Organic Chemistry Revision Sheets

Alkenes | Electrophilic Addition (with Br2)

Reaction
REACTANTS: Alkene and Bromine (Br2)
CONDITIONS: Non-polar organic solvent (or pure liquid bromine)
PRODUCT: Dibromoalkane
REACTION TYPE: Electrophilic Addition

REACTION:
(example of
ethene)

Mechanism
Br2 acts as an electrophile so the bromine-bromine bond is polarised by the carbon-carbon
double bond so the bromine atom with a partial positive charge accepts an electron pair
from the carbon-carbon double bond. During the reaction the carbon-carbon double bond
breaks, forming a postively charged carbon (carbocation). The negatively charged bromide
ion bonds with the carbocation. Br2 is 'added' across the double carbon-carbon bond. Addi-
tion reaction.

Notes:
• The high electron density in the carbon-carbon double bond (pi-bond) polarises the
bromine molecule to create the Br δ+ electrophile.
• This reaction is often used to identify an alkene as the colour of bromine water
changes from orange / brown to colourless when mixed with an alkene (due to the
above reaction).
 Organic Chemistry Revision Sheets
Alkenes | Electrophilic Addition (with HBr)

Reaction
REACTANTS: Alkene and HBr (Hydrogen Bromide)
PRODUCT(S): Bromoalkane
REACTION TYPE: Electrophilic Addition

REACTION:
(example of
ethene)

Mechanism
HBr acts as an electrophile because its hydrogen atom (with a partial positive charge)
accepts an electron pair from the carbon-carbon double bond. During the reaction the
carbon-carbon double bond breaks, forming a postively charged carbon ion (carbocation).
The negatively charged bromide ion bonds with the carbocation. HBr is 'added' across the
carbon-carbon double bond. Addition reaction.

Notes:
• If a primary or secondary carbocation can be
formed during the reaction, the secondary
carbocation will form more readily than the
primary carbocation - creating 'major' and
'minor' products*.
• The secondary carbocation is more stable due
to increased positive inductive effect from neigh-
bouring alkyl chains.
• *The product mixture will contain more of the
major product than the minor product.
 Organic Chemistry Revision Sheets
Benzene | Electrophilic Substitution (Halogenation, with Br2)

Reaction
REACTANTS: Benzene and Halogen
CONDITIONS: Halogen carrier (AlCl3, AlBr3 or Fe)
PRODUCT: Halogenated Arene (chloro-benzene, bromo-benzene)
REACTION TYPE: Electrophilic Substitution, Halogenation

REACTION:
(example of
benzene)

Mechanism
Bromine molecule acts as an electrophile because it is polarised sufficiently by a
halogen carrier (AlBr3) and accepts an electron pair from the delocalised ring of electrons
in the benzene ring. A carbon-bromine bond forms. The carbon-hydrogen bond breaks to
the give electron pair back to delocalised ring of electrons. Br replaces H on benzene ring.
Substitution reaction.

Notes:
• Benzene is unable to undergo halogenation without a halogen carrier as the delocalised elec-
tron ring is unable to polarilse the halogen moleucle enough to form an electrophile.
• The halogen carrier poalrises the halogen molecule to the point of enabling one of the halogen
atoms (now with a partial positive charge) to act as an electrophile and accept a pair of elec-
trons from benzene.
 Organic Chemistry Revision Sheets
Benzene | Electrophilic Subsititution, (Nitration, with HNO3)

Reaction
REACTANTS: Benzene and Nitric Acid
CONDITIONS: 55oC and conc. sulfuric acid (H2SO4)
PRODUCT: Nitrobenzene
REACTION TYPE: Electrophilic Substitution, Nitration

REACTION:
(example of
benzene)

Mechanism
Nitronium (NO2+) ion acts as an electrophile due to its positively charged nitrogen atom
accepting an electron pair from the delocalised ring of electrons in the benzene ring. A Car-
bon-nitrogen bond forms. The carbon-hydrogen bond breaks to give electron pair back to
delocalised ring of electrons. NO2+ ion replaces H on benzene ring - substitution reaction.

Notes:
• Nitronium ion is formed by the reaction of concentrated nitric acid with concentrated sulfuric acid

• H+ ion removed from benzene ring combines with hydrogen sulfate (HSO4-) ion
to reform catalyst H2SO4:
H+ + HSO4- → H2SO4
 Organic Chemistry Revision Sheets
Carbonyl Compounds | Nucleophilic Addition (KCN, H+)

Reaction
REACTANTS: Carbonyl (aldehyde or ketone) and KCN (in acid)
PRODUCT: Hydroxynitrile
REACTION TYPE: Nucleophilic Addition

REACTION:

Mechanism
Cyanide ion (:CN-) comes from KCN(aq) and acts as a nucleophile due to its lone pair
of electrons, attacking the carbon (with partial positive charge) in the carbonyl group.
Carbon-carbon bond forms. The carbon-oxygen double bond breaks to a single bond, giving
the oxygen a negative charge. The negative oxygen is protonated in dilute acid (H2SO4), form-
ing a hydroxyl group. Hydroxynitrile is formed. CN and H are added to the carbonyl. Addition
reaction.

Notes:
• HCN is sometimes written as the reactant, but HCN is very reactive and dangerous how-
ever. By using KCN in dilute acid, the same product can be formed as with HCN.

HCN + RR'CO → RR'C(OH)CN

• If a chiral carbon centre is formed in the product, the final product mixture will be racemic
containing both enantiomers in a 50:50 ratio. This is because carbonyl groups are planar and
there is equal chance of the :CN- nucleophile attacking the carbonyl group from above or
below the plane - producing two possible enantiomers in equal amounts.
 Organic Chemistry Revision Sheets
Carbonyl Compounds | Nucleophilic Addition (NaBH4)

Reaction
REACTANTS: Carbonyl (aldehyde or ketone) and NaBH4 or LiAlH4
PRODUCT: Alcohol
REACTION TYPE: Nucleophilic Addition, reduction

REACTION:
(example of
ketone)

Mechanism
Hydride ion (:H-) comes from reducing agent (NaBH4 or LiAlH4*) and acts as a nucleophile
due to its lone pair of electrons attacking the carbon (with partial positive charge) in the
carbonyl group. A carbon-hydrogen bond forms. The carbon-oxygen double bond breaks
to a single bond, giving the oxygen a negative charge. The negative oxygen is protonated by
water, forming a hydroxyl group and a hydroxide ion. Alcohol is formed, H is added to the
carbonyl.Addition reaction.

Notes:
• Aldehydes form primary alcohols when reduced.
• Ketones form secondary alcohols when reduced.
• *NaBH4 and LiAlH4 are reducing agents, they are able to provide hydride (:H-) ions that are
needed for the reduction of carbonyls.
 Organic Chemistry Revision Sheets
Halogenoalkanes | Nucleophilic Substitution (with OH-(aq))

Reaction
REACTANTS: Halogenoalkane and Sodium Hydroxide, NaOH (for OH- ions)
CONDITIONS: Aqueous ('aq' - water present)
PRODUCT(S): Alcohol and Halide Ion (sodium halide salt if sodium hydroxide used)
REACTION TYPE: Nucleophilic Substitution

REACTION:
(example of
bromoethane)

Mechanism
Hydroxide ion (OH-) acts as a nucleophile and attacks the partially positive carbon atom in
the carbon-halogen bond. The carbon-halogen breaks, forming alcohol and halide ion. OH
group is substituted for the halogen group.

Notes:
• Reaction must be carried out in aqueous conditions (in water), otherwise an elimination
reaction will occur and an alkene will be formed.
• The strength of the carbon-halogen bond (bond enthalpy) determines the speed of the reaction. The
stronger the bond, the slower the nucleophilic substitution reaction. C-F bond is strongest, giving the
slowest reaction; C-I bond is weakest, giving the fastest reaction.
 Organic Chemistry Revision Sheets
Alkanes | Free Radical Substitution

Reaction
REACTANTS: Alkane and Halogen
CONDITIONS: U.V (ultraviolet) light
PRODUCT(S): Halogenoalkane and Hydrogen Halide
REACTION TYPE: Free Radical Substitution

REACTION:
(example of
methane and
chlorine)

Mechanism
INITIATION STEP: Halogen molecule undergoes heterolytic fission to form radical species:

PROPAGATION STEP: Radical species reacts with alkane to form alkyl radical and HCl.
Alkyl radical then reacts with halogen molecule, reforming another halogen radical, creating
a chain reaction:

TERMINATION STEP: Radical species combine to end chain reaction:

Notes:
• Heterolytic fission is the even breaking of a covalent bond (each bonded atom gets an electron and
becomes a radical species).
• UV light provides the energy required for hetereolytic fission.
• Further substitution reactions can occur, eventually forming tetrachloromethane:
chloromethane to dichloromethane to trichloromethane to tetrachloromethane