Alcohols and Phenols

Alcohols and phenols are organic compounds with at least one

hydroxyl group attached to a saturated or an aryl carbon, respectively.
Enols are a related third class of compounds, with the hydroxyl group
attached to a vinylic carbon.
• Almost everyone is aware that the alcohol present in alcoholic beverages is
ethanol (also called ethyl alcohol or grain alcohol). However, many people
do not realize that in its pure state, or in solutions of high concentration,
this substance is poisonous. In the laboratory one may find containers
labelled “absolute ethanol,” “95% ethanol” and “denatured ethanol.”
• A third commonly encountered alcohol, isopropyl alcohol (“rubbing
alcohol” or 2-propanol), is also toxic. It has the ability to kill germs
and has a temporary lubricating effect during the rubbing process.
Unlike methanol, 2-propanol is not absorbed through the skin;
therefore it poses less of a health hazard.
• The phenol solution was an effective antiseptic, killing bacteria, and
as a result, a patient’s chances of surviving surgery improved greatly.
Phenol itself was rather strong for these purposes—it burns healthy
tissue—and substitutes were eventually found.
ALcohos
• Molecules of alcohols contain one or more hydroxyl groups (OH
groups) substituted for hydrogen atoms along the carbon chain. The
structure of the simplest alcohol, methanol (methyl alcohol), can be
derived from that of methane by putting an OH in place of one of the
H’s:
• The name, too, is derived from the name methane by replacing the
final e with ol (for alcohol).
• The general formula for an alcohol may be written as R—OH, where
R represents the hydrocarbon (alkane) portion of the molecule and is
called an alkyl group.
• In methanol, R is the methyl group CH3.
• Methanol is also called wood alcohol because it can be obtained by heating
wood in the absence of air, a process called destructive distillation.
• Methanol vapor given off when the wood is heated can be condensed to a
liquid by cooling below its boiling point of 65°C.
• Bioling points are high for alcohols compared to their respective alkanes
because the OH group in one alcohol molecule can form strong hydrogen bonds
with an OH in another molecule.
• Methanol is an important industrial chemical—nearly 3 × 1010 L was produced
worldwide in 2003.
• Some was made by destructive distillation, but most was synthesized from
hydrogen and carbon monoxide:
2H2(g)+CO(g)⟶CH3OH(l)
• This reaction is carried out at pressures several hundred times normal
atmospheric pressure, using metal oxides as catalysts.
• Methanol is mainly used to make other compounds from which plastics are
manufactured, but some is consumed as fuel in jet engines and racing cars.
• Methanol is also a component of nonpermanent antifreeze and automobile
windshield-washer solvent.
ETHANOL
• The second member of the alcohol family is ethanol (ethyl alcohol)― the
substance we commonly call alcohol.
• Ethanol is also known as grain alcohol because it is obtained when grain or
sugar ferments. Fermentation refers to a chemical reaction which is speeded
up by enzymes and occurs in the absence of air. (Enzymes, catalysts which
occur naturally in yeasts and other living organisms
• Ethanol can also be synthesized by adding H 2O to ethene, obtained
during petroleum refining:

• Ethanol is used as a solvent, in some special fuels, in antifreeze, and to

manufacture a number of other chemicals, most familiar with it as a
component of alcoholic beverages.
• Alcohol’s intoxicating effects are well known, and it is a mild depressant.
Prolonged overuse can lead to liver damage. Methanol also produces
intoxication but is much more poisonous than ethanol—it can cause
blindness and death. Denatured alcohol is ethanol to which methanol or
some other poison has been added, making it unfit for human
consumption. Most of the ethanol not used in alcoholic beverages is
denatured because in that form its sale is taxed at a much lower rate.
Phenols
• Compounds in which a hydroxyl group is bonded to an aromatic ring
are called phenols.
• The chemical behavior of phenols is different in some respects from
that of the alcohols, so it is sensible to treat them as a similar but
characteristically distinct group.
• A corresponding difference in reactivity was observed.
• This distinction carries over when comparing alcohols and phenols, so
for all practical purposes substitution and/or elimination of the
phenolic hydroxyl group does not occur.
Aldehydes and ketones
• Ketones are compounds in which an oxygen atom is bonded to a
carbon atom, which is itself bonded to two or more carbon atoms.
• ketones can be named using either the common system or the IUPAC
system. In the common system, ketones names are created by naming
the groups attached to the carbonyl carbon and then adding the
word ketone. Following are several examples:
• The five IUPAC rules apply to ketones, with one exception: After
dropping the ‐e ending of the alkane name, you add ‐one for ketones
(rather than ‐al, which designates aldehydes).
• In the IUPAC system, aromatic ketones are considered benzene
substituted aliphatic ketones.
• Many aromatic compounds retain their common names in the IUPAC
system. Following are two such examples:
• Synthesis of Ketones
• Common preparation methods:
• the oxidation of secondary alcohols,
• the hydration of alkynes,
• the ozonolysis of alkenes,
• Friedel‐Crafts acylation,
• the use of lithium dialkylcuprates,
• and the use of a Grignard reagent.
• Oxidation of secondary alcohols
• The oxidation of secondary alcohols to ketones may be carried out
using strong oxidizing agents, because further oxidation of a ketone
occurs with great difficulty. Normal oxidizing agents include
potassium dichromate (K 2Cr 2O 7) and chromic acid (H 2CrO 4). The
conversion of 2‐propanol to 2‐propanone illustrates the oxidation of a
secondary alcohol.
• Hydration of alkynes
• The addition of water to an alkyne leads to the formation of an
unstable vinyl alcohol. These unstable materials undergo keto‐enol
tautomerization to form ketones. The hydration of propyne forms
2‐propanone, as the following figure illustrates.
• Ozonolysis of alkenes
• When one or both alkene carbons contain two alkyl groups,
ozonolysis generates one or two ketones. The ozonolysis of
1,2‐dimethyl propene produces both 2‐propanone (a ketone) and
ethanal (an aldehyde).
• Friedel-Crafts acylation
• Friedel‐Crafts acylations are used to prepare aromatic ketones. The
preparation of acetophenone from benzene and acetyl chloride is a
typical Friedel‐Crafts acylation.
• Lithium dialkylcuprates
• The addition of a lithium dialkylcuprate (Gilman reagent) to an acyl
chloride at low temperatures produces a ketone. This method
produces a good yield of acetophenone.
• Grignard reagents
• Hydrolysis of the salt formed by reacting a Grignard reagent with a
nitrile produces good ketone yields. For example, you can prepare
acetone by reacting the Grignard reagent methyl magnesium bromide
(CH 3MgBr) with methyl nitrile (CH 3C&tbond;N).
Reactions of Aldehydes and Ketones
• Aldehydes and ketones undergo a variety of reactions that lead to
many different products. The most common reactions are:
• nucleophilic addition reactions, which lead to the formation of
alcohols, alkenes, diols, cyanohydrins (RCH(OH)C & triple bond;N),
and imines R 2C & double bond;NR), to mention a few representative
examples.
Reactions of carbonyl groups
• The main reactions of the carbonyl group are nucleophilic additions
to the carbon‐oxygen double bond. As shown below, this addition
consists of adding a nucleophile and a hydrogen across the
carbon‐oxygen double bond.
• Due to differences in electronegativities, the carbonyl group is
polarized. The carbon atom has a partial positive charge, and the
oxygen atom has a partially negative charge.

• Aldehydes are usually more reactive toward nucleophilic substitutions

than ketones because of both steric and electronic effects. In
aldehydes, the relatively small hydrogen atom is attached to one side
of the carbonyl group, while a larger R group is affixed to the other
side. In ketones, however, R groups are attached to both sides of the
carbonyl group. Thus, steric hindrance is less in aldehydes than in
ketones.
• Electronically, aldehydes have only one R group to supply electrons
toward the partially positive carbonyl carbon, while ketones have two
electron‐supplying groups attached to the carbonyl carbon. The
greater amount of electrons being supplied to the carbonyl carbon,
the less the partial positive charge on this atom and the weaker it will
become as a nucleus.
• Aldehydes and ketones undergo a variety of reactions that lead
to many different products. The most common reactions are
nucleophilic addition reactions, which lead to the formation of
alcohols, alkenes, diols, cyanohydrins
(RCH(OH)C&tbond;N), and imines R 2C&dbond;NR), to
mention a few representative examples.
• Addition of water
• The addition of water to an aldehyde results in the formation of a
hydrate.
The formation of a hydrate proceeds via a nucleophilic addition
mechanism.
1. Water, acting as a nucleophile, is attracted to the partially positive
carbon of the carbonyl group,
generating an oxonium ion.
• he oxonium ion liberates a hydrogen ion that is picked up by the
oxygen anion in an acid‐base reaction.
• Small amounts of acids and bases catalyze this reaction. This occurs
because the addition of acid causes a protonation of the oxygen of
the carbonyl group, leading to the formation of a full positive charge
on the carbonyl carbon, making the carbon a good nucleus.
• Adding hydroxyl ions changes the nucleophile from water (a weak
nucleophile) to a hydroxide ion (a strong nucleophile). Ketones
usually do not form stable hydrates.
• addition consists of adding a nucleophile and a hydrogen across the
carbon‐oxygen double bond.
Addition of alcohol
• Reactions of aldehydes with alcohols produce either hemiacetals (a
functional group consisting of one —OH group and one —OR group
bonded to the same carbon) or acetals (a functional group consisting
of two —OR groups bonded to the same carbon), depending upon
conditions. Mixing the two reactants together produces the
hemiacetal. Mixing the two reactants with hydrochloric acid produces
an acetal. For example, the reaction of methanol with ethanal
produces the following results:
A nucleophilic substitution of an OH group for the double bond of
the carbonyl group forms
the hemiacetal through the following mechanism:
1. An unshared electron pair on the alcohol's oxygen atom
attacks the carbonyl group.

2. The loss of a hydrogen ion to the oxygen anion stabilizes the

oxonium ion formed in Step 1.
The addition of acid to the hemiacetal creates an acetal through the
following mechanism:
1. The proton produced by the dissociation of hydrochloric acid
protonates the alcohol molecule in an acid‐base reaction.

2. An unshared electron pair from the hydroxyl oxygen of the hemiacetal

removes a proton from the protonated alcohol.
• The oxonium ion is lost from the hemiacetal as a molecule of water.

• A second molecule of alcohol attacks the carbonyl carbon that is

forming the protonated acetal.
• The oxonium ion loses a proton to an alcohol molecule, liberating the
acetal.
Addition of hydrogen cyanide
• The addition of hydrogen cyanide to a carbonyl group of an aldehyde
or most ketones produces a cyanohydrin. Sterically hindered ketones,
however, don't undergo this reaction.
Addition of ylides (the Wittig reaction)
• The reaction of aldehydes or ketones with phosphorus ylides
produces alkenes of unambiguous double‐bond locations.
• Phosphorous ylides are prepared by reacting a phosphine with an
alkyl halide, followed by treatment with a base. Ylides have positive
and negative charges on adjacent atoms.
• The following illustration shows the preparation of 2‐methylbutene by
a Wittig reaction.
Addition of ammonia derivatives
• Aldehydes and ketones react with primary amines to form a class of
compounds called imines.

The mechanism for imine formation proceeds through the

following steps:
1. An unshared pair of electrons on the nitrogen of the amine is
attracted to the partial‐positive carbon of the carbonyl group.
• 2. A proton is transferred from the nitrogen to the oxygen anion.

• The hydroxy group is protonated to yield an oxonium ion, which easily

liberates a water molecule.
• 4. An unshared pair of electrons on the nitrogen migrate toward the
positive oxygen, causing the loss of a water molecule.

• 5. A proton from the positively charged nitrogen is transferred to

water, leading to the imine's formation.
• Imines of aldehydes are relatively stable while those of ketones are
unstable. Derivatives of imines that form stable compounds with
aldehydes and ketones include phenylhydrazine,
2,4‐dinitrophenylhydrazine, hydroxylamine, and semicarbazide.
• Oximes, 2,4‐dinitrophenylhydrazones, and semicarbazones are often
used in qualitative organic chemistry as derivatives for aldehydes and
ketones.
Oxidations of aldehydes and ketones
• Aldehydes can be oxidized to carboxylic acid with both mild and
strong oxidizing agents.
• However, ketones can be oxidized to various types of compounds only
by using extremely strong oxidizing agents.
• Typical oxidizing agents for aldehydes include either potassium
permanganate (KMnO 4) or potassium dichromate (K 2Cr 2O 7) in acid
solution and Tollens reagent. Peroxy acids, such as peroxybenzoic
acid:
• Baeyer‐Villiger oxidation is a ketone oxidation, and it requires the
extremely strong oxidizing agent peroxybenzoic acid. For example,
peroxybenzoic acid oxidizes phenyl methyl ketone to phenyl acetate
(an ester).
Aldol reactions
• In addition to nucleophilic additions, aldehydes and ketones show an
unusual acidity of hydrogen atoms attached to carbons alpha (adjacent)
to the carbonyl group. These hydrogens are referred to as α hydrogens,
and the carbon to which they are bonded is an α carbon. In ethanal, there
is one α carbon and three α hydrogens, while in acetone there are two α
carbons and six α hydrogens.
• Although weakly acidic (K a 10 −19 to 10 −20), α hydrogens can react with strong
bases to form anions. The unusual acidity of α hydrogens can be explained by
both the electron withdrawing ability of the carbony group and resonance in
the anion that forms. The electron withdrawing ability of a carbonyl group is
caused by the group's dipole nature, which results from the differences in
electronegativity between carbon and oxygen.
• The anion formed by the loss of an α hydrogen can be resonance stabilized
because of the mobility of the π electrons that are on the adjacent carbonyl
group.
• The resonance, which stabilizes the anion, creates two resonance structures
— an enol and a keto form. In most cases, the keto form is more stable.
Halogenation of ketones
• In the presence of a base, ketones with α hydrogens react to form α
haloketones.

• Likewise, when methyl ketones react with iodine in the presence of a

base, complete halogenation occurs.
Cyclizations via aldol condensation
• Internal aldol condensations (condensations where both carbonyl
groups are on the same chain) lead to ring formation.
The mechanism for cyclization via an aldol proceeds through an
enolate attack on the aldehyde carbonyl.
1. The hydroxy ion removes a hydrogen ion α to the ketone
carbonyl.

2. The enolate ion attacks the aldehyde carbonyl, closing the ring.
• 3. The alkoxide ion abstracts a proton from water in an acid‐base
reaction.

• 4. The base removes a hydrogen ion to form a resonance‐stabilized

molecule.
• The benzoin condensation
• Aromatic aldehydes form a condensation product when heated with a
cyanide ion dissolved in an alcohol‐water solution. This condensation
leads to the formation of α hydroxy ketones.

• Mechanism
• https://www.cliffsnotes.com/study-guides/chemistry/organic-
chemistry-ii/aldehydes-and-ketones/reactions-of-aldehydes-and-
ketones
• https://www.cliffsnotes.com/study-guides/chemistry/organic-
chemistry-ii/aldehydes-and-ketones/aldehydes
• https://www.cliffsnotes.com/study-guides/chemistry/organic-
chemistry-ii/aldehydes-and-ketones/synthesis-of-aldehydes
• synthesis
• https://chem.libretexts.org/?title=Bookshelves/Organic_Chemistry/S
upplemental_Modules_(Organic_Chemistry)/Aldehydes_and_Ketones
/Synthesis_of_Aldehydes_and_Ketones/Synthesis_of_Aldehydes_%2
6_Ketones
• Nomenclature
• https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Supple
mental_Modules_(Organic_Chemistry)/Aldehydes_and_Ketones/Nom
enclature_of_Aldehydes_and_Ketones
ETHERS
Nomenclature of Ethers
• Ethers are compounds having two alkyl or aryl groups
bonded to an oxygen atom, as in the formula R1–O–R2.
• The ether functional group does not have a
characteristic IUPAC nomenclature suffix, so it is
necessary to designate it as a substituent. To do so the
common alkoxy substituents are given names derived
from their alkyl component (below):
• Ethers can be named by naming each of the two
carbon groups as a separate word followed by a space
and the word ether. The -OR group can also be named
as a substituent using the group name, alkox
Alkyl Name Alkoxy Group Name
Group
CH3– Methyl CH3O– Methoxy

CH3CH2– Ethyl CH3CH2O– Ethoxy

(CH3)2CH Isopropyl (CH3)2CHO– Isopropo

– xy
(CH3)3C– tert-Butyl (CH3)3CO– tert-
Butoxy
C6H5– Phenyl C6H5O– Phenoxy
• CH3-CH2-O-CH3 is called ethyl methyl ether or methoxyethane.
• The smaller, shorter alkyl group becomes the alkoxy substituent.
• The larger, longer alkyl group side becomes the alkane base
(parent)name.
• Each alkyl group on each side of the oxygen is numbered separately.
The numbering priority is given to the carbon closest to the oxgen.
The alkoxy side (shorter side) has an "-oxy" ending with its
corresponding alkyl group.
For example, CH3CH2CH2CH2CH2-O-CH2CH2CH3 is 1-propoxypentane.
If there is cis or trans stereochemistry, the same rule still applies.
•CH3CH2OCH2CH3, diethyl ether (sometimes referred to as
just ether)
•CH3OCH2CH2OCH3, ethylene glycol dimethyl ether
(glyme).
• Try to draw structures for the following compounds:
• 2-pentyl 1-propyl ether
• 1-(2-propoxy)cyclopentene
Common names
• Simple ethers are given common names in which the alkyl groups
bonded to the oxygen are named in alphabetical order followed by
the word "ether". The top left example shows the common name in
blue under the IUPAC name. Many simple ethers are symmetrical, in
that the two alkyl substituents are the same. These are named as
"dialkyl ethers".
• anisole (try naming anisole by the other two convention
Heterocycles
• In cyclic ethers (heterocycles), one or more carbons are replaced with
oxygen. Often, it's called heteroatoms, when carbon is replaced by an
oxygen or any atom other than carbon or hydrogen.
• In this case, the stem is called the oxacycloalkane, where the prefix
"oxa-" is an indicator of the replacement of the carbon by an oxygen
in the ring. These compounds are numbered starting at the oxygen
and continues around the ring. For example,
• Oxirane
• 1,2-epoxyethane, ethylene oxide, dimethylene oxide,
oxacyclopropane
• Furan(tetrahydrofuran, oxacyclopentane, 1,4-epoxybutane,
tetramethylene oxide)
• Dioxane(1,4-dioxacyclohexane)
• Try to draw structures for the following compounds-
• 3-bromoanisole
• 2-methyloxirane
• 3-ethylfuran
• If a substituent is an alcohol, the alcohol has higher priority.
• However, if a substituent is a halide, ether has higher priority.
• If there is both an alcohol group and a halide, alcohol has higher
priority.
• The numbering begins with the end that is closest to the higher
priority substituent.
• There are ethers that are contain multiple ether groups that are called
cyclic polyethers or crown ethers. These are also named using the
IUPAC system.
• Sulfides
• Sulfur analogs of ethers (R–S–R') are called sulfides, e.g., (CH3)3C–S–
CH3 is tert-butyl methyl sulfide. Sulfides are chemically more reactive
than ethers, reflecting the greater nucleophilicity of sulfur relative to
oxygen.
• Problems

1. diethyl ether;
2. 2-ethoxy-2-methyl-1-propane;
3. cis-1-ethoxy-2-methoxycyclopentane;
4. 1-ethoxy-1-methylcyclohexane;
5. oxacyclopropane; 6. 2,2-Dimethyloxacyclopropane
• Synthesis of Ethers
• There are two primary reactions to generate ethers:
• Either by Dehydration of Alcohols or
• By the Williamson Synthesis.
• Acyclic ethers can be prepared using Williamson's synthesis, which
involves reacting an alkoxide with a haloalkane.
• Alkoxides are created by reacting an alcohol with metallic sodium or
potassium, or a metal hydride, such as sodium hydride (NaH).
• To minimize steric hindrance and achieve a good yield, the haloalkane
must be a primary haloalkane.
• This is because the mechanism is SN2, where the oxygen atom does a
backside attack on the carbon atom with the halogen atom, causing
the halogen atom to leave with its electrons.
• Dehydration of Alcohols to Make Ethers
• Acid-catalyzed dehydration of small 1º-alcohols constitutes a
specialized method of preparing symmetrical ethers.
• As shown in the following two equations, the success of this
procedure depends on the temperature. At 110º to 130 ºC an SN2
reaction of the alcohol conjugate acid leads to an ether product. At
higher temperatures (over 150 ºC) an E2 elimination takes place.

2CH3CH2−OH+H2SO4→CH3CH2−O−CH2CH3+H2O(1)
130 C

CH3CH2−OH+H2SO4→CH2=CH2+H2O(2)
150 C
• In this reaction alcohol has to be used in excess and the temperature
has to be maintained around 413 K. If alcohol is not used in excess or
the temperature is higher, the alcohol will preferably undergo
dehydration to yield alkene.

• The dehydration of secondary and tertiary alcohols to get

corresponding ethers is unsuccessful as alkenes are formed easily in
these reactions.
• Williamson Ether Synthesis
• The Williamson Ether synthesis is the easiest, and perhaps the fastest,
way to create ethers.
• Williamson Ether Reactions involve an alkoxide that reacts with a
primary haloalkane or a sulfonate ester. Alkoxides consist of the
conjugate base of an alcohol and are comprised of an R group bonded
to an oxygen atom. They are often written as RO–, where R is the
organic substituent.
Sn2 reactions are characterized by the inversion of
stereochemistry at the site of the leaving group. Williamson
Ether synthesis is not an exception to this rule and the
reaction is set in motion by the backside attack of the
nucleophile. This requires that the nucleophile and the
electrophile are in anti-configuration.
• Ethers can be synthesized in standard SN2 conditions by coupling an
alkoxide with a haloalkane/sulfonate ester. The alcohol that supplies
the electron rich alkoxide can be used as the solvent, as well as
dimethyl sulfoxide (DMSO) or hexamethylphosphoric triamide
(HMPA).
• Intramolecular Williamson Ethers
• You can also use the Williamson synthesis to produce cyclic ethers.
You need a molecule that has a hydroxyl group on one carbon and a
halogen atom attached to another carbon. This molecule will then
undergo an SN2 reaction with itself, creating a cyclic ether and a
halogen anion. Another way of deriving ethers is by converting halo
alcohols into cyclic ethers. This reaction is prompted by the
deprotonation of the hydrogen attached to the oxygen by an OH-
anion. This leads to the departure of the halogen, forming a cyclic
ether and halogen radical.
• Another factor in determining whether a cyclic ether will be formed is
ring size.
• Three-membered rings along with five membered rings form the
fastest, followed by six, four, seven, and lastly eight membered rings.
The relative speeds of ring formation are influenced by both enthalpic
and entropic contributions.
• Ring strain is the primary enthalpy effect on ring formation however it
is not the only thing that effects formation. If this were the case, rings
with the most strain would be formed the slowest. The reason why
this is not the trend for ring formation is because of entropy
conditions. Smaller rings have less entropy making them more
favorable because of less ordering of the molecule.
• However, the reason why ring formation does not follow this trend is
because of another factor called the proximity effect. The proximity
effect states that the nucleophilic part of the carbon chain is so close
to the electrophilic carbon that a small amount of ring strain is
evident in the ground state of the molecule. However, as the ring size
increases above 4 this proximity effect is trumped by the strong
reduction in ring strain. Five and six membered rings have less strain
allowing them to form faster. However, as rings get larger (8,9,10 etc.
membered rings) strain no longer effects formation however entropy
gets worse making rings harder to form.
• https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Supplemental
_Modules_(Organic_Chemistry)/Ethers/Properties_of_Ethers/Physical_Pro
perties_of_Ether
• https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Supplemental
_Modules_(Organic_Chemistry)/Ethers/Reactivity_of_Ethers
• https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Supplemental
_Modules_(Organic_Chemistry)/Ethers/Reactivity_of_Ethers/Reactions_of
_Epoxides
• https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Supplemental
_Modules_(Organic_Chemistry)/Ethers/Reactivity_of_Ethers/Cleaving_Eth
ers
• https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Supplemental
_Modules_(Organic_Chemistry)/Ethers/Reactivity_of_Ethers/Reactions_of
_Epoxides
Chemical properties of
Alcohols
Chemical Properties of Alcohols
• Alcohols are some of the most important molecules in organic
chemistry. They can be prepared from and converted into many
different types of compounds.
• Alcohols contain the hydroxy functional group (-OH), bonded to a
carbon atom of an alkyl or substituted alkyl group.
• The functional group of an alcohol is the hydroxyl group, –OH. Unlike
the alkyl halides, this group has two reactive covalent bonds, the C–O
bond and the O–H bond.
• The electronegativity of oxygen is substantially greater than that of
carbon and hydrogen. Consequently, the covalent bonds of this
functional group are polarized so that oxygen is electron rich and
both carbon and hydrogen are electrophilic, as shown in the figure
below.
• Indeed, the dipolar nature of the O–H bond is such that alcohols are
much stronger acids than alkanes (by roughly 1030 times), and nearly
that much stronger than ethers.
• The most reactive site in an alcohol molecule is the hydroxyl group,
despite the fact that the O–H bond strength is significantly greater
than that of the C–C, C–H and C–O bonds, demonstrating again the
difference between thermodynamic and chemical stability.
Reactivity of Alcohols
• Dehydrating Alcohols to Make Alkenes
• This is a simple method of making gaseous alkenes such as ethene. If
ethanol vapor is passed over heated aluminum oxide powder, the
ethanol is essentially cracked to yield ethene and water vapor.

• The dehydration of ethanol to yield ethene

• In this process, ethanol is heated with an excess of concentrated
sulfuric acid at a temperature of 170°C. The gases produced are
passed through a sodium hydroxide solution to remove the carbon
dioxide and sulfur dioxide produced from side reactions. The ethene is
collected over water
• Elimination Reactions of Alcohols
• The elimination of water from an alcohol is called dehydration.
• Recalling that water is a much better leaving group than hydroxide
ion, it is sensible to use acid-catalysis rather than base-catalysis in
such reactions.
• Four examples of this useful technique are shown below. Note that
hydrohalic acids (HX) are not normally used as catalysts because their
conjugate bases are good nucleophiles and may create substitution
products. The conjugate bases of sulfuric and phosphoric acids are
not good nucleophiles, and do not participate in substitution under
typical conditions.
• Hydroxyl Group Substitution
• Nucleophilic Substitution of the Hydroxyl Group
• The chemical behavior of alkyl halides can be used as a reference in
discovering analogous substitution and elimination reactions of alcohols.
The chief difference, of course, is a change in the leaving anion from halide
to hydroxide. Because oxygen is slightly more electronegative than
chlorine (3.5 vs. 2.8 on the Pauling scale), the C-O bond is expected to be
more polar than a C-Cl bond. Furthermore, an independent measure of the
electrophilic characteristics of carbon atoms from their NMR chemical
shifts (both 13C and alpha protons) indicates that oxygen and chlorine
substituents exert a similar electron-withdrawing influence when bonded
to sp3 hybridized carbon atoms. Despite this promising background
evidence, alcohols do not undergo the same SN2 reactions commonly
observed with alkyl halides. For example, the rapid SN2 reaction of 1-
bromobutane with sodium cyanide, shown below, has no parallel when 1-
butanol is treated with sodium cyanide. In fact, ethyl alcohol is often used
as a solvent for alkyl halide substitution reactions such as this.
The key factor here is the stability of the leaving anion (bromide vs.
hydroxide). HBr is a much stronger acid than water (by more than 18
orders of magnitude), and this difference is reflected in reactions that
generate their respective conjugate bases. The weaker base, bromide,
is more stable, and its release in a substitution or elimination reaction
is much more favorable than that of hydroxide ion, a stronger and less
stable base.
• A clear step toward improving the reactivity of alcohols in SN2 reactions
would be to modify the –OH functional group in a way that improves its
stability as a leaving anion. One such modification is to conduct the
substitution reaction in a strong acid, converting –OH to –OH2(+). Because
the hydronium ion (H3O(+)) is a much stronger acid than water, its conjugate
base (H2O) is a better leaving group than hydroxide ion. The only problem
with this strategy is that many nucleophiles, including cyanide, are
deactivated by protonation in strong acids, effectively removing the
nucleophilic co-reactant required for the substitution. The strong acids HCl,
HBr and HI are not subject to this difficulty because their conjugate bases
are good nucleophiles and are even weaker bases than alcohols. The
following equations illustrate some substitution reactions of alcohols that
may be affected by these acids. As with alkyl halides, the nucleophilic
substitution of 1º-alcohols proceeds by an SN2 mechanism, whereas 3º-
alcohols react by an SN1 mechanism. Reactions of 2º-alcohols may occur by
both mechanisms and often produce some rearranged products. The
numbers in parentheses next to the mineral acid formulas represent the
weight percentage of a concentrated aqueous solution, the form in which
these acids are normally used.
• Although these reactions are sometimes referred to as "acid-
catalyzed," this is not strictly correct. In the overall transformation, a
strong HX acid is converted to water, a very weak acid, so at least a
stoichiometric quantity of HX is required for a complete conversion of
alcohol to alkyl halide.
• Electrophilic Substitution at Oxygen
• ecause of its enhanced acidity, the hydrogen atom of a hydroxyl group
is easily replaced by other substituents. A simple example is the facile
reaction of simple alcohols with sodium (and sodium hydride), as
described in the first equation below. Another such substitution
reaction is the isotopic exchange that occurs when mixing an alcohol
with deuterium oxide (heavy water). This exchange, which is catalyzed
by acid or base, is rapid under normal conditions because it is difficult
to avoid traces of these catalysts in most experimental systems.
• The mechanism by which these substitution reactions proceed is
straightforward. The oxygen atom of an alcohol is nucleophilic;
therefore, it is prone to attack by electrophiles. The resulting "onium"
intermediate then loses a proton to a base, forming the substitution
product. If a strong electrophile is not present, then the
nucleophilicity of the oxygen may be enhanced by conversion to its
conjugate base (an alkoxide). This powerful nucleophile then attacks
the weak electrophile. These two variations of the substitution
mechanism are illustrated in the following diagram.
• The preparation of tert-butyl hypochlorite from tert-butyl alcohol is
an example of electrophilic halogenation of oxygen, but this reaction
is restricted to 3º alcohols; 1º and 2º hypochlorites lose HCl,
forming aldehydes and ketones. In the following equation the
electrophile may be regarded as Cl(+).
• Oxidizing the different types of alcohols
• Primary alcohols
• Primary alcohols can be oxidized to either aldehydes or carboxylic
acids, depending on the reaction conditions. In the case of the
formation of carboxylic acids, the alcohol is first oxidized to an
aldehyde, which is then oxidized further to the acid.
• Using these reactions as a test for the different types of alcohols
First, the presence of an alcohol must be confirmed by testing for the -
OH group. The liquid would need to be verified as neutral, free of water
and that it reacted with solid phosphorus(V) chloride to produce a
burst of acidic steamy hydrogen chloride fumes. A few drops of the
alcohol would be added to a test tube containing potassium
dichromate(VI) solution acidified with dilute sulfuric acid. The tube
would be warmed in a hot water bath.
• Determining the tertiary alcohol
• In the case of a primary or secondary alcohol, the orange solution
turns green. With a tertiary alcohol, there is no color change. After
heating, the following colors are observed: