ALCOHOLS AND

SUSTITUTION AND
ELIMINATION REACTIONS

Fabio Andrés Castellanos Castillo

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Alcohols and Phenols
 Alcohols contain an OH group connected to a saturated C (sp3)
 They are important solvents and synthesis intermediates
 Phenols contain an OH group connected to a carbon in a
benzene ring
 Methanol, CH3OH, called methyl alcohol, is a common solvent,
a fuel additive, produced in large quantities
 Ethanol, CH3CH2OH, called ethyl alcohol, is a solvent, fuel,
beverage
 Phenol, C6H5OH (“phenyl alcohol”) has diverse uses - it gives
its name to the general class of compounds
Phenol Acidity
 Phenols (pKa ~10) are much more acidic than
alcohols (pKa ~ 16) due to resonance stabilization of
the phenoxide ion
 Phenols react with NaOH solutions (but alcohols do
not), forming soluble salts that are soluble in dilute
aqueous
 A phenolic component can be separated from an
organic solution by extraction into basic aqueous
solution and is isolated after acid is added to the
solution
Naming alcohols
 They are compounds which hydrogen has
been replaced by an OH group.

• Primary R CH2 OH

R
• Secondary CH OH
R
R
• Tertiary
R C OH
R
 Naming alcohols
 Alkyl group followed by the Word “alcohol”

OH

Ciclohexyl
alcohol

Isopropyl
OH alcohol
 Ejemplo

CH3CH2CH2CH2CHCH2OH
C
C CH2CH2CH3
Ejemplos
2 OH HO Br
3 1 2 3
4 6 1 5
5 H3C 4 CH3
2,3-dimethyl-1-cyclohexanol 3-bromo-2-pentanol

OH 2
2
H3C 3 1 3 1
4 6 4
OH
5
H3C
CH3
4-methyl-cyclopent-2-en-1-ol
3-ethyl-5-methyl-1-cyclohexanol
2-methyl-2-pentanol cis-1,4-cyclohexanediol 3-phenyl-2-butanol

Benzyl alcohol Allyl alcohol tert- butyl alcohol Ethylene glycol Glycerol
(Phenylmethanol) (2-propen-1-ol) 2-methyl-2-propanol 1,2-Ethanediol 1,2,r-propanetriol
Give the IUPAC name of the following compounds

Draw the structures that corresponding to the following IUPAC

names
(a) 2-Ethylbut-2-en-1-ol
(b) Cyclohex-3-en-1-ol
(c) trans-3-Chlorocycloheptanol
(d) 1,4-Pentanediol
(e) 2,6-Dimethylphenol
(f) O-(2-Hydroxyethyl)phenol
Phenol: b.p =181.7 °C Toluene: b.p =110.6 °C
 NUCLEOPHILES
R-Y + Nu R-Nu + Y
Nucleophiles Products Clase

- - -
Cl ,B r ,I R X Huros de alquilo

-
OH R OH
R'O-
R O R'
C N- R C N
O O
R' C R' C
- O R
O
R' C C: - R' C C R
-
SH R SH
 Two Different Substitution Reactions
 We can distinguish two reactions based on
their kinetics.

 First is SN2, depends on substrate AND

nucleophile concentration.

 Second is SN1, depends only on substrate

concentration.
SN2 Reaction
 80% ethanol -
CH 3 Br + NaOH CH 3 OH + Br
20% water 55oC

rate = k2[RBr][NaOH]

-
H O
80% ethanol -
CH 3 Br CH3 OH + Br
20% water

Rate dependence of the reaction

is interpreted in a way that
we expect a bimolecular reaction
with a concerted mechanism
SN2 substitution
nucleophilic
bimolecular
 SN2 Reaction
 Rate dependence is 2nd order

 Two molecules have to come together to form

new bonds

 Bimolecular reaction
 ENERGY PROFILE

Mechanism E
N
E
R
G
Y

HO- Br Br-

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 ENERGY PROFILE

E
N
E
R
G
Y

-
HO HO- Br Br-

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 ENERGY PROFILE

E
N
E
R
G
Y

-
HO HO- Br Br-

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 ENERGY PROFILE

E
N
E
R
G
Y

HO - HO- Br Br-

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 ENERGY PROFILE

E
N
E
R
G
Y

-
HO HO Br Br-

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 ENERGY PROFILE

E
N
E
R
G
Y

Br --
-
HO HO Br Br-

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 ENERGY PROFILE

E
N
E
R
G
Y

-
HO HO Br- Br-

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Stereochemistry
 Old bond is broken simultaneously with the
new bond formed.
 Well-defined outcome
 Stereochemistry is inverted
CH2CH3 CH2CH3
-
HO
H H CH3
H3C Br HO
(S)-2-bromobutane (R)-2-butanol
 Factors Affecting SN2
 Steric effects

Approaching the polarized carbon gets more and more difficult.

 Factors Affecting SN2
 Leaving Group
 I– > Br– > Cl– > F–
 The lower the basicity, the better the leaving group.

 Nucleophile
 HO– > H2O; CH3O– > CH3OH
 The better the base, the better the nucleophile
 NH2– > HO– > F–
The Leaving Group
 A good leaving group reduces the barrier to a
reaction
 Stable anions that are weak bases are usually
excellent leaving groups and can delocalize charge

26
Poor Leaving Groups
 If a group is very basic or very small, it is prevents
reaction

27
SN1 Reaction

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 SN1

CH 3 CH 3
80% etanol -
H 3C C Br + NaOH H 3C C OH + Br
20% agua 55oC
CH 3 CH 3

rate = k1[RBr]

Rate depends only on substrate concentration.

Two independent steps that differ significantly in speed.
Unimolecular

SN1 substitution
nucleophilic
unimolecular
 SN1
CH3 CH3
H3C C OH + Br-
80% etanol
H3C C Br + NaOH 20% agua
CH3 CH3

slow
O H
fast
CH3
H3C C + + Br-
CH3

Assuming the formation of a carbocation intermediate

as the rate-determining step, explains speed of reaction

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 SN1
Reaction profile

CH3
Br- Br CH3 -
OH
CH3

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 SN1

CH3
Br- Br CH3 -
OH
CH3
Bond gets longer

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 SN1

CH3
Br- Br CH3 -
OH
CH3
Bond gets longer
and longer
Rehybridization sp3  sp2

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SN1

CH3
CH3 -
Br - OH
CH3
Bond gets longer
and longer
Rehybridization sp3  sp2

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SN1

CH3
-
Br - CH3 OH

CH3
Bond gets longer
and longer
Rehybridization sp3  sp2
sp2-Hybridized intermediate formed

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SN1

CH3
-
Br - CH3 -
OH OH
CH3
Bond gets longer
and longer
Rehybridization sp3  sp2
sp2-Hybridized intermediate formed
Nucleophile approaches
Rehybridization sp2  sp3 takes place
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SN1

CH3
-
Br -
CH3 OH OH
CH3
Bond gets longer
and longer
Rehybridization sp3  sp2
sp2-Hybridized intermediate formed
Nucleophile approaches
Rehybridization sp2  sp3 takes place
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SN1

CH3
-
Br -
CH3 OH OH
CH3
Bond gets longer
and longer
Rehybridization sp3  sp2
sp2-Hybridized intermediate formed
Nucleophile approaches
Rehybridization sp2  sp3 takes place
Bond forms Copyright © 2010 Pearson
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SN1

CH3
-
Br -
CH3 OH OH
CH3
Bond gets longer
and longer
Rehybridization sp3  sp2
sp2-Hybridized intermediate formed
Nucleophile approaches
Rehybridization sp2  sp3 takes place
Bond forms Copyright © 2010 Pearson
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 SN1
 Rate dependence is 1st order

 Rate depends only on formation of cation

 Unimolecular reaction

 The intermediate requires rehybridization

sp3sp2
 Stereochemistry
 First, old bond is broken. In a second step,
we form new bond.
 We have a carbocation intermediate.
 This requires rehybridization sp3  sp2
 Stereochemical information is lost.
 Racemate formed.
OH OH
Br
HO-
+
 Factors Affecting SN1
 Cation stability
 3o alkyl halide > 2o alkyl halide > 1o alkyl halide.
 Leaving group
 The weaker the bond, the easier to break.
 RI > RBr > RCl > RF
 Nucleophile
 NO EFFECT.
 Comparison SN2 and SN1

SN2 SN1
One-step mechanism Two-step mechanism
Bimolecular Unimolecular
Inverted configuration racemate
Reactivity order: Reactivity order:
methyl > 1o > 2o > 3o 3o > 2o > 1o > methyl