September 25 CHEMISTRY 1 LECTURE

MENU
1. Commercially important alcohols
2. Naming Aldehydes and Ketones
3. Physical Properties of Aldehydes and Ketones
4. Reactions of Aldehydes and Ketones
5. Keto-Enol Tautomerism

Commercially Important Alcohols
1. Methanol CH
3
OH (wood alcohol). It is used as
solvent in
many industrial reactions. Methyl alcohol should never
be
bbbbbb applied directly to the body, neither should the
vapors be
inhaled because this substance can be absorbed through
the
skin and through the respiratory tract. Ingestion of as
little as
15 ml can cause blindness, and 30 ml can cause death.
Methyl alcohol can be derived by heating hard wood
in
a limited supply of air.
CO
CH
3
COOH
Coal or methane
[O]
CO
2H
2

CH
3
OH
O
2

acetic acid



CH
2
O
It is prepared commercially from CO.

formaldehyde



2. Ethanol CH
3
CH
2
OH (grain alcohol). In the hospital,
the word
Alcohol means ethyl alcohol. One of its important
property is
its ability to denature protein. Because of this, ethanol is
widely used as an antiseptic.

As an antiseptic it works best at a concentration of
70 %
in water. Pure alcohol coagulates protein on contact. If
pure
alcohol is poured over a germ, it would penetrate the cell
wall
of that organism in all directions, coagulating the protein just
inside the cell wall. This ring of coagulated protein would
then prevent the alcohol from penetrating farther into the
cell, and no more coagulation would take place. At this time
the cell would become dormant, but not dead. Under proper
conditions, the organism could again begin to function.

However, if only 70% is poured over a germ, the diluted
alcohol also coagulates the protein but at a slower rate, so
that it penetrates all the way through the cell before
coagulation can block it. Then all the cells are coagulated,
and the organism dies.

Ethanol can also be used for sponge baths to reduce the
fever of a patient. When alcohol is placed on the skin it
evaporates rapidly. To evaporate, alcohol requires heat,
which heat comes from the patients skin. So the alcohol
removes the heat from the patients skin and so lower the
body temperature.

A sponge bath will do the same thing, but water
evaporates more slowly so the heat evaporates more slowly
as well. Water sponge baths are in common use in more
hospitals because they are cheaper. For children, however,
it is kinder to allow them to play in a tepid bath. The alcohol
sponge bath cools them too rapidly and is uncomfortable.
Since alcohol is flammable it cannot be used in a room
where oxygen is in use.

Alcohol is used as a solvent for many substances.
Alcohol solutions are called tinctures. Tincture of iodine
consists of iodine dissolved in alcohol.

Ethyl alcohol is also used as a beverage. Its
concentration in drinks is expressed as proof. Alcohol
slows reaction time, so driving under the influence of alcohol
can be very dangerous. Alcohol is not a stimulant; it actually
depresses the nervous system and can remove an
individuals normal inhibitions. Excessive use of alcohol may
cause destruction of the liver, a condition known as cirrhosis.

Ethanol is obtained by fermentation of sugar from plant
sources. The starches present in grains can be converted
into sugar by malt. The sugar thus produced can be
fermented under the influence of the enzymes in yeast to
yield ethyl alcohol.

3. Isopropyl alcohol CH
3
CHOHCH
3
This is toxic and
should not
be taken internally. Since it is not absorbed through the
skin it
is commonly used as rubbing alcohol and as an
astringent.

4. Ethylene Glycol CH
2
CH
2
1,2-ethanediol
OH OH
Example of a dihydric alcohol
Has a high boiling point due to extensive H-bonding
Completely miscible with water
If taken internally, it is extremely toxic because it is
oxidized in the liver to oxalic acid. Oxalic acid crystallizes
as Ca oxalate, in the kidneys, causing renal damage
which can lead to kidney failure and death.
Antidote for ethylene glycol poisoning (and also for
CH
3
OH) is administration of high levels of ethyl alcohol.
This causes the liver enzymes to oxidize the ethyl
alcohol rather than the poisonous alcohol, which is
present in smaller amounts.
Ethylene glycol is used in preparations to moisten skin;
as antifreeze in car radiators; and as raw material in the
manufacture of the polymer Dacron.

H H H
5. Glycerol HCCCH sometimes called
glycerin
OH OH OH 1,2,3-propanetriol
In terms of body chemistry, glycerol is an important
alcohol especially as a constituent of fats.
By-product of soap manufacture and is used in the
preparation of cosmetics, hand lotions and in
suppositories
Used in the lab as lubricants for rubber tubing and
stoppers
When treated with nitric acid, glycerin forms
nitroglycerin, an explosive. Medicinally, nitroglycerin is
used to treat angina or heart pain. It causes dilation of
the coronary arteries, thus increasing the supply of blood
to the heart muscles.
Other alcohols include menthol, a cyclic alcohol, it has
a cooling, soothing effect and so is used as an ingredient
in cosmetics and shaving lotions; also in cough drops
and nasal sprays; alcohols of biologic importance
include cholesterol, retinol (Vitamin A) and tocopherol
(Vitamin E)


ALDEHYDES AND KETONES

1. NomenclatureAldehydes O
Aldehydes have the general formula RCH
Functional group, like ketone, is carbonyl group, C=O
The term aldehyde comes from the words alcohol
dehydration

Primary alcohol
oxidation
aldehyde

The IUPAC Names for aldehydes end in al. To name
an aldehyde in the IUPAC System, take the name of the
longest chain containing the aldehyde group, drop the
ending e , and replace it with the ending al. The
aldehyde group is always at the end of the chain, at
Carbon 1, with that number being understood and not
written.
The common name makes use of the trivial root and the
prefix aldehyde.

IUPAC NAME COMMON NAME
methanol
oxidation
methanal HCHO
(formaldehyde)
ethanol
oxidation
ethanal CH
3
CHO
(acetaldehyde)
propanol
oxidation
propanal CH
3
CH
2
CHO
(propionaldehyde)
butanol
oxidation
butanal CH
3
CH
2
CH
2
CHO
(butyraldehyde)

Name the following compound
Br
CH
3
CHCHCHCH
2
CH
2
CH
2
CHO 6-bromo-5,7-
dimethyloctanal
CH
3
CH
3


CH
3
*Draw the structure
CH
3
CHCH
2
CHO (a) 4,4-dichloro-2,3-
dimethylpentanal
3-methylbutanal (b) 2,3-dichloropropanal
(c) 3,5-dimethyloctanal

Aromatic aldehydes have the general formula ArCHO


CH
3
+ [O]
catalyst

CHO

Toluene
Benzaldehyde
Benzaldehyde is a colorless, oily liquid with a cherry-
almond
like odor, used in the preparation of flavoring agents,
perfumes, drugs, and dyes.

H H H
HO CHO CC
CO
H H
CH
3
O
Vanillin Cinnamic aldehyde
Vanillin occurs in vanilla beans Or cinnamaldehyde is
present and gives the particular taste in oil of
cinnamon, an oil found
and odor to vanilla extract. in cinnamon bark.
Both vanillin and cinnamic aldehyde can be prepared
synthetically
and both are used as flavoring agents.

2. NomenclatureKetones O
Ketones have the general formula RCR
Functional group, like aldehyde is, carbonyl group, C=O
The oxidation of a secondary alcohol yields a ketone.
The oxygen atom from the oxidizing agent reacts with
the H from the OH group and with the H attached to the
same C as the OH group, forming water and a new
class of compounds called ketones.
The carbonyl group in an aldehyde is at the end of a
chain, but in a ketone it is not.
H
CH
3
CCH
3
+ [O] CH
3
CCH
3
+ H
2
O
OH O
2-propanol propanone
(isopropyl alcohol) (acetone)

H
CH
3
CCH
2
CH
3
+ [O] CH
3
CCH
2
CH
3
OH O
2-butanol butanone

In the IUPAC System, the names of ketones end in
one. To name a ketone, take the name of the longest
alkane containing the carbonyl group, drop the ending
e, and add
one.

In the common naming system, each alkyl group
attached to the carbonyl group is named and the word
ketone is added afterward. Thus, butanone is commonly
known as methyl ethyl ketone.

Name the following compounds :
1. CH
3
CH
2
CCH
2
CH
2
CH
3
3-hexanone (ethylpropylketone)
O
Cl
2. CH
3
CCH
2
CCH
3
4,4-dichloro-2-pentanone
Cl O


Draw the structure of the following compounds:
1. 2,2-dimethyl-3-pentanone
2. methylethylketone
3. 3-chlorobutanone
4. hydroxyacetone

Aromatic ketones have the general formula ArCOAr or
ArCOR. The simplest aromatic ketone is acetophenone.
CCH
3
CCH
2
Cl
O O
Acetophenone
chloroacetophenone

Acetophenone has been used as
Chloroacetophenone is a
hypnotic but has been supplanted lachrymator and is
used
for this purpose by newer and as a tear gas.
safer drugs.

Among the aromatic ketones in the body are the sex
hormones estrone, progesterone, testosterone, and
androsterone.

3. Physical properties of Aldehydes and Ketones
C=O is polar
Liquid aldehydes and ketonesIMFA is dipole-dipole

Lower BP than alcohol because no Hbonding, and
RCOOH

Low mw RCHO and RCOR are more soluble in water
than are nonpolar compounds of comparable mw
(because the O atom of the C=O are Hbond
acceptors)

HCHO, CH
3
CHO and CH
3
COCH
3
(acetone) are infinitely
soluble in water. As the HC of the molecule increases,
aldehydes and ketones become less soluble in water.

Most aldehydes and ketones have strong odors
Ketones odorgenerally pleasant
perfumes
flavoring agents
aldehyde odor
low mwnot pleasant
high mwpleasant (perfume)


4. Characteristic reactions of Aldehydes and Ketones
Oxidation to Carboxylic Acid by a variety of Oxidizing
Agents
O K
2
Cr
2
O
7
O
H OH
H
2
SO
4
Hexanal hexanoic acid

Liquid aldehydes @ RT are so sensitive to oxidation
must be protected from contact with air during storage; done
by sealing in container with nitrogen gas


O O

CH + O
2
C
OH

Benzaldehyde Benzoic Acid

Ketones resist oxidation

Aldehyde Tollens Reagent Ag mirror (black/gray)
Ketone mild [O] No reaction
O
RCHO + 2Ag(NH
3
)
2
+
+ 3OH
-
RCO
-
+ 2Ag + 4NH
3

+ 2H
2
O
Carboxylic acid

Because of high cost, no longer used for oxidation of aldehydes but
still used for making (silvering) mirrors

Reduction
Aldehydes are reduced to primary alcohols.
Ketones are reduced to secondary alcohols.
O
H + H
2

TRANSITION METAL
OH
PENTANAL
CATALYST
1-PENTANOL

O + H
2

TRANSITION METAL

OH

CATALYST
CYCLOPENTANONE
CYCLOPENTANOL

Reduction of C=O slower than C=C

NaBH
4
O
-

H
3
O
+
=O H
OH

H
NaBH
4
reagent commonly used in the Lab for the reduction
of
aldehydes and ketones
its advantage over H
2
is that it does not reduce
C=C bonds
because there is no polarity on C=C bond.

Chemical reactions for distinguishing
aldehydes and ketones are based on the fact
that aldehydes are very easily oxidized to
acids, but ketones are not easily further
oxidized.

Mild OA like Tollens rgt and Fehlings rgt
are easily reduced by aldehydes to silver mirror
and brick red ppt of Cu
2
O respectively.

Aromatic aldehydes reduce Tollens but not
Fehlings reagent.

Ketones do not reduce either of the two
rgts.

Tollens test is based on the ability of the
aldehyde group to reduce silver ion in solution,
forming either a black deposit of free silver or a
silver mirror.

The aldehyde group is oxidized to acid in
the reaction.

Tollens reagent is made by reacting silver
nitrate solution with dilute ammonium
hydroxide.

Aldehydes and ketones may also be
differen-tiated by the Schiffs Fuchsin test. The
rxn with aldehydes produces a violet or
magenta color.

Methyl carbonyl compounds like
acetaldehyde and acetone form a yellow
crystalline ppt by rxn with I
2
in the presence of
dilute alcohol.

ALDEHYDES AND KETONES are
compounds that upon oxidation may produce
acids, react with halogen in the presence of a
base by substitution of -hydrogen (haloform
reaction). The rxn involves the removal of an
-hydrogen to form an enolate ion. Addition of
halogen to the enolate ion will initiate faster
substitution of -hydrogen by nucleophilic
halogen. Presence of electron attracting
halogen on the the -Carbon initiates further
replacement of remaining -hydrogen by
halogen. The resulting -ketone is readily
attacked by a base to initiate a CC bond
cleavage.

The reaction is represented as:

O O
-
O
RCCH
3
+ OH
-
RC=CH
2
RC
CH
3
+ H
2
O


+ I
2


ONa O O
CHI
3
+ RC=O RCI
3
RC
CH
2
I + I
-
Iodoform (yellow crystals)

Aldehydes and ketones with COCH
3

(methyl ketone) react similarly with Na
Nitroprusside which produce red blood solution
that eventually changes to wine red upon
addition of acetic acid. Absence of methyl
ketones changes blood red solution to yellow.

Schiffs reagent (fuchsin dye [magenta
color] + SO
2
) chemical name is bis-N-sulfuric
acid of p-rosaniline hydrochloride, is purple in
the presence of aldehydes but is very pale pink
in the presence of ketones. It is considered as
a general test for aldehydes since even
aromatic aldehydes give positive purple test.

Aldehydes Ag
mirror

TOLLENS
Ketones No
reaction


Aldehydes
Cu
2
O brick red

FEHLINGS
Ketones No
reaction


Tollens Ag
Mirror
Aromatic aldehydes
Fehlings No
reaction
Aldehydes
violet/magenta

SCHIFFS FUCHSIN TEST
Ketones very pale
pink

Methyl CH
3
CHO
yellow
carbonyl
IODINE crystals
crystalline
compounds CH
3
COCH
3

dilute alkali
precipitate


EXPERIMENTAL RESULTS

I. Physical Properties
Solubility : in H
2
O in
ethanol
HCHO soluble
soluble
CH
3
CHO soluble
soluble
Butyraldehyde soluble
soluble
Benzaldehyde insoluble
soluble
Acetone soluble
soluble

II. Chemical properties
Test for HCHO (Hehners Resorcinol Test)
method used for detecting the
presence of
methanol in alcoholic beverages;
specific
test for HCHO and indirectly for
methanol.
HCHO
resorcinol + concd sulfuric acid
pink-red color
at
junction of
2 liquids
CH
3
OH

CH
3
CH
2
OH No
reaction


III. Oxidation by Silver ion (Tollens Reagent)

HCHO + AgNO
3
soln + NH
3
HCOOH +
Ag
0


gray/silver ppt


IV. Oxidation by Copper ion (Fehlings /
Benedicts)

HCHO + Fehlings A + Fehlings B
Cu
2
O
brick
red ppt

Fehlings A CuSO
4
+ NaOH
Fehlings B sodium potassium tartrate

Benedicts Reagent CuSO
4
+ Na
2
CO
3
or
sometimes
Na citrate

V. Action of a Strong Base (Canizarro Rxn)

CH
3
CHO + NaOH CH
3
COONa +
CHI
3


yellow

iodoform
HCHO + NaOH No iodoform
formation


VI. General Test for Aldehydes

HCHO + Schiffs Rgt purple or
magenta
CH
3
COCH
3
+ Schiffs Rgt no reaction
(very pale
pink)

VII. Reaction with Phenylhydrazine

Certain cpds related to ammonia add to the
carbonyl group to form derivatives that are impt
chiefly for the characterization and
identification of aldehydes and ketones.

An aldehyde or ketone react with 2,4-
dinitro-
phenylhydrazine to form insol yellow or red
solid.

The products contain a carbon-nitrogen
double bond resulting from elimination of water
from the initial addition products.

C +:NH
2
NHC
6
H
5
CNHNHC
6
H
5

C=NNHC
6
H
5
+H
2
O
O phenylhydrazine OH
phenylhydrazone

Like ammonia, these derivatives of
ammonia are basic, and therefore react with
acids to form salts: phenylhydrazine
hydrochloride, C
6
H
5
NHNH
3
+
Cl
-



VIII. Autooxidation of Benzaldehyde

CHO + O
2

COOH

Benzaldehyde benzoic
acid

IX. Oxidation of Benzaldehyde

CHO + Tollens COOH
+ Ag gray

+ Fehlings NR
+ Schiffs rgt puple or
magenta
Preparation of HCHO:

CH
3
OH
pyridinium chlorochromate
HCHO

Hehners

Resorcinol test
pink-red color at
junction
specific test for HCHO and indirectly for
CH
3
OH

Preparation of CH
3
CHO:
H
2
SO
4
, HgSO
4
H
HC=CH + H
2
O HC
CH
H
O
What is paraldehyde?

Paraldehyde is C
6
H
12
O
3
is an acetaldehyde
polymer.
Acetaldehyde (b.p. 20
0
C) is often generated
from its higher boiling trimer by heating the trimer
with acid:

H O H
H
H
+ C C
3 CH
3
C=O CH
3
CH
3
acetaldehyde O O
paraldehyde
b.p. 20
0
C b.p.
125
0

H CH
3
Paraldehyde is a colorless, flammable, toxic liquid,
miscible with organic solvents, soluble in water;
melts @ 12.6
0
C, boils @ 125
0
C; used as a cheml
interme-diate, in medicine, and as a solvent; aka
para-acetaldehyde.
ALDEHYDES AND KETONES
o Aldehydes and ketones are functional
isomers.
o Both have the functional carbonyl group (-
C=O).
o Because of he great difference in the
electronegativity between C and O, a carbonyl
group has a

C and a

O (due to inductive
effect and pi delocalization).
The dipolar character of both groups result
in similar reactions:
1. addition of a variety of reagents at the
carbonyl group
2. reduction at the carbonyl group
3. condensation and polymerization
o Most aldehydes and ketones react by addition
at the carbonyl carbon, with groups like NH
3,
NaHSO
3
, HCN and RMgX. The addition
reactions are influenced by steric hindrance. If
the group attached to the carbonyl group are
large or bulky, some addition reactions are
completely prevented. Thus the addition of
NaHSO
3
or HCN occurs with aldehydes and
methyl ketones but not with other aliphatic
ketones.
TEST HCH
O
CH
3
CH
O
BUTANA
L
C
6
H
5
CH
O
ACETON
E
Odor
rrita-
ting
Irritating
irritating Almond-
like
fruity
Soly
In H2O
solu-
ble

soluble

soluble

insolubl
e

soluble
Soly solu-
in
C
2
H
5
O
H
ble soluble soluble soluble soluble
Tollen
s
Ag
0
mirror
Ag
0
mirror
Ag
0

mirror
Ag
0

mirror
negative
Feh-
lings
brick
red ppt
brick
red ppt
brick red
ppt
NR negative
Schiff
s
mage
nta
magen-
ta
magent
a
magent
a
pale pink