An Introduction to Organic Compounds

We can divide organic compounds into three classes:

1) Hydrocarbons: The hydrocarbons are compounds composed entirely of carbon

and hydrogen. The major classes of hydrocarbons are alkanes, alkenes, alkynes,
and aromatic hydrocarbons.
2) Compounds containing oxygen: Many organic compounds contain oxygen atoms
bonded to alkyl groups. The major classes of oxygen-containing compounds are
alcohols, ethers, ketones, aldehydes, carboxylic acids and acid derivatives.
3) Compounds containing nitrogen: Nitrogen is another element often found in the
functional groups of organic compounds. The most common “nitrogenous”
organic compounds are amines, amides and nitriles.

Alkanes

An alkane is a hydrocarbon that contains only single bonds. The alkanes are the simplest
and least reactive class of organic compounds because they contain only hydrogen and
sp3 hybridized carbon. Alkanes are also known as saturated hydrocarbons, because it
has the maximum number of bonded hydrogens.

Molecular Formulas of Alkanes

Alkanes in which the carbons form a continuous chain with no branches are called
straight-chain alkanes. The names of the four smallest straight-chain alkanes have
historical roots, but the others are based on Greek numbers. Alkane names generally
have the -ane suffix, and the first part of the name indicates the number of carbon
atoms.

Number of carbons Molecular formula Name

1 H–CH2–H Methane
2 H–(CH2)2–H Ethane
3 H–(CH2)3–H Propane
4 H–(CH2)4–H Butane
5 H–(CH2)5–H Pentane
6 H–(CH2)6–H Hexane
7 H–(CH2)7–H Heptane
8 H–(CH2)8–H Octane
9 H–(CH2)9–H Nonane
10 H–(CH2)10–H Decane

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The family of alkanes shown in the table is an example of a homologous series. A
homologous series (homos is Greek for “the same as”) is a family of compounds in which
each member differs from the one before it in the series by one methylene (-CH 2-)
group. The members of a homologous series are called homologs.

The general molecular formula for an alkane is C nH2n+2, where n = number of carbon
atoms in the carbon chain.

Alkyl substituent

Removing a hydrogen from an alkane results in an alkyl substituent (or an alkyl group).
Alkyl substituents are named by replacing the “ane” ending of the alkane with “yl.” The
letter “R” is used to indicate any alkyl group.

Common/trivial Names

If all alkanes had unbranched (straight-chain) structures, their nomenclature would be

simple. Most alkanes have constitutional (structural) isomers and we need a way of
naming all the different isomers. For example, there are two isomers of formula C 4H10.
The unbranched isomer is simply called butane (or n-butane, meaning “normal”
butane), and the branched isomer is called isobutane, meaning an “isomer of butane.”

Iso structural unit: a carbon bonded to a hydrogen and to two CH3 groups.

The three isomers of C5H12 are called pentane (or n-pentane), isopentane, and
neopentane.

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Constitutional isomers: Compounds that have the same molecular formula but differ in
the way the atoms are connected.

 Primary carbon: carbon bonded to only one other carbon. Primary hydrogens
are attached to a primary carbon.
 Secondary carbon: carbon bonded to two other carbons. Secondary hydrogens
are attached to a secondary carbon.
 Tertiary carbon: carbon bonded to three other carbons. Tertiary hydrogens are
attached to a tertiary carbon.

Systematic nomenclature

To avoid having to memorize the names of thousands of structural units, chemists have
devised rules for creating systematic names that describe the compound’s structure.

It is also called IUPAC nomenclature because it was designed by a commission of the

International Union of Pure and Applied Chemistry (abbreviated IUPAC and pronounced
“eye-you-pack”) in 1892.

The nomenclature of alkanes

The systematic name of an alkane is obtained using the following rules:

The main chain:

i. Determine the number of carbons in the longest continuous carbon chain. This
chain is called the parent hydrocarbon. The name of the parent hydrocarbon
becomes the alkane’s “last name.” The longest chain is rarely drawn in a straight
line; look carefully to find it.

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 ii. If a compound has two or more chains of the same length, the parent
hydrocarbon is the chain with the greatest number of substituents.

Numbering the main chain:

i. The groups attached to the main chain are called substituents because they are
substituted (in place of a hydrogen atom) on the main chain. We start the
numbering from the end nearest a branch so the numbers of the substituted
carbons will be as low as possible. The simple branched alkyl groups are usually
known by common names.

ii. If each end had a substituent in the same distance, we would start at the end
nearer the second branch point to get the lowest of the possible numbers.

iii. If the same substituent numbers are obtained in both directions, the
alphabetically first group receives the lower number.

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Naming the substituent groups:

i. The substituent’s name and the name of the parent hydrocarbon are joined into
one word, preceded by a hyphen that connects the substituent’s number with its
name.

ii. If more than one substituent is attached to the parent hydrocarbon, the
substituents are listed in alphabetical order, with each substituent preceded by
the appropriate number.

iii. If two or more substituents are the same, the prefixes “di,” “tri,” and “tetra” are
used to indicate how many identical substituents the compound has. The
numbers indicating the locations of the identical substituents are listed together,
separated by commas. There are no spaces on either side of a comma. There
must be as many numbers in a name as there are substituents. The prefixes “di,”
“tri,” “tetra,” “sec,” and “tert” are ignored in alphabetizing substituents.

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Branched substituents: Systematic name is obtained by numbering the alkyl substituent
starting at the carbon attached to the parent hydrocarbon. This means that the carbon
attached to the parent hydrocarbon is always the number-1 carbon of the substituent.
In a compound such as 4-(1-methylethyl)octane, the substituent name is in parentheses;
the number inside the parentheses indicates a position on the substituent, whereas the
number outside the parentheses indicates a position on the parent hydrocarbon. (If a
prefix such as “di” is part of a branch name, it is included in the alphabetization.)

Alkyl halides: named as substituted alkanes. The prefixes for the halogens end with “o”
(i.e. fluoro, chloro, bromo and iodo). Therefore, alkyl halides are also called haloalkanes.

The nomenclature of cycloalkanes

Cycloalkanes are alkanes with their carbon atoms arranged in a ring. Because of the ring,
a cycloalkane has two fewer hydrogens than an acyclic (noncyclic) alkane with the same
number of carbons. The general molecular formula for a cycloalkane is C nH2n.
Cycloalkanes are named by adding the prefix “cyclo” to the alkane name that signifies
the number of carbons in the ring.

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The rules for naming cycloalkanes resemble the rules for naming acyclic alkanes:

1. Cycloalkane with an alkyl substituent: the ring is the parent hydrocarbon. There
is no need to number the position of a single substituent on a ring.

2. If the ring has two different substituents: they are listed in alphabetical order
and the number-1 position is given to the substituent listed first.

3. If there are more than two substituents on the ring: they are listed in
alphabetical order, and the substituent given the number-1 position is the one
that results in a second substituent getting as low a number as possible or with
the one that has more substituents.

4. When the acyclic portion of the molecule contains more carbon atoms than the
cyclic portion (or when it contains an important functional group), the cyclic
portion is named as a cycloalkyl substituent.

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Nomenclature of Bicyclic Alkanes

Two or more rings can be joined into bicyclic or polycyclic systems. There are three ways
that two rings may be joined.

 Fused rings: most common, sharing of two adjacent carbon atoms and the bond
between them.
 Bridged rings: common, sharing of two nonadjacent carbon atoms (the
bridgehead carbons) and one or more carbon atoms (the bridge) between them.
 Spirocyclic compounds: relatively rare, two rings share only one carbon atom.

Name follows the prefix bicyclo and a set of brackets enclosing three numbers. All fused
and bridged bicyclic systems have three bridges connecting the two bridgehead atoms
(carbons common to the two rings). The numbers in the brackets give the number of
carbon atoms in each of the three bridges connecting the bridgehead carbons, in order
of decreasing size.

Numbering the ring systems for substituent positioning

a) Start with one of the bridgehead carbons and number it 1.

b) Proceed round the longest chain of carbons to the second bridgehead and
continue on round the next longest chain of carbons back towards the first
bridgehead carbon.
c) Pass over the first bridgehead carbon (it already has the number 1) and along the
shortest chain of carbons to the second bridgehead carbon again.

7,7-dimethylbicyclo[2.2.1]heptane
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The nomenclature of ethers

The common name of an ether consists of the names of the two alkyl substituents (in
alphabetical order), followed by the word “ether.” The smallest ethers are almost
always named by their common names.

The IUPAC system names an ether as an alkane with an RO substituent. The substituents
are named by replacing the “yl” ending in the name of the alkyl substituent with “oxy.”

Table: Priority of functional groups in naming organic compounds

Class Suffix Name Prefix name

Carboxylic acid -oic acid Carboxy
Ester -oate Alkoxycarbonyl
Amide -amide Amido
Nitrile -nitrile Cyano
Aldehyde -al Formyl
Ketone -one Oxo
Alcohol -ol Hydroxy
Amine -amine Amino
Alkene -ene Alkenyl
Alkyne -yne Alkynyl
Alkane -ane Alkyl
Increasing Ether Alkoxy
priority Alkyl halide Halo
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The nomenclature of alcohols

The IUPAC system uses suffixes to denote certain functional groups. The functional
group of an alcohol is the OH group, which is denoted by the sufffix “ol”. Thus, the
systematic name of an alcohol is obtained by replacing the “e” at the end of the name of
the parent hydrocarbon with “ol.”

When necessary, the position of the functional group is indicated by a number

immediately preceding the name of the parent hydrocarbon or immediately preceding
the suffix. The most recently approved IUPAC names are those with the number
immediately preceding the suffix.

The following rules are used to name a compound that has a functional group suffix:

1. The parent hydrocarbon is the longest continuous chain containing the

functional group. The parent hydrocarbon is numbered in the direction that gives
the functional group suffix the lowest possible number.

2. If there are two OH groups, the suffix “diol” is added to the name of the parent
hydrocarbon.

3. If there is a functional group suffix and a substituent, the functional group suffix
gets the lowest possible number.

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 4. If counting in either direction gives the same number for the functional group
suffix, then the chain is numbered in the direction that gives a substituent the
lowest possible number. Notice that a number is not needed to designate the
position of a functional group suffix in a cyclic compound, because it is assumed
to be at the 1 position.

5. If there is more than one substituent, the substituents are listed in alphabetical
order.

The nomenclature of amines

1. IUPAC system uses the suffix “amine” to denote the amine functional group. The
“e” at the end of the name of the parent hydrocarbon is replaced by “amine”.
The name of any alkyl group bonded to nitrogen is preceded by an “N” (in italics)
to indicate that the group is bonded to a nitrogen rather than to a carbon.

2. The substituents are listed in alphabetical order, and then a number or an “N” is
assigned to each one.

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Quaternary ammonium salts: Nitrogen compounds with four alkyl groups attached to
the nitrogen—thereby giving the nitrogen a positive formal charge. Their names consist
of the names of the alkyl groups in alphabetical order, followed by “ammonium” (all in
one word), and then the name of the accompanying anion as a separate word.

The physical properties of alkanes, alkyl halides, alcohols, ethers and amines

i. Boiling Point (bp)

The boiling point of a compound is the temperature at which the liquid form becomes a
gas (vaporizes). The boiling point of a compound depends on the strength of the
attractive forces between the individual molecules. If the molecules are held together by
strong forces, a lot of energy will be needed to pull the molecules away from each other
and the compound will have a high boiling point. On the other hand, if the molecules
are held together by weak forces, only a small amount of energy will be needed to pull
the molecules away from each other and the compound will have a low boiling point.

Van Der Waals Forces: Alkanes contain only carbons and hydrogens. The
electronegativities of carbon and hydrogen are similar. Alkanes, therefore, are neutral,
nonpolar molecules, so the attractive forces between them are relatively weak. The
nonpolar nature of alkanes gives them their oily feel.

However, electrons move continuously, and at any instant the electron density on one
side of a molecule can be slightly greater than that on the other side, causing the
molecule to have an instantaneous dipole.

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A temporary dipole in one molecule can induce a temporary dipole in a nearby
molecule. As a result, the (temporarily) negative side of one molecule ends up adjacent
to the (temporarily) positive side of another. Because the dipoles in the molecules are
induced, the interactions between the molecules are called instantaneous-dipole–
induced-dipole interactions. The molecules of an alkane are held together by these
interactions, which are known as van der Waals forces. Van der Waals forces are the
weakest of all the attractive forces.

The greater the area of contact between the molecules, the stronger the van der Waals
forces and the greater the amount of energy needed to overcome them. The boiling
points of the alkanes increase as their molecular weight increases, because each
additional methylene (CH2) group increases the area of contact between the molecules.

Branching in a compound lowers the compound’s boiling point by reducing the area of
contact.

Dipole–Dipole Interactions: The boiling points of a series of ethers, alkyl halides,

alcohols, or amines also increase with increasing molecular weight because of the
increase in van der Waals forces. The boiling points of these compounds, however, are
also affected by the polar C–Z bond.

Molecules with polar bonds are attracted to one another because they can align
themselves in such a way that the positive end of one dipole is adjacent to the negative
end of another dipole. These electrostatic attractive forces, called dipole–dipole
interactions, are stronger than van der Waals forces, but not as strong as ionic or
covalent bonds.

Hydrogen Bonds: Alcohols have much higher boiling points than ethers with similar
molecular weights, because they can form hydrogen bonds. A hydrogen bond is a
special kind of dipole–dipole interaction that occurs between a hydrogen that is
attached to an electronegative atom (oxygen, nitrogen, or fluorine) and a lone pair of an
electronegative atom in another molecule.

The length of the covalent bond in water is 0.96 Å, whereas a hydrogen bond is almost
twice as long (1.69–1.79 Å). Thus, a hydrogen bond is not as strong as an O—H covalent
bond, but it is stronger than other dipole–dipole interactions.

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Nitrogen is not as electronegative as oxygen. So, the hydrogen bonds between amine
molecules are weaker than those between alcohol molecules. An amine, therefore, has
a lower boiling point than an alcohol with a similar molecular weight. Tertiary amines
cannot form hydrogen bonds between their own molecules because they do not have a
hydrogen attached to the nitrogen (bp: primary>secondary>tertiary amine).

ii. Melting Point (mp)

The melting point of a compound is the temperature at which its solid form is converted
into a liquid. The increase in melting point is less regular than the increase in boiling
point because, in addition to the intermolecular attractions, the melting point is
influenced by the packing (the arrangement) in the crystal lattice. The tighter the fit, the
more energy is required to break the lattice and melt the compound.

Like their boiling points, the melting points increase with increasing molecular weight.
The melting point graph is not smooth, however. Alkanes with even numbers of carbon
atoms pack better into a solid structure, so that higher temperatures are needed to melt
them. Alkanes with odd numbers of carbon atoms do not pack as well, and they melt at
lower temperatures.

iii. Solubility

The process by which solvent molecules surround and interact with solute ions or
molecules is called solvation. The general rule of solubility is “like dissolves like.”
 Polar compounds dissolve in polar solvents: a polar solvent, such as water, has
partial charges that can interact with the partial charges on a polar compound.
The negative poles of the solvent molecules surround the positive pole of the
polar compound, and the positive poles of the solvent molecules surround the
negative pole of the polar compound. The clustering of the solvent molecules
around the polar molecules separates them from each other, which is what
makes them dissolve.
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  Nonpolar compounds dissolve in nonpolar solvents: van der Waals interactions
between solvent and solute molecules are about the same as those between
solvent molecules and those between solute molecules.

Alkanes: Alkanes are nonpolar, so they are soluble in nonpolar solvents and insoluble in
polar solvents such as water.

Alcohols: Alcohols with fewer than four carbons are soluble in water, but alcohols with
more than four carbons are insoluble in water. Thus, a OH group can drag about 3-4
carbons into solution in water.

Alcohols with branched alkyl groups are more soluble in water than alcohols with
unbranched alkyl groups with the same number of carbons.

Ethers: The oxygen of an ether can drag only about 3 carbons into solution in water.

Amines: Low molecular weight amines are soluble in water because amines can form
hydrogen bonds with water. Primary amines are more soluble than secondary amines
with the same number of carbons, because primary amines have two hydrogens that
can engage in hydrogen bonding with water.

Alkyl Halides: Alkyl halides have some polar character, but only alkyl fluorides have an
atom that can form a hydrogen bond with water. Alkyl fluorides, therefore, are the most
water soluble of the alkyl halides. The other alkyl halides are less soluble in water than
ethers or alcohols with the same number of carbons.

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 Rotation occurs about carbon–carbon single bonds
Conformational isomers: The different spatial arrangements of the atoms that result
from rotation about a single bond are called conformers or conformational isomers.

Chemists commonly use Newman projections to represent the three-dimensional

structures that result from rotation about a σ bond. A Newman projection assumes that
the viewer is looking along the longitudinal axis of a particular C—C bond. The carbon in
front is represented by a point (where three lines are seen to intersect), and the carbon
at the back is represented by a circle. The three lines emanating from each of the
carbons represent its other three bonds. The carbon with the lower number is placed in
the foreground in a Newman projection.

Dihedral/torsional angle: the angle between a substituent on the front atom and a
substituent on the back atom in the Newman projection.

 Eclipsed: dihedral angle between two atoms or groups is 0° (highest energy

state). When two larger/bulky groups are in eclipsed position, then it is called
totally eclipsed form.
 Gauche/skew (pronounced ‘goesh’): identical groups located at 60° with respect
to each other.
 Staggered/anti: identical groups are placed at 180° from one another (most
stable, lowest energy state). This conformation is called anti because the
identical groups are “opposed”.

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Conformational analysis: A molecule’s conformation changes from staggered to
eclipsed millions of times per second at room temperature. As a result, the conformers
cannot be separated from each other. At any one time, approximately 99% of the
ethane molecules will be in a staggered conformation because of the staggered
conformer’s greater stability, leaving only 1% in less stable conformations. The
investigation of the various conformers of a compound and their relative stabilities is
called conformational analysis.

Steric strain: strain experienced by a molecule (i.e., the additional energy it possesses)
when atoms or groups are close enough for their electron clouds to repel each other. In
general, steric strain in molecules increases as the size of the interacting atoms or
groups increases. There is greater steric strain in a gauche conformer than anti because
the two substituents are closer to each other.

Torsional strain: As molecule rotates toward an eclipsed conformation from staggered

conformation, its potential energy increases, and there is resistance to the rotation. This
resistance to twisting (torsion) is called torsional strain.

Reactions of Alkanes
Alkanes are the least reactive class of organic compounds. Their low reactivity is
reflected in another term for alkanes: paraffins. The name paraffin comes from two
Latin terms, parum, meaning “too little,” and affinis, meaning “affinity.” They attributed
this low reactivity to a lack of affinity for other reagents, so they coined the name
“paraffins.”

Most useful reactions of alkanes take place under energetic or high-temperature

conditions. These conditions are inconvenient in a laboratory because they require
specialized equipment and the rate of the reaction is difficult to control.

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 1) Combustion

Combustion is a rapid oxidation that takes place at high temperatures, converting

alkanes to carbon dioxide and water. Little control over the reaction is possible, except
for moderating the temperature and controlling the fuel/air ratio.

2) Cracking and Hydrocracking

Catalytic cracking of large hydrocarbons at high temperatures produces smaller

hydrocarbons. The cracking process usually operates under conditions that give the
maximum yields of gasoline (mixture of alkanes, C5–C8). In hydrocracking, hydrogen is
added to give saturated hydrocarbons.

Cracking without hydrogen gives mixtures of alkanes and alkenes.

3) Halogenation

Alkanes can react with halogens to form alkyl halides.

These halogenation reactions take place only at high temperatures or in the presence of
light (irradiation with light is symbolized by hv). Reactions of alkanes with chlorine and
bromine proceed at moderate rates and are easily controlled. Reactions with fluorine
are often too fast to control, however. Iodine reacts very slowly or not at all.

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 Free-Radical Halogenation
Radical chain reaction: reaction that has radical intermediates and repeating
propagation steps.

a) Initiation: Radicals are formed.

Heat or light supplies the energy required to break the Cl—Cl bond homolytically.

b) Propagation: A radical reacts to generate another radical.

 Step 1: A chlorine radical abstracts a hydrogen to generate an alkyl radical.

 Step 2: The alkyl radical reacts with Cl 2 to generate the product and a chlorine
radical.

The chlorine radical generated in step 2 goes on to react in step 1, continuing the chain.

c) Termination: combination of two radicals.

Any two radicals in the reaction mixture can combine to form a molecule in which all the
electrons are paired. Any two radicals can combine, so a radical reaction produces a
mixture of products.

In order to maximize the amount of monohalogenated product formed, a radical

substitution reaction should be carried out in the presence of excess alkane. Excess
alkane in the reaction mixture increases the probability that the halogen radical will
collide with a molecule of alkane rather than with a molecule of alkyl halide.

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Relative stabilities of alkyl radicals

A free radical is a species containing an atom with an unpaired electron. A free radical is
highly reactive because acquiring an electron will complete its octet.

Selectivity in Halogenation

In methane, all four hydrogen atoms are identical, and it does not matter which
hydrogen is replaced. In the higher alkanes, replacement of different hydrogen atoms
may lead to different products. In the chlorination of butane, for example, two
monochlorinated products are possible.

It is easier to form a secondary radical, because a secondary radical is more stable than
a primary radical. The more stable the radical, the more easily it is formed. That’s why 2-
chlorobutane is favoured over 1-chlorobutane.

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