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ALCOHOLS: Structure &

Physical Properties

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 Reaction Involving
Alcohols

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 Tests for Alcohols
•Jones Oxidation for
Primary and Secondary
Alcohols
•Lucas Test for Secondary
and Tertiary Alcohols

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 Jones Oxidation for Primary and
Secondary Alcohols
Jones reagent (chronic acid in sulfuric acid)

Positive Test
A positive test for aldehydes and primary or secondary alcohols consists in
the production of an opaque suspension with a green to blue color. Tertiary
alcohols give no visible reaction within 2 seconds, the solution remaining
orange in color. Disregard any changes after 15 seconds.
Complications
•Enols may give a positive test.
•Phenols give a dark colored solution which is not blue-green like a positive test.

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 Lucas Test for Secondary
and Tertiary Alcohols

Positive test
Appearance of a cloudy second layer or emulsion
•3o alcohols: immediate to 2-3 minutes
•2o alcohols: 5 -10 minutes
•1o alcohols: no reaction
Complications
The test applies only to those alcohols soluble in the reagent
(monofunctional alcohols lower than hexyl and some
polyfunctional alcohols.) This often means that alcohols with
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more than six carbon atoms cannot be tested.
 Phenol

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 Tests for Phenols
•Iron (III) Chloride Test for
Water-Soluble Phenols
•Iron (III) Chloride -
Pyridine Test for Water-
Insoluble Phenols

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 Iron (III) Chloride Test for
Water-Soluble Phenols

Procedure (for water-soluble phenols)

The iron (III) chloride test for phenols is not completely
reliable for acidic phenols, but can be administered by
dissolving 15 mg of the unknown compound in 0.5 mL of
water or water-alcohol mixture and add 1 to 2 drops of 1%
aqueous iron (III) chloride solution.

Positive Test
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red, blue, green, or purple color is a positive test. 23
 Iron(III) Chloride - Pyridine
Test for Water-Insoluble
Phenols

Procedure (for water-insoluble phenols or less reactive

phenols)
A more sensitive test for phenols consists of dissolving or
suspending 15 mg of the unknown in 0.5 mL of methylene
chloride and adding 3-5 drops of a 1% solution ferric chloride
in methylene chloride. Add a drop of pyridine and stir.
Positive Test (b)
Addition of pyridine and stirring will produce a color if
phenols or enols are present.
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 Carboxylic Acids, Esters,
Amines and Amides
Carboxylic Acids
Properties of Carboxylic Acids
Esters
Esterification and Hydrolysis

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 Carboxyl Group

Carboxylic acids contain the carboxyl

group on carbon 1.
O
||
CH3 — C—OH = CH3—COOH

carboxyl group

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 Properties

• Carboxylic acids are weak acids

CH3COOH + H2O CH3COO– + H3O+

• Neutralized by a base
CH3COOH + NaOH CH3COO– Na+ + H2O

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Tests for Carboxylic Acids

1.pH of an Aqueous
Solution
2.Solubility in Sodium
Bicarbonate

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 pH of an Aqueous Solution for
Carboxylic Acids
1. Water Solubility
Add approximately 1 mL of water to the test tube containing
your organic compound.  Shake the tube and/or stir with a glass
stirring rod. A soluble organic compound will form a
homogeneous solution with water, while an insoluble organic
compound will remain as a separate phase. You may add
additional water, up to 1.5 mL, if your compound does not
completely dissolve with the smaller amount.
2. Check the pH of the water to determine if your unknown is
partially or completely soluble in water and whether your
compound has changed the pH of the water.
 Litmus turns red: acidic compound
 Litmus turns blue: basic compound
 Litmus neutral: either water soluble general compound or insoluble
compound
 An organic compound which is soluble in water is typically a low
molecular weight polar compound of up to 5-6 carbon atoms or
less.
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 Sodium Bicarbonate Test for Carboxylic
Acids

Procedure
A few drops or a few crystals of the unknown sample are dissolved in
1mL of methanol and slowly added to 1 mL of a saturated solution of
sodium bicarbonate.
Positive Test
Evolution of a carbon dioxide gas is a positive test for the presence of
the carboxylic acid and certain phenols listed in the Complications
section.
Complications
Negatively substituted phenols such as nitrophenols,
aldehydrophenols, and polyhalophenols are sufficiently acidic to
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 Esters
In an ester, the H in the carboxyl group
is replaced with an alkyl group

O
||
CH3 — C—O —CH3 = CH3—COO —CH3

ester group

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 Esters in Plants

Esters give flowers and fruits

their pleasant fragances and
flavors.

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 Naming Esters

• Name the alkyl from the alcohol –O-

• Name the acid with the C=O with –ate
acid alcohol
O
|| methyl
CH3 — C—O —CH3
Ethanoate methyl ethanoate (IUPAC)
(acetate) methyl acetate (common)

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 Some Esters and Their
Names
Flavor/Odor
Raspberries
HCOOCH2CH3 ethyl methanoate (IUPAC)
ethyl formate (common)

Pineapples
CH3CH2CH2 COOCH2CH3
ethyl butanoate (IUPAC)
ethyl butyrate (common)

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 Learning Check CA 2
Give the IUPAC and common names of
the following compound, which is
responsible for the flavor and odor of
pears.

O
||

CH3 — C—O —CH2CH2CH3

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 Solution CA2
O
|| propyl
CH3 — C—O —CH2CH2CH3

propyl ethanoate (IUPAC)

propyl acetate (common)

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 Learning Check CA 3

Draw the structure of the following

compounds:

A. 3-bromobutanoic acid

B. Ethyl propionoate

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 Solution CA 3

A. 3-bromobutanoic acid
Br
|
CH3CHCH2COOH

B. Ethyl propionoate

O
||
CH3 CH2 COCH2CH3 CH3CH2COOCH2CH3

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 Esterification

• Reaction of a carboxylic acid and alcohol

• Acid catalyst
O
|| H+
CH3 — C—OH + HO—CH2CH3

O
||
CH3 — C—O—CH2CH3 + H2O

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 Hydrolysis

• Esters react with water and acid catalyst

• Split into carboxylic acid and alcohol
O
|| H+
H — C—O—CH2CH3 + H2O

O
||
H — C—OH + HO—CH2CH3

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 Saponification

Esters react with a bases

Produce the salt of the carboxylic acid and
alcohol
O
||
CH3C—OCH2CH3 + NaOH
O
||
CH3C—O– Na+ + HOCH2CH3
salt of carboxylic acid

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 Learning Check CA4

Write the equation for the reaction

of propionic acid and methyl alcohol
in the presence of an acid catalyst.

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 Solution CA4

O
|| H+
CH3CH2COH + HOCH3

O
||
CH3CH2COCH3 + H2O

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 Learning Check CA5

What are the organic products when

methylacetate reacts with

A. Water and an acid catalyst?

B. KOH?

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 Solution CA5

A.
O
||
CH3COH + HOCH3

O
||
B. CH3CO– K+ + HOCH3

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