Organic Chemistry Review NJC SH2 H2 Chemistry

Organic Chemistry Review

Type of Formulae Representation Characteristics

• does not show how the various atoms in the

Molecular Formula C3H6O3
organic compound are connected to one another

Condensed • shows the order of arrangement of atoms

CH3CH(OH)CO2H
Formula • bonds are not displayed

Displayed /
Full structural • shows ALL atoms and bonds in the molecule.
Formula

• Carbon atoms in a straight chain are drawn in a

zigzag manner
• each end of a line represents a carbon if other
Skeletal symbol of an atom is not written
Formula • C–H bonds at each C are not shown.
• each C forms 4 bonds. Any “missing” bond not
drawn out in a skeletal structure would be a C–H
bond.

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Organic Chemistry Review NJC SH2 H2 Chemistry
Cis-trans isomerism
Requirement : 2 different groups attached to each C in C=C.
We must show the trigonal planar arrangement around the C=C for cis and trans isomers.

H H H Br Note : Alkenes with four different substituents across

C=C also exhibit cis-trans isomerism.
C C C C
Another naming convention (E / Z) is used instead.
Br Br Br H **E/Z naming is not in H2 syllabus.
cis trans

Note: C=C in a ring cannot exhibit cis-trans

isomerism

Optical isomerism
Requirement : A chiral carbon (C atom bonded to 4 unique groups)
We must show the 3-D tetrahedral arrangement around the chiral C for optical isomers.

Optical activity of organic molecules

Organic
Molecule

No
Chiral
Chiral
Carbon
carbon

Not
Racemic Meso
meso/
mixture compound
racemic

Optically Optically Optically Optically

inactive inactive active inactive

Racemic mixture Meso compound

Equal amount of the 2 enantiomers A compound with 2 chiral carbons AND

-Rotation of plane of plane-polarised light by internal plane of symmetry
each enantiomer cancels out completely -Rotation of plane of plane-polarised light by
each chiral carbon cancels out completely

50 : 50 ratio
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Organic Chemistry Review NJC SH2 H2 Chemistry

Reaction Mechanisms for H2 Chemistry

A chemical equation shows the reactants and products of a chemical reaction in their stoichiometric
ratios. A reaction mechanism shows us the detailed reaction process which is not reflected in a
chemical equation.

Species reacting
Functional Group Reactive Site Reaction Type
with the C atom

Alkane
H H
Free Radical
Non-polar C−C and C−H bonds Free Radical
H C C H Substitution
H H

Alkene  electrons in C=C act as

H H Electrophilic
source of electrons Electrophile
Addition
(electron deficient)
C C
(break C=C  bond)
e− rich C attracts electrophile
H H

Arene Delocalised  electron cloud in

ring results in a region of high
Electrophile Electrophilic
electron density
(electron deficient) Substitution
e− rich C attracts electrophile

Halogenoalkanes + C in the polar C−Halogen

H H bond
+ -
Nucleophile Nucleophilic
H C C Br (electron rich) Substitution
e− deficient C attracts
H H nucleophile

Carbonyl
Compounds + C in the polar C=O bond Nucleophilic
H O - Nucleophile
Addition
+ e− deficient C attracts (electron rich)
H C C (break C=O  bond)
nucleophile
H H

Note:
Benzene rings prefer to undergo substitution rather than addition due to the resonance stabilisation from
delocalisation of the -electron cloud in benzene. Addition reaction would disrupt the aromatic stability and
hence it is not favourable.

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Organic Chemistry Review NJC SH2 H2 Chemistry
To describe the mechanism of a known organic reaction
(i) Name the type of reaction mechanism undergone.
(ii) Show reaction step-wise using equations – include intermediates or transition states. Indicate
fast and slow steps where necessary.
(iii) Indicate + and - on the molecule (if any).
(iv) Show movement of arrows: Electron flow from electron donor (bond or lone pair electrons) to
electron acceptor (atom or existing bond)

Breaking
bonds
Homolytic
(Half arrow to each atom)
and produce radicals
Cl Cl 2 Cl 
(arrow start
from the Heterolytic
covalent −
(Full arrow to the more I Cl I + + Cl
bond) electronegative atom) + -

Forming
bonds
(Arrow start H H
from lone pair H C+ .. OH− H C OH
electrons to
the H H
destination
atom)

H H H H
+
−
H C C H H Br H C C H + Br
− +
H

Breaking and
forming
bonds A  bond is formed when electron pair move to an existing sigma bond

FYI

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Organic Chemistry Review NJC SH2 H2 Chemistry
1 Free Radical Substitution (Alkane)

• Free radicals are atoms or groups of atoms which have a single unpaired electron.
• Free radicals are formed if a bond splits evenly - each atom getting one of the two electrons.
(homolytic fission)

Describe the mechanism of free radical substitution between propane, C3H8 and Cl2 (g), UV light
to give 2−chloropropane

Stage 1: Initiation
Important Note:
UV light / heat 1) Initiation stage
Cl 2Cl • must use half arrows to show homolytic fission
Cl

2) Propagation stage
Stage 2: Propagation • radical reacts with molecule to produce new
radical and new molecule
•
CH3CH2CH3 + Cl• → CH3CHCH3 + HCl • Use structural formula for alkane to clearly
show the C atom that contains the radical.
• indicate “•” directly next to the C radical.
CH3CHCH3 + Cl2 → CH3CHClCH3 + Cl•

Stage 3: Termination 3) Termination stage

• 2 radicals react to give a compound
• show any 2 equations
2 Cl• → Cl2

•
Cl• + CH3CHCH3 → CH3CHClCH3

• •
CH3CHCH3 + CH3CHCH3 → CH3CHCH3

CH3CHCH3

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Organic Chemistry Review NJC SH2 H2 Chemistry
Things to note for Free Radical Substitution :

(i) Expected yield for monosubstitution of alkane (Based on probability)

In higher members of alkanes, substitution of hydrogen atoms at different carbon atoms leads
to different products.

e.g. Butane reacts with chlorine in the presence of UV light to form two mono-substituted
products as shown below.

There are a total of 4 H that can be substituted to form 2-chlorobutane while there are a total of
6 H that can be substituted to form 1-chlorobutane

Assuming each H has an equal chance of being substituted by Cl, thus molar ratio of
1-chlorobutane and 2-chlorobutane formed is 60% : 40%, i.e. 3 : 2.

(ii) Rate of substitution at 1o, 2o & 3o carbon atoms (ONLY discuss using this factor when
question state that experimental yield is different from theoretical yield)

Based on the probability consideration, substitution of H atoms of butane would produce

1-chlorobutane and 2-chlorobutane in the expected molar ratio of 60% : 40%. However, the
experimental yields for 1-chlorobutane and 2-chlorobutane are 30% and 70% respectively.

*Explain the discrepancy between the expected and experimental ratios of the
monochlorinated products.
H H
H3C

C CH2CH3 H

C CH2CH2CH3

secondary radical primary radical

2-chlorobutane is formed via a secondary (2°) radical whereas 1-chlorobutane is formed via a
primary (1°) radical.

Secondary (2°) radical is more stable than primary (1°) radical as there are more electron-
donating alkyl groups which can decrease the electron deficiency of the radical.

Hence, secondary (2°) radical is formed preferentially and yield of 2-chlorobutane is higher than
the expected yield of 40%.

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Organic Chemistry Review NJC SH2 H2 Chemistry
2. Electrophilic Addition (Alkene)

Describe the mechanism of electrophilic addition between propene, C3H6 and HBr (g)
Step 1: e− rich C=C reacts with electrophile to give carbocation
Important Note:
- State the name of mechanism

- Show separation of charges (+/−) on

electrophile and charges on ions

- Between 2 species: Arrows ALWAYS

− flow from electron rich region (π
Step 2: carbocation reacts with e rich species bond of C=C or lone pair of
nucleophiles) to electron deficient
region (electrophile or carbocation)
Bond breaking within a molecule will
be from bond pair to − atom.

- Indicate the slow step

*Explain why 2–bromopropane is the major product.

Electrophile can attack either of the carbon atom in the C=C bond and hence leads to two possible
carbocations.

H H H H
H C C CH3 H C C CH3
+ +
H H
o o
2 carbocation 1 carbocation

The C+ in the 2o carbocation stabilized to a larger extent due to 2 electron-donating alkyl groups. This
more stable 2 carbocation is formed more abundantly in the rate-determining step, leading to a higher
yield of the product.

*Explain why the reaction of but-1-ene with HBr (g) produces a racemic mixture

H H H H
H C C CH2CH3 + HBr H C C CH2CH3
H Br

The product contains a chiral carbon that is produced in Step 2 of the electrophilic addition
mechanism where the Br− can attack the trigonal planar carbocation from either side with equal
probability. The two enantiomers are produced in equal amount. The products are a racemic mixture
which is optically inactive as the rotation of plane of plane-polarized light by each enantiomer cancels
out completely.

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Organic Chemistry Review NJC SH2 H2 Chemistry
3. Electrophilic Substitution (Benzene)

• Benzene resists addition reactions because that would involve breaking the delocalisation of
 electron and losing that stability.
• Electrophilic substitutions involves replacing H atom on benzene with
(i) Halogen atoms (e.g. –Cl using Cl2 and anhydrous AlCl3 catalyst)
(ii) Alkyl group (e.g. –CH3 using CH3Cl and anhydrous AlCl3 catalyst)
(iii) Ketone group (e.g. −COCH3 using CH3COCl and anhydrous AlCl3 catalyst)
(iv) Nitro group (e.g. –NO2 using conc HNO3 and conc H2SO4 catalyst)
Describe the mechanism of electrophilic substitution between benzene and Br2, anhydrous FeBr3

Step 1: reacts with catalyst to generate strong electrophile (+ charge)

Important Note:
(i) State the name of
Br2 + FeBr3 → FeBr4− + Br+ mechanism

(ii) Show reaction with

Step 2: e− rich benzene reacts with electrophile to give Arenium
catalyst to generate
carbocation strong electrophile

(iii) Arrows ALWAYS flow

from electron rich
region (π electron
cloud of benzene or
lone pair of
nucleophiles) to
Step 3: break C−H bond to restore aromaticity of benzene and electron deficient
region (electrophile)
regenerate catalyst
(iv) Indicate the slow step

(v) Show regeneration of

catalyst

*What about mechanism for the conversion of benzene to

• methylbenzene
Step 1 : CH3Br + FeBr3 → FeBr4− + +CH3
Steps 2 & 3 are similar to the example above

• phenylethanone O

Step 1 : CH3COBr + FeBr3 → FeBr4− + +COCH3 C

CH3
Steps 2 & 3 are similar to the example above

• nitrobenzene
Step 1 : HNO3 (conc) + 2H2SO4 (conc) → +NO2 + 2HSO4− + H3O+
Step 2 similar to the example above
Step 3 HSO4− reacts to regenerate H2SO4 catalyst

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Organic Chemistry Review NJC SH2 H2 Chemistry
4. Nucleophilic Substitution (Halogenoalkane, R−X)
Nucleophilic substitution involves nucleophiles of:
(i) Hydroxide ions from aqueous KOH or NaOH (forms alcohol, R−OH)
(ii) Cyanide ions (CN−) from ethanolic KCN or NaCN (forms nitriles, R−C≡N)
(iii) Ethanolic NH3 (forms amines, R−NH2)

SN2 Mechanism (two reactants in SLOW step) – for primary halogenoalkane

E.g. Mechanism of nucleophilic substitution between CH3CH2Cl and NaOH (aq), heat
Important Note
One-step showing nucleophile attacks from opposite side of the leaving (i) State the name of the
group halogen. mechanism

H −
H H (ii) Show separation of
– C
+
Br HO C
charges (+/−) on C–X
HO HO C Br + Br– and charges on ions
H − H
CH3 H CH3 CH3 (iii) Arrows ALWAYS
flow from lone pairs of
Reactant Transition State Product nucleophiles (electron
Inversion of rich) to electrophiles
Stereochemistry (electron poor)

Note: (iv) Must show and label

the transition state where
• Based on conservation of charges, the nucleophile (OH) is
o the transition state carries a negative charge if the nucleophile OPPOSITE the halogen
is an anion (−OH) atom (Br)
o the transition state carries no charge if the nucleophile is NH3
(v) Draw displayed
• Only 1 organic product is formed formula to show the
inversion of configuration
of the organic
compounds.

The energy profile or reaction pathway diagram for the SN2 mechanism is given below.

Rate = k[RX][Nucleophile]

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Organic Chemistry Review NJC SH2 H2 Chemistry
SN1 Mechanism (one reactant in SLOW step) – for tertiary halogenoalkane

E.g. Mechanism of nucleophilic substitution between tertiary R−X and NaOH (aq), heat

Step 1: breaking C−X bond to generate carbocation

Important Note
(i) State the name of
mechanism

(ii) Show separation of

charges (+/−) on C–X
and charges on ions
Step 2: Nucleophile reacts with the carbocation
(iii) Arrows ALWAYS flow
from lone pairs of
nucleophiles (electron
rich) to electrophiles
(electron poor)

(iv) Indicate the slow step

*Explain why the above reaction produces a racemic mixture

The product contains a chiral carbon that is produced in Step 2 of the mechanism where the HO− can
attack the trigonal planar carbocation from either side with equal probability. The two enantiomers are
produced in equal amount. The products are a racemic mixture which is optically inactive as the
rotation of plane of plane-polarized light by each enantiomer cancels out completely.

The energy profile or reaction pathway diagram for the SN1 mechanism is given below.

Rate = k[RX]

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Organic Chemistry Review NJC SH2 H2 Chemistry
5. Nucleophilic Addition (Carbonyl compounds)

HCN is added across the C=O bonds.

• Reagents used are either
o HCN with trace amount of NaCN is added OR
o HCN with trace amount of NaOH is added to produce NaCN
• Hence, a mixture of HCN and free CN− ions is produced.

E.g. Mechanism of nucleophilic addition between propanal and HCN with NaCN catalyst.
Step 1: Nucleophile (−CN from NaCN) reacts with +C of C=O to
Important Note
give anion intermediate (i) State the name of the mechanism

– (ii) Show separation of charges (+/−)

O
CH3CH2
C
−
O +
CN
− slow
CH3CH2
C
on C=O and charge on −CN ions

+ (iii) Show lone pair electrons on C of

−CN and on O−
H H CN
anion
(iv) Curly arrows to show flow of
electrons
• Lone pair from
Step 2: HCN reacts with anion intermediate to give cyanohydrin C of −CN to
+ C of C=O
and regenerate –CN
• C=O bond to − O


–
• lone pair on O− to + H of HCN
• H−CN bond to C
CH3CH2 O − CH3CH2 OH
fast −
C + H CN C + CN (v) Label step 1 as “slow”
+
H CN H CN

*Explain why a racemic mixture is produced from this reaction.

The product contains a chiral carbon that is produced in Step 2 of the mechanism where the
−
CN can attack the trigonal planar carbon of C=O from either side with equal probability. The
two enantiomers are produced in equal amount. The products are a racemic mixture which is optically
inactive as the rotation of plane of plane-polarized light by each enantiomer cancels out completely.

top face attack CN

50% enantiomer
probability C
OH CH2CH3
+
- O C
CH2CH3
-CN H
mirror Racemic
trigonal planar H H mixture
carbonyl OH CH2CH3
50% C
carbon probability enantiomer
bottom face attack CN

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Organic Chemistry Review NJC SH2 H2 Chemistry

Types of organic reactions (Part 1)

Type of
Examples Reaction sites
reaction
H H
Free radical Cl2(g) Relatively unreactive C atom in alkane
H C H H C Cl + HCl
substitution UV Break non-polar C−H bond
H H
Cl
Electrophilic Cl2(g) Electron rich C atom in benzene
+ HCl
substitution Break non-polar C−H bond
AlCl3
H H
Nucleophilic NaOH (aq) Electron deficient C atom in halogenoalkane
H C Cl H C OH + NaCl
substitution Heat Break polar C−X bond
H H
H H H H
Electrophilic HBr (g) Electron rich C atom in alkene
H C C H H C C H
addition Break C=C  bond
H Br
H H
Nucleophilic HCN Electron deficient C atom in carbonyl
H C O H C O
addition Trace NaCN Break C=O  bond
CN H
H H H H
NaOH in ethanol Elimination of HX or H2O from 2 adjacent C
Elimination H C C H H C C H + HBr atoms
H Br Heat Form new  bond

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Organic Chemistry Review NJC SH2 H2 Chemistry

Types of organic reactions (Part 2)

Type of
Examples Reaction sites
reaction
Oxidation of:
H
KMnO4 O • alkene
CH3 C O H CH3 C O H + H2O • alkyl side chain of benzene
Oxidation
H2SO4 (aq) • 1 and 2 alcohol
H
heat • aldehyde
• methanoic acid and ethanedioic acid
Reduction of:
H H H H • alkene
H2 (g) • nitrile
Reduction H C C H H C C H
• aldehyde & ketone
Pt H H • carboxylic acid
• amide
Reaction of alcohol/phenol/carboxylic acid
Redox CH3CH2OH + Na CH3CH2O-Na+ + 1/2 H2
with Na(s)
Hydrolysis of:
O O
H2SO4 (aq) • nitrile
Hydrolysis CH3 O C CH3 + H2O
heat
CH3 OH + HO C CH3 • ester
• amide
O conc H2SO4 O
Formation of ester and amide
Condensation CH3 OH + HO C CH3 CH3 O C CH3 + H2O Reaction of carbonyl with 2,4-DNPH
reflux

Acid-base O O Reaction of carboxylic acid/phenol with

reaction/ base.
CH3 C OH + NaOH CH3 C O-Na+ + H2O
Neutralisation Reaction of amine with acid.

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Organic Chemistry Review NJC SH2 H2 Chemistry
Compound Reagent and condition Type of reaction Product(s)

Alkane Limited Cl2 (g), UV light or heat

Free radical AND
CH3CH2CH3 substitution
+ HCl + HCl

H2 (g), Pt (catalyst)
OR Reduction
H2 (g), Ni (catalyst), high T&P

Br2 in CCl4 (non-polar inert solvent)

Electrophilic
<Distinguishing Test>
addition
Orange-red Br2 decolourises

Br2 (aq)
Electrophilic + HBr
<Distinguishing Test>
addition
Orange Br2 decolourises
(major pdt)
Alkene
H H H cold conc H2SO4 catalyst, followed by H2O, warm
Electrophilic
OR
H C C C H addition
H2O(g), conc H3PO4 catalyst, high temp and pressure
(major pdt)
H
Electrophilic
HBr (g)
addition
(major pdt)
KMnO4, NaOH(aq), cold
<Distinguishing Test> Oxidation (mild)
Purple KMnO4 decolourises, brown ppt MnO2 formed
KMnO4, H2SO4(aq), heat
<Distinguishing Test> Oxidation + CO2 + H2O
Purple KMnO4 decolourises (vigorous)

* Alkene cannot be reduced by LiAlH4 or NaBH4 (C=C is electron rich, and will repel the H− ion from LiAlH4/NaBH4)
** Alkene cannot be oxidized by acidified K2Cr2O7 (K2Cr2O7 is a weaker oxidizing agent as compared to KMnO4)

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Organic Chemistry Review NJC SH2 H2 Chemistry

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Organic Chemistry Review NJC SH2 H2 Chemistry
Compound Reagent and condition Type of reaction Product(s)
Electrophilic + HBr
Br2, Anhydrous1 AlBr3 / FeBr3 catalyst
substitution

Electrophilic
Conc HNO3, Conc H2SO4 catalyst, heat + H2O
substitution
Benzene
Electrophilic
CH3Cl, Anhydrous AlCl3 / FeCl3 catalyst + HCl
substitution

Electrophilic
substitution + HCl
, Anhydrous AlCl3 / FeCl3 catalyst
(acyl chloride)

1
Anhydrous condition is needed such that AlBr3 can act as a Lewis acid (electron pair acceptor) and react with Br2 to generate strong electrophile Br+.
If H2O is present, AlBr3 would react with H2O to give [Al(H2O)6]3+ (Refer to chapter : The Periodic Table), and loses the ability to react with Br2.

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Organic Chemistry Review NJC SH2 H2 Chemistry
Compound Reagent and condition Type of reaction Product(s)
H
Free radical
Cl2 (g), UV light or heat C H + HCl
substitution
Cl

Cl
Electrophilic + HCl & + HCl
Cl2, Anhydrous AlCl3 / FeCl3 catalyst
substitution CH3 Cl CH3

NO2
Methylbenzene Electrophilic + H2O & + H2O
Conc HNO3, Conc H2SO4 catalyst
substitution CH3 O 2N CH3
CH3

KMnO4, H2SO4 (aq), heat

Side chain
<Distinguishing Test> + H2O
oxidation
Purple KMnO4 decolourises

Side chain
oxidation O
KMnO4, NaOH(aq), heat
[Further acid-base
<Distinguishing Test>
rxn in alkali] C O−Na+ + H O
2
Purple KMnO4 decolourises, brown ppt MnO2 formed
RCOOH gives
RCOO−

Note:
1) alkyl group is 2/4-directing (Refer to Data Booklet), hence the new electrophiles would substitute the benzene H atom at C2 and C4 w.r.t. to methylbenzene.

2) alkyl group is weakly activating (Refer to Data Booklet), hence nitration of methyl benzene can occur at room temp.

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Organic Chemistry Review NJC SH2 H2 Chemistry
Compound Reagent and condition Type of reaction Product(s)
KMnO4, H2SO4 (aq), heat
<Distinguishing Test> Side chain
Purple KMnO4 decolourises, effervescence of CO2 oxidation + CO2 + H2O
that gives white ppt with limewater
Ethylbenzene
Side chain
CH2CH3 oxidation
KMnO4, NaOH(aq), heat [Further acid-base O
<Distinguishing Test> rxn in alkali] C O−Na+ + Na2CO3 + H2O
Purple KMnO4 decolourises, brown ppt MnO2 formed RCOOH gives
RCOO−
CO2 gives CO32−
CH3
No side chain oxidation
C CH3 KMnO4, H2SO4 (aq), heat - (No C−H, C−OH or C=O directly outside the
benzene ring)
CH3

Note:

C C C
H OH O
, , groups can undergo side chain oxidation by hot acidified KMnO4 to give benzoic acid.

Any additional C or H atom beyond the first carbon in the side chain will be oxidized to CO2 and H2O.

If hot alkaline KMnO4 is used, the benzoic acid produced undergoes acid-base reaction to give benzoate ion.

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Organic Chemistry Review NJC SH2 H2 Chemistry
Compound Reagent and condition Type of reaction Product(s)

KOH in ethanol (or any alcohol as solvent), heat Elimination of HCl

+ KCl + H2O

Nucleophilic
KOH (aq), heat + KCl
Halogenoalkane substitution
H H
H C C H
Nucleophilic
Excess1 NH3 in ethanol2, heat in sealed tube3 + NH4Cl
H Cl substitution

Nucleophilic
KCN in ethanol4, heat + KCl
substitution

No nucleophilic substitution
Cl KOH (aq), heat -
(partial double bond in benzene C-Cl)

* <Distinguishing test> for halogenoalkane: [AgCl white ppt, AgBr cream ppt, AgI yellow ppt]
1) NaOH(aq), heat [Nu Sub]
2) excess HNO3(aq) [remove OH−]
3) AgNO3 [precipitation of AgX]
1
If limited NH3 is used, R−X would be present in excess. The amine produced would act as a nucleophile and undergo further rounds of nucleophilic
substitution with R−X to give quaternary ammonium salt
e.g. 4 R−X + NH3 ⎯→ NR4+ X− + 3 HX
2
If NH3(aq) is used, NH3 would react with H2O to give OH−, another nucleophile that would interfere with the nucleophilic substitution reaction.
3
NH3 is volatile, a sealed tube is required to prevent evaporation of NH3 during heating
4
If KCN(aq) is used, −CN group will undergo hydrolysis when heated in presence of H2O

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Organic Chemistry Review NJC SH2 H2 Chemistry
Compound Reagent and condition Type of reaction Product(s)
Acidic hydrolysis
O
[Further acid-base
H2SO4 (aq), heat
rxn] CH3CH2C OH
NH3 gives NH4+ + NH4+
Alkaline hydrolysis
[Further acid-base O
NaOH (aq), heat rxn]
CH3CH2C O−Na+
RCOOH gives + NH3
Nitrile RCOO−
compounds H H
CH3CH2C≡N CH3CH2 C N
LiAlH4 in dry ether Reduction
H H

H2 (g), Pt (catalyst) H H
OR CH3CH2 C N
Reduction
H2 (g), Ni (catalyst), high T&P
H H

Note:
Hydrolysis of −CN group in RCN produces RCOOH and NH3. Acidic or alkaline medium is required to speed up the hydrolysis reaction.
RCOOH and NH3 would undergo further acid-base reaction with the acidic/alkaline medium.

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Organic Chemistry Review NJC SH2 H2 Chemistry
Compound Reagent and condition Type of reaction Products
1
Anhydrous SOCl2
Nucleophilic CH3CH2Cl + SO2 + HCl
<Distinguishing Test>
Substitution White fumes
White fumes observed
Anhydrous PCl3
Nucleophilic
CH3CH2Cl + H3PO3
Substitution

Anhydrous PCl5
Nucleophilic CH3CH2Cl + POCl3 + HCl
<Distinguishing Test>
Substitution White fumes
White fumes observed
HBr (g)
Nucleophilic
CH3CH2Br + H2O
Substitution
1°/ 2°/ 3° alcohol
e.g. CH3CH2OH Na(s)
<Distinguishing Test> Redox CH3CH2O− Na+ + ½ H2
Effervescence of H2(g) that “pops” with lighted splint
Excess conc H2SO4, heat
OR Elimination of H2O CH2=CH2 + H2O
Al2O3(s), heat

CH3COOH, conc H2SO4 catalyst, heat under reflux Condensation + H2O

Condensation + HCl

1
Anhydrous conditions are required for SOCl2/PCl3/PCl5 as these compounds react readily with H2O (Refer to chapter : The Periodic Table)

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Organic Chemistry Review NJC SH2 H2 Chemistry
Compound Reagent and condition Type of reaction Products

K2Cr2O7, H2SO4 (aq), heat with immediate distillation

<Distinguishing Test> Oxidation
Orange K2Cr2O7 turns green + H2O

Excess K2Cr2O7, H2SO4 (aq), heat under reflux

1° alcohol <Distinguishing Test> Oxidation CH3COOH + H2O
CH3CH2OH Orange K2Cr2O7 turns green

KMnO4, H2SO4 (aq), heat [or alkaline medium] Oxidation

<Distinguishing Test> [Further acid-base CH3COOH + H2O
Purple KMnO4 decolourises rxn if in alkali]

CH3CH2CH=CH2 + H2O
Excess conc H2SO4, heat
&
OR Elimination of H2O
CH3CH=CHCH3
Al2O3(s), heat
(Major product, more substituted alkene)
2° alcohol
CH3CH2CH(OH)CH3
K2Cr2O7 / KMnO4, H2SO4 (aq), heat
Oxidation
<Distinguishing Test>

* specific reaction
for alcohol with I2, NaOH (aq), warm O
OH <Distinguishing Test> Oxidative cleavage H/R C O−Na+ + CHI + KI + H2O
H/R C CH3 Yellow ppt of CHI3 3
(yellow ppt)
H

Note : 3° alcohol does not undergo oxidation

*e.g. CH3CH2OH and CH3CH(OH)CH3 both gives yellow ppt when reacted with warm alkaline I2.

22
Organic Chemistry Review NJC SH2 H2 Chemistry
Compound Reagent and condition Type of reaction Products
Na(s)
<Distinguishing Test> Redox O- Na+ + ½ H2
Effervescence of H2(g) that “pops” with lighted splint
Acid-base reaction/ O- Na+ + H2O
NaOH (aq) / KOH (aq)
Neutralisation
NO2 + H2O
+ H2O
Dilute HNO3
Electrophilic
<Distinguishing Test> OH & NO2 OH
substitution
Yellow ppt formed
(yellow ppt)
NO2
Conc HNO3
Electrophilic NO2 OH + 3 H2O
<Distinguishing Test>
substitution
Phenol Yellow ppt formed
NO2
(yellow ppt)
OH Br2 in CCl4 Br + HBr
+ HBr
(non-polar organic solvent) Electrophilic
<Distinguishing Test> substitution OH & Br OH
Orange-red Br2 decolourises
Br
Br2 (aq)
Electrophilic Br OH + 3 HBr
<Distinguishing Test>
substitution
Orange Br2 decolourises and white ppt formed
Br
(white ppt)
O
Condensation O C CH3 + HCl
*use NaOH (aq) to convert phenol to phenoxide
Neutral FeCl3 (aq)
Complex ion Observation:
<Distinguishing Test>
formation Violet complex formed
Violet complex formed
* −OH group in phenol cannot be substituted by halogen. (partial double bond in C-OH)
** Phenol does not react with carboxylic acid to form ester.
*** Phenol does not undergo oxidation.

23
Organic Chemistry Review NJC SH2 H2 Chemistry
Compound Reagent and condition Type of reaction Products

Nucleophilic
HCN with trace amount of NaCN / NaOH
addition

2,4−dinitrophenylhydrazine (2,4−DNPH)
NO2
NO2
H H
H H Condensation CH3 C N N NO2 + H2O
H N N NO 2
(orange ppt)
<Distinguishing Test> orange solid formed
K2Cr2O7 / KMnO4, H2SO4(aq), heat
Oxidation CH3COOH
Aldehyde <Distinguishing Test>
O Oxidation
Ammonical solution of AgNO3 containing [Ag(NH3)2]+
[Further acid-base
CH3 C H complex, heat
rxn in alkali] CH3COO− + Ag (silver mirror)
(Tollens’ reagent)
RCOOH gives
<Distinguishing Test>
RCOO−
Oxidation
Alkaline solution containing Cu2+ tartrate complex,
[Further acid-base
heat CH3COO− + Cu2O
rxn in alkali]
(Fehling’s solution1) (brick red ppt)
RCOOH gives
<Distinguishing Test>
RCOO−
LiAlH4 in dry ether
OR Reduction CH3CH2OH
NaBH4 in ethanol
H2 (g), Pt (catalyst)
OR Reduction CH3CH2OH
H2 (g), Ni (catalyst), high T&P
O
C benzaldehyde cannot be oxidized by Fehling’s solution.
Note: H

24
Organic Chemistry Review NJC SH2 H2 Chemistry
Compound Reagent and condition Type of reaction Products

Nucleophilic
HCN with trace amount of NaCN / NaOH
addition

2,4−dinitrophenylhydrazine (2,4−DNPH)
NO2 + H2O
NO2 CH3 H
H H Condensation CH3 C N N NO 2
Ketone H N N NO 2
O (orange ppt)
CH3 C CH3 <Distinguishing Test> orange ppt formed
OH
LiAlH4 in dry ether
OR Reduction CH3 C CH3
NaBH4 in ethanol1 H
OH
H2 (g), Pt (catalyst)
OR Reduction CH3 C CH3
H2 (g), Ni (catalyst), high T&P
H
*specific reaction O
for carbonyl with I2, NaOH (aq), warm O−Na+ + CHI
Oxidative cleavage H/R C + KI + H2O
O <Distinguishing Test> 3
Yellow ppt of CHI3 (yellow ppt)
H/R C CH3

1
NaBH4 in ethanol can only reduce carbonyl compounds. (NaBH4 is a weaker reducing agent as compared to LiAlH4)

*e.g. CH3CHO and CH3COCH3 both gives yellow ppt when reacted with warm alkaline I2.

25
Organic Chemistry Review NJC SH2 H2 Chemistry
Compound Reagent and condition Type of reaction Products
Na(s) or Mg(s) CH3CH2COO− Na+ + ½ H2
<Distinguishing Test> Redox
Effervescence of H2(g) that “pops” with lighted splint
Acid-base reaction/
NaOH (aq) / KOH (aq) CH3CH2COO− Na+ + H2O
Neutralisation
NaHCO3 (aq) / Na2CO3 (aq)
Acid-base reaction/
<Distinguishing Test> CH3CH2COO− Na+ + H2O + CO2
Neutralisation
Effervescence of CO2(g)

Carboxylic acid Acid-base reaction/

NH3 (aq) CH3CH2COO− NH4+
CH3CH2COOH Neutralisation

CH3CH2OH, conc H2SO4 catalyst, heat under reflux Condensation

+ H2O

Anhydrous SOCl2 /PCl3 /PCl5 O

Nucleophilic
<Distinguishing Test>
Substitution CH3CH2 C Cl
White fumes of HCl + side products

LiAlH4 in dry ether Reduction CH3CH2CH2OH

Methanoic acid KMnO4, H2SO4 (aq), heat [or alkaline medium]

O Oxidation CO2 + H2O
<Distinguishing Test>
[Further acid-base [if in alkaline medium
Purple KMnO4 decolourises and effervescence of
C rxn if in alkali] CO2 + 2NaOH ⎯→ Na2CO3 + H2O]
H OH CO2(g)
Ethanedioic acid KMnO4, H2SO4 (aq), heat [or alkaline medium]
O O Oxidation 2 CO2 + H2O
<Distinguishing Test>
[Further acid-base [if in alkaline medium
C C Purple KMnO4 decolourises and effervescence of
rxn if in alkali] CO2 + 2NaOH ⎯→ Na2CO3 + H2O]
HO OH CO2(g)
* Carboxylic acid cannot be reduced by H2 (g), Pt (Catalyst) (-COOH is resonance stabilized, more resistant towards reduction)
** Carboxylic acid cannot form ester with phenol

26
Organic Chemistry Review NJC SH2 H2 Chemistry
Compound Reagent and condition Type of reaction Products
H2O (l) CH3CH2COOH + HCl
<Distinguishing Test if limited amount of H2O> Hydrolysis *white fumes of HCl will be observed if limited
White fumes of HCl amount of H2O is used

AgNO3 (aq)1 Hydrolysis followed CH3CH2COOH + HCl(aq)

<Distinguishing Test> White ppt of AgCl formed by precipitation Cl−(aq) + Ag+(aq)⎯→ AgCl (s)

CH3CH2OH Condensation
+ HCl
Acyl chloride
O O
OH
CH3CH2 C Cl Condensation O C CH2CH3 + HCl
*Add NaOH (aq) to phenol to convert it to phenoxide
for better yield

NH3 (g) Condensation

+ HCl

CH3CH2NH2 Condensation + HCl

H2SO4 (aq) / HNO3 (aq) / HCl (aq), heat Acidic hydrolysis CH3CH2COOH + CH3CH2OH
Ester
O
Alkaline hydrolysis
CH3CH2 C OCH2CH3 [Further acid-base
NaOH (aq) / KOH (aq), heat rxn] CH3CH2COO− Na+ + CH3CH2OH
RCOOH gives
RCOO−
1. Acyl chloride reacts with excess water to give a highly acidic solution containing carboxylic acid and HCl (aq)

27
Organic Chemistry Review NJC SH2 H2 Chemistry
Compound Reagent and condition Type of reaction Products

Acid-base reaction/
H2SO4 (aq) / HNO3 (aq) / HCl (aq) CH3CH2CH2NH3+
Neutralisation

Nucleophilic + CH3CH2CH2NH3+Cl−
limited CH3Cl, heat
substitution

Amine excess CH3Cl, heat

Nucleophilic
CH3CH2CH2NH2 substitution + Cl−

Acid-base reaction/
CH3COOH (aq) CH3CH2CH2NH3+ CH3COO−
Neutralisation

CH3COCl Condensation + HCl

Acid-base reaction/ +
NH3
H2SO4 (aq) / HNO3 (aq) / HCl (aq)
Phenylamine Neutralisation
Br
NH2 Br2 (aq)
Electrophilic Br NH2
<Distinguishing Test> + 3 HBr
substitution
Orange Br2 decolourises, white ppt formed.
Br
(white ppt)
Nitrobenzene Step 1: Sn, conc HCl, heat
Step 2: followed by excess NaOH (aq) Reduction NH2 + 2 H2O
NO2 [To remove excess H+]

*Nitrobenzene CANNOT be reduced by H2(g), Pt(s) or LiAlH4 in dry ether.

28
Organic Chemistry Review NJC SH2 H2 Chemistry
Compound Reagent and condition Type of reaction Products
Acidic hydrolysis
[Further acid-base
H2SO4 (aq) / HNO3 (aq) / HCl (aq), heat CH3CH2COOH + NH4+
rxn]
NH3 gives NH4+
Alkaline hydrolysis
Amide [Further acid-base
O NaOH (aq) / KOH (aq), heat rxn] CH3CH2COO− + NH3
CH3CH2 C NH2 RCOOH gives
RCOO−

LiAlH4 in dry ether Reduction CH3CH2CH2NH2

H H O
Amino acids
H H O Acid-base reaction/ H
+
H2SO4 (aq) / HNO3 (aq) / HCl (aq) N C C OH
Neutralisation
H N C C OH H R
R H H O
Acid-base reaction/ -
* R group may also NaOH (aq) / KOH (aq) H N C C O + H2O
Neutralisation
react with H+ / OH− R

Acidic hydrolysis H H O
Polypeptides Conc. HCl / Conc H2SO4, Prolonged heating
[Further acid-base H
+
N C C OH
rxn]
H H −NH2 gives −NH3+ H R
N C C Alkaline hydrolysis H H O
[Further acid-base -
R O Conc. NaOH / Conc KOH, Prolonged heating rxn] H N C C O
n RCOOH gives
R
RCOO−
* Amide cannot be reduced by H2, Pt (Catalyst)

**Amide is neutral

29
Organic Chemistry Review NJC SH2 H2 Chemistry
Comparing oxidation reactions

CH2CH3 OH O H
H H R O C
R R O O
C C R C OH R C OH R C OH R C C C
R H H HO OH
H R R

KMnO4, R R
NaOH (aq), R C C H
cold
OH OH
R COOH O O O COOH 2 CO2 + H2O
C O
KMnO4, + CO2(g)
R C C C
H2SO4 (aq), R R OH R R R OH
heat O C
OH

O O O COOH
K2Cr2O7,
H2SO4 (aq), C C C
heat under R OH R R R OH
reflux

[Ag(NH3)2]+ O COO−
complex, C
heat R O−
(Tollens’
reagent)
Cu2+ alkaline O
complex,
C
heat R O−
(Fehling’s
solution)

30
Organic Chemistry Review NJC SH2 H2 Chemistry
Comparing reduction reactions

NO2
R R O O O O
C C R C N R C R C R C R C
R H H R OH NH2

H H
R R H
R C OH R C OH
H2 (g), Pt R C C H R C N H
H R
H H H H
(1° alcohol) (2° alcohol)

H H H
H H
R C OH R C OH R C OH
LiAlH4 in dry R C N H R C N H
ether H R H
H H H H
(1° alcohol) (2° alcohol) (1° alcohol)

H H
R C OH R C OH
NaBH4 in
ethanol H R

(1° alcohol) (2° alcohol)

*NaBH4 can only reduce the carbonyl groups

** Alkene cannot be reduced by LiAlH4 (C=C is electron rich, and will repel the H− ion from LiAlH4)
*** Carboxylic acid and amide are resonance stabilized, they can only be reduced by LiAlH4.
****nitrobenzene can only be reduced using Sn, conc HCl, heat, followed by excess NaOH(aq)

31
Organic Chemistry Review NJC SH2 H2 Chemistry
Relative reactivity towards electrophilic substitution (Refer to Data Booklet)
CH3 NO2 OH NH2

Electron density in
Normal Slightly higher Lower Significantly higher Significantly higher
benzene
Reagents and Br2 in CCl4 or Br2 in CCl4 or
Br2 with anhydrous Br2 with anhydrous Br2 with anhydrous
conditions for Br2(aq) Br2(aq)
FeBr3 catalyst FeBr3 catalyst FeBr3 catalyst
Substitution by -Br [No catalyst] [No catalyst]
Reagents and conc HNO3 conc HNO3 conc HNO3 HNO3 (aq) or
Acid base reaction
conditions for conc H2SO4 catalyst conc H2SO4 catalyst conc H2SO4 catalyst conc HNO3
with HNO3
Substitution by –NO2 heat strong heating [No catalyst]
*Alkyl groups are weakly activating while −OH and −NH2 groups are strongly activating as a result of resonance.

Relative reactivity towards nucleophile/hydrolysis

Acyl chlorides Alkyl chlorides

Chlorobenzene Chloro alkene

Cl
C C Cl

The presence of highly electronegative O
atom and Cl atom attached to the carboxyl
C atom makes the C atom highly electron-
deficient (+), hence most susceptible to
nucleophilic attack.
Reacts less readily than acyl chlorides.
Rate of reaction of C−I > C–Br > C–Cl
Depends on the strength of C–X bond
(refer to Bond Energy in Data Booklet)
Resistant towards nucleophilic substitution.
1) C atom of C–Cl is electron rich due to
delocalized π electrons of benzene/ electron rich
C atom in C=C. This repels nucleophile.
2) Partial double bond character of C–Cl bond
due to the overlapping of the p orbital of Cl with
the π electron cloud of the benzene ring/C=C

32
Organic Chemistry Review NJC SH2 H2 Chemistry
Comparing reactions of alcohol, phenol and carboxylic acid
Alcohol (Neutral) Carboxylic acid
Phenol (Very weak acid) (Weak acid)

OH

H O
− + − +
Na R C O Na + 1/2 H2 O Na + 1/2 H2
C + 1/2 H2
− +
H R O Na

O
NaOH (strong base) O−Na+ + H2O + H2O
C
R O−Na+
O
NaHCO3/Na2CO3 (weak base) C + CO2 + H2O
R O−Na+
O
NH3 (weak base) C + NH4+
−
R O
H O
Anhydrous PCl5/PCl3/SOCl2 R C Cl
C
H R Cl
H
HX (g) R C X + H2O
H

33
Organic Chemistry Review NJC SH2 H2 Chemistry
Relative strength of acids [An acid is a proton (H+) donor]
We can compare relative strength of acids by comparing the relative stability of the conjugate base formed during acid dissociation.

The more stable the conjugate base is (with respect to the other conjugate base), the acid dissociates more readily into H+ and its
conjugate base.

Comparing between different functional groups (Recommended to show the acid dissociation equilibrium for all acids)
The electron-donating alkyl group (R-) destabilize the
alkoxide ion by intensifying its negative charge. R-O− is
Alcohol − +
R OH + H2O R O + H3O less stable than HO−. Alcohol dissociates less readily into
(Neutral)
H+ and its conjugate base as compared to water.
Hence alcohol is less acidic than water. Alcohol is neutral.
Water −
H OH + H2O H O + H3O+
(Neutral)
Negative charge on the phenoxide ion is dispersed into
the benzene ring as a result of resonance, resulting in
Phenol − phenoxide ion being more stable than HO− ion. Phenol
OH + H2O O + H3O+
(Very weak acid) dissociates more readily into H+ and its conjugate base as
compared to water.
Hence phenol is more acidic than water.
Negative charge on carboxylate ion is dispersed
significantly over 2 highly electronegative O atoms as
a result of resonance, resulting in carboxylate ion being
Carboxylic acid O O more stable than HO− and phenoxide ion. Carboxylic acid
−
(Weak acid) R C OH + H2O R C O + H3O+ dissociates more readily into H+ and its conjugate base as
compared to water and phenol.
Hence carboxylic acid is more acidic than water and
phenol.

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Organic Chemistry Review NJC SH2 H2 Chemistry
Relative strength of acids [An acid is a proton (H+) donor]
Comparing between compounds with same functional group

Presence of additional electron-donating and electron-withdrawing groups

CH3 CH3 • Electron-donating groups (−alkyl) increase the intensity of the
negative charge on the conjugate base, thus the dissociation
− into H+ and conjugate base is less favourable. Hence this
OH + H2O O + H3O+
decreases the acidity of the compound.

−
OH + H2O O + H3O+

NO2 NO2 • Electron-withdrawing groups (−NO2) decrease the intensity of

the negative charge on the conjugate base, thus the
− dissociation into H+ and conjugate base is more favourable.
OH + H2O O + H3O+
Hence this increases the acidity of the compound.

Distance of electron-withdrawing groups

Cl O Cl O • The nearer the electron-withdrawing groups, the greater

− +
CH3CH C OH + H2O CH3CH C O + H3 O the extent of dispersing the intensity of the negative
charge on the conjugate base, thus the dissociation into
Cl O Cl O H+ and conjugate base is more favourable. Hence this
− increases the acidity of the compound.
CH2CH2 C OH + H2O CH2CH2 C O + H3O+

35
Organic Chemistry Review NJC SH2 H2 Chemistry
Relative strength of bases [A base is a proton (H+) acceptor]
We can compare relative strength of bases by comparing the relative availability of lone pair electrons on N to accept H+.

The greater the electron density on N atom, the more available the lone pair electrons on N to accept H+ (with respect to the other base),
the stronger the base.
Amide
(neutral) Due to significant delocalization to adjacent C=O (highly electronegative O atom), the lone pair of
O electrons on N is NOT available to accept H+.
 Hence amide is neutral.
R C NH2
Phenylamine
(Very weak base) Due to slight delocalization of lone pair of electrons on N into the benzene ring, this decreases
the electron density on N atom and it is less available to accept H+ as compared to ammonia.

NH2 Hence phenylamine is a weaker base than ammonia.

Ammonia
(weak base)

Primary amine The electron-donating alkyl group (R-) increases the electron density on N atom and it is more
(weak base) available to accept H+ as compared to ammonia.

Hence amine is a stronger base than ammonia.

Secondary amine
(weak base) The greater number of electron-donating alkyl group (R-) bonded to N atom, the greater the electron
density on N atom and it is more available to accept H+.

Hence secondary amine is a stronger base than primary amine.

36
Hybridization for O and N atom in organic chemistry

O and N atom can undergo hybridization similar to carbon. The type of hybridization
depends on the number of electron regions (bond pair regions + lone pair regions)
around the atom.

Hybridization Number of electron regions Examples

H
  H

H C O H C N H
sp3 4
H H H H
3
sp O sp3 N
H
C

O
H
C N

sp2 3
H H H
sp2 O sp2 N

sp 2 H C N 
sp N

37