chemistry (which isn’t very useful)
o Arrow-pushing
 Nucleophiles attack electrophiles
  The tail of the arrow must be PRECISELY AT the source of the
electrons (e.g lone pair) and the head be EXACTLY AT the atom
where the new bond is formed
 there can’t be ambiguity

 Reaction Mechanisms – Non-polar molecules

o Homolytic fission & fusion occurs
o Only non-polar mechanism in the As is Free-Radical Substitution (Alkanes)

 Factors Affecting Reactivity & Stability

o Generally, organic species with a charge on it are less stable. Therefore,
anything that disperses the charge increases stability & vice versa (intensify ->
destabilise)
o Mesomeric/Resonance/Delocalisation effect
 Generally the strongest/most dominant effect
 Delocalisation occurs when 3 or more p-orbitals on 3 or more adjacent
atoms overlap | note when you need to explain delocalisation in exam,
useful to draw these and say XXX atoms are sp2 hybridised:

(in enolate ion)

  A π-electron cloud is formed, in which the involved atoms gain partial
double bond character
 More effective resonance occurs when the orbitals are small (more
effective orbital overlap) and the orbitals are of similar size (so 3p of
Cl and 2p of C will not have efficient resonance
 Note efficient resonance is NOT the same as “no resonance”
o Induction
 Arises due to a difference in electronegativity
 an EN atom will withdraw electronic density from the atom adjacent to
it -> creating a partial positive charge
 Occurs via σ bonds and decreases with distance
 Groups with EN atoms are inductively electron withdrawing groups
(eg Cl, -OH, -NH2)
 Alkyl groups are electron donating (via hyperconjugation; H3)
 A H2 way to explain it is using sp2/sp3 character
 In carbon radicals/carbocations, the geometry is sp2 with
adjacent sp3 alkyl carbons
 sp2 orbitals have greater s character -> smaller -> attracts
electrons more strongly to the nucleus -> higher EN
 therefore EN of sp2 > EN of sp3
 However they will still be in the EN
ballpark of EN of carbon, so
compared to the inductive effect of
an actual EN atom like N/O/F/Cl,
this effect is weaker
 Sterics
o Steric hindrance results from the repulsion between electron clouds of groups
of substituents
o This a) hinders approach b) there is less “area” for the incoming nucleophile to
attack; electrophile is “shielded”

o The steric factor is affected by:

 Larger groups -> more steric hindrance
 More groups -> more steric hindrance
Chapter 9 – Isomerism
 Isomers are molecules with the same molecular formula but different arrangement of
atoms (bonding wise, or in space)
o They have different IUPAC names, and thus are different molecules
 3 types of isomerism in H2
o Constitutional (structurual)
o Cis-trans
o Enantiomerism
 Constitutional (structural) isomerism
o Same molecular formula, different structural formula (i.e. different ways of
connecting the same number of each type of atom) – You can clearly see the
differences in connection clearly on paper
o Ways to obtain structural isomers:
 [chain isomers] Change the carbon chain: branch the carbon chain (or
you could say, move the terminal -CH3 to a different carbon)
 [positional isomers] Different position of the SAME functional group
 [functional group isomers] The same type of atoms and bonds, but a
different functional group
 Ketone R’CHOR & Aldehyde RCHO
 Ester HCOOR & Carboxylic acid RCOOH
 Alcohol R-OH & Ether R-O-R’
 Alkene + Alcohol & Ketone/Aldehyde

 Deducing possible constitutional isomers (is in syllabus!)

o Identify the Degree of Unsaturation (DOU)
o Identify likely functional group(s) with said DOU (DOU 1 with O, probably
looking at ketone/aldehyde, or alcohol + alkene?)
o Using the number of carbon atoms, draw all possible carbon chains: start with
straight, then gradually increase the extent of branching until you get
everything
o Place the functional groups placed at all possible different positions on the
carbon chains
o Repeat the step with other possible functional group/combinations of FGs
 What’s DOU?
 1
o Formula: DOU= [ 2ηC + 2 - ηH - η X + η N ]
2
 η: number of _ atoms (not amount, like in stoichio)
 C, H, N refer to usual carbon/hydrogen/nitrogen
 X: any halogen
o Each (1) DOU indicates presence of 1 π bond/ring
 note triple bond constitutes 2 π bond; 2 DOU
 Saturated = only single bonds
 However cos rings like cycloalkane exist, a non-zero DOU doesn’t
imply there is unsaturation
o Derivation of DOU:
 2C + 2 = max number of hydrogens in a saturated alkane
 - H = removing number of hydrogens to see “missing H”
 - X = halogens substitute themselves hydrogen; in this context they
behave identically
 + N = Nitrogen will bring in another H atom, so we must remove that
(think: CH3 -> CH2NH2)
 Why no O? it doesn’t affect the number of hydrogens
 C – C -> C – O – C
 C – H -> C – O – H
 Stereoisomerism (quick intro)
o Same molecular & structural formula [bonding and functional groups
identical] but different arrangement of atoms in 3D space
o Two types: Cis-trans & Enantiomerism
 Stereoisomerism: Cis-trans
o Conditions for cis-trans
 Covalent bond with restricted rotation (π bond or ring)
 Non-identical groups attached to each end of said bond
o In alkenes:
 [unlike the conformational ‘isomerism’ of alkanes] rotating the C=C
bond with respect to the other end is not possible without breaking the
π bond

 there is restricted rotation about the C=C bond due to the π bond
  If the two groups on each end of the alkene are different, then the
alkene can be cis-trans:
 “cis” – identical groups on the same side
 “trans” – identical groups on opposite sides

o Other molecules:
 cycloalkenes – only cis isomer can exist
 larger ringed alkenes are able to accommodate the trans form
 Cycloalkanes can be cis-trans if there are non-identical groups attached
to each carbon
 NOTE: by right these are kinda both enantiomers and cis-trans
isomers … :(

 Enantiomerism
o A molecule’s mirror image is non-superimposable onto itselfjust fyi, this should actually be
“superposable” hehe; superimpose just means to put one on top of another

o Fun fact, your body is also chiral too! case in point, look at your left and right
hands; they’re mirror images :)
o Conditions for enantiomerism (state both in exams)
 (very often) contain one or more chiral centres
 do not possess an internal plane of symmetry
o What is a chiral centre?
 An atom with tetrahedral geometry around it that is bonded to 4
different groups

 Chiral centres are denoted with an asterisk *

 Now this is where it is important to recognise implicit hydrogens, as
they can be one of the 4 groups!

(there is a H on each chiral C)

o Cases with >1 chiral centre:
 A molecule with >1 chiral centre can exhibit enantiometrism if they
don’t possess an internal plane of symmetry:
  FYI, A and C are known as diastereomers as their mirror images are
non-superimposable (so they are stereoisomers) but they are not mirror
images of each other
 Meso compounds
 Meso compound are stereoisomers with 2 or more chiral
centres but no optical activity due to an internal plane of
symmetry

 P and R are hence diastereomers, with P also being meso

 Properties of enantiomers
o Physical Properties:
o Identical (the EXACT same) physical properties
 density, electrical conductivity, colour, melting/boiling point
o Rotates plane-polarised light in opposite direction to each other
 a sample that is “optically active” is said to contain chiral molecules
 each enantiomer is rotating the light by the same angle though
 FYI it is not possible to predict the direction of rotation based off the
structure
 Therefore, regarding 50/50 mixture of enantiomers:
 a 50/50 mixture of enantiomers is known as a racemic mixture
  the clockwise rotation caused by one is cancelled out by the
anticlockwise rotation of the other
 thus, racemic mixtures are optically inactive
o Chemical properties
 Identical chemical properties except when the other reagent is chiral
 think: left hand doesn’t fit into a right handed glove
 Since the human body is chiral, enantiomers will have vastly different
biological properties, especially relevant for drug action
 Calculating the number of stereoisomers
o If a molecule has m chiral centres and n double bonds, the maximum number
of stereoisomers it can form is 2m+n
o The actual number of stereoisomers is determined by considering internal
planes of symmetry

Chapter 10 – Alkanes
 Alkanes are the simplest and least reactive homologous species in organic chemistry
 They can called Hydrocarbons; for they only contain hydrogen and carbon
 Alkanes have the general formula
 Alkanes only contain sp3 hybridised carbon
o Straight chain – connected in a continuous line
o Branched – carbons within the chain may be connected to more than 2 other
carbon atoms
 Straight/branches alkanes have a general formula CnH2n+2
o Cycloalkanes – closed rings of carbon atoms
 General formula: CnH2n
 Alkanes can exhibit constitutional isomerism & enantiomerism
 Physical properties
o Alkanes are non-polar; usual id-id story
o Immiscible with water, and less dense than water (will float in water)
o Boiling point increases regularly with increasing number of carbon atoms in a
chain
o RECAP: Branched alkanes have lower boiling point than straight chain alkane
of the same Mr; surface area of contact for id-id forces
o Melting point
 Packing effect becomes significant now (arrangement of molecules in
a solid crystal lattice
  Boiling point is a measure of the id-id surface area
 Generally, the more densely packed something is, the higher the
melting point, especially for covalent compounds since packing
efficiency affects surface area of contact and in turn, dispersion forces
o Viscosity
 Viscosity increases with number of carbon atoms present
 id – id increase
 long molecules tend to “tangle” with each other
 Chemical Properties
o Combustion
 Complete combustion (use Stoichiometry): CxHy + (x+ 0.25y)O2 ->
xCO2 + 0.5yH2O
 Incomplete combustion gives carbon and carbon monoxide
 2CH4 + 3O2 -> 2CO + 4H2O
 CH4 + O2 -> C + 2H2O
 Free-radical substitution (FRS)
o UV light is necessary to break strong covalent bonds to form radicals
(covalent bond broken homolytically)
o C – H won’t break but Cl – Cl will (compare their BE values: C-H is 410 vs Cl
- Cl 244kJmol-1)
o FRS is known as a chain reaction as a radical reacts to regenerate another
radical allowing the reaction to continue
o As the reaction is self-sustaining, only a short burst of UV light is needed to
break Cl-Cl bond in the initiation step; in fact, prolonged exposure to UV light
may cause an uncontrolled explosion as too many reactive radicals are formed
(bond forming is exothermic, remember)
 Formation of FRS side-products
o Extent of substitution is difficult to control
 You can favour mono-sub with excess alkane
  Favour multi-sub with excess halogen
o CH4 + Cl2 can give CH3Cl, CH2Cl2 etc
o Position of substitution is also difficult to control (all H atoms are susceptible
to substitution)
 Ratio of products formed are determined by 2 factors:
 Stability of radical intermediate
 Statistical probability of attack
 Stability of alkyl radicals
o Alkyl groups are electron donating, compensating for the electronic deficiency
of carbon radicals [this same story will re-appear for carbocations in Alkenes]
o Therefore the more alkyl groups attached to the carbon radical, the more stable
it is
o 3º radical most stable, followed by 2º, then 1º
 Predicting ratio of products
o (if data is given) Ratio of products can be calculated by:
 (Relative reactivity of that H) x (ratio of that H against total)
 If not, use statistical probability, then discuss variations of that based
off reactivity
 More stable intermediate, more likely to form the corresponding
product
o Number of hydrogens at a given position (symmetry very important here!!!!)

o all 6 terminal hydrogens are the same!!!

o these 2 products are

the same!!!!
o FYI, the fewer the number of monosubstituted products, the greater the
alkane’s symmetry
 o 1 product only, all 6 -CH3
groups are the same
 Reactivity of different halogens
o F2 least reactive, I2 most reactive
o Explained with BE (X-X) & BE(C-X) + ΔHrxn = BE (reactants) – BE
(products)
o BE(X-X) will tell you how endothermic the initiation step is
o More endothermic, less likely (higher Ea)
 Some environmental chemistry (this is actually in syllabus)
o Petroleum is distilled from crude oil (a mixture of hydrocarbons)
o While it is an important energy source, it is a non-renewable resource (it
doesn’t regenerate itself as quickly as humans can use it)
o Recycling & its importance
 Importance (just smoke something)
 Is a key component of Reduce – Reuse – Recycle
 prevent waste of potentially useful materials
 reduce consumption of fresh raw materials
 Reduce pollution in:
o Air – incineration
o Water – landfills (harmful chemicals are released from
rubbish in landfills)
 Large amounts of energy are used in production from raw
materials i.e. recycling lowers energy consumption
 Preserve natural resources for future generations
o Environmental consequences (with some recap from Kinetics)
 Carbon monoxide
 Arise from incomplete combustion of fuel
 A pollutant and toxin as it bonds irreversibly with haemoglobin
in blood -> blood can nolonger transport oxygen -> eventually
you die >:(
 If you want to read for fun:
https://chemistry.stackexchange.com/questions/33780/why-
does-carbon-monoxide-have-a-greater-affinity-for-hemoglobin-
than-oxygen
 Nitrogen oxides (must memorise equations pls)
 Formed inside combustion chambers of motor vehicles (high
temperature allows strong covalent bonds in N2 to be broken)
 o N2 (g) + O2 (g) -> 2NO (g)
o 2NO (g) + O2 (g) -> 2NO2 (g)
 Photochemical smog (A mixture of ozone, nitrogen oxides,
unburnt hydrocarbons and other gases) causes respiratory
issues & harms plants
 Acid rain
o NO2 dissolves in water to give nitrous & nitric acid
o 2NO2 (g) + 2H2O (l) -> 2HNO3 (aq) + HNO2 (aq)
o NO2 also catalyses the formation of sulfuric acid (via
SO3, think periodicity)
 SO2 (g) + NO2 (g) -> SO3 (g) + NO (g)
 SO3 (g) + H2O (l) -> H2SO4 (aq)
 regeneration:
NO (g) + 0.5O2 (g) -> NO2 (g)
 CFC (chlorofluorocarbons)
 Ozone depletion
 Catalytic converter
o Removes pollutant gases via oxidation/reduction
 Nitrogen oxides
2NOx + 2x CO -> N2 + 2x CO2
e.g. 2NO + 2CO -> N2 + 2CO2
 Carbon monoxides
2CO + O2 -> 2CO2
 Unburnt hydrocarbons
CxHy + (x+ 0.25y)O2 -> xCO2 + 0.5yH2O
o contains some transition metal catalyst like platinum alloy
o is heterogenous catalyst … adsorb … blah blah blah
o Lead “poisons” the catalyst (destroy catalytic action)
 Enhanced greenhouse effect
o Definition (WAS ACTUALLY TESTED IN A LEVEL 2022 P2)!!!!
 Increased temperature on Earth’s surface due to the release of
greenhouse gases from human activities
o Greenhouse gases:
 CO2, CH4, H2O vapour, NO, SF6, CFC/HFC/PFCs etc.
Chapter 11 – Alkenes
 Alkenes are unsaturated hydrocarbons containing the C=C double bond
o they have fewer than the maximum number of hydrogens
 General formula CnH2n (for 1 DOU from C=C bond only)
 [Recap] Structure & Bonding in ethene

 Exhibits cis-trans isomerism

o FYI:
 Cycloalkenes with up to 7 carbon atoms cannot exist as the trans
isomer (technically cyclohept-1-ene can, but it’s really unstable,
30minute half life at 0ºC)
 > 8 C atoms can exhibit cis-trans
 Physical properties
o Boiling point of homologous series: usual id – id story
o Boiling point of cis/trans alkenes: cis isomer has higher boiling point
 Cis isomer is more polar as it has a net dipole moment, allowing for
stronger pd-pd interactions
 Trans isomer only has id-id interactions
 o Melting point of cis/trans alkenes: trans isomer has higher melting point
 Again, it’s the same packing density story from before
 The trans isomer packs better due to the higher symmetry
 trans isomer is straighter, cis isomer looks more like a “U”
o Solubility
 Soluble in non-polar solvents (favourable pdpd)
o Density
 Alkenes are less dense than water
 The more carbons present, the stronger the pd-pd attraction, the closer
the molecules will be, the higher the density
o Viscosity
 More pd-pd, more viscous
 Straight chain alkenes more viscous than branched alkenes
 Reactions of alkenes
o In nucleophilic addition the electrophile is added first ALWAYS hence you
can’t have a product where there are 2 nucleophiles present :(
o Stability of the intermediate determines where the nucleophile goes to in
nucleophilic addition
o Carbocation intermediates:
 C+ sp2 hybridised/trigonal planar about the C+
 C+ is electron deficient and will attract nucleophiles
 Give racemic mixtures because nucleophile can attack from either side
of the plane WITH EQUAL PROBABILITY
o Stability of carbocation intermediate (found in many other places too, if u
have a carbocation the story is the exact same)
 all about dispersing the positive charge ON THE CARBON ATOM
 bonded to more electron donating alkyl groups, positive charge
dispersed more, more stable; therefore 3º C+ most stable, followed by 2º
etc.
 electron withdrawing substituents like halogens will destabilise
carbocation as the intensify the positive charge
 Resonance: there can be delocalisation of the positive charge over the
benzene ring, dispersing the … etc (same with radicals BTW)
 Addition across an asymmetrical alkene
 o Different intermediate stability – the more stable intermediate forms the major
product/in greater proportion
o note it doesn’t mean if the intermediate is less stable, the corresponding
product isn’t formed: it is but in smaller amounts
o If you’re worrying about steric hindrance around the carbocation:
 The step forming carbocation intermediate has the higher Ea and thus
affects rate of formation (in layman terms, the stable intermediate
tends to form first and then the nucleophile’s attack follows after that)
o Markonikov’s Rule
 just learn this for the exam incase you need to state in in the exam like
“explain why this follows but don’t follow it
 The H atom (electrophile) adds onto the C atom of the double bond
that holds the greater number of H atoms
 Comparing resonance VS inductive effects
o Consider 2-chlorobut-1-ene undergoing electrophilic substitution: what is the
carbocation formed?
o Carbon 2 has 2 alkyl groups but EN Cl atom inductively withdrawing density
o Carbon 1 has fewer alkyl groups but weaker inductive effect from Cl
o However, C2 has resonance structure where all atoms have octet configuration
(h3 concept) and therefore is more stable:
Chapter 12 – Arenes
 All about benzene rings
 Aromaticity refers to the extra stability of benzene & its structural relatives due to the
delocalisation of electrons
 Extra nomenclature stuff
 Physical properties
o Colourless liquid at r.t.p, the rest is id-id story
o Substituents on the benzene however can introduce their own types of bonding
e.g. phenol & H-bonding = phenol higher boiling point
 Structure of benzene
o Each carbon atom is trigonal planar, sp2 hybridised
o C-C-C bond angle is 120º
o C-H bond is s – sp2
o remaining unhybridised p orbital of the 6 carbons forms side-on overlap
equally to give a delocalised π electron cloud
o π electron cloud is electrophilic
o each carbon-carbon bond is identical in length, with both bond length and
bond energy between C-C and C=C (partial double bond character)
o quick reminder that the BE of C-C in benzene is a specific value and is
GIVEN IN THE DATA BOOKLET
o When doing enthalpy calculations with benzene, you need to (if applicable)
break all 6 benzene C-C bonds and then form the required number of
C-C/C=C bonds from there to convert from the resonance structure to the
normal Kekule structure
 Drawing of benzene
o There are 2 structures: Kekule (left) and Resonance (right)

o While the resonance structure is more accurate, it makes electron-counting

more accurate & understandable
o e.g for electrophilic substitution, it’s easier to see the 4 delocalised electrons in
the intermediate with Kekule structures (altho this is NOT what to draw in As)
 Reactivity of benzene VS alkenes
o While both electron-rich benzene and alkenes are nucleophiles
o the delocalisation in the π electron cloud results in resonance stabilisation
giving extra stability.
o Hence, the π electron cloud in benzenes are less susceptible to attack by
electrophiles
o Hence, (big concept here) benzene requires stronger electrophiles
o The electrophilic substitution of benzene results in the aromaticity being
preserved.
o unlike electrophilic addition, where the π bond is broken, leading to
aromaticity being destroyed
 Electrophilic substitution
o The pre-requisite is the generation of a STRONGER electrophile to attack the
benzene ring
o The initial attack of the benzene ring is the slow step as the delocalisation of
the 6 π electrons is disrupted
o Shape of intermediate:
 About Lewis Acid catalysts
o The Fe in FeBr3 accepts a LP from the Br in Br2, creating the electrophile Br+
o Lewis acid catalysts must be in ANHYDROUS conditions as water is also a
Lewis base (also Fe3+ can form [Fe(H2O)6]3+ aqua complex, and is no longer
electron-deficient)
 Substituents
o Electron-donating groups EDG direct the electrophile to 2,4,6 positions
o Electron-withdrawing groups EWG direct the electrophile to 3 position
o Overall electron-donating groups increase electron density, hence benzene
ring is activated to electrophilic attack. They are called activating groups.
o Overall electron-withdrawing groups
o There is a table on this in the Data booklet
o Recap: Inductive effect & delocalisation
o Atoms with lone pairs of electrons directly joined to the benzene ring can
donate the LP into the benzene ring via delocalisation (eg -OH, -OR, -NH2 etc)
o Atoms with double/triple bonds to EN atoms like N/O will withdraw electron
density via delocalisation
o (disclaimer this is a lot easier with formal charges & resonance structures but
that’s h3)
 Rules regarding the directing effect
o With 1 substituents, position of electrophile E is just what’s given in the Data
Booklet
o what if there are multiple groups?
o 1) If both can direct to a common position, E will go to said position
o If each directs to a different position, then follow the directing effect of the
more strongly activating (or if both are deactivating, least deactivating group)
o Steric factors: Substitution between 1,3 substituents rarely occurs because of
steric hindrance
o Between 2 and 4th position, 4th is favoured as major product because of steric
hindrance from the substituent
o NO substitution on places where there is no hydrogen
 [FYI] why the directing effects?
o resonance! concept still the same, it’s about the stability of carbocation
intermediate
o put the positive charge under the EDG, make sure the EWG cannot have the
positive charge under it
o has come out in higher order A level question before
Chapter 15 – Halogen Derivatives
 this is where Organic Chem starts to become more “fun”
 Physical Properties
o Immiscible with & denser than water
o pd-pd & id-id story as per normal
o note the main intermolecular forces in halogenoalkanes are id-id and hence
iodo compounds have the highest boiling point (I has many electrons)
 Nucleophilic Substitution SN
o The C – X bond is reactive due to halogen atoms being EN -> polarised bond
with C having partial positive charge
o The halogen atom is substituted for another nucleophile like OH-
o SN2 is bimolecular nucleophilic substitution , 2 molecules reacting in rate
determining (slow) step
 Rate = k[RX][Nu:]
o SN1 is unimolecular nucleophilic substitution, 2 molecules reacting in rate
determining (slow) step
 Rate = k[RX]
o Energy profile diagrams of SN2 and SN1 respectively
o Stereochem
 SN2
 If the original R-X molecule is chiral, the stereochem around
the electron-deficient carbon will be inverted
 think of it as opening an umbrella the wrong way around

 If you start off with a pure mixture of enantiomers, will yield a

pure product (that is optically active)
 SN1
 All about the carbocation intermediate story from alkenes
 Recap: 1) trigonal planar about C+ 2) attack from top & bottom
of plane with equal probability 3) if product is chiral, racemic
mixture formed
 o Factors favouring SN1 VS SN2
 SN1
 more stable carbocation intermediate
 more sterically hindered C in C-X
 Commonly seen in tertiary halogenoalkanes; but don’t forget
benzene & delocalisation stuff
 SN2
 Less steric hindrance about the C in C-X
 less stable carbocation intermediate
 Commonly seen in primary halogenoalkanes
 Note that this is a bit of an overgeneralisation, something like

is sterically hindered by the tert-butyl

group
 Reactivity of halogenoalkanes
o All about the strength of the C-X bond
o As size of halogen atom increases, the C-X bond length increases and thus
extent of orbital overlap decreases, so C-X bond strength decreases
(decreasing Ea)
o C-F bond strong, unlikely to undergo nucleophilic substitution
 Reactivity of halogenoarenes
o Delocalisation
 The lone pair of electrons on the halogen atom delocalise into the
benzene ring, giving the C-X bond partial double bond character and
strengthening it
 This logic also applies to alkenes e.g. chloroethene; LP delocalise into
the C=C bond, or phenols
 remember that while 3p – 2p resonance in chlorobenzene is not
efficient, PARTIAL DOUBLE BOND CHARACTER STILL
EXISTS.
  Note that fluorine, while it has 2p orbitals like carbon, is way too EN
to want to donate its electrons so the resonance isn’t super efficient
either
 and this is why we say that halogen groups are electron-withdrawing:
they withdraw inductively (cos EN), while the
mesomeric/delocalisation effect is not very strong
 net electron flow is still to the halogen atom
o Sterics
 The rear of the C-X bond is blocked by the benzene ring (assuming
SN2)
 The π electron cloud of the benzene ring will also repel the lone pair of
electrons on the nucleophile
o Your benzene ring also cannot invert itself (assuming SN2)
 Environmental effects
o Fluoroalkanes are less reactive than chloroalkanes due to strong C-F bond
o Chlorofluorocarbons (CFCs):
 Are inert & non-flammable
 Are non-toxic
 liquify under pressure and vaporise ready when pressure is released
 odourless
 Hence they are used in refrigerants, aerosol propellants and fire
extinguishers
o Effects of CFCs on Ozone
 low reactivity of CFCs (strong C-F/Cl bond) means they are stable &
have a long life span
 they can diffuse into the atmosphere, where UV light can and
eventually will cleave the weaker C-Cl bond
 Cl radicals will destroy the ozone layer
 in other words, CFCs = destroy ozone
 (not sure if this impt) to protect ozone layer, ban CFCs or use
alternatives (eg hydrofluorocarbons)
Chapter 16 – Hydroxy Compounds
 FYI “hydroxy” refers to the -OH group, while “hydroxyl” refers to OH radicals
 Phenols (Ph-) specifically refer to an -OH group bonded to a benzene ring
 About the nomenclature of alcohols, note that -OH can be part of another functional
group (carboxylic acid -COOH), and you DON’T call them alcohols
 remember ethers R-O-R are constitutional isomers of alcohols
 Physical properties
o -OH group undergoes hydrogen bonding
o The non-polar part of an alcohol will still have id-id forces
o The strength of hydrogen bonding will remain relatively constant with
increasing alkyl chain length (but id-id becomes stronger, so boiling point will
increase)
o Solubility
 Alcohols are soluble in water because of H bonding
 Alcohols are great solvents because they dissolve in both organic &
inorganic compounds with the id-id carbon chain & pd-pd/hydrogen
bonding -OH group
 Solubility in water decreases with increasing carbon chain length: 1)
id-id increases 2) energy released from hydrogen bonding less able to
overcome stronger id-id in the alcohol (on top of H-bonding in water)
3) hydrogen bonding is affected by long non-polar alkyl chain
 Meth/Eth/Propanol are miscible with water
 butanol is only soluble in water
 Phenols are only moderately soluble because of the large aryl group is
non-polar
 Reactions of alcohols
o Alcohols combust, use stoichio to find the mole ratio
 Acidity of alcohols
o O – H bond can break to release H+ ion
o Alcohols are weaker acids than water, and hence are neutral
o Alkyl groups in conjugate base R – O- conjugate base are electron donating,
intensifying negative charge, destabilising it
o Electron-withdrawing groups (via say inductive effect like -CH2Cl or
resonance in phenols) will disperse negative charge, stabilising the conjugate
base (and hence increase acidity of alcohols)
 Acidity of phenols
o Phenols are acidic (more so than alcohols/water at least)
o Negative charge on a phenoxide ion can delocalise over the benzene ring,
dispersing the negative charge, stabilising the conjugate base
 o Same inductive rules apply as before: EWGs on the benzene ring (i.e.
deactivated benzene) will enable the ring to withdraw more electron density
from the negatively charged oxygen atom, stabilising the phenoxide ion
further
o The opposite is true too: EDGs decreases acidity as benzene is less able to
withdraw electron density from the negatively charged O, resulting in less
stable phenoxide ion
 Non-reactivity of phenols towards nucleophilic sub. SN
o Same reason as halogenoarenes:
o Delocalisation
 The lone pair of electrons on the halogen atom delocalise into the
benzene ring, giving the C-O bond partial double bond character and
strengthening it
 this time the delocalisation is more effective as O has 2p orbitals :)
o Sterics
 The rear of the C-OH bond is blocked by the benzene ring (assuming
SN2)
 The π electron cloud of the benzene ring will also repel the lone pair of
electrons on the nucleophile
o Your benzene ring also cannot invert itself (assuming SN2)
Chapter 17 – Carbonyl Compounds
 The carbonyl C=O FG specifically refers to C=O that is bonded to either CARBON
and/or HYDROGEN
 fast and quick way to memorise which FG is which: AldeHydes contain a Hydrogen
 Ketones need at least 3 carbons, the smallest ketone being propanone
 Physical properties of aldehydes/ketones
o Carbonyl group is polar due to the C=O bond
o pd – pd interactions exist ontop of id-id, increasing boiling point compared to
alkanes
o However they don’t have hydrogen bonding, hence boiling point is lower than
alcohol/carboxylic acid (for the same length of alkyl chain)
o Just like alcohols, carbonyl componds have both polar & non-polar regions,
making them effective solvents
o Smaller aliphatic ketones are able to form hydrogen bonds with water
molecules (LP on the O of C=O)

o
o With longer (non-polar) alkyl chain, solubility decreases, extent of pd-pd/H
bonding decreases, while id-id increases, so solubility decreases
 Nucleophilic Addition
o C in C=O bond is the electrophile
 O is the more EN atom
 delocalisation of π electrons over the O atom

the structure on the right can be stabilised by a Lewis acid catalyst

(such as the H+ cation!), leading to the carbonyl carbon having a
greater positive charge
o Reactivity of aldehydes/ketones towards nucleophilic additions
 Sterics
 The 2 bulky alkyl substituents in ketone (compared to 1 in
aldehyde)
 While the carbonyl carbon is indeed sp2 hybridised and sterics
is less significant, it still exists (remember molecules are really
small & atoms are super close together
 also MOT says that there is actually an angle of attack
  Electronics
 Ketones have 2 electron-donating alkyl groups, lowering the
carbonyl carbon’s partial positive charge and hence its
electrophilicity
 Delocalisation
 In say, benzaldehyde, the electrons of the benzene delocalise
over the carbonyl carbon, lowering the partial positive charge
 Formation of racemic products
o very similar to carbocation story
o The geometry about the sp2 hybridised carbonyl carbon is trigonal planar
o the nucleophile can attack the electron-deficient carbonyl carbon from either
the top or the bottom of the plane WITH EQUAL PROBABILITY
o hence leading to the formation of a racemic product if the resulting sp3 carbon
that is formed is chiral
 NaBH4 VS LiAlH4

o Both are sources of hydride ions H-, but LiAlH4 is the stronger reducing agent,
and is thus less selective (reacts with a bunch more stuff)
o because of this hydride ion, LiAlH4 MUST be anhydrous
o NOTE this means that LiAlH4 cannot reduce alkenes as alkenes are electron
rich (no electrophile for hydride ion to attack)
o Li+ VS Na+: Li+ smaller, higher charge density more able to accept lone pair of
electron from O atom in C=O/polarise C=O bond, increasing electrophilicity
of carbonyl carbon if LiAlH4 is used
o Al Vs B: Al is less EN (EN decreases down the group), this more of the
negative charge in LiAlH4 is held by the H atom
Chapter 18 – Carboxylic Acid Derivatives
 The carbon in C=O is less electrophilic than in carbonyl compounds as there is
delocalisation of the lone pair of the -OH/-O- group

 Hence, carboxylic acid groups, while containing the “carbonyl” group, because
differently from normal carbonyl compounds
 Nomenclature of carboxylic acid groups
o Carboxylic acid can only be found at the end of a carbon chain
o Carboxylic acid groups have the highest priority, so if u have that, your parent
chain will contain those 2 -COOH groups
o You can use “carboxy” as a substituent for molecules with 3 or more -COOH
groups e.g. 3-(carboxymethyl)hexanedioicacid

o There exists this annoying stuff tho (citric acid):

o apparently because of the need to have 3 COOH groups, there will be at least
one COOH group as a side chain; hence, tricarboxylic acid ⇒ the 3 C-atoms
are not part of the parent
o … oh well. nomenclature is 1 mark.
 Physical properties
 o Hydrogen Bonding is stronger than that of alcohols as the electron-
withdrawing C=O group causes the H atom to be more positively charged (and
hence, polarised O-H bond)
o Remember dimerization of pure carboxylic acids/solvated in solvents that
can’t form H-bonding

o carboxylic acids are soluble in water (because of hydrogen bonding)

o carboxylate salts are soluble in water (because of ion-dipole interactions)
o solubility decreases with longer alkyl groups/benzene
 Acidity of Carboxylic Acids
o Carboxylic acids are weakly acidic

o The acidity is all about the stability of the carboxylate conjugate base
 Comparing acidity (strongest to weakest)
o Carboxylic acid > Phenol > Water > Alcohol [exam may ask u to compare.
must say why alcohol is destabilised and not just be elimination]
o Negative charge in carboxylate ion is delocalised equally over two highly EN
O atoms, dispersing the negative charge and carboxylate anion is highly
stabilised
o conversely, phenol is a weaker acid as the negative charge on O is delocalised
over less EN C atoms, thus stability is lower
o Alkyl groups in conjugate base R – O- conjugate base are electron donating,
intensifying negative charge, destabilising it
o EDGs intensify negative charge on carboxylic acid, destabilising conjugate
base (hence acidity decreases)
 e.g ethanoic/propanoic/butanoic acid
 the length of alkyl change doesn’t affect acidity greatly (their pKa
values are super similar)
o EWGs disperse negative charge on carboxylic acid, stabilising conjugate base
(hence acidity increases)
o Usual factors of inductive effects & proximity apply here too
 o just remember: intensify negative charge -> destabilise & vice versa
o Electrons of benzene will delocalise into the COO- group, destabilising the
conjugate base (and decreasing acidity)
o Usual EDG (activating) & EWG (deactivating) rules apply to benzene too:
less activating, electrons are less able to delocalise into COO- group etc.
 Carboxylic acids are less electrophilic as the lone pair of the O atom bonded to H can
delocalise into the C=O group, lowering partial positive charge on the electron
deficient C atom


Carboxylic acid derivatives

 are compounds where the -OH is replaced by something else.
 For this chapter, esters and acyl chlorides will be covered: RCOOR & ROCl
 Nomenclature
o Acyl chlorides are called “-oyl chloride”
o Ester: “(the R bonded to C-O-R)oate” e.g. phenylethanoate
 Physical Properties
o pd-pd story
o unable to form H bonding as there is no H atom directly bonded to the EN O
atom
o Esters are insoluble in water, acyl chlorides hydrolyse in water to give HCl gas
o Acyl chlorides have a sharp, irritation odour (probably because of the
hydrolysis to give HCl)
o Esters smell pleasant, sweet or fruity (or just smell like something you’ve
encountered IRL like glue)
 Reactivity of Carboxylic acid & its derivatives [not in Learning Outcomes]

o Reactivity increases with increased electronic density of the carbonyl carbon

o Electronic Effects
 Inductive: All the above have 2 EN groups bonded to the carbonyl
carbon which should increase electron deficiency
  Resonance: However, extent of the LP delocalisation differs:
 3p orbital of Cl has poor & inefficient orbital overlap with the
2p orbital of sp2 hybridised orbitals of carbonyl C, therefore
extent of delocalisation is not as significant
 Both O and N have their LP in 2p orbitals which allows for
effective delocalisation of the LP over the C=O, decreasing
electronic deficiency of C atom
 as N is less EN than O, the extent of delocalisation is greater is
amides than carboxylic acids
 Therefore
 Cl is net electron-withdrawing
 O and N are net electron-donating
o Leaving group stability (H3)
 -Cl is a very good leaving group, followed by -OH, and NH2 is a really
bad leaving group
 Reactivity of Acyl Chlorides VS other chloro-compounds (is in exams)
Chapter 19 – Nitrogen Compounds
 Remember that for substituents of amines, the degree of substitution is dependent of
the number of R groups bonded TO THE AMINE NITROGEN
 Nomenclature of secondary & tertiary amines

 Physical properties of amines

o they smell bad :(
o usual id-id & hydrogen bonding story
o remember tertiary amines cannot form hydrogen bonds but have weaker pd-pd
forces
o amines have weaker H bonding than alcohol b/c of bond polarisation
o Aliphatic amines (of <4 C) are soluble in water b/c of hydrogen bonding
o Larger amines have disrupted hydrogen bonding & more energy required to
overcome the id-id in amines
 Basic nature
o Amines act as Lewis bases by donating their lone pair of electrons
o Basicity is determined by the availability of the lone pair on the N atom (you
can technically talk about the conjugate acid but it’s more annoying)
o Gaseous amines
 Tertiary amines are the most basic as there are more electron-donating
groups on the N atom, increasing electronic density and hence
increasing the availability of the lone pair on N to be donated
o Phenylamines
 The lone pair of electrons of N is donated into the benzene ring,
lowering the electronic density on the N atom, thus the lone pair is less
available to be donated
 also affected by the usual benzene factors
 EDGs will decrease extent of delocalisation of the lone pair,
increasing its availability to be donated
 EWGs will increase extent of delocalisation of the lone pair,
increasing its availability to be donated
o Amides
 Amides are NEUTRAL.
 Large extent of delocalisation of the lone pair of the N atom over the
adjacent C=O group, reducing electron density and hence the lone pair
availability such that it is no longer available to be donated
 o Aqueous Amines (FYI)

 Solvent effects are covered to a greater extent in H3

 Secondary amines have the “midway” alkyl EDG effect & moderately
reduced H bonding
 Primary and tertiary have 1 factor that does not favour it significantly:
Primary – no EDG | Tertiary – hydrogen bonded disrupted the most
 I guess by that logic you can remember that secondary amines are the
most basic… ???
 for phenylamines with N bonded to the benzene ring, if we consider amides to be
neutral, why do we talk about lone pairs from N delocalising into the benzene ring?
o the 2p orbital still forms a continuous overlap withe the benzene ring, and the
ring can act as an electron sink
o however the ring will be less activated as a) lone pair can now choose to
delocalise over C=O or benzene ring b) it will prefer to do so over C=O as
negative charge is over an EN O atom

Amino Acids
 Introduction
o A mixture of ABE & Organic Chem
o Amino acids consist of carboxylic acid & amine groups
o α-amino acids just refer to the -NH2 group being bonded to the α carbon of the
carboxylic acid group
o FYI, amino acids are formed via the nucleophilic addition of NH3, followed by
SN using CN, then hydrolysing the CN to give CO2H
o This is known as Strecker Synthesis
 Zwitterions
o Amino acids have both base (amine) and acid (carboxylic acid), and can
undergo intra-molecular acid-base reaction to form dipolar ions with no net
electrical charge, known as zwitterions
o by this logic you can also call amino acids “amphoteric”

 Physical properties of amino acids

o As a result of zwitterions:
o (this is often hidden in the question) amino acids are CRYSTALLINE
SOLIDS
o High melting point because of ionic bonds
o Amino acids are more soluble in water due to ion-dipole interactions
 Acid-base behaviour of amino acids
o Just your usual inductively withdrawing effects for COO- conjugate base
o For the NH3+ portion, easier to explain using the acid itself: presence of COO-
EWG polaries the N-H bond more, decreasing the bond strength and
increasing the ability for N to donate the third H atom as H+
 Titration curves of Amino acids
o fully protonated amino acids will behave as polyprotic acids that deprotonate
separately (join a bunch of weak acid – strong base titration curves)
o you will have MBCs where pH = pKa of specific group
o remember that a species is protonated if pH < pKa and deprotonated if pH >
pKa
o in other words, lowest pKa deprotonates first (carboxylic acid)
o to find the isoelectronic point pI:
 Find the species with no net electrical charge
 See how many deprotonations have occurred, N
 the isoelectronic point is at the Nth equivalence point
 Peptides & Proteins
o A peptide bond just refers to an amide bond
o Formed via condensation, broken via hydrolysis
o weird naming convention:
 A dipeptide is formed using 2 amino acid molecules and only have
ONE peptide bond
 A tripeptide is formed using 3 amino acid molecules and only have 3-1
= 2 peptide bonds
 the name follows the number of constituent monomers, not the number
of peptide groups ;-;
 therefore, a pentapeptide is a tetra amide etc.
o Proteins are very very long polypeptides with Mr > 5000
o They are hydrolysed in their constituent amino acids by either using enzymes,
or heating under reflux with acid/alkali for several hours (IMPORTANT) due
to the sheer number of peptide bonds that need to be broken
 Sequencing questions
o When you hydrolyse peptides/proteins, you’ll be left with fragments that you
may need to piece together in order to form the constituent atom
o a few types:
 they can give it in a word format (compre passage?)
 they can give you the constituent amino acids and you join then to get
the amino acid
 2 runs of enzymes, overlapping fragments/sections across the two runs
to get the whole acid: you need to see what is common across the two
runs and whatnot
Chapter 20 – Applications: Elucidation & Synthesis
 you have to be comfortable with the reactions, beyond that it is a thought process
 A process of Elucidation
Step 1: Degree of Unsaturation
o If molecular formula is given, calculate DOU immediately
In case you’ve forgotten:
2C + 2 - H - X + N
2
 1 DOU represents a π bond or a ring
 If DOU >4, likely benzene is present (benzene itself has 4 DOU; 3 π
bonds & a ring)
o TIP:
Step 2: READ THE QUESTION.
o What other novel info are you given? (e.g. J contains 2 fused 6 membered
rings)
o Go through the question slowly, and extract whatever information you
possible can from each step, sentence by sentence.
o Reactions normally give you functional groups & fragments (especially if
product of reaction is given, can tell you structures found in the original
molecule)
o When they say “only organic compound formed”, BEWARE of CO2 produced
o Join your fragments obtained from the info given & reactions to help you
elucidate a structure
o You can double check your structure against the DOU, or sometimes when
DOU is lost, you know certain functional groups containing DOU have been
cleaved off in say oxidative cleavage
o If your number of carbons is low (3 and below), there is only 1 parent chain
possible – straight chain :)
 Presenting Elucidation answers
o for EACH reaction provided, state:
 type of reaction
 functional group present/absent (for negative test)
 Write the name of said FG instead of its structure
 if gas is evolved/there is a gas test given, state the identity of the
gas/ppt/fumes/whatever (except the orange ppt with 2,4DNPH)
 Looking at the number of atoms gained/lost can also help deduce what
changes are occurring
 Synthesis
o Compare the number of C atoms in starting material VS product
 Do you need step up/step-down reactions?
o If not, identify what is changing from the reactant to the product
o it may be useful to do retro-synthesis, where u must use a double lined arrow
Organic Chemistry Reaction Summary & Explanations
Mechanisms
 General rules
o You need to WRITE THE NAME of the mechanism in!!!!
o Always state slow/fast where applicable
o you must indicate the driving force (partial positive charges)
o Be accurate with your arrow pushing: head pointing directly to the
electrophile, tail coming directly from electron source
o If there is a positive/negative charge, put it ON the atom carrying said charge
Reactions
 Alkanes
o Alkane + Cl2/Br2 (g), UV light/heat
 Greenish-yellow Cl2 decolourises
 Reddish-brown Br2 decolourises
 Alkenes
o Cl2/Br2 (g) / Br2 in CCl4
 Greenish-yellow Cl2 decolourises
 Reddish-brown Br2 decolourises
 Occurs because the electron-rich C=C bond polarises Br-Br bond
 Br-Br is added across the C=C bond
o Br2 (aq), room temp.
 Reddish-brown Br2 decolourises
 Br attaches first, followed by OH (water is nucleophile then
deprotonated)
o steam, H3PO4 catalyst, high temperature & pressure
 Water is added across the C=C bond, H+ as electrophile (OH- added to
the other carbon)
 Lab method: conc. H2SO4, cold, followed by H2O
o H2 (g), Ni/Pt/Pd catalyst
 H2 added across the C=C bond
o Mild oxidation: KMnO4, dilute NaOH, cold
  Why NaOH? make KMnO4 weaker (if u look at data booklet, basic
MnO4- reduces with fewer electrons, hence extent of oxidation is
lower)
 -OH added to both sides of C=C
 Brown MnO2 precipitate forms (not the usual result from KMnO4)
o Oxidative cleavage: dilute H2SO4, KMnO4, heat
 C=C -> C=O | O=C (add =O)
 -H becomes -OH
 (EASubstitution) Regular/Mildly activated benzene
o Needs a catalyst to generate stronger electrophile
o X2 + FeX3 (X=Cl or Br)/Fe(s) (Al can be used inplace of Fe)
 normal benzene – warm
 methylbenzene – room temp.
 X2 decolourises + white HX fumes formed
o R-X + AlX3
 normal benzene – warm
 methylbenzene – room temp.
 R- will be substituted onto the benzene
 white HCl(g) formed
 note that if R- group is alkane, can undergo FRS
o conc. HNO3, conc. H2SO4
 maintain at 55ºC -> benzene
 maintain > 55ºC -> deactivated benzene
 maintain < 55ºC -> activated benzene
 nitrobenzene, pale oily liquid, formed
 (EASubstitution) Highly activated benzene (lone pair delocalisation)
o O/N bonded to the benzene ring
o Phenol + Br2 (l)/Br2 in CCl4
 monosub occurs + HBr
o Phenol/Phenylamine + Br2 (aq)
 2,4,6 trisub occurs + HBr
 this is because the Br – Br bond is polarised by the polar H2O ->
stronger electrophile
o Phenol + conc. HNO3, room temp
 2,4,6 trisub (because there are just more ions hanging around …)
 pale yellow liquid (remember nitrobenzene)
o Phenol + HNO3 (aq), room temp
 monosub occurs (less electrophile)
 pale yellow liquid (remember nitrobenzene)
o A better way to get monosub
 Use a phenyl ester with O bonded to benzene/phenylamine with N
bonded to benzene ring
  as the LP of O/N delocalises into both benzene ring & adjacent C=O
group, not as activated
 therefore monosub occurs (preferrable at 4 position because of steric
hindrance from the whole ester/amide)
 once u get the mono sub, hydrolyse the ester/amide to get your
phenol/phenylamine respectively
 Other reactions of benzene
o dilute H2SO4, KMnO4, heat

 Halogen Derivatives
o dilute NaOH, heat
 only reaction where water is actually used for this chapter
 -X replaced by -OH
o ethanolic KCN, heat
 -X replaced by -CN
o ethanolic conc. NH3, heat in sealed tube
 -X replaced by -NH2
  if NH3 in excess, mono-sub favoured
 if RX in excess, multi-sub favoured as the R-NH2 also behaves like a
nucleophile
 RX + NH3 -> RNH2 + HX
 RNH2 + RX -> R2NH + HX
 R2NH + RX -> R3N + HX
o ethanolic KOH, heat
 dehydrohalogenation; HX eliminated & C=C formed
o Test to identify halogen in RX
 Add NaOH & heat -> add excess HNO3 -> add AgNO3
 test to confirm that HNO3 is in excess with litmus paper (you
really need to remove OH- because Ag(OH)2 is insoluble and
will mess with your AgX ppt
 do the silver halide QA test in data booklet thingy
 Or u can use ethanolic AgNO3
 Besides the QA AgX test, AgI forms the fastest, followed by
AgBr, then AgCl
 (Concept is a combination of H3 stuff – polar protic solvent
favours SN1, which means leaving group stability is the more
important factor)
 Hydroxy Compounds
o Alcohol/Phenol + Na (s)
 Redox reaction, H2 (g) formed alongside conjugate base
o Phenol + NaOH
 Acid-base reaction, phenoxide & H2O formed
o Tertiary alcohol + conc. HCl
 -OH replaced by -Cl
 solution turns cloudy (no more hydrogen bonding from alcohol,
halogenoalkane not soluble)
o Primary/Sec Alcohol + HCl, ZnCl2 catalyst
 reaction mechanism is SN1
 -OH replaced by -Cl
 solution turns cloudy
o (questionable) Lucas Test

o Alcohol + conc. HBr/NaBr & conc. H2SO4, heat

 the latter generates HBr in situ
 -OH replaced by -Br
o Reactions with phosphorous trihalides
  3ROH + PCl3 -> 3RCl + H3PO3
 6ROH + 2P + 3Br2 -> 6RBr + 2H3PO3
 6ROH + 2P + 3I2 -> 6RI + 2H3PO3
 PBr3/PI3 is generated in situ (2P + 3I2 -> 2PI3)
o Alcohol + PCl5, room temp.
 -OH replaced by -Cl
 dense white HCl fumes produced
o Alcohol + SOCl2/SOBr2
 -OH replaced by -Cl
 SO2 gas & white HCl gas as products
 mechanism is nucleophilic addition
o Dehydration of alcohol
 Elimination of H + OH, C=C formed
 a few reagents u can use
 excess conc. H2SO4, heat (may also be an unwanted oxidising
agent)
 conc. H3PO4, heat (hence this is used)
 Al2O3, heat (if u want to prevent hydrolysis/protonation of other
groups)
 forms cis-trans isomers (why specifically? h3 content.)
 Phenols do not undergo dehydration.
o Condensation
 Alcohol + Carboxylic Acid + few drops of conc. H2SO4, heat
 H2SO4 is a catalyst here
 remember “half & half” principle
 reversible reaction (hydrolysis of resulting ester)
 Alcohol + Acyl Chloride, room temperature
 white HCl fumes produced
 goes to completion
 Phenol + Acyl chloride, room temp.
 white HCl fumes produced
 ONLY way to get a phenyl ester
o Oxidation of alcohols
 Primary Alcohol -> Aldehyde -> Carboxylic Acid
 Alcohol -> Aldehyde:
 K2Cr2O7, dilute H2SO4, heat with immediate distillation
 K2Cr2O7 is a weaker OA
 in this case the type of heating is important
 Alcohol -> Carboxylic Acid
 KMnO4, dilute H2SO4, heat under reflux
 K2Cr2O7, dilute H2SO4, heat under reflux
 Secondary Alcohol -> Ketone (no further [O])
  KMnO4, dilute H2SO4, heat under reflux
 K2Cr2O7, dilute H2SO4, heat under reflux
o Iodoform test: dilute NaOH, I2 (aq)
 may say alkaline I2 (aq)
 yellow CHI3 ppt formed
 the -CH3 can be anything analogous e.g. CHI2
 have fun memorising the coefficients in the equation

o Phenol + neutral FeCl3, room temp

 violet complex
 Carbonyl Compounds
o HCN + trace KCN (catalyst), cold
 gives a cyanohydrin (see left)
 cold is IMPORTANT because HCN is a
toxic gas so u want to keep it as a liquid
 HCN can be created in situ with KCN +
H2SO4
o 2,4 DNPH (2,4-dinitrophenylhydrazine)
 condensation
 orange ppt formed
 you don’t need to write out the full name of 2,4 DNPH in full
 but u need to know its structure (especially if they ask u to draw
products)

o LiAlH4 in dry ether

 Aldehyde/Ketone -> Alcohol
o Oxidation (all are Aldehyde -> Carboxylic Acid)
  dilute H2SO4, KMnO4, heat
 dilute H2SO4, K2Cr2O7, heat
 Fehling’s test
 The tartate ion in Fehling’s copper (II) tartrate prevents
Cu(OH)2 ppt from forming by forming a complex

 Tollens’ test
 Silver mirror formed
 Freshly prepared in the lab: 1) NaOH + AgNO3 to form
Ag(OH)2 ppt 2) NH3 (aq) added until precipitate just dissolves

 Iodoform test: dilute NaOH, I2 (aq)

 Tests for methyl ketones
 yellow CHI3 ppt formed

 Carboxylic Acids
o Acid-base
 with Na (s), forms H2 gas
 with Na2CO3, forms CO2 gas & carboxylate ion
 (speaking of this, FYI, phenol will react with CO32- to give HCO3-, but
not H2CO3)
o Condensation (nucleophilic acyl substitution)
 with PCl5 -> ROCl (acyl chloride) + POCl3 + HCl
 can also use PCl3 (gives H3PO3)/SOCl2 (gives SO2)
 Acyl chlorides react with like almost everything
 room temperature with all reactions involving acyl chlorides
  hydrolysis with water to give carboxylic acid & white HCl
fumes
 + amines -> gives amides
o Reduction with LiAlH4
 Gives primary alcohol
 only LiAlH4 is strong enough to reduce carboxylic acids
o Hydrolysis of ester/amide
 dilute NaOH/H2SO4, heat
 the C-O/C-N bond is cut
 Forms carboxylic acid in acidic /carboxylate in basic conditions &
alcohol
 Nitrogen compounds
o Amines react like a normal base (eg RNH2 + HCl -> RNH3+Cl-)
o nitrobenzene + Sn, conc HCl -> phenylamide
o Amide + LiAlH4 -> amine + water
 remember to kick out your OH!!!

Additional recap of Redox reactions

Oxidation

 dilute H2SO4, KMnO4, heat (which decolourises)

o Oxidative cleavage of alkenes
o Side chain oxidation of benzenes (can be done with NaOH)
o primary Alcohols -> Carboxylic Acid
o Aldehyde -> carboxylic acid
o secondary Alcohol -> Ketones
 dilute H2SO4, K2Cr2O7, heat (turns from orange to green)
o does not oxidise alkenes
o primary Alcohols -> aldehyde (if there is immediate distillation)
o aldehyde -> carboxylic acid
o (thus) primary alcohol -> carboxylic acid (without distillation)
o secondary Alcohol -> Ketones
 Mild oxidation: KMnO4, dilute NaOH, cold -> brown MnO2 ppt formed
 Iodoform is also oxidation (your -CH3 thingy becomes -OH)
 Further oxidation of products
o Terminal alkene R=CH2 -> R=O + CO2
o stuff like methanal oxidises to form H2CO3 -> CO2 (g)
o Ethanedioic acid/if there is a -H instead of -OH that can oxidise H to -OH ->
CO2

Reduction
  H2 (g), Ni catalyst
o Alkene -> Alkane
o Aldehyde/Ketone -> Alcohol
o -CN -> -CH2NH2
 LiAlH4 in dry ether (acting as hydride ion H-)
o does not reduce alkenes
o Aldehyde/Ketone/Carboxylic Acid -> Alcohol
o Ester -> C=O side becomes aldehyde (then alcohol); C-O side becomes
alcohol directly
o Amide -> Amine
o -CN -> -CH2NH2
 NaBH4
o Weaker RA than LiAlH4; only reduces aldehydes & ketones
 Sn, conc. HCl
o Nitrobenzene -> Phenylamine

Sneaky (and often hidden) acid-base behaviour :(

always be careful when you want to use acids/base ; double check your reaction conditions
check to see if protonation/deprotonation occurs
 Neutral: Amides & Alcohols
 Acidic groups (deprotonate): Phenols, carboxylic acid (check if this is formed after
some oxidation reaction!!! very common!!!)
o Only carboxylic acid will react with carbonate to give CO2 gas
 Basic groups (protonate): Amines, Phenylamines

Step Up & Step Down

 Ways to get -CN on something
o Halogenoalkane + ethanolic KCN
 note this does mean you need to convert your alcohols to
halogenoalkanes with something like PCl5
o Aldehyde/Ketone + HCN, trace KCN, cold
 Further reactions of -CN (nitrile)
o Acidic hydrolysis: dilute H2SO4, heat
 Gives carboxylic acid & NH4+
o Basic hydrolysis: dilute NaOH, heat
 Gives carboxylate base & NH3
o Reduction: H2, Ni catalyst, high pressure / LiAlH4 in dry ether
 -CN -> -CH2NH2
 Iodoform Test
 Remember that oxidative cleavage/side chain oxidation also removes carbons