I 1

Chapter 6

Enthalpy i heat energy exchange betweenthe rein systemandsurroundings

Energy hemolyticcleavage X y X c y
heterocytic cleavage X Y X c
7
Bond dissociation E amount of energy necessary to break the bad homolytically

takes heat from surrounding

AH Bond E broken BE formed

d
gives heat to surrounding

Entropy measure of disorder

IS total ASays t A Sarr A B At B IS S O
cyclic acyclic as O
Entropy 00 spontaneous

Gibbs free energy IG IH TAS

IG 40 exersonic spontaneous
AG s O endergonic not spontaneous

products
Equilibrium constant keg reactants

AG RTbiked
rate constant
Raton p
rate K reactants
concentration of reactants
1
First order Rate KEA t i A X Y
Secondorder Rate KEA EB At B XD
Third Order Rate KEATEBI 2A t B X

Rate constant depends on

a of
molecules
 n m ewes
1 Activation E Eat KT
f 1 in Ea
1 az
oafmolecules
2 Temperature
I Ti
I sE
Ea
3 Steric conditions geometry of reactants ad orientation of collision
catalyst and enzymes lowerthe Ea Rate9

n
l
thermodynamicallyfavored CTD CTD athigh
kinetically favored D Etf
at low
M transition States
Transition stats cannot be isolated whereas
intermediates can

Hammond Postulate

Exothermic Reactant Transition state

Endothermic Transitionstate Product

Nucleophiles electron rich atom that is able to

donate e
Electrophiles electron deficient atom that is able to
accept E
 Nucleophilic Substitution Reactions

Sµ2 2 molecules effect the rate

w
Nucleophilic substitution rate k C electrophilic substrate Nucleophile

concerted Mechanism

g
Nuc Il G
s
J Nuo t Lai
backside attack mustbe
stable
Protontransfer
Togeneralize Protontransfer LossofLc Nuattack optional
optional

Backside attack
of Nu changes Rts configuration is a chiralcenter
of substitution
Inversion
is present
of configuration

LG
there must be a good LG
Y
shouldcreate partial chargeselectrophilic center
LG must be more stable than NUwhen it leaves
Electrophilic center on substrate notbecrowded is betterthan20
must
NU
There must be a strong Nu
Nucleophilicity
1 charge He a H Areal 0 charge is morenucleophilic
2 Polarizability Nucleus sizeIn Nucleophillicity T
3 Solvent Proticsolvents stabilise Nu
Aprotic solvents has a crowded Stcenterthatcannotbe reached
byNU
of a q sap AHA MoreE is required
T.ae
to reach Eabarrier

Good LG Aprotic Solvents Protic Solvents

Tosylate Acetone Dmf water Ethanol
Mesylate Dmso HmpA Methanol Ammonia
Triflate Acetonitrile Acetic acod

NU of 7 A ions in protic solvents I 7 Br Cl F

NU of 7A ions in aprotic solvents F Cl 7 Br I

Swe 3 single rate

o.nu
TEG 7
It
intermediate
carbocation
4 Na
racemic mixture

To generalize Protontransfer LossofLG Carbocation NUattack Protontransfer

optional Rearrangement optional
optional
rate k C electrophilic substrate
 Intermediate must be stable
30 carbocations stabilize charge better by hypercoryugation
since intermediate has sp2 hybridization attack of Nu can be from
e
bothsides racemic mixture production

If the solvent acts as NU Solvolysis RXn

Strong NU weak NU CAbase

a HS Sulphur H2O
containing
Br Rs Nu'sarestrong meat
z CN Eton

for Sna for Sn2

Good G Good G
weak Nu Strong Nu
Protic Solvent stabilizes Aprotic Solvent
30substrate intermediate Less crowded substrate
to

i Qi
o F

É O R
E
If Of
e

9OH YeBr
r
i
y
B
of

É
g 1 Tsa
o

i
Nantation
g n
 Elimination Reactions
Presence of a base a anelectrophile with LG is required
An alkene is produced

more stable
É Mase in substituent
results in more stability

E 2Alkenes

RI Rz
r Ir Bye
Concerted mechanism

21
4,54 Jc L t H Base t X
Z
rate k I base substrate
gp2

Stepwise mechanism
Base
Et d c
I
yegg Y CI
xD
rate k substrate

t carbocation rearrangement can occur

A proton transfer
Determining Products of Elimination Rxn's

more substitute
PIETY
Regioselectivity idk
when both B
position has y I 1 zaitsev product
is always obtained

y y 2 When B Position chiral and there is only

is
1H LGA Hp must be anticoplanar forHp
gym mm p
Stereospecificity determine product

If Not stereospecific E or Z product will beobtained

Stereoselectivity
EL O ET If possible both cis trans forms
when 2h
at Bposition

I
wedge
y
T

Aaaa
El VEZ 30 7 20 10
Reactivity of