Chapter 7.

Alcohols, Phenols, and Thiols

General formula: alcohol --- R–OH phenol --- Ar–OH
thiol --- R–SH thiolphenol --- Ar–S-H
–OH --- hydroxyl group:
in an alcohol, –OH is attached to an alkyl group;
in a phenol, –OH is attached to an aryl group (or aromatic ring).

7.1 Nomenclature of Alcohols

(1) In the IUPAC system, the hydroxyl group in alcohols is shown by the suffix –ol.
The common name of alcohol = alkyl group name + space + alcohol
5 4 3 2 6 5 4 3
CH3CH2CH2CHOH 2-pentanol CH3CHCH2CHOH 5-chloro-3-hexanol
CH3 or sec-pentyl alcohol Cl CH2CH3
1 2 1
(2) For unsaturated alcohols, two endings (suffixes) are needed: one for double bond
(-en) or triple bond (-yn), and one for the –OH (-ol). The suffix -ol is put last in the
name and –OH group takes priority for the numbering.
1 2 3 4 5 2 1
CH3CHC CCH3 3-pentyn-2-ol H 4 3 CH2CH2OH
C C
OH ClCH2 Cl
5 (Z)-3,5-dichloro-3-penten-1-ol
1
Examples:
Cl OH
CH2CH2OH CH3CHOH

CH3
1-chloro-4-methylcyclohexanol 2-phenyl-ethanol 1-phenylehtanol

7.2 Classification of Alcohols

primary (1º) alcohol: R CH2 OH (including CH3OH)
secondary (2º) alcohol: R CH OH
R
R
tertiary (3º) alcohol: R C OH
R CH3
Examples: CH2CH2OH CH3CHOH CH3 C OH

1º 2º 3º
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7.3 Nomenclature of Phenols
(1) Phenols --- names as derivatives of the parent compounds (simple phenol).

3 2
Br
4 1
OH CH3CH2 OH CH3CH2 OH
5 6
Br
phenol (parent) p-ethylphenol 2,6-dibromo-4-ethylphenol
NO2

OH
o-nitrophenol

(2) The hydroxyl group (-OH) is named as a substituent when it occurs in the same
molecule with carboxylic acid (-COOH), aldehyde (-CHO), or ketone (>C=O)
functionalities, which have the priority in naming.
OH
O
HO COOH HO C CH3 CHO

p-hydroxy benzoic acid p-hydroxyacetophenone o-hydroxybenzaldehyde

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7.4 Hydrogen Bonding in Alcohols and Phenols
Phenomenon:
the order of boiling point (bp): alcohols > ethers > hydrocarbons (at similar MW)
CH3CH2OH CH3OCH3 CH3CH2CH3
MW 46 46 44
bp +78.5oC - 24oC - 42oC
Intermolecular
interaction: hydrogen bond > dipole-dipole > van der waals interaction
Explanation:
the hydrogen bonds between alcohol or phenol molecules can be formed.
the hydrogen bond ~ 20 -40 kJ/mol, it is weaker than
   
R   R   covalent bond, it is an intermolecular force. This force
O H O H can hold molecules together. When heating the
molecules, the hydrogen bonds need to be broken first
a hydrogen bond to separate them apart to let the molecules into vapor/gas
phase. So the bp of alcohol or phenol is high.
The other phenomenon: lower MW alcohols are miscible with water.
Explanation: the alcohol molecules can mix with water to form the hydrogen-bonded
network, which is similar to the one formed by water molecules themselves.
   
  however, when the hydrocarbon chain
   
R H length of R increases, the water solubility
    decreases. (see Table 7.1 on pg.207)
4  
7.5 General Review on Acidity and Basicity
(1) Brønsted-Lowry Definition:
Acid --- a proton donor; Base --- a proton receptor.

H O  H Cl H O H  Cl
H H
base acid conjugate acid conjugate base
of water of hydrogen chloride

HA  H2O H3O+  A-

at the equilibrium
H3O+ A-
Ka =
HA
Ka equilibrium constant, ionization constant, or acidity constant
it is used to measure the strength or acidity of an acid.
pKa = -log Ka the smaller pKa → the larger Ka → the stronger the acid.
e.g. hydrogen cyanide HCN pKa = 9.2, acetic acid (CH3COOH) pKa = 4.7
So the Ka of HCN is larger than the Ka of CH3COOH. Therefore CH3COOH is
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stronger acid. (this problem 7.7 in the book pg.210)
(2) Lewis Definition:
Lewis acid --- substance that can accept an electron pair.
Lewis base --- substance that can donate an electron pair.

H O  H+ H O H
H (HCl) H
Lewis base Lewis acid

O H  NH3 H O  H NH3
H
Lewis acid Lewis base (conjuagate (conjuagate
(acid) (base) base of H2O) acid of NH3)

Here water can be a Lewis acid or a Lewis base depending on the case.
So water is amphoteric, which means it can be acidic or basic.
7.6 The acidity of Alcohols and Phenols
Alcohols and phenols are weak acids, similar to water.
R O H R O  H+ Ar O H Ar O  H+

alcohol alkoxide ion phenol phenoxide ion

6
In book pg 211. Table 7.2 lists the pKa’s of several alcohols and phenols in aqueous
solution. From the table, we can conclude:
(1) Phenols are stronger acids than alcohols.
Reason: the phenoxide ion can be stabilized by resonance. So the negative

charge
O will be delocalized
O to the ortho
O and para O
positions on the aromatic ring.

R O

charge localized
charge delocalized in phenoxide ion in alkoxide ion

Since the phenoxide ion is stabilized, the equilibrium shifts to the direction to form
the ion. So phenols are easier to be ionized and they are stronger acids than
alcohols.
(2) If alcohols or phenols have electron withdrawing group on the alkyl group or
aromatic ring, the acidity (pKa) of the alcohols or phenols increases.
Reason:
forHalcohols,
H  F
H the inductive H
effect
H --- stabilize
polar bonds the alkoxide
place ion.charge near the
positive

C C negative charge on an alkoxide ion to stabilize
H  F C C
H - 
The ion --- this effect called --- inductive effect
O  F -O
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ethoxide ion 2,2,2-trifluoroethoxide ion CF3CH2OH’s pKa = 12.4 < CH3CH2OH’s pKa = 15.9
For inductive effect, all electron withdrawing groups increases acidity by stabilizing
the conjugate base. Electron-donating groups decreases acidity because they
destabilize the conjugate base.
For phenols, e.g. p-nitrophenol’s pKa = 7.2 phenol’s pKa = 10.0,
Here the -NO2 group stabilize the p-nitrophenoxide in two ways:
-NO2 group --- strong electron withdrawing group --- strong inductive effect.
The negative charge on the oxygen can be delocalized to aromatic ring’s ortho and
para positions as well as the oxygen atoms of -NO2 group --- by resonance effect.
(see pg 212 in your book)
Exercise: problem 7.11 on pg 212 of the book
2-chloroethanol --- -Cl electron withdrawing group --- acidity ↑ by inductive effect compared
with ethanol
p-chlorophenol --- inductive and resonance effect --- acidity ↑↑ compared with phenol
p-methylphenol --- -Me electron donating group ( + resonance) --- acidity ↓↓ compared with
phenol
phenol is more acidic than ethanol because of the resonance effect.
The order of increasing acidity is
ethanol < 2-chloroethanol < p-methylphenol < phenol < p-chlorophenol
Base on the acidity of alcohols and phenols:
2RO H  2K 2RO K  H2
- +
RO H  NaH RO- Na+  H2
alcohol potassium alcohol sodium potassium
alkoxide hydride alkoxide
alkoxides --- very strong base, stronger than NaOH/KOH 8
For phenols:

OH  Na+ OH- O-Na+  HOH

phenol sodium phenoxide

This type of reaction is not working for alcohols.
7.7 The Basicity of Alcohols and Phenols
In addition to be acting as weak acids, both alcohols and phenols can function as
weak bases.
H
for later reactions by
R O H  H+ R O H
R+  H2O
SN1 or E1 mechanisms
alkyloxonium ion carbocation
H
O H  H+ O H +  H2O

phenyloxonium ion phenyl cation

7.8 Dehydration of Alcohols to Alkenes (Elimination Reactions of Alcohols)

Alcohols can be dehydrated by heating with a strong acid.
9
This reaction is an elimination reaction, which can undergo E1 or E2
mechanisms depending on the alcohols used.
Similar to alkyl halides: tertiary alcohols --- E1 mechanism
H 3C H3 C H
H3C C OH  H+ H3C C OH
H 3C H3 C

H3C H H3C
H3C C OH H3C C+  H2O
H3C H3C
E1 H CH3 CH3
CH2 C+ CH2 C  H+
CH3
CH3

primary alcohols --- E2 mechanism

H
CH3CH2 O H  H+ CH3CH2 O H
E2 H H
CH2 CH2 O H CH2 CH2  H+  H2O

10
For alcohol dehydrations,
(1) They all start with the protonation of –OH of alcohols
(2) The ease of dehydration: 3º > 2º > 1º
When an alcohol can dehydrate to give different alkenes, the alkene with the most
substituted double bond usually is the major product.
CH3 H+
heat
CH3  CH2
HO
H2O
major minior

7.9 The Reactions of Alcohols with Hydrogen Halides (Substitution Reactions)

R OH  H X R X  H OH
alcohol X = Cl, Br, I alkyl halide
This reaction is a substitution reaction and it can undergo SN1 or SN2 mechanism
depending on the alcohol.
Reaction rate: tertiary alcohol > secondary alcohol > primary alcohol
Mechanism: tertiary alcohols --- SN1, primary alcohols --- SN2,
secondary alcohols
rt --- either SN1 or SN2
(CH3)3C OH  H Cl
15 min
(CH3)3C Cl  H OH
catalyst
heat, ZnCl2
CH3CH2CH2CH2 OH  H Cl several hours CH3CH2CH2CH2 Cl  H OH
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For the substitution reaction:
(1) They all start with the protonation of –OH of alcohols
(2) The ease of halogenation: 3º > 2º > 1º
SN1 Mechanism--- tertiary alcohols
H3C H 3C H
H3C C OH  H+ H3C C OH
H3C H 3C
H3C H H3C
H3C C OH H3C C+  H2O
H3C H3C
CH3 CH3
fast
CH3 C+  Cl- CH3 C Cl
CH3 CH3
SN2 Mechanism--- primary alcohols H
CH3CH2CH2CH2 O H  H+ CH3CH2CH2CH2 O H
CH3CH2CH2 H

Cl- C O H CH3CH2CH2CH2Cl  H2O

H
12 H
For the hydrogen halides, the reaction rate: HI > HBr > HCl
This is because the nucleophilic ability order is I- > Br- > Cl-. The stronger the
nucleophile, the faster the reaction.
7.10 Other Ways to Prepare Alkyl Halides from Alcohols
(1) Reaction with Thionyl Chloride --- prepare alkyl chloride
O
R OH  Cl S Cl
heat
RCl  HCl  SO2
thionyl chloride
(2) Reaction with Phosphorus Halides --- prepare alkyl chloride or bromide
3 R OH  PX3 3 RX  H3PO3 (X = Cl or Br)
phosphorus
halide

Both of these methods are very useful to make primary and secondary halides from
the corresponding alcohols because these alcohols are slow to react with hydrogen
halides.
7.11 A Comparison of Alcohols and Phenols (see 7.7)
Phenol can not be converted into phenyl halides by reacting with HX, phosphorus
halides, or thionyl halides.
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7.12 Oxidation of Alcohols to Aldehydes, Ketones, and Carboxylic Acids
OH O O
oxidizing agent oxidizing agent
R C H R C H R C OH
H
losing H gaining O
primary alcohol aldehyde acid

OH O
oxidizing agent
R C H R C R'
R'
losing H
secondary alcohol ketone

R''
oxidizing agent
R C H no reaction
R'
tertiary alcohol

the oxidizing agent:

Jones’ reagent --- CrO3 dissolved in aqueous sulfuric acid and acetone
this oxidizes primary alcohol into acid and secondary
alcohol into ketone. (CrO3 H2SO4, acetone)
PCC --- pyridinium chlorochromate N+ H CrO3Cl-
this oxidizes primary
alcohols into aldehydes.
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 Examples: O
CrO3
CH3CH2CH2CH2CH2CH2OH CH3CH2CH2CH2CH2C OH
H+, acetone
1-hexanol 1-hexanoic acid
O
PCC
CH3CH2CH2CH2CH2CH2OH CH3CH2CH2CH2CH2C H
CH2Cl2, 25oC
1-hexanol 1-hexanal

O
CrO3
CH2CH2CHCH3 CH2CH2CCH3
H+, acetone
OH
4-phenyl-2-butanol 4-phenyl-2-butanone

O
PCC
CH2CH2CHCH3 CH2CH2CCH3
CH2Cl2, 25oC
OH
4-phenyl-2-butanol 4-phenyl-2-butanone

In human body, similar oxidation reaction are catalyzed by enzyme, together with
coenzyme (NAD+) in liver, it is an important step for getting rid of imbibed alcohol.
First the ethanol is oxidized into acetaldehyde (toxic to body), then further oxidized
into acetic acid, eventually into carbon dioxide and water (nontoxic).
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7.13 Alcohols with More Than One Hydroxyl Group
Glycols --- has two adjacent –OH groups
Ethylene glycols: CH2 CH2 antifreeze in automobile radiators, miscible with water
it has very high boiling point (bp) (> ethanol).
OH OH
More than two –OH groups:
Glycerol: CH2 CH CH2 syrupy, colorless, water-soluble, high bp liquid,
sweet taste; It has soothing quality --- daily facial cream,
OH OH OH
shaving cream, soap and cough drop / syrupy.
CH2 ONO2
glyceryl trinitrate --- shock-sensitive explosive (strong)
CH ONO2 (nitroglycerine) also used as vasodilator in medicine
CH2 ONO2
triesters of glycerol --- fats and oils (study later)
Sorbitol: CH2 CH CH CH CH CH2 it is water soluble, very sweet like cane
sugar --- sugar substitute for diabetics
OH OH OH OH OH OH

7.14 Aromatic Substitution in Phenol (Electrophilic substitution of phenol)

-OH is a very strong activating group for the aromatic ring, so phenol’s electrophilic
aromatic
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substitution reaction is fast and under very mild conditions.
e.g.

OH + HONO2 O2N OH + H2O

(dilute)
Br

H2O
OH + 3 Br2 Br OH + 3 HBr

Br
brown solution white precipitate
This reaction can be used for testing phenol.

7.15 Oxidation of Phenols

Phenols are easily oxidized. They can be used as antioxidants --- preventing

oxidation of substances sensitive to air oxidation.

Na2Cr2O7
HO OH o
H2SO4, 30 C
O O
e.g.
hydroquinone 1,4-benzoquinone
coloress yellow
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7.16 Thiols, the Sulfur Analogs of Alcohols and Phenols
-SH group --- sulfhydryl group --- the functional group of thiols
(1) Naming
Alkane name + thiol (or alkyl group name with mercaptan)
CH3CH2CH2SH 1-propanethiol or n-propyl mercaptan

Phenol analogs:
SH thiophenol or phenyl mercaptan

Thiols are also called mercaptans because of the following reaction:

2 RSH + HgCl2 (RS)2Hg + 2 HCl
mercaptan mercaptide
(2) Preparation and Properties
Alkyl thiols --- can be synthesized from alkyl halides by nucleophilic
substitution with sulfhydryl ion, SH-.
R X -
SH R SH X-
thiols --- intense and unpleasant smell.
e.g. skunk’s odor --- from thiol compounds
Thiols are more acidic (smaller pKa) than alcohols. They react with aqueous
base to give thiolates. RSH Na+ OH- RS-Na+ H2O
18 sodium thiolate
 RSH CH3O-Na+ RS-Na+ CH3OH
sodium thiolate
Thiols are easily oxidized into disulfides --- containing –S-S- bond, by hydrogen
peroxide or iodine.
oxidation
2 RS H RS SR
reduction
thiol disulfide
This reaction can also go in the reverse way by using a reducing reagents.
This reversible oxidation-reduction reactions can be used for manipulate protein
structures since proteins have disulfide linkages.
e.g. perm the hair (hair --- consists of fibrous protein --- keratin), treat hair with
reducing agent to break hair’s disulfide cross-links, then shape the hair, finally treat
the reduced hair with oxidizing agent to reform the disulfide cross-links to hold the
hair in new shape.

Homework: 7.26 a,b; 7.27 c,d,e,i; 7.31; 7.33; 7.38; 7.44 a

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