Information

Alcohols, ethers, thiols, and phenols.

Alcohols, ethers and thiols

Alcohols are built with carbohydrate chains and hydroxyl (-OH) group attached to them. Ethanol
belongs to a homologous series called alcohols with general formula CnH2n+1OH. All members of
the series shows similar properties. They differ only in the length and structure of the
hydrocarbon chain. Alcohols are derived from alkanes by substituting an OH group for an H
atom.
H H
H C C OH
H H

R OH
general formula of alcohols

ethanol

They are named from parent alkane by omitting the final e and adding the ending ol.
CH3 OH

methanol

CH3CH2OH

ethanol

CH3CH2CH2OH

propan-1-ol

CH3CH(OH)CH2CH3

propan-2-ol

CH3CH2CH2CH2OH

butan-1-ol

For alkohols containing more than two C atoms,

isomeric compounds are possible. To distinghish
between these, it is necessery to label the position
of the OH group. The hydrocarbon-chain is always
numbered from the end with gives the lowest
number for the position of the functional group.
Thus, CH3CH2CH2CH2OH is named butan-1-ol, not
butan-4-ol. Propan-1-ol and propan-2-ol are
isomers.

Classification of alcohols
Alcohols can be classified by the number of carbon atoms bonded to the -OH group carbon. A
primary (1o) alkcohol contains one carbon bonde to the C-OH carbon. A secondary (2o) alcohol
contains two carbon bonded to the C-OH carbon. A tertiary (3o) alcohol contains three carbons
bonded to the C-OH carbon.

one carbon

two carbons

three carbons

CH3

CH3
CH3

CH2 OH

CH3

CH OH

CH3

CH OH
CH3

Primary (1 )

Secondary (2 )

Tertiary (3 )

Alcohols (cont.)
Some alcohols, particularly biologically occurring ones (sacharides), contain more than one OH
group in their molecule. They are known as polyhydric alcohols.Examples of their names:
H H
HO C C
H OH

H H
HO C C OH
H H
ethane-1,2-diol

H
C OH
H

propane-1,2,3-triol

Compounds, in which the OH group is directly attached to the benzene ring are called phenols.
The presence of the aromatic ring modifies properties of the OH group and they react other
way than aliphatic alcohols.

water

alcohol

H O

H
O H
H

R O
H
O R
H

Physical properties of alcohols. On can think of alcohols

as being derived for water by replacing one of the H
atom by an alkyl group. Like water molecules, alcohol
molecules are polar because of the polar OH bond. In
both water and alcohols, there is a special sort of strong
attractive force between the molecules due to hydrogen
bonds. Hydrogen bonds are not so strong as covalent
bonds, but are stronger than the other attractive forces
between covalent molecules.

represents a hydrogen bond

Alcohols (cont.)

R O
H
O H
H

When the liquid boils, these forces must be broken so the molecule escape
from the liquid to form a gas. This explains why the boiling points of
alcohols are higher than the those of corresponding alkanes with the similar
relative molecular mass (Mt). For example, ethanol (Mt = 46) is a liquid, while
the propane (Mt = 44) is a gas in RT. Hydrogen bonding between alcohol and
water molecules explains why the two liquids mix together.

Name

Formula

Solubility [g/100 g water]

Methanol

CH3OH

Miscible in all proportions

Ethanol

CH3CH2OH

Miscible in all proportions

Propan-1-ol

CH3CH2 CH2 OH

Miscible in all proportions

Butan-1-ol

CH3CH2 CH2 CH2OH

8.0

Pentan-1-ol

CH3CH2 CH2 CH2 CH2OH

2.7

Hexan-1-ol

CH3CH2 CH2 CH2 CH2 CH2 OH

0.6

Table shows the solubility of some alcohols in water. As the hydrocarbon-chain becomes longer,
the influence of the OH group on the properties of the molecule becomes less important. So the
properties of higher alcohols get more and more like those of the corresponding alkane.

Substitution reactions of alcohols

In strongly acidic solution alcohols undergo substitution readily because a protonated alcohol
contains a very weakly basic leaving group water. All alcohols undergo readily with HI and HBr
to yield alkyl halides.
H

CH3CH2

OH

CH3CH2

OH

Br

CH3CH2

Br

+ H2O

very weak base, good leaving group

All alcohols undergo readily with HI and HBr to yield alkyl halides.
1o, 2o or 3o ROH + HI (HBr)

RI (RBr)

+ H2O

Tertiaty alkohols , allilic alcohols, and benzylic alcohols react readily with HCl: primary and
secondary alcohols are less reactive and required a catalyst, such as zink chloride, ZnCl2.
Summary of the reactivity of differrent types of alcohols
CH3OH;

10 ROH;

2o ROH;

3o ROH;

allylic and benzylic alcohols

Increasing reactivity toward HX

Elimination reactions of alcohols

When heated with the strong acid, an alcohol with -hydrogen can undergo dehydration (loss of
water) to yield an alkene.
H

OH

CH2

CCH3

CH2 C

CH3

CH3

-hydrogen

OH

CH2

CCH3

CH3

CH2 CHCH3

H2O

H2O

H
H

OH

CH2

CH

CH2 CH2

H2O

Summary of the reactivity of primary, secondary and tertiary of alcohols toward dehydration
10 ROH;

2o ROH;

3oROH;

Increasing ease of dehydration

Esters of alcohols
Under the proper reaction conditions alcohols and acids react, losing water, to yield esters.
Reaction of alcohol with carboxylic acid yields carboxylic ester, called simply ester. These
compounds will be discuss in in lecture about carboxylic acids. Reaction of the alcohol with
the inorganic acid or its chloride can yield an inorganic ester of an alkohol, a compound in
which the HO- of the inorganic acid is replaced by OR of the alcohol.
HO

NO2

nitric acid

HO

O
POH
OH

phoshoric acid

RO

NO2

an alkyl nitrate

RO

O
POH
OH

an alkyl phosphate

Phoshate groups are common leaving groups in biochemical reactions; phosphate esters are
biologically synthetic intermediates and energy storehouses in living organisms.

Oxidation of alkohols
Depending of the conditions of reaction, primary alcohols can be oxidised to aldehydes or to
carboxylic acids. Secondary alcohols, however, can be oxidized only to ketones. Tertiary
alcohols resist oxidation in alkaline solutions. In acidic solutions tertiary alcohols undergo
dehydration to yield alkenes, which then are oxidized.

[O]
0

1 ;

RCH2OH

loss of 2 H

O
RCH
aldehyde

2 ;

3 ;

[O]

OH
RCHR'

OH
RCR'
R''

loss of 2 H

O
RCR'
ketone

[O]
no reaction

[O]
gain of O

O
RCOH
carboxylic acid

Ethers
Ethers are derived from alkanes by substituting an alkoxy group (-OR) for an H atom. For
example.
CH3CH2-O-CH2CH3
CH3CH2CH2-O-CH3

ethoxyethane
methoxypropane

The longer hydrocarbon chain is chosen as a parent alkane.

Physical properties of ethers. One can think of ethers as being derived from water by replacing
both the H atoms by alkyl groups.
R
H

O
H

O
R'

Ether molecules are only slightly polar and the attractive forces between molecules are relatively
weak. There are no H atoms attached to the oxygen to form hydrogen bonds between ether
molecules. The boiling point of an ether is similar to that of the alkane with corresponding relative
molecular mass. Like alkanes, the lower ethers are very volatile and dangerously flammable.
Ethers are only slightly soluble in water, but mix well with other nonpolar molecules such as
alkanes.

Thiols
Thiol is an organosulfur compoud that contains a sulfur-hydrogen bond (S-H). Thiols are the
sulfur analogue of an alcohol. The SH functional group is referred to as either a thiol group or a
sulfhydryl group. Thiols are often referred to as mercaptans. Thiols and alcohols have similar
molecular structure. The C-S-H angles approach 90. In the solid or molten liquids, the
hydrogen-bonding between individual thiol groups is weak, the main cohesive force being van
der Waals interactions between the highly polarizable divalent sulfur centers. Due to the small
electronegativity difference between sulfur and hydrogen, an S-H bond is less polar than the
hydroxyl group. Thiols have a lower dipole moment relative to the corresponding alcohol.
Nomenclature. The preferred method (used by the IUPAC) is to add the suffix -thiol to the name
of the alkane. The method is nearly identical to naming an alcohol. Example: CH3SH would be
methanethiol, etc. An older method, the word mercaptan replaces alcohol in the name of the
equivalent alcohol compound. Example: CH3SH would be methyl mercaptan, just as CH3OH is
called methyl alcohol.
Physical properties. Many thiols have strong odours resembling that of garlic. The odours of
thiols are often strong and repulsive, particularly for those of low molecular weight. Skunk spray
is composed mainly of low molecular weight thiol compounds. Most gas odorants utilized
currently contain mixtures of mercaptans and sulfides, with t-butyl mercaptan as the main odour
constituent.
Thiols show little association by hydrogen bonding, with both water molecules and among
themselves. Hence, they have lower boiling points and are less soluble in water and other polar

Thiols

Just as H2S is more acidic than H2O, thiols are more acidic than alcohols. The reason for the greater
acidity is that the larger sulphur atom can better disperse the negative charge of the anion. Thiols can
be prepared by nucleophillic substitution reaction of alkyl halides and sodium hydrogen sulphide (Na
SH) .
CH3CH2

Br

SH

CH3CH2

SH

Br

One important reaction of the thiols is their conversion to disulphides (RS-SR) when treating with
midl oxidizing agent such as O2 or H2O2
CH3CH2S-H + H-SCH2CH3 CH3CH2-S-S-CH2CH3 + H2O

The thiol groups in proteins can be oxidized to disulphide groups. The S-S- bridge bonds two
protein molecules and hold them in their necessery shapes
SH

SH

SH

SH

[O]

The precipitation of enzymes and other soluble proteins containing SH groups by heavy metal
ions such as Hg2+ is a principal reason that compounds containing these ions are poisonous.

Phenols
Compounds that have a OH group directly attached to benzene ring are called phenol. Thus,
phenol is a specific name for hydroxybenzene and it is the general name for family of
compounds derived from hydroxybenzene.
H3C

OH

OH
4-methylphenol

phenol

Compounds that have a OH group attached to polycyclic benzoid ring are chemically similar to
phenol, but they are calle naphthols and phenathrols (name derived from name of parent
polycyclic arene).
OH
8

OH
1

3
5

10

OH
2

7
3

9-phenanthrol

2-naphtol

1-naphtol

The methyl phenols are commomlly called cresols.

CH3
HO

CH3

4-methylphenol
(p-cresol)

HO
3-methylphenol
(m-cresol)

H3C
HO
2-methylphenol
(o-cresol)

Phenols (cont.)
The benzenediols have also trivial names
HO

OH

HO

HO

OH

HO
1,2-benzenediol
(catechol)

1,3-benzenediol
(resorcinol)

1,4-benzenediol
(hydroquinon)

Naturally occuring phenols

OH
HO

HO

HO

OH

HO
1,2-benzenediol
(catechol)

1,3-benzenediol
(resorcinol)

1,4-benzenediol
(hydroquinon)

OH

OH

OH
O
OH

H
H

H
Y

HO
estradiol
(fermale sex hormone)

HO

CH3 Z

CONH2
OH

N(CH3)2

tetracyclines (antibiotics)
(Y = Cl, Z = H: aureomycin
Y = H, Z = OH; terramycin))

Reactions of phenols
Although phenols are stucturally similar to alcohols, they are much stronger acids. Greater acidity of
phenol relative to alcohols using of resonanse theory.

OH
+

H2O

moderate resonance
stabilization

H3O

phenoxide ion
large resonance stabilization
charge is delocated

Anion is more
stabilized than
the acid

Reactions of phenols
Reactions with strong bases.
OH

NaOH

O Na

Phenols react with carboxylic acids anhydrides and acyl chlorides to form esters. Those
reactions are quite similar to those of alcohols

OH

O
RC

2O

O
OH

+ RCCl

CR +

RCO-

O
O

CR

+ Cl

Reactions of phenols (cont.)

Williamson synthesis. Phenols can be converted to ethers through Williamson synthesis.
NaOH,

OH

Na X

RX (X = Cl, Br, I, OSO3R)

Cleavage of alkyl aryl esters. When alkyl aryl esters react with stron acid as HI or HBr, the reaction
produces an alkyl halid and phenol. The phenol does not react further to produce an aryl halide
because the carbon-oxygen bond is very strong, and because phenyl cations do not form readily.

OR

CH3

conc. HX, heat

OCH3

conc. HBr, heat

CH3

RX

CH3 Br

Nitration, sulphonation, and Friedel-Crafts reactions of phenols are similar to those undergo
by arenes.