MODULE 5

Organic Chemistry (Lecture) – Mrs. Jocelyn Albelda

BS PSYCHOLOGY– BSCOS1A-1 (LB1-LB2, 1ST SEM, A.Y 2022-2023)

HYDROCARBON DERIVATIVES more closely related are the

3 (NON CARBONYL GROUPS) cycloalkanes, compounds in which
the carbon atoms are joined in a ring,
or cyclic fashion.
ORGANIC HALIDES
➔ organic halides are a large ADDITIONAL INFO
class of natural and synthetic
chemicals. HALOGENS:
➔ contain one or more halogens F – fluorine
(fluorine, chlorine, bromine, or Br – bromine
iodine) combined with carbon Cl – chlorine
and other elements. I – iodine
➔ chlorine is by far the most At – astatine
abundant of the halogens and
is the only one needed (as
chloride ions) in relatively
large amounts by humans. SULFUR-CONTAINING
They play a key role in brain COMPOUNDS
function by mediating the
action of the inhibitory
transmitter GABA. They are THIOL
also used by the body to ➔ a thiol is a compound that
produce stomach acid. contains an SH functional
➔ iodine is needed in trace group. The -SH group itself is
amounts for the production of called a mercapto group.
thyroid hormones, such as
thyroxine. DISULFIDE
➔ a disulfide is a compound
ADDITIONAL INFO containing an -S-S- linkage.
(Organic) sulfides have the
Many synthetic organic structure R-S-R′ and are
compounds, such as plastic therefore the sulfur analogs of
polymers, as well as a few natural ethers.
organic compounds, contain
halogen atoms. NITROGEN-CONTAINING
COMPOUNDS
Alkanes react with halogens to
produce halogenated hydrocarbons, AMINES
the simplest of which have a single ➔ occur widely in all living
halogen atom substituted for a organisms.
hydrogen atom of the alkane. Even

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MODULE 5
Organic Chemistry (Lecture) – Mrs. Jocelyn Albelda
BS PSYCHOLOGY– BSCOS1A-1 (LB1-LB2, 1ST SEM, A.Y 2022-2023)

For instance:
For similar reasons, the presence
● morphine - used as a
of nitro groups in aromatic
pain reliever - can be
compounds retards electrophilic
obtained from the
aromatic substitution but
opium poppy plant.
facilitates nucleophilic aromatic
● atropine which is
substitution.
isolated from the
Atropa belladonna, or
deadly nightshade
plant. Lesson 1: Aliphatic and
➔ contain a nitrogen atom with a Aromatic Halides
lone pair of electrons.

NITRILE
➔ any organic compound with a
−C≡N functional group. The
prefix cyano- is used
interchangeably with the term
nitrile in literature.
➔ used to be known as
cyanides;
➔ the smallest organic nitrile is
ethanenitrile, CH3CN, (old
name: methyl cyanide or
acetonitrile - and sometimes The alkyl (aliphatic) halides rank as
now called ethanenitrile). one of the most useful classes of
organic compounds because they
ADDITIONAL INFO often serve as starting materials for
the preparation of numerous other
The nitro group is one of the most families.
common explosophores (a
functional group that makes a Meanwhile, aryl (aromatic) halides
compound explosive) used can exhibit unique patterns of
globally. properties and reactivity. In this topic,
we will begin with the preparation and
The nitro group is also strongly principles of IUPAC nomenclature of
electron withdrawing. Because of organic halides. Then, we will
this property, C−H bonds alpha continue with concepts of structure
(adjacent) to the nitro group can and bonding and see how structure
be acidic. affects the properties of organic
halides.

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MODULE 5
Organic Chemistry (Lecture) – Mrs. Jocelyn Albelda
BS PSYCHOLOGY– BSCOS1A-1 (LB1-LB2, 1ST SEM, A.Y 2022-2023)

ring, the halide substituents

are alphabetized and numbers
IUPAC NOMENCLATURE OF
(locants) are added to locate
ALIPHATIC AND AROMATIC
these substituents.
HALIDES
Instead of numbers, terms
The IUPAC system uses the name of like:
the parent alkane with a prefix ortho- (1,2),
indicating the halogen substituents, para- (1,4), or
preceded by a number indicating the meta- (1,3) may be
substituent’s location. used.

The prefixes are fluoro-, chloro-,

bromo-, and iodo-.

● Alkyl halides with simple alkyl

groups (one to four carbon
atoms) are often called by
common names.
● Those with a larger number of PREPARATION/SOURCES OF
carbon atoms are usually ORGANIC HALIDES
given IUPAC names.

COMMON IUPAC Aliphatic halides may be prepared

NAME NAME through the following methods:
➔ alkenes reacting with
CH3Cl methyl chloro- hydrogen halides such as
chloride methane HCl, HBr, and HI.
➔ alkenes reacting with Cl2 and
CH3CH2Cl ethyl chloro- Br2 undergoing anti-addition.
chloride ethane ➔ alkenes reacting with Cl2 and
CH3CH2CH2Cl propyl chloro-
Br2 by a radical chain-reaction
chloride propane pathway.
➔ alcohols undergoing
nucleophilic substitution
reactions with hydrogen
AROMATIC HALIDES halides.
➔ prefixes or substituents
(fluoro-, chloro-, bromo-, or On the other hand, two main
iodo-) are placed before the methods for preparing of aromatic
word ‘benzene’. halides:
➔ If there are two or more halide ➔ halogenation of aromatic
substituents in the benzene

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MODULE 5
Organic Chemistry (Lecture) – Mrs. Jocelyn Albelda
BS PSYCHOLOGY– BSCOS1A-1 (LB1-LB2, 1ST SEM, A.Y 2022-2023)
compounds by electrophilic
substitution reactions.
➔ preparation by way of aryl
diazonium salts.
CLASSES OF ALIPHATIC
HALIDES
Primary (1˚)
➔ has one carbon group
attached to a C-X bond.
Secondary (2˚)
➔ has two carbon groups
attached to a C-X bond.
Tertiary (3˚)
➔ has three carbon groups
attached to a C-X bond.
Many of the properties of alkyl
halides are oftentimes linked to their
respective classification. In some
cases, alkyl halides with primary
carbon are more reactive compared
to those alkyl halides with secondary
or tertiary carbons. In other cases,
the reverse is true.
STRUCTURE OF HALIDES
The carbon that bears the functional
group is sp3-hybridized in alcohols
and alkyl halides. The bond angles at
carbon are approximately tetrahedral.
Carbon–halogen bond distances in
alkyl halides increase in the order:
C–F (140pm) < C–Cl (179 pm) <
C–Br (197 pm) < C–I (216 pm)
● In a carbon-halogen (C–X)
bond, the carbon atom bears
a partial positive charge while
the halogen atom bears a
partial negative charge,
shown in the figure below,
making C–X bonds polar in
general.
● Aliphatic halides also do not
exhibit intermolecular
hydrogen bonding. As a
result, they have higher
melting and boiling points than
similar alkanes, but lower than
alcohols.
PROPERTIES OF HALIDES
Boiling Point
● The boiling point of alkyl
halides increases as one
descends the periodic table;
alkyl fluorides have the lowest
boiling points, alkyl iodides the
highest. This trend matches
the order of increasing
polarizability of the halogens.
Polarizability
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MODULE 5
Organic Chemistry (Lecture) – Mrs. Jocelyn Albelda
BS PSYCHOLOGY– BSCOS1A-1 (LB1-LB2, 1ST SEM, A.Y 2022-2023)
➔ is the ease with which the
electron distribution around an
atom is distorted by a nearby
electric field.
➔ It increases down a group
because atomic size
increases. Hence, the larger
electron clouds are farther
from the nucleus and are
readily distorted.
● Boiling points of halogenated
compounds also increase with
an increase in the size of the
alkyl group.
Solubility and Density
● All alkyl halides are insoluble
in water.
● A mixture of alkyl halide and
water results in the formation
of two layers.
● Chlorinated and fluorinated
alkyl halides are generally
less dense than water
whereas brominated and
iodinated alkyl halides are
denser than water. However,
density increases with
polyhalogenation.
For example:
CH2Cl2, CHCl3, and CCl4, are
all denser than water.
Lesson 2: Sulfur-Containing
Compounds
ORGANIC-SULFUR COMPOUNDS
A series of organic compounds
analogous to oxygen is known for
sulfur, knowing that sulfur is the
element below oxygen in the periodic
table.
Some of organic-sulfur groups are:
➔ thiols (mercaptans),
➔ dialkyl sulfides (thioethers),
➔ disulfides,
➔ thio acids,
➔ dithio acids,
➔ thials (thio aldehyde), and
➔ thioenes (thio ketones).
General structures:
Thiols or Mercaptans
➔ sulfur analogs of alcohols and
phenols.
➔ the nomenclature of these
compounds usually parallels
that of alcohol; in fact, some
mercaptans are simply named
as ‘thioalcohol’.
EXAMPLES:
CH3SH – methyl mercaptan,
methanethiol, methyl thioalcohol
C6H5SH – phenyl mercaptan,
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MODULE 5
Organic Chemistry (Lecture) – Mrs. Jocelyn Albelda
BS PSYCHOLOGY– BSCOS1A-1 (LB1-LB2, 1ST SEM, A.Y 2022-2023)

or thiophenol in its desired shape or style.

3. Finally, hair is kept using
Sulfides or Thioethers rollers and blowers.
➔ sulfur analogs of ethers.

EXAMPLES: Lesson 3: Amines, Nitriles &

C2H5―S―C2H5 – diethyl Nitro Compounds
sulfide or ethyl sulfide
H3C―S―C6H5 – methyl AMINES
phenyl sulfide or thioanisole ➔ occur widely in all living
organisms.
➔ contain a nitrogen atom with a
DISULFIDES
lone pair of electrons. the
➔ disulfides are important
nitrogen lone pair explains
substances. The amino acid
both the basic and
cysteine contains a disulfide
nucleophilic character of
link. The cross linked disulfide
amines.
bonds of cysteine are found in
keratin (hair).
EXAMPLES:
➔ The more S-S bonds, the
Morphine
stronger and less flexible the
➔ used as a pain reliever
bonds are.
➔ can be obtained from the
➔ Breaking of hair occurs
opium poppy plant.
because when pulled far
Atropine
enough, H-bonds between
➔ isolated from the Atropa
carbonyl and amide groups
belladonna, or deadly
break. If not broken
nightshade plant.
completely, hair can spring
back.

What happens during hair perming

and curling?
1. Hair is exposed to reducing
agents so it breaks the former
disulfide cross-links between
cysteine residues.
2. Next, hair is then exposed to
an oxidizing agent so sulfur in
cysteine forms new disulfide
cross-links with neighboring
cysteine. This exposure to
redox reaction keeps the hair

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MODULE 5
Organic Chemistry (Lecture) – Mrs. Jocelyn Albelda
BS PSYCHOLOGY– BSCOS1A-1 (LB1-LB2, 1ST SEM, A.Y 2022-2023)

CLASSES OF AMINES
IUPAC NOMENCLATURE OF
AMINES
Amines are classified by the number
of alkyl groups bonded to the N atom. ● For simple 1˚ amines, the
suffix -amine is added to the
Primary (1˚) name of the alkyl substituent
➔ contains one C–N bond and (e.g. methylamine).
has the general structure ● Alternatively, the suffix -amine
RNH2. can be used in place of the
Secondary (2˚) final -e in the name of the
➔ contains two C–N bonds and parent compound (e.g.
has the general structure methenamine).
R2NH. ● Amines with more than one
Tertiary (3˚) functional group are named by
➔ contains three C–N bonds and adding -amino as a prefix on
has the general structure R3N. the parent molecule.
● Prefixes -di or -tri are added to
The figure below shows that 1˚, 2˚, the alkyl group for
and 3˚ amines have a lone pair on symmetrical 2˚ and 3˚ amines.
the nitrogen atom.
Common Systematic
name name

methyl
CH3NH2 methanamine
amine

CH3CH2N ethyl
ethanamine
H2 amine

CH3CH2C propyl
propanamine
H2NH2 amine

QUATERNARY AMMONIUM IONS N-substituted parent amines

➔ nitrogen-containing
compounds that do not
contain the nitrogen lone pair.
➔ When these ions are paired
with anions, they are called
quaternary ammonium
salts.
➔ unsymmetrically substituted 2˚
and 3˚ amines
The largest alkyl substituent is
chosen as the parent name while the
other alkyl groups are N-substituents
to the parent.

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MODULE 5
Organic Chemistry (Lecture) – Mrs. Jocelyn Albelda
BS PSYCHOLOGY– BSCOS1A-1 (LB1-LB2, 1ST SEM, A.Y 2022-2023)

separated by distillation.
● simple methylated amines can
be prepared by reaction of
ammonia with methanol in the
presence of an alumina
catalyst.
● primary and secondary
amines can have
intermolecular hydrogen
bonding.
STRUCTURE OF AMINES

Amine Nitrogen (N)

➔ sp3 hybridized,
➔ has a trigonal shape,
➔ with C–N–C bond angle of
~109.5. Boiling point
● primary and secondary
In a carbon-nitrogen (C–N) bond, the amines have higher boiling
carbon atom bears a partial positive points than compounds that
charge while the nitrogen atom bears do not have intermolecular
a partial negative charge since hydrogen bonding (e.g.
nitrogen is more electronegative than ethers).
carbon. Consequently, the C–N ● however, 1˚ and 2˚ amines
bonds are polar in general. have lower boiling points than
alcohols, as alcohols have
stronger intermolecular
hydrogen bonds.
PROPERTIES OF AMINES

The following properties can be

observed:
● amines have characteristic
foul odors like rotting fish,
urine, and bad breath.
● amines with fewer than five
carbons are water-soluble due
to hydrogen bonding.
● monomethylated,
dimethylated and
trimethylated amines can be
Basicity of Amines
● amines are proton (H+)
acceptors, hence,
Brønsted-Lowry bases.
● They also react with acids
such as HCl to form
water-soluble salts. In this

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MODULE 5
Organic Chemistry (Lecture) – Mrs. Jocelyn Albelda
BS PSYCHOLOGY– BSCOS1A-1 (LB1-LB2, 1ST SEM, A.Y 2022-2023)

reaction, a water-insoluble gives stronger highs than the

amine accepts a proton from cocaine hydrochloride, which
the strong acid. This makes crack cocaine more
acid-base reaction (shown addictive.
below), results in the
formation of ammonium salts Cocaine hydrochloride, an
which are water-soluble ionic ammonium salt, can be converted
solids. back to its free amine or free base
form, “crack cocaine,” by treating it
with a strong base.

Lesson 3: Amines, Nitriles, &

Nitro Compounds

NITRILES
➔ also known as cyano
compounds,
➔ are organic compounds that
contain the cyano functional
group represented as −C ≡ N.
➔ The general formula of the
Ammonium Salts, Medications family of nitriles is RCN and
➔ Ammonium salts are used as the general structure is
the active ingredients in R⸺C≡N.
medications, including
ephedrine, used as a NITRO COMPOUNDS
bronchodilator in the ➔ organic compounds that
decongestant Sudafed. contain the nitro functional
group, -NO2.
Diphenylhydramine found in
Benadryl, used for relief of itching Aliphatic Nitro Compounds
and pain from skin irritations and ➔ the nitro group is attached to
rashes. an alkyl group.
➔ represented by the general
Ammonium Salts, Cocaine formula RNO2.
➔ The salt of cocaine (cocaine
hydrochloride) is smuggled Aromatic Nitro Compounds
and used illegally on the ➔ attached to a benzene ring or
street. The solid product, a an aryl group.
free amine, is rapidly ➔ represented by ArNO2.
absorbed when smoked and NITRILES and NITRO

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MODULE 5
Organic Chemistry (Lecture) – Mrs. Jocelyn Albelda
BS PSYCHOLOGY– BSCOS1A-1 (LB1-LB2, 1ST SEM, A.Y 2022-2023)
COMPOUNDS
● both N-containing derivatives
of hydrocarbons.
● both compounds contain a
polar functional group that
affects the compounds’
properties.
Acrylonitrile is processed in many
quantities by the process of
ammoxidation which depends on the
oxidation state of the propylene in
presence of ammonia and catalyst.
This compound forms an important
constituent of the polymeric
substances, also which includes
acrylic textile fibers, synthetic rubbers
as well as thermoplastic resins.
Some compounds of nitriles are
mainly manufactured by heating up of
carboxylic acids with the ammonia
compound in presence of some
catalysts. This is a process which is
employed in the preparation of nitriles
from oils and fats, these products are
being used as the softening agents in
substances such as synthetic
rubbers, textiles, plastics and also in
the making of amines.
Nitrile compounds are also formed by
the process of heating amides with
the phosphorus pentoxide compound.
They can also be reduced to some
primary amines by reacting lithium
aluminum hydride or getting it
hydrolyzed to carboxylic acids in
presence of acid or base.
PROPERTIES OF NITRILES
The chemical and physical properties
of nitriles are given below:
● Nitriles are somewhat like
colorless solids and liquids
having unique odors.
● They have boiling points
measuring between 82-118
°C.
● Nitriles exhibit strong
dipole-dipole movements and
also the van der Waals forces
of dispersion between the
molecules.
● They also show high polarity
and electronegativity.
● These are said to be highly
soluble in water, and the
solubility decreases as the
length of the chain increases.
REACTIONS OF NITRILES
Nitrile undergoes various process of
reactions:
Hydrolysis
➔ the hydrolysis of nitriles in the
presence of an acid or a base
produces carboxamides and
carboxylic acids efficiently.
Reduction
➔ nitriles are reduced to primary
and tertiary amines by treating
them with lithium aluminum
hydride.
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MODULE 5
Organic Chemistry (Lecture) – Mrs. Jocelyn Albelda
BS PSYCHOLOGY– BSCOS1A-1 (LB1-LB2, 1ST SEM, A.Y 2022-2023)

➔ the reduction process occurs systems.

in the presence of some
catalysts.
NOMENCLATURE, SOURCES,
Alkylation PREPARATION, USES &
➔ the alkylation of nitrile PROPERTIES OF NITRILES
compounds leads to the
formation of nitrile anions. Ethanenitrile, CH3CN, (old name:
methyl cyanide or acetonitrile).
The other reactions are nucleophilic ➔ the smallest organic nitrile
addition reactions, Friedel–Crafts
acylation, etc. Hydrogen cyanide, HCN, doesn't
usually count as organic, even
though it contains a carbon atom.
USES OF NITRILES

(Nitriles) finds its uses in various

medical and industrial application:

● Nitriles are used in the Notice the triple bond between the
manufacture of nitrile gloves, carbon and nitrogen in the -CN
seals, and hoses as they group.
exhibit resistance to
chemicals. The three simplest nitriles are:
● They are used as an
antidiabetic drug which is CH3CN ethanenitrile
used in the treatment of CH3CH2CN propanenitrile
breast cancers. CH3CH2CH2CN butanenitrile
● The compound of nitrile called
as pericyazine is used in
treating opiate dependence as NOMENCLATURE,
antipsychotic. CLASSIFICATION,
● This compound is found in PREPARATION, USES &
many plant and animal PROPERTIES OF
sources. NITRO-COMPOUNDS
● They are utilized in the
applications of oil resistant Aliphatic nitro compounds can be
substances and also for classified as:
low-temperature uses. 1. Primary Nitroalkanes: The
● They are also employed in nitro group is attached to a
automotive systems, hydraulic primary carbon atom.
hoses and also in aircraft

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MODULE 5
Organic Chemistry (Lecture) – Mrs. Jocelyn Albelda
BS PSYCHOLOGY– BSCOS1A-1 (LB1-LB2, 1ST SEM, A.Y 2022-2023)

2. Secondary Nitroalkanes: The

nitro group is attached to a
secondary carbon atom​.
3. Tertiary Nitroalkanes: The
nitro group is attached to a
tertiary carbon atom.
Nitro compounds are named by using
the prefix nitro- before the name of

the parent hydrocarbon.

Nitroalkanes
➔ aliphatic nitro compounds

Nitroarenes
➔ aromatic nitro compounds.

The position of the nitro group and

other substituents if any are indicated
by Arabic numerals.

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