Acids & Bases in Organic Chemistry

 Many of the organic reactions you will

study involve acid-base reactions.

 Understanding these reactions will require

you to:
 recognize organic compounds that can
serve as acids or bases

 throw away the idea that anything with an

OH is a base and anything with an H is an
acid!!!
 Acids & Bases in Organic Chemistry
 Common definitions of acids and bases:
 Arrhenius acids and bases
 Bronsted-Lowry acids and bases
 Lewis acids and bases

 Bronsted-Lowry Acid
 any substance that can donate a proton
(H+ ion)

 Bronsted-Lowry Base
 any substance that can accept a proton
 Acids & Bases in Organic Chemistry
 Common acids (materials with acidic protons)
used in organic chemistry:
 Inorganic acids:
 HCl
 HBr
 HI Strong acids
 H2SO4
 H3PO4 ..
O
 Carboxylic acids
R C O H
 H
.. . H
O . .. .. ..
. . H O H H O H
Acids & H Bases
. O. H
- .
in Organic
R
. .
H . O. H
O H
Chemistry
R C O H .C C C H H C C C H
- .. C C C H H C C C H
 Common acids
H
(materials
H H with acidic H
H H
protons) used or found in organic
chemistry: H .. ..
. . . .
 Phenols
.
H O. H O HH . O . H
O H
- .. C ..
O C C H H C C C H

C O HH H
Alcohols R O H H

 WaterH O H ..
O H
H
 Terminal Alkynes R C C H
. . .
O. H H . O. H
C C H H C C C H
 - .. H H H
C C C H C C
Acids & Bases in Organic
H Chemistry
H ..
O H
 Common bases (or basic substances) used R
..
or found in organic chemistry: O H
R
 Hydroxide ion
R
 NaOH or KOH H O H

R
 Alkoxide ions H O H
 Sodium methoxide
- +
CH3O Na

Sodium ethoxide
- +
 CH3CH2O Na

CH3
 Potassium t-butoxide - +
CH3CO K
CH3
 H . O. H H . O. H
- .. C C C H H H
H CChemistry
Acids & Bases in Organic C C H
HNH3 H H
 Common bases (or basic substances) used
or found in organic chemistry: .. O H
CH 3 R
O -H+
CH3CO K (CH3CH2)3N
 Sodium hydride N
NaH R C C H
CH3
 SodiumNaH
amide H
NaNH2

H O R
H
 Amines or ammonia NH3 R N
H O H
 Carbanions ..- CH3
R
-
C R'
-
+ CH3CH2O Na
+
- + CH
CH3CH2O Na CH3CO Na
R"
CH3
 Acids & Bases in Organic Chemistry
Example: Complete the following acid-base
reactions.
Ca(OH) + HCl
Ca(OH)
Ca(OH)222 ++ HCl
HCl

CH3COH
CH H + NaOH
CH33CO
CO222H ++ NaOH
NaOH

NaH +++ CH
NaH
NaH CHCH
CH CHOH
CH
3
OH
OH
2
33 22

CHC3CC CH
CH
CH CH +++ NaNH
CH NaNH2
NaNH
33 22
 Acids & Bases in Organic Chemistry
 Acid-base reactions always produce a new
acid and a new base:
 conjugate acid:
 The new acid formed when the base
gains a proton
– always found on the product side
 conjugate base:
 The new base formed by removing a
proton+from
Ca(OH) HCl an acid
– always found on the product side
2

CH3CO2H + NaOH CH3CO2Na + H2O

Conj. base Conj. acid
NaH + CH3CH2OH
 CH3CO2H + NaOH
Ca(OH)2 + HCl
Acids & Bases in Organic Chemistry
NaH + CH3CH2OH
CH3CO2H + NaOH
 The strength of an acid or base is
CH3C it CH + NaN
determined by the extent to which
ionizes: NaH + CH3CH2OH
+ - + -
HA + H2O H3O + A Ka = [H3O ][A ]
CH3C CH + NaN
[HA]

Ca(OH)2 + HCl + -
B .. + H2O Kb = [BH ][OH ]
+ -
BH + OH
CH3CO2H + NaOH CH3CO2Na + H2O
[B]

 Ca(OH) + dissociation
Ka = acid
2
HCl constant
NaH + CH CH2OH
 Kb = base 3 dissociation constant
CH CO H + NaOH CH CO Na + H O
 Acids & Bases in Organic Chemistry
 The relative strength of an acid can be
determined using:
 the magnitude of Ka (or pKa)
 As Ka increases, the strength of the acid
increases.
 As pKa decreases, the strength of the acid
increases.
 structural trends
 The strength of an acid, HX, depends on
– the electronegativity of the atom containing
the acidic hydrogen (i.e. the electronegativity
of X)

– the stability of the conjugate base, X-

 Acids & Bases in Organic Chemistry
 Within the same period (row), acidity
increases as the electronegativity of element
X increases (i.e. left to right)
 electronegative elements can bear a negative
charge more easily
H-C < H-N < H-O < H-F

 Within a group, the strength of an acid

increases moving down the group
 negative charge is more stable when spread
out over a larger region (i.e. larger ion)
HCl is stronger than HF
 .. . .
O.O.O
. .... ..
Acids
CH C
&
OH
Bases
...... in Organic
. O.O.. Chemistry
.O
CH3 CC OH
CH 33
OH ......
CH
CH
CHC OH
3 CC .. OH
 Acidity increases when the charge
33 ..OH
on the
..
conjugate base can be delocalized over two
or more atoms through resonance.

.. . ... . . .. . ... . . ....

. .
---
....
..
O.O.O. . O.O.O. . O
.O.O....
.... ......
...... ..-
..-.-
CH C OH CH C OOO...
3 CC ..
CH
CH CH
CH C OOO
3 CC ..
CH
3 CC ..
CH
CH 33 ..OH
OH.. 33 .... 33 ....
Stronger acid
pKa = 4.74

.. ...-
CH3CH2..
OH CH3CH2O
...
Weaker acid
pKa = 15.9
 Acids & Bases in Organic Chemistry
 You must be able to predict the relative
strength of various acids:

 pKa values (see Table 1-5) indicate the

following relative acidities:
– strong inorganic acids > carboxylic acids
> phenols > alcohols ~ water > terminal
alkynes > alkanes

 Be able to use structural trends.

 CH3CO2H CHCH CO2
3 3 CH3

Acids & Bases in Organic Chemistry

-
CH3CO2
CH3 N
N
 The strength
CH3CO K of a base(CH
- +
is CH
inversely
) N related
3 2 3
to its conjugate acid.
 Strong CH
acids form conjugate bases with
(CH3CH2)3N 3
negligible basicity.
-
HCl Cl -
N HCl Cl
 Weak acids form stronger conjugate bases.
NCH CO H CH3CO2
-
CH3OH
-
CH3O
3 2

-
 Substances with
-
negligible acidity
NH3 form
NHvery
2
HCl CHconjugate
strong 3
Cl bases.
- -
(CH3CH2CH CH3
- +
CHNH
3
CO3 K NH2 )3N4
-
CH3CH
OH CH
- 3O
3
 Acids & Bases in Organic Chemistry
 You should be able to:
 use the relative strength of various acids to
predict the relative strengths of their conjugate
bases

 use the strength of acids and bases to predict

whether an acid/base equilibrium favors
reactants or products.

 Equilibrium favors the weaker acid (or the

weaker base).
 -

HCl
AcidsCl-& Bases in NH3
NH
Organic Chemistry
2

-
CH4 reaction
Example: Does the following CHfavor
3 the
reactants
CH OH or products?
CH O
-

3 3

- -
CH3CH2OH + CH3NH CH3CH2O + CH3NH2
 .. .
.
.
Acids & Bases in Organic Chemistry
 The following reaction does not look like a
“classic” acid-base reaction...neither reactant
gains or loses an H+.
.. .. ..
O .. ..-
O
...-
CH3C H O.
+ CH3.. CH3C H
..
OCH3
..
Lewis acid Lewis base

 It is, however, a Lewis acid-base reaction.

 The Lewis acid-base definition is the broadest

definition of acids and bases.
 .
.
. .
Acids & Bases in Organic Chemistry
 Lewis acid: .. .
.
 an electron pair acceptor .
 an electrophile
 “electron lover”
 a substance that accepts a pair of
electrons to form a new bond

.. .. ..
O .. ..-
O
...-
CH3C H O.
+ CH3.. CH3C H
..
OCH3
..
Lewis acid
 Acids & Bases in Organic Chemistry
 Lewis Base:
 an electron pair donor
 a nucleophile
 “nuclei lover”
 a substance with a pair of electrons
that can be donated to another nucleus
to form a new bond

B + H A B H + A

Lewis Lewis
Base Acid
 Acids & Bases in Organic Chemistry
Examples of Lewis Acid/Base Reactions
H
O O
CH3C H + H Cl CH3C H + Cl

Lewis Lewis
base acid

O O
CH3C H + CH3O CH3C H
OCH3
Lewis Lewis
acid base
 Curved Arrows
 Curved arrows are used to show the
movement of electrons during a chemical
reaction.
 Electrons always move from the electron
donor to the electron acceptor.

 The curved arrow always starts at the pair

of electrons used to form the new bond.

 Curved arrows DO NOT show the movement

of atoms or charges!!!!
 Curved Arrows
 You should be able to used curved arrows
correctly to show the movement of
electrons for:

 Converting one resonance structure into

another

 Lewis acid/base reactions

 Curved Arrows
Example: Used curved arrow to show the movement
of electrons in the following reactions. Identify the
nucleophile and the electrophile.

CH3CH2O + CH3Br CH3CH2OCH3 + Br

O O
CH3CCH3 + CH3O CH3C CH2 + CH3OH
 Curved Arrows
Example: Use curved arrows to show the
interconversion of the following resonance
structures.

O O
H2C H2C