ALCOHOLS AND PHENOLS ALCOHOLS AND PHENOLS

CLASS XII CLASS XII

Introduction
Alcohols are substituted hydrocarbon molecules containing one or more -OH
group bound to a saturated sp
3
hybridized carbon atom. The more common
alcohols are derived from saturated hydrocarbons or alkanes that contain
hydroxyl groups linked to alkyl radicals. They may be regarded as being
derived from them by replacing one or more hydrogen atoms by hydroxyl
groups, even though they are not prepared in this way. The hydroxyl group
is the functional group that characterizes the alcohols.
However, alcohols differ from bases such as NaOH or KOH in that they do not
furnish hydroxide ion (OH
-
) in water nor do they have other properties of
bases. This is because the alcohols are covalent compounds while the
inorganic bases are ionic compounds.
Phenols are an important class of aromatic compounds that are hydroxyl
derivatives of aromatic hydrocarbons. The hydroxyl group is directly linked
(and not as a part of a side chain) to the carbon atoms of the benzene rings.
Interestingly, it was the first compound that was to be specifically employed
as an antiseptic (Lister, 1867) under the name of carbolic acid. In solution,
phenol acts as an antiseptic (0.2% solution) or a disinfectant (1% solution).
Ethers are hydrocarbon molecules with -C-O-C- as the functional group.
Here, oxygen is bound to two organic (alkyl) groups i.e., R-O-R' where R and
R' may be same or different alkyl or aryl groups or one of them may be an
alkyl group and the other aryl group. They can be straight or branched
chains, cyclic rings, saturated and unsaturated and aromatic compounds.
All of these molecules are widely represented in nature and are important in
industry and as pharmaceuticals. For instance, ethanol is used as a solvent,
as a fuel (can be mixed with petrol), used to make 'ethyl esters' and is the
'potent' chemical present in alcoholic drinks. Ordinary spirit used for polishing
wood contains ethanol the hydroxyl compound. Most of the biomolecules of
nature like cellulose (used to make paper and cloth), lactose in milk, glucose,
sucrose and fructose found in vegetables and fruits contain large amounts of
-OH groups. Their use is so widespread that many have common names. For
example:

Some of the large variety of plastic materials that we see around is derived
from phenolic resins and plastics. Ethers are widely used as solvents both in
the laboratory and industry because of their almost inert nature and good
dissolving power. Life would have been different without these compounds.


Classification
Alcohols are compounds of the general formula ROH, where R is any alkyl or
substituted alkyl group. The group may be open-chain or cyclic; it may
contain a double bond, a halogen, an aromatic ring, or additional hydroxyl
groups. Based on these possibilities all alcohols are divided into two broad
categories called aliphatic alcohols and aromatic alcohols.
Aliphatic Alcohols
The aliphatic alcohols are a homologous series of compounds containing one
or more hydroxyl groups [-OH] attached to an alkyl radical.
The aliphatic alcohols can be regarded as derivatives of alkanes in which one
or more hydrogen atoms have been replaced by hydroxyl groups [-OH]. The
general formula of saturated aliphatic alcohols is C
n
H
2n+1
OH, where n=1,2,3,
etc. The saturated carbon chain is often designated by the symbol R, so that
ROH can represent any alcohol in the homologous series.
Methanol and ethanol are the first two members of the series.
Methanol: CH
3
-OH
Ethanol:
The next two members of the series are propanol and butanol, whose names
also end in ...ol, which means the molecule is an alcohol.
Propanol: CH
3
-CH
2
-CH
2
-OH
Butanol:
Other examples of aliphatic alcohols with a closed ring cyclclic structure are,

Compounds of this type with one hydroxyl group per molecule are known as
monohydric alcohols.
Aromatic Alcohols
Any of the compounds containing the hydroxyl group in a side chain to a
benzene ring are aromatic alcohols. An aromatic alcohol where a methanol is
bonded to a benzene is benzyl alcohol.

Mono, Di, Tri or Polyhydric Compounds
Aliphatic and aromatic alcohols and phenols are classified as monohydric,
dihydric, trihydric and polyhydric compounds according to the number of
hydroxyl groups in their molecules. Monohydric alcohols have one hydroxyl
group per molecule, dihydric alcohols have two hydroxyl groups and
polyhydric alcohols contain three or many hydroxyl groups in their structures
as shown below:


Monohydric alcohols are classified according to the hybridization of the carbon
atom i.e., sp
3
or sp
2
to which the hydroxyl group is attached.
Compounds Containing sp
3
C-OH Bond
The sp
3
hybridized monohydric alcohols are classified into three categories as
primary (1), secondary (2) and tertiary (3) in the same manner as alkyl
halides.

This classification is important because the type of reaction an alcohol
undergoes depends on what is attached to its carbon. If the carbon to which
the -OH group attached also binds to one carbon atom, the alcohol is
designated primary (1). If two carbons are attached to that carbon, the
alcohol is secondary (2) and if three carbons are attached the alcohol is
tertiary (3). This terminology refers to alkyl substitution of the carbon atom
bearing the hydroxyl group (colored blue).

Allylic Alcohols
When the hydroxyl group is attached next to the double bonded carbon atom
(C=C) then such compounds are called allylic alcohols. The carbon atom to
which the hydroxyl group is attached is sp
3
hybridized in such compounds.

Allylic alcohols can also be primary, secondary and tertiary as follows:

Benzylic Alcohols
In aromatic compounds when the hydroxyl group is attached to a carbon
atom bonded to a benzene ring benzylic alcohols result. Similar to the allylic
alcohols, the carbon atom to which the hydroxyl group is attached is sp
3
hybridized in such compounds.

Compounds Containing sp
2
C-OH Bond
Vinylic Alcohols
Sometimes the hydroxyl group is directly attached to double bonded carbon
atoms (C=C). In such compounds the carbon atom to which the -OH group is
attached is sp
2
hybridized and they have special names like vinylic alcohols.
The replacement of hydroxyl group for these types of hydrogen atoms results
in alkyl alcohols having the corresponding common names.

Aryl Alcohols or Phenols
Aryl alcohols or phenols are hydoxyl derivatives of aromatic hydrocarbons,
which are derived by replacing hydrogen atom attached to sp
2
hybridized
carbon atom(s) of the benzene ring by a hydroxyl group. For example,

Ethers
Like alcohols ethers are divided into two broad categories called aliphatic
ethers and aromatic ethers.
Aliphatic Ethers
Aliphatic ethers are those in which R and R' are both alkyl groups. For
example,

Ethers in which the two alkyl groups R and R' are identical they are simple
ethers or symmetrical ethers e.g., CH
3
.O.CH
3
.
Aromatic Ethers
Aromatic ethers are those in which either one or both R and R' are aryl
groups. For example,


Aromatic ethers are further subdivided into phenolic ethers and diaryl ethers.
Phenolic Ethers
Ethers in which one of the groups is aryl while the other group is alkyl are
called phenolic ethers or alkyl aryl ethers. Examples are:

Diaryl Ethers
In diaryl ethers both the groups are aryl groups. For example:
C
6
H
5
-O-C
6
H
5

Diphenyl ether

Both aliphatic and aromatic ethers are also classified as symmetrical and
unsymmetrical ethers.
Symmetrical Ethers
Many simple ethers are symmetrical, in that the two alkyl substituents are the
same CH
3
.O.CH
3
. These are named as 'dialkyl ethers'. Examples are: CH
3
-
CH
2
-O-CH
2
-CH
3
, diethyl ether (sometimes referred to as ether), and CH
3
-O-
CH
2
-CH
2
-O-CH
3
, ethylene glycol dimethyl ether (glyme).
Unsymmetrical Ethers
If the ethers are different they are mixed ethers e.g., CH
3
.O.CH
2
H
5
and are
called unsymmetrical ethers.



Nomenclature
Alcohols
Since the vast majority of alcohols have their -OH groups attached to
alkanes, their names are most easily generated by using those alkanes as
their base. Alcohols have the highest priority of the groups so if an -OH is
present it's an alcohol.
Common System
The common name for alcohols is generated simply by taking the name of
the alkane chain and adding alcohol to the end. This is how common names
are usually generated. The isopropyl alcohol molecule provides an example.
In CH
3
-CHCl-CH
3
if one replaces the Cl in isopropyl chloride with -OH
isopropyl alcohol is obtained.
For monofunctional alcohols, this common system consists of naming the
alkyl group followed by the word alcohol.

One should also know the common names of a few popular alcohols:

IUPAC System
Alcohols are given IUPAC names based on the alcohol being derivatives of
the parent alkane. This is common for the carbon-carbon double and triple
bonds which have the respective suffixes ene and yne. In the IUPAC system
of nomenclature, functional groups are normally designated in one of two
ways: the presence of the function may be indicated by a characteristic suffix
and a location number.
Alcohols are usually named by the first procedure and are designated by an
ol suffix, as in ethanol, CH
3
CH
2
OH (note that a locator number is not needed
on a two-carbon chain). On longer chains the location of the hydroxyl group
determines chain numbering.

A stepwise process for naming alcohols is as follows:
Find the longest carbon chain which includes the carbon to which the -
OH group(s) is attached. Select this as parent chain containing the hydoxyl
group. Name the molecule as if it were an alkane, replacing -e with -ol.

With complex alcohols containing multiple functional groups, the longest
chain will be the hydroxy-containing chain with the largest number of
principle functional groups such as alcohol, alkene etc., but not halide,
sulfide, ether etc.
Number the longest chain from the hydroxyl group end. Start counting
from the end closest to the -OH group.

Place the -OH location prior to that chain name using numbers (if
required to remove ambiguity).

When more than one -OH functionality is present i.e., polyhydric
alcohols retain the 'e' of alkane and use the endings '-diol', '-triol,' etc., for
two or three hydroxy groups in the molecule.

Number all the substituents by position on the chain. The positions of
the substituent alkyl (or other) groups are denoted by using the lowest
possible numbers for the associated carbon atoms in the main chain. If
there is more than one 'type' of substituent e.g., methyl.... and ethyl..
etc., they are written out in alphabetical order in composing the final name
(di, tri are ignored in using this rule).
Many functional groups have a characteristic suffix designator, and only one
such suffix (other than "ene" and "yne") may be used in a name. When the
hydroxyl functional group is present together with a function of higher
nomenclature priority, it must be cited and located by the prefix hydroxy
along with an appropriate number. For example, lactic acid has the IUPAC
name 2-hydroxypropanoic acid.
Cycloalcohols (Cycloalkanols) are named on the basis of the number of
carbon atoms in the ring (minimum 3) and the prefix 'cyclo' and the suffix
'ol'. The OH attached to the carbon is numbered 1. The prefix alkane name
e.g. 'prop' has an 'a' added but leaves out the end 'ne' if more than one OH
group e.g., in mono-hydroxy alcohols it is propan... and in diols/triols etc., it
is propane.
Other examples of IUPAC nomenclature are shown below, together with the
common names often used for some of the simpler compounds.
Common Name IUPAC Name Structure
methanol methanol

ethanol ethanol

n-propanol 1-propanol

isopropanol 2-propanol

n-butanol 1-butanol

sec-butanol 2-butanol

isobutanol 2-methyl-1-propanol

tert-butanol 2-methyl-2-propanol

cyclohexanol cyclohexanol

octanol or caprylic
alcohol
2-octanol
ethylene glycol ethane-1,2-diol

glycerol propane-1,2,3-triol

menthol 5-methyl-2-isopropyl
cyclohexanol

D-glucose 2,3,4,5,6-
pentahydroxyhexanal

Phenols
The general formula for monohydric phenols is ArOH, Ar = phenyl,
substituted phenyl, or any other aryl group.
When the -OH is attached directly to a benzene ring the molecule is called a
phenol.

Common System
All substituted phenols are named as derivatives of phenol. The substituted
compounds are named in terms of ortho, meta and para in the common
system.

IUPAC System In the IUPAC system all substituted phenols are named as
derivatives of phenol. The position of the substituent with respect to hydroxyl
group is indicated by Arabic numerals with the carbon carrying the OH group
being numbered 1 e.g., ortho (1,2- disubstituted), meta (1,3-disubstituted)
and para (1,4-disubstituted).

If there is a 'higher ranking' functional group in the molecule, the substituent
OH is called by the prefix 'hydroxy'. Example:

In the IUPAC name the di, tri and poly hydroxy phenols are named as
hydroxyl derivatives of benzene.

Ethers
Ethers are compounds having two alkyl or aryl groups bonded to an oxygen
atom, as in the formula R
1
-O-R
2
.
Common System
In simple ethers containing no other functional groups, name the two alky or
aryl groups linked to the oxygen atom in alphabetical order and add the word
ether, e.g., CH
3
CH
2
-O-CH
2
CH
2
CH
3
(Ethyl propyl ether)

In case of symmetrical ether the prefix 'di' is used before the name of the
alkyl or aryl group.

IUPAC System
The ether functional group does not have a characteristic IUPAC
nomenclature suffix, so it is necessary to designate it as a substituent. The
ether functional group is named as an alkoxy substituent on the parent
compound. Ethers are named on the basis of the longest carbon chain with
the O-R or alkoxy group. The common alkoxy substituents are given names
derived from their alkyl component, e.g. methoxy CH
3
O- or ethoxy CH
3
CH
2
O-
etc., treated as a substituent group.
Alkyl Group Name Alkoxy Group Name
CH
3
- Methyl CH
3
O- Methoxy
CH
3
CH
2
- Ethyl CH
3
CH
2
O- Ethoxy
(CH
3
)
2
CH- Isopropyl (CH
3
)
2
CHO- Isopropoxy
(CH
3
)
3
C- tert-Butyl (CH
3
)
3
CO- tert-Butoxy
C
6
H
5
- Phenyl C
6
H
5
O- Phenoxy


The parent compound is the longest carbon chain if both are alkyl groups;
but with any primary functional group (alkene, alcohol, aldehyde, acid etc.)
ethers become substituent groups on that primary chain, for example:
CH
3
CH=CHCH
2
OCH
2
CH
3
is 1-Ethoxy-2-butene.



Structure of Functional Groups
In alcohols, phenols and ethers the carbon-oxygen bond is the most powerful
bond that makes their chemistry different. A carbon-oxygen bond is a
covalent bond () between sp
3
hybridized carbon and oxygen atoms. Here,
oxygen with its 6 valence electrons prefers to share two electrons by bonding
with carbon, leaving the remaining 4 non-bonding electrons as 2 lone pairs.
Alcohols
In alcohols the simplest representatives of the C-O bond can be thought of
organic derivatives of water. They also contain hydroxyl (OH) group as the
functional group attached to an alkyl group.
Bond Length
The bond lengths for C-O bonds and O-H bonds are in the range of 143 and
96 picometer respectively, which is shorter than that of C-C or C-H bonds.
The shortening of C-O and O-H is due to increasing electronegativity of O
(Electronegativity C vs O = 2.55 : 3.44).

Bond Poarity
An alcohol molecule is dipolar in nature with the oxygen carrying a partial
negative charge (
-
) and carbon and hydrogen each carrying a partial positive
charge (
+
). For example in the case of methanol, the charge separation is as
follows:

This is supported by the face that the methanol has a dipole moment of 1.71
D.
Bond Strength
The C-O bond strength is larger compared to C-N or C-C, for example, it is
91 kcal/mol (298 K) in methanol (87 in methyl amine and 88 in ethane).
Bond Angle
All the C-C-H, H-C-H, C-O-H, C-C-O or H-C-O bond angles are approximately
109
o
in all the non-cyclic alcohols or alkanols. This is slightly less than the
tetrahedral angle (109 28) due to the repulsion between the two lone
electron pairs of oxygen. As the CO bond is strongly polarized towards
oxygen many alcohols are water soluble.

Phenols
In phenols the hydroxyl (OH) functional group attached to an aryl group.

Phenol had a lower dipole moment of 1.54 D than methnaol. Shortened
single bonds are found in phenols (136 pm). This is due to partial double
bond character of the sp
2
hybridized carbon of the benzene ring, and
conjugation of unshared electron pair of oxygen with the aromatic ring.

Ethers
In ethers, the oxygen atom forms a bridge between two alkyl groups by
forming two single bonds each with the alkyl C atoms just like the one in
water where the oxygen forms a bridge between the two hydrogen atoms.
The structure of diethyl ether (Ethoxy ethane) is shown below.

Two of the four sp
3
orbitals of the oxygen atom overlap with sp
3
orbitals of
the alkyl groups to form two sp
3
-sp
3
() bonds with the C-O bond length of
141 pm almost equal to that in alcohols. The remaining two sp
3
orbitals of
oxygen contain a lone pair of electrons each.
The four electron pairs, i.e., the two bond pairs and two lone pairs of
electrons on oxygen are arranged approximately in a tetrahedral
arrangement. The bond angle of 110
o
is slightly greater than the tetrahedral
angle due to the repulsive interaction between the two bulky (-R) groups.


Alcohols and Phenols
As mentioned earlier, alcohols refer to a class of chemical compounds
consisting of atoms of carbon, hydrogen and oxygen. A variety of alcohols
exist and they contain at least one hydroxyl group (OH
-
) as the functional
group in them. The oxygen atom of the hydroxyl group is bonded to the
carbon atom.
Although alcohols are mostly soluble in water they do not get ionized by
water i.e., no hydroxide ion (OH
-
) is formed. Hence, alcohols have the
characteristic property of the alcoholic group.
For example, in alcohols like ethanol and phenol, -OH is the functional group.

Preparation of Alcohols
Hydration of Alkenes:
In an aqueous acid solution, alkenes add water across the double () bond
thereby saturating the molecule producing an alcohol. The reaction is region
selective since only the more highly substituted alcohol is produced
(Markovnikov's rule).

In accordance with Markovnikov's rule reaction with water and sulphuric acid
as catalyst gives the predicted product. In these reactions molecular
rearrangement often occurs which indicates that the reaction involves a
carbocation intermediate. The reason why Markovnikov's Rule always results
in the more substituted alcohol can be understood if one looks at the reaction
mechanism proposed for this reaction.
In the first step the hydrogen ion from the acid catalysts attaches itself to
the alkene at the double bond to the carbon which will result in the most
stable carbocation.

In the next step the carbocation attaches itself to an oxygen atom of a water
molecule with the aid of a lone pair making the oxygen atom positively
charged oxonium ion.

In the final step, a water molecule pulls a hydrogen ion off the oxygen atom
to produce the final alcohol.

The obvious synthetic problem with this reaction is that it may undergo
molecular rearrangement thereby producing more than one alcohol. In
addition it always produces the more substituted alcohol.
Hydroboration-oxidation
Alkenes react with diborane (B
2
H
6
) to form trialkylboranes, which upon
subsequent treatment with alkaline H
2
O
2
gives alcohol.

The principal adding reagent in this reaction is borane (BH
3
), but borane is
much too reactive in air to be stored in a bottle. Therefore diborane is used
in a tetrahydrofuran solvent (THF) where it cleaves and the resulting borane
molecules are stabilized by complexing with the oxygen atom in the cyclic
ether, THF. Borane adds across the double bond of the alkene, with one of
the hydrogens attaching to the more substituted sp
2
carbon and the boron
attaching to the least substituted sp
2
carbon.



This is because boron being a larger atom needs more room and is less
sterically hindered on the least substituted carbon. As long as boron has
hydrogen attached to it, this reaction will occur again with another alkene
molecule until the boron is attached to three alkene molecules producing the
organoborane an addition product. Even the organoboranes will react with
air, so they must be kept in a suitable solvent like THF.
Organoboranes are useful in themselves. They can be used to produce
alkanes from alkenes by reduction of the organoborane with acetic acid
under reflux conditions or alcohol by oxidation with hydrogen peroxide in
presence of aqueous NaOH.

This replaces boron with a hydrogen atom on each of the three organic
groups attached to the boron thus producing three molecules of alcohol for
every one molecule of the organoborane.
Oxymercuration-reduction
Alkenes react with mercuric acetate (CH
3
COO)
2
Hg to form adducts which
upon reduction with NaBH
4
in basic medium gives alcohol.

This reaction occurs in 3 stages. In the first part mercury (II) acetate,
Hg(oAc)
2
forms a bridged species with the mercury atom, bridging the two
sp
2
carbons.



Then in the second step a water molecule attaches itself to the least
substituted of the sp
2
carbons in the bridged ring intermediate with the aid of
a lone pair on the oxygen atom of the water molecule. This produces the
oxonium intermediate and breaks the bridged structure.
In a third step an acetate ion pulls a hydrogen ion off the oxygen to produce
the hydroxy organo mercury product. Now a strong reducing agent sodium
borohydride in basic solution is added to the mercury compound when the
mercury group is replaced by a hydrogen atom to produce the final alcohol
product.
Like the hydration reaction, the oxymercuration-reduction reaction is region
selective and follows Markovnikov's rule, producing only the more substituted
alcohol. However, no molecular rearrangement is possible in this reaction
indicating that no carbocation is produced. This is a distinct advantage over
acid catalyzed hydration giving less product mixing.
Hydrolysis of Haloalkanes
Haloalkanes on treatment with aqueous solution of KOH or moist silver oxide
(Ag
2
O/H
2
O) give alcohols.



Reduction of Acyl (Carbonyl) Compounds
An acyl compound is one that has a carbon doubled bonded to an oxygen
(C=O) in its molecule. This group is also referred to as a carbonyl group.
There are several categories of acyl compounds:
Aldehydes
Ketones
Carboxylic Acids
Esters
Acyl compounds may undergo reduction with a suitable reducing agent. The
reducing agent undergoes oxidation in the process.
Organic Reducing Agents There are four reducing agents that will reduce
one or more of the acyl compounds.
Lithium Aluminum Hydride, LiAlH
4
(LAH)
Sodium Borohydride, NaBH
4
(NBH)
H
2
/Cu + CuCr
2
O
4
at 5000psi, 175
o
C
H
2
/Pt
Lithium aluminum Hydride is stronger than sodium borohydride and will
reduce any of the acyl compounds to products shown above. Indeed, lithium
aluminum hydride is so reactive that it must be prepared in a totally
anhydrous environment as it reacts explosively with water.
Sodium Borohydride is a weaker reducing agent that is less effective and is
capable of reducing only the aldehydes and ketones; it will not reduce
carboxylic acid or ester functions.
The use of hydrogen gas in the presence of Cu and copper (II) chromate is
called 'hydrogenolysis' and is a common way of reducing esters in small scale
laboratory reductions. This is also called high pressure hydrogenation and
copper and copper (II) chromate serves as catalysts.
The fourth method uses hydrogen gas in the presence of a noble metal such
as platinum to reduce aldehydes, ketones, and carboxylic acids.

Aldehydes
These can be reduced to primary alcohols in presence of platinum or
palladium metals or sodium borohydride.


Ketones
These can be reduced to secondary alcohols in presence of sodium
borohydride.


Carboxylic Acids
These acids are reduced to primary alcohols via aldehydes by lithium
aluminum hydride.

Esters
Esters are reduced to two alcohols, one from the acid fragment of the ester
and one from the alcohol fragment by hydrogenolysis.
Reaction with Organometallic Reagents
Organometallic reagents are organic compounds that are bonded to a metal.
There are a number of important organometallic reagents. Of these, two are
important in the synthesis of alcohols i.e., organomagnesium (Grignard's
reagent), R
-+
MgX and organolithium, R
-
Li
+
.
Grignard's reagent react with aldehydes, ketones and esters to form addition
products (adducts).

Upon decomposition with water in presence of dilute HCl or H
2
SO
4
, the
adducts give alcohol.

When a Grignard's reagent reacts with formaldehyde a primary alcohol is
produced. Indeed, this is the only way to prepare a primary alcohol via an
organometallic reagent.

Grignard's reagent reacts with all other aldehydes to produce secondary
alcohols.

Grignard's reagent reacts with ketones to produce tertiary alcohols.

Hydrolysis of Esters
Alcohols are prepared from naturally occurring esters by hydrolysis with
aqueous alkalis. This reaction is called saponification reaction.

Reaction of Primary Amines
Primary aromatic amine reacts with nitrous acid to form a diazonium salt,
which liberates nitrogen to form an unstable carbonium ion. These carbonium
ions react in aqueous medium to form an alcohol.

Preparation of Phenols
Phenols are prepared by the reaction of benzene derivatives with different
reagents.
Alkali Treatment of Haloarenes
Chlorobenzene is converted into phenol when it is heated with 6-8% aqueous
NaOH at temperatures above 623 K under 300 atm. pressure. This reaction
is also called as Dow's process.

Hydrolysis of Aromatic Diazonium Salts
Aromatic diazonium salts on treatment with water or preferably with dilute
acid form phenols. The reaction is usually carried out by adding the solution
of a diazonium salt to a large volume of boiling dilute sulphuric acid. The
acidic conditions minimize the side reaction of the coupling of the phenol with
diazonium salt.

This is one of the most convenient methods of preparing phenols.
Reaction with Grignard's Reagent
When a solution of an aryl halide (bromo benzene) in dry ether is treated
with magnesium, an aryl magnesium halide (phenylmagnesium bromide) is
formed.

When oxygen is bubbled through an ethereal solution of phenylmagnesium
bromide, it forms an addition product.

The treatment of the adduct with dilute mineral acid gives phenol.

Alkali Fusion of Benzene Sulfonic Acid
This is one of the oldest methods useful for the industrial synthesis of
phenol. When benzene sulphonic acid is fused with NaOH at 300-350
o
C, it
forms sodium benzene sulphonate as an intermediate. The reaction is
followed by an acidification reaction to neutralize the phenoxide and give
phenol. This reaction occurs via the addition-elimination mechanism with
SO
3
2-
functioning as the leaving group.

Acidic Oxidation of Cumene
Oxidation of cumene (2-phenylpropane or isopropylbnezene) at the benzylic
position gives hydroperoxide which upon subsequent hydrolysis with aqueous
acid cleaves to give phenol and acetone.

Low-cost reagents and important products make this process attractive.
Decarboxylation of Salicyclic Acid
Phenol is obtained by the decarboxylation of sodium salt of salicyclic acid
with soda lye (CaO + NaOH) followed by acidification with dilute HCl.

Physical Properties
The physical properties of an alcohol are best understood if one thinks of it
as a composite of an alkane and water. As such it contains a lipophilic,
alkane-like group and a hydrophilic, water-like hydroxyl group. The hydroxyl
-OH group gives the alcohol its characteristic physical properties, while the
alkyl group which modifies these properties.
Boiling Point:
Alcohols have a very high boiling point when compared to the related
alkanes.
Boiling point increases with increasing molecular weight.
The boiling point of the diols is quite high, hence their use as an
additive to car radiators.
Melting Point:
Melting point increases with increasing molecular weight, expectedly,
because of the of van der Waal attraction.
Symmetric branching increases melting point.
Specific Gravity:
Specific gravity or density increases with increasing molecular weight.
Alkyl alcohols are less dense than water, cyclic alcohols are
approximately the same as water, and aromatic alcohols and diols are
greater than water.
Water Solubility:
Lower weight alcohols, up to C
4
, are infinitely soluble in water.
Solubility decreases with increasing molecular weight as
hydrophobicity of alkyl groups dominates the nature of the molecule.
Most diols are infinitely soluble in water.

Name M.P.
o
C B.P.
o
C S.G. 20
o
C Solub g/100
Methyl -97 0.793 I
Ethyl -115 0.789 I
n-Propyl -126 0.804 I
n-Pentyl -78.5 0.817 2.3
n-Octyl -15 0.825 0.05
n-Decyl 6 0.829 ----
Isopropyl -86 0.789 I
Isobutyl -108 0.802 10.0
tert-Butyl 25.5 0.789 I
Cyclohexanol 24 0.962 ---
Allyl -129 0.855 I
Benzyl -15 1.046 4
Ethylene Glycol -16 1.113 I
Propylene Glycol 1.040 I
Glycerol 18 1.261 I
Acidity of Alcohols:
Alcohols are weakly acidic, as might be expected due to their similarity to
water. They can also function as weak Lewis bases, becoming protonated to
give oxonium ions:

pK
a
values: CH
3
CH
2
OH = 16.0; H
2
O = 15.7; CH
3
OH = 15.5; HCl = -7.0.
Hydrogen Bonding
Alcohols and phenols differ significantly from hydrocarbons (alkanes,
alkenes, alkynes, and aromatics) and alkyl halides in their melting points and
their boiling points. Hence, for short chain alcohols and for phenols one finds
much higher boiling points than one would expect on the basis of their sizes.
The most dramatic differences occur with the smallest molecules: methane
(MW = 16), chloromethane (MW = 50), and methanol (MW = 32) with
boiling points of -161.4 C, -23.7 C, and 64.5 C, respectively. Thus in alcohols
boiling points are not related to size. They obviously require a different
explanation.
Compound M
W
Boiling Pt
(C)
Sol. in Water
(g/100mL)
CH
3
CH
2
OH 46 78 100% Soluble
CH
3
CH
2
CH
3
44 -42 Insoluble
CH
3
CH
2
CH
3
OH 60 97 100% Soluble
CH
3
CH
2
CH
2
CH
3
58 0 Insoluble
CH
3
CH
2
CH
2
CH
2
CH
2
OH
88 138 2.3 g/100mL
CH
3
CH
2
CH
2
CH
2
CH
3
C
H
2

86 69 insoluble
The high boiling points of alcohols can be explained by the existence of
hydrogen bonds (H-bonds). This is the same explanation for the incredibly
high boiling point of water (water has about 4 H-bonds per molecule, vs.
about 2 for alcohols). Hydrogen bonds involve a very strong polar attraction
combined with very small atomic radii, resulting in a partial covalent bond
being formed. Although this bond is significantly weaker than the covalent
bonds common in organic molecules (i.e. 400 kJ/mol for O-H bonds vs. about
20 kJ/mol for an H-bond), but is much stronger than the weak van der Waals
forces holding alkanes together (about 0.4 - 0.8 kJ/mol).

The -OH group is highly polar and is capable of hydrogen bonding with other
alcohol molecules and also to other neutral molecules and to anions. This
property is particularly important in defining boiling point and aqueous
solubility. The increased intermolecular bonding increases the energy needed
to boil by decreasing the vapor pressure. As expected the polar nature
increases with the diols.
Chemical Reactions
The functional group of the alcohols 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. Accordingly, alcohols and phenols will undergo two distinct
types of reactions.
Reactions involving the cleavage of the O-H bond with substitution or
removal of hydrogen as a proton.
Reactions involving the cleavage of the C-O bond with substitution or
removal of OH group.
Nature of the -OH Group
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 a result, there is a low electron density on H atom of -OH
group alcohol, and with H
+
character being more, alcohols are acidic (pKa ~
16).
Acidity of Alcohols
Nevertheless, alcohols are weaker acids than water (pK
a
~ 14) because the
electron releasing inductive effect of the alkyl groups increases the electron
density around the oxygen atom. As a result the electrons of the O-H bond
are not sufficiently attracted towards the oxygen atom and so the release of
proton becomes difficult.
On comparing the acidity of primary, secondary and tertiary alcohols the
electron releasing inductive effect of the alkyl groups is maximum in tertiary
alcohol and minimum in primary alcohols. Thus, primary alcohols are the
strongest acids while tertiary alcohols are the weakest. The acidic strength of
alcohols follows the order:
Primary > Secondary > Tertiary
In addition, the presence of lone pairs in the alcohol O atom makes it a
region of high electron density. Alcohol oxygen atoms are Lewis bases and
allow the ability to alcohols to react as either bases or nucleophiles at the
oxygen atom.
Indeed, the dipolar nature of the O-H bond is such that alcohols are much
stronger acids than alkanes - by roughly 10
30
times, and nearly that much
stronger than ethers which are oxygen substituted alkanes that do not have
an O-H group. 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.
Removal of the proton generates the anion - alkoxide ion. Alkoxides are
important bases in organic chemistry.
Acidity of Phenols
In some respects, the chemical behavior of phenols is different from that of
the alcohols, so it is sensible to treat them as a similar but characteristically
distinct group.
In contrast, with phenols the substitution of the hydroxyl hydrogen atom is
even more facile, and makes them roughly a million times more acidic than
equivalent alcohols.

This phenolic acidity is further enhanced by electron-withdrawing
substituents ortho and para to the hydroxyl group, as displayed.

The alcohol cyclohexanol is shown for reference at the top left. It is
noteworthy that the influence of a nitro substituent is over ten times stronger
in the para-location than it is in meta, despite the fact that the latter position
is closer to the hydroxyl group. Furthermore additional nitro groups have an
additive influence if they are positioned in ortho or para locations. The
trinitro compound shown at the lower right is a very strong acid called picric
acid.
Why is phenol a much stronger acid than cyclohexanol? To answer this
question one must evaluate the manner in which an oxygen substituent
interacts with the benzene ring. In electrophilic aromatic substitution
reactions, an oxygen substituent enhances the reactivity of the ring and
favors electrophile attack at ortho and para sites. It is proposed that
resonance delocalization of an oxygen non-bonded electron pair into the pi-
electron system of the aromatic ring was responsible for this substituent
effect.
The resonance stabilization in these two cases is very different. The
contributing structures to the phenol hybrid all suffer charge separation,
resulting in very modest stabilization of this compound. On the other hand,
the phenolate anion is already charged, and the canonical contributors act to
disperse the charge, resulting in a substantial stabilization of this species.
The conjugate bases of simple alcohols are not stabilized by charge
delocalization as in phenols, so the acidity of these compounds is similar to
that of water.
An energy diagram showing the effect of resonance on cyclohexanol and
phenol acidities is shown below. Since the resonance stabilization of the
phenolate conjugate base is much greater than the stabilization of phenol
itself, the acidity of phenol relative to cyclohexanol is increased. However,
phenols are weaker acids than carboxylic acids (pK
a
= 5) or even carbonic
acids (pK
a
= 7).

The phenolate negative charge is delocalized on the ortho and para carbons
of the benzene ring and comes from the influence of electron-withdrawing
substituents at those sites. Electron withdrawing substituents (e.g., NO
2
) can
make phenols as acidic as many carboxylic acids.

Electron donating substituents like -NH
2
, -OR, -R etc., which destabilize the
phenoxide ion tend to decrease the acid strength of phenols. The table given
below summarizes some of these facts.
Compound pKa Compound pKa
Phenol 10.0
o-Methoxyphenol 10.0 p-Methoxyphenol 10.2
o-Methylphenol 10.3 p-Methylphenol 10.3
o-Chlorophenol 8.6 p-Chlorophenol 9.4
o-Nitrophenol 7.2 p-Nitrophenol 7.2
m-Nitrophenol 8.4
The -OH group is a poor leaving group and needs to be converted to a better
leaving group before substitution can occur.
Reactions Involving the Cleavage of the O-H Bond
Both alcohols and phenols readily undergo cleavage of the O-H Bond. The
ease of cleavage follows the sequence:
Phenols > primary alcohols > secondary alcohols > tertiary alcohols
Electrophilic Substitution at Oxygen
Substitution of the Hydroxyl Hydrogen
Because of its enhanced acidity, the hydrogen atom on the hydroxyl group is
rather easily replaced by other substituents. A simple example is the facile
reaction of simple alcohols with alkali metals like sodium or potassium similar
to water to give the alkoxide:

The mechanism by which many substitution reactions of this kind take place
is straightforward. The oxygen atom of an alcohol is nucleophilic and is
therefore prone to attack by electrophiles. The resulting 'onium' intermediate
then loses a proton to a base, giving the substitution product. If a strong
electrophile is not present, 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.
Like the alcohols, the phenolic hydroxyl hydrogen is rather easily replaced by
alkali metals.

However, phenol reacts easily with alkalis itself to form phenoxides or
phenates.

Alcohols do not react with NaOH solution and so this test distinguishes
phenols from alcohols.
Reaction with Alkyl Halides
Alkyl substitution of the hydroxyl group leads to ethers. Alkoxide salts react
with alkyl halides to give ethers by the Williamson ether synthesis reaction.

This reaction provides examples of both strong electrophilic substitution, and
weak electrophilic substitution. The weak electrophilic substitution is a S
N
2

reaction and is generally used only with primary alkyl halide reactants
because the strong alkoxide base leads to E
2
elimination of secondary and
tertiary alkyl halides.
Primary alkyl halides are most reactive (E
2
competes with more hindered
substrates). Thus unsymmetrical ethers are best prepared with the less
hindered member being the alkyl halide, and the more hindered member
being the alkoxide. For example, if we use a tertiary alkoxide ion and a
methyl halide the S
N
2
reaction will predominate:

However, if a primary (or any other) alkoxide ion attacks a tertiary halide the
reaction is blocked by steric hindrance and thus the E
2
elimination is
preferred:

The reaction of phenols with alkyl halides is carried out by first dissolving
phenols in NaOH solution to form the phenoxide and then heating it with the
alkyl halide to from the ether.


The phenate ion is an excellent nucleophile.
Reaction with Carboxylic Acids Alcohols react with carboxylic acids in the
presence of a few drops of concentrated H
2
SO
4
or dry HCl acid as catalyst, to
form esters.

This reaction is called Fischer esterification reaction and is usually slow and
exothermic. Phenols do not easily undergo the esterification reaction with
carboxylic acids because the reaction is endothermic.
Reaction with Acid Chlorides and Anhydrides
When alcohols or phenols are treated with acid chlorides or anhydrides in the
presence of a base such as pyridine or dimethylaniline, the H-atom of the -
OH group is replaced by the acyl (RCO-) group to form esters.



Phenols react with acid chlorides or acetic anhydride to give phenyl acetate.

Similar to acylation, the introduction of acetyl (CH
3
CO) group in alcohols or
phenols is known as acetylation.
The reaction of alcohols and phenols with benzoyl chloride in presence of
aqueous NaOH is called Schotten Baumann reaction.

Reaction with Grignard's reagent
Both alcohols and phenols react with Grignard's reagent to form
hydrocarbons.

Reactions Involving the Cleavage of the C-O Bond
A step toward improving the reactivity of alcohols in breaking the C-O bond
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 strong acid
so that -OH is converted to -OH
2
(+)
. Since the hydronium ion (H
3
O
(+)
) is a
much stronger acid than water, its conjugate base (H
2
O) 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
acid, effectively removing the nucleophilic co-reactant needed 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. Nucleophilic substitution of 1 -alcohols proceeds by a S
N
2

mechanism, whereas 3 -alcohols react by a S
N
1
mechanism. Reactions of 2 -
alcohols may occur by both mechanisms and often produce some rearranged
products.
Action of Halogen Acids
Alcohols when treated with halogen acids (HX) get converted into
haloalkanes. This reaction does not occur with phenols. The nature of alcohol
and the halogen acid both influence the rate of the reaction.
Primary and secondary alcohols form chloroalkanes when hydrochloric acid
gas is passed through alcohol in the presence of anhydrous zinc chloride
(Groove's process).

ZnCl
2
is a Lewis acid and it readily coordinates with the oxygen atom of the
alcohols. As a result, the C-O bond weakens and breaks to form carbocation,
which reacts with chloride ion to form chloroalkanes. Thus, anhydrous ZnCl
2

helps in the cleavage of the C-O bond.
Tertiary alcohols are very reactive and therefore, they react readily with
concentrated HCl even in the absence of zinc chloride.

The three classes of alcohols show difference in reactivity with HCl. In fact
this is one of the methods called Lucas test that is used to distinguish them
from one another. For example, primary alcohols on reacting with Lucas
reagent (conc. HCl and ZnCl
2
) does not produce turbidity at room
temperature while in case of tertiary alcohols, turbidity is produced
immediately since they form the halides easily.
Similarly, when an alcohol is heated with hydrobromic acid (48%) bromo
alkanes are obtained. HBr can also be generated in situ (during the reaction)
by the action of concentrated H
2
SO
4
on KBr or NaBr.

On heating alcohols with constant boiling hydroiodic acid (57%) generated in
situ by the action of phosphoric acid on potassium iodide, iodoalkanes are
obtained.

Secondary and tertiary alcohols cannot be used to prepare respective
bromides and iodides unlike alkyl chlorides. This is because secondary and
tertiary alcohols undergo dehydration on heating with concentrated H
2
SO
4
, to
form alkenes.
The order of reactivity of halogen acids on alcohols is in accordance with the
bond dissociation energies of H-X bonds:
HI > HBr > HCl
Reactivity of alcohols towards this reaction is:
Tertiary > Secondary > Primary
The cleavage of C-O bond becomes easy and reactivity increases when the
polarity of C-OH increases with the number of electron releasing groups on
the -carbon atom of the alcohol.
Action of Phosphorus Halides
Phosphorus halides react with alcohols to form haloalkanes. The action of
phosphorus pentachloride (PCl
5
) or phosphorus trichloride (PCl
3
) on alcohols
brings about the cleavage of C-O bond.


Likewise, bromoalkanes and iodoalkanes are generated by the action of
phosphorus tribromide (PBr
3
) and phosphorus tri-iodide (PI
3
) respectively on
alcohols. As PBr
3
and PI
3
, are not very stable compounds, they are prepared
in situ by the action of red phosphorus on Br
2
, or I
2
, as follows:




Treatment of phenols with PCl
5
gives only a small amount of chlorobenzene,
the major product being tiphenyl phosphate.
Action of Thionyl Chloride
By refluxing alcohols with thionyl chloride in the presence of pyridine, chloro
alkanes can also be prepared from alcohols.

Phenols do not react with thionyl chloride.
Action of Ammonia
When a mixture of the vapours of an alcohol and ammonia are passed over
heated alumina (Al
2
O
3
) at 633 K, a mixture of primary, secondary and
tertiary amines is produced.



The reaction of ammonia on phenol give aniline under severe conditions only,
as phenol is less reactive towards nucleophilic displacement reactions.

Reaction with Zinc Dust
Phenols but not alcohols on distillation with zinc dust give the corresponding
aromatic hydrocarbon. For example,

Reactions Involving the Alcohol Molecule as a Whole
There are two types of reactions that alcohols are prone to and engage in;
one is essentially the reverse of addition of water to an alkene. This is called
dehydration (the loss of water from an alcohol). The other is called oxidation.
This reaction results in loss of hydrogen and the conversion of the C-O single
bond to a double bond.
Dehydration of Alcohols
In the case of dehydration either water is removed as the reaction
progresses or the equilibrium already favors alkene production. The
dehydration of alcohols as a method of synthesizing alkenes with the
products usually predicted by Zaitsev's rule - the more highly substituted
alkene will be the major product. This reaction is acid catalyzed, commonly
being carried out in sulphuric acid or heated alumina requiring higher
temperatures.
Tertiary and secondary alcohols react under mild conditions, such as with
phosphoric acid at lower temperatures.
Different products are obtained under different reaction conditions and
temperature e.g., ethers are obtained when excess alcohol is used.

The mechanism of the dehydration reaction is an E
1
elimination reaction:
Alcohols act as bases due o the presence of lone pair of electrons on the
oxygen atom. Therefore they react with strong mineral acid to form the
oxonium salts in the first step.
In the 2
nd
slow step the C-O bond weakens due to the presence of positive
charge on the highly electronegative oxygen. As a result, the protonated
alcohol readily eliminates a molecule of water to form ethyl carbocation.

In step 3 the ethyl carbocation being a reactive chemical species looses a
proton to form the ethene molecule.
The relative ease of dehydration is as follows:
Tertiary > Secondary > Primary
This path is essentially the reverse of the water addition path. For interior -
OH groups, the final location of the C=C bond depends on the branching of
the alkane. For example:

In general, the double bond will locate on the carbons with the most
branching, although frequently there will be some of the other product
present.
Oxidation of Alcohols
Simple 1 and 2-alcohols in the gaseous state lose hydrogen when exposed to
a hot copper surface. This catalytic dehydrogenation reaction produces
aldehydes and ketones. In the case of tertiary alcohols alkenes are produced.
Since the carbon atom bonded to the oxygen is oxidized, such alcohol to
carbonyl conversions are generally referred to as oxidation reactions. Gas
phase dehydrogenations of this kind are important in chemical
manufacturing.

However, when alcohol oxidations are carried out in solution, the hydroxyl
hydrogen is replaced by an atom or group that is readily eliminated together
with the alpha-hydrogen. The most important reactions of alcohols are their
oxidation to aldehydes, ketones, and carboxylic acids (carbonyl compounds)
and may be viewed as follows:

The outcome of oxidation reactions of alcohols depends on the substituents
on the carbinol carbon. In order for each oxidation step to occur, there must
be H on the carbinol carbon.
Primary alcohols are oxidized to aldehydes, which in turn may be oxidized to
acids, both containing the same number of carbon atoms as the original
alcohol. Secondary alcohols are oxidized to ketones with the same number of
carbon atoms as the original alcohol. Tertiary alcohols are not normally
oxidized since it would be necessary to break a C-C bond (C-C bonds are
very strong and stable, thus resistant to reaction without destabilizing
structural relations or high energy).

While secondary alcohols can be oxidized to ketones, only under drastic
conditions further can oxidation occur, when for instance, carboxylic acids
with lesser number of carbon atoms than the original alcohol is formed.

Tertiary alcohols cannot be oxidized easily (no carbinol bond C-H) and only
under strong acid oxidizing agents they convert to a mixture of ketone and
an acid each containing lesser number of carbon atoms than the original
alcohol.

Common oxidizing agents consisting of chromate and manganate species are
summarized below.

Primary alcohols can be oxidized to aldehydes or further to carboxylic acids.
In aqueous media, the carboxylic acid is usually the major product. However,
they can be oxidized to aldehydes by the careful selection of an oxidizing
agent like PCC or PDC in dichloromethane. The best reagent for laboratory
scale reactions is pyridinium chlorochromate, C
5
H
6
NCrO
3
Cl (PCC), in
dichloromethane solvent:

Other oxidizing agents, such as sodium dichromate (Na
2
Cr
2
O
7
) in aqueous
acid or chromium trioxide (CrO
3
), continue the oxidation process to the
carboxylic acid product. The intermediate aldehydes are not generally
isolated because they are oxidized to acids too rapidly:

Secondary alcohols are readily oxidized to ketones:

In each case a chromate ester of the alcohol substrate is believed to be an
intermediate, which undergoes an E
2
like elimination to the carbonyl product.
The oxidation state of carbon increases by 2; while the chromium is reduced
and decreases by 3. Since chromate reagents are a dark orange-red color (VI
oxidation state) and chromium III compounds are normally green, the
progress of these oxidations is easily observed. Indeed, this is the chemical
transformation on which the Breathalizer test is based.
Jones' reagent: a solution of sodium dichromate in aqueous sulphuric
acid
Oxidation of Phenols
Generally phenols are more easily oxidized than simple alcohols. Oxidation
can be achieved by reaction with silver oxide (Ag
2
O) or chromic acid
(Na
2
Cr
2
O
7
), or other oxidizing agents.
Particularly important are the oxidation of 1,2- and 1,4-benzenediol
(pyrocatechol and hydroquinone, respectively) and their derivatives.

These types of systems are important in biological redox-systems such as
coenzyme Q and vitamin K.
Here's a closer look at the two one electron transfers that are believed to
take place when hydroquinone is oxidized to benzoquinone.

Loss of a proton and an electron generates a phenoxy radical.

Loss of a second proton and a second electron completes the oxidation.
Electrophilic Reactions
Phenols are potentially very reactive towards electrophilic aromatic
substitution. This is because the hydroxy group -OH, is a strongly activating,
ortho-/para- directing substituent. Substitution typically occurs para to the
hydroxyl group unless the para position is blocked, then ortho substitution
occurs.

The strong activation often means that milder reaction conditions than those
used for benzene itself can be used. Phenols are so activated that
polysubstitution and oxidation can be a problem at times.
Halogenation
Phenols react with halogens in the presence of less polar solvents like CS
2
,
CHCl
3
and CCl
4
to give ortho and para isomers of monohalophenols.

Phenols when treated with chlorine or bromine water give polyhalogen
derivatives in which all the H-atoms present at the ortho- and para- positions
with respect to OH group are replaced by chlorine and bromine atoms.

Nitration With dilute HNO
3
at 293 K phenol give mixtures of ortho and para
isomers of mononitrophenols.

The yield of mononitrophenols is quite low due to the partial oxidation of the
ring by HNO
3
. However, if phenol is first treated with nitrous acid,
nirosophenol is formed which on further oxidation with dilute nitric acid yields
good yeild of mononitrophenol.
The ortho and para isomers can be separated by steam distillation. o-
nitrophenol undergoes intramolecular hydrogen bonding while p-nitrophenol
undergoes intermolecular hydrogen bonding. While o-nitrophenol is steam
volatile and p-nitrophenol is less volatile due to the association of molecules
and so can be separated by distillation.

With concentrated nitric acid and in the presence of sulphuric acid, phenol
gives 2,4,6-trinitrophenol (picric acid). The yield is low due to oxidation of
phenol.

Sulphonation
When phenol is treated with concentrated H
2
SO
4
sulphonation occurs. A
mixture of ortho- and para- isomers are obtained. If the sulphonation is
carried at low temperatures (293 K), the ortho isomer predominates and at
high temperatures (2373 K) the para isomer is the chief product.

Alkylation and Acylation
The alkylation and acylation reaction, known as 'Friedel-Craft reaction', is
carried by treating phenol with alkyl chloride or acyl chloride in the presence
of a catalyst like anhydrous aluminium chloride. For example,


Carboxylation of Phenols (Kolbe-Schmitt reaction) Heating the
nucleophilic phenolate salt with carbon dioxide under high
pressure/temperature results in regioselective ortho-substitution.

On further acidification the o-and p-isomers of o-hydroxybenzoic acid are
formed. This process is also known as the Kolbe-Schmitt synthesis.

However, o-hydroxybenzoic acid is the main product and is commonly known
as salicyclic acid. This is the starting material for preparing 2-acetoxybenzoic
acid (aspirin) which is widely used as analgesic and antipyretic. The
acetylation of salicylic acid produces aspirin.

Reimer-Tiemann Reaction
On treating phenol with chloroform in the presence of aqueous sodium or
potassium hydroxide at 340 K followed by hydrolysis of the resulting product,
gives 2-hydroxybenzaldehyde (salicylaldehyde) as the major product and 4-
hydroxybenzaldehyde as a minor product.
If instead of chloroform, CCl
4
is used salicyclic acid is formed as the major
product.
The Reimer-Tiemann reaction occurs by the generation of dichlorocarbene
(:CCl
2
) electrophile which attacks the ortho- para- electron rich centres to
substitute the hydrogen atom at these positions.


Some Commercially Important Alcohols
Methanol (Wood Alcohol)
Methanol or Methyl Alcohol can be obtained by the destructive distillation of
wood, hence its popular name of wood alcohol. Commercially, methanol is
prepared by the hydrogenation of carbon monoxide in the presence of a
metal oxide catalyst such as zinc oxide and chromic oxide under high
temperature and pressure.

Methane is also used for producing methanol.


Properties
Methanol is a clear, colourless, organic liquid with a pleasant odour. It is
inflammable and has a high calorific value and hence it is used as a fuel.
It burns with a good smokeless flame.

Methanol is used mostly for industrial purposes. It is an important solvent for
many substances used in dyes, drugs etc. When mixed with water, the
mixture does not freeze even at sub-zero temperatures. Hence, in cold
countries, it is used as antifreeze for automobile radiator.
It is used as a starting material for making other organic compounds e.g.,
when methanol is oxidized by acidified potassium permanganate or
potassium dichromate, formaldehyde is formed.

Formaldehyde on further oxidation gives formic acid.

Methanol is highly poisonous. If consumed it causes blindness due to
destruction of the cells of the optic nerve. If consumed in large amount, it
can cause death.
Spurious alcohol or illicit liquor is often made by improper distillation or by
using methylated spirit. It is cheap and is mostly made available to the lower
strata of our society. Spurious alcohol contains higher percentage of methyl
alcohol which is poisonous. Consumption of such liquor may cause blindness,
serious health problems and even death. Sometimes, to give the consumer
gets a pronounced feeling of 'intoxication', other chemicals are mixed with
ethyl alcohol. Such mixtures can prove to be exceedingly poisonous and can
cause severe damages to the body organs, nervous system resulting in
death.
Ethanol
Ethanol or ethyl alcohol has been used for thousands of years especially in
the form of wine. Usually the term 'alcohol' refers to ethanol.
The raw materials used for the preparation of alcohol are plant products that
contain some form of starch or sugar. Grapes, barley, rice, potatoes, apples
etc., are examples of such materials. The process of converting the starch to
sugar is called fermentation.
Today, most of the alcohol produced in the world is by the fermentation of
molasses, a brownish syrupy liquid obtained in the sugar industry. It contains
a large amount of sugar, which cannot be further crystallized. Yeast is added
to these molasses, and it is allowed to ferment for usually three weeks. The
enzyme maltase present in yeast converts the sucrose of molasses to
glucose.

Yeast also contains an enzyme zymase, which converts glucose to ethanol
and carbon dioxide.

The alcohol so formed is separated by fractional distillation to obtain rectified
spirit. The product-rectified spirit contains about 96% ethanol and 4% water.
Pure alcohol (100% alcohol) called 'absolute alcohol' is obtained from this
product by distillation with benzene (C
6
H
6
).
Ethanol is also be obtainable from petroleum products. During the cracking of
petroleum, large quantities of ethene (ethylene) are produced. This can be
hydrated using sulphuric acid as a catalyst to produce ethanol.

Water molecule adds to an alkene molecule across the double bond in the
presence of dilute acids and a catalyst. For example, ethane gives ethanol
when a mixture of ethene and steam is passed over phosphoric acid and
silica under a pressure 65 atm, and at 300 C

Properties
Ethanol is colourless and has a pleasant odour. Its boiling point is 78
o
C and
its freezing point is -114
o
C. It is soluble in water and almost all the organic
solvents. It is highly intoxicating in nature. It is combustible and burns with a
blue flame.
Ethanol is used for many industrial applications because of some
characteristic reactions. The products formed are starting materials for
carrying out many organic reactions both at industry and laboratory. For
example,
When a piece of sodium is dropped in ethyl alcohol, bubbles of hydrogen gas
are observed.

Ethanol reacts with phosphorus trichloride to form ethyl chloride.

When treated with concentrated H
2
SO
4
at 170
o
C, ethyl alcohol undergoes
dehydration to form ethane.

At lower temperature of 140
o
C, and when present in excess, ethyl alcohol
forms a pleasant smelling substance called diethyl ether.

Alcohols on oxidation give aldehydes. The aldehydes on further oxidation
give carboxylic acids.

Based on these reactions important uses of alcohol are as follows:
Ethyl Alcohol is used as a solvent for many organic solutes, especially
which are insoluble in water.
It is used in the preparation of perfumes.
It is used in the manufacturing of 'power alcohol', which is 80%
mixture of petrol (gasoline) and 20% absolute alcohol. It can be used to
generate power as a motor fuel and help to save gasoline. As absolute
alcohol does not mix with petrol, benzene, ether or tetralin is added into
this mixture.
Ethyl Alcohol is used in making tinctures and medical syrups.
It is used as a solvent for paints, varnishes, dyes etc.
It is used in the production of many organic compounds.
It is used in alcoholic beverages.
The chemical usage and common usage of the term 'alcohol' differ.
Chemically, the term alcohol refers to a group of organic compounds having -
OH group in their composition; the common man reference to alcohol relates
to ethyl alcohol or ethanol. Ethyl alcohol has a variety, of uses as seen
above, especially as a solvent. But by far the greatest use of ethyl alcohol is
in the form of alcoholic beverages, such as wine, beer, rum, brandy, whisky
etc.
Alcohol consumed in sizeable amounts is detrimental and affects the nervous
system In small quantities it may serve as a source of energy, but
consumption of alcohol is a habit forming activity.. If consumed over a period
of time, alcohol can ruin one's health especially the liver, which gets affected
by cirrhosis. . The person loses his or her sense of balance and mental ability
when consumed in excess and this type of consumption often ruins family life
and can have tragic consequences.
Alcoholic drinks are heavily taxed by the government, so as to discourage
people from over consumption. Certain state have banned alcoholic drinks
altogether, inspite of the taxes being a sizable revenue earning for state
government coffers. Alcohol used for industrial and surgical purposes is not
taxed heavily. But in order to prevent unscrupelous people fromm buying and
consuming industrial and surgical alcohol, it is mandatory that ethyl alcohol
be mixed with a certain percentage of highly poisonous methyl alcohol or
methanol. This renders the ethyl alcohol unfit for human consumption. This
mixture is called 'Methylated Spirit'. If chemicals like copper sulphate or
pyridine are added to ethyl alcohol it is called 'denatured alcohol'. Both these
mixtures are prepared so as to prevent people from drinking alcohol heavily.


Ethers
Ethers can be prepared by the following general methods.
Preparation of Ethers
Williamson Ether Synthesis
Ethers are usually prepared from alcohols or their conjugate bases. One important
procedure is the Williamson Ether Synthesis mentioned earlier. This reaction proceeds
by an S
N
2
reaction of an alkoxide nucleophile with an alkyl halide. The substitution
reaction permits the convenient synthesis of both symmetrical and non-symmetrical
ethers.
This type of reaction happens in two steps. The alcohol firstly reacts with sodium (or
some other substance that removes a proton from the alcohol (-OH) group. Then a
haloalkane is added to a solution of the resulting anion, when the alkyl nucleophile from
the haloalkane attaches to it. Na
+
ion is a spectator ion forming a halide salt.

For preparation of ethers with different R groups bound to oxygen (non-symmetrical
ethers), all one has to do is use an alcohol with one organic group and an organic
chloride with a different group. Reactions of a secondary alkyl alkoxide and a primary
aryl halide and vice versa are shown as two examples of this procedure.

In this case unsymmetrical ether benzyl isopropyl ether is obtained. As there are two
different combinations, two different types of reactants are possible, one usually better
than the other. Since alkoxide anions are strong bases, the possibility of a competing E
2

elimination also occurs here. Bearing in mind the factors that favor substitution over
elimination, a primary alkyl halide is a preferred reactant as it gives a better and
cleaner yield of benzyl isopropyl ether than does other reaction which generates
considerable elimination product. Best yields of unsymmetrical ethers are obtained
when the alkyl halides are primary and the alkoxides are tertiary.
Aryl halides are much less reactive than alkyl halide and so are usually prepared by
treating sodium phenoxide with alkyl halides.
Alkoxy Mercuration
A second general ether synthesis involves the oxymercuration reaction. The alcohol
reactant is used as the solvent, and a trifluoroacetate mercury (II) salt is used as
nucleophile in preference to the acetate).
Alkenes readily react with mercury (II) trifluoroacetate acetate in the presence of an
alcohol to give alkoxy mercurial compounds, which on reduction with NaBH
4
in basic
medium gives ethers in high yield. Reactions of butene and cyclopentene as examples
of this two-step procedure are given below.

Note that this reaction gives ether in accordance with Markovnikov's addition rule and
does not involve a carbocation and competing elimination reaction.
Dehydration of Alcohols
Symmetrical ethers (R-O-R) can be prepared by gently heating an alcohol in the
presence of an acid catalyst like concentrated sulphuric acid. This process is very
similar to that used to dehydrate an alcohol to an alkene. The primary difference is that
dehydration uses somewhat higher temperatures.

The yield of ether depends upon the nature of the alcohol whether it is 1, 2, or 3 . The
formation of ethers from these alcohols is best achieved when alcohol is used in excess.
However, the order of dehydration of alcohols leading to the formation of ethers follows
the sequence,
Primary > Secondary > Tertiary
Acid-catalyzed dehydration of small 1 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 110 C to 130 C an S
N
2
reaction of the
alcohol conjugate acid leads to an ether product. At higher temperatures (> 150 C) an
E
2
elimination takes place.


The dehydration of an alcohol to either an alkene or ether shows the reactions to
proceed over a relatively narrow temperature range (20 for ethanol). Such a narrow
range of conditions suggests that when these reactions are carried out one may obtain
more than one product and such is frequently the case.
Catalytic Dehydration
Dehydration of alcohols can also be achieved by passing the vapours of an alcohol over
alumina (Al
2
O
3
) at 623 K (350 C).
For example,

The order of the ease of dehydration of alcohols is,
Tertiary > Secondary > Primary
Reaction of Alkyl Halides with Dry Silver Oxide
Haloalkanes can also be converted into ethers by heating with dry silver oxide.

Reaction With Grignard's Reagent
Higher ethers can be produced by the action of -halo ethers with Grignard's reagent.


Reaction With Diazomethane
Ethers can be prepared by the reaction of diazomethane with alcohols in the presence
of tetrafluoroboric acid (HBF
4
) as catalyst.
Physical Properties
Physical State
Higher Ethers are gases at ordinary temperature while the other lower members are
colourless liquid with a characteristic 'ether smell'.
Dipole Nature
The C-O bonds in ethers are slightly polar because of greater electronegativity of
oxygen than carbon atom. Since the two C-O bonds in ethers are inclined to each other
at an angle of 110
o
the two dipoles do not cancel each other and thus they a dipole
moment of 1.15-1.3 D.
Boiling Points
Ethers are isomeric with monohydric alcohols but their boiling points are much lower
than the isomeric alcohols. This is because unlike alcohols ethers do not form hydrogen
bonds and exit as associated molecules. Further the weak polarity of the C-O bonds do
not affect the boiling points of ethers which are comparable with those of alkanes of
same molecular masses.
Diethyl ether (MW 74): 308 K; butyl alcohol (MW 74): 351 K; pentane (MW 72) 309 K
Solubility
Ethers have water solubilities intermediate between alkanes and alcohols. Because
ethers have no O-H bonds, they cannot participate in hydrogen bonding to the same
extent that alcohols do. Nevertheless, the oxygen in the ether can form a hydrogen
bond to the hydrogen in water. The presence of only single site on the ether for a
limited kind of hydrogen bonding interaction means that ethers generally have
significantly smaller solubilities in water than do alcohols. Still they have higher
solubilities than any hydrocarbon.
As their molecular mass increases, the solubility of ethers in water decreases due to
corresponding increase in the hydrocarbon portion of the molecule. Ethers are fairly
soluble in common organic solvents like alcohol, benzene, chloroform, acetone etc.
Chemical Reactions
Ethers are generally unreactive and make good as solvents. They do not react with
halogens, nucleophiles or mild acids or bases. They are widely used as solvents for a
variety of organic compounds and reactions, suggesting that they are relatively
unreactive themselves. With the exception of the alkanes, cycloalkanes and
fluorocarbons, ethers are probably the least reactive, common class of organic
compounds. The inert nature of the ethers relative to the alcohols is undoubtedly due to
the absence of the reactive O-H bond.
Reactions of Ethereal Oxygen
The ethereal O atom is a region of high electron density due to the presence of lone
pairs. Hence, ether oxygen atoms are Lewis bases undergoing reactions involving the
formation of co-ordinate bonds.
Formation of Oxonium Salts
The oxygen atom of ether has two lone pairs of electrons. As a result they behave as
Lewis bases and thus dissolve in cold concentrated inorganic acids to form stable
oxonium salts. For example,

Formation of Coordination Complexes
Ethers form coordinate bonds with Lewis acids such as BF
3
, AlCl
3
, FeCl
3
, Grignard's
reagent etc., to produce complexes called as etherates.

The etherate complexes from Grignard's reagent dissolve in ether and that is the
reason Grignard's reagent are usually prepared in ethers.
Reactions Involving the Cleavage of C-O bond
Like an alcohol -OH group, the -OR group is a poor leaving group and needs to be
converted to a better leaving group before substitution can occur.
The most important reaction of ethers is their cleavage by strong acids. Alkyl ethers are
cleaved by the strong acids HI or HBr in a nucleophilic substitution reaction similar to
that of alcohols. Aqueous HI is the acid most commonly used, but HBr also works
sometimes.

Protonation of the ethereal oxygen creates a good leaving group, a neutral alcohol
molecule. The halide ion, bromide or iodide are both good nucleophiles. Depending on
the structure of the alkyl groups, the reaction can be S
N
1
or S
N
2
.
Reaction with Halogen Acids
The cleavage of the C-O bond by strong halo acids is the most common reaction of
ethers. This occurs by S
N
1
or E
1
mechanisms for 3-alkyl groups or by an S
N
2
mechanism
for 1-alkyl groups. The conjugate acid of the ether is an intermediate in all these
reactions as shown below.

Ethers are readily cleaved by hydroiodic acid at 373 K to form an alcohol and an alkyl
halide.

However, if excess of acid is used the alcohol first formed reacts further with the
halogen acid to form the corresponding alkyl halide.

The reaction is a typical nucleophilic substitution, taking place via a S
N
1
or S
N
2

mechanism.
Primary and secondary alkyl ethers are attacked by iodide ion to give an S
N
2

mechanism with acid catalysis:

Firstly, ether being Lewis bases undergoes protonation to form oxonium salts as the
intermediate. Protonation of the alcoholic oxygen takes place to make a better leaving
group. This step is very fast and reversible.
In the second step the formed protonated ether undergoes nucleophilic attack by the
halide ion. The halide ion functions to displace the good leaving group, neutral alcohol
molecule, by cleaving the C-O bond. This results in the formation of an alkyl bromide
and an alcohol.
Note that the iodide attacks the less hindered alkyl group, so in the unsymmetrical
ethers alkyl halide is always formed from the smaller alkyl group.
Protonation of tertiary ethers in acid lead to spontaneous cleavage to give a carbocation
intermediate, resulting in either an S
N
1
or E
1
mechanism for cleavage:

There is a similarity to the analogous alcohol reactions when 'water' is lost, except an
alkyl group has been substituted for the H of water to give an alcohol leaving group.
The order of halogen acids follow the sequence:
HI > HBr > HCl
In case of alky aryl ethers the products are always phenol and alkyl halide and never an
aryl halide and alcohol.
.
This occurs because the phenol formed in this reaction does not react further, since S
N
2
,
S
N
1
and E
1
reactions do not take place on aromatic rings.
Reaction with Sulphuric Acid
Ethers undergo hydrolysis reaction to from alcohols when heated with dilute sulphuric
acid under pressure.

When heated with concentrated sulphuric acid alcohol and alkyl hydrogen sulphates are
formed.

Reaction with Acid Chlorides and Anhydrides
When ethers are treated with acid chlorides or anhydrides in the presence of anhydrous
ZnCl
2
or AlCl
3
esters and alkyl halide are formed.


Reaction with Phosphorus Pentachloride
The action of phosphorus pentachloride (PCl
5
) on ethers brings about the cleavage of C-
O bond leading to the formation of alkyl halide.

Reactions Involving the Alkyl Group
Action of Air and Light
Ethers in which oxygen is bonded to 1 - and 2 -alkyl groups are subject to peroxide
formation in the presence of air (gaseous oxygen) and light.

This reaction presents an additional hazard to the use of these flammable solvents,
since peroxides decompose explosively when heated or struck. The mechanism of
peroxide formation is believed to be free radical in nature due to the presence of two
unpaired electrons molecular oxygen.
Action of Halogens
Ethers react with chlorine or bromine to give substitution products. The extent of
halogenation depends on the reaction condition. For example,


Electrophilic Substitution Reactions
Like phenols, the aromatic ethers having the alkoxy group undergo electrophilic
substitution reactions of the benzene ring at ortho- and parap- positions.

Halogenation
Anisole reacts with halogens in the presence of less polar solvents like CS
2
, CHCl
3
and
CCl
4
to give ortho and para isomers of monohaloanisoles.

Nitration
With concentrated HNO
3
/H
2
SO
4
the nitrating mixture at 293 K anisole give mixtures of
ortho and para isomers of mononitroanisoles.

Friedel-Craft's Alkylation and Acylation
The alkylation and acylation reaction, known as 'Friedel-Craft reaction', is carried by
treating anisole with alkyl chloride or acyl chloride in the presence of a catalyst like
anhydrous aluminium chloride. For example,


Using Ethers as Protective Groups
Due to their relative lack of chemical reactivity, ethers have proven to be useful
protective groups for alcohols and phenols. By converting a hydroxyl function to ether,
its acidity and ease of oxidation (in the case of 1 and 2-alcohols) can be suppressed to
such a degree that normally incompatible reactions, such as those employing Grignard
reagents, may be carried out.


Summary
Alcohols contain -OH functional group attached to a saturated sp
3
hybridized
carbon atom like alkane (R-OH), while phenols have a -OH group attached to the
carbon atoms of an aromatic ring (Ph-OH).
Ethers are organic molecules with -C-O-C- as the functional group.
Alcohols are divided into two broad categories - aliphatic alcohols and aromatic
alcohols.
Aliphatic and aromatic alcohols and phenols are classified as monohydric,
dihydric, trihydric and polyhydric according to the number of hydroxyl groups in
their molecules.
Alcohols containing sp
3
C-OH bond are classified into three categories as primary
(1), secondary (2) and tertiary (3). These can be allylic or benzylic alcohols
(attached to next to double bonded carbon atom).
Alcohols containing sp
2
C-OH bond are named as vinylic alcohols (directly
attached to double bonded carbon atoms) or aryl alcohols or phenols that are
hydoxyl derivatives of aromatic hydrocarbons.
Ethers are of two broad categories - aliphatic or aromatic ethers which can be
symmetrical and unsymmetrical ethers.
Alcohols are named using the -ol ending. On longer chains the location of the
hydroxyl group determines chain numbering.
Phenols are named using the word 'pheno' at the end. All substituted phenols
are named as derivatives of phenol with the position of the substituent with respect
to-OH group indicated by Arabic numerals.
The ether functional group is named as an alkoxy substituent on the parent
compound.
Alcohols and phenols are dipolar in nature with the oxygen carrying a partial
negative charge (
-
) that allows them to participating in hydrogen bonding.
Ethers have a tetrahedral geometry with two sp
3
orbitals of oxygen contain a
lone pair of electrons each.
Alcohols are prepared by
- hydration of alkenes (i) in presence of an acid and (ii) hydroboration-oxidation
reaction (iii) oxymercuration-reduction
- hydrolysis of haloalkanes
- reduction of carbonyl compounds by (i) catalytic reduction and (ii) the action of
Grignard's reagents
- hydrolysis of esters and
- reactions of primary amines.
Phenols may be prepared by
- alkali treatment of haloarenes
- alkali fusion of benzene sulfonic acid
- hydrolysis of diazonium salts
- decarboxylation of salicyclic acid
- acidic oxidation of cumene and
- reaction of Grignard's reagents.
Alcohols, phenols and ethers are soluble in water because of the ability to form
intermolecular hydrogen bonds with water. Solubility of alcohols in water decreases
as the size of the organic group increases.
Alcohols and phenols have higher boiling and melting points due to hydrogen
bonding. Ethers do not hydrogen bond, and are more like alkane in their properties.
Alcohols and phenols are weak acids. Alcohols are similar to water in acidity;
phenols are more acidic than alcohols or water. Electron withdrawing groups in
phenol increase its acidic strength and electron releasing groups decrease it.
Alcohols and phenols undergo reactions involving the cleavage of the O-H Bond,
the C-O bond and the whole alcohol molecule.
Alcohols undergo nucleophilic substitution with hydrogen halides, carboxylic
acids, acid chlorides and acid anhydrides and Grignard's reagent.
The cleavage of C-O bond in alcohols and phenols takes place by halogen acids,
phosphorous halides, thionyl chloride, ammonia and zinc dust (phenol only).
Dehydration of alcohols gives alkenes predicted by Zaitsev's rule.
On oxidation, primary alcohols yield aldehydes with mild oxidizing agents and
form carboxylic acids with strong oxidizing agents while secondary alcohols yield
ketones. Tertiary alcohols are resistant to oxidation.
The presence of -OH group in phenols activates the aromatic ring towards
electrophilic substitution like sulphonation, nitration, halogenation, and Friedel-Craft
reaction at ortho and para positions.
In presence of sodium hydroxide, phenol generates phenoxide ion which is even
more reactive than phenol.
Phenol undergoes Reimer-Tiemann reaction to yield salicylaldehyde and Kolbe's
reaction to yield hydroxyl acids.
Methanol and ethanol are the two commercially important alcohols used both in
the industry and in the laboratory.
Ethers are prepared by
- Williamson synthesis
- alkoxy Mercuration
- dehydration of alcohols
- reaction of alkyl halides with dry silver oxide
- reaction of Grignard's Reagent and
- reaction with diazomethane.
The boiling points of ethers resemble those of alkanes while their solubility is
comparable to those of alcohols due to the polar nature of the C-O bond.
Ethers undergo reactions involving the reactions of ethereal oxygen, the
cleavage of C-O bond and the alkyl group.
Reaction of ethereal oxygen leads to the formation of oxonium salts and
complexes.
The C-O bond in ethers can be cleaved by hydrogen halides, sulphuric acid,
phosphorous pentachloride, acid chlorides and anhydrides.
Ethers are subject to peroxide formation in the presence of air and light.
In electrophilic substitution, the alkoxy group activates the aromatic ring and
directs the incoming group to ortho and para positions.
Ethers are useful protective groups for alcohols and phenols.