acids and bases electrophiles and nucleophiles organic
TRANSCRIPT
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Chapters 2 & 6
Organic Chemistry, 8th Edition
John McMurry
Acids and Bases
Electrophiles and Nucleophiles
Organic Reaction Mechanisms
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Acidi e basi di Brønsted-Lowry
• Gli acidi donano protoni ad un accettore. Tutti gli acidi di Brønsted-
Lowry contengono un protone ionizzabile.
• Le basi accettano protoni da un donatore. Tutte le basi di Brønsted-
Lowry contengono un doppietto solitario o un legame p.
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Acidi e basi di Brønsted-Lowry
pKa = - logKa
pKb = - logKb Kw = KaKb pKw = pKa + pKb
• Più grande è la Ka (bassa pKa) più l’acido è forte.
• La basicità di basi diverse si può confrontare guardando i valori di pKa dei rispettivi acidi
coniugati (in chimica organica di solito si usano i valori di pKa)
Equazione di van 't Hoff
DG° = -RTlnK
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Acidi e basi di Brønsted-Lowry
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Acidi e basi di Brønsted-Lowry
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Acidi e basi di Brønsted-Lowry
AcidoBase
coniugatapKa
HF F- 3.5
HCl Cl- -7
HBr Br- -8
HI I- -9
H2O OH- 15.7
H2S SH- 7.05
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Acidi e basi di Brønsted-Lowry
pKa = 15.9
pKa = 4.76
pKa = 0.23
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Molecole organiche complesse hanno molti siti
acidi o basici
Morfina
basico
acido
basico
basico
basico
Acidi e basi di Brønsted-Lowry
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Lewis Acids and Bases
• A Lewis acid accepts an electron pair from a donor. Lewis acids have a
low energy empty orbital.
• A Lewis base donates an electron pair to an acceptor. Lewis bases have
a high energy full orbital (lone pair or p bonds).
empty
Lewis acid
full
Lewis base
+
product
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Lewis Acids and Bases
Brønsted-Lowry and Lewis
acids Lewis acids
• All Brønsted-Lowry acids are Lewis acids. Not all Lewis acids are Brønsted-Lowry acids.
• Only species with ionizable protons are Brønsted-Lowry acids. Any electron acceptor is a L.A.
• All Brønsted-Lowry bases are also Lewis bases. They must have either a lone pair or a π bond.
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• Organic reactions can in most cases be described as reactions between
electron poor species (Lewis acids) and electron rich species (Lewis
bases).
• The electron poor species (Lewis acid) is called electrophile.
• The electron rich species (Lewis base) is called nucleophile.
• The movement of electrons is indicated with curved arrows.
electrophile nucleophile
Reactions Between Lewis Acids and Bases
Lewis acid Lewis base
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12
Electrophiles and Nucleophiles
New bond
electrophile
New bond
nucleophile
Lewis acid
Lewis acid Lewis base
Lewis base
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13
Nu
Nu E
E
• Nucleophiles and electrophiles may also contain polarized bonds
Electrophiles and Nucleophiles
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How to Write an Organic Reaction
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In a sequence, the individual steps are numbered.
Inorganic byproducts
are generally omitted
1° step
2° step
How to Write an Organic Reaction
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Organic Reactions
• Type of reaction (bond breaking/bond formation):
substitution
addition
elimination
rearrangement/transposition
• Mechanism = movement of electrons:
ionic (polar)
radicalic
pericyclic
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In a general substitution reaction, an atom or group Y replaces an atom
or group Z at carbon.
Substitutions involve breaking and forming s bonds.
Y replaces Z
Substitutions
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Eliminations
In an elimination reaction two s bonds are broken and one p bond is formed.
1 p bond is formed2 s bonds are broken
reagent
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Additions
In an addition reaction a p bond is broken and two new s bond are formed.
s bonds are formedp bond
is broken
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Additions and Eliminations
Eliminations are the inverse of additions. A p bond is formed in
eliminations and a p bond is broken in additions.
a p bond is broken
Elimination
Addition
a p bond is formed
+ XY
–XY
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Rearrangements or Transpositions
In a rearrangement or transposition the bonding pattern of a single reagent
changes giving a constitutional isomer.
1-butene 2-butene
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Bond Breaking and Forming
Omolysis
Radical
radicals are formed in
radical (omolitic) reactions
Heterolysis
Carbocation
Carbanion
ions are formed or
react in polar (ionic)
reactions
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Bond Formation
A new bond can be formed in two ways:
From two radicals each contributing a single electron.
From a nucleophile contributing an electron pair and an electrophile
accepting the electron pair. Nu and E may be ions or neutral
molecules
Energy is released in the formation of a bond
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Bond Dissociation Energy
Bond dissociation energy is the energy necessary to break a bond
omolytically.
DH° = bond dissociation energyBreaking a bond requires
energy
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The bond dissociation energy is a measure of the strength of the bond.
The stronger the bond, the higher its dissociation energy.
In general, shorter bonds are stronger.
Bond dissociation energies decrease along a group.
DH° = 109 kcal/mole 84 kcal/mole 70 kcal/mole 56 kcal/mole
halogen size and bond length
bond strength
Bond Dissociation Energy
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A Reaction Mechanism……
Accounts for all reagents and products and their ratios.
Describes in which order bonds are broken and formed and the rates of
individual steps.
A multistep reaction involves the formation of one or more reactive
intermediates.
Reactive
intermediate
In a concerted reaction reagents are directly converted into products in
a single step.
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Carbocations, Carbanions, Radicals
C sp2 planar
C sp3 tetrahedral
empty p orbital
lone pair sp3
C sp2 planar
Singly occupied p
orbital
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Radicals and carbocations are electrophiles because the carbon atom
does not have a full octet.
Carbanions are nucleophiles because the carbon atom has a lone pair.
no octet full octet with a
lone pair
radical carbocation carbanion
electrophiles nucleophile
Carbocations, Carbanions, Radicals
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Transition State Theory - Energy Diagrams
DG≠ = DH≠ -TDS#
• The energy diagram describes the geometric transformation of
reactants into products.
• Each point of the energy diagram represent a particular
geometry of the reactant system
• The transition state structure is the one at highest energy and its
structure is intermediate between the structures of reagents and
products..
Eyring equation
van 't Hoff equation is related to equilibriumDG° = -RTlnK
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Energy Diagrams
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Energy Diagrams
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Complete energy diagram for the two-step reaction:
Energy Diagrams