INORGANIC & ORGANIC CHEMISTRY
(Midterms)
Lecture 1: ALCOHOLS AND ALKYL
HALIDES: INTRODUCTION TO REACTION
MECHANISMS
Section 1.5: FUNCTIONAL GROUPS
Functional Groups-1
– alkanes are not generally considered to be
functional groups (although C-H bonds can
be reactive)
– the multiple bonds in alkenes and alkynes
are considered functional groups
– the six-membered rings consisting of sp2
hybridized carbons in arenes are considered
functional groups
– in this chapter, there will be a focus on
alcohols (ROH) and alkyl halides (RX, X=F,
Br, Cl, I)
Survey of Functional Groups-1
Survey of Functional Groups-2
Alkyl Halides / Haloalkanes
– alkyl halides are also known as haloalkanes
– alkyl halides are compounds in which one
or more hydrogen atoms in an alkane have
been replaced by halogen atoms (fluorine,
chlorine, bromine, or iodine).
– alkyl halides are represented by R-X (R =
alkyl group; X = F, Cl, Br, or I)
Types of Organic Halides
1. Alkyl Halides – have a halogen atom (X)
bonded to a C-C bond.
2. Vinyl Halides – have a halogen atom (X)
bonded to a C=C bond.
3. Aryl Halides – have a halogen atom (X)
bonded to an Ar-C bond.
Classification for Alkyl Halides
– the number of alkyl groups attached to the
carbon to which the halogen is bonded
determines whether an alkyl halide is primary,
secondary, or tertiary.
1. Primary (1°) Alkyl Halides – have one R
group attached to the carbon linked to the
halogen.
2. Secondary (2°) Alkyl Halides – have two
R groups attached to the carbon linked to
the halogen.
3. Tertiary (3°) Alkyl Halides – have three R
groups attached to the carbon linked to the
halogen.
Alcohols
– the organic compound which has -OH
functional group are called alcohols.
– the general formula for alcohol is
CnH2n+1OH / R-OH.

Classification of Alcohol
➢ Substitutive nomenclature (preferred) –
– on the basis of -OH group attached to the
the halogen is treated as a “halo-”
carbon atom, alcohols are divided into three
substituent on an alkyl chain
categories:

1. Primary Alcohol – when the carbon atom

attached to the hydroxyl group is bonded
to only one carbon atom.
2. Secondary Alcohol – when the carbon
atom attached to the hydroxyl group is
bonded to two carbon atoms.
3. Tertiary Alcohol – when the carbon atom
attached to the hydroxyl group is bonded
to three carbon atoms.
Two Types of Nomenclature-2
– when the carbon chain bears both a halogen
and an alkyl substituent, the two are
considered of equal rank, and the chain is
numbered so as to give the lower number to
the substituent nearer the end of the chain.

Types of Alcohol

– depending on the number of hydroxyl groups

attached, alcohols can be classified into four
types:
1. Monohydric Alcohols – contain one -OH
group; e.g., CH3CH2-OH
2. Dihydric Alcohols – contain two -OH
groups, and are also called diols and
glycols; e.g., 1,2-ethandiol
3. Trihydric Alcohols – contain three -OH
groups, and are also called triols or
glycerols; e.g., 1,2,3-propantriol
4. Polyhydric Alcohols – contain more than
three -OH groups; e.g., sorbitol
Section 5.3: IUPAC NOMENCLATURE OF
ALCOHOLS
Two Types of Nomenclature-3
– the two types of nomenclature we saw for
alkyl halides apply to alcohols as well:
➢ Functional Class nomenclature – the
alcohol is named as an “alkyl alcohol”; the
alkyl group is treated as a substituent.

➢ Substitutive nomenclature (preferred) –

the alcohol is named as an “alkanol”, with
a number before “alkan” or “ol” to denote
the position of the -OH group.
Section 5.2: IUPAC NOMENCLATURE OF
ALKYL HALIDES

Two Types of Nomenclature ➢ Either the “n-alkanol” or “alkan-n-ol”

– two types of nomenclature for alkyl halides:
➢ Functional Class nomenclature – the
alkyl group is treated as the “positive”
portion of a halide salt.
names are acceptable.
Substitutive Nomenclature
– when using the substitutive convention, it is
important that the parent chain includes the -
OH or -X substituent
– for the purposes of numbering, the -OH
group takes precedence over halogen
substituents and alkyl groups.
– the carbon bonded to -OH or -X is sp3
hybridized and tetrahedral.
– the C-O and C-X bonds are polarized
toward the more electronegative O or X atom.
– the carbon atom bonded to O or X is
partially positive.

Alcohols that contain more than one

hydroxyl group

➢ Alcohols containing two hydroxyl groups

are named -diols.
➢ Alcohols containing three hydroxyl groups
are named -triols.
➢ A number giving the position of each of the
hydroxyl groups is needed in these cases.
Section 5.4: CLASSES OF ALCOHOLS
AND ALKYL HALIDES
Substitution Pattern
Dipole Moments
– because the C-O and C-X bonds are
polarized, alcohols and alkyl halides are
polar.
– dipole moments are comparable to that of
water.
– note the direction of the dipole vector and
the implied partial charges on C, O, and X.

– alcohols, alkyl halides, and other organic

compounds are often classified by
substitution pattern.
– the key question is: how many alkyl groups
are attached directly to the carbon that bears
the functional group? Electrostatic Potential Maps

➢ One alkyl group: primary (1 degree)
➢ Two alkyl groups: secondary (2 degrees)
➢ Three alkyl groups: tertiary (3 degrees)
– substitution pattern can profoundly affect
the reactivity of a carbon.
– in both compounds, the heteroatom bears
significant negative charge.
– in methanol, the O-H hydrogen bears most
of the positive charge.

– in chloromethane, the nearby C-H

hydrogens bear most of the positive charge.

Section 5.5: BONDING IN ALCOHOLS

AND ALKYL HALIDES

Hybridization, Geometry, and Bonding

 Section 5.6: PHYSICAL PROPERTIES OF
ALCOHOLS AND ALKYL HALIDES:
INTERMOLECULAR FORCES (I)
Dipolar Forces
– alcohols and alkyl halides are polar. Hence,
their molecules engage in dipole-dipole and
dipole-induced dipole forces.
– these forces are much stronger than
London forces, and cause the boiling and
melting points of alkyl halides and alcohols to
be higher than those of alkanes.
– why is the boiling point of ethanol
abnormally high? – hydrogen bonding
Hydrogen Bonding
– alcohols contain a highly polarized O-H
bond, which can engage in a special type of
dipole-dipole interaction called a hydrogen
bond.
– the partially negative O on one molecule is
attracted to the partially positive H on another.
– hydrogen bonding occurs only in
compounds containing O-H or N-H bonds.
– hydrogen bonds are directional – they
involve a small degree of electron sharing.
Boiling Points
– boiling points increases with molecular
weight.
– boiling points of alcohols are quite high due
to hydrogen bonding.
– as polarizability of the halogen increases,
boiling point increases.
Polarizability
– the ability of the electron cloud around an
atom to distort its shape is called
polarizability.
– polarizability is greater for larger halogens;
greater polarizability means a larger boiling
point.
– alkyl fluorides show roughly the opposite
trend – fluorine is not very polarizable.
Solubility
– alkyl halides are insoluble in water.
– alcohols with low molecular weight (small
hydrocarbon portions) are soluble in water in
all proportions.
– alcohols can hydrogen bond with water.
– alcohols with long alkyl chains remain
insoluble due to the hydrophobic effect.
Physical Properties
Solubility: All organic halides are insoluble in
water and soluble in common organic
solvents.
Boiling Point: The boiling points increases
with increasing in molecular weights.
Therefore, the boiling points increases in the
order (F > Cl > Br > I)
Electronegativities Order: (F > Cl > Br > I)
Bond Length Order: (C-F < C-Cl < C-Br < C-I)
– alkyl halides are weak polar molecules
– density correspond to the molecular weight
– Density Order: (F < Cl < Br < I)
 Uses of Alkyl Halides Section 5.6: PHYSICAL PROPERTIES OF
ALCOHOLS AND ALKYL HALIDES:
1. Solvents – degreasers and dry cleaning INTERMOLECULAR FORCES (II)
fluid
2. Reagents for synthesis of other Reactivity Trends: Examples
compounds
3. Anesthetic - halothane is CF3CHClBr
4. CHCl3 used originally (toxic and
carcinogenic)
5. Freons, chlorofluorocarbons, or CFC’s
Freon 12, CF2Cl2, now replaced with – tertiary ROH react with HCl and HBr in
Freon 22, CF2CHCl, not as harmful to minutes; secondary and primary require HBr
ozone layer and elevated temperatures.
6. Pesticides – DDT banned in the U.S.

Section 5.7: PREPARATION OF ALKYL

HALIDES FROM ALCOHOLS AND
HYDROGEN HALIDES

Substitution Reactions

– alcohols and alkyl halides differ only in the Structure and Properties
group bound to the alkyl group (-OH or -X).
– a reaction that replaces -OH with -X or vice – R-O-H portion of alcohol is similar to the
versa is called a substitution reaction. structure of water.

➢ The oxygen and two atoms bonded to it

lie in the same plane.
➢ The bond angle is 104°.

– alkyl halides are valuable precursors to – hydroxyl groups are very polar because of
other organic functional groups – they significantly different electronegativities.
represent a synthetic “hub.”
➢ Hydrogen bonding can form between
– we will study this reaction to gain insight
alcohol molecules.
into reaction mechanism and general
principles of reactivity. Hydrogen Bonding
Reactivity Trends

– the reactivity of hydrogen halides parallels

their acidity.

– the reactivity of alcohols depends on

substitution pattern.

Physical Properties of Alcohol

– the solubility of alcohol in water depends

upon the length of alkyl chain in the alcohol
– they are weak acid
– they have higher boiling point than alkane,
alkene, and alkyne
 Chemical Properties of Alcohol
– on reacting with active metals such as
sodium (Na+), potassium (K+), and aluminum
(Al+3), they yield corresponding
alkoxides/phenoxides and hydrogen.
– on reacting with carboxylic acids, acid
chlorides, and acid anhydrides, they form
esters.
– on treating with protic acid, e.g.,
concentrated H2SO4 or H3PO4, they undergo
dehydration.
Results of Hydrogen Bonding
– alcohols boil at much higher temperatures
than hydrocarbons of similar molecular
weight.
– alcohols with fewer than five carbons are
very soluble in water.
– alcohols with five to eight carbons are
moderately soluble in water.
– as the nonpolar (R) portion of the alcohol
gets larger, the water solubility decreases.
Solubility of Alcohols
– very large alcohols are not soluble in water.
– hydrophobic – “water-fearing”; used to
describe the nonpolar region of a molecule.
– hydrophilic – “water-loving”; used to
describe the polar region of a molecule.
– an increase in the number of hydroxyl
groups will increase the influence of the polar
hydroxyl group.
➢ Diols and triols are more water soluble
than alcohols with only a single hydroxyl
group.
Section 5.6: IMPORTANT ALKYL
HALIDES AND ALCOHOLS
Structure and Uses of Alkyl Halides
1. Ethylchloride
– chloroethane or monochloroethane,
commonly known by its old name
Ethylchloride, is a chemical compound
with chemical formula C2H5Cl, once
widely used in producing tetraethyllead, a
gasoline additive.
– chloroethane is produced by hydro
chlorination of ethene:
Uses of Ethylchloride:
– used to produce tetraethyllead (TEL), an
anti-knock additive for gasoline.
– sed in the production of cellulose, dyes,
medicinal drugs, and other commercial
products, and as a solvent and refrigerant.
– used as a mild topical anesthetic to numb
the skin prior to ear piercing, skin biopsies,
etc., and is also used in the treatment of
sports injuries.
– used to convert cellulose to ethylcellulose, a
thickening agent and binder in paints,
cosmetics, and similar products.
2. Chloroform
– chloroform or trichloromethane is an
organic compound with the formula
CHCl3.
– it is a colorless, sweet-smelling, dense
liquid.
– it is a precursor to PTFE
(polytetrafluoroethylene).
– it is also a precursor to various
refrigerants.
– in industry, chloroform is produced by
heating a mixture of chlorine and
methane. At 400°C - 500°C, a free radical
halogenation occurs, yielding chloroform.
Uses of Chloroform:
– used as a solvent for lacquers, floor
polishes, resins, adhesives, alkaloids, fats,
oils, and rubber.
– used in making fluorocarbon-22, a
refrigerant.
–used to extract and purify penicillin.
–used for extraction and purification of
alkaloids.
– chloroform was popular as an anesthetic
from the mid-1800s to around 1900, but it
was found to cause death from paralysis. It
also depresses most of the body’s other
organs, including the blood vessels, liver,
pancreas, and kidneys. It is toxic to the liver
and chloroform was replaced by safer
compounds after about 1940.
– relieves the pain of childbirth.
3. Trichloroethylene
– it is a halocarbon commonly used as an
industrial solvent.
– it is a clear non-flammable liquid with a
sweet smell.
– when 1,2-dichloroethane heated with
chlorine at 400° is produced to
trichloroethylene.
Uses of Trichloroethylene:
– main use is in the vapor degreasing of
metal parts.
– used as an extraction solvent for greases,
oils, fats, waxes, and tars, a chemical
intermediate in the production of other
chemicals, and as a refrigerant.
– used in consumer products such as
typewriter correction fluids, paint
removers/strippers, adhesives, spot
removers, and rug-cleaning fluids.
– used in the past as a general anesthetic.
4. Tetrachloroethylene
– it is a volatile chlorinated organic
hydrocarbon that is widely used as a
solvent with the chemic formula C2Cl4.
– it is non-flammable liquid at room
temperature, evaporates easily into the
air and has a sharp sweet odor.
– it is prepared by thermal decomposition
of hexachloroethane.
Uses of Tetrachloroethylene:
– used as an excellent solvent for organic
materials.
– widely used in dry cleaning.
– used to degrease metal parts in the
automotive and other metalworking
industries, usually as a mixture with other
chlorocarbons.
– appears in a few consumer products
including paint strippers and spot removers.
– used in aerosol preparations.
5. Dichloromethane
– (DCM or methylene chloride) is an
organic compound with the formula
CH2Cl2.
– this colorless, volatile liquid with a
moderately sweet aroma is widely used
as a solvent.
– although it is not miscible with water, it
is miscible with many organic solvents.
– DCM is produced by treating
chloromethane with chlorine gas at 400°C
- 500°C.
Uses of Dichloromethane:
– a useful solvent for many chemical
processes.
– widely used as a paint stripper and a
degreaser.
– used in the food industry to decaffeinate
coffee and tea, as well as to prepare extracts
of hops and other flavorings.
– used as a blowing agent for polyurethane
foams.
– used in shoe manufacturing.
– a solvent in paint removers, degreasing
fluids, aerosol propellants, and hair lacquers.
6. Tetrachloromethane
– also known as carbon tetrachloride
(CCl4).
– was formerly used in fire
extinguishers, as a precursor to
refrigerants, and as a cleaning agent.
– it is a colorless liquid with a “sweet”
smell that can be detected at low levels.
– it is mainly produced from methane:
Uses of Tetrachloromethane:
– used to produce the chlorofluorocarbon
refrigerants R-11 (trichlorofluoromethane) and
R-12 (dichlorodifluoromethane).
–used in the detection of neutrinos.
– useful solvent for halogenations.
– widely used as a dry cleaning solvent, and
metal degreasing solvent.
– one of the most potent hepatotoxins (toxic
to the liver), so that it is widely used in
scientific research to evaluate
hepatoprotective agents.
– used as a starting material (building block)
for making other chemicals and is used in
some consumer products.
7. Iodoform
– also known as tri-iodomethane, carbon
triiodide, and methyl triiodide.
– it is the organo iodine compound with
the formula CHI3.
– a pale yellow, crystalline, volatile
substance, it has a penetrating and
distinctive odor, and analogous to
chloroform, sweetish taste.
– iodoform was prepared by ethanol or
acetone with iodine.
Uses of Iodoform:
– occasionally used as a disinfectant.
– was used in medicine as a healing and
antiseptic dressing for wounds and sores.
– the active ingredient in many ear powders
for dogs and cats, along with zinc oxide and
propanoic acid, which are used to prevent
infection and facilitate removal of ear hair.
Section 5.6: IMPORTANT ALKYL
HALIDES AND ALCOHOLS
8. Ethyl Alcohol
– also known as alcohol, ethanol, and
drinking alcohol, is a chemical compound,
a simple alcohol with the chemical
formula C2H12O6 or CH3CH2OH.
– ethanol in alcoholic beverages and fuel
is produced by fermentation. Certain
species of yeast metabolize sugar,
producing ethanol and carbon dioxide.
Uses of Ethyl Alcohol:
– used in medical wipes and most common
antibacterial hand sanitizer gels as an
antiseptic. Ethanol kills organisms by
denaturing their proteins and is effective
against most bacteria, fungi, and many
viruses.
– may be administered as an antidote to
methanol and ethylene glycol poisoning.
– ethyl alcohol increases the secretion of
acids in the stomach.
– used as a central nervous system
depressant. It can lift mood, cause feelings of
euphoria, and decrease anxiety.
– the largest single use of ethanol is as an
engine fuel and fuel additive.
– ethanol is miscible in water, and is a good
general purpose solvent. It is found in paints,
tinctures, markers, and personal care
products such as mouthwashes, perfumes,
and deodorants.
9. Chlorobutanol
– (trichloro-2-methyl-2-propanol), is
commonly used as a chemical
preservative in a wide range of cosmetic
and pharmaceutical products.
– the antibacterial and antifungal
properties of the substance inhibit
microbial growth for extended periods of
time.
– chlorobutanol is formed by the simple
nucleophilic addition of chloroform and
acetone in the presence of KOH/NaOH.
Uses of Chlorobutanol:
– topically along with clove oil as dental
analgesic.
– employed as a sedative and hypnotic.
– used as a pharmaceutical aid
(antimicrobial) antiseptic and local anesthetic.
– used at a concentration of 0.5% as a
preservative in injections, eye drops, and
mouth washes, salves, creams, and
ointments, as well as cosmetics.
10. Cetostearyl Alcohol
– also known as ceteraryl alcohol or
cetylstearyl alcohol, is a mixture of fatty
alcohols, consisting predominantly of
cetyl and stearyl alcohols and is
classified as a fatty alcohol.

Uses of Cetostearyl Alcohol:
– used in the cosmetic industry as an
opacifier in shampoos, or as an emollient,
emulsifier, or thickening agent in the
manufacture of skin creams and lotions.
– employed as a lubricant for nuts and bolts,
and is the active ingredient in some “liquid
pool covers.”
– used as an emulsion stabilizer, opacifying
agent, and foam boosting surfactant, as well
as an aqueous and non-aqueous viscosity-
increasing agent.
– imparts an emollient feel to the skin and can
be used in water-in-oil emulsions, oil-in-water
emulsions, and anhydrous formulations.
11. Benzyl Alcohol
– an aromatic alcohol with the formula
C6H5CH2OH, and is denoted as BnOH.
– a colorless liquid with a mild pleasant
aromatic odor.
– prepared by the hydrolysis of benzyl
chloride using KOH/NaOH:
Uses of Benzyl Alcohol:
– used as a general solvent for inks, waxes,
shellacs, paints, lacquers, and epoxy resin
coatings.
– used in e-liquid for e-cigarettes to enhance
the flavors used.
– use of benzyl alcohol as a 5% solution has
been approved by the U.S. FDA for the
treatment of head lice in children older than
six months and in adults.
– as a dye solvent, it enhances the process of
dying wool, nylon, and leather. It also has use
as a photographic developer, and as an
insect repellent.
– used as a bacteriostatic preservative at low
concentration in intravenous medications,
cosmetics, and topical drugs.
12. Glycerol
– also called glycerine or glycerin.
– a simple polyol compound.
– a colorless, odorless, viscous liquid that
is sweet-tasting and non-toxic. The
glycerol backbone is found in those
lipids known as glycerides.
– glycerol is generally obtained from plant
and animal sources where it occurs in
triglycerides, esters of glycerol with long-
chain carboxylic acids. The hydrolysis,
saponification, of these triglycerides
produces glycerol.
Uses of Glycerol:
– glycerol having antimicrobial and antiviral
properties is widely used in FDA-approved
wound and burn treatments.
– used as an effective marker to measure
liver disease.
– widely used as a sweetener in the food
industry.
– a component of glycerin soap.
– used in medical, pharmaceutical, and
personal care preparations, often as a means
of improving smoothness, providing
lubrication, and as a humectant.
13. Propylene Glycol
– (propane-1,2-diol) is an organic
compound with the chemical formula
CH3CH(OH)CH2OH.
– a viscous, colorless liquid, which is
nearly odorless but possesses a faintly
sweet taste.
– containing two alcohol groups, it is
classed as a diol.
Uses of Propylene Glycol:
– a synthetic liquid substance that absorbs
water.
– also used to make polyester compounds,
and as a base for deicing solutions.
– used by the chemical, food, and
pharmaceutical industries as antifreeze when
leakage might lead to contact with food.
– used in various edible items such as coffee-
based drinks, liquid sweeteners, ice cream,
whipped dairy products, and soda.
– used as a solvent in many pharmaceuticals,
including oral, injectable, and topical
formulations.
Lecture 2: ALCOHOL REACTIONS
– alcohols are compounds in which a
hydroxyl group (-OH group) is attached to a
saturated carbon atom.
– classification depending upon number of 3. Catalytic Hydrogenation of Aldehydes
hydroxyl group. and Ketones
– alcohols containing one such -OH group are – reduction of aldehyde and ketone to
called monohydric alcohols. form alcohol.
– those with two -OH groups are dihydric
alcohols.
– three -OH groups are trihydric alcohols.
– many -OH groups are known as polyhydric
alcohols.

4. From Aldehyde and Ketone using

Grignard reagents (alkyl magnesium
halide)
Classification of Monohydric Alcohol

5. Reduction with Lithium Aluminium

Hydride

Methods of Preparation of Alcohols

1. Hydrolysis of Alkyl Halides

– alkyl halides react with aqueous
potassium hydroxide to form alcohol.

6. Reduction of Acid Chlorides and

Esters
– acid chlorides and esters undergo
reduction with LiAlH4 to form primary
alcohol.
2. Hydration of Alkenes
– water adds to alkene in presence of
acid catalyst form alcohol.

7. Reduction of Epoxides
– epoxides contain polar C-O bonds that
react with nucleophile are reduced with
metal hydride reagents, like lithium
aluminium hydride to form alcohol.

8. Oxymercuration-Demercuration of
Alkenes
– mercuric acetate and water add to
alkenes called as oxymercuration.
– reduction of oxymercuration product in
presence of sodium borohydride to form
alcohol called as demercuration.
9. Hydroboration-Oxidation of Alkenes
– addition of borane to alkene, forming an
alkylborane and oxidation of alkylborane
to form alcohol.
Reactions of Alcohols
1. Reaction with Metals to Form Salt
– alcohols react with Li, Na, K to liberate
hydrogen and metal oxides.
2. Formation of Alkyl Halides
– alcohols react with HBr to HI to produce
alkyl bromides or alkyl halides.
a. Action of Halogen Acids on Alcohol
(Formation of Alkyl Halides)
– alcohols react with HBr to HI to produce
alkyl bromides or alkyl halides.
b. Action of Phosphorus Halides on
Alcohol (Formation of Alkyl Halides)
– alcohols react with phosphorus halides
to produce alkyl halides.
c. Action of Thionyl Chloride on Alcohol
(Formation of Alkyl Halides)
– alcohols react with thionyl chloride in
the presence of pyridine to produce alkyl
halides.
3. Formation of Ester
– alcohol react with carboxylic acid in the
presence of strong acid to form esters.
 6. Oxidation of Alcohol
4. Formation of Carboxylic Acid – alkyl halide undergo reduction with
– oxidation of primary alcohols and nascent hydrogen in presence of
aldehydes: primary alcohols and reducing agent like Zn/HCl to form
aldehydes on oxidation with sodium or alkanes.
potassium dichromate and sulphuric acid, – +O2 = aldehyde
or potassium permanganate, give the
corresponding carboxylic acids.

7. Catalytic Dehydrogenation of Alcohol

– alcohol undergo reduction with nascent
hydrogen in presence of reducing agent
like Zn/HCl to form alkanes.

5. Dehydration of Alcohol
– when alcohol is heated in the presence
of sulphuric acid to form alkene by
elimination of water.

8. Reaction with Grignard Reagents

(Formation of Alkanes)
– alcohols react with Grignard reagents
(R-Mg-X) to form alkanes.

9. Reduction of Alcohol to Form Alkane

– alcohol undergo reduction with
concentrated hydriodic acid and
phosphorus to form alkanes.
 Identification Test for Alcohol

– solution of alcohol and sodium metal gives

hydrogen gas indicate alcohol.
– alcohol and phosphorus chloride evolves
HCl confirms alcohol. 3. Action of Halogen Acids on Alcohol
– alcohol and acetyl chloride produce – alcohols react with HBr or HI to produce
separate layer of ester and HCl gas evolves, alkyl bromides or alkyl halides.
indicates -OH group.
– Lucas Test: alcohol, HCl, and zinc chloride
to form alkyl halides or precipitate confirms
secondary and tertiary alcohol.
– Dichromate Test: alcohol is treated with
sodium dichromate in sulfuric acid, primary
alcohol gives acid, secondary alcohol gives
ketone means color of product is green, but
tertiary alcohol does not react under 4. Action of Phosphorus Halides on
condition. Alcohol
– alcohols react with phosphorus halides
Lecture 3: ALKYL HALIDES REACTIONS to produce alkyl halides.
– alkyl halides are the derivatives of alkanes
in which hydrogen atom is replaced by a
halogen atom F, Cl, Br, or I.
– alkyl halides are represented by R-X, R-
alkyl group, X-halogen like chloro, fluoro,
bromo, and iodo group.

5. Action of Thionyl Chloride on Alcohol

Preparation Methods of Alkyl Halides – alcohols react with thionyl chloride in
the presence of pyridine to produce alkyl
1. Halogenation of Alkane halides.
– it involves the substitution of H-atoms of
alkanes by as many halogen atoms i.e.,
by chlorine (chlorination); by bromine
(bromination); by iodine (iodination); or by
fluorine (fluorination).
– methane reacts with chlorine in the
presence of ultraviolet light or at high
temperature (300°) to yield methyl
chloride or chloromethane and hydrogen
chloride.
6. Halogen Exchange Reaction
– the alkyl bromide is heated with
concentrated solution of sodium iodine in
acetone to form alkyl iodide.

2. Addition of Hydrogen Halides

– alkenes react with hydrogen halides
(HCl, HBr, or HI) to form alkyl halides.
7. Hunsdiecker Reaction
– silver salt/silver halide of carboxylic acid
react with halogen to give unstable
intermediate which is decarboxylated to
form alkyl halides.
SN2: Bimolecular Nucleophilic Substitution

– it is a concerted process, bond breaking

and bond formation takes place
simultaneously.
– this type of reaction is classified as
bimolecular because the alkyl halide and
nucleophile are involved in rate determining
step.
– rate: k[alkyl halide][nucleophile]

Reactions of Alkyl Halides

1. Nucleophilic Substitution Reaction

➢ Nucleophile – any reagent that donates SN1 versus SN2
an unbonded/unshared pair of electrons
to form a new covalent bond.
➢ Nucleophilic substitution reaction in which
one nucleophile is substituted for another.
➢ Two types of nucleophilic substitution
reactions: SN1: unimolecular nucleophilic
substitution; SN2: bimolecular nucleophilic
substitution.

Factors Affecting on SN1 and SN2

a. Substitution by Hydroxyl Group

– alkyl halides react with aqueous
potassium hydroxide (KOH) to form
alcohol.

b. Substitution by Amino Group

SN1: Unimolecular Nucleophilic
– alkyl halides react with alcoholic
Substitution
solution of ammonia to form amines.
– in this reaction, bond breaking between
carbon and leaving group is complete before
bond formation with nucleophile.
– this type of reaction is classified as
unimolecular because only the alkyl halide is
involved in rate determining step.
– rate: k[alkyl halide]
c. Substitution by Alkynyl Group
– alkyl halides react with sodium
acetylides to form higher alkynes.
d. Substitution by Alkoxy Group
– alkyl halides react with sodium
methoxide to form ethers.
– sodium alkoxide is prepared by
dissolving sodium in alcohol.
– this method of making alcohol is called
as Williamson ether synthesis.
e. Substitution by Thiol Group
– alkyl halides react with potassium
hydrosulfide to form thiols.
f. Reaction with Potassium Sulphide
– alkyl halides react with potassium
sulphide to form dialkyl sulfides.
g. Reaction with Silver Salt of Carboxylic
Acid
– alkyl halides react with silver salt of
carboxylic acid to form ester.
h. Reaction with Sodium Cyanide
– alkyl halides react with sodium cyanide
in ethanol to form alkyl cyanides.
2. Reduction of Alkyl Halides
– reduction: forming alkanes
– alkyl halides undergo reduction with
nascent hydrogen in presence of
reducing agent like Zn/HCl to form
alkanes.
3. Elimination Reaction:
Dehydrohalogenation of Alkyl Halides
– de: removal
– when alkyl halide is heated with
alcoholic solution of sodium hydroxide to
form alkene and hydrogen halide.
4. Wurtz Reaction
– higher alkanes are produced by heating
an alkyl halide with sodium metal in dry
ether. Two molecules of alkyl halide lose
their halogen atoms as NaX. This net
result is the joining of two alkyl groups to
yield symmetrical alkane having even
number of carbon atoms.
5. Reaction with Metal: Formation of
Grignard Reagents
– alkyl magnesium halides (Grignard
reagent) are obtained by treating alkyl
halides with magnesium in anhydrous
ether to give alkanes.
Lecture 4: THIOLS
Thiol
– organic compound with a -sulfhydryl (-SH)
group.
– thiols or mercaptans, are sulfur analogs of
alcohols.
– the -SH group is called the mercapto, or
sulfhydryl group.
– known for their foul smell.
– responsible for the smell of rotten eggs and
sewage.
– responsible for the scent of skunks.
Thiols: Sulfur Analogues of Alcohols
– thiols (mercaptans) contain the -SH group
and resemble alcohols in structure and
reactivity.
– the terrible odor of thiols is legendary.
– there are some important differences in
reactivity between thiols and alcohols.
Nomenclature of Thiols
➢ Substitutive nomenclature – the IUPAC
nomenclature system adds the ending -
thiol to the name of the alkane, but
without dropping the final -e.
➢ Functional Class nomenclature – names
for simple thiols are derived by naming the
alkyl group bonded to -SH and adding the
word mercaptan.
– in compounds containing other functional
groups, the presence of an -SH group is
indicated by the prefix mercapto-.
– according to the IUPAC system, -OH takes
precedence over -SH in both numbering and
naming:
Physical Properties of Thiols
– thiols contains nonpolar covalent S-H
bonds.
➢ Thiols show little association by hydrogen
bonding.
➢ Thiols have lower boiling point than those
of alcohols, even though thiols have
higher molecular masses, because thiols
do not possess the strong hydrogen
bonding of alcohols.
➢ Thiols are less soluble in water and other
solvents in comparison with same MW
alcohols.
Characteristic Reactions of Thiols
Oxidation/Reduction – conversion of thiols to
disulfides and vice versa.
➢ Thiols are readily oxidized by O2.
➢ Thiols are susceptible to oxidation, must
be stored in air tight containers.
➢ In return, disulfides are easily reduced to
thiols by several reducing agents.
Reactivity of Thiols
– thiols are considerably more acidic than
alcohols and water.
– naturally, thiolate anions are less basic than
alkoxides, but they are excellent nucleophiles
toward C.
– thiohydroxide (SH–) can be used to prepare
thiols from alkyl halides or pseudohalides.
Oxidation of Thiols
– at first glance, oxidation of thiols should
produce thiocarbonyl compounds.
– however, sulfur is a strong nucleophile
toward oxygen – sulfoxides are the usual
products of oxidation from thiols.
– precursor to sulfonates.
– oxidation can also produce a disulfide; the
sulfur analogue of a peroxide (RO2R) cannot
generally be prepared this way.
– this type of oxidation is important in a
biological context.
Importance of Thiols
– many proteins contain thiol groups and
disulfides critical to maintaining their three-
dimensional shape and their proper
functioning.
– lead and mercury salts react with thiol
groups, altering the physiological functioning
of the proteins involved.
– a common source of lead is from flakes of
paint manufactured prior to 1980. The use of
lead tetraethyl as a gasoline additive also
introduces lead into the environment,
however its use has been phased out.
– mercury from insecticides and other
sources enters the food chain through fish
from contaminated rivers, lakes, and streams.
Mercury has a physiological effect similar to
that of lead.
Section 16.7: ETHERS
Ethers
– oxygen atom bonded to two carbon atoms.
– contain and –O– between two carbon
groups.
– dimethyl ether or methoxymethane is the
simplest ether.
– diethyl ether or ethoxyethane is the most
abundant/common ether.
Synthesis of Ethers
– the oxygen in a protonated alcohol ROH2+ is
electrophilic.
– the oxygen of an alcohol ROH is
nucleophilic.
– when ROH is heated with an acid catalyst,
nucleophilic O in ROH attacks the
electrophilic carbon, displacing water.
– the product is a symmetric ether.
– only primary alcohols can be used; 2
degrees and 3 degrees alcohols undergo
elimination (dehydration).
– diols can react intramolecularly to give cyclic
ethers.
Section 17.1: NOMENCLATURE OF
ETHERS
– ethers can be named as alkoxyalkanes
(substitutive) or as alkyl alkyl’ ethers
(functional class).
– ethers with identical R groups are
symmetrical; ethers with different R groups
are unsymmetrical.
– cyclic ethers have unique names; the
oxygen is treated as position 1.
➢ Functional Class nomenclature – named
by listing the alkyl names in alphabetical
order followed by ether.
➢ Substitutive nomenclature – the shorter
alkyl group and the oxygen are named as
an alkoxy group attached to the longer
hydrocarbon.
– numbering the longer alkane gives: 1-
methoxypropane.
– treat all R-O- groups that you find in a
molecule as alkoxy groups or branches
(substituents), and follow the previous rules we
have covered for all other families.
Section 17.2: STRUCTURE AND BONDING
IN ETHERS
Structure and Bonding
– the oxygen in alkyl ethers is sp3 hybridized,
but the typic bond angle is wider than 109.5
degrees due to strain.
– the ether oxygen behaves largely like a CH2
unit from a conformational perspective.
Section 17.3: PHYSICAL PROPERTIES OF
ETHERS
– ethers are slightly polar molecules.
➢ The oxygen carries a partial positive
charge, and the carbons carries the
partial negative charge.
➢ Weak IMFA exist between ether
molecules in liquid form.
➢ Boiling points of ethers are close to
alkanes of similar molecular weight.
➢ Ethers have lower boiling points than
alcohols.
 Characteristic Reactions of Ethers
– ethers are resistant to chemical reactions.
➢ Does not react with K2Cr2O7 (oxidizing
agent).
➢ Does not react with H2 with transition
metal catalyst (reducing agent).
➢ Unaffected with most acids and bases at
room temperature.
– ethers are generally inert and offers good
solvent properties. Diethyl ether and THF are
excellent solvents in organic synthesis
laboratories.
Physical Properties of Ethers
– ether molecules, unlike alcohols, lack the
ability to hydrogen bond with themselves.
– boiling and melting points are similar to
alkanes of comparable size.
– ethers can hydrogen bond with H-bond
donors such as water.
– solubility of ethers in water is generally high
as a result.
Importance of Ethers
Anesthetics
– inhibit pain signals to the brain.
– such as ethyl ether CH3-CH2-O-CH2-CH3
were used for over a century, but caused
nausea and were flammable.
– developed by 1960s were nonflammable.
Ethers can hydrogen bond with H-bond
donors such as water.
Methyl tert-butyl ether (MTBE)
– is one of the most produced organic
chemicals.
– is a fuel additive used to improve gasoline
combustion.
– use is questioned since the discovery that
MTBE has contaminated water supplies.
Section 17.4: CROWN ETHERS
Crown Ethers: Applied Basicity
– the most important principle of reactivity for
ethers is that the ether oxygen can act as a
Lewis base.
– cyclic polyethers have multiple oxygens that
can bind (chelate) to a Lewis acid at multiple
points.
– crown ethers are cyclic polyethers of
various sizes that bind various cations.
Complexation of Cations
– the Lewis basic cavity of a crown ether
provides a “pocket” where cations can bind.
– for example, addition of 18-crown-6
increases the solubility of KF in benzene, a
nonpolar solvent.
Section 17.5: PREPARATION OF ETHERS
– symmetrical ethers can be prepared via acid-
catalyzed condensation of alcohols, a
substitution process.
– ethers can also be prepared via addition of
O and H across C=C, acid-catalyzed
hydration.
Section 17.6: THE WILLIAMSON ETHER
SYNTHESIS
Williamson Ether Synthesis
– alkoxides (RO–) are great nucleophiles;
reaction of RO– with an alkyl halide RX forms
a new C–O bond.
– this is an attractive method for the synthesis
of ethers.
– to avoid E2 elimination, the alkyl halide
should be primary.
– the substitution of the alkoxide is largely
irrelevant.
 Section 17.7: REACTIONS OF ETHERS: A Step 2: Halide ion attacks one of the
REVIEW AND A PREVIEW electrophilic carbons; alcohol is formed as a
leaving group.
Reactivity of Ethers

– ethers are unreactive in general, except in

combustion reactions with O2. Ethers are
highly flammable.
– ethers are oxidized slowly over time to
explosive hydroperoxides. – a similar mechanism leads to displacement
of H2O from the alcohol by X–.

– hydrohalic acids can cleave ethers to alkyl

halides.

Section 17.8: ACID-CATALYZED CLEAVAGE

OF ETHERS

– hydrohalic (HCl, HBr, HI) acids protonate

(+H to ethers) ethers, converting -OR to –
(H)OR+ (a good leaving group!).
– nucleophilic attack by halide ion X–
produces an alkyl halide.

– heat and excess of HX are typically used,

causing a second nucleophilic substitution to
occur.

Mechanism

Step 1: Protonation generates a good leaving

group within the ether.

➢ Both carbons attached to O become

electrophilic.
➢ The intermediate is “primed” for
nucleophilic substitution.