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Alcohol and Ether 2018-2019 PDF
Alcohol and Ether 2018-2019 PDF
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
ETHER STRUCTURE
CLASSIFICATION OF ALCOHOLS AND ETHERS
CLASSIFICATION OF ALCOHOLS
ALCOHOLS
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
ALCOHOLS
Alkylalcohol (Alkyl + alcohol)
COMMON NAME CH3OH = Methylalcohol
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
20
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
24
NOMENCLATURE OF ETHERS
• 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
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
OH O
OH
isopropyl methyl ether
2-methyl-1-propanol
O
O
diethyl ether methyl propyl ether
ISOMERS OF ALCOHOLS
OPTICAL ISOMERS
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
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
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.
O
R’ R
Ether molecules cannot form hydrogen bonds with other ether molecules.
R OH + M R OM + 1/2 H2
Alkoxides are formed
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)
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)
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
1.
2.
3.
6. REACTION WITH NITRIC ACID (HNO 3 )
H2SO4
H3C CH2 OH + HO NO 2 H3C CH2 O NO 2 + H2O
Ethanol Ethyl nitrate
OH O
(O)
H 3 C CH CH 3 + H3 C C CH3 + H 2O
+
Na2Cr2O7/ H Acetone
Isopropyl alcohol
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
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
Specific Example
Δ
O + PCl5 2 Cl + POCl3
PREPARATION OF ALCOHOLS AND ETHERS
1. PREPARATION OF ALCOHOLS
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
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
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
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
O OH
LiAlH4
H3C C CH 3 H 3C CH CH3
O
LiAlH4
H3C C OH H3C CH2 OH
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
O Na
O CH3
CH3I Na I
! Note that
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
78
THE EFFECT OF
CONSUMING
ALCOHOL
IMPORTANT ALCOHOLS (CONTINUED)
• 2-Propanol (isopropyl alcohol) is the main
component of rubbing alcohol.