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CHEM 344
ORGANIC REACTION MECHANISM
FOR CHEMISTRY’ STUDENTS, COLLEGE OF SCIENCE
PRE-REQUISITES COURSE; CHEM 241
CREDIT HOURS; 2 (2+0+0)
Prof. Mohamed El-Newehy Dr. Zainab Almarhoon
http://fac.ksu.edu.sa/melnewehy https://fac.ksu.edu.sa/zalmarhoon
Chemistry Department, College of Science, King Saud University
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INTRODUCTION
ACIDS AND BASES
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ACID–BASE REACTIONS
o Many of the reactions that occur in organic chemistry are either acid–base reactions
themselves or they involve an acid–base reaction at some stage
o Arrhenius regarded acid-base reactions as occurring only in water,
- An Arrhenius acid is a source of H+ ion.
- An Arrhenius base is a source of -OH ion.
The Arrhenius acid-base theory provided a good start toward understanding
acid-base chemistry, but it proved much too limited in its scope.
o Two classes of acid–base reactions are fundamental in organic chemistry:
Brønsted–Lowry
Lewis acid–base reactions
ACID–BASE REACTIONS
BRØNSTED-LOWRY DEFINITION
o Brønsted–Lowry acid–base reactions involve the transfer of protons
A Brønsted-Lowry acid is a proton (H+) donor.
A Brønsted–Lowry acid is a substance that can donate (or lose) a proton
A Brønsted-Lowry base is a proton (H+) acceptor.
A Brønsted–Lowry base is a substance that can accept (or remove) a proton
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ACID–BASE REACTIONS
BRØNSTED-LOWRY DEFINITION
o Liquid water is in equilibrium with solvated hydroxide and solvated protons.
o We typically use a value related to the equilibrium constant to define the
concentration of these solvated ions in water.
o The water dissociation constant, Kw = 1 x 10-14.
o pH and pOH are important values for acidic and basic solutions.
o These are the log base 10 of the hydrogen ion concentration or of the hydroxide ion
concentration, respectively.
THE STRENGTH OF BRØNSTED–LOWRY ACIDS AND BASES
THE ACIDITY CONSTANT, Ka
o In contrast to strong acids such as HCl and H2SO4, acetic acid is a much weaker acid
At 25oC, in a 0.1 M acetic acid solution, only
about 1% of the acetic acid molecules ionize
o Equilibrium constant (keq)
o For dilute aqueous solutions, the concentration of water is essentially constant and
the Keq expression can be written in terms of the acidity constant (ka)
o At 25oC, the acidity constant (ka) for acetic acid is 1.76 x 10−5
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THE STRENGTH OF BRØNSTED–LOWRY ACIDS AND BASES
THE ACIDITY CONSTANT, Ka
o For any weak acid dissolved in water
o An acid with a large value of Ka
a strong acid
o An acid with a small value of Ka
a weak acid
THE STRENGTH OF BRØNSTED–LOWRY ACIDS AND BASES
ACIDITY AND pKa
o For acetic acid, the pka is 4.75
o The larger the value of the pKa, the weaker the acid
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THE STRENGTH OF BRØNSTED–LOWRY ACIDS AND BASES
ACIDITY AND pKa
o Relative Strength of Selected Acids & Their Conjugate Bases
THE STRENGTH OF BRØNSTED–LOWRY ACIDS AND BASES
PREDICTING THE STRENGTH OF BASES
o The stronger the acid, the weaker its
conjugate base
o The larger the pKa of the conjugate acid,
the stronger the base
o Since CH3O+H2 is a stronger acid than H3O+,
H2O is a stronger base than CH3OH
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FACTORS AFFECTING ACID STRENGTH
RELATIONSHIPS BETWEEN STRUCTURE AND ACIDITY
o The stronger the H–X bond, the weaker the acid.
The strength of H–X bond
H–F > H–Cl > H–Br > H–I
o The stronger the acid, the weaker the conjugate base.
Thus acidity increases as we
descend a vertical column in a group
in the Periodic Table
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FACTORS AFFECTING ACID STRENGTH
RELATIONSHIPS BETWEEN STRUCTURE AND ACIDITY
o The higher the electronegativity of an atom, the easier it will acquire a
negative charge.
Thus acidity increases from left to right when we compare compounds in the
same row of the Periodic Table
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FACTORS AFFECTING ACID STRENGTH
RELATIONSHIPS BETWEEN STRUCTURE AND ACIDITY
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FACTORS AFFECTING ACID STRENGTH
THE EFFECT OF HYBRIDIZATION
o The higher the percent of s-character of the hybrid orbital, the closer the lone pair is
held to the nucleus, and the more stable the conjugate base.
Relative acidity of the hydrocarbons Relative basicity of the carbanions
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FACTORS AFFECTING ACID STRENGTH
INDUCTIVE EFFECTS
o The inductive effect of a group can be electron donating or electron Withdrawing
o When electron density is pulled away from the negative charge through bonds by
very electronegative atoms, it is referred to an electron withdrawing inductive effect.
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FACTORS AFFECTING ACID STRENGTH
INDUCTIVE EFFECTS
o More electronegative atoms stabilize regions of high electron density by an electron
withdrawing inductive effect.
o The more electronegative the atom and the closer it is to the site of the negative
charge, the greater the effect.
o The acidity of H—A increases with the presence of electron withdrawing groups in A.
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FACTORS AFFECTING ACID STRENGTH
RESONANCE EFFECTS
o when we compare the acidities of ethanol and acetic acid, we note that the latter is
more acidic than the former.
o When the conjugate bases of the two species are compared, it is evident that the
conjugate base of acetic acid enjoys resonance stabilization, whereas that of ethanol
does not.
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FACTORS AFFECTING ACID STRENGTH
RESONANCE EFFECTS
o Resonance delocalization makes CH3COO¯ more stable than CH3CH2O¯, so CH3COOH
is a stronger acid than CH3CH2OH.
o The acidity of H—A increases when the conjugate base A:¯ is resonance stabilized.
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FACTORS AFFECTING ACID STRENGTH
SUMMARY OF THE FACTORS THAT DETERMINE ACIDITY
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FACTORS AFFECTING ACID STRENGTH
COMMONLY USED ACIDS IN ORGANIC CHEMISTRY
o In addition to the familiar acids HCl, H2SO4 and HNO3, a number of other acids are
often used in organic reactions.
o Two examples are acetic acid and p-toluene-sulfonic acid (TsOH).
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FACTORS AFFECTING ACID STRENGTH
COMMONLY USED BASES IN ORGANIC CHEMISTRY
o Common strong bases used in organic reactions are more varied in structure.
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FACTORS AFFECTING ACID STRENGTH
IT SHOULD BE NOTED THAT:
o Strong bases have weak conjugate acids with high pKa values, usually > 12.
o 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.
o Carbanions, negatively charged carbon atoms, are especially strong bases. A common
example is butyllithium.
o Two other weaker organic bases are triethylamine and pyridine.
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ACID–BASE REACTIONS
LEWIS ACIDS AND BASES
o G. N. Lewis defined acids and bases in a broader scheme
An acid as a molecule that forms a covalent bond by accepting a pair of electrons
Lewis Acids are electron pair acceptors
A base as a molecule that forms a covalent bond by donating a pair of electrons.
Lewis Bases are electron pair donors
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ACID–BASE REACTIONS
LEWIS ACIDS AND BASES
o In Lewis acid–base theory, the attraction of oppositely charged species is
fundamental to reactivity
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ACID–BASE REACTIONS
LEWIS ACIDS AND BASES
o Carbocations are electron deficient; they have only six electrons in their valence shell.
o Carbocations are Lewis acids
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ACID–BASE REACTIONS
LEWIS ACIDS AND BASES
o By accepting an electron pair from a Lewis base, a carbocation fills its valence shell
o All Lewis acids are electrophiles.
o Carbon atoms that are electron poor because of bond polarity, but are not
carbocations, can also be electrophiles
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ACID–BASE REACTIONS
LEWIS ACIDS AND BASES
o Carbanions are Lewis bases
o A nucleophile is a Lewis base that seeks a positive center such as a positively charged
carbon atom
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ACID–BASE REACTIONS
HOW TO USE CURVED ARROWS IN ILLUSTRATING REACTIONS
o show the direction of electron flow in a
reaction mechanism
o point from the source of an electron
pair to the atom receiving the pair
o always show the flow of electrons from
a site of higher electron density to a
site of lower electron density
o never show the movement of atoms.
Atoms are assumed to follow the flow
of the electron
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