Organic reactions 

are chemical reactions involving organic compounds. The basic types of

organic  reactions are addition reactions, elimination reactions, substitution
reactions, pericyclic reactions, rearrangement reactions, photochemical reactions and redox
reactions. In organic synthesis, organic reactions are used in the creation of new organic
molecules. Organic chemistry has a strong tradition of naming a specific reaction to its
inventor or inventors and a long list of so-called named reactions exists in this area.
The oldest organic reactions are combustion of organic fuels and saponification of fats
to make soap.

Substitution reaction: A substitution reaction is defined as a reaction, in which an

atom or a group of atoms attached to a carbon atom is removed and another takes it place.
The substitution reactions which are brought about by nucleophilic reagents or nucleophiles
are called nucleophilic substitution reactions.
The nucleophiles attack the substrate at a position of low density. It should be noted
that during nucleophilic substitution reaction, the degree of unsaturation at the respective
carbon atom remains the same. The nucleophilic substitution reaction can be represented as
follows:

The nucleophiles must possess an unshared electron pair. They may be neutral or
negatively charged while a substrate may be neutral or positively charged. The examples of
nucleophilic reactions are as follows:
 SN2 reaction: Consider the following reaction, which involves alkaline hydrolysis of
methyl bromide:

where the substitution of a nucleophile, -Br occurs by a nucleophile, -OH. The rate of the
reaction depends on the concentration of both the reactants. Hence, it is called SN2
(Substitution, Nucleophilic, Second order/Bimolecular)
Rate = k [CH3Br] [:OH¯]
Thus, if the concentration of one of the reactants is doubled, the rate of reaction will
be doubled and if it is halved, the rate will become half.
The mechanism of the reaction is as follows:
The OH¯ ion attacks the carbon atom from the side opposite to that of bromine atom.
The attacking nucleophile, i.e., OH¯ ion cannot approach the methyl bromide molecule from
the other side due to repulsion by the negatively polarised bromine.

When the hydroxyl ion approaches the carbon atom, it starts sharing its lone pair of
electrons with the carbon atom, resulting in diminishing its negative charge. At the same
time, the bond between bromide ion and carbon starts breaking. The bromide ion starts
withdrawing the electron pair, developing the negative charge.
This gives rise to the transition state, in which partial making (of oxygen atom of
hydroxyl ion and carbon atom) and partial breaking ((of bromide ion and carbon atom) takes
place. Thus, in this state, carbon is partially bonded to both, -OH and –Br and the three
hydrogens and the carbon carbon are coplanar.
 Such a transition state is characterised by maximum potential energy and minimum
stability. Hence, it quickly transforms into the final stage. Finally, the carbon-oxygen bond is
completely formed and carbon-bromine bond is completely broken, with the separation of
bromine atom as bromide (Br¯) ion.

At the same time, the tetrahedral configuration of carbon is restored by turning of the
remaining three bonds joining the hydrogen atoms to carbon atom to the side opposite to their
original one. The energy required for breaking a bond is compensated by the formation of the
other bond. Thus, the overall reaction is a concerted process, which occurs through
simultaneous breaking of the old bond and formation of the new bond in one step without the
formation of any intermediate.
The overall reaction can be shown as follows:
 The energy changes occurring in SN2 reaction can be represented by as energy profile
diagram as follows:

SN1 reaction: Consider the following reaction, which involves alkaline hydrolysis of
tertiary butyl bromide:
[(CH3)3Br] + KOH [(CH3)3OH] + KBr
where the substitution of a nucleophile, -Br occurs by a nucleophile, -OH. The rate of the
reaction depends on the concentration of only alkyl halide (here tertiary butyl bromide).
Hence, it is called SN1 (Substitution, Nucleophilic, First order/Unimolecular)
Rate = k [(CH3)3Br]
The mechanism of the reaction is as follows:
The first step involves slow ionisation of C–Br bond to form a bromide ion (Br¯) and
a carbonium ion [(CH3)3+]. The second step involves reaction between carbonium ion and
hydroxyl ion (OH¯) to yield an alcohol.
The first step is a slow and reversible one, hence rate determining. The second step is
a fast one, as the carbon atom of the carbonium ion has only six electrons in the outermost
orbit and therefore, it shows a strong tendency to accept a pair of electrons form any
compound possessing an unpaired electron pair.
The carbon atom in a carbonium ion is sp 2 hybridised and therefore, all the atoms in
this ion are coplanar.
The overall reaction can be shown as follows:
(i)

(ii)

The energy changes occurring in SN1 reaction can be represented by as energy profile
diagram as follows:
 The diagram shows that each step of SN1 reaction has its transition step. Although the
structure of a transition step is intermediate between that of the starting material and that of
the product, it is state of maximum potential energy. Therefore, the transition state
corresponding to the first step of SN1 reaction will be very much similar to the highly
energetic carbonium ion than to the stable starting material.

Distinguishing features of SN2 and SN1 reactions:

SN2 Reactions SN1 Reactions
(1) Most of the SN2 reactions follow second (1) All SN1 reactions follow first order
order kinetics. Sometimes follow first order kinetics.
kinetics but proceed by SN2 mechanism.
(2) The attack of the nucleophile takes place (2) The attack of the nucleophile takes place
exclusively from the back side. from the back as well as front side, though
back side attack predominates.
(3) Complete inversion of the configuration (3) In case of optically active alkyl halides,
of the product takes place. partial racemisation of the product takes
place.
(4) Reaction rate is determined mainly by (4) Reaction rate is determined by electronic
steric factors. factors.
(5) No rearrangement is possible (5) Rearranged products can be formed.
(6) The order of reactivities of alkyl halides (6) The order of reactivities of alkyl halides
is: Methyl > Primary > Secondary > is: Tertiary > Secondary > Primary >
Tertiary halides. Methyl halides.
(7) SN2 reactions are favoured by strong (7) SN1 reactions are favoured by mild
nucleophiles. nucleophiles.
(8) SN2 reactions are favoured by high (8) SN2 reactions are favoured by low
concentration of the nucleophiles. concentration of the nucleophiles.
(9) SN2 reactions are favoured by solvents (9) SN2 reactions are favoured by solvents
of low polarity. of high polarity.

Comparison between Transition state and Intermediate:

Transition state Intermediate
(1) It possesses more energy than (1) It possesses less energy than transition
intermediate. state.
 (2) It is not a definite molecular species. (2) It is a definite molecular species.
(3) It is a transient and unstable arrangement (3) It is a stable species as compared to
of the atoms at an intermediate stage of transition state.
reaction.
(4) It gets characterized by the presence of (4) The partially broken bonds and partially
partially broken bonds and partially formed formed bonds are not observed in case of
bonds. intermediate.
(5) It cannot be isolated. (5) It can be isolated.

Elimination reaction: An elimination reaction is defined as a reaction, in which a

molecule loses two atoms or groups, without being replaced by other atoms or groups.
Generally, an elimination reaction involves loss of atoms or groups from adjacent carbon
atoms, resulting in the formation of a π-bond between these carbon atoms. Thus, an
elimination reaction is the reverse of an addition reaction.

E2 reaction: Consider the following reaction, which involves action of sodium

ethoxide on 1-bromopropane to form propene:

The rate of the reaction depends on the concentration of alkyl halide (here 1-
bromopropane) and the concentration of the base (sodium ethoxide). Hence, it is called E2
(Eliminaion, Bimolecular)
Rate = k [CH3CH2CH2Br] [C2H5O¯]
The mechanism of the reaction involves the abstraction of the proton from β-carbon
atom by the base with simultaneous removal of the halide ion with the pair of bonding
electrons from the α-carbon atom.
The overall reaction can be shown as follows:
 E1 reaction: Consider the following reaction, which involves action of strong
solution of alcoholic alkali on 2-bromo-2-methylpropane (tert-butyl bromide) to form 2-
methylpropene:

The rate of the reaction depends on the concentration of only alkyl halide (here tert-
butyl bromide). Hence, it is called E1 (Eliminaion, Unimolecular)
Rate = k [(CH3)3CBr]
The first step involves slow ionisation of C–Br bond to form a bromide ion (Br¯ ) and
a carbonium ion [(CH3)3+] The second step involves loss of β-proton from the carbonium ion
with the help of a base to yield an alkene.
The overall reaction can be shown as follows:

On this basis, the formation of 2-methylpropene from 2-bromo-2-methylpropane is

explained as follows:
(i)

(ii)

Four factors affect the rate of

the SN2 reaction:
Substrate
The substrate plays the most important part in determining the rate of the reaction. This is
because the nucleophile attacks from the back of the substrate, thus breaking the carbon-
leaving group bond and forming the carbon-nucleophile bond. Therefore, to maximise the
rate of the SN2 reaction, the back of the substrate must be as accessible as possible. This
means that methyl and primary substrates react the fastest, followed by secondary substrates.
Tertiary substrates will not show in SN 2 reactions, because of steric hindrance. Structures that
can form highly stable cations by simple loss of the leaving group, for example, as a
resonance-stabilized carbocation, are especially likely to react via an SN1 pathway in
competition with SN2.

Nucleophile
As in the substrate, steric hindrance affects the nucleophile's strength. The methoxide anion,
for example, is both a strong base and nucleophile because it is a methyl nucleophile, and is
thus very much unhindered. On the other hand, tert-butoxide, is a strong base, but a poor
nucleophile, as its three methyl groups give stearic hindrance. Nucleophile strength is also
affected by charge and electronegativity: nucleophilicity increases with increasing negative
charge and decreasing electronegativity. A strong/anionic nucleophile always favours SN 2
substitution.

Solvent
The solvent affects the rate of reaction because solvents may or may not surround a
nucleophile, thus hindering or not hindering its approach to the carbon atom. Polar aprotic
solvents, are better solvents for this reaction than polar protic solvents because polar protic
solvents form hydrogen bonds with the nucleophile, hindering it from attacking the carbon
with the leaving group. Examples: DMSO, DMF, acetone etc. In polar aprotic solvent,
nucleophilicity parallels basicity.

Leaving group
The stability of the leaving group as an anion and the strength of its bond to the carbon atom
both affect the rate of reaction. The more stable the conjugate base of the leaving group is,
the more likely that it will take the two electrons of its bond to carbon during the reaction.
Therefore, the weaker the leaving group is as a conjugate base, and thus the stronger its
corresponding acid, the better the leaving group. Examples of good leaving groups are
therefore the halides (except fluoride, due to its strong bond to the carbon atom) and tosylate
whereas HO− and H2N− are not.

Since SN1 reaction is first order reaction so the factors that affect SN1 reaction are:

Rate is directly proportional to [alkyl halide]

1. weak nucleophile with low concentration is required

2. Better leaving group is required for the reaction
3. Formation of carbocation should be stable
4. Alkyl halide is sterically hindered
5. Polar protic solvent with high dielectric constant is required.

The factors that influence an E1 or E2 reaction are almost exactly the same as the factors
that influence the SN1/SN2 pathway.  Cation stability, solvents and basicity play
prominent roles. 
However, basicity may be the single most important of these factors. Because
strong bases can be thought of as very reactive nucleophiles, it is possible that they tilt
the likely reaction towards E2.  These compounds are so reactive that they are much
more likely to abstract a proton than be directed to the electrophilic carbon.  Even under
conditions that might otherwise be expected to lead to an SN1 or E1 reaction, if the base
is strong, E2 will frequently prevail. If there is no beta-hydrogen to abstract, then there
will be no elimination of any kind.
Characteristics of an E2 Reaction Kinetics
– Second order Mechanism – Single step Identity of R group
– More substituted halides react faster Rate: R 3CX > R 2CHX > RCH2X
– Stronger bases favour the reaction
– Better leaving group leads to faster reaction rates reaction rates
– Favored by polar aprotic solvents
– reactions are stereoselective, resulting in the formation of trans-double bonds
preferably

Characteristics of an E1 Reaction Kinetics

– First order Mechanism
– Two steps Identity of R group
– More substituted halides react faster Rate: R3CX > R2CHX > RCH2X
 – Favoured by weaker bases such as H2O and ROH
– Better leaving group leads to faster reaction rates.
– the rate determining step involves the C—X bond cleavage
– Favoured by polar protic solvents, which can stabilize the ionic intermediates.

There is a certain level of competition between the elimination reaction and nucleophilic

substitution. More precisely, there are competitions between E2 and SN2 and also between
E1 and SN1. Substitution generally predominates and elimination occurs only during precise
circumstances. Generally, elimination is favoured over substitution when
 stearic hindrance around the α-carbon increases.
 a stronger base is used.
 temperature increases (increase entropy)
 the base is a poor nucleophile. Bases with steric bulk, (such as in Potassium tert-
butoxide), are often poor nucleophiles.
The reaction rate is influenced by the reactivity of halogens, iodide and bromide being
favoured. Fluoride is not a good leaving group, so eliminations with fluoride as the leaving
group have slower rates than other halogens.

Oxidation-Reduction Reactions

 Oxidation is the loss of electrons or an increase in oxidation state by

a molecule, atom, or ion.
 Reduction is the gain of electrons or a decrease in oxidation state by a molecule,
atom, or ion.
The chemical species from which the electron is stripped is said to have been oxidized, while
the chemical species to which the electron is added is said to have been reduced. Although
oxidation reactions are commonly associated with the formation of oxides from oxygen
molecules, oxygen is not necessarily included in such reactions, as other chemical species
can serve the same function. The reaction can occur relatively slowly, as with the formation
of rust, or more quickly, in the case of fire. There are simple redox processes, such as the
oxidation of carbon to yield carbon dioxide (CO2) or the reduction of carbon by hydrogen to
yield methane (CH4), and more complex processes such as the oxidation of glucose (C6H12O6)
in the human body.
 Oxidizing agents:
o Peroxy acid
o Jones reagent
o KmnO4
o osmium tetroxide (OsO4)
o Tollens’ reagent’
o Pyridinium chlorochromate (PCC)

Reducing agents:
 Lithium aluminium hydride (LiAlH4), a very strong reducing agent.
 Hydrogen without or with a suitable catalyst e.g. a Lindlar catalyst.
 Sodium amalgam (Na(Hg))
 Amalgam (chemistry)#Zinc amalgam (Zn(Hg)) (reagent for Clemmensen reduction)
 sodium borohydride, hydrogen peroxide, hydrazine

Swern oxidation: It involves the oxidation of alcohols (in the presence of other
groups) to aldehydes or ketones by oxalyl chloride, dimethyl sulfoxide and a base
(trimethylamine) at low temperature.

General reaction:

Mechanism: It involves the following steps: (i) Dimethyl sulfoxide reacts with oxalyl
chloride to give dimethylchlorosulfonium ion, which reacts with an alcohol to yield the new
sulfonium ion. (ii) The base abstracts an acidic proton from the sulfonium ion to form
carbanion, which removes the proton from the carbon adjacent to the oxygen to give
aldehyde or ketone and dimethyl sulfide.
Applications:

(i)

(ii)
 Oppenauer oxidation: It involves the oxidation of alcohols to ketones in the
presence of aluminium tertiary-butoxide in benzene or toluene.
This reaction is the reverse of Meerwein-Ponndorf reaction. As the reaction is
reversible, in order to carry out the reaction in the forward direction, either a large excess of
ketone or a carbonyl compound (or ketone) that forms an alcohol whose boiling point is
higher than the ketone required for the reaction should be used.

General reaction:

Mechanism: The aluminium tertiary-butoxide reacts with alcohol to form the

aluminium alkoxide of the alcohol, which is oxidised through a cyclic transition state to form
respective ketone and isopropanol.

(i)

(ii)

(iii) (CH3)2CHO-Al(OCHMe2)2 + 3Me3COH Al(OCMe3)3 + 3(CH3)2CHOH

 Applications:
(i) The reaction is specific to alcohols. Therefore, the reaction is specially used to
prepare a ketone from a secondary alcohol having other oxidizable groups.
(a)

(b)

(ii) The reaction is useful to prepare steroid ketones.

(iii) The reaction finds its use for the oxidation of formats to carbonyl group.
 Meerwein-Ponndorf (Verley) reduction: It involves the reduction of carbonyl group
to the corresponding alcohols in presence of aluminium isopropoxide.

General reaction:

Mechanism: The reaction proceeds with the formation of co-ordination bond between
carbonyl oxygen and aluminium. The reaction further involves the formation of a cyclic
transition state. An intramolecular transfer of hydride ion from the carbinol carbon to the
carbonyl carbon takes place, which simultaneously reduces the carbonyl compound and
oxidises an isopropoxide group to acetone.
 When isopropyl alcohol is used as H-donor, the Al-alkoxide thus formed equlibrates with
isopropyl alcohol to form the product (alcohol) and Al-isopropoxide.

If Al-isopropoxide is in excess, the Al-alkoxide is hydrolysed by dilute aHCl to get the

product alcohol.

Applications: Aliphatic and aromatic aldehydes and ketones are reduced by this
method. The advantage of this method is that it is specific for carbonyl group and therefore, it
can be used for reducing aldehydes and ketones containing some other reducible group, such
as, a double bond, a nitro or an ester group, which are not reduced under these conditions.
(i)

(ii)

(iii)

Bechamp reduction:
The Bechamp reduction is used to reduce aromatic nitro compounds to their
corresponding anilines, using zero valent iron powder in acidic conditions. The Bechamp
reaction is broadly applicable to aromatic nitro compounds. It is a process of three steps in
series, namely adsorption of aromatic nitro compound on the iron surface, surface reaction of
aromatic nitro compound to corresponding anilines and desorption of the product from the
iron surface.
Aliphatic nitro compounds are more difficult to reduce. Tertiary aliphatic nitro
compounds, however, are converted in good yield to the amine compound using the Bechamp
reduction.

Condensation reaction: A condensation reaction is a class of an organic addition

reaction that proceeds in a step-wise manner to produce the addition product and a water
molecule is removed as a by-product. (Hence, the name condensation). Similar to water
molecule, other smaller molecules like ammonia, ethanol or acetic acid may be formed as a
by-product.
The reactions occur in acidic or basic conditions or in the presence of a catalyst. This
type of reaction is involved in the formation of peptide linkages and ester bond.
Example:
(i) The polymer, Nylon-6,6 involves the formation of a peptide linkage between
hexamethylene diamine and adipic acid.

(ii) The polymer, PET (polyethylene terephthalate) involves the formation of an ester
linkage between terephthalic acid ethylene glycol.
 (iii) Claisen condensation:

Friedal-Craft Alkylation Reaction: The reaction involves an introduction of an

alkyl group into an aromatic ring. It is carried out by treating the aromatic compound with the
alkyl halide in the presence of Lewis acid.

General reaction:

Mechanism: It is an electrophilic aromatic substitution. The electrophile is a

carbocation generated from an alkyl chloride with AlCl3 (Lewis acid) in an acid-base
equation.

In certain cases, there is no free carbocation involved. Instead, the alkyl group is
transferred directly to the aromatic ring from the polar complex formed between an alkyl
chloride and AlCl3 (Lewis acid).

The intermediate ion formed after the electrophilic attack is stabilized by resonanace.
Finally, the intermediate ion reacts with the anion produced in the formation of carbonium
ion to give the final alkylated product and the halogen hydride and the catalyst.
 In alkyl halides, the order of the reactivity for an alkyl group is: tertiary > secondary >
primary and for halogens: F > Cl > Br > I.

Applications: The reaction is useful in synthetic organic chemistry. Some of the

applications are as follows:
(i) Preparation of toluene from benzene.

(ii) Preparation of isopropyl benzene (Cumene) from benzene.

(iii) Preparation of diphenylmethane from benzene.

(iv) Preparation of dibenzyl from benzene and ethylene chloride.

Friedal-Craft Acylation Reaction: The reaction involves an introduction of an acyl

group into an aromatic ring. It is carried out by treating the aromatic compound with the acyl
halide or an acid anhydride in the presence of Lewis acid.

General reaction:

Mechanism: The mechanism of acylation can be explained either through the

formation of acylium ion (Mechanism I) or through the formation of a dipolar complex
(Mechanism II).

Mechanism I: This mechanism is similar to the carbocation mechanism for the

alkylation, involving the formation of an acylium ion (R-CO+) as an electrophile. The
acylium ion is considerably more stable than the carbocation as every atom in acylium ion
has an octet of electrons. The formation of an acylium ion requires slightly more than one
mole of the catalyst per mole of the acid chloride, while with an acid anhydride, slightly more
than two moles of the catalyst per mole of the anhydride are required. The mechanism is
shown as follows:
(i) Generation from the acylium ion:
(a) From Acid chloride:

(b) From Acid anhydride:

(ii) Electrophilic attack of the acylium ion:

(iii) Formation of the product:

 Mechanism II: The reaction of an acid chloride (or acid chloride formed from an acid
anhydride) with AlCl3 (Lewis acid) yields an acid chloride-aluminium chloride dipolar
complex which can act as the acylating agent. Subsequent electrophilic attack of the complex
on the aromatic ring, followed by the loss of a proton and then hydrolysis leads to the
formation of the ketone.
 Applications: The reaction is useful in synthetic organic chemistry. Some of the
applications are as follows:
(i) Preparation of Acetophenone.

(ii) Preparation of benzophenone.

(iii) Preparation of p-methoxypropiophenone.

(iv) Preparation of anthraquinone.

Application of Friedel Crafts Acylation in the sysnthesis of Aspirin:
Aspirin is the common name for the compound acetylsalicylic acid, widely used as a
fever reducer and as a pain killer.
To prepare aspirin, salicylic acid is reacted with an excess of acetic anhydride. A
small amount of a strong acid is used as a catalyst which speeds up the reaction. The excess
acetic acid will be removed with the addition of water. The aspirin product is not very soluble
in water so the aspirin product will precipitate when water is added. Since acetic acid is very
soluble in water, it is easily separated from the aspirin product. The synthesis reaction of
aspirin is shown below:

A “purified product” can be obtained through recrystallization of the crude product in

hot ethanol.