Enzymatic Oxidation

Ethanol is the alcohol least toxic to humans. Ingestion of methanol can lead to blindness and acidosis. Propanol
and higher alcohols are more toxic than ethanol but are rarely abused. Ethylene glycol, a common ingredient in
antifreeze, is also toxic. Deaths of animals and humans have occurred from drinking antifreeze containing
ethylene glycol. The lower toxicity of ethanol is due to the body's ability to metabolize it into acetic acid, an
important chemical in many biochemical processes in the body.
Ethanol is metabolized to acetaldehyde in the liver by an enzyme called alcohol dehydrogenase. Acetaldehyde is
quite toxic and is rapidly metabolized to acetic acid by another enzyme (acetaldehyde dehydrogenase).

Acetic acid is used in the body as a building block for fats, carbohydrates, and as an energy source. The products
of metabolism of other alcohols are responsible for their toxic effects. Methanol is metabolized to formaldehyde
and formic acid, products that are responsible for toxicity. Ethylene glycol is metabolized to oxalic acid which
binds calcium ions and is probably responsible for the kidney failure associated with ethylene glycol ingestion.
Oxidation of Secondary Alcohols

Secondary alcohols can be oxidised to

ketones, no further:

2o alcohol ketone
A secondary alcohol such as 2-propanol can be oxidized to a ketone
by elimination of H2. Ketones usually resist further oxidation.
 Oxidizing Reagent

2o Aldehyde
Alcohol H2
H 2O
O

Reduction of the Reagent

 Isopropanol [-H2] Acetone
“propan-2-ol”
Oxidation of Tertiary Alcohols

• Tertiary alcohols cannot be

oxidised
(no carbinol C-H)

3o alcohol
A tertiary alcohol such as 2-methyl-2-propanol, is resistant to oxidation
because there are no hydrogen atoms on the carbon containing the -OH group.
 Dehydration of Alcohols
• Reaction type: 1,2- or b-
Elimination
• When heated with strong acids
catalysts (most commonly H2SO4,
H3PO4), alcohols typically undergo
a 1,2-elimination reactions to
generate an alkene and water.
• Also known as dehydration since
it involves the removal of a
molecule of water.
• Alcohol relative reactivity order : 3o
> 2o > 1 o (The rate of reaction
is determined by the slowest step in the
mechanism - the formation of the carbocation.
Alkenes that can produce a 3 o carbocation
react more rapidly than those producing 2 o or
1o carbocations)
• Other common strong acids such
as HCl, HBr or HI are less suitable
catalysts as
nucleophillic substitution reactions
will probably interfere.
Dehydration of alcohols
Dehydration

C2H5-OH C2H5-OH C2H5-OH

HO- C2H5

H2SO4 H2SO4 H2SO4

HSO4
H5C2 -O- C2H5 C 2H 4
C2H5

H 2O H 2O H2SO4 H 2O H2SO4
80°C 140°C 180°C
Methods for the synthesis of ethers starting from alcohols:

R-OH R-OH
Na HO-R

[R-O]- Na+

R’ X

R-O- R’ R-O- R
The Iodoform (Haloform) Test
• This test is used to detect the presence of specific structures:
any secondary alcohol with a methyl group adjacent to
the carbon bearing the -OH group will give a positive
iodoform test (i.e., a yellow precipitate is observed).
R
(R’=CH3) CH OH
CH3
• Formation of iodoform proceeds by the sequence of reactions
shown below
 Positive iodoform test for 2-
pentanone (left). 3-pentanone
(right) gives a negative test.

O - O -
OH / H2O O
OH / I2
R C R C R C + CHI3
CH3 CI3 O

O O O
- -
OH / I2 OH / H2O
CH3 CI3 O
 Haloform Reaction
• a test for the existence of the CH3-CO- group in a molecule. This
could be part of an alcohol ( C-O single bond ) or part of a carbonyl
compound ( C=O double bond ).
• “the Reactant” Characteristic for a class of compounds that
containe ; a methyl end group attached to a carbinol or carbonyl
atom
– Ethanol ……(used to differentiate between methanol & ethanol)
– Methyl -2° Alcohols
– Acetaldehyde
– Methyl – Ketones
• “the Reagent” - Halogens [I2 ,Br2 ,Cl2 ]
in alkaline medium [ NaOH ,H2O]
• “the Products”
– Carboxylic acid (with one fewer C )
– Haloform precipitate [Iodoform/Bromoform/Chlroform]

Carboxylic acid
1° alcohol Aldehyde (with one fewer C )
[ethanol only] [ethanal only]

2° alcohols Ketones
[with methyl end group only] [with methyl end group only]
Haloform ppt.
 methyl- 2° alcohols
Ethyl Alcohol

Oxidation
“dehyrogenation”
(elimination of hydrogen)
by Halogenation

Acetaldehyde
methyl- Ketones

3 Substitution “replacement” 3
of α-Hydrogens
3 by Halogenation 3

Iodal Tri,halo-methyl- Ketones

Cleavage of C/C
Hydroxide-induced
by Hydrolysis

Tri,halo-methane
Sod-formate Tri,Iodo-methane Carboxylate “Haloform”
“Iodoform” (with one fewer C)
the methyl end group
the tri-halo methyl group
is a very bad leaving group
is a very good leaving group
 Common Name: Iodoform
Chemical Name: Triiodomethane
Formula: CHI
Color: yellow
State: solid
 ESTERIFICATION “Ester
•
formation”
Esterification of a carboxylic acid by an alcohol to give an ester
• is a reversible reaction as shown in equation 4. Normally only
60 to 70% of the potential amount of the ester is formed at
equilibrium.
• The reverse reaction, the reaction of an ester with water to
give an alcohol and an acid, is called Hydrolysis.
Hydrolysis
• The equilibrium can be shifted to the right, to give more ester,
by the addition of excess acid or alcohol (normally the latter),
or by removal of water by using a dehydrating agent as
conc.H2SO4 .
• The water produced in this reaction is formed from :-
– Its H atom …… from the hydroxyl group of the alcohol.
– Its OH group ... From the hydroxyl group of the carboxylic acid.
• The mixture of rection is added to NaHCO3 sol .for :-
– Neutralizes the excess of both acetic & sulphoric acids
– Reacts with the acids forming CO2 which carry aster and spread it.
• Formation of the ester is more favorable if water is not a
product. This is the case when either the acid anhydride or the
acid chloride is used.
 △
+ +

Carbonyl atom0

Carbinol atom0
 △
+ +
✗
≈

conc. H2SO4
≈

NaHCO3
H2SO4
EXAMPLE OF MONOHYDRIC ALIPHATIC ALCOHOLS

ETHANOL
 NAME Ethyl Alcohol
CHEMICAL NAME Ethanol
ALTERNATE CHEMICAL absolute alcohol; anhydrous alcohol;
NAMES dehydrated alcohol
ALTERNATE CHEMICAL
NAMES
ethyl hydrate; ethyl hydroxide

CHEMICAL FORMULA C2H6O

MOLECULAR WEIGHT 46.07
MELTING POINT -114.1° C
BOILING POINT 78.5° C
FLASH POINT 13° C
10.6 g/kg (young rats), 7.06 g/kg (old
LD50
rats) orally
 Methods Of
Production :
• Fermentation of sugars & starch ; in
brewing and wine-making.
• Addition of Steam (Water) to Ethene
(ethylene gas produced from the cracking
process of petroleum products);

+
very high pressure using
phosphoric acid (H3PO4)
as a catalyst at 330°C
 Uses of Ethanol
• Very common Solvent :
– In Perfumes & Cosmetics
– In many industrial processes
– In paints, resins, soaps, dyes, polishes
– In drugs
• Fuel :
– general
– Car fuel in some countries
• Special Thermometers :
to measure low temperature down to -50° C

• Alcoholic Liquors (prohibited)

 Forms
Absolute ethanol 100% conc.

Pure ethanol 96% conc.

Converted ethanol
85-90% conc. + 10-15% Methanol
“Methylated Spirits”
Both alcohols are poisonous in such quantities, so a purple
dye is added to stop people drinking it!
This a very common industrial solvent, used in many
processes. It is also the solvent often used in paints,
resins, soaps and dyes.
EXAMPLE OF DI -HYDRIC ALIPHATIC ALCOHOLS

Ethylene Glycol
)ethane diol-1,2( ethanediol
 since it has two [-OH] groups ….one at each end

physically chemically

the Hydrogen bonding effect increases The reactivity of molecule increases

⇑B.P .(197℃,
greater2.5 times that of ethanol)
⇑viscosity ⇑solubility
⇓volatility aromatic
carboxylic acids Na metal

Polar organic compounds H2O

polyesters
Organic solvent miscible with water
it interferes with the
intermolecular bonding mono- or binary
between water molecules glycol derivatives
and prevents them from
Constituent of solidifying until the Polyester
temperature has been plastics
•Liquids used in hydraulic breakreduced to much lower
than normal.
•Used in printing ink,ball-pen inks Polyester
antifreeze for cars fibers
 benzene

Di-methyl benzene

Di-aromatic acid

diol

Poly-ester
 Polyester Polymers

• Polyester Fibers “Dacron and Fortrel” :

Its characteristic properties; strong & clean. Used
in:-
1) clothing and linens
2) photographic films
3) ropes and filter construction
4) mixed with steel cord in the manufacture
of tires
5) Surgical sutures

• Polyester Plastics (molding)

– Soft drink Bottles
Diols are often used as antifreeze in car radiators
Preparation of Diols :

Toxic effects:
Ethylene glycol is metabolized to oxalic acid which binds calcium ions and is probably
responsible for the kidney failure associated with ethylene glycol ingestion.
EXAMPLE OF Tri -HYDRIC ALIPHATIC ALCOHOLS

Glycerol “Glycerin”
 Glycerol “Glycerin”

- -
-
Physical properties

• Transparent • Completely miscible in

• Viscous water
• Sweet taste • High boiling point
Source in Nature
• Glycerol is the alcoholic portion of the natural ester
“tri-glycerides”
“tri-glycerides [fats & oils]
Preparation

+
G Fatty Acid G Fatty Acid
L L
Y Y
C Fatty Acid 3H2O C Fatty Acid
E E
R R
O O
Fatty Acid L Fatty Acid
L

Fatty Acid

Fatty Acid

Fatty Acid
 Hydrolysis

Ester Alcohol+Organic Acid

Acid-Base reaction
inorganic
Base
Esterification

inorganic
Acid

Salt
of organic acid
Importance of Glycerol
• Biologically; in the human body :
• Important role in conversion of fats to
carbohydrates &vice versa
• Formation of lipids…. Storage &
structural
• Industrial; in the manufacture
of :
• Cosmetics
• Drugs
• Explosives
• Textiles (it renders them soft& flexible)
 +

O
O

H2C OH HO R'
H2C O R'
O O

HC OH
HO R" HC O R"
O
O
H2C OH
H2C O R'''
HO R'''
Nitroglycerol “Nitroglycerin” …….
(dynamite)