PCH 203...

FUNCTIONAL GROUP CHEMISTRY:

Introduction.

Definations: (i) Functional Groups, in the field of organic chemistry, are generally understood to be
specific substituent atoms or groups atoms or bonds (moieties) that are attached to specific organic
molecules. These moieties (the part of the molecule which can be found in many other molecules as
well) are known to be responsible for the chemical reactions of the molecules they are attached to
participate in. Essentially functional groups in organic molecules are a particular grouping of
components in such molecules in which their distinctive chemical reactions are accountable. The same
functional group will behave in a similar fashion, by undergoing similar reactions, regardless of the
compound of which it is a part. Functional groups also play an important part in organic compound
nomenclature; combining the names of the functional groups with the names of the parent alkanes
provides a way to distinguish compounds.

In organic chemistry, the most common functional groups are carbonyls (C=O), alcohols (-OH), carboxylic
acids (CO2H), esters (CO2R), and amines (NH2). It is important to be able to recognize the functional
groups and the physical and chemical properties that they afford compounds.

♢Characteristics/functions of Functional Groups:

●They exhibit distinct features and properties that are independent of the molecules to which they are
attached.

●Their properties can be further modified with the help of other functional groups and these groups can
also be interconverted.

●Covalent bond mostly link the atoms of these groups and the group as a whole to the molecule.

In the case of polymers, the functional groups are known generally to be attached to the nonpolar core
of the carbon atoms in each repeating unit of the corresponding polymer, infusing the carbon chain with
specific chemical characteristics.

● Some functional groups are observed to have an ionic charge on them, as observed in carboxylate
salts containing the -COO– ionic group. When these groups are attached to molecules, they convert the
molecule into either complexions or polyatomic ions.
●In a coordination complex, the functional group that is bound to the central atom is commonly
described as a ligand.

●The presence of functional groups in a molecule is also found to affect the solubility and the tendency
to form complexes of the molecule in question. If the functional groups of the solute and the solvent
interact well, the solubility increases.This explains the high solubility of sugar in water both contain the
-OH (hydroxyl) group, sugar can be easily dissolved in water.

● In a chemical environment wherein a highly electronegative functional group is attached to a less

●Functional groups also play an important part in organic compound nomenclature; combining the
names of the functional groups with the names of the parent compounds provide a way to distinguish
compounds.

■Functional Groups and Reactivity of organic compounds.

The functional groups in organic compounds are known to significant roles in directing and controlling
organic reactions. Alkyl chains are often observed to be non reactive, and the direction of site-specific
reactions difficult;where as unsaturated alkyl chains with the presence of functional groups allow for
higher reactivity and specificity. Often, compounds are functionalized with specific groups for a specific
chemical reaction. Functionalization refers to the addition of functional groups to a compound by
chemical synthesis. Through routine synthesis methods, any kind of organic compound can be attached
to the surface. In materials science, functionalization is employed to achieve desired surface properties;
functional groups can also be used to covalently link functional molecules to the surfaces of chemical
devices.

■Some more functional groups containing elements such as nitrogen and oxygen featuring different
hybridizations of the carbon-nitrogen and the carbon-oxygen bonds are illustrated below.
 Nomenclature of
Common Functional Groups

1. Hydrocarbons

Alkanes, alkenes, alkynes (and sometimes the derivatives of benzene) are represented by the symbol R.
these groups are also referred to as hydrocarbon groups since they contain only carbon and hydrogen
atoms. However, they may vary in the types of bonds between two carbon atoms, such as double or
triple bonds.

The reactivity of these groups varies due to the nature of the carbon-carbon bond. Some groups are
made up of a long, branched alkane or a ring-structured alkane, which are assigned specific names.
Examples include names such as bornyl and cyclohexyl.

The hydrocarbon functional groups may have an ionic charge on them. The positively charged structures
are referred to as carbocations whereas the negatively charged hydrocarbons are called carbanions.

2. Haloalkanes Haloalkanes, or alkyl halides, are the functional groups which contain a bond between a
carbon atom and a halogen. The prefix used to denote a halogen is ‘halo-’. For example, the compound
CH3F can be called fluoromethane, and the prefix here is fluoro.

The suffix used to denote a halogen is the ‘halide’. For example, the same compound, fluoromethane
(CH3F) can also be referred to as methyl fluoride, the suffix being fluoride.

The carbon-halogen bond varies in strength and stability based on the halogen. For example, the
carbon-iodine bond in alkyl iodides is quite weak but the carbon-fluorine bond in alkyl fluorides is quite
strong and stable.

Excluding these alkyl fluorides, all the alkyl halides readily undergo elimination reactions or nucleophilic
substitution reactions.
3. Oxygen-Containing Functional Groups.The properties of the functional groups containing a carbon-
oxygen bond are entirely dependant on the hybridization of the carbon-oxygen bond.

This can be explained by the electron donating effect of the sp3 hybridization of oxygen which can be
observed in alcohols in sharp contrast with the electron withdrawing effect of the sp2 hybridized oxygen
which can be observed in the carbonyl groups which contain a carbon-oxygen double bond.

■The suffixes used in the nomenclature of compounds which have a functional group containing a C-O
bond are tabulated below along with lexamples.

ALCOHOLS:
Alcohols are organic compounds in which the hydroxyl functional group (-OH) is bound to a carbon
atom. Alcohols are an important class of molecules with many scientific, medical, and industrial uses.

General formula. ...CnH2n+2OH

Nomenclature of Alcohols

According to the IUPAC nomenclature system, an alcohol is named by dropping the terminal “-e” of the
parent carbon chain (alkane, alkene, or alkyne in most cases) and the addition of “-ol” as the ending. If
the location of the hydroxyl group must be specified, a number is inserted between the parent alkane
name and the “-ol” (propan-1-ol) or before the IUPAC name (1-propanol). If a higher priority group is
present, such as an aldehyde, ketone or carboxylic acid, then it is necessary to use the prefix “hydroxy-”
instead of the ending “-ol.”

Alcohols are classified as primary, secondary, or tertiary, based upon the number of carbon atoms
connected to the carbon atom that bears the hydroxyl group.

The alcohol functional group: Alcohols are characterized by the presence of an -OH group, which is
generally in a bent shape, like that of water.

Structure and Physical Properties of Alcohols

The structure of an alcohol is similar to that of water, as it has a bent shape. This geometrical
arrangement reflects the effect of electron repulsion and the increasing steric bulk of the substituents
on the central oxygen atom. Like water, alcohols are polar, containing an unsymmetrical distribution of
charge between the oxygen and hydrogen atoms. The high electronegativity of the oxygen compared to
carbon leads to the shortening and strengthening of the -OH bond. The presence of the -OH groups
allows for hydrogen bonding with other -OH groups, hydrogen atoms, and other molecules. Since
alcohols are able to hydrogen bond, their boiling points are higher than those of their parent molecules.

Alcohols are able to participate in many chemical reactions. They often undergo deprotonation in the
presence of a strong base. This weak acid behavior results in the formation in an alkoxide salt and a
water molecule. Hydroxyl groups alone are not considered good leaving groups. Often, their
participation in nucleophilic substitution reactions is instigated by the protonation of the oxygen atom,
leading to the formation a water moiety—a better leaving group. Alcohols can react with carboxylic
acids to form an ester, and they can be oxidized to aldehydes or carboxylic acids.

Alcohols have many uses in our everyday world. They are found in beverages, antifreeze, antiseptics,
and fuels. They can be used as preservatives for specimens in science, and they can be used in industry
as reagents and solvents because they display an ability to dissolve both polar and non-polar substances.