Organic Chemistry

08/14/2015

Chapter 8
8.1
A substitution reaction occurs when leaving group is replaced with
nucleophile.
Elimination reaction a proton from the beta position is removed
together with the leaving group forming a double bond. RXN is called beta
elimination or 1,2-elimination and can be accomplished with any good
leaving group.
When leaving group is halide reaction is dehydrohalogenation
Water is dehydration
Product of elimination reaction possesses a C=C double bond called an
alkene
8.2
Naming alkenes
1. Identify parent, longest chain that includes pi bond. Suffix ene to
indicated C=C double bond.
2. When numbering, pi bond should receive lowest number position.
3. ID substituents
4. Assign locant to substituent.
5. Arrange substitutents alphabetically
Page 347 simple alkene names
8.4
Double bond comprised of sigma bond and pi bond.

Sigma bond is result of overlapping sp^2-hybridized orbital.

Pi bond result of overlapping p orbitals.
Double bond do not exhibit free rotation at room temp, gives rise to
stereoisomerism
Page 348
8.5
A cis alkene will be less table than its stereoisomeric trans alkene. Instability
is attributed to steric strain exhibited by cis isomer
Difference in energy between stereoisomeric alkenes can be quantified by
comparing heats of combustion.
Alkenes are more stable when they are highly substituted. Reason is an
electronic effect (through bonds)
Alkyl groups can stabilize a carbocation by donating electron density to
neighboring sp^2-hybridized carbon atom (C+). Effect is called
hyperconjugation, stabilizing effect bc it enables delocalization of electron
density.
8.6
Alkenes can be prepared via elimination reactions, which a proton and
leaving group are removed to form a pi bond.
Page 356
Elimination reaction exhibits at least 2/4 patterns. 1) proton transfer 2)loss
of leaving group
In a concerted process base abstracts a proton and the leaving group leaves
simultaneously

In a stepwise process the leaving group leaves then the base abstracts a
proton.
8.7
Many elimination reactions exhibit second-order kinetics with rate equation
that has following form:
Rate = k[substrate][base]
Rate is linearly dependent on concentrations of 2 different compounds
(substrate and base).
Bimolecular elimination reactions are called E2 reactions. E = elimination 2
= bimolecular
Rate of an SN2 process with a tertiary substrate is so slow can be assumed
that the substrate is inert under such reaction conditions.
Tertiary substrates undergo E2 reactions quite rapidly.
A substitution reaction occurs when the reagent functions as a nucleophile
and attacks an electrophilic position
An elimination reaction occurs when the reagent functions as a base and
abstracts a proton
With tertiary substrate, steric hindrance prevents the reagent fron function
as nucleophile at an appreciable rate, but reagent can still function as base
without encountering much steric hindrance
Tertiary substrates react readily in E2 reactions even more than primary
substrates
In energy diagram of E2 process, focus transition state.
3rd substrate, both R groups are alkyl groups
1st substrate both R groups are H atoms.

In transition state C=C double bond forming.

3rd substrate, transition state exhibits partial double bond thats more highly
substituted, therefore, transition state will be lower in energy.
Trans state is lowest in energy when 3rd substrate used, therefore, energy of
activation is lowest for 3rd substrate.
When elimination reaction produce more than 1 possible product.
Ex. When B position not identical, double bond can form in 2 diff regions of
molecule, example of regiochemistry. Reaction is said to produce 2 diff
regiochemical outcomes. More substituted alkene is observed to be major
product.
Reaction is said to be regioselective. More substituted alkene is called
Zaitsev product.
When both substrate and base are sterically hindered, less substituted
alkene is major product
Less substituted is often called Hofmann product.
When sterically hindered bases used, Hofmann product becomes major
product.
The regiochemical outcome of an E2 reaction can often be controlled by
carefully choosing the base
Page 361 sterially hindered bases
Ex. Compound with 2 identical B position. 2 possible steroisomeric alkenes
produced. Page 364 trans predominates over cis. Reaction said to be
seteroselective bc substrate produces 2 stereoisomers in unequal amount

Case where B position contains only 1 proton. 2 B position. 1 position w no

protons other with 1 proton. No mixture of stereoisomer obtained, only 1
stereoisomeric product.
Why?
Focus alignment of orbitals in transition state. Trans state, pi bond forming.
(pi bond is overlapping p orbitals). Therefore, trans state must involve
formation of p orbitals positioned such that they can overlap with each other
while forming. To achieve this orbital overlap, 4 atoms must all lie under
same plane: proton at B position, leaving group, 2 C atoms that bear
pi bond. 4 atoms must be coplanar.
C-C single bond free to rotate before reaction occurs.
2 ways to achieve coplanar arrangement
Page 365 picutres
Anti-coplanar conformation is staggered syn-coplanar formation is
eclipsed (relative positions of proton and leaving group)
Elimination of syn-coplanar involves trans state of higher energy b/c of
eclipsed geometry.
Elimination occurs more rapidly via anti-coplanar. Most cases, elimination
occur exclusively via anti-coplanar leading to 1 specific stereoisomeric
product
Oage 365 picture
Req for coplanarity not absolute. Small deviation tolerated.
Periplanar proton and leaving group are nearly coplanar (dihedral angle of
178 or 179 not 180). In such conformation, orbital overlap significant
enough for E2 rxn to occur.
Sufficient for proton and leaving group to be anti-periplanar

Anti-periplanar arrangement determine stereoisomerism of product.

Stereoisomeric product of E2 process depends on configuration of starting
alkyl halide.
Predict configuration of resulting alkene is 1. Analyze substrate carefully 2.
Draw newman projection 3. Determine stereoisomeric product obtained
E2 rxn said to be stereospecific bc stereoisomerism of product depends on
stereoisomerism of substrate
Stereospecificity of E2 rxn only relevant when B position has 1 proton
Page 366
B proton must be anti-periplanar to leaving group for rxn to occur. That req
determine stereoisomeric product obtained.
If B position has 2 protons, either protons can be arranged to anti-periplanar
to leaving group. Results both stereoisomeric product obtained.
More stable isomeric alkene predominates. Page 366
Stereoselective E2 rxn: Substrate itself not necessarily stereoisomeric,
substrate can produce 2 stereoisomeric products, found 1 stereoisomeric
product formed in higher yield.
Stereospecific E2 rxn: Substrate is stereoisomeric and stereochemical
outcome dependent on which steroisomeric substrate used.
Anti-periplanar conformation req with substituted cyclohexanes. E2 rxn occur
from chair conformation where leaving group occupies axial position Page
369 picture
Leaving group occupy axial, anti-periplanar with neighboring proton.
Cyclohexane ring, E2 rxn only occur from chair conformation where leaving
group is axial. E2 rxn only take place when leaving group and proton are on
opposite side of ring (one on wedge other on dash)

If no such protons, E2 rxn cannot occur at appreciable rate.

If 1 proton can be anti-periplanar with leaving group, only one product
obtained.
For substituted cyclohexane, rate of E2 rxn greatly affected by time leaing
group spends in axial position
8.8
e2 rxn 2 major issues before drawing products: regiochemistry and
stereochemistry
8.9
Stepwise mechanism, E1 pathway
Elimination rxn exhibit 1st order kinetics w rate eq with form of
Rate = k [substrate]
Like SN1 rxn, rate linearly depends on concentration of only 1 compound
(substrate)
Observation consistent with stepwise mechanism, which rate-determining
step not involve base.
Rate determining step is 1st step in mechanism (loss of leaving group)
Step involves only 1 chemical entity, said to be unimolecular
Unimolecular elimination rxn called E1 rxns E-elimination 1-unimolecular
In E1, rate sensitive to nature of starting alkyl halide, tertiary halide react
most readily.

Stepwise mechanism involve formation of carbocation intermediate, rate of

rxn dependent on stability of carbocation.
Tert substrate lower energy of activation, react more readily. Prim substrate
unreactive toward E1 mechanism, bc prim carbocation too unstable.
Step 1 of E1 process identical to SN1 process. Loss of leaving group form
carbocation intermediate
E1 rxn generally accompany by competing SN1 rxn & mix of products
obtained
OH- bad leaving group, in SN1 OH must be protonated to make better
leaving group. Same in E1
If substrate is alcohol, strong acid will be req to protonate OH group. Conc
aq H2SO4 commonly used.
Page 374 rxn elimination of water forming an alkene--- dehydration rxn.
E1 process exhibit regiochemical preference for Zaitsev product.
More substituted (Zaitsev) is major product.
Regiochemical outcome of E2 rxn can be controlled by choosing base
(sterically hindered/not SH)
E1 rxn cannot be controlled. Zaitsev product generally obtained.
E1 are not stereospecific. Do not req anti-periplanarity for rxn to occur.
E1 are stereoselective. Cis and trans products are possible, preference to
trans stereoisomer

8.10
compare 2 core step of E1 with 2 core step of SN1.
Sn1 have up to 3 addl step
E1 only up to 2 addl step
-proton transfer before first core step
-carbocation rearrangement in between 2 core steps
proton transfer req at beginning of E1. Necessary when leaving group is OH.
Must be protonated, so acid is needed. Page 377
e1 mechanism involve formation of carbocation intermediate via hydride
shift or methyl shift. Page 378. Rearrangement occur between 2 core step of
e1 mechanism.
E1 can have many steps
-have atleast 2 core step (loss of leaving group & proton transfer) and addl
2 step 1. Before 2 core stop possible proton transfer 2. Inbetween 2 core
step possible carbocation rearrangement
page 379 picture mechanisms.
Number of humo in energy diagram of e1 always = number of step in
mechanism. Steps range from 2-4.
Case where carbocation rearrangement possible, products obtained from
rearrangement and w.o rearrangement.
8.11

e2 process = 1 concerted step and rarely accompanied by other steps.

Carbocation never formed, no possible carbocation rearrangement
E2 req use of strong base. Not common to see e2 with proton transfer at
beginning of mechanism.
E2 mechanism req 3 curved arrows. 1st tail lone pair of base, head to proton
at B position. 2nd tail on C-H bond thats breaking, head to bond between A
and B positions. 3rd drawn to show loss of leaving group.
8.12
Substitution vs Elimination: Identifying the reagent
1. determine function of reagent
2. aanalyze substrate and determine expected mechanism
3. consider relevant regiochemical and stereochemical requirements
A substitution rxn occurs when the reagent functions as a nucleophile
Elimination rxn occurs when reagent functions as base
First step is determine whether reagent is strong or weak nucleophile and
whether it is strong or weak base.
Nucleophilicity is a kinetic phenomenon and refers to rate of rxn
Basicity is thermodynamic phenomenon and refers to position of
equilibrium
Nucleophilicity refers to rate which nucleophile will attack electrophile

Factors: charge, polarizability (often more important than charge---ability

of atom to distribute electron density unevenly result of external
influences----directly related to size and number of electrons distant from
nucleus)
OH stronger nucleophile than water
Sulfur is large and many electrons distant from nucleus, highly
polarizable. Most halogens share this.
Basicity
Thermodynamic phenomenon refers to position of equilibrium.
In proton transfer, equilibrium favor weaker base --- quantitative (pKa
values) and qualitative (using 4 factors to determine relative stability of
base with negative charge)
Categorize reagents into 4 groups
Reagents that only function as nucleophiles. Strong nucleophiels bc highly
polarizable, but weak base bc conjugate acid are fairly acidic ----substitution rxn is occurring (not elimination)
Reagents function only as bases, not nucleophiles. H+ ion elimination, not
sub, will occur
Reagents both strong nucleophiles/strong base
OH- (hydroxide) and RO- (alkoxide) ions. Gen used bimolecular process
(SN2 and E2)
Reagents weak nucleophile/weak base include H2O & alcohols (ROH) gen
used unimolecular process(SN1 & E1)
8.13
Identifying the mechanism

3 main step for predict product of substitution and elimination.

1. ID function of reagent (4)
a. Each category explore expected outcome with primary,
secondary, tertiary substrate.
Nucleophile only reagent only SUBSTITUTION reactions
A. primary ----- only SN2
B. secondary ---- SN2 + SN1 (SN2 gen favored)
C. tertiary ---- SN1
Base only reagent --- only ELIMINATION reactions
Primary, secondary, tertiary ------ E2 process
Strong base/nucleophile BIMOLECULAR reactions (SN2 & E2)
A. primary ----- SN2 major & E2 minor ----------exception tertbutoxide is sterically hindered alkoxide, favors E2 over SN2 enables
conversion of primary alkyl halide into alkene,
B. secondary ------ E2 major & SN2 minor
C. tertiary ---- SN2 pathway too sterically hindered. E2 is observed
Weak base/nucleophile
A. primary ---- react slowly with weak nucleophile/bases SN2 + E2 is
not practical
B. secondary ---- reaction produce mixture of too many products SN2
+ SN1 + E1 + E2 not practical. If substrate alcohol, treatment with conc.
H2SO4 produces E1 rxn. (acid serves as proton source to protonate OH)
water serve as weak base to complete E1

C. tertiary ----- unimolecular pathways predominate SN1 + E1. SN1

gen favored. Sensitive to rxn conditions, temp being most significant.
Increase in temp enhance both, but greater to E1. If substrate alcohol,
treatment with conc. H2SO4 produces E1 rxn. (acid serves as proton source
to protonate OH) water serve as weak base to complete E1

Page 389 master flowchart

8.14
Predicting products
Page 391
9.1
Addition reactions common reaction of alkenes, characterized by
addition of 2 groups across double bond, pi bond broken in process
Table 9.1
9.2
Many case addition reaction is reverse elimination reaction
Addition favored at low temperature, elimination favored high
temperature.
Page 406
[delta]G must be negative for equilibrium to favor products.

[delta]G = ([delta]H)---enthalpy term + (-T[delta]S)---entropy term

[delta]H --- dominant factor is generally bond strength.
Bond broken bond fored = [delta]H
If [delta]H is negative, rxn is exothermic, generally case for addition
rxns
-T[delta]S entropy term.
Term will always be positive for addition rxn. 2 molecules joining
together will produce 1 molecule decrease in entropy, [delta]S will be
negative. T in kelvin will always be + resulting in T[delta]S being positive
number
For [delta]G to be negative enthalpy must be larger than entropy.
Low temp, entropy is small & enthalpy term dominates. [delta]G will
be negative, products favored over reactants equilibrium constant K > 1
High temp, entropy is large and will dominate over enthalpy. [delta]G
will be positive, reactants favored over products . Equilibrium K < 1,
reverse process (elimination) will be thermodynamically favored at high
temperatures
9.3
Treatment of alkenes with HX (X=Cl, Br, or I) results in addition rxn
called hydrohalogenation. H and X are added across pi bond
When alkene is unsymmetrical ultimate placement of H and X must be
considered

2 vinylic positions where X can be placed.

H gen placed at vinylic position already bearing larger number H
atoms.
Halogen gen place at more substituted position
Regiochemical preference called Markovnikov addition observed for
HI, HCl,
Rxn proceed with regiochemical preference said to be regioselective
Purified reagents Markovnikov addition observed
Impure reagents anti-markovnikov addtition sometime occurs
Peroxides (ROOR) even in trace, would cause HBr to add across alkene
in anti-markovnikov fashion
Hydrohalogenation mechanisn for markovnikov addition of HX to
alkenes
1. pi bond of alkene protonated generates carbocation intermediate
2. intermediate attacked by Br- ion
observed regioselectivity attributed to 1st step of mechanism (proton
transfer)
Transition state for formation of tertiary carbocation will be lower in
energy than transition state formation of secondary carbocation.

Regioselectivity of an ionic addition reaction deteremined by

preference for reaction to proceed through more stable carbocation
intermediate
Many cases hydroalogenation involes formation of chirality center.
1 new chirality center formed, 2 possible products expected,
represents enantiomers
Enantiomers produced in equal amounts (racemic mixtures).
Stereochemical outcome for rxn explained by proposed mechanism
Constitutional isomer same molecular formula, different
constitution.
Carbon 4 bonds, nitrogen 3 bonds, oxygen 2 bonds, hydrogens and
halogens 1 bond
Drawing Lewis structures:
1. Draw individual atoms
2. Connect atoms that form more than 1 bond
3. Connect H atoms
4. Pair unpaired electrons
Formal charge on atoms that dont exhibit appropriate number of
valence electrons
Calculate formal charge
1. Determine appropriate number of valence electrons

2. Determine actual number of valence electrons

3. Assign formal charge
Electronegativity ability of atom to attract electrons. Increase left to
right, bottom to top
If difference of electronegativity:
<0.5 covalent bond
0.5< difference <1.7 polar covalent bond. Withdrawal of electrons toward
more electronegative atom is called induction
>1.7 ionic bond
Locate partial charges from induction
1. Identify all polar covalent bonds
2. Determine direction of each dipole
3. Indicate location of partial charges
Electron density probability of finding electron in particular region
Atomic orbital (AO) are s, p, d, and f individual atom
1. Aufbau principle lowest energy orbital filled first
2. Pauli exclusion principle each orbital accommodate max 2 electrons
with opposite spon.

3. Hunds rule 1 electron placed in each degenerate orbital before pairing

electrons up
Identify electron configuration
1. Place valence electron in AO using 3 rules.
2. ID number valence electron in each AO
Constructive interference produce wave with larger amplitude
Destructive interference produce node (wave canceling)
Molecular orbitals mathematically combined atomic orbitals entire
molecule
Highest occupied molecular orbital HOMO
Lowest unoccupied molecular orbital LUMO
Sigma bond result from overlap of hybridized atomic orbital, pi bond result
from overlap of p orbital, triple bond (2 pi bond) result 2 overlapping p
orbitals
Single<double<triple in strength
Triple<double<single in length
# sigma bonds + # lone pairs = steric number (indicates how many
hybridized orbitals necessary)

sp3-hybridized steric number 4

-no lone pairs tetrahedral with 109.5 bond angle
-1 lone pair trigonal pyramidal <109.5 bond angle (107-NH3)
-2 long pair bend <<109.5 bond angle (105-H2O)
sp2-hybridized steric number 3
- no lone pair trigonal planar 120 bond angle
- 1 lone pair bent
sp-hybridized steric number 2
- no lone pair linear 180 bond angle
FIGURE 1.43 3 hybridization states 5 common geometries
Predicting geometry
1. Determine steric number
2. Determine hybridization and electron geometry
3. ignore lone pairs and describe resulting geometry
Geometry only relevant when atom connected to at least 2 atoms
Compound with more than 1 polar bond use vector sum or molecular
dipole moment
Interdual molecules