Intermediates have certain, albeit short, lifetime.

Jumping to highest point transition

Jumping onto desk is intermediate
Intermediate is not in the process of forming or breaking bonds
Figure 6.24
In exothermic process, transition state is closer in energy to reactants
than to products, therefore, structure of transition state more closely
resembles the reactants.
Endothermic process, transition state is closer in energy to products,
therefore, transition state more closely resembles the products.
Principle is called the Hammon postulate
6.7
Ionic reactions (polar reactions) involve the participation of ions as
reactants, intermediates, or products. Most case, ions are present as
intermediates.
Ionic reactions occur when one reactant has site of high electron
density and other has site of low electron density
Electron-rich center is nucleophile. Characterized by ability to react
with a positive charge or partial positive charge. Nucleophile center is
capable of donating pair of electrons. Lewis base
Polarizability is ability of atom to distribute electron density unevenly
in response to external influences. Directly related to size of atom
(specifically number of electrons distant from the nucleus) --- ex. Sulfur
is very large and has many electrons distant from nucleus, electron
density can be unevenly distributed when comes near electrophile. HSis strong nucleophile.
Electron-deficient center is electrophile. Characterized by ability to
react with negative charge or partial negative charge. Capable of
accepting pair of electrons. Lewis acid
Carbocation has an empty p orbital that functions as a site that can
accept a pair of electrons, making compound electrophilic.
6.8
Nucleophillic attack nucleophile attacking an electrophile
Page 260 figures

Loss of a leaving group

Page 261
Proton transfer characterized by 2 curved arrows.
Rearrangement:
Carbocation rearrangements. Carbocations are stabilized by
neighboring alkyl groups.
Bonding MO with neighbor C-H bond overlaps with empty p orbital,
placing its electron density in the empty orbital called
hyperconjugation stabilizes empty p orbital
Figure on page 263 stability
Two common carbocation rearrangements: hydride shift or methyl
shift
6.9
Page 266 figure with 4 characteristic patterns
Concerted process is utilizing 2 arrow-pushing patterns simultaneously
6.10
Never place tail of curved arrow on positive charge
Head of curved arrow must be placed to show either formation of bond
or formation of a lone pair
Never draw arrow that gives more than 4 orbitals to second row
element
All curved arrows must accomplish one of four characteristic arrow
pushing patterns
6.11
Can carbocation become more stable via rearrangement?
Identify any H or CH3 attached directly to neighboring carbon atoms
Would new carbocation be more stable?
Then it will shift
Tertiary carbocation will shift if newly formed carbocation is tertiary
and is stabilized by resonance.
Page 271 figure
Carbocation is called allylic carbocation, positive charge located at
allylic position.
6.12
Nucleophilic attack
Page 273

Reversible rxn arrow used if nucleophile is capable of functioning as

good leaving group after attack occurs. ex, water H2O weak base
Irreversible rxn arrow used if nucleophile is poor leaving group. ex,
methyl group H3C- strong base
Loss of a leaving group
Reversible if leaving group is capable of functioning as good
nucleophile. Most can, so irreversible rxn arrow rare.
Proton transfer
Irreversible rxn arrow used for rxn which acids differ by more than 10
pKa units. Page 274
If between 5 and 10 units, reversible/irreversible used dependent on
context.
Carbocation rearrangement
Most stable carbocation dominates equilibrium. Energy difference
between secondary and tertiary is often significant, carbocation
rearrangement will generally drawn as irreversible process.
7.1
Substitution reactions one group is exchanged for another.
Substitution reaction can occur when a suitable electrophile is treated
with a nucleophile (insert example)
Substrate is reffering to electrophile in a substitution reaction, for
electrophile to function as substrate it must contain leaving group
(group capable of separating from the substrate)
Leaving group serves 2 critical functins:
1. Withdraws electron density via induction, rendering adjacent
carbon atom electrophilic.
2. Can stabilize any negatie chage that may develop as result of
leaving group separating from substrate.
Halogens (Cl, Br, and I) are common leaving groups.
7.2
Halogenated organic compounds are commonly used as electophiles in
substitute reactions
Naming halogenated organic compunds (compounds containing
halogens)
1. Identify and name parent
2. Identify and name substituents
3. Number parent chain and assign a locant to each substituent
4. Assemble the substituents alphabetically

a. Halogens are treated as substituents and receive names fluoro-,

chloro-, bromo-, and iodob. When chirality center is present, configuration must be indicated
at beginning of name (page 289)
c. Systematic name (IUPAC) treats halogen as substituent, calling
compound halo-alkane. Common name treat compound as alkyl
substituent, called alkyl halide or organohalide.
Carbon atom described in terms of proximity to halogen using greek
letters. Alpha is carbon directly connected to halogen. Beta is carbon
connect to alpha position.
Alkyl halide only has one alpha position, as many as 3 beta positions.
Alkyl halide are classified as primary, secondary, tertiary based on
number of alkyl groups attached to alpha position
7.3
Page 293 arrow pushing patterns.
Every substitution reactions exhibits at least 2 of 4 patterns:
Nucleophilic attack and loss of a leaving group.
Two possible mechanisms for a substitution reactions:
1. Concerted process nuclephilic attack and loss of leaving group
occur simultaneously
2. Stepwise process loss of the leaving group occurs first followed
by nuclephilic attack.
7.4
SN2 refer to bimolecular second order substitution reactions.
Consistent with a concerted mechanism because only one mechanistic
step. Makes sense rate should be dependent on concentration of both
nuclephile and substrate
When alpha position is chirality center.. if reactant exhibits S
configuration, product exhibit R configuration, reaction proceeds with
inversion of configuration
Nucleophile can only attack from back side (opposite side of leaving
group)
Back-side attack why?
1. lone pair of leaving group create region of high electron density
effectively blocking front side of substrate, nucleophile can only
approach from back side.
2. Molecular orbital (MO) theory (?>??????????????)

Observed stereochemical outcome for an SN2 process (oinversin of

configuration) is consisten with a concerted mechanism.
Stereospecific configuration of product dependent on configuration of
starting material.
Mehtyl halides and primary alkyl halides rect most quickly with
nucleophiles. Secondary alkyl halides react more slowly, teriary alkyl
halides are essentially unreactive toward SN2. Trend consistent with
concerted process
If transition state is high energy, Ea will be large rate will be slow. Low
in energy, Ea will be small and rate is fast
7.5
Stepwise process
1. loss of leaving group to form carbocation intermediate
2. then nucleophilic attack on carbocation intermediate
Rate-determining step step with highest energy transition state
Rate = k[substrate]
Increase/decrease concentration of nucleophile has no measurable
effect on rate. Rate is first order. Rate determing step involves only one
chemical entity, it is unimolecular. SN1
SN1 reactions, tertiary substrates react most quickly, methyl and
primary substrates are mostly unreactive
Leaving group leaves first, results in formation of carbocation (step is
rate determining step) once carbocation forms, nucleophile captures it
quickly. Rate only dependent on how quickly leaving group leaves to
form carbocation. Dominant factor is carbocation stability.
Formation of tertiary carbocation smaller Ea than secondary.
Larger Ea associated with 2nd
3rd substrate generally substitution via SN1 process
1st substrate generally substitution via SN2 process
Nucleophile attack more often happen on side opposite leaving group,
preference for inversion over retention.
7.8
To identify rection mechanism as SN2 or SN1 in 2 ways:
-if substitution takes place at chirality center, expect inversion of
configuration (SN2) or racemization (SN1)

-if substrate susceptible to carbocation rearrangement: rearrangement

(SN1) no possible (SN2)
Four factors for which rxn will occur:
-substrate
-leaving group
-nucleophile
-solvent
substrate identity is most important factor to distinguish between
SN2 and SN1
SN2 rxn due to steric hindrance in transition state. Methyl and 1st
substrate favored.
SN1 rxn due to carbocation stability. 3rd favored.
2nd can proceed through either, must go to nucleophile.
Alltlic halide and benzylic halide can react either SN2 or SN1.
SN2 b/c relatively unhindered
SN1 b/c loss of leaving group generates resonance-stabilized
carbocation
Vinyl halids and aryl halides unreactive in substitution rxns
SN2 not observed generally at sp2-hybridized center (b/c back-side
attack sterically encumbered)
SN1 not observed b/c loss of leaving group would generate unstable
carbocation

Methyl and primary substrates favor SN2.

Tertiary substrates favor SN1.
Secondary substrates and allylic and benzylic substrates can
often react via either mechanism.
Vinyl and aryl substrates do not react via either mechanism.

Nucleophile
SN2 rate dependent on concentration and strength of nucleophile.
Strong nucleophile speed up rate, weak slow down rate.
SN1 not affected by concentration or strength of nucleophile, b/c
nucleophile doesnt participate in RDS

Strong nucleophile favor SN2

Weak nucleophile disfavor SN2, allows SN1 to compete
successfully
Page 322 common nucleophile (flashcards)

Leaving group
Both mechanism sensitive to identity of leaving group.
SN1 more sensitive b/c RDS of SN1 is LOALG to form carbocation. Rate
of step sensitive to stability of carbocation and stability of leaving
group, leaving group must be highly stabilized in order for SN1 process
to be effective
Good leaving groups conjugate bases of strong acids.
Page 323 and 324 halide sulfonate ions - leaving group (flashcards)
Most common LG are halides and sulfonate ions.
Halide iodide is best LG b/c weaker base.
Sulfonate ion triflte group is best tosylate is most common
Solvent effects
Protic solvent constain at least one H atom connected directly to
electronegative atom - used for SN1 rxn
Polar aprotic solvent no H atom connect directly to electronegative
atom. used to favor SN2 rxn effect of PAS on rate of SN2 rxn is
significant
Page 325 table 7.2
Solvent can impact order of reactivity of halides, strongest to weakest
nucleophile
In protic solvents: I->Br->Cl->FIn polar aprotic solvents: F->Cl->Br->IF is strongest b/c least stable anion. Protic solvent F is most tightly
bound to solvent shell & least available to function as nucleophile
(must shed part of solvent shell to do so)
Polar aprotic solvent, no solvent shell, fluoride free to function as
strong nuclephile.
Table 7.3 Page 326
7.9
When selecting reagents for substitution rxn:
-substrate identity indicate what process to use: methyl or primary
SN2. Tertiary SN1 used. Secondary try to use SN2 b/c avoids issue of
carbocation rearrangement and provide > control over stereochemical
outcome
-nuclephile and solvent consistent with mechanism: SN1 weak
nucleophile in protic solvent. SN2 strong nucleophile in polar aprotic
solvent.
-leaving group: SN1 use acid to protonate OH group. SN2 OH group
generally converted into tosylate.
Chapter 8

Elimnation reaction characterized by the formation of a pi bond