ALCOHOL AND ETHER

Organic Chemistry
Evi Elfrida

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

 Properties depends on number of carbon
atoms attached (R)

CLASSIFICATION

Primary (1°)
1° 2°
Secondary 2°

Tertiary(3°)
3°

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

 BASIC PROPERTIES
The Hydroxyl group is said
to be Hydrophilic,where as the
• The hydroxyl functional group (-OH), bonded to a carbon
alkyl (hydrocarbon) end is
atom of an alkyl group.
hydrophobic
• The hydroxyl groups form hydrogen bonds with water.

Hydrogen Bonds

Strong intermolecular force

Alcohols are more polar than hydrocarbons,

and are better solvents for polar substances.

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

 SOLUBILITY BOILING POINTS
• OH- pass on a greater water solubility on
• Hydrogen bonding by the hydroxyl
organic molecules.
group increases boiling points.
Water is a hydrogen-bonding solvent, and
therefore the dipole of the hydroxyl group can
interact favorably with the hydroxyl group of Example:

H2O

• The longer the carbon chain in an alcohol • The boiling points of the alcohols
is, the lower the solubility in polar solvents increase as the number of carbon
and the higher the solubility in nonpolar atoms increases.
solvents.

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

Boiling Point of Alcohols and Alkanes of comparable size and shape
BOILING INTERMOLECUL BOILING INTERMOLECUL
ALCOHOL ALKANE
POINT (K) FORCES POINT (K) FORCES

Ethanol 352 Hydrogen Bonds Propane 231 Van der Waals

Hydrogen Bonds
Propanol 371 Butane 273 Van der Waals

Hydrogen Bonds
Butanol 390 Pentane 309 Van der Waals

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

 Synthesis Alcohols

Production of Alcohols
Organic Chemistry

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

1. Nucleophilic Substitution Product : Primary Alcohol

Primary haloalkanes can produce primary alcohols when they are reacted with
aqueous Sodium Hydroxide (NaOH) or Potassium Hydroxide (KOH).
The equation of the reactions becomes :

CH3CH2Cl + NaOH 🡪 CH3CH2OH + Na+Cl-

Chloroethane + sodium hydroxide 🡪 ethanol + sodium chloride

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

2. Hydrolysis / Alkene Hydration (Addition)
Product : Secondary or Tertiary Alcohol

Alkenes are hydrolysed by using

concentrated sulphuric acid to
produce secondary or tertiary
alcohol. The equation of the
reactions becomes :

1 2 3

Will join with the

alkene group

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

Grignard Reactions
• Used Grignard Reagent producing
• Primary Alcohol

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

• Secondary Alcohol

• Tertiary Alcohol

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

Reaction of Alcohols
Organic Chemistry

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

Reactions that may also involve breaking of C-C or C-H bonds

1 Dehydration

Alcohol + H2SO4 🡪 Alkene + H2O

CH3-CH2-CH2-OH CH3 –CH = CH2 + H2O

1-Propanol Propene

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

Reactions in which the O-H bond is Broken

1 Esterification

O O
|| ||
CH3-CH2- OH + CH3-C-OH 🡪 CH3-C-O-CH2CH3 +H2O
Ethanol + Ethanoic acid 🡪 Ethyl Ethanoate + Water
Acid catalyst

Reversible
Evi Elfrida | Grade 11 | Santa Laurensia Senior High School
Reactions in which the O-H bond is Broken

2 Alcohol reacts with metal

Alcohol reacts with metals such as sodium in behaviour that is more

gently than it is react with water. This reactions produces metal
alkoxyde and hydroen gas

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

Reactions in which the C-O bond is Broken

2 Alcohol reacts with halogen acid (HX)

The reaction involving the breaking of C-O bond causes the lose of
the hydroxyl group and to be replaced with other ion

Ethanol + Hydrogen chloride 🡪 chloroethane + H2O

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

Oxidizing agents: KMnO4, H2CrO4, Na2Cr2O7, atmospheric oxygen, etc

1 Oxidation of Primary Alcohols

• Primary alcohols 🡪 aldehydes 🡪 carboxylic acid

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

2 Oxidation of Secondary Alcohols

• Secondary alcohols 🡪 ketones

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

3 Oxidation of Tertiary Alcohols
• Tertiary alcohols cannot be oxidized

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

Applications
-
Alcohols

Organic Chemistry

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

ETHER
Evi Elfrida | Grade 11 | Santa Laurensia Senior High School
NOMENCLATURE Common names

Group name
Alkyl Generic name
Examples “ether”
CH3–O–CH2CH2CH3
methyl propyl ether
CH3–O–CH3
dimethyl ether

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

 x
NOMENCLATURE

Diethyl
Primary ether

Diisopropyl
Secondary ether

Tertiary
Di-tert-butyl
ether

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

Boiling Points
No intermolecular induced dipole bond
PROPERTIES
No H bond
Low boiling points
Easy to be broken down
Comparison
CH3CH2CH2CH2CH3 Mr: 44 36 °C No intermolecular H bond
pentane

CH3CH2OCH2CH3 Mr: 46 35 °C
diethyl ether No intermolecular H bond

CH3CH2CH2CH2OH Mr: 46 117 Yes intermolecular H bond

butyl alcohol
°C
Evi Elfrida | Grade 11 | Santa Laurensia Senior High School
Properties
Bonding
Does not have -OH Cannot engage in
hydrogen bonding with
each other

Can form hydrogen bonds with

other molecules
(alcohols, amines, etc)

Good solvent
Evi Elfrida | Grade 11 | Santa Laurensia Senior High School
 Synthesis Ethers

Production of Ethers
Organic Chemistry

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

 1 D Dehydration of Alcohols

• This direct reaction requires elevated temperatures (125-140 Celcius)

• The reaction is catalyzed by acids, usually Sulfuric acid.
• The method is effective for generating symmetrical ethers, but not unsymmetrical
ethers
Usually: H2SO4 . Acts as a
catalyst

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

 2 D Williamson Ether Synthesis

• This is a nucleophilic displacement of alkyl halides by alkoxides

• This leaving group could be iodide, bromide or sulfonate

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

Reaction of Ethers

Organic Chemistry

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

1) Ethers can not reacts with metal such as Na
2) Ethers reacts with PCl5

1) Ethers reacts with HX ( X = F, Cl,Br, I)

4) Combustion

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

Applications
-
Ethers
Organic Chemistry

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

ALDEHYDE
Organic Chemistry

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

 NOMENCLATURE

A. Physical Properties
▪ Aldehydes are polar and acidic.
▪ The smaller molecules of aldehydes such as formaldehyde and acetaldehyde are soluble in water.
▪ This solubility decreases as the main chain becomes longer, but their boiling points are increasing.
▪ The smaller alkanals have stingy smell, while the longer ones have fragrant smell.

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

Reaction of Aldehyde
1. Oxidation to carboxylic acids
The aldehydes are usually refluxed with acidified potassium dichromate(VI) as oxidizing agent
R-COH + [O] 🡪 R-COOH
Example : CH3CH2CHO + [O] 🡪 CH3CH2COOH
Propanal + oxidizing agent 🡪 propanoic acid
Formaldehyde 🡪 Primary Alcohol

Acetaldehyde 🡪 Secondary Alcohol

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

Production of aldehyde

Oxidation of primary alcohol

CH3-OH + [O] 🡪 CHOH
Methanol + oxidizing agent 🡪 methanal
Identification of Aldehyde
Distinguishing between aldehyde and ketones
▪ Aldehydes produce carboxylic acids when treated with oxidizing agents. Ketones are not oxidized by these reagents
▪ The effect of oxidizing agents on aldehydes
Oxidizing agent conditions Observation on the oxidation
Acidified potassium dichromate (VI) Boil gently The orange solution turns green
(reflux)

Fehling’s solution (alkaline solution of Warm Red precipitate

Cu2+ complex ion)
Tollens’s reagent (an aqueous solution of warm A silver mirror form on the sides of the test
silver nitrate in excess ammonia) tube fromthe colorless solution

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School
KETONE
Organic Chemistry

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

PROPERTIES
Physical properties
OF KETON
• Ketones are polar because they have carbonyl group as consequence of the fact that the electronegativity of the oxygen centre is greater than that
for carbonyl carbon.
• Thus ketones are nucleophilic at oxygen and electrophylic at carbon. The carbonyl group interacts with water by hydrogen bonding

Preparation of Ketones
R-CH(OH)- R’ + [O] 🡪 R-CO-R’ + H2O
Example : CH3-CH(OH)-CH2CH3 + [O] 🡪 CH3-CO-CH2CH3 + H2O
2-butanol + oxidizing agent 🡪 2-butanone + water
Evi Elfrida | Grade 11 | Santa Laurensia Senior High School
CARBOXYLIC ACID

Organic Chemistry

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

Nomenclature of Carboxylic Acids
Structural formula Systematic name Common name
HCOOH Methanoic acid Formic acid
CH3COOH Ethanoic acid Acetic acid
CH3CH2COOH Propanoic acid Propionic acid
CH3CH2CH2COOH Butanoic acid Butyric acid

A. Properties of Carboxylic Acid

• Carboxylic acids tend to have higher boiling points than water. This is because they tend to form stabilized dimers.
• In evaporating or boiling a carboxylic acid, it requires either the bonds of these dimers are broken or the entire dimer
molecules are vaporized.
• This process needs high entalphy of vaporization, causing the increase in boiling points.

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

A. Properties of Carboxylic Acid

Solubility

Carboxylic acids are polar. Because they are both hydrogen-bond acceptors (the carbonyl) and hydrogen-bond donors

(the hydroxyl), they also participate in hydrogen bonding.

Odor

The strong smell of vinegar is an example that carboxylic acids have strong smells

Reactivity

Carboxylic acids are weak acids. It means they only partially dissociate to H+ and RCOO- in neutral solvent. This is due to

the polarity of the carbonyl group.

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

a. Reaction with metals
For example : Ethanoic acid + Sodium 🡪 Sodium ethanoate + Hydrogen
2CH3COOH + 2Na 🡪 2CH3COONa + H2
b. Reaction with metal oxides
2CH3COOH + CaO 🡪 Ca(CH3COO)2 + H2O
Ethanoic acid + Calcium oxide 🡪 Calcium ethanoate + water
c. Neutralization reaction
CH3COOH + NaOH 🡪 CH3COONa + H2O
Ethanoic acid + sodium hydroxide 🡪 Sodium ethanoate + water

d. Ester formation (Esterification)

Carboxyl acid can be reacted to produce ester by reacting it with a primary alcohol.
CH3COOH + CH3CH2CH2-OH 🡪 CH3 –COOCH2CH2CH3 + H2O
Ethanoic acid + propanol 🡪 Propanyl ethanoate + water

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

A. Preparation of Carboxylic Acids
a. Oxidation of primary alcohol
Strong oxidizing agent is required for further oxidizing of alcohol. If the agent is not strong enough, the product
will be an aldehyde.

b. Oxidation of primary aldehyde

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

ESTER

Organic Chemistry

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

 A. Properties of Esters
• Ester have fragrant smells, unlike carboxylic acids. Esters are
more polar than ethers but less polar than alcohols.
• They participate in hydrogen bonds as hydrogen-bond
acceptors, but cannot act as hydrogen-bond donors, unlike
alcohols.
• This ability to participate in hydrogen bonding confers some
water-solubility.

Ester Aroma Ester Aroma Ester Aroma

Methyl acetate Sweety Ethyl formiate Rum Propyl formiate Leaf
Methyl propionate Fruity Ethyl acetate Jackfruit Propyl acetate Celery

Methyl isobutyrate Flowery Ethyl isobutyrate Citrus Propyl isobutyrate Grape

Methyl hexanoate Jackfruit Ethyl hexanoate Wine Propyl hexanoate Cheese

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School

A. Reactivity
1. Hydrolysis
R –COOR’ + H2O ⇋ R –COOH + R’—OH
For example : CH3COOCH3 + H2O ⇋ CH3COOH + CH3OH
Methyl ethanoat + water ⇋ Ethanoic acid + methanol

2. Reaction with an alkali

This reaction is also called saponification (Saponifikasi) because it is used in soap manufacturing.
R –COOR’ + NaOH 🡪 R –COONa + R’—OH
For example : CH3 –COO—CH2CH3 + NaOH 🡪 CH3COONa + OH—CH2CH3
Ethyl ethanoate + Sodium hydroxide 🡪 sodium ethanoate + ethanol

B. Production of Ester
The equation of formation (Esterification) is as follows :
R –COOH + R—OH ⇋ R –COOR’ + H2O
CH3COOH + CH3CH2OH ⇋ CH3COOCH2CH3 + H2O
Ethanoic acid + Ethanol ⇋ Ethyl ethanoate + water

Evi Elfrida | Grade 11 | Santa Laurensia Senior High School