Alcohols
Definition of Alcohols
Alcohols (R-O-H)
Alcohol is any organic comp. in
which a hydroxyl group (-OH) is
bound to saturated, sp3 C atom of
an alkyl or subst alkyl gp.
General formula: CnH2n+1OH.
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Alcohols (R-OH)
▸ The simplest alcohols are CH3OH and
CH3CH2OH.
▸ MeOH was obtained by heating wood in
absence of air & called wood alcohol.
▸ Today, catalytic reduction of CO.
400oC
CO + 2 H2 CH3OH
ZnO
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Alcohols (R-OH)
MeOH is toxic to humans by its breakdown by enzyme
alcohol dehydrogenase in liver by forming formic acid
and formaldehyde which cause permanent blindness
by destruction of optic nerve.
Ethanol is also used as solvent and raw material. It is
produced by fermentation of grains and sugars & also
obtained by acid catalyzed hydration of ethylene.
250oC
H2C CH2 + H2O CH3CH2OH
H3PO4
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Ethanol
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Naming Alcohols
Classification of Alcohols
Depends on the C which has the –OH group attached.
primary alcohols are compounds of the type RCH2OH. Secondary alcohols are compounds of the type
R2CHOH, and tertiary alcohols are compounds of the type R3COH.
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The IUPAC of Alcohols
Simple alcohols are named as derivatives of parent
alkane, using the suffix –ol:
1. Select the longest carbon chain containing the OH
gp & derive parent name by replacing the –e with
–ol.
2. Number the chain so that OH gp are attached to
the lowest numbered carbons.
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The IUPAC of Alcohols
Simple alcohols are named as derivatives of parent
alkane, using the suffix –ol:
3.Number substituents according to their position on
the chain & write the name & listing substituents in
alphabetical order.
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The IUPAC of Alcohols
c
v
c c c c
c v v v
v
c c c c c v
v v v v v c
v c
v
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The IUPAC of Alcohols
▸ Simple alcohols have common names accepted by
IUPAC, example, CH3-OH called methyl alcohol;
(CH3)2CH-OH called isopropyl Alcohol.
CH2OH CH3
H3C C OH H2C CHCH2OH
CH3
benzyl alcohol tert-butyl alcohol allyl alcohol
(phenylmethanol) (2-methyl-2-propanol) (2-propen-1-ol)
OH
HOCH2CHCH2OH HOCH2CH2OH
glycerol ethylene glycol
(1,2,3-propanetriol) (1,2-ethanediol)
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Physical Properties of Alcohols
1-Hydrogen Bonding and boiling point
▸ Alcohols have nearly the same geometry as
water. The R-OH bond angle has tetrahedral
value (109o in methanol) & oxygen atom is sp3-
hybridized. Because of H-bonding, alcohols
have higher boiling points than hydrocarbons
& alkyl halides.
▸ Ex: 1-Propanol (MW = 60, bp = 97oC),
Butane (MW = 58, bp = -0.5oC)
Chloroethane (MW14 = 65, bp = 12.5oC).
1-Hydrogen Bonding and boiling point
These intermolecular interactions must be overcome for a
molecule to break free from liquid and to vapor state so
boiling temperature is raised.
R R R R R R
O O O O O O
H H H H H H
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2-Acidity and Basicity
▸ Like water, alcohols are both weakly basic and weakly
acidic.
▸ As weak bases:
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2-Acidity and Basicity
▸ Like water, alcohols are both weakly basic and weakly
acidic.
▸ As weak acids, alcohols dissociate in dilute aq. solution:
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2-Acidity and Basicity
The strength of any acid HA in water can be expressed by
an acidity constant, Ka:
[A ][H3O ]
Ka = pKa = -log Ka
[HA]
Simple alcohols are about as acidic as water, but
substituent groups have a significant effect.
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▸ The key factor in determining acidity is the stability of
alkoxide.
▸ Any factor which makes the alkoxide more stable will
increase the acidity of the acid.
▸ focus on resonance and adjacent electron-withdrawing
groups.
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▸ Alcohols where the conjugate base (alkoxide)
is resonance stabilized will be more acidic. The classic
example is cyclohexanol and phenol.
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▸ Inductive effects are also important. Electron-
withdrawing halogen substituents stabilize an
alkoxide ion by spreading charge over a larger
volume, making alcohol more acidic.
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▸ Since fluorine is more electronegative than chlorine
which is more electronegative than bromine which is
more electronegative than iodine, the inductive effect
will be highest for CF3 and lowest for CI3.
▸
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▸ A Practice Question
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2-Acidity and Basicity
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2-Acidity and Basicity
▸ Alcohols react with strong bases such as NaH, NaNH2 and
Grignard reagents. Alkoxides are bases used as reagents in
organic chemistry.
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CH3OH + NaH CH3O Na + H2
2-Acidity and Basicity
methanol sodium methoxide
CH3CH2OH + NaNH2 CH3CH2O Na + NH3
ethanol sodium ethoxide
OH + CH3MgBr O MgBr + CH4
cyclohexanol bromomagnesium
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cyclohexoxide
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Preparation of Alcohols
1. Hydration of Alkenes
Hydroboration/ oxidation
yields product of syn,
Boron hydride non-Markonikov
(borane) hydration
Mercury(II) Oxymercuration/reduction
acetate yields product of
Markonikov
hydration
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Markovnikov's rule
(Markovnikov addition)
In an addition reaction of a protic acid HX (hydrogen
chloride, hydrogen bromide, or hydrogen iodide) to
an alkene or alkyne, the hydrogen atom of HX
becomes bonded to the carbon atom that had the greatest
number of hydrogen atoms in the starting alkene or alkyne.
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2- Reduction of Carbonyl Compounds
[a. Reduction of aldehydes and ketones]
▸ Ketones converted to 2o alcohol
▸ Aldehydes converted to 1o alcohol
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2- Reduction of Carbonyl Compounds
[a. Reduction of aldehydes and ketones]
▸ Many reagents are used to reduce aldehydes and ketones to
alcohols, but sodium borohydride is usually chosen because
of its safety & ease of handling, can be used in either water or
alcohol solution & give a high yield of alcohol.
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LiAlH4, is another
reducing agent. It is
much more reactive but
more dangerous than
NaBH4. It reacts violently
with water and
decomposes explosively
when heated above
120oC.
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2- Reduction of Carbonyl Compounds
[b. Reduction of Carboxylic Acids and Esters]
▸ NaBH4 reduces esters very slowly & does not reduce
carboxylic acids at all.
▸ Reduction of carboxylic acids & esters is usually carried out
with LiAlH4. All carbonyl groups including acids, esters,
ketones and aldehydes are rapidly reduced by LiAlH4.
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2- Reduction of Carbonyl Compounds
[c. From Reaction of Carbonyl Compounds with Grignard Reagents]
▸ Alkyl, aryl and vinylic halides react with magnesium in dry
ether or tetrahydrofuran solution to generate Grignard
reagents, RMgX.
▸ These Grignard reagents react with carbonyl compounds to
yield alcohols.
▸ Grignard formation:
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2- Reduction of Carbonyl Compounds
[c. From Reaction of Carbonyl Compounds with Grignard Reagents]
▸ These Grignard reagents react with carbonyl compounds to yield
alcohols.
▸ Grignard reagents react with
▸ Formaldehyde to give 1o alcohols.
▸ Aldehydes to give 2o alcohols.
▸ Ketones to give 3o alcohols.
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Grignard reagents are excellent carbon-based nucleophiles
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1) with formaldehyde:
MgBr O CH2OH
1. ether
+ C
H H 2. H3O
cyclohexylmagnesium formaldehyde cyclohexylmethanol
bromide (1o alcohol)
2) with aldehyde:
OH CH3
MgBr
CH3 CHCH2CHCH 3
O
+ 1. ether
CH3CHCH2CH
2. H3O
phenylmagnesium 3-methylbutanal 3-methyl-1-phenyl-1-butanol
bromide (2oalcohol)
3) with ketone:
OH
O
1. CH3CH2MgBr, ether CH2CH3
2. H3O
1-ethylcyclohexanol
cyclohexanone 47 (3o alcohol)
Reaction of Grignard Reagents With Esters
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▸ Carboxylic acids do not give addition
products with Grignard reagents because the
acidic carboxyl hydrogen reacts with the
basic Grignard reagent to give a
hydrocarbon and the magnesium salt of the
acid.
O O
RMgBr + C RH + C
' '
R OH R O MgBr
carboxylic acid carboxylic acid salt
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Quiz
Q.1
What the IUPAC name of the following product?
A. 2-hydroxy-3-methyl hexane
B. 2- methyl-3-hydroxy hexane
C. 2-hydroxy-3-methyl pentane
D. 2- methyl-3-hydroxy pentane
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Q.2
Which is more acidic ?
A. (CH3)3COH.
B. (CF3)3COH.
C. CH3CH2OH.
D. CF3CH2OH.
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Q.3
Pick the major product in the following reaction?
CH3 CH3
CH3
H2O2 O CH O 3 HNaHSO 3 OH
CH
H2O2OH
CH3Os OH OH 3
O4 O O OH O NaHSO 3 OH
OH H OH
Os H H OH
trans-methycyclohexanol
O O 1-methyl
H
H cis-1,2-cyclohexanediol
H
trans-methycyclohexanol
A B
1-methyl
CH3 OH
CH 3 cis-1,2-cyclohexanediol
NaBH4 CH3 CH
aBH4
H
O CH3
OH
OH
H3O
H3O
H
OH3
OH
CH3
A
O
HgOAc OH
1-methycyclohexanol
H
HgOAc
1-methy-1,2-epoxy-
1-methycyclohexanol 1-methyl
cyclohexane trans-1,2-cyclohexanediol
1-methy-1,2-epoxy-
C 1-methyl
cyclohexane D
trans-1,2-cyclohexanediol 53
Q.4
Direct oxidation of 1-methylcyclohexene by borane gives alcohol according to
Markonikov rule?
A. True.
B. False.
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1) with formaldehyde:
MgBr O
Q.5 +
H
C
H
1. ether
2. H3O
cyclohexylmagnesium formaldehyde cyclohexyl
bromide reaction?
What is the product obtained from the following (1o al
2) with aldehyde:
A. 3-methyl-1-phenyl-1-butanol MgBr
B. 1-methyl-3-phenyl-1-butanol +
CH3
CH3CHCH2CH
O
1. ether
C. 3-methyl-1-phenyl-1-pentanol 2. H3O
phenylmagnesium 3-methylbutanal 3-met
D. 1-methyl-3-phenyl-1-pentanol bromide
3) with ketone:
O
A O
1. CH3CH2MgBr, ether
2. H3O
cyclohexanone 1-ethylcyclo
(3o alco
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Q.6
What the IUPAC name of the following product?
A. 2,4,6-trimethylcyclohexan-5-ol
B. 1,3,5-trimethylcyclohexan-2-ol
C. 2,4,6-trimethylcyclohexan-1-ol
D. 1,3,5-trimethylcyclohexan-4-ol
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Q.7
Pick the major product in the following reaction?
1) with formaldehyde:
MgBr O
1. ether
+ C
H H 2. H3O
A. B.
cyclohexylmagnesium formaldehyde cycloh
bromide (1
C. D. 2) with aldehyde:
MgBr
CH3 O
+ 1. ether
CH3CHCH2CH
2. H3O
phenylmagnesium 3-methylbutanal 3
A
bromide
3) with ketone:
O
57 1. CH3CH2MgBr, ether
Q.8
What the IUPAC name of the following product?
A. 3-Phenyl-1-butanol
B. 1-Phenyl-2-butanol
C. 2-Phenyl-3-butanol
D. 3-Phenyl-2-butanol
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Thanks!
Any questions?
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