Chapter 7

Alcohols, Phenols and Ethers

Learning Check
Write the main product for the reaction of
2-Methyl-2-butanol when it undergoes
1. reaction with Na.
CH3 CH3
CH3CCH2CH3 + Na CH3CCH2CH3
OH ONa

2. dehydration.
CH3 CH3
CH3CCH2CH3 H2SO4
CH3C=CHCH3
OH
C. Halogenation of Alcohols
(nucleophilic substitution reaction)
H+
R—OH + HBr R—Br + H2O
Reaction rates ：
Tertiary ＞ Secondary ＞ Primary
Lucas test:
Lucas reagent (anhydrous ZnCl2 in concentrated
HCl solution), used for distinguishing alcohols.
In this reaction, the produced alkyl halide is not
soluble and the solution becomes cloudy.
ZnCl2 + HCl
(CH3)3C - OH (CH3)3C - Cl
R.T.
Tertiary Instantly

CH3CH2CHCH3 ZnCl2 + HCl CH3CH2CHCH3

OH heat Cl
Secondary 10 minutes later
ZnCl2 + HCl
CH3(CH2)3OH CH3(CH2)3Cl
Primary heat No change
(Several hours)
Learning Check
Distinguish the following compounds by simple
chemical test.
(1) 2,3-dimethyl-2-butanol
(2) 3,3-dimethyl-1-butanol
(3) 3-methyl-2-pentanol

1 cloudy immediately
Lucas reagent
2 heat, no change
3 heat, cloudy after 10 min
D. Oxidation of Alcohols

1. Oxidation and Reduction

• In an oxidation, there is an increase in the
number of C-O bonds. There is a loss of H.
• In a reduction, there is an decrease in the
number of C-O bonds. There is a gain of H.
D. Oxidation of Alcohols
2. Oxidation of different alcohols

K2Cr2O7/H+ Overoxidation
RCH2OH RCHO RCOOH
aldehyde carboxylic acid
R – CH – R K2Cr2O7/H+
R2C=O ketone
OH
R
K2Cr2O7/H+
R–C–OH no product
R
D. Oxidation of Alcohols
3. Oxidation of ethanol in the body
In the body,
• enzymes in the liver oxidize ethanol.
• aldehyde product impairs coordination.
• blood alcohol over 0.4% can be fatal.
O O
║ ║
• CH3CH2OH CH3CH CH3COH 2CO2 + H2O

ethanol acetaldehyde acetic acid

Effects of Alcohol on the Body
Learning Check
Under K2Cr2O7/H+ condition, write the main
oxidation products of the following alcohols:
H CH3 O CH3
K2Cr2O7/H+
(1) CH3C CHCH3 CH3C CHCH3
OH
K2Cr2O7/H+
(2) CH3CH2CH2OH CH3CH2COOH

K2Cr2O7/H+
(3) OH O
7.2 Phenol
2.1 Structure and Nomenclature

H
OH

p- conjugation
Structure of phenol
To name a phenol
• with two substituents, assign C-1 to
the carbon attached to the –OH.
• number the ring to give the other
substituent the lowest number.
OH OH
1 1

3
Cl 4
Br
3-Chlorophenol 4-Bromophenol
2.2 Chemical Properties
A. Acidity of phenols
OH
R-COOH＞ H2CO3 ＞ ＞ H2O ＞ ROH
OH ONa

NaOH

ONa OH
CO2
NaHCO3
B. Electrophilic substitution of phenols
As the p- conjugation in phenol structure,
electrophilic substitution is promoted by the
hydroxyl group.
1. Bromination
OH
OH
Br2• H2O Br Br + HBr

Br
White precipitate, used for identification
2. Nitration
OH OH
OH
20%HNO3 NO2+
25 ℃
NO2

3. Sulfonation OH
SO3H
OH 25 ℃
98% H2SO4
100 ℃

100 ℃ HO3S OH
C. Reaction with FeCl3

Enols(—C = C—OH) can react with Fe3+

forming a red–violet color complex.

OH Enol structure in phenol

OH + FeCl3 Violet color

FeCl3 acts as indicator for the enol form.

Learning Check
1. Choose the best answer
Substance which has the fastest reaction rate
with metal Na is ( D ) 。
A. 2-methyl-2-butanol B. 2-propanol
C. ethanol D. methanol
2. Give the product for the reaction
HOCH2 OH NaOH
HOCH2 ONa
Phenols in Our Life
Phenol is used in antiseptics and disinfectants.
Derivatives of phenol are the active ingredients in the
essential oils of vanilla, cloves, thyme and nutmeg.
7.3 Ethers
Ether
A ether is a substance that has organic groups
bonded to the same oxygen atom.

3.1 Structure and Nomenclature

..
Structure ： R—O—R’
.. C—O—C
ether bond
O
Dimethyl ether
H3C CH3
Nomenclature ：

CH3-O-CH2CH3 Ethyl methyl ether

C2H5 O Ethyl phenyl ether

CH3CH2 CH 2CH CH2CH3

OCH3
3-Methoxyhexane
Cyclic ether:

O
epoxyethane
CH3

O 1,2-epoxypropane
CH2Cl

O 3-chloro-1,2-epoxypropane
O

1,3-epoxypropane

O
1,4-epoxybutane
Tetrahydrofuran (heterocycle)
Crown ether

O O

12-crown-4
O O

O
O O

18-crown-6
O O
O
3.2 Chemical Properties
A. Cleavage of ether bond
(nucleophilic substitution reaction)

R—O—R´+ HX R´X + ROH

HX
RX + H2O

Reactivity: HI > HBr >> HCl

Examples ：

CH3CH2—O—CH3 HI CH3CH2—OH + CH3I

Produce the least substituted alkyl halide

O CH2CH3 HI OH + CH3CH2I

p- conjugation
Learning Check
write the main products of the following reactions:

O OH
HBr
+ CH3Br

HI
OH
O
I
B. Ring opening of epoxyethane

H-OH / H+or OH—

HO-CH2CH2-OH

o H-OR / H+or OH— HO-CH CH -OR

2 2

XMg - R
XMgO-CH2CH2-R
Et2O
H2O/H+ HO-CH CH -R
2 2

H-NHCH3 HO-CH2CH2-NHCH3
Two different kinds of ring opening:

1. Acid catalyzed
CH3
O H
+ H-OCH3 HOCH2 C CH3
OCH3

2. Base catalyzed
OH
O
+ H-OCH3 OH CH3O CH2 C CH3
CH3
Mechanism of acid catalyzed ring opening

R H R H
+
H H H H H

O O
H

R H Nu H
Nu: H
H H
intermediate R
HO H OH

SN1 reaction, nuclephiles mainly

attack more substituted carbon
Mechanism of base catalyzed ring opening

Nu:
Nu: R Nu
R H R H H
H H H H H
O H
O
O
transition state
SN2 reaction, nuclephiles mainly
attack less substituted carbon
Learning Check
write the main products of the following reactions:
CH3
O H
+ CH3CH2OH HOCH2 C CH3
OCH2CH3
OH
O OH
+ CH3CH2OH CH3CH2O CH2 C CH3
CH3
O Cl
HCl
HO CH2CH CH3

O
OH
+ CH3NH2 CH3NH CH2CH CH3
Ethers as Anesthetics
Anesthetics
• inhibit pain signals to the brain.
• diethyl ether CH3─CH2─O─CH2─CH3 was used for over a century,
but it caused nausea and was flammable.
• new ethers developed in the 1960’s were safer and nonflammable.
Chapter 8

Aldehydes and Ketones

Carbonyl Group in Aldehydes and Ketones

Carbonyl Group
• in an aldehyde is
attached to at least
one H atom.

• in a ketone is
attached to two
carbon groups.
1.1 Structure

C O

The double bond in carbonyl group is composed

of one  bond and one  bond.

+ -
C O Polarity of the double bond
1.2 Nomenclature
A. Naming aldehydes
An aldehyde
• has an IUPAC name in which the -e in the
alkane name is changed to -al.
• has a common name for the first four
aldehydes that use the prefixes: form (1C),
acet (2C), propion (3C), and butyr (4C),
followed by aldehyde.
A. Naming aldehydes
B. Naming ketones
• as IUPAC, the -e in the alkane name is
replaced with -one.
• With a common name, the alkyl groups
attached to the carbonyl group are named
alphabetically followed by ketone.

O IUPAC Common
CH3 C CH2 CH3 2-butanone ethyl methyl ketone

H3C O 4 - methyl
cyclohexanone
Learning Check
Name the following compounds according to IUPAC system
5 4
CH3CH2 3 2 1
C CH CHO
H3C
3-Methyl-2-pentenal
O
1 3
CH2 C CH CH3
CH3
3-Methyl-1-phenyl-2-butanone
1.3 Physical Properties
Aldehydes and ketones have
•polar carbonyl groups (C=O).
+ -
C=O
•attractions between polar groups.
+ - + -
C=O C=O
•without an H on the oxygen, aldehydes and
ketones cannot form hydrogen bonds.
Comparison of Boiling points

Can form hydrogen

bonds with water.
Have higher
solubility in water.
1.4 Chemical Properties
A. Nucleophilic addition
1. Mechanism of addition
- OA
-
R   Nu-, slow
+ R A+, fast R C
O
C O C
R' R' Nu R' Nu
negative oxygen
ion intermediate

R Nu
General Reaction: C O + H-Nu R C OH
R R
(H) (H)
Relative reactivities ：

a. Electronic effect
Fewer alkyl substituents
increase reactivity.

b. Steric effect
Smaller substituents
increase reactivity.
Example: rank the active sequence of nucleophilic
addition of carbonyl compounds below.
CH3 O CHO
HCHO CH3CHCHO CH3CCH3
£¨ 1£© £¨ 2£© £¨ 3£© £¨ 4£©
O
CH3 O
CCH2CH3
CH3CHCH2CCH2CH3 CH3CHO
£¨ 5£© £¨ 6£© £¨ 7£©

（ 1 ） （ 7 ）（ 2 ）（ 4 ） （ 3 ）（ 5 ）（ 6 ）