Chemistry 1103

Charlie Bond
MCS Rm 4.16/4.27
Charles.Bond@uwa.edu.au
What is Organic Chemistry?
Organic Reactions I II
Alkanes (Ch 21)
Conformational Analysis (Ch 21)
Stereochemistry I II III (Ch 22)
Alkyl Halides I II (Ch 24)
Alcohols and Ether I II (Ch 24)

Alcohols - Nomenclature
IUPAC names
the parent chain is the longest chain that
contains the -OH group
number the parent chain in the direction that
gives the -OH group the lower number
change the suffix -e to -ol

Common names
name the alkyl group bonded to oxygen
followed by the word alcohol
2

Alcohols - Nomenclature
OH
OH
Ethanol
(Ethylalcohol)

OH
1Propanol
(Propylalcohol)

2Propanol
(Isopropylalcohol)

OH
OH
1Butanol
(Butylalcohol)

OH
2Butanol
(secButylalcohol)
OH

2Methyl1propanol
(Isobutylalcohol)
OH

Cyclohexanol
2Methyl2propanol
(tertButylalcohol) (Cyclohexylalcohol)

Alcohols - Nomenclature
Compounds containing
two -OH groups are named as diols,
three -OH groups are named as triols, etc.

CH2 CH2
OH OH
1,2Ethanediol
(Ethyleneglycol)

CH3 CHCH2
HO OH
1,2Propanediol
(Propyleneglycol)

CH2CHCH2
HO HO OH
1,2,3Propanetriol
(Glycerol,Glycerin)
4

Polyols and sugars

Larger alcohol-containing molecules are of massive
importance in biochemistry as they are used by cells as
fuel, starting materials for making essential molecules
(e.g. ribose in DNA), and to store information.

Ignose and Godnose

Albert Szent-Gyorgyi isolated ascorbic
acid and wanted to call the compound
Ignose in his publication (as it resembles
the sugars glucose and fructose). The
journal editor refused and so he tried to
call it Godnose instead.

Eventually they settled on hexuronic acid,

until Charles King discovered that it was
the same compound as vitamin C
isolated from lemons.

Physical Properties
Alcohols are polar compounds
both the C-O and O-H bonds are polar
covalent
H
H
H

+ C
O

+
H

Hydrogen Bonding
Association of ethanol molecules in the liquid
state (only two of the three possible hydrogen
bonds to the upper oxygen are shown here).

Boiling Points

alcohols have higher boiling points and are

more soluble in water than hydrocarbons
Molecular Boiling
Weight
Point Solubility
(g/mol)
(C) inWater

StructuralFormula

Name

CH3OH
CH3CH3

methanol
ethane

32
30

65
89

infinite
insoluble

CH3CH2 OH
CH3CH2 CH3

ethanol
propane

46
44

78
42

infinite
insoluble

CH3CH2 CH2OH
CH3CH2 CH2CH3

1propanol
butane

60
58

97
0

infinite
insoluble

CH3CH2 CH2CH2CH2OH 1pentanol

88

2.3g/100g

HOCH2CH2CH2CH2 OH 1,4butanediol
CH3CH2 CH2CH2CH2CH3 hexane

90
86

138
230
69

infinite
insoluble

Acidity of Alcohols
Most alcohols are about the same or
slightly weaker acids than water
CH3 O H +

O H
H

+
CH3 O + H O H
H

[CH3 O- ][H3 O+]

K a =
= 3.2x1016
[CH3 OH]
pK a =15.5

aqueous solutions of alcohols have the same

pH as that of pure water
10

Acidity of Alcohols
pKa values for several low-molecular-weight alcohols
Compound

Structural
Formula

hydrogenchloride
aceticacid

HCl
CH3 COOH

7 Stronger
acid
4.8

CH3 OH

15.5

H2 O

15.7

CH3 CH2 OH

15.9

methanol
water
ethanol
2propanol
2methyl2propanol

pKa

(CH3 )2 CHOH 17
(CH3 )3 COH

18

Weaker
acid

*AlsogivenforcomparisonarepKa valuesforwater,
aceticacid,andhydrogenchloride.

11

Acidity of Phenols
Phenols are significantly more acidic than
alcohols
OH + H2 O
Phenol
CH3 CH2 OH + H2 O
Ethanol

O + H3 O+

pKa =9.95

Phenoxideion
+

CH3 CH2 O- + H3 O
Ethoxideion

pKa =15.9

12

Acidity of Phenols
the greater acidity of phenols compared with
alcohols is the result of the greater stability of
the phenoxide ion relative to an alkoxide ion
O:

O:

: O:

:O:

O:

:
:

ThesethreeKekul
structuresare
equivalent

Thesethreecontributingstructures
delocalizethenegativechargeonto
thecarbonsofthering
13

Rule of Thumb for OH pKa

Compound
Alkylsulfonates
Carboxylic acids
Phenols
Alcohols

pKa
0
5
10
15

14

Basicity of Alcohols
In the presence of strong acids, the oxygen atom of an
alcohol behaves as a weak base
proton transfer from the strong acid forms an oxonium
ion
H2SO4
+
+
+ H O H
CH3 CH2 -O H + O H
CH3 CH2 -O-H

H
H
H
Ethanol Hydroniumion
Ethyloxoniumion
(pKa1.7)
(pKa2.4)

thus, alcohols can function as both weak acids and

weak bases
15

Reaction with Active Metals

Alcohols react with Li, Na, K, and other active metals to
liberate hydrogen gas and form metal alkoxides
Na is oxidized to Na+ and H+ is reduced to H2
2CH3 CH2 OH + 2Na

2CH3 CH2 O-Na+ + H2

Sodiumethoxide

alkoxides are somewhat stronger bases that OH alkoxides can be used as nucleophiles in nucleophilic
substitution reactions
they can also be used as bases in -elimination
reactions
16

Conversion of ROH to RX
Conversion of an alcohol to an alkyl halide
involves substitution of halogen for -OH at
a saturated carbon
the most common reagents for this purpose
are the halogen acids, HX, and thionyl
chloride, SOCl2

Is -OH a good leaving group?

17

Conversion of ROH to RX
water-soluble 3 alcohols react very rapidly
with HCl, HBr, and HI
CH3
25C
CH3COH + HCl
CH3
2Methyl2
propanol

CH3
CH3 CCl + H2 O

CH3
2Chloro2
methylpropane

low-molecular-weight 1 and 2 alcohols are

unreactive under these conditions
18

Conversion of ROH to RX
water-insoluble 3 alcohols react by bubbling gaseous
HCl through a solution of the alcohol dissolved in
diethyl ether or THF
OH
CH3
1Methyl
cyclohexanol

HCl

0C
ether

Cl

+ H2O

CH3
1Chloro1methyl
cyclohexane

1 and 2 alcohols require concentrated HBr and HI to

form alkyl bromides and iodides
OH + HBr
Br + H2 O
1Butanol

1Bromobutane
(Butylbromide)
19

Reaction of a 3 ROH with HX

3 Alcohols react with HX by an SN1 mechanism
Step 1: a rapid, reversible acid-base reaction
transfers a proton to the OH group
CH3

CH3 H
+
+
CH3-C O
CH H
3

O H

+
CH3-C O H + H O H

H
CH3
2Methyl2propanol
(tertButylalcohol)

rapidand
reversible

Anoxoniumion

this proton-transfer converts the leaving group from

OH-, a poor leaving group, to H2O, a better leaving
group
20

Reaction of a 3 ROH with HX

Step 2: loss of H2O from the oxonium ion gives a 3
carbocation intermediate
CH3 H
+
CH3-C O
CH H

slow,rate
determining
SN 1

Anoxoniumion

CH3
+

CH3 -C

CH3
A3carbocation
intermediate

O H
H

Step 3: reaction with halide ion completes the reaction

CH3
CH3-C+ +
CH3

Cl

fast

CH3
CH3-C Cl

CH3
2Chloro2methylpropane
(tertButylchloride)

21

Reaction of a 1 ROH with HX

1 alcohols react by an SN2 mechanism
Step 1: proton transfer to OH converts the leaving
group from OH-, a poor leaving group, to H2O a better
leaving group
rapidand
reversible
+
OH + H O H

+ O H

H
Anoxoniumion

of H2O by Br Step 2: nucleophilic displacement

slow,rate
Br

O
H

H determining
SN2

Br

+ O

H
H

22

Reaction of ROH with HX

Same as for alkyl halides: Reactions are
governed by a combination of electronic
and steric effects
neverreactbySN2

governed
bystericfactors
IncreasingrateofdisplacementofH2 O

SN2

3alcohol2alcohol1alcohol
SN 1

Increasingrateofcarbocationformation

neverreactbySN1

governedby
electronicfactors
23

From MasteringChem
What is wrong with this mechanism

24

Dehydration of Alcohols
An alcohol can be converted to an alkene
by elimination of H and OH from adjacent
carbons (a -elimination)
1 alcohols must be heated at high
temperature in the presence of an acid
catalyst, such as H2SO4 or H3PO4
2 alcohols undergo dehydration at somewhat
lower temperatures
3 alcohols often require temperatures only at
or slightly above room temperature
25

Dehydration of Alcohols
CH3 CH2 OH
OH

H2 SO4
o

180 C

CH2 =CH2 + H 2 O

H2 SO4

+ H2 O

140oC
Cyclohexanol

CH3
CH3 COH
CH3

Cyclohexene

H2 SO4
50oC

CH3
CH3 C=CH2 +
2Methylpropene
(Isobutylene)

H2 O

26

Dehydration of Alcohols
When isomeric alkenes are obtained, the
more stable alkene (the one with the
greater number of substituents on the
double bond) generally predominates
(Zaitsevs rule)
rule
OH
85% H3PO4
CH3CH2CHCH3
CH3CH=CHCH3 + CH3CH2 CH=CH2
heat
2Butanol
2Butene
1Butene
(80%)
(20%)
27

Dehydration of a 2 Alcohol
A three-step mechanism
Step 1: proton transfer from H3O+ to the -OH
group converts OH-, a poor leaving group, into
H2O, a better leaving group
rapidand
HO
+ reversible
CH3 CHCH2 CH3 + H O H
H

+H
O

CH3 CHCH2 CH3 + O H

Anoxoniumion
H

28

Dehydration of a 2 Alcohol
Step 2: loss of H2O gives a carbocation
intermediate
+
H

CH3CHCH2 CH3

slow,rate
determining

+
CH3CHCH2CH3 + H2O
A2carbocation
intermediate

Step 3: proton transfer from an adjacent

carbon to H2O gives the alkene and
regenerates the acid catalyst
H

+
rapid
CH3 -CH-CH-CH3 + O H
H
E1

+
CH3 -CH=CH-CH3 + H O H
H

29

Dehydration of a 1 Alcohol
A two-step mechanism
Step 1: proton transfer gives an oxonium ion
CH3 CH2 -O-H + H O H
H

rapidand
reversible

H
CH3 CH2 O

+ O H
H

Step 2: proton transfer to solvent and loss of

H2O gives the alkene and regenerates the
acid catalyst
H

H slow,rate
H O + H C CH2 O determining
E2
H
H
H

H
H
+
HO H + C C + O H
H
H
H
H

30

Hydration-Dehydration
Acid-catalyzed hydration of an alkene and dehydration of
an alcohol are competing processes
C C

+ H2O

acid
catalyst

Analkene

H OH
Analcohol

large amounts of water favor alcohol formation

scarcity of water or experimental conditions where
water is removed favor alkene formation
Le Chateliers Principle
31