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ALCOHOLS AND

PHENOLS
Alcohols
organic compounds containing
hydroxyl groups (-OH).

Similar to alkanes where one or more


hydrogen atoms is replaced by an
-OH group

General formula CnH2n+1OH


Alcohol Nomenclature
1. Find the longest carbon chain containing the -OH.
-If there is a chain with more carbons than the one containing the
OH group it will be named as a substituent.

2. Drop the -e from the alkane, add -ol.

2. Number the chain, starting from the end closest to


the -OH group.
use a number to indicate position of OH group

3. Number and name all substituents.

4. -When multiple alcohols are present use di, tri, etc before the ol
but after the parent name. eg) 2,3-hexandiol.

5. Cyclic alcohols have cyclo- before the parent


name
-numbering begins at the OH group, going in direction that gives
substituents lowest possible numbers 3
Naming Alcohols

CH3
OH
CH3 CH CH2OH
CH3 CH CH2CH3
2-methyl-1-propanol
2-butanol

CH3 OH
CH3 C OH
CH3
Br CH3
2-methyl-2-propanol
3-bromo-3-methylcyclohexanol

4
Naming Alcohols
Naming Diols
Two numbers are needed to locate the two
-OH groups.
Use -diol as suffix instead of -ol.

HO OH

Hexane-1,6-
diol 7 octene-2,4-
diol

6
Classification of Alcohols
Alcohols can be classified as primary,
secondary or tertiary

Classification is based on the number


of alkyl groups attached to the
carbon to which the OH group is
bonded
Classification of Alcohols
Primary alcohols
Carbon which carries the -OH group is
only attached to one alkyl group.

Methanol is counted as a primary alcohol


even though there are no alkyl groups
attached to the carbon with the -OH group
on it.
Classification of Alcohols
Secondary alcohols
Carbon with the -OH group attached
is joined directly to two alkyl groups,
which may be the same or different.
Classification of Alcohols
Tertiary alcohols
Carbon atom holding the -OH group
is attached directly to three alkyl
groups, which may be any
combination of same or different.
CH3
CH3 C OH
CH3
Phenols
Compounds that have a OH attached to the
carbon atom of an aromatic ring
(hydroxybenzene).

-OH group is assumed to be on carbon 1.


Phenols
Compounds with additional substituents are
named as substituted phenols

ortho- for 1,2; meta- for 1,3; and para- for 1,4
are used when there is only one other
substituent.

If there are two or more additional


substituents, each must be numbered,
beginning at the OH and going in direction
that gives the substituent the lowest number.
Hydrogen Bonding
Recall hydrogen bonding?

Alcohols -H bonds exists between the slightly +ve


H atoms and e- lone pairs on oxygen in other
molecules.

Alkanes - the only intermolecular forces are van


der Waals dispersion forces.

H bonds are much stronger than these and


therefore it takes more energy to separate alcohol
molecules than it does to separate alkane
molecules.
Solubility of Alcohol in Water
The small alcohols are completely
soluble in water.

Solubility decreases as the hydrocarbon


chain in the alcohol increases.

Only the first 3 alcohols are soluble in


water.
Solubility of Alcohol in Water
Consider ethanol in pure water- the
main intermolecular attractions are H
bonds.
Solubility of Alcohol in
Water
As the hydrocarbon chain gets longer
it interferes with the ability of the OH
group to H bond with water.
Phenol Solubility
Phenol is fairly soluble in water (even
with 6 Cs) because it partially
ionizes in water (its a weak acid)
Bpt of Alcohols and Phenols
Alcohols and phenols have relatively high bp

Phenols tend to have higher bpt than alcohols


of similar molecular weight because they
have stronger intermolecular hydrogen
bonding.

Principle: The greater the forces of


attraction the higher the boiling point or
the greater the polarity the higher the
boiling point.
Boiling Point of Alcohols
The boiling point of an alcohol is
always much higher than that of the
alkane with the same number of
carbon atoms.

The boiling points of the alcohols


increase as the number of carbon
atoms increases.
Acidity of alcohols
Acidity of alcohols vary

Some are as acidic as water whereas


others are much less acidic.

Acidity decreases as substitution on


the alkyl group increases

A more highly substituted alkyl group


inhibits solvation of the alkoxide ion
Acidity of Alcohols
Substitution by e- withdrawing
groups (eg. halogens) enhances the
acidity of alcohols because they help
to stabilize the alkoxide ion.
Acidity of phenols
Phenols are more acidic than alcohols

Phenols are more acidic because the anion


that forms upon loss of the proton is
stabilized by resonance

Phenol is 100 million times more acidic


than cyclohexanol!

Because of their high acidity, phenols are


often called carbolic acids.
Resonance Structure of
Phenoxide
Anion formed by loss of a hydrogen ion is also
resonance stabilized.
Substituent Effect on
Acidity

Substituents, located ortho or para to


the -OH group, can influence the acidity
of the phenol due to resonance and / or
inductive effects.

e- withdrawing groups increases acidity

e- donating groups decreases acidity


Oxidation/Reduction
OIL, RIG

Most organic compounds are uncharged


and gain/loss of e-s is not very apparent.

OXIDATION: addition of O or O2 ,loss of H2,


addition of an oxidizing agent (X2
halogens).

REDUCTION: addition of H2 (H-), loss of O or


O2, loss of halogen.
Oxidation/Reduction
addition or loss of H+, H2O, alkyl
halide (HX) is neither an oxidation or
reduction
Oxidation of Alcohols
Alcohols can be oxidized by a number of
reagents:

acidified sodium or potassium


dichromate(VI) solution (Na2Cr2O7/H2SO4)-
when oxidation occurs the orange
dichromate(VI) ions is reduced to green
chromium(III) ions.

Permanganate

Nitric acid
Oxidation of Alcohols
This reaction is used to make
aldehydes, ketones and carboxylic
acids.

Used to distinguish between 1o, 2o


and 3o alcohols.
Oxidation of Alcohols
Primary alcohols
Can be oxidised to either aldehydes
or carboxylic acids depending on the
reaction conditions.

The alcohol is first oxidised to an


aldehyde which is then oxidised
further to the acid.
Oxidation of Alcohols
Primary Alcohol
Obtaining the aldehyde is usually difficult
because most oxidizing agents are strong
enough to oxidize the 1oprimary alcohol to
the carboxylic acid.

Pyridinium chlorochromate (PCC) complex


of chromium trioxide, pyridine and HCl.

PCC oxidizes most primary alcohols to


aldehydes.

PCC can also oxidize secondary alcohol to


ketones.
Oxidation of Alcohols
Secondary alcohols
Secondary alcohols are oxidized to
ketones.
Oxidation of Alcohols
Tertiary alcohols

Tertiary alcohols aren't oxidised by acidified


sodium or potassium dichromate(VI) solution.

The oxidising agent is removing the hydrogen


from the -OH group, and a hydrogen from the
carbon atom attached to the -OH.

Tertiary alcohols don't have a hydrogen atom


attached to that carbon.
Summary
TO REAGENT PRODUCT
OXIDIZE
SECONDARY CHROMIC ACID KETONE
ALCOHOL OR PCC

PRIMARY PCC ALDEHYDE


ALCOHOL

PRIMARY CHROMIC ACID ACID


ALCOHOL
Formation of Alkoxide Ions
Deprotonation of alcohols gives alkoxide anions

React methanol and ethanol with sodium


metal.

1
CH3CH2OH + Na CH3CH2O Na + /2 H2

React less acidic alcohols with more


reactive potassium.
(CH3)3C OH + K (CH3)3CO K + 1/2 H2

=>

34
Formation of Alkoxide ion
Reactivity of alcohols towards sodium and
potassium decreases in the order

Methyl > 1o > 2o > 3o

Sodium reacts quickly with primary alcohols


and some secondary alcohols

Potassium is more reactive than sodium and


is usually used with tertiary alcohols and
some secondary alcohols.
Dehydration of Alcohols
When heated with strong acids catalysts
(H2SO4, H3PO4), alcohols typically
undergo a 1,2-elimination reactions to
generate an alkene and water.

Dehydration since it involves the


removal of a molecule of water.

Other common strong acids such as


HCl, HBr or HI are less suitable catalysts
as nucleophilic substitution reaction will
probably interfere.
Dehydration of Alcohol
Dehydration is favored by using heat
(endothermic reaction) and a solvent other
than water (lower concentration of H 2O)

Alcohol relative reactivity order : 3o > 2o >


1o

In fact this reaction only works with 3


and 2 alcohols
Dehydration of Alcohol
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


at or slightly above room temperature
Dehydration of Alcohols
Zaitsevs rule states that the more
substituted alkene will be the major product

Reaction of secondary or tertiary alcohols


usually proceeds via an E1 mechanism
which proceeds via a carbocation
intermediate, that can often undergo
rearrangement.

Primary alcohols will proceed via an E2


mechanism since the primary carbocation is
highly unfavorable.
Dehydration of Alcohols to
Form Alkenes
OH
H3O+
+ + H2O
Heat
H

OH
H3O+
H + CH3 + H2O
Heat
CH3
Mechanism of Acid-Catalyzed
Dehydration of an Alcohol
First, the acid catalyst protonates the
alcohol

Next, H2O is eliminated to form a


carbocation

Finally, a proton is removed to form


an alkene + H3O+
Mechanism of Acid-Catalyzed
Dehydration of an Alcohol

H H H
OH
O
O
+ +
O H H
H H

H H
O O
+
H H

+ O + O
H H H H H
Conversion to Alkyl Halides

Alkyl halides can also be formed by


reaction of alcohols with H-X acids.

R-OH + H-Br R-Br + H2O


The nature of R determines whether the reactions
proceed via SN1 or SN2 mechanisms.

(If R is primary alkyl SN2


If R is tertiary alkyl SN1).

Hydrochloric Acid
H-Cl reacts in the same way, although often Zinc (II)
chloride (a Lewis acid) is added to help compensate
for the lower nucleophilicity of chloride ion.

The mixture of HCl and ZnCl2 is called the Lucas


Reagent.
Lucas Test
Lucas reagent HCl and ZnCl2

2o and 3o alcohols react with Lucas


reagent by SN1 mechanism

1o alcohol react by SN2 mechanism


which is slower than the SN1 reaction of
2o and 3o substrates

1o carbocation is too unstable


Lucas Test
Tertiary alcohol -forms immediate white
ppt as the alcohol is converted to the
water insoluble alkyl chloride by a S N1
reaction.

Secondary alcohol- reacts after about 3-


5 minutes.

Primary alcohol- does not react.


SN1 - mean "substitution,
nucleophilic, unimolecular"
E1 - "elimination, unimolecular

SN2 -means "substitution,


nucleophilic, bimolecular
Formation of
Phenoxide Ion
Phenol reacts with hydroxide ions to
form phenoxide ions
O H O
+ OH
+ HOH
pKa =15.7
pKa =10

48
Formation of Phenoxide Ion
Reaction of Phenol with Sodium
Carbonate
Phenol isn't acidic enough to react with
carbonate.

The carbonate ions isnt a strong enough


base to take a hydrogen ion from the
phenol.

Unlike the majority of acids, phenol


doesn't give carbon dioxide when you
mix it with one of these.
Nitration of Benzene
Electrophilic substitution reaction

If you are going to substitute an -NO2


group into the ring, then the
electrophile must be NO2+. This is called
the "nitronium ion" or the "nitryl cation

HNO3 + 2H2SO4 NO2+ + 2HSO4- + H3O+


Nitration of Benzene
Halogenation of Benzene
Two electrons from the delocalised system are used to
form a new bond with the slightly positive chlorine atom
and in the process the ring gains a positive charge.

Notice that the chlorine-chlorine bond breaks,


transferring a chloride ion to the AlCl3 to make an AlCl4-
ion.

One of the aluminium-chlorine bonds breaks and both


electrons from it are used to join to the hydrogen.

Removing the hydrogen from the ring forms the HCl


which is also produced in the reaction, and the
aluminium chloride catalyst is re-generated.
phenol
The -OH group attached to the
benzene ring in phenol has the effect
of making the ring much more
reactive than it would otherwise be.

-OH group has a 2,4-directing


effect.
Phenol with Bromine Water
If bromine water is added to a
solution of phenol in water, the
bromine water is decolourised to
form 2,4,6-tribromophenol.
With dilute nitric acid
Phenol reacts with dilute nitric acid
at room temperature to give a
mixture of 2-nitrophenol and 4-
nitrophenol.
With concentrated nitric acid, more
nitro groups substitute around the
ring to give 2,4,6-trinitrophenol.
References
http://www.chemhume.co.uk/
http://www.mhhe.com/
http://www.chemgapedia.de/
http://chemwiki.ucdavis.edu/
http://catchingchenistry.blogspot.com
/

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