S

tructural
A &

cid-Base

Roldan M. de Guia
Department of Biochemistry
Faculty of Pharmacy
University of
Santo Tomas
 Structural Effects
ele ct ron d eloca li zati on

.. ..
.. NH2
CH2 CH Cl :
.. O
.. C ..
NH2

..
Cl : :O:
..
CH3 C
..
O
.. H
 Structural Effects
electron delocalization (Resonance)
 Structural Effects
electron delocalization (Resonance)
 Structural Effects
electron delocalization (Resonance)

:O:
H
:O: C H

.. .. -
:O :O: ..
NH2
N+
 Structural Effects
Hyp ercon jugat io n
H
H C CH CH2
H

+
H H H
..- + ..- ..-
H C CH CH2 H C CH CH2 H C CH CH2
H H +
H
 Structural Effects
Hyperconjugation

Dienes

CH2 CH CH CH2 cumulative

conjugated

isolated
 Structural Effects
Hyperconjugation
H H H
+ +
H C H H C H H C H

- ..

..
-
 Structural Effects
Hyperconjugation

H O H
+ -
O
H C C H C C
H H H H

O
O
 Structural Effects
+
CH3 CH3
+
CH2 + CH3
CH2 +
C
H3C CH3

H
- -
:CH3 O2N C:
H

H
. CH C.
3

H
 Structural Effects
Induct ive Eff ect
Ele ct ron at tr ac ti ng in duc ti ve
with excess positive charges

+ + +
R N R NH3 NO2
R
those with electronegative atoms
F
NH2 OH OCH3 Cl
Br
groups exhibiting orbital electronegativity

C N N N

those with easily polarizable valence electrons

-
I
 Structural Effects
Induct ive Eff ect
Ele ct ron at tr ac ti ng in duc ti ve
δ+ δ−
H3C Cl

δ+ δ++ δ− δ−
δ+
CH3 CH2 Cl CH3 CH2 O
H δ+

CH3
+
H3C N CH3

--
 Structural Effects
Induct ive Eff ect
Ele ct ron re pe lling i nd uct ive effec t
alkyl groups
CH3

negative groups
- - -
COO S O

O -
H3C S H3C
H3C C --
CH C N
O
H3C
 Structural Effects
St eric Ef fe ct
 Structural Effects
Hyd ro gen B ond ing
+ δ+
F H δ F H

δ+
O H δ+ O H

δ+
N H δ+ N H

H O
H
O H
F OH
OH
R H O H O
O
H R C C R
O H
H O H
O H O
R C O

O H
 Acids and
Bases
Brønsted–Lowry Acids and Bases
• An acid is a proton donor
• A base is a proton acceptor

acid base

base acid

Note that water can act as an acid or a

base
 Acids and
Bases
Brønsted–Lowry Acids and
Bases

acid base conjugate conjugate

base acid

Every acid–base reaction involving proton transfer

has two conjugate acid–base pairs.
 Acids and
Bases
Lewis Acids and Bases
• A Lewis acid is an electron pair
acceptor.
(think empty orbital)

A Lewis base is an electron pair

donor.
(think filled orbital)

The result of a Lewis acid–base reaction is often

called an adduct.