Organic Chemistry, Fourth Edition

Janice Gorzynski Smith

University of Hawai’i

Chapter 2
Lecture Outline
Prepared by Layne A. Morsch
The University of Illinois - Springfield

Copyright © 2014 The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
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In this chapter
• Acid-base concepts in organic reactions
• Inductive effect
• Resonance effect
• Common Acids and Bases in OrgChem
• Nucleophiles and Electrophiles

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 Brønsted-Lowry Acids and Bases

• A hydrogen atom without its electron is a proton.

H+ = proton

• A Brønsted-Lowry acid is a proton donor.

•It must have a proton.

• A Brønsted-Lowry base is a proton acceptor.

•It must be able to form a bond to a proton.

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 Brønsted-Lowry Acids and Bases

Figure 2.1

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 Acidic and Basic Sites in Morphine
Some molecules contain both hydrogen atoms and lone
pairs and thus, can act either as acids or bases, depending
on the particular reaction.

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 Reactions of Brønsted-Lowry Acids and
Bases
• A Brønsted-Lowry acid base reaction results in the transfer of
a proton from an acid to a base.
• The electron pair of the base B: forms a new bond to the
proton of the acid forming the conjugate acid of the base.
• The acid H-A loses a proton, leaving the electron pair in the
H-A bond on A. This forms the conjugate base of the acid.

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 Reactions of Brønsted-Lowry Acids and
Bases
• The movement of electrons in reactions can be illustrated
using curved arrow notation.

• Because two electron pairs are involved in this reaction, two

curved arrows are needed.

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 Examples of Brønsted-Lowry Acid-Base
Reactions
• A double reaction arrow (indicating equilibrium) is used
between starting materials and products to indicate that the
reaction can proceed in the forward and reverse directions.

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 General Reactivity

These reactions illustrate a general pattern of reactivity:

• Electron-rich species react with electron-deficient

species
• Bases are electron rich
• While the H of an acid has a partial positive charge
making it electron deficient

• Therefore, acids and bases react with one another

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 Acid Strength and pKa
• Acid strength is the tendency of an acid to donate a proton.

• The more readily a compound donates a proton, the stronger

an acid it is.

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 Acid-Base Equilibrium

• Acidity is measured by an equilibrium constant.

• When a Brønsted-Lowry acid H-A is dissolved in water, an

acid-base reaction occurs, and an equilibrium constant can
be written for the reaction.

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 Acidity Constant
• Because the concentration of the solvent H2O is
essentially constant, the equation can be rearranged
and a new equilibrium constant, called the acidity
constant, Ka, can be defined.

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 Ka and pKa
• It is generally more convenient when describing acid
strength to use “pKa” values than Ka values.

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Acidity of Some Common Compounds

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 Outcome of Acid-Base Reactions
• The position of the equilibrium depends on the relative
strengths of the acids and bases.
• Equilibrium always favors formation of the weaker acid
and base.

• Because the pKa of the starting acid (25) is lower

than that of the conjugate acid (38), equilibrium
favors the products.
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 Steps in Solving Acid-Base Reaction Equilibria

Step [1] Identify the acid and base in the starting materials.
Assume –NH2 is the base because it bears a net
negative charge. That makes HCCH the acid.

Step [2] Draw the products of proton transfer and identify

the conjugate acid and base in the products.
Acetylene gives up its proton to –NH2.

Step [3] Compare the pKa values of the acid and the
conjugate acid. Equilibrium favors formation of
the weaker acid with the higher pKa. The pKa of
NH3 is higher; therefore products are favored.
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 Factors that Determine Acid Strength

• Anything that stabilizes a conjugate base A:¯ makes

the starting acid H-A more acidic.

• Four factors affect the acidity of H-A. These are:

• Element effects
• Inductive effects
• Resonance effects
• Hybridization effects

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 Comparing the Acidity of Any Two Acids

• Always draw the conjugate bases.

• Determine which conjugate base is more stable.

• The more stable the conjugate base, the more acidic

the acid.

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 Element Effects—Trends in the
Periodic Table
Why does H2O have a much lower pKa than CH4?

Since oxygen is much more electronegative than carbon,

it more readily accepts a negative charge.

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 Element Effects—Trends in the
Periodic Table
Across a row of the periodic table, the acidity of H-A
increases as the electronegativity of A increases.

Positive or negative charge is stabilized when it is spread

over a larger volume.

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 Element Effects Down a Column in the
Periodic Table
• Down a column of the periodic table, size, and not
electronegativity, determines acidity.
• The acidity of H-A increases as the size of A increases.

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 Inductive Effects
• An inductive effect is the pull of electron density through 
bonds caused by electronegativity differences of atoms.

• More electronegative atoms stabilize regions of high electron

density by an electron withdrawing inductive effect.

• The more electronegative the atom and the closer it is to the

site of the negative charge, the greater the effect.

• The acidity of H-A increases with the presence of electron

withdrawing groups in A.

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 Inductive Effects in Trifluoroethanol
• In the example below, note that 2,2,2-trifluoroethanol is
more acidic than ethanol.

• The reason for the increased acidity of 2,2,2-

trifluoroethanol is that the three electronegative
fluorine atoms stabilize the negatively charged
conjugate base.

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 Rationale for Inductive Effects

Figure 2.2

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 Resonance Effects
• Delocalization of charge through resonance influences acidity.

• Acetic acid is more acidic than ethanol, even though both

conjugate bases have the negative charge on the same
element, O.

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Comparison of Ethoxide and Acetate ions
• The conjugate base of ethanol has a localized charge.

• The conjugate base of acetic acid is resonance

delocalized.

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 Electrostatic Potential Plots of Ethoxide
and Acetate
Figure 2.3

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 Hybridization Effects
Consider the relative acidities of three different compounds
containing C-H bonds.

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 Stability of Conjugate Bases
The higher the percent of s-character of the hybrid orbital,
the more stable the conjugate base.
Figure 2.4

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 Summary of Factors that Determine Acid
Strength
Figure 2.5

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How To: Determine the Relative Acidity of Protons
Step [1] Identify the atoms bonded to hydrogen, and
use periodic trends to assign relative acidity.
• The most common H-A bonds in organic compounds
are C-H, N-H and O-H.
• Acidity increases left to right across a row, the relative
acidity of these bonds is C-H<N-H<O-H.
• H atoms bonded to C atoms are usually less acidic
than H atoms bonded to any heteroatom.

Step [2] If the two H atoms in question are bonded to

the same element, draw the conjugate bases
and look for other points of difference.
• Do electron-withdrawing groups stabilize the conjugate
base?
• Is the conjugate base resonance stabilized?
• How is the conjugate base hybridized?
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Commonly Used Acids in Organic Chemistry

• The familiar acids HCl and H2SO4 are often used in

organic reactions.
• Various organic acids are also commonly used (e.g.,
acetic acid and p-toluenesulfonic acid (TsOH)).

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Commonly Used Bases in Organic Chemistry

• Common strong bases used in organic reactions are

more varied in structure.

Figure 2.6

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 Characteristics of Strong Organic Bases

• Strong bases have weak conjugate acids with high pKa

values, usually > 12.

• Strong bases have a net negative charge, but not all

negatively charged species are strong bases. For example,
none of the halides F¯, Cl¯, Br¯, or I¯, is a strong base.

• Carbanions, negatively charged carbon atoms, are especially

strong bases. A common example is butyllithium:

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Other Common Bases in Organic Chemistry

• Amines (e.g., triethylamine and pyridine) are organic bases.

• They are basic due to having a lone pair on N.

• They are weaker bases since they are neutral, not negatively
charged.

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 Example: Aspirin
• Aspirin (acetylsalicylic acid) is one of the most well known
drugs. It functions as an analgesic, anti-pyretic and anti-
inflammatory agent.

• In ionic form, it is soluble in the aqueous blood stream and

transported to tissues where it is needed.
• When protonated, it becomes neutral and can pass
through cell membranes to inhibit certain chemical
reactions. 36
 Lewis Acids and Bases
• A Lewis base is an electron pair donor.
• Lewis bases are structurally the same as BrØnsted-Lowry
bases. Both have an available electron pair—a lone pair or
an electron pair in a  bond.
• A BrØnsted-Lowry base always donates this electron pair
to a proton, but a Lewis base donates this electron pair to
anything that is electron deficient.

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 Lewis Acids
• A Lewis acid is an electron pair acceptor.
• Any species that is electron deficient and capable of accepting
an electron pair is also a Lewis acid.
• All BrØnsted-Lowry acids are also Lewis acids, but the reverse
is not necessarily true.
• Common Lewis acids (which are not BrØnsted-Lowry acids)
contain elements in group 3A that can accept an electron pair
because they do not have filled valence shells.

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 Lewis Acid-Base Reactions

• In a Lewis acid-base reaction, a Lewis base donates an

electron pair to a Lewis acid.

• This is illustrated in the reaction of BF3 with H2O. H2O

donates an electron pair to BF3 to form a new bond.

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 Electrophiles and Nucleophiles
• Lewis acid-base reactions illustrate a general pattern
in organic chemistry.

• Electron-rich species react with electron-poor species.

• A Lewis acid is also called an electrophile.

• When a Lewis base reacts with an electrophile other
than a proton, the Lewis base is also called a
nucleophile.
• In this example, BF3 is the electrophile and H2O is the
nucleophile.

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 Lewis Acid-Base Reactions that Form
One New Covalent Bond
• Note that in each reaction below, the electron pair is not
removed from the Lewis base.
• Instead, it is donated to an atom of the Lewis acid and
one new covalent bond is formed.

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 Drawing Products of Lewis Acid-Base
Reactions
• In other Lewis acid-base reactions, one bond is
formed and one bond is broken.

• To draw the products of these reactions, keep in mind

the following steps:
• Always identify the Lewis acid and base first.
• Draw a curved arrow from the electron pair of the
base to the electron-deficient atom of the acid.
• Count electron pairs and break a bond when needed
to keep the correct number of valence electrons.

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 Alkene-HCl Reaction

• The reaction between cyclohexene and HCl can be

treated as a Lewis acid-base interaction.

• HCl acts as the Lewis acid, and cyclohexene, having

a  bond, is the Lewis base.

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 Drawing the Product of the Reaction of
HCl with Cyclohexene
• The electron pair in the  bond of the Lewis base forms
a new bond to the proton of the Lewis acid, generating
a carbocation.
• The H-Cl bond must break, giving its two electrons to
Cl, forming Cl¯.
• Because two electron pairs are involved, two curved
arrows are needed.

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