Chapter 6 Lecture

Understanding Organic Reactions
Writing ations for Organic Reactions

~ ations for organic reactions are sally drawn with a
single reaction arrow ({ etween the starting material and
prodct.
~ îhe reagent, the chemical s stance with which an organic
compond reacts, is sometimes drawn on the left side of the
e ation with the other reactants. At other times, the reagent
is drawn a ove the arrow itself.
~ Althogh the solvent is often omitted from the e ation, most
organic reactions take place in li id solvent.
~ îhe solvent and temperatre of the reaction may e added
a ove or elow the arrow.
~ îhe sym ols ³h÷x and ³ x are sed for reactions that re ire
light and heat respectively. c
Ô

¦
~ When two se ential reactions are carried ot withot
drawing any intermediate compond, the steps are sally
nm ered a ove or elow the reaction arrow. îhis convention
signifies that the first step occrs efore the second step,
and the reagents are added in se ence, not at the same
time.
]
inds of Organic Reactions
~ A s stittion is a reaction in which an atom or a grop

of atoms is replaced y another atom or grop of atoms.
~ In a general s stittion, Y replaces Z on a car on atom.
m
~ § stittion reactions involve onds: one ond reaks
and another forms at the same car on atom.
~ îhe most common examples of s stittion occr when Z is
a hydrogen or a heteroatom that is more electronegative than
car on.
w
~ limination is a reaction in which elements of the
starting material are ³lostx and a î ond is formed.

~ In an elimination reaction, two grops X and Y are removed
from a starting material.
~ îwo onds are roken, and a î ond is formed etween
adjacent atoms.
~ îhe most common examples of elimination occr when X = H
and Y is a heteroatom more electronegative than car on.

~ Addition is a reaction in which elements are added to the
starting material.
u
~ In an addition reaction, new grops X and Y are added to
the starting material. A î ond is roken and two
onds are formed.

~ Addition and elimination reactions are exactly opposite.
A î ond is formed in elimination reactions, whereas a î
ond is roken in addition reactions.
c
ºlassify each of the following as either s stittion,
elimination or addition reactions.
a

s stittion

addition
c elimination
cc
Ñond Making and Ñond Ñreaking
~ A reaction mechanism is a detailed description of how onds
are roken and formed as starting material is converted into
prodct.
~ A reaction can occr either in one step or a series of steps.
c¦
~ Regardless of how many steps there are in a reaction, there
are only two ways to reak (cleave a ond: the electrons in
the ond can e divided e ally or ne ally etween the two
atoms of the ond.
c]
~ Homolysis and heterolysis re ire energy.
~ Homolysis generates ncharged reactive intermediates with
npaired electrons.
cm
~ Heterolysis generates charged intermediates.
~ îo illstrate the movement of a single electron, se a half-
headed crved arrow, sometimes called a fishhook.
~ A fll headed crved arrow shows the movement of an
electron pair.
cw
~ Homolysis generates two ncharged species with
npaired electrons.
~ A reactive intermediate with a single npaired electron is
called a radical.
~ Radicals are highly nsta le ecase they contain an
atom that does not have an octet of electrons.
~ Heterolysis generates a car ocation or a car anion.
~ Ñoth car ocations and car anions are nsta le
intermediates. A car ocation contains a car on
srronded y only six electrons, and a car anion has a
negative charge on car on, which is not a very
electronegative atom.
c
Ô
î

c
~ Radicals and car ocations are electrophiles ecase they
contain an electron deficient car on.
~ ºar anions are ncleophiles ecase they contain a car on
with a lone pair.
cu
Heterolytically cleave each of the car on-hetratom
onds and la el the organic intermediate as a
car ocation or car anion
a

car ocation

car anion
c
~ Ñond formation occrs in two different ways.
~ îwo radicals can each donate one electron to form a two-
electron ond.
~ Alternatively, two ions with nlike charges can come together,
with the negatively charged ion donating oth electrons to
form the reslting two-electron ond.
~ Ñond formation always releases energy.
¦
~ A nm er of types of arrows are sed in descri ing organic
reactions.
¦c
Use arrows to show the movement of electrons in the
following reactions.
a
Î Î
Î Î
¦
^ ^
c

¦¦
Ñond Dissociation nergy
~ îhe energy a sor ed or released in any reaction, sym olized

y H0, is called the enthalpy change or heat of reaction.
~ Ñond dissociation energy is the H0 for a specific kind of

reaction²the homolysis of a covalent ond to form two
radicals.
¦]
~ Ñecase ond reaking re ires energy, ond dissociation
energies are always positive nm ers, and homolysis is always
endothermic.
~ ºonversely, ond formation always releases energy, and ths is
always exothermic. For example, the H²H ond re ires +104
kcal/mol to cleave and releases ±104 kcal/mol when formed.
¦m
~ ºomparing ond dissociation energies is e ivalent to
comparing ond strength.
~ îhe stronger the ond, the higher its ond dissociation energy.
~ Ñond dissociation energies decrease down a colmn of the
periodic ta le.
~ Generally, shorter onds are stronger onds.
¦w
Which has the higher ond dissociation energy?
a H-ºl or H-Ñr
^ ^
^ ^
c ^ ^ ^
¦
~ Ñond dissociation energies are sed to calclate the enthalpy
change ( H0 in a reaction in which several onds are roken
and formed.
¦
¦u
Ñond dissociation energies have some important limitations.
~ Ñond dissociation energies present overall energy changes

only. îhey reveal nothing a ot the reaction mechanism or
how fast a reaction proceeds.
~ Ñond dissociation energies are determined for reactions in
the gas phase, whereas most organic reactions occr in a
li id solvent where solvation energy contri tes to the
overall enthalpy of a reaction.
~ Ñond dissociation energies are imperfect indicators of energy
changes in a reaction. However, sing ond dissociation
energies to calclate H° gives a sefl approximation of the
energy changes that occr when onds are roken and
formed in a reaction.
¦
ºalclate H for each of the following reactions, knowing
H of O2 and O-H = 119 kcal/mol, H of º-H = 104 kcal/ml
and H of one º=O = 128 kcal/mol.
a
º m ¦ ¦
º¦ ¦ ¦
Ñonds Ñroken Ñonds Formed
º-H = 4 x 104 kcal/mol º-O = 2 x -128 kcal/mol

= 416 kcal/mol = -256 kcal/mol
O-O = 2 x 119 kcal/mol O-H = 4 x -119 kcal/mol
= 238 kcal/mol = -476 kcal/mol
H = 416 + 238 = H = -256 + -476 =

+654 kcal/mol -732 kcal/mol
H = 654 + -732 kcal/mol = -78 kcal/mol

]
îhermodynamics
~ For a reaction to e practical, the e ili rim mst favor

prodcts and the reaction rate mst e fast enogh to form them
in a reasona le time. îhese two conditions depend on
thermodynamics and kinetics respectively.
~ îhermodynamics descri es how the energies of reactants and
prodcts compare, and what the relative amonts of reactants
and prodcts are at e ili rim.
~ inetics descri es reaction rates.
~ îhe e ili rim constant, e , is a mathematical expression that
relates the amont of starting material and prodct at
e ili rim.
]c
~ îhe size of e expresses whether the starting materials or
prodcts predominate once e ili rim is reached.
~ When e 1, e ili rim favors the prodcts (º and D and the
e ili rim lies to the right as the e ation is written.
~ When e 1, e ili rim favors the starting materials (A and Ñ
and the e ili rim lies to the left as the e ation is written.
~ For a reaction to e sefl, the e ili rim mst favor the
prodcts, and e 1.
~ îhe position of the e ili rim is determined y the relative
energies of the reactants and prodcts.
~ G° is the overall energy difference etween reactants and
prodcts.
]¦
Ô
§

]]
~ G° is related to the e ili rim constant e y the following
e ation:
~ When e 1, log e is positive, making G° negative, and

energy is released. îhs, e ili rim favors the prodcts when
the energy of the prodcts is lower than the energy of the
reactants.
~ When e 1, log e is negative, making G° positive, and
energy is a sor ed. îhs, e ili rim favors the reactants when
the energy of the prodcts is higher than the energy of the
reactants. ]m
~ ºomponds that are lower in energy have increased sta ility.
~ îhe e ili rim favors the prodcts when they are more sta le
(lower in energy than the starting materials of a reaction.
~ Ñecase G° depends on the logarithm of e , a small change in
energy corresponds to a large difference in the relative amont
of starting material and prodct at e ili rim.
]w
~ îhese e ations can e sed for any process with two states in
e ili rim. As an example, monos stitted cyclohexanes exist
as two different chair conformations that rapidly interconvert at
room temperatre, with the conformation having the s stitent
in the roomier e atorial position favored.
~ nowing the energy difference etween two conformations
permits the calclation of the amont of each at e ili rim.
]
nthalpy and ntropy
~ G° depends on H° and the entropy change, §°.
~ ntropy change, §°, is a measre of the change in the
randomness of a system. îhe more disorder present, the higher
the entropy. Gas molecles move more freely than li id
molecles and are higher in entropy. ºyclic molecles have
more restricted ond rotation than similar acyclic molecles and
are lower in entropy.
~ §° is (+ when the prodcts are more disordered than the
reactants. §° is (- when the prodcts are less disordered than
the reactants.
~ Reactions reslting in increased entropy are favored.
~ G° is related to H° and §° y the following e ation:
]
~ îhis e ation indicates that the total energy change is de
to two factors: the change in onding energy and the
change in disorder.
~ îhe change in onding energy can e calclated from ond
dissociation energies.
~ ntropy changes are important when
îhe nm er of molecles of starting material differs
from the nm er of molecles of prodct in the
alanced chemical e ation.
An acyclic molecle is cyclized to a cyclic one, or a
cyclic molecle is converted to an acyclic one.
]u
~ In most other reactions that are not carried ot at high
temperatre, the entropy term (î §° is small compared to the
enthalpy term ( H0, and therefore it is sally neglected.
]
nergy Diagrams
~ An energy diagram is a schematic representation of the energy
changes that take place as reactants are converted to prodcts.
~ An energy diagram plots the energy on the y axis verss the
progress of reaction, often la eled as the reaction coordinate, on
the x axis.
~ îhe energy difference etween reactants and prodcts is H°. If
the prodcts are lower in energy than the reactants, the reaction
is exothermic and energy is released. If the prodcts are higher
in energy than the reactants, the reaction is endothermic and
energy is consmed.
~ îhe nsta le energy maximm as a chemical reaction proceeds
from reactants to prodcts is called the transition state. îhe
transition state species can never e isolated.
~ îhe energy difference etween the transition state and the
starting material is called the energy of activation, a.
m
~ For the general reaction:
~ îhe energy diagram wold e shown as:
mc
~ îhe energy of activation is the minimm amont of energy
needed to reak the onds in the reactants.
~ îhe larger the a, the greater the amont of energy that is
needed to reak onds, and the slower the reaction rate.
~ îhe strctre of the transition state is somewhere etween the
strctres of the starting material and prodct. Any ond that is
partially formed or roken is drawn with a dashed line. Any atom
that gains or loses a charge contains a partial charge in the
transition state.
~ îransition states are drawn in rackets, with a sperscript
do le dagger (Á.
m¦
Ô
§

xample 1
m]
Ô
§

xample 2
mm
Ô
§

xample 3
mw
Ô
§

xample 4
m
Ô
^

m
~ ºonsider the following two step reaction:
~ An energy diagram mst e drawn for each step.

~ îhe two energy diagrams mst then e com ined to form an
energy diagram for the overall two-step reaction.
~ ach step has its own energy arrier, with a transition state at
the energy maximm. mu
m
w
Ô

wc
inetics
~ inetics is the stdy of reaction rates.
~ Recall that a is the energy arrier that mst e exceeded
for reactants to e converted to prodcts.
w¦
inetics
~ îhe higher the concentration, the faster the rate.

~ îhe higher the temperatre, the faster the rate.
~ G°, H°, and e do not determine the rate of a reaction.
îhese antities indicate the direction of the e ili rim and
the relative energy of reactants and prodcts.
~ A rate law or rate e ation shows the relationship etween
the reaction rate and the concentration of the reactants. It is
experimentally determined.
w]
~ Fast reactions have large rate constants.
~ §low reactions have small rate constants.
~ îhe rate constant J and the energy of activation a are inversely
related. A high a corresponds to a small J.
~ A rate e ation contains concentration terms for all reactants in
a one-step mechanism.
~ A rate e ation contains concentration terms for only the
reactants involved in the rate-determining step in a mlti-step
reaction.
~ îhe order of a rate e ation e als the sm of the exponents of
the concentration terms in the rate e ation.
wm
~ A two-step reaction has a slow rate-determining step, and a fast
step.
~ In a mlti-step mechanism, the reaction can occr no faster than
its rate-determining step.
~ Only the concentration of the reactants in the rate-determining
step appears in the rate e ation.
ww
ºatalysts
~ §ome reactions do not proceed at a reasona le rate nless a

catalyst is added.
~ A catalyst is a s stance that speeds p the rate of a reaction. It
is recovered nchanged in a reaction, and it does not appear in
the prodct.
Ô
î

w

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Chapter 6 Lecture

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Understanding Organic Reactions

Writing ations for Organic Reactions

~ A s stittion is a reaction in which an atom or a grop

~ îhe energy a sor ed or released in any reaction, sym olized

~ Ñond dissociation energy is the H0 for a specific kind of

c ^ ^ ^

~ Ñond dissociation energies present overall energy changes

º-H = 4 x 104 kcal/mol º-O = 2 x -128 kcal/mol

H = 416 + 238 = H = -256 + -476 =

H = 654 + -732 kcal/mol = -78 kcal/mol

~ For a reaction to e practical, the e ili rim mst favor

§

~ When e 1, log e is positive, making G° negative, and

~ îhe energy diagram wold e shown as:

~ An energy diagram mst e drawn for each step.

~ îhe higher the concentration, the faster the rate.

~ §ome reactions do not proceed at a reasona le rate nless a

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Chapter 6 Lecture

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Chapter 6 Lecture

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Available Formats

Understanding Organic Reactions

Writing  ations for Organic Reactions

~ A s stittion is a reaction in which an atom or a grop

~ îhe energy a sor ed or released in any reaction, sym olized

~ Ñond dissociation energy is the H0 for a specific kind of

c ^ ^ ^

~ Ñond dissociation energies present overall energy changes

º-H = 4 x 104 kcal/mol º-O = 2 x -128 kcal/mol

H = 416 + 238 = H = -256 + -476 =

H = 654 + -732 kcal/mol = -78 kcal/mol

~ For a reaction to e practical, the e ili rim mst favor

§   

~ When e 1, log e is positive, making G° negative, and

~ îhe energy diagram wold e shown as:

~ An energy diagram mst e drawn for each step.

~ îhe higher the concentration, the faster the rate.

~ §ome reactions do not proceed at a reasona le rate nless a

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Writing ations for Organic Reactions

c ^ ^ ^

§

~ When e 1, log e is positive, making G° negative, and