Chapter 4: B.

Secondary Alkyl Halide:

- R-CH-R or R-CH-X-R
HALOGEN DERIVATIVES OF THE
HYDROCARBONS Ex: secondary propyl chloride or 2-chloro-propane
CH₃-CH-Cl-CH₃ or CH₃-CH-CH₃
|
OBJECTIVES: Cl
- classify the halogen derivatives,
- name alkyl halides using the common and IUPAC C. Tertiary alkyl halides:
systems - R₃C-X
- describe the physical and chemical properties of Ex: tertiary butyl chloride
alkyl halides; and polyhaloalkanes Cl
- describe the uses of alkyl halides; and |
polyhaloalkanes CH₃ - C – CH₃
|
- give examples of polyhaloalkanes CH₃
- outline the methods of preparation of some
polyhaloalkanes
Halogen derivatives
 may be mono-, di-, tri-, etc., substitution
Classifications products according to the number of
of Aliphatic Halogen Derivatives halogen atoms present in the molecule.

1. Alkyl halides: monohalogen derivatives of The monohalogen derivatives of alkyl halides are
alkanes subdivided into:
A. primary (1°), RCH₂-X;
2. Dihalides or halogen derivatives of
B. secondary (2°), R₂CH-X; and
unsaturated hydrocarbons
C. tertiary (3°), R₃C-X
3. Polyhaloalkanes: Polyhalogen derivatives
of alkanes; polyhalides Types depending on the nature of the alkyl group or
the position of the halogen atom in the molecule.
ALKYL HALIDES
Alkyl Halides
 Aka Halogen alkanes or Haloalkanes. o For example, the molecular formula C₄H₉Cl
can represent the following four isomeric
 an alkane that contains one or more mono-halogen derivatives:
halogen substituents.

 have the general formula “RX” where R is a. CH₃CH₂CH₂CH₂-Cl

an alkyl or substituted alkyl group and X is a (1-chlorobutane)
halogen group (F, Cl, Br, I)
b. Cl
Alkyl Halides are classified as primary, secondary, |
CH₃CH₂CHCH₃
or tertiary alkyl halides depending on whether the
(2-chlorobutane)
halogen is joined to a primary, secondary, or tertiary
carbon atom c. CH₃
|
3 Classification CH₃CHCH₂-Cl
A. Primary alkyl halide: (1-chloro-3-methylpropane)
- R-CH₂-X
- R(carbon chain like methyl) d. CH₃
- X (the halogen like F,Cl,Br,I) |
CH₃—C—Cl
|
Example: ethyl chloride CH₃
CH₃CH₂Cl or CH₃CH₂ (2-chloro-2-methylpropane)
|
Cl
Di-, tri-, and tetrachloromethanes Example 1: Common Name and IUPAC
 examples of di-, tri-, and tetra halogen 1. CH₃CH₂CH₂Br
derivatives respectively: - Common name: propyl bromide
- IUPAC name: 1-bromopropane
1. CH₂Cl₂
Dichloromethane 2. Cl
(CN: methylene chloride) |
CH₃CH
|
2. CHCl₃ CH₃
Trichloromethane - Common name: isopropyl chloride
(CN: chloroform) - IUPAC name: 2-chloropropane
-
3. CCl₄ Example 2: IUPAC
Tetrachloromethane
(CN: carbon tetrachloride) 1. CH₃CHCH₂CH₂CH₃
|
Br
These halogen derivatives are excellent solvents for
nonpolar and slightly polar substances. - 2-bromopentane

NOMENCLATURE OF ALKYL HALIDES 2. CH₃CHCH₂CHCH₂CH₃

| |
A. COMMON NAME CH₃ Br
- consist of two parts:
- 4-bromo-2-methylhexane
o the name of the alkyl group plus the stem of
the name of the halogen, with the ending -
Exercises
ide.
1. Give common and IUPAC names for each
Examples:
compound.
CH₃F : methyl fluoride
CH₃CH₂Cl : ethyl chloride
a. CH₃CH₂I
CH₃CH₂CH₂CH₂I : butyl iodide
- Common Name: ethyl iodide
- IUPAC name: iodoethane
B. IUPAC NAME
- uses the name of the parent alkane with a
b. CH₃CH₂CH₂CH₂F
prefix indicating the halogen substituents,
- Common Name: n-butyl fluoride
preceded by a number indicating the
- IUPAC name: 1-fluorobutane
substituent’s location.
2. Give the IUPAC name for each compound
- The prefixes are fluoro-, chloro-, bromo-,
and iodo-.
a. CH₃CHCHCH₃
| |
Examples: Cl CH₃
CH₃F : fluoromethane
CH₃CH₂Cl : chloromethane - 2-chloro-3-methylbutane
CH₃CH₂CH₂CH₂I : 1-iodobutane
b. CH₃CHCH₂CHCH₂Br
Alkyl halides | |
CH₃ Cl
- simple alkyl groups (one to four carbon
atoms) are often called by common names.
 1-bromo-2-chloro-4-methylpentane
- Those with a larger number of carbon atoms
are usually given IUPAC names.
 PHYSICAL PROPERTIES OF - increases as the molecular mass increases.
ALKYL HALIDES
- Alkyl bromides and alkyl iodides are heavier than
water while alkyl chlorides are lighter.
1. Odor
- in the pure state, have a pleasant odor while - The order is RI>RBr>RCl.
all the higher alkyl halides do NOT have any odor.
6. Solubility
2. Color - slightly soluble in water. However, they are soluble
- in its pure state, is colorless. in organic solvents such as ethers, alcohols, and
benzene.
* The exception is iodoalkanes and bromoalkanes
when exposed to light after storing for a long period
develop color. CHEMICAL PROPERTIES OF
ALKYL HALIDES
- The decomposition of halogens in the presence of
light is the explanation for the production of color. 1. Nucleophilic Substitution Reaction
 A nucleophile interacts with haloalkane in
- Many of the volatile-nature halogen compounds
this form of reaction, which has a partial
have a sweet smell.
positive charge on the carbon atom that is
3. Melting Point bound to the halogen. A replacement
- dependent on the strength of a compound’s lattice response takes place and leaves a halogen
structure. atom (called the leaving group is a halide
ion). Since a nucleophile initiates the
- almost identical boiling points in isomeric substitution reaction, it is called the
dihalobenzene, but the difference can be seen in nucleophilic substitution reaction.
the melting points.
2. Elimination Reaction
- Therefore, in the crystal lattice, greater numbers of
 If a haloalkane with a hydrogen atom is
molecules are compactly packed. Therefore, greater
heated with potassium hydroxide alcoholic
energy is needed to split the lattice structure,
solution, it can lead to the removal of the
thereby increasing the temperature of the
hydrogen atom from the β-carbon atom and
compound’s melting point.
the halogen atom from the alpha-carbon
 Alkyl halides in crystal lattice form has atom. As the β-hydrogen atom is involved in
higher melting point than the non-crystal elimination, it is also referred to as the β-
alkyl halides removal reaction. Alkene is formed as one of
the products.
4. Boiling Points A. (CH₃CH₂Cl) + NaOH → Alkene
Alkyl halide Ethanol (CH₂=CH₂)
- have high boiling points. Heat
- The boiling points of the same alkyl group of the B. Alkyl halide + KOH → Alkene
haloalkanes are in the order RCl<RBr<RI. (CH₃CH₂Br) (HBr) (CH₂=CH₂)

- The boiling points of isomeric alkyl halides “An elimination reaction (Dehydrohalogenation)”)
decrease as there is no increase in the branching in
the alkyl group. If there are the same halogens then 3. Reaction with Metals
the boiling point depends on the molecular mass  In order to provide compounds containing
and increases as the molecular mass increases as carbon-metal bonds, most organic chlorides,
bromides and iodides react with certain
an increase in the size of the alkyl group, the
metals. These compounds are classified as
magnitude of van der Waals forces increases. The organometallic compounds. A substance
order is R-X<R-CH₂-X<R-CH₂-CH₂-X. formed by the dry ether reaction of
haloalkanes to magnesium metal (Grignard
- If there is an increase in the number of halogen reagent) reacts actively with any proton
atoms, there is an increase in the boiling point of the source to form hydrocarbons. Thus, avoiding
compound as well since the van der Waal force of proton sources around Grignard reagents is
attraction increases. important to prevent unintended
hydrocarbon formation.
5. Density
USES OF SOME ALKYL HALIDES Other Examples of Polyhalo-alkanes
- Freon
1. Methyl chloride, ethyl chloride, and ethyl - DDT
bromide are used as local anesthetics - Teflon
(their quick evaporation causes a freezing
effect); THE HALOFORMS
- methyl bromide is used as a fumigant for - are trihalogen derivatives of methane.
rats and weevils.
Examples:
2. They were used as refrigerants, aerosol
- Chloroform/trichloromethane (CHCl₃)
propellants, for generating foamed plastics
- Bromoform/tribromomethane (CHBr₃)
(e.g., expanded polystyrene, polyurethane
- Iodoform/triiodomethane (CHI₃)
foam), and as solvents for dry cleaning and
degreasing.
Preparation of
3. Some fully fluorinated compounds are being
considered as potential blood substitutes
Chloroform and Iodoform
in surgery. o Haloform reaction
o This is the reaction between ethyl alcohol
4. Chloramphenicol, a chlorine-containing (or acetone or any compound with the
antibiotic produced by soil microorganisms, potential methyl carbonyl, CH-CO-, group),
is very effective for treating typhoid fever. an alkali (NaOH or Na₂CO₃), and a halogen.

5. They are used as solvents for relatively A. CHLOROFORM PREPARATION

non-polar compounds and as starting - can be prepared in the laboratory through the
materials for synthesizing a wide range of following:
organic compounds.
1. Distilling a mixture of ethyl alcohol (or
6. They are also used in extinguishers for acetone) and bleaching powder. (This is
burning materials. also haloform reaction. The bleaching
powder supplies the alkali and chlorine.

POLYHALO-ALKANES
 Organic compounds in which two or more
hydrogen atoms of an alkane have been
replaced by halogen atoms (fluorine,
chlorine, bromine, or iodine).
2. Distilling a mixture of choral hydrate and
 These halogen atoms can be the same or sodium hydroxide.
different and can be attached to the same or
different carbon atoms within the alkane - Reaction:
chain. They are also commonly known as CCl₃CHO·H₂O + NaOH → CHCl₃ + HCOONa +H₂O
polyhalogen compounds.
B. IODOFORM PREPARATION
Examples o may be prepared by heating a mixture of
Compound Formula # of Halogen ethyl alcohol (acetone), sodium
Atoms hydroxide (or sodium carbonate) and
Dichloromethane CH₂Cl₂ 2 chlorine atoms iodine. This is a haloform reaction.
Chloroform CHCl₃ 3 chlorine atoms
(Trichloromethane) Examples:
Carbon Tetrachloride CCl₄ 4 chlorine atoms a. From ethyl alcohol, sodium carbonate, and
(Tetrachloromethane) iodine:
Iodoform CHI₃ 3 iodine atoms
(Triiodomethane)
 D. C₂H₅OH + 3Na₂CO₃ + 4I₂ → CHI₃ USES OF
(Triiodomethane/iodoform) + HCOONa +
5NaI + 2H₂O + 3CO₂
CHLOROFORM AND IODOFORM

b. From ethyl alcohol, sodium hydroxide and 1. Chloroform

iodine: - used in the building, paper and board industries,
and in pesticide and film production
E. C₂H₅OH + 6NaOH + 4I₂ → CHI₃
(Triiodomethane/iodoform) + HCOONa + - used as a solvent for lacquers, floor polishes,
5H₂O resins, adhesives, alkaloids, fats, oils and rubber

- used in medicine as an anesthetic, sedative and

PROPERTIES OF
antiseptic
CHLOROFORM AND IODOFORM
- used in dry cleaning
1. Chloroform or trichloromethane, CHCl
 heavy colorless liquid with a sweet ethereal 2. Iodoform
odor and sweet taste, insoluble in water but - used in medicine as a surgical dusting powder
soluble in organic solvents. Its boiling point (antiseptic) and disinfectant for wounds
is 61.2 degrees Celsius. It is heavier than
water; its specific gravity is 1.525. It is - used as a component in medicines for healing and
nonflammable. It is a man-made by-product antiseptic dressing of wounds and sores
formed when chlorine is used to disinfect
water. - used for sterilizing instruments used for surgery

 Chloroform is oxidized in the presence of

oxidizing agents like acid-dichromate or
OTHER HALOGEN DERIVATIVES
atmospheric oxygen to form phosgene (or AND THEIR USES
carbonyl chloride) and HCl or sometimes Halogen derivatives are important reagents in
chlorine. Phosgene is a poisonous gas, and synthetic work. Many of them serve as solvents,
for this reason, chloroform which has been refrigerants, insecticides, and in the manufacture of
exposed to air and sunlight, is entirely unfit plastics.
for use as an anesthetic.
1. AS SOLVENTS:
Reactions: A. Methylene chloride
- 2 CHCl₃ + O₂ (AIR) → 2 COCl₂ (phosgene) + HCl  dichloromethane and methylene
dichloride
- 4CHCl₃+3O₂(acid-dichromate)→4 COCl₂+Cl₂+2 H₂O
 clear, colorless liquid with a slightly
3. Test for chloroform: sweet scent that is primarily used
4. isocyanide test or carbylamine test or as an industrial solvent and also
Hoffman’s test as a potent paint stripper and
paint thinner.
 Chloroform treated with aniline (or primary
amine) and alcoholic sodium hydroxide  used in the manufacture of
gives a nauseating or obnoxious odor of silicones, methyl cellulose, and
phenyl isocyanide. synthetic rubber.

- Reaction: CHCl₃ + C₆H₅NH₂ (aniline) + 3 NaOH → B. Trichloroethylene (TCE)

C₆H₅NC (phenyl isocyanide) + NaCl + H₂O  used as a solvent for degreasing
metal parts during the manufacture
2. Iodoform is a yellow solid with characteristic of a variety of products.
medicinal or antiseptic odor, insoluble in water, but
soluble in organic solvents.
  can be found in consumer
products, including wood finishes,  It’s a type of plastic sprayed on
adhesives, paint removers, and various items and then baked to
stain removers. create a nonstick, waterproof,
noncorrosive, and nonreactive
 can also be used in the surface.
manufacture of other chemicals.
B. Vinyl chloride / Chloroethene
 is an organochloride with the formula
C. Tetrachloroethane H₂C=CHCl.
 used as a solvent for degreasing
metals, in paint removers, varnishes,  is a colorless gas that burns easily. It
lacquers, photographic film, rust does not occur naturally and must
removers, resins and waxes, be produced industrially for its
extraction of oils and fats, and as an commercial uses to produce plastics
alcohol denaturant in organic
synthesis.  An important industrial chemical
chiefly used to produce polyvinyl
2. USED IN REFRIGERANTS: chloride.
A. Freon-12 or dichlorodifluoromethane (R-12)
 colorless gas usually sold under the 4. USED IN INSECTICIDES:
brand name Freon-12, and a o DDT or dichloro-diphenyl-trichloroethane,
chlorofluorocarbon halomethane CCl₃-CH(C₆H₄Cl)₂; Methoxychlor, a
(CFC) used as a refrigerant and compound which has methoxy groups
aerosol spray propellant. (CH₃O-) in place of the chlorine in the
phenyl groups of DDT; p-dichlorobenzene is
 Its manufacture was banned in a well-known larvicide for moths.
developed countries in 1996 and
developing countries in 2010 out of A. Dichloro-diphenyl-trichloroethane (DDT)
concerns about its damaging effect  colorless, tasteless, and almost
on the ozone layer. odorless crystalline chemical
compound, an organochloride.
 Its only allowed usage is as a fire Originally developed as an
retardant in submarines and aircraft. insecticide, it became infamous for
its environmental impacts.
B. Freon-22 (chlorodifluoromethane, CHClF₂)
 R22 refrigerant, or R22 freon, is a B. Methoxychlor
cooling compound used in both air  a white crystalline solid that is often
conditioners and heat pumps that dissolved in a liquid carrier such as
harms the ozone layer when diesel oil.
released into the air.  can cause illness by inhalation, skin
absorption, and/or ingestion.
3. USED IN PLASTICS:
 The primary hazard is the threat to
A. Teflon
the environment. Immediate steps
 a polymer of tetrafluoroethylene
should be taken to limit its spread to
(C₂F₄), vinyl chloride (koroseal
the environment.
products).

 not a product in itself, but rather a  If dissolved in a liquid carrier, it can

brand name for a product. easily penetrate the soil and
contaminate groundwater and
 It refers to a chemical coating nearby streams.
known as polytetrafluoroethylene
(PTFE).  used as a pesticide.
 CHLOROFLUOROCARBONS AND THE
C. P-Dichlorobenzene (Paradichlorobenzene) OZONE LAYER
 is a synthetic, white crystalline solid Alkanes substituted with both fluorine (F) and
that is practically insoluble in water chlorine (Cl) atoms have been used as the
and soluble in ether, chloroform, dispersing gases in aerosol cans, as foaming
carbon disulfide, benzene, alcohol agents for plastics, and as refrigerants.
and acetone.

 used primarily as a space deodorant

in products such as room  Chlorofluorocarbons
deodorizers, urinal and toilet bowl  contribute to the greenhouse effect
blocks, and as an insecticide in the lower atmosphere.
fumigant for moth control.
 also diffuse into the stratosphere,
HALOGENATED HYDROCARBONS AND where they are broken down by
HEALTH ultraviolet (UV) radiation to release
Cl atoms. These in turn break down
 Once widely used in consumer products, the ozone (O₃) molecules that
many chlorinated hydrocarbons are protect Earth from harmful UV
suspected carcinogens (cancer-causing radiation.
substances) and also are known to cause
severe liver damage.

An example is carbon tetrachloride (CCl₄),

once used as a dry-cleaning solvent and in
fire extinguishers, but no longer
recommended for either use. Even in small
amounts, its vapor can cause serious illness
if exposure is prolonged. Moreover, it reacts
with water at high temperatures to form
deadly phosgene (COCl₂) gas, which makes
the use of CCl₄ in fire extinguishers
particularly dangerous.

 Bromine-containing compounds
 widely used in fire extinguishers and
as fire retardants on clothing and
other materials.

 are toxic and have adverse effects

on the environment, scientists are
engaged in designing safer
substitutes for them, as for many
other halogenated compounds.