Important Name Reactions

Aldol Condensation

Aldol condensation is a reaction that occurs when an α-hydrogen aldehyde reacts with a dilute base
to produce β-hydroxy aldehydes termed aldols.

The condensation of two different aldehydes and ketones is known as crossed aldol condensation. It
provides a mixture of four products when both of them include α-hydrogen atoms.

Balz-Schiemann Reaction

The Balz Schiemann Reaction Mechanism describes the synthesis and subsequent thermal
degradation of an aromatic fluoroborate to yield the corresponding aryl fluoride. Günther Schiemann
and Günther Balz, two German scientists, are credited with coining the term the reaction.

Aromatic amines, nitrous acid, and fluoroboric acid are the primary reactants. Aromatic amines
perform diazotization under the impact of nitrous acid. Now, fluoroboric acid is added to produce the
appropriate aryl diazonium salt. Now, the heat-sensitive aryl diazonium salt is thermally
decomposed, yielding aryl fluoride, nitrogen, and boron trifluoride.

An example of a Balz-Schiemann reaction would be the following: the conversion of a phenyl amine
into a phenyl fluoride using fluoroboric acid, nitrous acid, and the addition of heat:
Carbylamine Reaction

Hofmann isocyanide synthesis is another name for the Carbylamine reaction. Isocyanides are
produced by combining a primary amine, chloroform, and base.

The addition of an amine to the intermediate formed by the dehydrohalogenation of chloroform is

part of the Carbylamine reaction mechanism. Dichlorocarbene refers to this intermediate.

The carbylamine reaction can be written as:

R-NH2 + CHCl3 + 3KOH → RNC (Carbylamine) + 3KCl + 3H2O

Cannizzaro Reaction

The Cannizzaro reaction, named after Stanislao Cannizzaro, is a chemical reaction in which two
molecules of a non-enolizable aldehyde are disproportionated by a base to produce a carboxylic acid
and a primary alcohol.
The Cannizzaro Reaction Mechanism explains how two molecules of an aldehyde are converted into
one molecule of alcohol and one molecule of carboxylic acid. A nucleophilic acyl substitution on an
aldehyde is followed by the leaving group attacking another aldehyde, completing the reaction.

Clemmensen Reduction

Aldehydes or ketones can be converted to alkanes via the Clemmensen reaction, which involves zinc
amalgam and hydrochloric acid. The Clemmensen reduction is given the name after a Danish
chemist, Erik Christian Clemmensen.

This reaction is particularly efficient in aryl-alkyl ketones reduction produced in Friedel-Crafts

acylation. The reduction of cyclic ketones or aliphatic compounds with zinc metal provides optimal
results from the reaction.

Etard Reaction

The Etard Reaction is named after Alexandre Léon Étard, a French chemist. The Etard Reaction is a
chemical reaction that uses chromyl chloride to directly oxidise a heterocyclic bound or aromatic
methyl group to an aldehyde. Toluene, for example, can be converted to Benzaldehyde by the Etard
reaction, as shown below:
Finkelstein Reaction

In the Finkelstein reaction, halogen atoms are exchanged in a Substitution Nucleophilic Bimolecular
reaction (SN2 Reaction). It is named after Hans Finkelstein, a German chemist.

It is an organic reaction in which the metal halide salt is used to exchange one alkyl halide for
another alkyl halide. By taking advantage of the poor solubility of acetone in newly formed metal
halide salt, this reaction takes place in an equilibrium phase. The Finkelstein reaction has a single-
step SN2 reaction with stereochemistry inversion as its mechanism.

Friedel-Crafts Reaction

Friedel Crafts reaction is another electrophilic substitution reaction. Alkylation and acylation
reactions are the two main categories of Friedel-Crafts reactions. The American chemist James Crafts
and the French chemist Charles Friedel developed these reactions in the year 1877.
Gabriel Phthalimide Synthesis

The Gabriel synthesis converts primary alkyl halides to primary amines through a chemical reaction.
Traditionally, potassium phthalimide is used in the reaction.

There are three steps in the Gabriel Phthalimide Synthesis Mechanism. The synthesis is named after
German chemist Siegmund Gabriel and is used to make primary amines from primary alkyl halides.

The Gabriel Phthalimide synthesis has the major advantage of avoiding excessive alkylation. The
reaction of potassium hydroxide with phthalimide also produces a suitable nucleophile in the form of
an imide ion. The imide ion performs a nucleophilic substitution reaction on the alkyl halide, yielding
N-alkyl phthalimide as an intermediary.

Gattermann Reaction

A process of formylation of compounds with aromatic rings is known as the Gattermann reaction,
after German scientist Ludwig Gattermann. Gattermann formylation and Gattermann salicylaldehyde
synthesis are other names for the same reaction. The Friedel-Crafts reaction and the Gattermann
reaction are similar.

By treating it with Cu/HCl or Cu/HBr, respectively, the Gattermann reaction is used to produce
chlorobenzene or bromobenzene from benzenediazonium chloride.

Gattermann-Koch Reaction

The first step in the Gattermann-Koch reaction mechanism is the formation of reactive species with
the help of acid. The main objective of the reaction is to attach a formyl group (-CHO group) to an
aromatic system. The Gattermann-Koch reaction is illustrated in the example below.

Substrates made of phenol and phenol ether cannot be used in the Gattermann-Koch reaction.
Traces of copper(I) chloride are usually needed when zinc chloride is used as a catalyst in the
Gattermann-Koch reaction because it functions as a co-catalyst.

Grignard Synthesis

The addition of alkyl/vinyl/aryl magnesium halides to any carbonyl group in an aldehyde or ketone is
explained by the Grignard reaction mechanism. The reaction is considered a significant technique for
forming carbon-carbon bonds. The alkyl, vinyl, or aryl magnesium halides are known as Grignard
reagents.
The Grignard reactions and reagents are named after the French scientist Francois Auguste Victor
Grignard, who made the discovery and was honoured with the 1912 Nobel Prize in Chemistry.

Grignard reagents resemble organolithium reagents in that they are strong nucleophiles and capable
of forming carbon-carbon bonds. The nucleophilicity of the reagent is further increased when an
amido group substituent (amido magnesium halides are known as Hauser Bases) is used in place of
the alkyl group substituent.

Kolbe’s Electrolysis Reaction

The Kolbe reaction, also known as the Kolbe Schmitt reaction, is a type of addition reaction that was
named after Hermann Kolbe and Rudolf Schmitt. Phenoxide ion is produced when phenol is reacted
with sodium hydroxide. When it comes to electrophilic aromatic substitution reactions, the
phenoxide ion is more reactive than the phenol.

As a result, it conducts a weak electrophilic substitution reaction with carbon dioxide. The primary
result is ortho-hydroxybenzoic acid (salicylic acid). This reaction is commonly known as Kolbe’s
reaction.

The Kolbe reaction is initiated by the nucleophilic addition of phenoxide to carbon dioxide, which
results in the formation of salicylate.

Ozonolysis

The process of using ozone to break the unsaturated bonds in alkenes, alkynes, and azo compounds
(compounds with the functional diazenyl functional group)is known as ozonolysis. This is an organic
redox reaction.
Alkenes can be oxidised by ozone to produce alcohols, aldehydes, ketones, or carboxylic acids.
Alkynes are subjected to ozonolysis to produce acid anhydrides or diketones. The acid anhydride
undergoes hydrolysis to produce two carboxylic acids if water is present in the reaction. Elastomer
ozonolysis is also referred to as ozone cracking. The double bonds in elastomers are broken by a trace
amount of ozone gas in the atmosphere. The ozonolysis of azo compounds produces nitrosamines.

Reimer-Tiemann Reaction

A type of substitution reaction called the Reimer-Tiemann reaction is named for the chemists Karl
Reimer and Ferdinand Tiemann. The process involves ortho-formylation of C6H5OH (phenols).

An aldehyde group (-CHO) is added at the ortho position of the benzene ring when phenols, or
C6H5OH, are treated with CHCl3 (chloroform) in the presence of NaOH (sodium hydroxide), resulting
in the formation of o-hydroxybenzaldehyde. The Reimer Tiemann reaction is the common name for
the reaction.
The conversion of phenol to salicylaldehyde (2-hydroxy benzaldehyde) is a notable example of the
Reimer-Tiemann reaction.

Rosenmund Reduction

Rosenmund Reduction Mechanism describes the way acyl chlorides are preferentially reduced into
aldehydes. The reaction was named after Karl Wilhelm Rosenmund since he initially described it in
1918.

In the Rosenmund reaction, molecular hydrogen reacts with the acyl chloride in the presence of a
palladium on the barium sulfate-based catalyst. Due to its small surface area, barium sulphate
reduces the palladium’s activity and prevents over-reduction. A poison can be added to completely
deactivate the palladium catalyst should the necessity for additional palladium activity reduction
arise (as in the case of highly reactive acyl chlorides).

By using hydrogen gas over palladium that has been poisoned by barium sulphate, the Rosenmund
reduction converts acid chlorides into aldehydes. Below is an illustration of this catalytic
hydrogenation of acyl chlorides to aldehydes.

Due to the strong reactivity of hydrogen gas, it easily initiates a substitution in the acyl chloride,
producing HCl and the desired aldehyde.

Sandmeyer Reaction

Sandmeyer reaction is a form of substitution reaction which is widely used in the formation of aryl
halides from aryl diazonium salts. Catalysts for this process include copper salts like chloride,
bromide, or iodide ions. It is noted that unique transformations of benzene can be performed via the
Sandmeyer reaction. The modifications comprise hydroxylation, trifluoromethylation, cyanation, and
halogenation.
A good example of a radical-nucleophilic aromatic substitution is considered to be a Sandmeyer
reaction. This reaction is a helpful method for substituting various amino groups on aromatic rings.
The amino group that is joined to an aromatic ring is turned into a diazonium salt during the
Sandmeyer reaction, which can then be converted into different functional groups.

Stephen Reduction Reaction

The addition of gaseous hydrogen chloride to the provided nitrile initiates the Stephen Reaction
Mechanism. The reaction is called Stephen aldehyde synthesis after its inventor Henry Stephen. The
reaction involves the formation of aldehydes from nitriles using tin(II) chloride and hydrochloric acid,
followed by the quenching of the iminium salt with water. Another useful byproduct of this process is
ammonium chloride.

The Stephan reaction is used to produce acetaldehyde from methyl cyanide, as shown in the diagram
below.

As indicated above, when nitrile is reduced with stannous chloride and hydrogen chloride gas (in
ethyl acetate solvent), an imine intermediate is generated. The equivalent aldehyde is obtained by
hydrolysis of this imine intermediate.

Swarts Reaction

Alkyl fluorides are often produced from alkyl chlorides or alkyl bromides using the Swarts reaction.
This is performed by heating the alkyl chloride/bromide in the presence of the fluoride of heavy
metals (silver fluoride or mercurous fluoride). If potassium fluoride or sodium fluoride are used, the
reaction will still proceed, but the yield will be much lower. This reaction was first confirmed by
Frederic Jean Edmond Swarts in 1892.

The Swarts reaction mechanism is very straightforward: a new bond between fluorine and carbon is
formed once the metal fluorine bond is broken. The displaced chlorine or bromine atoms now
combine with the metal. The term “Swarts reagent” refers to the antimony trifluoride and chlorine
combination. According to Swarts’ rule, the fluoride that is produced after fluorination will always
have a lower boiling point than the corresponding chloride.

Williamson Ether Synthesis

The Williamson ether synthesis, which is the standard procedure for producing ether, involves the
nucleophilic displacement of a halide ion or other suitable leaving group by an alkoxide ion.

The name of the reaction was popularised after Alexander William Williamson created it in 1850.
Deprotonated alcohol and an organohalide are combined in the Williamson Ether Synthesis
reaction to produce ether.

 Williamson Ether Synthesis usually occurs as an SN2 reaction of a primary alkyl halide with an
alkoxide ion. This chemical reaction demonstrated how ethers are structured.

 This reaction can only be effective if the alkyl halide is primary or secondary, requiring
the SN2 pathway for synthesis.

 The ethers produced in this method are more complex structures and include more carbon
atoms than either of the initial materials.

Wolff Kishner Reduction

A hydrazone anion is first created in the Wolff Kishner reduction mechanism, which subsequently
releases the nitrogen atom to produce a carbanion. This carbanion then produces a hydrocarbon
when it interacts with the water in the system. The solvent used for this process is diethylene glycol.
Aldehydes and ketones are converted to alkanes in this organic reduction mechanism. Some carbonyl
compounds can be easily reduced to alkanes because they are stable under strongly basic conditions
(The carbon-oxygen double bond becomes two carbon-hydrogen single bonds).

Step 1:

The aldehyde or ketone undergoes hydrazine treatment. The hydrazone for the reaction is produced.
The reaction is seen below.

Step 2:

Step 3:

Step 4:
Step 5:

Although the method generally begins with the condensation of hydrazine to produce hydrazone,
using a pre-formed hydrazone can offer benefits including a shorter reaction time, reactions that
happen at room temperature, or extremely mild reaction conditions. Different solvents and reaction
temperatures are also required for the preformed hydrazone substrates that can be used in this
reaction.

Wurtz Reaction

In Wurtz’s reaction, an example of an organic chemical coupling reaction, sodium metal reacts with
two alkyl halides in the presence of a dry ether solution to produce a higher alkane and a compound
that contains both sodium and the halogen.

This reaction has the name of the French chemist Charles Adolphe Wurtz, who also discovered the
aldol reaction. For the synthesis of alkanes in organic and organometallic chemistry, the Wurtz
reaction is a highly efficient process. With the use of sodium and dry ether solution, two distinct alkyl
halides are coupled in this reaction to produce a longer alkane chain.

Wurtz Fittig Reaction

The Wurtz-Fittig reaction mechanism can be understood either through the organo-alkali mechanism
or the radical mechanism. The Wurtz-Fittig reaction is named after the chemists Charles Adolphe
Wurtz and Wilhelm Rudolph Fittig and refers to the chemical reaction that occurs when aryl halides,
alkyl halides, sodium metal, and dry ether are combined to produce substituted aromatic
compounds.

If the alkyl halide is chemically more reactive than the aryl halide, the alkyl halide will first form the
carbon sodium bond and then act as an aryl halide’s nucleophile, which will aid in the formation of
asymmetrical products in the reaction. If the reactants are created with halogens of different
periods, the deviation in reactivity between the alkyl halide and aryl halide can be obtained
conveniently.

Fischer Esterification

Fischer esterification is an organic reaction used to convert carboxylic acids in the presence of excess
alcohol and a potent acid catalyst, producing an ester as the end product. This ester is produced
along with water. Below are a few examples of Fischer esterification reactions.
Azeotropic distillation or adsorption using molecular sieves are two methods used for removing
water from the system during this esterification process. It serves as an explanation of a nucleophilic
acyl substitution reaction. The substitution is focused on the nucleophilicity of the alcohol and the
electron affinity of the carbonyl carbon.

Haloform Reaction

The Haloform reaction is a chemical reaction that produces haloforms by halogenating methyl
aldehyde or methyl ketone in the presence of a base.

As shown above, when the methyl ketone is treated with the bromine halogen in an aqueous sodium
hydroxide solution, polyhalogenation occurs, followed by the cleavage of the methyl group. The
carboxylate and tribromomethane, which is the necessary haloform, are the end products of the
reaction.

Hell–Volhard–Zelinsky Reaction

Hell Volhard Zelinsky Reaction Mechanism is distinctive among halogenation reactions in that it
occurs without the use of a halogen carrier. At the alpha carbon, the reaction is used to halogenate
carboxylic acids.
Carl Magnus Von Hell, Jacob Volhard, and Nikolay Zelinsky are the chemists who gave their names to
this reaction. The reaction is initiated by adding one molar equivalent of diatomic bromine and one
molar equivalent of phosphorus tribromide (catalytic quantity).

The fluorination and iodination of carboxylic acids are not possible with the HVZ reaction. If the Hell
Volhard Zelinsky reaction is carried out at extremely high temperatures, hydrogen halide may be
eliminated from the product, resulting in the formation of beta-unsaturated carboxylic acids.

Hoffmann Bromamide Reaction

The standard Hoffmann Bromamide reaction process involves attacking the amide with a strong base
such as an alkali, resulting in deprotonation and the subsequent formation of an anion.

A primary amide is converted into a primary amine with one less carbon atom using this reaction
process. This is done by heating the primary amide with a solution of water, a strong base, and a
halogen (chlorine or bromine). The following is an example of the reaction.

This method produces primary amines that are not affected by secondary or tertiary amines. The
Hoffmann degradation of amide is another name for the reaction. The primary amide is converted
into an isocyanate intermediate when bromine reacts with sodium hydroxide to produce sodium
hypobromite (NaOBr).

Water now attacks this isocyanate intermediate, beginning a sequence of proton transfer steps. The
ammonium cation, which was created when water attacked the isocyanate intermediate, is
quenched by the heat conditions to produce the necessary amine product. This results in the
explosion of carbon dioxide gas.
Fischer Indole Synthesis Reaction

The Fischer indole synthesis has become the most popular method to prepare indole rings since its
discovery in 1883 by Emil Fischer. In essence, the Fischer indole synthesis can be regarded as the
cyclization of an arylhydrazone, prepared from aryl hydrazine and aldehyde or a ketone by treatment
with an acid catalyst or effected thermally to form the indole nucleus. The mechanism has been the
subject of intensive investigations for over a century, and many intermediates have been isolated and
characterized.

The Fischer indole synthesis reaction is given below.

There has probably been more work carried out on the synthesis of indoles than on any other single
heterocyclic system, and consequently, many routes are available; ring syntheses of benzofurans and
benzo thiophenes have been much less studied. The Fischer indole synthesis now more than 100
years old, is still widely used – an aryl hydrazone is heated with an acid, a multi-step sequence
ensues, ammonia is lost, and indole is formed.

The synthesis is often carried out by subjecting an equimolar mixture of the aryl hydrazine and
aldehyde or ketone directly to the indolization conditions without isolation of the hydrazone.
Similarly, aryl hydrazones, prepared by reduction of the corresponding aryldiazonium salt or N-
nitroso arylalkylamine or by a palladium mediated coupling reaction, can be subjected to the
indolization conditions directly in the presence of the carbonyl moiety without isolation of the aryl
hydrazone. Such methods are useful when the aryl hydrazone intermediates are unstable or toxic.

Fischer Indole Synthesis Reaction Mechanism

The arylhydrazone prepared from condensation of an aryl hydrazine and a carbonyl compound,
undergoes protonation and isomerization to the enamine tautomer. The protonated enamine
tautomer then undergoes an irreversible electrocyclic rearrangement that is [3,3] – sigmatropic
rearrangement where the N-N bond is broken.

The resulting double imine then re-aromatizes the benzene ring to provide an anilino imine, whose
nucleophilic amine group attacks the imine intramolecularly to afford the amino indoline. Loss of a
molecule of ammonia and aromatization then deliver the indole.

The hydrazine behaves as an amine towards a carbonyl compound and forms the imine like the
product, a hydrazone. The cycle rearrangement involves the enamine tautomer of this hydrazone and
proceeds because the cyclic flow of electrons forms a strong C-C bond whilst cleaving a weak N-N
bond. This produces what appears to be a di-imine.

One of these is involved in rearomatization and creates nan aromatic amine. This then attacks the
other imine function, and we get the nitrogen equivalent of a hemiketal. Finally acid catalysed
elimination of ammonia gives the aromatic indole system.

Drawbacks of Fischer Indole Synthesis

Unfortunately, the reaction fails with acetaldehyde and cannot, therefore be used to synthesize
indole itself. It is possible to use the keto acid pyruvic acid instead and decarboxylate the product to
yield indole.
Features of Fischer Indole Synthesis

The key characteristics of the Fischer Indole Synthesis are:

 The indole formation can be done in a single pot because it is not required to separate the
intermediate aryl hydrazones.

 Unsymmetric ketones give two region-isomeric 2,3-displaced indols with a region-selectivity

depending on medium acidity, hydrazine substitution and steric effects.

 1,2-diketones can give both mono-indoles and bis-indoles, which are usually formed by
strong acid catalysts in refluxing alcohols.