Alcohols

Alcohols, Phenols and Ethers
Dr. Parin Kanaiya

GSFC University
• Alcohols are compound in which a hydroxyl (-OH) group
is attached to saturated carbon atom.
• Ethyl alcohol is the alcohol of wine, beer and whiskey
• Ethyl alcohol may be the first organic chemical routinely
manufactured by humans.
• The hydroxyl group is the functional group of alcohol.
• Alcohols containing one hydroxyl group are called
Monohydric alcohol
• Alcohol with two, three or more hydroxyl groups are
known as Dihydric Alcohols, Trihydric Alcohols and
Polyhydric Alcohols respectively
Functional Groups
• Alcohols –OH group
• Phenol- OH group off of an aromatic ring
• Ethers- R-O-R, where R is an alkyl group or aromatic ring
• Aldehydes- *terminal H
• Ketones- *no terminal H

More Functional groups
• Thiols- R-SH *thio means sulfur!
• Ester- R-COO-R
• Carboxylic acid- R-COOH
• Amines- R-NH2, R2NH, or R3N
• Amides- R-CON-R
Connection between alcohols, ethers, thiols
and phenols
• All of these groups are derived from the structure of water,
with a few substitutions.
• Alcohols- remove one H from water and add an alkyl group
• Thiols- replace the O in an alcohol with an S
• Ethers- remove both H atoms from water and add two alkyl
groups in their place
• Phenols- replace the alkyl group from alcohols with an aromatic
ring
• *Functional groups are important because they determine the

“function” and properties of the molecule
 Alcohols and phenols are formed when a
hydrogen atom in a hydrocarbon, aliphatic
and aromatic respectively, is replaced by –OH
group.
 An alcohol contains one or more hydroxyl
(OH) group(s) directly attached to carbon
atom(s), of an aliphatic system (CH3OH) while
a phenol contains –OH group(s) directly
attached to carbon atom(s) of an aromatic
system (C6H5 OH).
 Thesubsitution of a hydrogen atom in a
hydrocarbon by an alkoxy or aryloxy group
(R–O/Ar–O) yields another class of compounds
known as ‘ethers’, for example, CH3OCH 3.
 Alcohols and phenols may be classified as
mono–, di–, tri- or polyhydric compounds
depending on whether they contain
one, two, three or many hydroxyl groups
respectively.
 Monohydric alcohols may be further classified
according to the hybridisation of the carbon
atom to which the hydroxyl group is
attached.
 (i) Compounds containing C sp 3− OH bond:
 Primary, secondary and tertiary alcohols :

 Allylic
alcohols: In these alcohols, the —OH
group is attached to a sp3hybridised carbon
next to the carbon-carbon double bond, that
is to an allylic carbon.
 Benzylicalcohols: In these alcohols, the —OH
group is attached to a sp3—hybridised carbon
atom next to an aromatic ring.
Alcohols
• Classified as primary, secondary and tertiary,
depending on whether the carbon attached to
the OH group is connected to 1, 2 or 3 other
carbon atoms.
• Polyhydroxy alcohols or polyols- molecules that

have more than 1 –OH group per molecule
Practice
• For the following, determine if they are primary,
secondary or tertiary alcohols:
• 1) CH3OH
• 2) CH3CH(OH)CH3
• 3)CH3CH(CH3)CH2OH
• 4) CH3C(CH3)2OH
IUPAC Naming of Alcohols
• 1) Select the longest continuous chain of carbon atoms
containing the hydroxyl (OH) group.
• 2) Number the carbons so that the lowest number carbon is
closest to the –OH group.
• 3) Name the parent alcohol by replacing the –e at the end of
the alkane name with an –ol.
• Designate the position of the –OH group by placing the
hyphenated carbon number in front of the parent alcohol
name.
• 4) Name each side chain or branch alphabetically, and use
numbers to designate its position off the main chain.
 Cyclicalcohols are named using the prefix
cyclo and considering the —OH group
attached to C–1.
Practice Naming and Drawing Alcohols
• 3)3,3-dimethyl-2-
hexanol
• 1)
• 4) 2-ethyl-1-pentanol
• 5) 2-bromo-4-ethyl-3-
• 2) heptanol
Common Names
• Alcohols have a lot of • 3) sec-butyl alcohol
common names so it is
important to recognize • 4) tert-butyl alcohol
these for safety in lab.
• Examples:
• 1) isopropyl alcohol
• 2) n-butyl alcohol
Physical properties of alcohols
• High boiling points • What part of their structure
compared to their alkanes accounts for their high boiling
points?
• Example:
Methane -162°C • Most are soluble in water.
Methanol 65°C Solubility becomes lessened
as the carbon chain
lengthens. WHY?
• Boiling points of alcohols
increases with the
• Predict the effect of dihydroxy
increasing number of
alcohols on solubility in water.
carbon atoms.
Making alcohols
• Generally, the reverse of the reactions that we have discussed
so far are the ones used to make alcohols.
• 1. Preparation from alkene compound
• 2. Alkaline hydrolysis of an alkyl halide (primary and secondary
alcohols only)
• 3. Alcohol by Grignard reagents
• 4. Preparation of alcohol by fermentation method
• 5. Catalytic reduction of aldehydes and ketones to make
primary and secondary alcohols. Alcohols from carbonyl
compounds.
• 6. Hydrolysis of esters
• These starting materials are expensive, so specific methods are
devised for specific alcohols.
2. Alkaline hydrolysis of an alkyl halide (primary
and secondary alcohols only)
• Alkyl halides react with aqueous spdium
hydroxide to form alcohols.
• R-X + NaOH  R-OH +NaX
H2O,Heat
CH3CH2-Br +NaOH  CH3CH2-OH + NaBr
 Alcohols are produced by the reaction of
Grignard reagents with aldehydes and
ketones.
 The first step of the reaction is the
nucleophilic addition of Grignard reagent to
the carbonyl group to form an adduct.
 Hydrolysis of the adduct yields an alcohol.
 5. By reduction of carboxylic acids and esters:
 Carboxylic acids are reduced to primary alcohols
in excellent yields by lithium aluminium
hydride, a strong reducing agent.
 However, LiAlH 4is an expensive reagent, and
therefore, used for preparing special chemicals
only.
 Commercially, acids are reduced to alcohols by
converting them to the esters , followed by their
reduction using hydrogen in the presence of
catalyst (catalytic hydrogenation).
 Diborane (BH 3) 2reacts with alkenes to give
trialkyl boranes as addition product. This is
oxidised to alcohol by hydrogen peroxide in the
presence of aqueous sodium hydroxide.
 The addition of borane to the double bond takes
place in such a manner that the boron atom gets
attached to the sp2 carbon carrying greater
number of hydrogen atoms.
 The alcohol so formed looks as if it has been
formed by the addition of water to the alkene in a
way opposite to the Markovnikov’s rule.
 In this reaction, alcohol is obtained in excellent
yield.
Hydroxyl Group Importance
• The –OH group is a gateway to many organic
reaction AND biochemical reactions as well.
• Example: Fats are degraded from alkanes to
alkenes…then hydrated to form an alcohol.
• Then, the alcohol is oxidized to form a ketone.
This process is necessary to use energy from fats.
• 10% of infants that die of SIDS cannot degrade
fats. It is hypothesized that this lack of ability to
use fat for energy may be a leading cause of SIDS.
Methanol
• Used to be made by heating wood in a non-oxygen
atmosphere…called destructive distillation.
• Early 1920s, began catalytic hydrogenation of carbon
monoxide…
• CO + 2 H2  CH3OH
• Requires catalysts, high temp and high pressure
• Can be made from coal as well, significant as a non-
petroleum source
• Is useful in conversion to manufacture of other
chemicals, polymers, etc.
Ethanol
• Aka: grain alcohol, ethyl alcohol, spirit
• Earliest and most widely known alcohol
• Prepared by fermentation of starch and sugar (for drinking)
• Pure ethanol is hygroscopic (water seeking), reaches
equilibrium at 95.6% ethanol.
• For industrial uses, it is made by acid-catalyzed addition of
water to ethylene.
• Uses: intermediate in manufacture of acetaldehyde, acetic
acid, ethyl acetate and diethyl ether
• Ethanol for industrial use is usually denatured by adding
small amounts of methanol and other chemicals that are
hard to remove and cannot be consumed.
Isopropyl alcohol (2-propanol)
• Synthesized from propene and water,
catalyzed by acid…2 propanol, not 1-propanol,
is produced because of Markovnikov’s rule.
• Low-cost alcohol, used in production of

acetone
• Principle component in rubbing alcohol
• Also used as an industrial solvent
Acidic/basic properties of aliphatic alcohols
• Similar to water… which • Small alcohols, like

is amphiprotic or methanol and ethanol,
amphoteric, which have same acid strength
means it can act as an as water. Larger acids
acid OR base in are weaker.
solution.
• In strong acids, it will
accept a proton and
become an oxonium
ion.
• Chemical Reactions of Alcohols
• 1. Reactions involving cleavage of O-H bond
• Reaction of Alcohol with active metals
• Reaction of Alcohol with acids
• Oxidation of alcohol
• 2.Reactions involving cleavage of C-O-H bond
• Reaction of alcohol with halogen acid
• Reaction of alcohol with phosphorous
tribhromide
• 3. Dehydration of alcohol
• 4. Reduction of alcohol
Reaction with alkali metals
• Just like water, alcohols react with group 1 metals to form an
anion and hydrogen gas.
• Example:
2 CH3CH2OH + 2 Na  2 Na+ + -OCH2CH3 + H2(g)
• The resulting anion is called an alkoxide ion (RO-) and is a

stronger base than hydroxide! These are used in industry
when a strong base is required.
• Primary>secondary>tertiary alcohols as far as reaction with
sodium and potassium. As molar mass of alcohol increases,
the reactivity decreases.
esterification
• Alcohols can react with carboxylic acids to
form esters and water.
• Important reaction…discussed more in later
chapter.
Oxidation of alcohols
• Carbon atoms exist in progressively higher stages of oxidation
in different functional groups:
Alkanes  Alcohols  aldehydes and ketones  carboxylic
acids  carbon dioxide
• Converting alcohols to aldehydes, ketones and carboxylic acids

allows scientists to make plastics, antibiotics, fertilizers, etc.
• Common oxidizing agents: oxygen from the air, KMnO4 in basic

solution, K2Cr2O7 in acidic solution.
Oxidation of alcohols
Dehydration of Alcohols
• 2 types:
• 1) Intramolecular dehydration of alcohols forms alkenes
• Sulfuric acid is used as well as heating up the reaction
• Water is removed from a single alcohol molecule
• Secondary and tertiary alcohols yield alkenes
• If there are two neighboring carbons that have hydrogens that
may leave with the OH group, follow Saytzeff’s rule.
• Saytzeff’s rule: If there is a choice of positions for the carbon-
carbon double bond, the preferred location is the one that
gives the more highly substituted alkene.
• Example: 2-butanol  2-butene + 1-butene
Dehydration of alcohols
• 2) Intermolecular dehydration of alcohols forms
ethers
• Two alcohol molecules come together, eliminate
water and form an ether…(called a condensation
reaction)
• ONLY works for primary alcohols!!!!
• Depends on temperature and number of
reactant molecules…lower temps and higher
concentration of alcohol yield ethers.
Practice
• 1) Determine the products when the following
react with potassium dichromate and
concentrated sulfuric acid:
• A) 1-propanol
• B) 2-propanol
• C) cyclohexanol
Oppenauer oxidation, named after Rupert Viktor Oppenauer, is a gentle
method for selectively oxidizing secondary alcohols to ketones. The reaction is
the opposite of Meerwein–Ponndorf–Verley reduction. The alcohol
is oxidized with aluminium isopropoxide in excess acetone.
Allyl alcohol
• Allyl alcohol (IUPAC name: prop-2-en-1-ol) is

an organic compound with the structural
formula CH2=CHCH2OH.
• Like many alcohols, it is a water-soluble, colourless
liquid.
• It is more toxic than typical small alcohols. Allyl alcohol
is used as a raw material for the production of glycerol,
but is also used as a precursor to many specialized
compounds such as flame-resistant materials, drying
oils, and plasticizers.
• Allyl alcohol is the smallest representative of
the allylic alcohols.
• In principle, allyl alcohol can be obtained
by dehydrogenation of propanol. In the laboratory, it has
been prepared by the reaction
of glycerol with oxalic or formic acids.
• From Propene: Propene is first converted in to allyl chloride
by high temperture chlorination. Allyl chloride is then
treated with aqueous NaOH at 150oC under pressure.
• CH2=CHCH3 + Cl2 → CH2=CHCH2Cl + HCl
• CH2=CHCH2Cl + NaOH → CH2=CHCH2OH + NaCl
• From Glycerol: Allyl alcohol may also be obtained by heating
glycerol with oxalic acids at 230oC.
Ethylene glycol (1,2-ethanediol)
• Simplest alcohol containing 2 –OH groups
• Prepared from ethylene, derived from petroleum
• Common uses:
• Preparation of synthetic fibers such as Dacron and Mylar
• Major ingredient in “permanent” antifreeze for vehicles
• As a solvent in paint and plastics industries
• In the formulation of printing ink and ballpoint pen ink
• EXTREMELY TOXIC IF INGESTED!!!!!
Glycerol (1,2,3-propanetriol)
• Also known as glycerine
• Syrupy liquid with a super sweet taste, about 0.6 times as sweet
as cane sugar.
• It’s a by-product of processing animal and vegetable fats to
make soap and other products.
• Made commercially from propene
• Uses:
• Raw material in manufacture of polymers and explosives
• An emollient in cosmetics
• Humectant in tobacco products
• Sweetener
The pinacol–pinacolone rearrangement is a method for converting a 1,2-diol to a
carbonyl compound in organic chemistry. The 1,2-rearrangement takes place
under acidic conditions. The name of the rearrangement reaction comes from
the rearrangement of pinacol to pinacolone.
• The Bouveault–Blanc reduction is a chemical reaction in which
an ester is reduced to primary alcohols using absolute
ethanol and sodium metal. It was first reported by Louis
Bouveault and Gustave Louis Blanc in 1903. Bouveault and Blanc
demonstrated the reduction of ethyl oleate and n-butyl oleate
to oleyl alcohol.

Alcohols

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Alcohols

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Alcohols, Phenols and Ethers

Dr. Parin Kanaiya

• Phenol- OH group off of an aromatic ring

• Ethers- R-O-R, where R is an alkyl group or aromatic ring

• Ketones- *no terminal H

• Carboxylic acid- R-COOH

• Amines- R-NH2, R2NH, or R3N

• *Functional groups are important because they determine the

 Primary, secondary and tertiary alcohols :

• Polyhydroxy alcohols or polyols- molecules that

• Low-cost alcohol, used in production of

• Similar to water… which • Small alcohols, like

• The resulting anion is called an alkoxide ion (RO-) and is a

• Converting alcohols to aldehydes, ketones and carboxylic acids

• Common oxidizing agents: oxygen from the air, KMnO4 in basic

• Allyl alcohol (IUPAC name: prop-2-en-1-ol) is

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