Organic Chemistry 1

A B C

Can you name these compounds?

General Mechanism Rules and
Definitions
• Arrows show the movement of electrons
• Double headed arrows show a PAIR of
electrons moving
• Single head arrows show a singular electron
moving

• A lone pair is represented by a two dots

When drawing an arrow from a lone pair of a

electrons it must start from the centre of the
lone pair

• Delta δ+ Positive = It is the less

electronegative atom in the covalent bond

• Delta δ- Negative = It is the more

electronegative atom in the covalent bond
General Mechanism Rules and Definitions
• Free radical; A reactive species with an unpaired electron
• Nucleophile; An electron pair donor
• Substitution; replacement of the halogen by the nucleophile; C-Halogen bond breaks and
a bond forms between the carbon and the nucleophile
• Elimination: removal of small molecule (often water) from the organic molecule
• Bond Enthalpy; Heat energy required for the homolysis of the Carbon halogen bond
• Electrophile = An electron pair acceptor
• Addition reaction = 2 molecules join together to form 1
• Dehydration reaction; removal of water from a molecule
• Hydrolysis; a reaction where the molecule is split by the addition of water.
• Aliphatic : straight or branched chain organic substances
• Aromatic or arene: includes one or more ring of six carbon atoms with delocalised
bonding.
Free Radical Substitution Ozone
Purpose: Alkane -> Halogenoalkane Cl● + O3 -> CLO● + O2
Reagent; Cl2, Br2 ClO ● + O3 -> 2O2 + Cl●
Overall; CH4 + Cl2 -> CH3CL + HCL Overall; 2O3 -> 3O2
Initiation:
Cl2 -> 2Cl● Cl ● is a catalyst because it is:
Propagation: 1. Regenerated
CH4 + Cl● -> ●CH3 + HCL 2. Unchanged
●CH3 + Cl2 -> CH3CL + Cl● 3. Does not appear in the overall equation

Termination: Electrophilic Addition

2 ●CH3 -> C2H6 Conditions; Room Temperature but with Bromine NOT in UV
●CH3 + Cl● -> CH3Cl light.
2Cl● -> Cl2 Reagents:
Conditions Bromine -> Di halogenoalkane
1. UV light, Temperature > 400; supplies energy to HBr / HCl -> Halogenoalkane
break covalent bond Sulfuric Acid -> alkyl hydrogensulfate
2. Limited amount of Cl2 to prevent further substitution Bond Fission; Heterolytic Fission
reactions

Mechanism of Bond Breakage; Homolytic Fission; one

electron goes to each atom
Why does bromine, a non-polar molecule react with alkenes? (Common Exam
Question)

- C=C double covalent bond consists of one sigma (σ) bond and one pi (π) bond
- π bonds are exposed and have high electron density (many electrons
contained in this area)
- Pi bond electrons repel the electron pair in the Br-Br bond
- Induces a dipole and Br becomes polar and electrophilic
- Delta Positive Br is attracted to the double bond
Carbocations and Stability

Theory

- major product is formed via the most stable carbocation intermediate

Order of Stability
Tertiary > Secondary > Primary

- more stable because the methyl groups on either side of the carbon are electron releasing
- This is called the Inductive Effect
- This reduces the charge on the ion which stabilizes it
Nucleophilic Substitution Nucleophilic Elimination
Conditions; Aqueous Solution, Heat under reflux; For Purpose; Halogenoalkane -> Alkene
ammonia use excess to prevent further substitution Reagent; Concentrated Potassium Hydroxide , Cold
Lower temp and less concentrated Role of Hydroxide Ions; Base (Proton Acceptor)

Reagents; Conditions
- Ammonia; Produces Amine 1. In Ethanol -> acts as a solvent
- Hydroxide Ions; Produces Alcohol 2. Heat
- Cyanide Ions; Produces Nitrile
Products; Alkene and Water
- Occurs because C-Halogen bond is polar; halogen is
more electronegative than carbon. Carbon is partially
positive and lone pair on electrophile is donated to
positive carbon.
Rate of hydrolysis of halogenoalkanes
Method
1. Add the same amount of AgNO3 added to the same volume of haloalkane in a
beaker / flask
2. Same temperature
3. Record time taken for silver halide precipitate to form
4. Rate = amount / time -> shorter time = higher rate

Explanation
RI > RBR > RCL ; fastest to slowest

C-I is the weakest bond so hydrolyzed the quickest

because as you go down the group electronegative decreases; so, the bond weakness
increases.
Less energy is required for the homolysis of the carbon halogen bond giving a faster rate
of reaction.
C/CL bond is the strongest bond

Ag+ (aq)+ I- (aq)-> AgI (s)-> yellow precipitate

Acid Catalysed Elimination
Purpose: Alcohol -> Alkene
Reagent; Concentrated Phosphoric/ Sulfuric Acid
Conditions
1. Warm under reflux

Role of reagent; dehydrating agent/ catalyst

Uses
1. Can generate addition polymers without using monomers derived from crude oil

Primary Alcohols CANNOT be dehydrated

Acid Catalyzed Addition
Purpose: Alkene -> Alcohol
Reagent; Concentrated Phosphoric Acid

Conditions
- High temperature -> 300 to 600°C
- High pressure 70 atm
- Catalyst; concentrated H3PO4
- Excess alkene
- Excess water

Advantages:
- no waste products -> high atom economy
- easier to separate products

Disadvantages:
- too high of a pressure to do in lab
Nucleophilic Addition
Purpose
1. Reduction of carbonyls; NABH4 in aqueous ethanol; NABH4 is a reducing agent.
2. Ketone/Aldehyde -> Carboxylnitrile; Sodium cyanide (NaCN) and dilute sulfuric acid.

HCN is not readily used in the formation of hydroxynitrile; it is a toxic gas that is difficult to contain.

NaCN and KCN are preferable over HCN.

NaCN will completely ionize resulting in a higher concentration of the CN- ion
HCN is a weak acid an will only partially ionize

- The formation of carboxylnitirle can often form a Racemic mixture (contain equal amounts of each
enantiomer)
- They will rotate plane polarized light in opposite directions, so the effect cancelled out
- molecule is trigonal planar
- attack can occur from above or below the plane / from either side of the molecule
- chiral carbon created with 4 groups attached
Electrophilic Substitution
Nitration OF Benzene
Purpose; Benzene -> nitrobenzene
Reagents: concentrated nitric acid in the presence of concentrated sulfuric acid (catalyst)
Mechanism: Electrophilic substitution
Electrophile: +NO2

Equation for the formation of the electrophile, naming the type of reaction. (2)
HNO3 + 2H2SO4 -> +NO2 + 2HSO4 - + H3O+
Type of Reaction: acid-base reaction

Conditions; Low temperature of 60 degrees; At higher temperatures, a second nitro group can be substituted

1. Important in Synthesis
2. Can synthesise TNT
3. Can form amines from which dyestuffs are manufactured.

Reformation of the catalyst at the end of the reaction

H+ + HSO4- -> H2SO4

 Mechanism for nitration

Feedback From Examiners

• + Must be next to N not near O
• horseshoe must not extend beyond C2 to C6 but can be
smaller
• + not too close to C1
• + on H in intermediate loses mark
Reducing a nitroarene to aromatic
amines

Reagent: Sn and HCl or Fe and HCl

Conditions: Heating
Mechanism: reduction

HCL -> the ionic salt C6H5NH3+Cl - will be formed, which is soluble in water; it is a weak acid
NaOH -> insoluble phenylamine
Electrophilic Substitution
Friedel-Crafts acylation
Purpose: benzene -> phenyl ketone
Reagents: acyl chloride in the presence of anhydrous aluminium chloride catalyst
Conditions: heat under reflux (50OC)
Mechanism: Electrophilic substitution

Equation for formation of the electrophile. AlCl3 + RCOCl -> [RCO]+ + [AlCl4 ] –

in organic synthesis because they introduce a reactive functional group on to the benzene ring.

Equation of reformation of catalyst; H+ + AlCl4 - -> AlCl3 + HCl

Nucleophilic Addition Elimination with Acyl Chlorides (Most
commonly assessed)
Conditions: room temp
• Acyl chloride + water -> carboxylic acid (White steamy fumes of HCL)
• Acyl chloride + alcohol -> ester (White steamy fumes of HCL)
• Acyl Chloride + Ammonia -> primary amide (white smoke of NH4Cl)
Acyl Chloride + Primary Amine -> secondary amide
Nucleophilic Addition Elimination with Acyl Chlorides (Most commonly
assessed)
Esters

Formed when Carboxylic acids react

with alcohols, in the presence of a
strong acid catalyst, to form esters
and water.

Esters have two parts to their names,

eg methyl propanoate.

The bit ending in -yl comes from the

alcohol that has formed it and is next
to the single bonded Oxygen

The bit ending in -anoate comes from

the carboxylic acid and includes the
C in the C=O bond.
Name this Ester
Ester Hydrolysis
Acid Hydrolysis
• Reagents: dilute acid (HCl)
• Conditions: heat under reflux
• The reverse reaction of ester formation.
• Carboxylic acid and an alcohol are formed
• This reaction is reversible and does not give a good yield of the products.

Base Hydrolysis
• Reagents: dilute sodium hydroxide
• Conditions: heat under reflux
• Forms carboxylic acid salt and alcohol

• The carboxylic acid salt product is the anion of the carboxylic acid.
• The anion is resistant to attack by weak nucleophiles such as alcohols, so the reaction is not reversible.

• Using excess sodium hydroxide will ensure the ester is completely hydrolysed.

• Addition of a strong acid to the carboxylic acid salt will convert the salt to the carboxylic acid form.
Amide

Carboxylic Acid Derivative where hydroxyl group has been replaced with ammonia / amine
Can be primary secondary and tertiary
Formed when acyl chloride reacts with ammonia / amine
Naming Amides
Naming Amides
Name this Amide
Amide Hydrolysis
Primary and Secondary amides can be hydrolysed by concentrated acids or
alkalis.

Primary
HCl Forms a carboxylic acid and an ammonium salt
NaOH Forms ammonia and the carboxylic acid salt

Secondary
HCl forms a carboxylic acid and an amine salt
NaOH forms the amine and the carboxylic acid salt
Reduction of Amides

Amide -> Amine

LiALH4
Reflux
Reflux is used when heating organic reaction mixtures for long periods

A mixture of liquids is heated to boiling point for a prolonged time

Vapour is formed which escapes from the liquid mixture and it changed back into
liquid and returned to liquid mixture

When heating under reflux, you aim to keep all the chemicals inside the reaction vessel

Example reactions where heating under reflux could be used include:

• The production of a carboxylic acid from a primary alcohol using acidified
potassium dichromate
• The production of an ester from an alcohol and acid in the presence of an acid
catalyst

The condenser prevents organic vapors from escaping by condensing them into
liquids

The end of the condenser must never be sealed as the build of gas pressure could
cause the apparatus to explode

Anti bumping Granules are added to the flask to prevent vigorous , uneven boiling by
making small bubbles rather than large bubbles
Recrystallisation and Purity
Method:
1. Dissolve the impure crystals in the minimum volume of hot solvent
2. Filter the hot solution through a hot fluted filter paper
3. Let the solution cool in ice and recrystallize
4. Filter the crystals by suction filtration / using a Buchner funnel under reduced pressure
5. Dry the crystals between two sheets of filter paper
6. Wash and dry

Minimum amount of hot solvent is used;

• to obtain a saturated solution
• dissolves both the compound and its impurities

Hot filtrate is filtered;

• To remove any insoluble impurities
Brainpow
• Heat to prevent crystals reforming during filtration er
Read Mor

Cooled in ice;
• Ice increases the yield of crystals / more crystals formed

Washed with cold water;

• To remove soluble impurities
Recrystallisation and Purity
Method:
1. Dissolve the impure crystals in the minimum volume of hot solvent
2. Filter the hot solution through a hot fluted filter paper
3. Let the solution cool in ice and recrystallize
4. Filter the crystals by suction filtration / using a Buchner funnel under reduced pressure
5. Dry the crystals between two sheets of filter paper
6. Wash and dry

Why is the suction filtration used

- water pump connected to the Büchner flask reduces the pressure and speeds up filtration
- Air passes through the sample not just round it

Buchner Funnel is more useful than a Gravity funnel because;

1. Quicker
Brainpow
2. Sample is drier er
Read Mor

Explain why the yield might be greater than expected

- crystals are not dried properly

Explain why the yield might be lower than expected

- crystals lost during filtering / washing
- product stays in solution after recrystallisation
- other side reactions occur
Determining Melting Point Range of a Solid

Method
- place the sample in a capillary tube
- place the tube into melting point apparatus and head slowly
- record the temperature when the solid starts to melt and the temperature when it
has melted completely

If there are impurities

1. Melts over a wider range
2. Melting point lower than true melting point

If Pure;
1. Sharp melting point
2. melting point matches data source value

Pure samples might sometimes appear to melt at a temperature different from their melting
point because the temperature on thermometer not the same as the sample