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ALCOHOL AND ETHER

ETHER AS ANESTHETIC
A Look Back At That
Time
Curious George Huffed
Ether
Alcohols And Ethers
DEFINITION AND
CLASSIFICATION
STRUCTURE

NOMENCLATURE ISOMERS

PHYSICAL AND
CHEMICAL PREPARATION
PROPERTIES

ALCOHOLS AND
ETHERS IN NATURE
DEFINITION AND STRUCTURE
ALCOHOLS ETHERS
DEFINITION compounds in compounds in
which a hydroxyl which oxygen
group (-OH) is atoms are
attached to a bonded to two
saturated carbon carbon atoms
by single bond

GENERAL R-OH,Ar-OH R-O-R, Ar-O-R,


STRUCTURAL Ar-O-Ar
FORMULA

GENERAL CnH2n+2O CnH2n+2O


MOLECULAR CnH2n+1OH
FORMULA
ALCOHOL STRUCTURE

ETHER STRUCTURE
CLASSIFICATION OF ALCOHOLS AND ETHERS
CLASSIFICATION OF ALCOHOLS

ALCOHOLS

Based on number of Based on position of


–OH group –OH group

Monohydroxy Alcohols
Primary Alcohols
Dihydroxy Alcohol
Trihydroxy Alcohols
Secondary Alcohol
Polyhydroxy Alcohols Tertiary Alcohols
Monohydroxy Alcohols

Methanol CH3OH

Ethanol C2H5OH
Dihydroxy Alcohols

1,2-ethanediol C2H4(OH)2
Ethylene glycol

Trihydroxy Alcohols

propane-1,2,3-triol
C3H5(OH)3
Glycerin, glycerine,
Polyhydroxy Alcohols
- contain more than three -OH groups
Based on position of –OH group
The -OH is The -OH is The -OH is
attached to a attached to a attached to a
C atom which C atom which C atom which
is attached to is attached to is attached to
one others two others three others.
CLASSIFICATION
OF ETHERS

• A mixed (or unsymmetrical) ether:


is an ether which the two R groups
present are not the same.
• R-O-R’  R ≠ R’

• A simple (or symmetrical ) ethers: is


an ether in which the two R groups
present are the same.
• R-O-R’  R = R’
Always happy
like diethyl ether
NOMENCLATURE OF ALCOHOLS AND ETHERS

ALCOHOLS
Alkylalcohol (Alkyl + alcohol)
COMMON NAME CH3OH = Methylalcohol

Alkanol (Alkane + ol) NOT ALKOL


IUPAC NAME CH3OH = Methanol
IUPAC NAMING
1. Longest carbon chain containing the alcohol.

2. OH suffix gets the lowest possible number.


3. Find also lowest possible number for other substituent.

4. For more than one substituent they are listed in alphabetical order.
NAME THESE:
CH3 OH
CH3 CH CH2OH CH3 CH CH2CH3
2-methyl-1-propanol 2-butanol

CH3 OH
CH3 C OH
CH3 Br CH3
2,2-dimethyl-2-propanol 3-bromo-3-methylcyclohexanol
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UNSATURATED ALCOHOLS
• Hydroxyl group takes precedence. Assign that carbon the lowest
number.
• Use alkene or alkyne name.

Br
OH
HO
CH2 CHCH2CHCH3
4-penten-2-ol (old) Cl
pent-4-en-2-ol
(1997 revision of IUPAC rules 2-bromo-7-chloroocta-7-en-3,5-diyn-1-ol
Functional Group Precedence in Nomenclature
Functional Group Name as Suffix Name as Prefix
Principal Groups
Highest Carboxylic Acids -oic acid carboxy
Priority
–carboxylic acid
Esters -oate alkoxycarbonyl
-carboxylate
Aldehydes -al formyl
-carbaldehyde
Ketones -one oxo
Alcohols -ol hydroxy
Amines -amine amino
Alkenes -ene alkenyl
Alkynes -yne alkynyl
Alkanes -ane alkyl
Eter -ane alkoxy
what is this based on?
It’s an arbitrary agreement by IUPAC. Although note that there is
some correlation between the oxidation state of the carbon and the
priority (more oxidized groups tend to be higher priority).
HYDROXY SUBSTITUENT
• When -OH is part of a higher priority class of compound (alcohol as
alkyl), it is named as hydroxy.
• Example:

OH priority

C H 2C H 2C H 2C O O H

4-hydroxybutanoic acid

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NOMENCLATURE OF ETHERS

Common • Alkylalkylether (R≠R’)


Name (R=alphabetically)

• Dialkylether (R=R’)

Example:
NOMENCLATURE OF ETHERS
IUPAC Name Alkoxyalkane
Alkoxy: the shortest chain
Alkane:The longest chain
Examples
CH3 (b)
O
(a) CH3
CH3CHCH2 O CH3
1-Methoxy-2-methylpropane

Methoxy cylohexane
CH2CH3
(d) O
H3C
(c) CH3CH2CH2 O CH2CH2CH2CH3

Propoxy butane

1-Ethoxy-1-methylcyclohexane
NAMING CYCLIC ETHERS
• Can Use Replacement Nomenclature (oxa  O replaces CH2)
• Also Many Common Name (Acceptable to Use)
O O

Oxacyclopropane Oxacyclobutane O
(oxirane, ethylene oxide) (oxetane)

O
O
Oxacyclohexane
(tetrahydropyran)
O
Oxacyclopentane 1,4-Dioxacyclohexane
(tetrahydrofuran) (1,4-dioxane)
ISOMERS OF ALCOHOLS AND ETHERS
ALCOHOLS ETHERS
STRUCTURAL STRUCTURAL
ISOMERS ISOMERS
1. CHAIN ISOMERS 1. CHAIN ISOMERS
2. POSITION ISOMERS 2. METAMERISM
3. FUNCTIONAL ISOMERS 3. FUNCTIONAL ISOMERS
STEREOISOMERS
1. OPTICAL ISOMERS

Stereoisomers: Isomers that differ in the spatial


orientation of their component atoms
Chain and
Positional
Isomer of
Alcohol
CHAIN ISOMER OF ETHER (C 5 H 12 O)
O O
O

butyl methyl ether tert-butyl methyl ether sec-butyl methyl ether

O O O
isobutyl methyl ether ethyl propyl ether ethyl isopropyl ether
Functional Isomers
Have the same molecular formula but different in the kind of functional
groups

ALCOHOL AND ETHER ARE


FUNCTIONAL ISOMER
Example

How many functional isomers are there in a compound with molecular


formula C3H8O?
OH

OH O

1-propanol 2-propanol methoxyethane


C 4 H 10 O ISOMERS
OH
OH
1-butanol 2-methyl-2-propanol
OH
2-butanol
O
We have 7 structures

OH
isopropyl methyl ether
2-methyl-1-propanol
O
O
diethyl ether methyl propyl ether
ISOMERS OF ALCOHOLS
OPTICAL ISOMERS

Molecules that differ three-dimensionally by the placement of


substituents around one or more atoms in a molecule
How optical isomers arise?
the next diagram shows what happens if you rotate
molecule B.

They still aren't the same - and there is no way that you can
rotate them so that they look exactly the same.These are
isomers of each other.
Optical Isomer?
• At least has 1 chiral carbon
• Has the ability to rotate the plane of
polarised light

Example : Optical isomer of Butan-2-ol


ISOMER OF ETHER

Metamerism
• Isomers with the same molecular formula but different alkyl groups
(around the functional group) are called metamers.
Physical properties of alcohol
C H3 C H2 C H2 O H
1. Solubility
alkane-like (non-polar) polar O-H bond

Alcohols consist of:


–a non-polar (alkane-like) chain
–a polar hydroxyl group

Low-molecular-weight alcohols are completely soluble in water, but


their alkane counterparts have limited solubility in water
H3C OH
non polar polar
very soluble in water • The water-solubility of alcohols
depends on the length of the
alkyl chain in the alcohol.
H3C CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 CH2 OH
polar
• Monohydroxy alcohols having
non polar
chains longer than three
insoluble in water
carbons are not very water-
soluble

–OH group is polar and capable of


hydrogen bonding.
This makes low molecular weight
alcohols highly soluble in water.
Solubility of Alcohol in water
2. Boiling Points
Alcohols have higher boiling points than alkanes of similar molecular weight

Boiling points London forces


Ethane: -89oC
London + H-bonding
Methanol: 65oC
London + H-bonding
Ethanol: 78oC
London + more
1,2-Ethane diol: 197oC H-bonding

• We already saw that the boiling points of alkanes increase with


increasing chain length. The same is true for alcohols.

• Alcohols with more than one hydroxyl group (polyhydroxy alcohols)


have higher boiling points than monoydroxy alcohols.
PHYSIC AL PROPERTIES OF ALCOHOLS

• Alcohols have higher boiling


points than alkanes of the
same chain length (because
they hydrogen bond to each
other; the intermolecular
forces for alkanes are only
London forces)

Remember:
• H-bonding is the strongest
intermolecular force.
• London forces are weak by
comparison.
Physical Properties of Ether
1. Solubility
Ethers containing up to 3 carbon atoms are soluble in water, due to their
hydrogen bond formation with water molecules.

Ethers can form hydrogen bonds with water molecules

The solubility decreases with increase in the number of carbon


atoms.
2. Boiling Points
• Ethers have an O atom, but there is no H attached.
• Thus, hydrogen bonds cannot form between ether molecules.

O
R’ R
Ether molecules cannot form hydrogen bonds with other ether molecules.

CH3CH2CH2CH3 CH3 O CH2CH3 CH3CH2CH2OH


Butane Methoxyethane 1-Propanol
(n-butane) (ethyl methyl ether) (Propyl alcohol)

M.W. = 58 M.W. = 60 M.W. = 60


b.p. = - 0.5°C b.p. = 7.9 °C b.p. = 97.2°C
CHEMICALS PROPERTIES OF ALCOHOL
1. Reaction with active metals
2. Esters formation (Esterification)
3. Reaction with sulphuric acid (Dehydration)
a.Alkenes formation
b.Ethers formation
c.Alkyl hydrogen sulphate
4. Alkyl halides formation (R-X)
a.Reaction with thionyl chloride (SOCl2)
b.Reaction with phosphorus halides (PX3 or PX5)
5. Reaction with hydrogen halides (HX)
6. Reaction with nitric acid (HNO3)
7. Oxidation
1. REACTION WITH ACTIVE METAL

•The metal replaces the hydrogen atom in the


alcohol group forming a salt and hydrogen gas

R OH + M R OM + 1/2 H2
Alkoxides are formed

M = Na, Mg, Al, etc.


Example:

Na
1 H 3C C H2 OH H 3C C H2 ON a + 1/2 H 2
S o d iu m e t h o x id e
C H3 C H3
M g
2 H 3 C C OH H 3C C O 2 Mg
H H
M a g n e s iu m is o p r o p o x id e

CH 3 CH
Al 3
3 H 3C C OH H3C C O 3 Al
H H
A l u m in i u m i s o p r o p o x i d e
2. ESTER FORMATION (ESTERIFICATION)

An alcohol reacts with an alkanoic acid to form an ester and water.


F r om alc oh o l
O O
R OH + R C OH R C O R + H 2O
A lc o h o l C a r b o xy lic a cid E s ter W a te r

Example:
O O
H3C CH2 OH + H3C CH2 C OH H3C CH2 C O CH2 CH3 + H2O
Ethanol Propanoic acid diethyl ester
Mechanism of esterification
3. DEHYDRATION (REACTION WITH SULPHURIC ACID)

• Dehydration, like dehydrohalogenation, is a  elimination reaction in


which the elements of OH and H are removed from the  and  carbon
atoms respectively.

50
DEHYDRATION OF ALCOHOL

a. Alkene Formation
At 180oC alcohols undergo dehydration with conc. H2SO4 to give alkenes.

H H H H
H 2SO4(Conc.) Excess
H C C H C C + H 2O
H OH 180 oC H H

b. Ether Formation
At 140oC alcohols undergo dehydration with conc. H2SO4 to form ether
(symmetrical ether)
Conc. H2SO4
2 H3C CH2 OH H3C CH2 O CH2 CH3 + H2O
140 Co
Ethanol Diethyl ether
c. Alkyl Hydrogen Sulphate Formation
At room temperature alcohols react with conc. H2SO4 to form alkyl hydrogen
sulphate

Room H3C CH2 O SO2OH


H3C CH2 OH + HO SO2OH Temperature + H2O
Ethyl hydrogen sulphate
Ethanol
4. ALKYL HALIDES FORMATION (R-X)
a. Reaction with thionyl chloride (SOCl2)
H 3C C H 2 OH + SOC l2 H3 C CH 2 Cl + SO 2 + HCl
Eth an ol Eth yl chloride

b. Reaction with phosphorus halides (PX3 or PX5)


H3C CH2 OH + PCl5 H3C CH2 Cl + POCl3 + HCl
Ethanol Ethyl chloride

3 H3C CH2 OH + PCl3 3 H3C CH2 Cl + H3PO3


Ethanol Ethyl chloride
5. REACTION WITH HYDROGEN HALIDES (HX)

• HCl reacts with alcohols only in the presence of catalyst


(anhydrous ZnCl2).
• No catalyst is required in the case of HBr or HI.

H3C CH2 OH + HBr H3C CH2 Br + H2 O


Ethanol Ethyl bromide
EXAMPLE:

1.

2.

3.
6. REACTION WITH NITRIC ACID (HNO 3 )

• Alkyl nitrates or nitrate ester are formed


• Use sulphuric acid as a catalyst
example

H2SO4
H3C CH2 OH + HO NO 2 H3C CH2 O NO 2 + H2O
Ethanol Ethyl nitrate

highly flammable liquid


7. OXIDATION
• Different types of alcohols give different products on
oxidation.
• Most widely used oxidizing agents are KMnO4 + H2SO4 and
Na2Cr2O7 + H2SO4

a. Primary alcohols are oxidized to aldehydes


O O
(O) (O)
H3C CH2 OH + H3C C H H3C C OH
+ +
Na2Cr2O7/ H Acetaldehyde Na2Cr2O7/ H Acetic acid
Ethyl alcohol
b. Secondary alcohols are oxidized to ketones

OH O
(O)
H 3 C CH CH 3 + H3 C C CH3 + H 2O
+
Na2Cr2O7/ H Acetone
Isopropyl alcohol

c.Tertiary alcohols do not undergo oxidation under normal conditions


OH
(O)
H 3C C CH 3 + N O R E A CT IO N ( N R)
+
N a2 C r 2 O 7 / H
C H3
te rt- buty l a lco hol

There is no H on the C—OH to oxidize.


ALCOHOL OXIDATION EXAMPLES

(2) After mixing, the ethanol is oxidized, and


(1) The tube on the left contains orange
chromium is reduced, forming a grayish green
K2Cr2O7 and is next to the colorless ethanol.
precipitate.
EXAMPLE:

H2CrO4
OH O

cyclopentanol cyclopentanone

H2CrO4 H2CrO4
OH O

butanol H
butanal
OH

O
butanoic acid
CHEMICAL PROPERTIES OF ETHER
1. Cleavage of ethers by acids
 Ethers are cleaved by HX to an alcohol and a haloalkane.
General Equation

Heat
R O R' + HX R X + R' OH
Ether Conc. acid Alkyl halide alcohol

Specific Example

Heat
CH3 O CH3 + HBr CH3 Br + HO CH3
Dimethyl ether Hydrogen bromide Methyl bromide Methyl alcohol
Note: If two or more equivalents of acid are used
further dehydration can occur on formed alcohols which
may react further to form a second mole of alkyl halide.

Example

Heat
CH3CH2OCH2CH3 + 2 HBr 2 CH3CH2Br + H2O
Diethyl ether Excess Ethyl bromide
Hydrogen bromide
Examples:

O OH
HBr, H2O
CH2CH3 CH3CH2 Br
+
Reflux

Ethyl phenyl ether Phenol Bromoethane

OCH2CH3 OH
100OC
CH3CHCOOH + HI CH3CH2 I + CH3CHCOOH
H2O
2-Ethoxypropanoic acid Iodoethane Lactic acid
2. Reaction with PCl5
 Reaction between Ethers and PCl5 will form alkyl chloride
 PCl5 on heating will result cleavage of carbon-oxygen bond

General Equation

R-O-R + PCl 5 2 alkyl halide + POCl 3

Specific Example

Δ
O + PCl5 2 Cl + POCl3
PREPARATION OF ALCOHOLS AND ETHERS

1. PREPARATION OF ALCOHOLS

1. Hydrolysis of alkyl halides with aqueous NaOH

Starting Material : Alkyl Halide


Reagent : Aqueous NAOH

Example:
H 2O
H3C CH 2 B r + Na O H H 3C C H2 O H + N aB r
E thy l b ro m ide E th yl alc oh ol
2. Hydration of alkenes

Starting Material : Alkenes


REMEMBER
Reagent : 1. H2SO4 (form alkyl hydrogen sulphates) REACTION
Markovnikov rule is followed ON
2. H2O (hydrolysis yield alcohols) ALKENE!!!!!!

example
OSO3H
H3C CH CH2 + HOSO3H H3C CH CH3
Propene Isopropyl hydrogen sulphate

OSO3H H OH
H3C CH CH3 + O H H3C CH CH3 + H2SO4
Isopropyl alcohol
3. Addition of Grignard Reagents (RMgX) to aldehydes and ketones

Starting material : 1. Aldehyde Formaldehyde form Primary alcohol


Other aldehyde form Secondary alcohol

2. Ketone (form tertiary alcohol)


Reagent : Grignard reagent, than hydrolysis with H2O

O OMgX OH
H 2O
C + R M gX C C + M g X( O H )
H+
R R
A ld e h y d e G rig n a r d A d d itio n A lc o h o l
o r k etone rea ge nt c om p oun d
Primary alcohols are obtained by treating Grignard reagents with formaldehyde

O OMgX OH
H 2O
H C H + RMgX H C H + H C H
H
R R
Formaldehyde 1O Alcohol

Secondary alcohols are obtained by treating Grignard reagents with other


aldehyde

O OMgX OH
H2O
H3C C H + RMgX H3C C H + H 3C C H
H
R R
Acetalldehyde 2 O Alcohol
Tertiary alcohols are obtained by treating Grignard reagents with
ketones

O OMgX OH
H2O
H3C C CH3 + RMgX H3C C CH3
H+
H3C C CH3
R R
Acetone 3O Alcohol
4. Reduction of aldehydes and ketones

Starting Material : 1. Aldehydes (form primary alcohol)


2. Ketone (form secondary alcohol)
Reagent : H2 with catalyst Ni or
LiAlH4
O
Ni
Example H3 C C H + H2 H 3C CH2 OH

Acetaldehyde Ethyl alcohol (1 o)

O OH
LiAlH4
H3C C CH 3 H 3C CH CH3

Acetone Isopropyl alcohol (2 o)


5. Reduction of acids with lithium alumunium hydride (LiAlH4)

Starting material : Carboxylic Acid


Reagent : LiAlH4

O
LiAlH4
H3C C OH H3C CH2 OH

Acetic acid Ethyl alcohol


6. Acid-hydrolysis of esters

Starting material : Ester


Reagent : H2O with Acid (catalyst)
PREPARATION OF ETHERS

1. Intermolecular dehydration of alcohols .(only symmetric ethers)

• This method is used for industrially preparation for


symmetric ethers. REMEMBER
REACTION
IN
• In the presence of acid, two molecules of an alcohol
ALCOHOL!!
may lose water to form an ether.

R' OH + R" OH H+
R' O R" + H2O
heat /140°C
2. The Williamson synthesis of ethers
• The reaction of a sodium alkoxide; RONa or a sodium phenoxide; ArONa with an alkyl
halide to form an ether is known as the Williamson synthesis.
• It is an important laboratory method for the preparation of symmetrical and
unsymmetrical ethers.
• The reaction involves nucleophilic substitution of an alkoxide ion for a halide ion.

General Equations
R O- Na+ + R' X R O R' + NaX
Sodium alkoxide Alkyl halide Alkyl ether

Ar O- Na+ + R' X Ar O R' + NaX


Sodium phenoxide Alkyl halide Aryl ether
Examples

CH3CH2Br CH3CH2 O Na CH3CH2 O CH2CH3 NaBr

O Na
O CH3
CH3I Na I

! Note that

The alkoxide is commonly made by adding Na or K to the alcohol


Examples
+
OH O Na OCH2CH 3
Na CH 3CH 2 Br
+ NaBr

sodium
cyclohexanol ethoxycyclohexane
cyclohexyloxide

OH OCH3
1) Na

2) CH3-I

3,3-dimethyl-2-pentanol 2-ethoxy-3,3-dimethypentane
IMPORTANT ALCOHOLS
• Methanol (wood alcohol): CH3OH
– Useful as a solvent and industrial starting material
– Highly toxic, if taken internally causes blindness and/or death

• Ethanol (ethyl alcohol, grain alcohol): CH3CH2OH


– Produced commercially from ethylene and through biological (yeast)
fermentation of carbohydrates
– Useful as a solvent, industrial starting material, fuel (gasohol),
and found in alcoholic beverages
– Moderately toxic
OXIDATION OF ETHANOL IN THE BODY
In the body,
• ethanol is oxidized by enzymes in the liver
• aldehyde product impairs coordination

78
THE EFFECT OF
CONSUMING
ALCOHOL
IMPORTANT ALCOHOLS (CONTINUED)
• 2-Propanol (isopropyl alcohol) is the main
component of rubbing alcohol.

• 1,2,3-Propanetriol (glycerol) is used as a


food moistening agent (nontoxic) and for
its soothing qualities (soaps).

• Cholesterol is a waxy steroid found in cell


membranes and transported in blood
stream. High level can lead to heart disease.

• Antifreezes - 1,2-ethanediol (ethylene glycol)


and 1,2-propanediol
ETHERS AS SOLVENTS

• Ethers are widely used as solvents because


– they can dissolve nonpolar and polar substances.
– they are unreactive toward strong bases.
• Diethyl ether has a long history of medicinal use as an anesthetic and industrial
use as a solvent
• Anisole is a pleasant-smelling aromatic ether used in perfumery
• Tetrahydrofuran (THF) is a cyclic ether that is often used as a solvent