When you know chemistry, there’s a new

level of looking at the world around you.

The voltage needed to create an electron is about one million
volts. This is the voltage that creates a bolt of lightning. This
voltage pushes electrons from the sky to the ground, but the
electrons are slowed down by the air. If they weren’t, it would
be possible that two electrons accelerated by a million volts
striking the ground would give off light of enough energy to
create a new electron.
 Alcohol Chemistry
Alcohols are derivatives of hydrocarbons in which an –OH
group has replaced a hydrogen atom.
Alcohols have one or more hydroxyl (–OH)
functional groups
A family of compounds with the same general
formula, similar chemical properties and a graduation
in physical properties.
No. of Molecular Name
carbon atoms formula

1 CH3OH methanol

2 C2H5OH ethanol

3 C3H7OH propanol

4 C4H9OH butanol

5 C5H11OH pentanol

6 C6H13OH hexanol
Chemistry
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 Structure of alcohol

 Hydroxyl (OH) functional group

 Oxygen is sp3 hybridized
 O – H bond is polar
Classification of alcohol – monohydroxy derivative
OH OH OH OH
H H H R H R R R
H H R R
Methanol 10 alcohol 20 alcohol 30 alcohol
CH3
CH3 CH CH2OH
 Primary: carbon with –OH is bonded to one other carbon. OH
 Secondary: carbon with –OH is bonded to two other carbons. CH3 CH3 CH CH2CH3
 Tertiary: carbon with –OH is bonded to three other carbons. CH3 C OH
 Aromatic (phenol): -OH is bonded to a benzene ring. OH
CH3
If you choose
to stay in this
class…

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the text at the same time.
For example, I’m using
motion paths with either
a fade in zoom or a fade
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animation with a movie
clip from the Matrix.
 IUPAC Nomenclature – general rules

 Identify the parent chain: Longest chain having –OH group – Replace letter ‘e’
of parent alkane by letter ‘ol’ with the appropriate position number
before the name.
 Number the parent chain: Carbon having –OH group should have lowest
number.
 Name the substituents and place them alphabetically in front of the parent
chain.
 Assign stereochemistry (stereocenters present in molecule).
OH
OH 2 4
4 1
OH 1
3 2 5 2 3
H 4
H 3 1 H
3-methylbutan-1-ol (S)-4-methylpentan-2-ol 2-methyl-4-phenylbutan-2-ol
 IUPAC Nomenclature – Polyhydroxy compounds

When there is more than one OH group, the name must specify the total number
and positions of the functional groups.
An alcohol with two OH groups is a diol, one with three OH groups is a triol, and
so on. Note that the ‘e’ on the end of the alkane root name is retained

OH OH
1
2 1 1
3 2 OH HO 4 3 2
2 OH
OH HO OH HO 1 OH
OH
propane-1,2,3-triol ethane-1,2-diol ethane-1,2-diol butane-1,2,3,4-tetraol

OH OH
HO
OH
OH OH
hexane-1,2,3,4,5,6-hexaol
(sorbitol)
 IUPAC Nomenclature – cyclic alcohols

The ring is the parent chain, give number to the ring so as the hydroxyl group
carbon of the ring has lowest number.
The name of parent alcohol is cycloalkanol.
Arrange the substituents alphabetically before the name of parent alcohol
with number where they are attached.
OH
OH
OH
OH

cyclopropanol cyclobutanol cyclopentanol cyclohexanol

OH
OH

3-methylcyclopentanol 3-methylcyclohexanol

When two OH groups or substituents are present and are attached to different C
atoms in the saturated ring, stereoisomers are possible then specify their
stereochemistry with number before the name of parent alcohol.
OH
OH OH
OH
HO HO
HO HO
cis-cyclohexane-1,4-diol trans-cyclohexane-1,4-diol
 CH3
Naming Alcohols CH3CH CH CH3 3-methyl-2-butanol
OH
1. Name the parent compound – 4 carbons = butane
2. Replace the –e with –ol = butanol
3. Number the parent chain to minimize number of carbon with the –OH
group = number from right to left
4. Identify, name, and number all substituents = methyl on C-3
CH3

OH must be at C-1 3-methylcyclohexanol

OH
1. Name the parent compound – 6 carbon ring = cyclohexane
2. Replace the –e with –ol = cyclohexanol
3. Number the ring to minimize number of carbon with the –OH group =
number counter-clockwise.
4. Identify, name, and number all substituents = methyl on C-3
 Physical Properties of alcohols
• R-O-H has a structure similar to that of water,
• Hydroxyl group is very polar,

• Hydrogen bonds can form readily.

Aq. solution
Pure form
 Physical Properties of alcohols

Alcohols have abnormally high boiling CH3CH2CH3 bp -42 oC

points relative to their molecular CH O CH bp -23 oC
3 3
weights due to their ability to hydrogen
bond. CH3CH2OH bp +78.5 oC

Low molecular weight alcohols (up to 5-6 CH3CH2OH very soluble

carbons) are soluble in water – CH3OCH3 barely soluble
Because of polar nature of –OH group CH3CH2CH2CH2OH, 7 g per 100 mL
HOCH2CH2CH2CH2OH is very soluble

Solubility decreases as the size of the alkyl group increases -

Ratio of hydroxyl
groups to carbons in
the chain determines
solubility
 Oil
Na+ Cl- droplet

S
S
O
S4- SO4
-
O
S O4
- -S
4
O O
- -
4 4

Oil
droplet
 Acidic and basic properties of alcohol
Alcohols can act both so donate a proton (acts as a Brønsted acid) and accept a proton (acts
as Brønsted base). Aliphatic alcohols act as weak acids and bases.

pKa of alcohol is 13 - 16

Protonation of alcohols by mineral acids is analogous to the formation of the oxonium

ion which is important for nucleophilic substitution reaction in which it converts –OH into
the molecule with a good leaving group (i.e. H2O)

H +
H
O + H O
H
 Synthesis/Preparations Reduction
of alcohols R3 R1

R2 Hydration
H
Nucleophilic R3 R1
Substitution B2H6
R3 R1 R3 R1 R2 H
H H B
R2 X R2 H

4
2 SO
R3 R1

H2O2/HO-
R3 R1

t.c 2 O
cH
HO

H
R2 O

on
-
R2 O
R1 -H - aldehyde

ca
R1 -H - aldehyde
R3 R1
H2/Pt, Pd, Ni, Ru R3 R1 NaBH4 R3 R1
Reduction
R4 Reduction
R2 O or LiAlH4
R2 OH R2 O
ketone ketone
R3 R1 R2
+ H R1
1. MgBr 2. H3O
H HgOAc
R2 O R3
H H
acid or its derivative
R1 - OH, OR, X, NR2, etc R1 H2O Hg(OAc)2
R1 R1
R R4 H R1 H
Epoxide
O O O
acid or its derivative ketone R4 -H - aldehyde H H
R - OH, OR, X,
R2 = R3 = H
NR2, etc; R4 - H By using Grignard reagent
 From alkene – Hydration (acid catalyzed)
Addition of water to the carbon-carbon double bond of an alkene produces an alcohol

Reversible reaction

From alkene – Hydration (by using mercury(II) acetate)

From alkene – Hydration (by using borane in presence of alkaline peroxide)
Hydrolysis of alkyl halides
Reduction of aldehydes and ketones - Hydrogenation

Heterogeneous catalysis
Reduction of aldehydes and ketones – Hydride reducing agent
 Synthesis of alcohol - Using Grignard reagent

H R2 MgBr
1. R3 H
H R3
H 10 - alcohol
O 2.H3O +
R2 OH
Formaldehyde
R1 R2
H 1. MgBr R3 R1
R3
O H 20 - alcohol
Aldehyde 2.H3O+ R2 OH
Synthesis by
using Grignard R1 R2
1. MgBr R3 R1
Reagent R4 R3
R4 30 - alcohol
O 2.H3O+ R2 OH
ketone
R2
R1 1. MgBr R2 R1
R3
R 30 - alcohol
O 2.H3O+ R3 O
acid or its derivative
R - OH, OR, X, NR2, etc; R4 - H
R2
1. MgBr R3 OH
R3
O 10 - alcohol
Epoxide 2.H3O+ R2
 HX
R H R Substitution - SN1 / SN2
X = Br, I O X
H
HCl/ZnCl2 Lucas Test - Zn2+
R lewis acid
Cl

H2SO4
R H R Dehydration
O -H2O Elimination - E1 / E2
H H
R Williamson
Reactions of H2SO4 R H OH R O
R
O synthesis
Alcohol -H2O H
H H
O
Reactions POCl3 R P Cl R
Dehydration
R py O Cl
of alcohols OH H H
Alcohol 2 Na R1X
R R R1 Synthesis of ether
ONa O
H H
Br
PBr3 Br-
R P R
O Br Br
H H Synthesis of
Cl alkyl halide
Cl-
SOCl2 R S R
O O Cl
H H
oxidation R Reagent - Cu/heat, CrO3, H2CrO4,
O Na2Cr2O7, KMnO4, PCC, PDC, COCl2,
aldehyde/ketone HIO4, etc.
R1COOH R1
R Ester synthesis
C
O O
H
 Substitution Reactions

Computation between
substitution product, and
elimination product.
But
substitution product is
major, because
elimination product will
undergo addition reaction
with HX.

Carbocation
rearrangement
 Synthesis of alkyl halide – using PX3

Synthesis of alkyl halide – using SOCl2

 Dehydration – using POCl3

Elimination – ring expansion of cyclic alcohols

To minimize the ring/angle strain

 Dehydration

Carbocation
rearrangement
Saitzev’s rule of elimination reaction
 Dehydration - Williamson ether synthesis

Computation between
elimination & substitution

Alcohols are converted into ethers by the formation of corresponding alkoxide ion
followed by the reaction with alkyl halide, a reaction is known as Williamson ether
synthesis.
2 R OH + 2 Na R O-Na+ + H2
CH3
O + H3C I O
 Oxidation of alcohol – important for functional group interconversion

Reduction Carbonyl
Alkene Alcohol

Oxidation

If tertiary + H+ and heat

NO REACTION Dehydration
If primary
If secondary
Aldehyde
Ketone
Carboxylic acids
Oxidation of alcohol

Swern oxidation
 Ester formation

The reaction between an alcohol and a carboxylic acid or acyl chloride produces an ester.

Reversible

An alternative method of preparing esters is the condensation reaction between an acyl

chloride and an alcohol in which HCl is eliminated. The librated HCl is neutralized by
weak base.
• What product would be formed from the reaction of the following?
a. 2-bromobutane and hydroxide ion
b. (R)-2-bromobutane and hydroxide ion
c. (S)-3-chlorohexane and hydroxide ion
d. 3-iodopentane and hydroxide ion

• Give the product formed from the reaction of each of the following alcohols with
a. an acidic solution of sodium dichromate:
b. by Swern oxidation of:
1. 3-pentanol 3. 2-methyl-2-pentanol 5. cyclohexanol
2. 1-pentanol 4. 2,4-hexanediol 6. 1,4-butanediol
 Chemistry of Phenol

Phenols are compounds that have a hydroxyl group bonded directly to a benzene
or benzenoid ring i.e. on sp2 hybridized carbon atom.

The parent compound of this group, C6H5OH, called simply phenol.

OH OH
sp2 hybridized carbon OH
Aromatic ring

phenol naphthalen-1-ol naphthalen-2-ol

 Nomenclature of phenol derivatives

An old name for benzene was phene, and its hydroxyl derivative came to be called
phenol which acceptable name by IUPAC.
The names methyl phenols are also accepted by IUPAC, are known as o-, m-, and
p-cresol.

The common names for the two hydroxy derivatives of naphthalene are 1-
naphthol and 2-naphthol is also acceptable.
6
HO HO CH3 HO 1 5 HO 1
2
OH HO 1 2
3
3
2
4 6 4 6
HO 3 5
4 OH
phenol 5
m-cresol
pyrocatechol resorcinol hydroquinone
(1,2-benzenediol) (1,3-benzenediol) (1,4-benzenediol)

OH
OH

naphthalen-1-ol naphthalen-2-ol
(1-Naphthol) (1-Naphthol)
(-Naphthol) (-Naphthol)
Numbering of the ring begins at the hydroxyl-substituted carbon and proceeds
in the direction that gives the lower number to the next substituted carbon.
Substituent's are cited in alphabetical order.
HO HO Cl

Cl
A B

For the compounds containing phenolic OH and carboxylic or acyl group, the
during predication of IUPAC nomenclature, Carboxyl and acyl groups are
consider as parent group and the phenolic hydroxyl is the substituent.
OH
H3COC 1 2 HOOC 1 2
3
3
6 4 6 4 OH
5 5
1-(2-hydroxy-4-methylphenyl)ethanone 4-hydroxybenzoic acid
 Resonance stabilization of phenoxide ion
Phenol is planar, with a C-O-H bond angle of 1090, which is almost the same as the
tetrahedral angle and not much different from the bond angle C-O-H (108.50) of
methanol.

The carbon–oxygen bond distance (136 pm) in phenol is slightly less than that in
methanol (142 pm). The shorter C-O bond length is observed due to the partial
double-bond character that results from conjugation of the unshared electron pair
of oxygen with the aromatic ring. This resonance is used to explain many
properties of phenol.
Some of them are listed here. The hydroxyl oxygen is less basic (less electron
density); the hydroxyl proton more acidic, in phenols than in alcohols;
Electrophiles attack the aromatic ring of phenols much faster than they attack
benzene.
H H H
O O O H H
O O

phenol
Resonance structures of phenol (Stable)
(Stable)
 Physical properties and acidic character
Because of acidic property of phenol, it was known as carbolic acid.
Phenols are more acidic than alcohols but less acidic than carboxylic acids.
The ionization constants pKa of carboxylic acids have of approximately 5; whereas
the pKa’s of alcohols are in the range of 16 to 20 and of phenol is 10.

The more acidic character of phenol than ethanol is explained by comparing the
ionization equilibria for phenol and ethanol.
H2 H2
C C - +
H3C O
H H3C O H+ Ka = 10-16 (pKa = 16)
ethanol ethoxide ion
+
HO Na-O
+ H+ Ka = 10-10 (pKa = 10)

phenol phenoxide
1. The negative charge in ethoxide ion is localized on oxygen and is stabilized only
by solvation forces but the negative charge in phenoxide ion is stabilized both by
solvation and by electron delocalization (resonance effect of pi-electron of ring)
into the ring.
2. The OH group of phenol is attached to an sp2 carbon that is more
electronegative than the sp3 carbon to which the OH group of alcohol is attached.
Greater inductive electron withdrawal by the carbon stabilizes the conjugate base by
decreasing the electron density of its negatively charged oxygen.

OH O- O O O

H+ +

phenol
Resonance structures of phenolate ion

The substituent attached to phenol ring affect the acidic character of it.
- electron donating group decreases the acidity because of less stabilization of
phenoxide ion intermediate
- -electron withdrawing substituent such as nitro group shows substantial change
in acidity.
 Question
• Which one of the following has the lowest pKa?

• A) B)

• C) D)
 Question

• Which of the following compounds is more acidic?

• A) o-Cresol
• B) o-Chlorophenol
• C) o-Methoxyphenol
• D) o-nitrophenol
• E) m-nitrophenol
 PHENOL - REACTIONS OF THE OH GROUP

Water phenol is a weak acid

it dissolves very slightly in water to form a weak acidic solution
it is a stronger acid than aliphatic alcohols
the ring helps weaken the O-H bond and stabilises the resulting anion

C6H5OH(aq) C6H5O¯(aq) + H+(aq)

NaOH phenol reacts with sodium hydroxide to form a salt - sodium phenoxide
it is ionic and water soluble

C6H5OH(aq) + NaOH(aq) ——> C6H5O¯ Na+(aq) + H2O(l)

Sodium phenol reacts with sodium to form an ionic salt - sodium phenoxide
hydrogen is also produced
this reaction is similar to that with aliphatic alcohols such as ethanol

2C6H5OH(s) + 2Na(s) ——> 2C6H5O¯ Na+(s) + H2(g)

 Physical properties and acidic character

The physical properties of phenols are strongly influenced by the hydroxyl group, which
permits phenols to form hydrogen bonds with other phenol molecules and with
polar molecules like water, alcohol and carboxylic acid.
 Phenols have higher melting points and boiling points.
 Phenols are more soluble in water than arenes and aryl halides of comparable
molecular weight.
 The hydroxyl oxygen is less basic (less electron density), and the hydroxyl proton
more acidic, in phenols than in alcohols.

H H H
H O
H O H H O O H
H H H
O O O O H O
H H H
H H H O O
O O O

Intermolecular H-bonding - phenol Intermolecular H-bonding - aq. phenol

O H O H

N O O
H
O O
Intramolecular H-bonding - o-nitrophenol, salicylic acid
 Preparation of phenols
Pyrolysis of sodium benzene sulfonate

+
HO3S NaO3S Na-O +
HO
NaOH NaOH H
H2O 3500 H2O
phenol

In this process, benzene sulfonic acid is reacted with aqueous sodium hydroxide.
The resulting salt is mixed with solid sodium hydroxide and fused at a high
temperature. The reaction proceeds by the addition-elimination mechanism of
nucleophilic aromatic substitution.
 Preparation of phenols
Dow process

Cl HO
dilute NaOH
3000/3000 psi
1-chlorobenzene phenol

In the Dow process, chlorobenzene is reacted with dilute sodium hydroxide at

300°C and 3000 psi pressure. It is Nucleophilic substitution reaction.
 Preparation of phenols
Air oxidation of cumene
H3C CH3 CH3
H H3C
O
O H HO
O2 H3O+ O
100-1300 +
H3C CH3
cumene Cumene phenol
hydroperoxide
The mechanism for the formation and degradation of cumene hydroperoxide is
given below. The cumene hydroperoxide was formed by a free radical chain
reaction. A radical initiator abstracts a hydrogen from cumene lead to formation of
a tertiary free radical. The creation of the tertiary free radical is the initial step in the
reaction.
H3C CH3 CH3 CH3
H3C CH3 H3C H3C
H O H
O
+ -RH O2
R +
Initiation 100-1300
cumene cumene
CH3
H3C
O
H3C CH3 O H
+

Cumene
hydroperoxide
 Preparation of phenols
Air oxidation of cumene
The cumene hydroperoxide undergoes degradation in presence of acid catalyst. In
the first step, a pair of electrons on the oxygen of the hydroperoxide’s “hydroxyl
group” is attracted to a proton of the H3O+ molecule, forming an oxonium ion
which undergoes dehydration forming new oxonium ion. A phenide ion shift to
the oxygen atom (which creates a tertiary carbocation) stabilizes the positively
charged oxygen. The carbocation is stabilized by an acid-base reaction with a water
molecule, leading to the formation of an intermediate which undergoes degradation
in presence of acid catalyst forming phenol and acetone.
H3C CH3
O H3C CH3 H3C CH3 H3C
O H O H CH3
H+ O
H O+ + H H O
O
Cumene
hydroperoxide oxonium ion H H
O

O HO H H
O H H+ O H -H+ O
+
H3C CH3 O CH3 O CH3 O CH3
phenol CH3 CH3 CH3
H
 Preparation of phenols
Synthesis from aniline
H2N NO2 HO NO2
1. NaNO2, H2SO4, H2O
2. H2O, heat
3-nitrobenzenamine 3-nitrophenol

The most important synthesis of phenols in the laboratory is from amines by

hydrolysis of their corresponding diazonium salts, as shown below.
 Reactions of phenols
Isomerisation

HO H H
O
[Tautomerism of phenol]
phenol
(enol form - stable) (keto form)

Phenol is unusual in that its enol tautomer is more stable than its keto tautomer
because the enol tautomer is aromatic, but the keto tautomer is not.
 Reactions of phenols

Although a hydroxyl group strongly activates an aromatic ring toward electrophilic

attack, an oxyanion substituent is an even more powerful activator. Electron
delocalization in phenoxide anion leads to increased electron density at the
positions ortho and para to oxygen.
HO -
O O O O
+
H +

phenol phenoxide
Resonance stabilization of
negative charge
 Reactions of phenols

Electrophilic substitution reactions

The electrophile attacks either on hydroxyl oxygen or the aromatic ring, therefore
the reactions of phenols classified in two types – electrophilic aromatic substitution
and O – substitution reactions.

OH OH OH OH
H H H H Relatively
ortho Y Y Y Y stable

OH OH OH
HO
meta
+ Y+ H H H

phenol Y Y Y
OH OH OH OH
Relatively
para stable

Y H Y H Y H Y H

The –OH group is activating so the electrophilic substitution occurs at o- and or p-

position rather than meta-position which can be explain by the stabilization of
intermediate cation as below.
 Reactions of phenols
Sulfonation
HO SO3H
+ HO
HO
SO3H
Br
H2SO4 100 0
4-bromophenol
Br 2 l
Nitration C H 2C
H
C lC 2 0 Br
HO 0 Bromination
HO HO HO
HNO3 Br2
+ acetic acid H2O, 250
O2N NO2 50 phenol Br Br
O
2-nitrophenol 4-nitrophenol 2,4,6-tribromophenol
COH AlC Cl
) 0 l
H 3 3 , 60 3
Friedel-Crafts alkylation (C OH O
PO 4
H3
HO
+ HO
O
C(CH3)3 (74%) (16%)
Friedel-Crafts acylation
 Reactions of phenols
Nitrosation:

On acidification of aqueous solutions of sodium nitrite, the nitrosonium ion (:N≡O+)

is formed, which is a weak electrophile and attacks the strongly activated ring of a
phenol. The product is a nitroso phenol
O
N
OH
HNO2, H2SO4, H2O OH
00 C
naphthalen-2-ol
1-nitrosonaphthalen-2-ol
(99%)
 Reactions of phenols

Reaction with arenediazonium salts:

Adding a phenol to a solution of a diazonium salt formed from a primary aromatic
amine leads to formation of an azo compound. The reaction is carried out at a pH
such that a significant portion of the phenol is present as its phenoxide ion. The
diazonium ion acts as an electrophile toward the strongly activated ring of the
phenoxide ion.

C6H5
N N
N N C6H5
OH
C6H5N2Cl OH OH
00 C +
naphthalen-2-ol
(E)-1-(phenyldiazenyl) (Z)-1-(phenyldiazenyl)
naphthalen-2-ol naphthalen-2-ol
 Reactions of phenols
Kolbe–Schmitt carboxylation reaction (synthesis of aspirin):
The best known aryl ester is O-acetylsalicylic acid, better known as aspirin. The first
step in the industrial synthesis of aspirin is known as the Kolbe–Schmitt
carboxylation reaction.
The phenolate ion reacts with carbon dioxide under pressure followed by the
treatment of acid to form o-hydroxybenzoic acid, also known as salicylic acid.
Acetylation of salicylic acid with acetic acid anhydride forms acetylsalicylic acid
(aspirin)
-
O O OH O
HO O
base + pressure O- O-
O C O
H
phenol phenoxide
O H+

O O O O OH O

OH O OH

Acetyl salicylic acid Salicylic acid

aspirin
 Reactions of phenols
The Kolbe–Schmitt reaction is an equilibrium process governed by thermodynamic
control.
OH O
-
HO O O-
base + O C O O-
rather HO
than O
phenol phenoxide Salicylate anion p-hydroxybenzoate
strong base: ka anion
weakest base: ka
of conjugate acid, a base: ka of conjugate
of conjugate acid,
10-10 acid, 3.3 x 10-5
1.06 x 10-3
H
O O-
intra-molecular Hydrogen
O bonding in salicylate anion
 Reactions of phenols
Synthesis of aryl ethers:
Aryl ethers are best prepared by the Williamson method. Alkylation of the
hydroxyl oxygen of a phenol takes place readily by treating a phenoxide anion with
an alkyl halide. The synthesis is normally performed only by heating a solution of
the phenol and alkyl halide in the presence of a suitable base such as potassium
carbonate.
HO -
O
base Br SN2 O
+
allyl K2CO3
phenol bromide acetone
phenoxide allyl phenyl ether
Allyl aryl ethers undergo an interesting reaction, called the Claisen
rearrangement, on being heated. The allyl group migrates from oxygen to the ring
carbon ortho to it.
HO Br O HO
*
+ *
allyl K2CO3
acetone *
phenol bromide allyl phenyl ether o-allyl phenol
(73%)

aromatization
O O
rearrangement
*
*
H
 Reactions of phenols
Acylation of phenol
Acylation agents, such as acyl chlorides and carboxylic acid anhydrides, can react with
phenols either at the aromatic ring (C-acylation) or at the hydroxyl oxygen (O-acylation):
O O OH O
HO O O
R O R R
O + R HO
R +
R Cl O
phenol Aryl ester Aryl ketones
(O-acylation) (C-acylation)
Friedel Craft reaction
In the absence of aluminum chloride (lewis acid), however, O-acylation occurs instead.
HO O
NaOH/H2O O C7H15
+ C7H15 Cl + HCl
O
phenol phenyl octanoate
HO OH O O
NaOH/H2O O O O
+ 2 + sodium acetate
O O
resorcinol 1,3-diacetoxybenzene
Acid anhydride to a more powerful acylating agent by protonation of one of its carbonyl
oxygens. Addition of a few drops of sulfuric acid is usually sufficient.
OH O O O
H2SO4
+ + sodium acetate
O O
F F
4-fluorophenol 4-fluorophenyl acetate
(84%)
 Synthesis of aryl ethers:
the Fries rearrangement
The C-acyl isomers are more stable, which will be formed more effectively by
using aluminum chloride as catalyst. It is more effective catalyst for the conversion
of aryl esters to aryl ketones. This isomerization is called the Fries rearrangement.

OH O
O O C6H5
AlCl3 C6H5 + HO
C6H5 O
phenyl benzoate o-hydroxybenzophenone p-hydroxybenzophenone
(9%) (64%)
Give each of the following compounds a systematic name, and indicate whether
each is a primary, secondary, or tertiary alcohol:
OH
OH Cl
HO
(a) (b) (c)

OH OH Cl

(d) OH
(e) (f)
• Write structural formulas for each of the following compounds:
(a) Pyrogallol (1,2,3-benzenetriol) (c) 3-Nitro-1-naphthol
(b) o-Benzylphenol (d) 4-Chlororesorcinol
 OH
OH Cl
(a) HO
(b) (c)
pentan-1-ol 4-methylcyclohexanol 5-chloro-2-methylpentan-2-ol

OH Cl
OH

OH
(d) (e) (f)
5-methylhexan-3-ol 2,6-dimethyloctan-4-ol 4-chloro-3-ethylcyclohexanol

OH OH
HO OH
OH
OH NO2 OH Cl
benzene-1,2,3-triol 3-nitronaphthalen-1-ol 2-benzylphenol 4-chlorobenzene-1,3-diol
•Give the major product obtained from the acid-catalyzed hydration of each of the
following alkenes:

(a) (b)
(c) (d)
(a) (b)
(c) (d)

OH OH

OH
+ OH

OH
 Problems
Give the major product obtained of the following reactions -
OH
(a) + Br K2CO3
OCH3 acetone

ONa OH
(b) + Cl OH

CHO
(c) HNO3, acetic acid, heat
HO
OCH3

O
H heat
(d) N

O
 OH O
(a) + Br K2CO3
OCH3 acetone OCH3
OH
ONa OH O OH
(b) + Cl OH

CHO O2N CHO

(c) HNO3, acetic acid, heat
HO HO
OCH3 OCH3

O OH
H heat H
(d) N N

O O
 Reactions of phenols
• Write a balanced chemical equation for each of the following reactions:
(a) Phenol - sodium hydroxide

(b) Product of part (a) + ethyl bromide

(c) Product of part (a) + butyl p-toluenesulfonate

(d) Product of part (a) + acetic anhydride
(e) o-Cresol + benzoyl chloride
(f) m-Cresol + ethylene oxide
(g) 2,6-Dichlorophenol + bromine

(h) p-Cresol + excess aqueous bromine

 O
ONa O
O S O
O
O
(a) (b) (c) (d)

Cl Br
O OH OH
O OH

O Br Cl Br
(e) (f) (g) (h)
Give the product formed from the reaction of each of the following alcohols with

a. an acidic solution of sodium dichromate:

b. the reagents required for a Swern oxidation:
1. 3-pentanol
2. 2-methyl-2-pentanol
3. Cyclohexanol
4. 1-pentanol
5. 2,4-hexanediol
6. 1,4-butanediol
Write chemical equations, showing all necessary reagents, for the preparation of 1-
butanol by each of the following methods:

(a) Hydroboration–oxidation of an alkene

(b) Use of a Grignard reagent
(c) Use of a Grignard reagent in a way different from part (b)
(d) Reduction of a carboxylic acid
(e) Reduction of a methyl ester
(f) Reduction of a butyl ester
(g) Hydrogenation of an aldehyde
(h) Reduction with sodium borohydride
Write structural formulas for each of the following compounds:
(a) Pyrogallol (1,2,3-benzenetriol) (c) 3-Nitro-1-naphthol
(b) o-Benzylphenol (d) 4-Chlororesorcinol
Which is the stronger acid in each of the following pairs? Explain your reasoning.

(a) Phenol or p-hydroxybenzaldehyde

(b) m-Cyanophenol or p-cyanophenol
(c) o-Fluorophenol or p-fluorophenol
Write a balanced chemical equation for each of the following reactions:

(a) Phenol _ sodium hydroxide

(b) Product of part (a) + ethyl bromide
(c) Product of part (a) + butyl p-toluenesulfonate
(d) Product of part (a) + acetic anhydride
(e) o-Cresol + benzoyl chloride
(f) m-Cresol + ethylene oxide
(g) 2,6-Dichlorophenol + bromine
(h) p-Cresol + excess aqueous bromine