UoITC | BMIC 14.12.

2024

Functional Groups
in Organic Chemistry
By Sara S. Ali
Organic Chemistry Course | Fall Semester

Supervised by Prof. Dr. Hussien L. Algboory

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Introduction
A functional group is a group of atoms in a molecule with distinctive chemical
properties, regardless of the other atoms in the molecule. The atoms in a
functional group are linked to each other and to the rest of the molecule by
covalent bonds. For repeating units of polymers, functional groups attach to their
nonpolar core of carbon atoms and thus add chemical character to carbon
chains. Functional groups can also be charged, e.g. in carboxylate salts
(−COO−), which turns the molecule into a polyatomic ion or a complex ion.
Functional groups binding to a central atom in a coordination complex are called
ligands. Complexation and solvation are also caused by specific interactions of
functional groups.

Functional groups are critical not only in organic chemistry but also in
biochemistry, materials science, and pharmaceutical chemistry. They are
responsible for the diverse reactivity and biological activity of natural and
synthetic compounds. For example, the hydroxyl group (OH) is a hallmark of
alcohols, imparting hydrophilicity and reactivity in hydrogen bonding, while the
carbonyl group (C=O) defines aldehydes and ketones and participates in
nucleophilic addition reactions. This paper aims to explore the historical
evolution, classification, and behavior of functional groups.

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Discovery
In 1832, lacking his own laboratory facilities at Kassel, Wöhler worked with
Justus Liebig in his Giessen laboratory. In that year, Wöhler and Liebig published
an investigation of the oil of bitter almonds. Through their detailed analysis of the
chemical composition of this oil, they proved by their experiments that a group of
carbon, hydrogen, and oxygen atoms can behave chemically as if it were the
equivalent of a single atom, take the place of an atom in a chemical compound,
and be exchanged for other atoms in chemical compounds. Specifically, their
research on the oil of bitter almonds showed that a group of elements with the
chemical composition C7H5O can be thought of as a single functional group,
which came to be known as a benzoyl radical. In this way, the investigations of
Wöhler and Liebig established a new concept in organic chemistry referred to as
compound radicals, which had a profound influence on the development of
organic chemistry. Many more functional groups were later identified by
subsequent investigators with wide utility in chemistry.

By the 1850s and 1860s, chemists like August Kekulé and Alexander
Butlerov were advancing the structural theory of organic chemistry, which
clarified how atoms were connected in molecules.Chemists realized that certain
groups of atoms consistently behaved in specific ways during chemical reactions,
regardless of the molecule they were part of. These consistent behaviors led to
the concept of functional groups—portions of molecules responsible for their
chemical properties and reactivity.The exact term functional group gained traction
in the late 19th century, as organic chemistry matured and classification systems
became more formalized. It marked a shift from thinking of molecules as simple
atom arrangements to understanding specific reactive parts of molecules.

Liebig laboratory, 1909

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Common Functional Groups
I. Hydrocarbyl Group

A hydrocarbyl group is a univalent group derived from a hydrocarbon by

removing one or more hydrogen atoms. Hydrocarbyl groups are classified based
on the type of hydrocarbon they are derived from:
1. Alkyl group (from alkanes, saturated hydrocarbons):

Alkyl groups are not stable compounds themselves, they are simply parts
of larger compounds and are named by replacing the-ane ending of the parent
alkane with an-yl ending. For example, removal of a hydrogen from methane,
CH4, generates a methyl group,–CH3, and removal of a hydrogen from ethane,
CH3CH3,generates an ethyl group,–CH2CH3.Similarly, removal of
ahydrogenatomfromtheendcarbonofany straight-chain alkane gives the series of
straight-chain alkyl groups shown in Table 1. Combining an alkyl group with any
of the functional groups listed earlier makes it possible to generate and name
many thousands of compounds.

(Table 1) alkyl groups are generated by removing a hydrogen from an end carbon, branched
alkyl groups are generated by removing a hydrogen atom from an internal carbon. Two 3-carbon
alkyl groups and four 4-carbon alkyl groups are possible.

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 Inductive effects, in connection with polar covalent bonds, result from the shifting of electrons in
a σ bond in response to the electronegativity of nearby atoms. In the present instance, electrons
from a relatively larger and more polarizable alkyl group can shift toward a neighboring positive
charge more easily than the electron from a hydrogen. Thus, the more alkyl groups attached to
the positively charged carbon, the more electron density shifts toward the charge and the more
inductive stabilization of the cation occurs.

(Fig. 1) A comparison of inductive stabilization for methyl, primary, secondary, and tertiary
carbocations. The more alkyl groups that are bonded to the positively charged carbon, the more
electron density shifts toward the charge, making the charged carbon less electron-poor (blue in
electrostatic potential maps).

2. Alkenyl group (from alkenes, unsaturated hydrocarbons with double

bonds):

● Vinyl group (CH₂=CH-)

3. Alkynyl group (from alkynes, hydrocarbons with triple bonds):

● Ethynyl group (C≡C-)

4. Aryl group (from aromatic hydrocarbons):

● Phenyl group (C₆H₅-)

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 II. Halogens

In organic chemistry, the halogen group refers to a set of elements from

Group 17 of the periodic table. These elements are fluorine (F), chlorine (Cl),
bromine (Br), iodine (I), and astatine (At). Halogens are highly reactive
nonmetals due to their high electronegativity and tendency to gain electrons to
achieve a stable octet configuration.

1. The addition of X2

● Halogens bonded to carbon produce haloalkanes (e.g., CH₃Cl — methyl

chloride) and haloarenes (e.g., C₆H₅Cl — chlorobenzene).
● The C–X bond (carbon–halogen bond) is polar due to the difference in
electronegativity.

2. Halogenation

Bromine And Chlorine add rapidly to alkenes to yield 1,2-dihalides, a

process called halogenation. For example, nearly 50 million tons of
1,2-dichloroethane (ethylene dichloride) are synthesized worldwide each year,
much of it by addition of Cl2 to ethylene. The product is used both as a solvent
and as starting material for the manufacture of poly(vinyl chloride), PVC, the third
most widely synthesized polymer in the world after polyethylene and
polypropylene. Fluorine is too reactive and difficult to control for most laboratory
applications, and iodine does not react with most alkenes.

A possible mechanism for the reaction of bromine with alkenes might involve
electrophilic addition of Br+ to the alkene, giving a carbocation intermediate that
could undergo further reaction with Br− to yield the dibromo addition product.

When the halogenation reaction is carried out on a cycloalkene, such as

cyclopentene, only the trans stereoisomer of the dihalide addition product is
formed, rather than the mixture of cis and trans isomers that might have been

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expected if a planar carbocation intermediate were involved. We say that the
reaction occurs with anti-stereochemistry, meaning that the two bromine atoms
come from opposite faces of the double bond—one from the top face and one
from the bottom face.

An explanation for the observed stereochemistry of addition was suggested in

1937 by George Kimball and Irving Roberts, who proposed that the reaction
intermediate is not a carbocation but is instead a bromonium ion , formed by
electrophilic addition of Br+ to the alkene. (Similarly, a chloronium ion contains a
positively charged, divalent chlorine, R2Cl+.) The bromonium ion is formed in a
single step by interaction of the alkene with Br2 and the simultaneous loss of Br−.

Alkene halogenation reactions occur in nature just as they do in the

laboratory but are limited primarily to marine organisms living in halide-rich
environments. These biological halogenation reactions are carried out by
enzymes called haloperoxidases, which use H2O2 to oxidize Br− or Cl− ions to a
biological equivalent of Br+ or Cl+. Electrophilic addition to the double bond of a
substrate molecule then yields a bromonium or chloronium ion intermediate just
as in the laboratory, and reaction with another halide ion completes the
process.Halomon, for example, an antitumor pentahalide isolated from red alga,
is thought to arise by a route that involves twofold addition of BrCl through the
corresponding bromonium ions.

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 III. Hydroxyl Group

In chemistry, a hydroxy or hydroxyl group is a functional group with the

chemical formula −OH and composed of one oxygen atom covalently bonded to
one hydrogen atom. In organic chemistry, alcohols and carboxylic acids contain
one or more hydroxyl groups. Both the negatively charged anion HO−, called
hydroxide, and the neutral radical HO·, known as the hydroxyl radical, consists of
an unbonded hydroxy group. According to IUPAC definitions, the term hydroxyl
refers to the hydroxyl radical (·OH) only, while the functional group −OH is called
a hydroxyl group.

(Fig. 2) Sulfuric acid contains two hydroxyl groups.

Water, alcohols, carboxylic acids, and many other hydroxy-containing

compounds can be readily deprotonated due to a large difference between the
electronegativity of oxygen (3.5) and that of hydrogen (2.1). Hydroxy-containing
compounds engage in intermolecular hydrogen bonding increasing the
electrostatic attraction between molecules and thus to higher boiling and melting
points than found for compounds that lack this functional group. Organic
compounds, which are often poorly soluble in water, become water-soluble when
they contain two or more hydroxyl groups, as illustrated by sugars and amino
acids.

The hydroxyl group is pervasive in chemistry and biochemistry. Many

inorganic compounds contain hydroxyl groups, including sulfuric acid, the
chemical compound produced on the largest scale industrially.

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Hydroxyl groups participate in the dehydration reactions that link simple
biological molecules into long chains. The joining of a fatty acid to glycerol to
form a triacylglycerol removes the −OH from the carboxy end of the fatty acid.
The joining of two aldehyde sugars to form a disaccharide removes the −OH from
the carboxyl group at the aldehyde end of one sugar. The creation of a peptide
bond to link two amino acids to make a protein removes the −OH from the
carboxyl group of one amino acid.

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Summary and Conclusion

Functional groups are an essential part of organic chemistry as they determine

the reactivity and properties of molecules. From hydrocarbyl groups like alkyl,
alkenyl, and aryl, to halogens and hydroxyl groups, each functional group has its
own role in influencing chemical behavior. By studying functional groups,
chemists can predict how molecules will behave in reactions and design new
materials, medicines, and polymers. The classification and understanding of
these groups remain fundamental not only in organic chemistry but also in
biology and industry, helping scientists explore new frontiers in science and
technology.

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References

Clayden, J., Greeves, N., & Warren, S. (2012). Organic Chemistry. Oxford
University Press.

Carey, F. A., & Giuliano, R. M. (2014). Organic Chemistry. McGraw-Hill

Education.

Smith, J. G. (2017). Organic Chemistry: An Introduction. McGraw-Hill Education.

March, J., & Smith, M. B. (2001). Advanced Organic Chemistry: Reactions,

Mechanisms, and Structure. Wiley.

Vollhardt, K. P. C., & Schore, N. E. (2018). Organic Chemistry: Structure and

Function. W. H. Freeman.

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