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Hydroxyl Compounds
Alcohols & Phenols
CONTENT
1
Introduction
1.1
Classification of alcohols
1.2
General formula
1.3
Nomenclature
Preparation of Alcohols
3.1
From Alkenes through Hydration
3.2
From Alkyl Halides through Nucleophilic Substitution
3.3
From Aldehydes and Ketones through Reduction
3.4
From Carboxylic Acids through Reduction
Independent
Learning
subtopic
14 Hydroxyl Compounds
LEARNING OUTCOMES
Candidates should be able to:
(a)
combustion
substitution to give halogenoalkanes
reaction with sodium
oxidation to carbonyl compounds and carboxylic acids
dehydration to alkenes
(b)
(c)
(d)
deduce the presence of a CH3CH(OH) group in an alcohol from its reaction with alkaline aqueous iodine to
form tri-iodomethane
(e)
(f)
(i)
with bases
(ii)
with sodium
(iii)
REFERENCES
1.
Peter Cann & Peter Hughes (2002). Chemistry for Advanced Level. Chapter 27.
2.
3.
Philip S. Bailey, Jr. & Christina A. Bailey (2000). Organic Chemistry A Brief Survey of Concepts & Applications.
Prentice Hall. Chapter 6.
1
Introduction
Alcohols are compounds of the general formula ROH, where R is any alkyl or substituted alkyl group. All alcohols
contain the hydroxyl (OH) group, which, as the functional group, determines the properties characteristic of this
family of compounds.
CH3 OH
CH3
H
CH3CH2OH
HO
CH(CH3)2
Ethanol
Often
found
in
alcoholic
beverages and in modern
thermometers.
Menthol
HO
Estradiol
14 Hydroxyl Compounds
Phenols are compounds in which the the hydroxyl (OH) group, is directly attached to an aromatic ring. Phenols differ
markedly from alcohols in both physical and chemical properties.
OH
1.1
Classification of alcohols
Alcohols can be subdivided into 3 different classes (similar to halogenoalkanes). An alcohol is classified as a primary,
secondary, or tertiary alcohol according to the kind of carbon that bears the OH group:
R = alkyl or aryl
General formula
Saturated aliphatic alcohols have the general formula CnH2n+1OH, where n is the number of carbon atoms.
Name
Structural formula
methanol
CH3OH
ethanol
CH3CH2OH
propan-1-ol
CH3CH2CH2OH
propan-2-ol
CH3CH(OH)CH3
Displayed formula
1.3
Nomenclature
Alcohols are named by replacing the terminal e of the corresponding alkane name with ol.
H
H C H
H
H
H C OH
H
Methane
Methanol
The longest carbon chain containing the hydroxyl group is considered the parent structure.
14 Hydroxyl Compounds
Number the alkane chain beginning at the end nearer the hydroxyl group, and use the appropriate number to
indicate the position of the OH group.
OH
Heptan-3-ol
Number the substituents according to their positions on the chain, and write the name listing the substituents in
alphabetical order.
The OH functional group is named as a hydroxy substituent when it appears on a structure with a higher priority
functional group or when the structure is too difficult to name as a simple alcohol.
CH3
OH
CH
CH2 C
OH
3-hydroxybutanoic acid
Compounds that have a hydroxyl group directly attached to a benzene ring are called phenols.
Exercise 1
Name and classify the following alcohols or phenols.
CH3 OH
(i)
CH3
CH
(ii)
CH2 Br
OH
(iii)
CH2OH
Br
CH3
CH3
1-bromo-3,3-dimethylbutan-2ol
o
(2 alcohol)
phenylmethanol
o
(1 alcohol)
5-bromo-2-methylphenol
(phenol)
14 Hydroxyl Compounds
2.1
Alcohols and phenols have nearly the same geometry around the oxygen atom as water.
2.2
Alcohols and phenols have significantly higher boiling points than those of the hydrocarbons with similar relative
molecular masses.
o
Compound
Mr
b.p. / C
Compound
Mr
b.p. / C
C2H6
30
-88
CH3OH
32
65
C3H8
44
-42
C2H5OH
46
78
C4H10
58
C3H7OH
60
97
C5H12
72
36
C4H9OH
74
118
C6H5CH3
92
111
C6H5OH, phenol
94
182
The boiling point of an alcohol is higher than that of an alkane of similar relative molecular mass.
Reason: More energy is required to overcome the intermolecular hydrogen bonding in alcohols which is
stronger than the dispersion forces in alkanes.
2.3
14 Hydroxyl Compounds
Alcohols are more soluble in water compared to their corresponding alkanes due to their ability to form
hydrogen bonds with water molecules.
Solubility of alcohols in water decreases with increasing carbon number due to the increasing length of the
hydrophobic non-polar hydrocarbon chain.
CH3CH2CH2CH2CH2CH2 OH
non-polar
2.4
polar
Phenols are moderately soluble in water due to their large hydrophobic non-polar phenyl group; but dissolve
completely when warmed.
Alcohols and phenols dissociate to slight extent by donating a proton each to water, generating a H 3O and an
Compound
CH3CH2OH
H2O
C6H5OH
pKa
16
15.7
10
As can be seen from the pKa values, CH3CH2OH is a weaker acid as compared to water, while phenol is a stronger acid
as compared to water.
2.4.1 Alcohols
CH3CH2
In alcohols, the OH bond can break to give H and RO (alkoxide ion). The extent of dissociation is lower
than that of water. Therefore alcohols do not turn litmus red.
H O
+ H+
hydroxide ion
CH3CH2 O
ethoxide ion
pKa = 15.7
H+
pKa = 16
Alkyl groups are electron-donating and will intensify the negative charge on the alkoxide ion.
Thus the alkoxide ion is destabilized. Deprotonation does not take place as easily.
electron donating effect
H
CH3
C
H
14 Hydroxyl Compounds
H
H C OH
H
methanol
pKa = 15.5
CH3
CH3 C OH
CH3
2-methyl-propan-2-ol
pKa = 18
Exercise 2
Arrange the alcohols in order of acid strength, giving your reasoning.
CH3CH2OH
In order of increasing acid strength:
(CH3)3COH <
CH2ClCH2OH
(CH3)3COH
(CH3)2CHOH
Reasons:
The more stable the alkoxide formed, the stronger is the alcohol as an acid.
Alkyl groups are electron-donating, intensifying the negative charge on the alkoxide ion and thus
destabilizing it.
(CH3)3COH with three methyl groups, followed by (CH 3)2CHOH which has two methyl groups and CH3CH2OH
which has one methyl group.
Electron-donating effect on the alkoxide is most in (CH3)3COH followed by (CH3)2CHOH and then
CH3CH2OH.
CH2ClCH2OH has an electron-withdrawing group (chloro group) thus it disperses the negative charge on
alkoxide ion and stabilizes it.
14 Hydroxyl Compounds
2.4.3 Phenol
3
Phenols are more acidic than alcohols. The pH of a 0.1 mol dm phenol solution in water is 5.4 so it will turn universal
indicator solution yellow.
CH3CH2
CH3CH2 O
O H
H+
H+
The negative charge on the phenoxide ion can be delocalised over the benzene ring as shown in the diagrams below.
This stabilises the phenoxide ion.
In the phenoxide ion, a p-orbital of the oxygen is able to overlap with the -orbital of the carbon atom in the ring. The
negative charge is able to spread around the benzene ring to some extent, thus the phenoxide anion is stabilised by
resonance. The phenoxide anion is less likely to accept a proton to form phenol. This makes phenols slightly stronger
acids than aliphatic alcohols.
2.4.4 Effect of Ring Substituents on Acidity of Phenols
Similar to alcohols, the presence of electron-withdrawing groups (e.g., NO2, F, Cl, Br, I, COCH3, CO2H, CN,
CO2R), in the ring enables the ring in turn to withdraw more electron density from the oxygen, thus stabilising the
phenoxide ion further and promoting the ionisation process.
OH
Cl
OH
OH
Cl
Cl
Cl
2,4,6-trichlorophenol
pKa = 7.6
4-chlorophenol
pKa = 9.4
phenol
pKa = 10
The presence of electron-releasing groups (e.g., CH3, NH2, OH, OCH3) decreases the acidic strength of phenols by
reducing the delocalisation of negative charge on oxygen into ring, and destabilising the conjugate base.
OH
OH
OH
CH3
benzene-1,4-diol
pKa = 10.35
Crystal Cheong / Low YZ / Jolin Lim / Grace Chua
4-methylphenol
pKa = 10.3
OH
phenol
pKa = 10
8
14 Hydroxyl Compounds
Conclusions
Phenols are more acidic than water as the phenoxide ion can be stabilized by the delocalization of the negative
charge over the benzene ring.
Alcohols are weaker acids than water as alcohols have electron donating alkyl groups which intensify the negative
charge on the alkoxide ion, thus destabilizing it.
Electron-withdrawing groups stabilize the conjugate bases (i.e., alkoxide or phenoxide anions) formed by
dispersing the negative charge on the alkoxide or phenoxide ion, resulting in increased acidity.
Electron-donating groups destabilise the conjugate bases (i.e., alkoxide or phenoxide anions) formed by
intensifying the negative charge on the alkoxide or phenoxide ion, resulting in decreased acidity.
Exercise 3
Arrange the following phenols in order of acidity (1 for the most acidic, 5 for the least acidic).
Preparation of Alcohols
Alcohols occupy a central position in organic chemistry. They can be prepared from many other organic compounds
(alkenes, alkyl halides, aldehydes, etc.) and they can be transformed into an equally wide assortment of organic
compounds.
3.1
14 Hydroxyl Compounds
There are two methods commonly used for the hydration of alkenes to form alcohols.
Industrial method
Laboratory method
1. Conc. H2SO4
2. H2O, warm
3.2
Nucleophilic substitution of alkyl halides produces the corresponding alcohols in high yield.
RCH2 X
3.3
+ OH
heat under reflux
RCH2 OH + X
LiAlH4
in dry ether
LiAlH4
in dry ether
For the reduction of aldehydes and ketones, the reducing agents used may be:
o Lithium aluminium hydride in dry ether
o hydrogen with nickel catalyst, high T & high P
o sodium borohydride (NaBH4) in methanol
3.4
For the reduction of carboxylic acids, the only reducing agent used is:
o Lithium aluminium hydride in dry ether
+ H2O
10
14 Hydroxyl Compounds
Alcohols are versatile starting materials for the preparation of a variety of organic compounds. Alcohols undergo
reactions involving various combinations of the cleavage of the CO and OH bonds of the hydroxyl group.
Combustion
Ethanol can be used as a fuel. It burns in air to form carbon dioxide and water.
CH3CH2OH(l) + 3O2(g) 2CO2(g) + 3H2O(l)
4.2
Hc = 1367 kJ mol
Halogenation
Alcohols can be converted to alkyl halides using many different methods. However, all these methods involve the
substitution of the OH group with the halogen atom via the breaking of the CO bond.
conc HCl
11
14 Hydroxyl Compounds
For bromination, HBr is produced by heating solid NaBr in the presence of concentrated H2SO4. The acid serves as
both a catalyst and as a dehydrating agent, removing water as it is formed.
NaBr / conc H2SO4
heat
Comments:
X = Br, I
12
4.3
14 Hydroxyl Compounds
Dehydration
+ H2O
Reagents & Conditions:
Dehydration cannot take place when there is no hydrogen atoms bonded to the carbon atom adjacent to the carbon
atom with the hydroxyl group.
Examples:
H
R H
C H
R C C H
R OH
OH
or
Sometimes a mixture of alkenes is formed, depending on the position of the hydroxyl group.
H H H
H H H
H H H
CH3
OH H
- H2O
CH3 CH
C3CH
C2CH=CH
C H2
Hbut-1-ene
but-1-ene
+ 3 C CCHC3CH=CHCH
CH
H
3
cis-but-2-ene
&
H
trans-but-2-ene
but-2-ene
Exercise 4
Give structures of all products formed when 1-methylcyclohexanol reacts with each of the following reagents.
(a) phosphorus pentachloride
(b) NaBr, conc H2SO4, heat
(c) hot concentrated sulfuric acid (excess)
CH3
OH
1-methylcyclohexanol
13
4.4
14 Hydroxyl Compounds
Alcohols react with reactive metals such as sodium and potassium to form alkoxides together with hydrogen gas. This
reaction involves the breaking of the OH bond.
In this reaction, the alcohols act as acids. The reaction is similar to that of sodium with water except that it is much
+
slower (ethanol is a much weaker acid than water). This reaction shows that alcohols have replaceable H . However,
they are not acidic enough to either react with alkalis (e.g., NaOH) or liberate CO2 from carbonates.
4.5
Esterification
Alcohols react with carboxylic acids and acyl chlorides to form esters in a condensation process.
4.5.1 With carboxylic acids
Reagents & Conditions: Carboxylic acid and alcohol with few drops of conc. H2SO4,
heat under reflux
Observation:
Sweet smelling liquid formed
This reaction is slow and reversible. Concentrated sulfuric acid acts as both a catalyst as well as a dehydrating agent.
4.5.2 With acyl chlorides
This reaction is very rapid due to the high reactivity of the acyl chloride and does not require heating.
14
4.6
14 Hydroxyl Compounds
Oxidation
For the oxidation of alcohols, the alcohols must have at least one hydrogen atom bonded to the carbon atom to
which the hydroxyl group is attached.
Two common reagents and conditions used for the oxidation of alcohols:
o
Oxidation to aldehydes
Once the aldehyde is formed in the reaction vessel, it will come into contact with more oxidant and this will
lead to further oxidation to form carboxylic acid. This can be avoided by distilling the aldehyde away from
the reaction mixture as soon as it forms. This is possible as the aldehyde lacks intermolecular hydrogen
bonding and thus has a lower boiling point than the corresponding alcohol.
15
14 Hydroxyl Compounds
2+
Purple solution (MnO4 ) turns colourless (Mn )
16
14 Hydroxyl Compounds
2+
Purple solution (MnO4 ) turns colourless (Mn )
Tertiary alcohols have no hydrogen on their hydroxyl-bearing carbon and thus are not oxidized.
However, in the presence of strong oxidising agents at elevated temperatures, the oxidation of tertiary
alcohols leads to the cleavage of various carbon-carbon bonds at hydroxyl-bearing carbon atom, resulting in a
complex mixture of products.
Exercise 5
Draw the structures of the organic compounds formed by oxidation of each of the following compounds.
K2Cr2O7 / dilute H2SO4
(a)
heat under reflux
O
O
HO
O
OH
CH3
(b)
CO2H
CO2H
17
4.7
14 Hydroxyl Compounds
This reaction can only take place for an alcohol containing a methyl group and a hydrogen atom attached to
the carbon with the hydroxyl group.
Ethanol (R = H) is the only primary alcohol that gives positive tri-iodomethane test.
The tri-iodomethane reaction is also a method of breaking a CC bond and removing a methyl, CH3 group. It is
therefore a useful method of shortening a carbon chain by a single carbon atom (step-down reaction).
Examples:
H
I2 (aq)
/ NaOH
(aq)
aq
alkaline
iodine
CH3
H
CHI3
warm
+
O
OH
CH2CH3
CH3
I2 (aq)
/ NaOH
(aq)
aq
alkaline
iodine
CH3CH2
CHI3
warm
OH
Exercise 6
Which of the following alcohols give positive tri-iodomethane reaction?
OH
OH
OH
OH
Answer: A & D
18
14 Hydroxyl Compounds
Exercise 7
The video clip, (http://www.youtube.com/watch?v=W4gmxGHIwIs), shows the reactions of four organic
compounds, labelled as A, B, C and D.
The compounds are ethanol, propan-1-ol, 2-methylpropan-2-ol and cyclohexene but not necessarily in that order.
Watch the video and identify the compounds from your knowledge of the reactions of organic compounds that you
have learnt.
Reaction with Na
Reaction with hot
acidified K2Cr2O7
Tri-iodomethane
test
A
Effervescence
Solution remains orange
2-methylpropan-2-ol
x
B
No effervescence
cyclohexene
x
x
C
Effervescence
D
Effervescence
Orange solution
turns green
Yellow ppt
ethanol
Most phenols are colourless solids. The melting point of phenol is 42 C. The presence of hydrogen bonds makes the
melting point of phenols higher than those of hydrocarbons of comparable relative molecular mass.
There are two sites for reaction to take place in phenol:
O
H
A comparison with alcohols
Phenols
Breaking of C-O bond
Why is the breaking of C-O bond for phenol more difficult than alcohols?
The C-O bond in phenol is very strong, due to the delocalisation of the lone pair of electrons on the oxygen over the
benzene ring.
This gives rise to the partial double bond character and thus strengthens the C-O bond.
Hence, for phenols, there are no reactions in which the C-O bond breaks, unlike the case of alcohols.
Thus, phenols do not react with PCl5 or SOCl2 or HCl or HBr.
The absence of fumes of HCl on adding PCl5 to phenols clearly distinguishes a phenol from an alcohol.
Why does the breaking of O-H bond for phenol occur more readily than alcohols?
See Section 2.4.3.
19
5.1
14 Hydroxyl Compounds
With metals
+ Na
With bases
+ NaOH
+ H2
+ H2O
Alcohols
Phenols
Sodium metal
5.1.2 Esterification
With carboxylic acids
Phenols do not react with carboxylic acids to form esters as they are weaker nucleophiles than alcohols. This is due to
the delocalization of the lone pair of electrons on the oxygen atom into the benzene ring. Hence, phenol is not
nucleophilic enough to undergo esterification in the usual way (that is, by heating with a carboxylic acid in the
presence of a few drops of concentrated H2SO4)
With acyl chlorides
Phenoxides can react with acyl chlorides to form esters.
O
Cl
+
O
O
O
propanoyl chloride
+ Cl-
phenoxide
phenoxide
(form from
Formed
fromphenol
phenolwith
withNaOH)
NaOH
phenyl propanoate
20
14 Hydroxyl Compounds
Phenol is first converted to the phenoxide salt by reacting with Na(s) or NaOH(aq) to form phenoxide ion, a stronger
nucleophile, before reacting with the acyl chloride to form the ester. This will give a high yield.
OH
OH -
H2O
Cl -
Cl
Reaction may also occur between phenol and acyl chlorides directly. However, this will give a lower yield.
5.1.3 Oxidation
Phenols are not oxidized because they do not have a hydrogen atom on the hydroxyl-bearing carbon.
5.2
Due to the delocalisation of the lone pair of electrons of oxygen into the benzene ring, the electron density in the ring
is greatly increased, making phenol much more susceptible to electrophilic attack than benzene. Hence, the presence
of the OH group highly activates the benzene ring towards electrophilic substitution and no catalyst is required.
The hydroxyl group on phenol is 2, 4 directing.
5.2.1 Bromination
With aqueous bromine (bromine water)
Phenol reacts with aqueous bromine at room temperature without the need of a Lewis acid catalyst (e.g., FeBr 3) to
produce a white precipitate of 2,4,6-tribromophenol.
21
14 Hydroxyl Compounds
5.2.2 Nitration
With dilute HNO3
Phenols react with dilute HNO3 at room temperature to yield mono-substituted nitro compounds.
With concentrated HNO3
Phenols react with concentrated HNO3 (without concentrated H2SO4) at room temperature to yield a tri-substituted
product.
5.3
Phenol reacts with neutral aqueous iron(III) chloride to form a violet complex.
This reaction is used as a characteristic test for the presence of phenolic group. The colour of the complexes may
vary slightly if other substituents are attached to the ring.
Crystal Cheong / Low YZ / Jolin Lim / Grace Chua
22