(July 9 discussion) 3.

Addition - the opposite of elimination

reaction. From unsaturated bonds (double
Exercise 2.1
and triple bonds) that turns into saturated
Basic terms bonds (single)

 Lewis base – electron pair donor

- The structure contains at least a lone pair of
electron or a free electron
- In an organic reaction, a lewis base is also
known as a nucleophile - All reactions involves an alkyl halide as one
of the reactants however the most common
 Nucleophile – Interacts with a positive reaction that uses the alkyl halide are
regions and usually carries a formal or partial substitution and elimination because that’s
negative charge the first reactants that they have to
- As a lewis base, a nucleophile has an perform the reaction
available pair of electron ready to donate
- An addition reaction may or may not have an
alkyl halide
 Lewis acid – electron pair acceptor
- In an organic reaction, a lewis acid works the SN1 reaction vs SN2 reaction
same way as a electrophile
In a substitution reaction, aside from the alkyl
 Electrophile – Loves and attracts electron halide (substrate), another one will be acting as
pairs and usually carries a formal or partial a nucleophile (lewis base)
positive charge  SN = Substitution nucleophilic
 1 = unimolecular (multi step)
 Acid – in an organic reaction, every acid is  2 = bimolecular ( one step)
considered as a bronsted – acid (proton
donor) SN1 reaction

- In a SN1 reaction, there are transitions and

 Base – In an organic reaction, every base is intermediates
considered as a bronsted – base
Transitions and intermediates
Base vs nucleophile
 Transitions state – the highest energy state
- A base only interacts with an acidic proton
which the reactants must meet
(H) while a nucleophile reacts with any atom
 Intermediate – has a relatively lower energy
that has a formal or partial positive charge.
than the transition but higher than that of
the reactants or products.
Note: This goes the same way with acids vs
- These are short-lived species.
electrophiles.
- Usually when there’s an intermediate, it will
The different organic reactions involve several steps.

1. Substitution – an organic molecules turns Why? Because the reactants does not linearly
into another molecule because one part is result to the products
being replaced via substitution. (Replace a
A→B
group with another group)
B→C

A→C

Where B is the intermediate

Without the formation of the intermediate, the

2. Elimination – it usually involves saturated
product cannot be produces.
hydrocarbons (single bond) forming
unsaturated bond (double or triple bonds) SN2 reaction
- Elimination reactions of products are
- In a SN2 reaction, only transitions are
always unsaturated
involved and therefore is only a one step
process: reactants to products
 Substrate d. For SN2 (one step) – nucleophile attack and
loss of leaving group at the same time
 Alkyl halide – acts as a substrate and is
usually the starting reactant in organic
reaction Personal notes: Youtube and powerpoint

Chapter 6-11
- In a substitution reaction, the substrate
contains the leaving group and the Energy diagrams
electrophilic site (E+)

- In an elimination reaction, the substrate

contains the leaving group and the acidic
proton (beta-hydrogen)

Nature of substrate

 The nature of the substrate affects the

organic reaction (SN1 or SN2)

1. Primary – Connected to one carbon atom

2. Secondary – connected to two carbon atoms
 Transition state – the highest energy state
3. Tertiary – connected to 3 carbon atoms
in the diagram where structures are too
unstable to be observed
 Intermediate – A lower energy state than
the transition state. It is more stable

- Two points on an energy diagram that are

close in energy should be similar in
structure.

E1 and E2 reaction The Hammond postulate

- Hammond’s postulate states that the

 E = Elimination
transition state of a reaction resembles
 1 = Unimolecular (multi step)
either the reactants or the products, to
 2 = Bimolecular (one step)
whichever it is closer in energy.
- At higher temperature the reaction favor
elimination better than substitution

Zaitsev rule

- Followed by elimination reaction

- The most stable product will always have a
double bond with more groups attached.

More group = major product

Markovnikov's rule

- Followed by the addition reaction

Patterns of mechanism

a. For E2 (one step) – proton transfer and loss

of leaving group at the same time

b. For E1 (multi step) – loss of leaving group

and then proton transfer
 Endothermic – Reactant’s energy <
c. For SN1 (multi step) – loss of leaving group Product’s energy
then nucleophile attack  Exothermic – Reactant’s energy > product’s
energy (More stable products)
 Nucleophile vs electrophile

 Nucleophiles - Nucleophiles donate

electrons because they either have a
negative charge or they have lone pair(s) of
electrons in their valence shells 3. Proton transfer (acid/base) – when a
negative or electronegative atom uses a lone
 Electrophiles - Electrophiles are electron pair of electrons to grab a proton.
acceptors while nucleophiles are electron
donors. Electrophiles accept electrons
because they are either positively charged or
they have empty valence shells

How to determine the strength of a nucleophile

4. Rearrangements – a molecule’s carbon
1. Charge - nucleophilicity increases as the skeleton is rearranged to give the original
density of negative charge increases. molecule a structural isomer.

2. Electronegativity - A highly electronegative

atom is a poor nucleophile because it is
unwilling to share its electrons. As (Methyl shift)
electronegativity increases, nucleophilicity
decreases.  Hydride shift – the shift or movement of
the hydrogen ion

3. Steric hindrance - The bulkier a nucleophile

is, the more difficult it is to attack the
substrate, and the weaker the nucleophile
becomes.
 Methyl shift – the shift of an entire
methyl group

4. Effect of Solvent - A polar aprotic solvent Chapter 7

preferentially solvates cations, leaving an Substitution reaction
almost "bare" nucleophile. This increases its
nucleophilicity - Is a somewhat single displacement reaction
where one group transfers to another
Arrow pushing molecule while the other simply leaves.
 Double headed arrows – movement of 2 - The leaving group always takes a pair of
electrons electrons with it
 Single headed arrows – movement of 1 - Substitution always occurs at the alpha
electron carbon

Patterns of mechanism Alkyl halide structure

1. Nucleophilic attack – when an nucleophile

seeks out an electrophile to form a new
bond

Sn1 vs Sn2
2. Loss of leaving group – when a group in a
 SN1 – multistep process (Step wise)
substrate breaks away taking away with it 2
 SN2 – one step process
electron pairs.
 Which would be favored? Vinylic vs allylic
SN1 SN2
Tertiary Primary  Vinylic carbons - one of the two atoms that
If both secondary share the double bond.
Polar protic solvent Polar aprotic solvent  Allylic carbons - the carbon atom adjacent
Weak nucleophile Strong nucleophile to the double-bonded carbon atom

Syn addition vs anti-addition

 protic – has hydrogens that can be released
 Syn addition – both incoming groups comes
Chapter 8: Elimination and addition from the same side. Either both from the top
or both from the bottom
Elimination reaction  Anti-addition – the incoming group comes
 Elimination reaction – All elimination from both opposite sides
reactions involves losing a leaving group and
proton transfers
- Unlike substitution, Elimination reactions
occurs at the beta hydrogen

E1 vs E2 Radical reaction

Which would be favored?  Radical – is any species or atom with an

E1 E2 unpaired number of electrons
Tertiary (unlikely Tertiary - An atom with odd pairs of electrons
primary) - Free radicals are formed when bond breaks
Polar protic solvent Polar aprotic solvent homolytically
Weak base Strong base
Bond cleavages

Zaitsev rule and product  Heterolytic – Are formed when to different

atoms are separated forming two different
- Also called as the saytzeff’s rule ions. The more electronegative ion will
- the more highly substituted alkene is the attract the electrons
more likely product of an elimination  Homolytic – two atoms of the same kind
reaction that are bonded to each other. When a
- The higher the number of carbon attached to bond breaks, the electrons are distributed
the carbon double bond, the more stable the equally to the
product is

Addition reaction - Free radicals do not have a formal charge

but are unstable because of an incomplete
- the reverse or opposite of the elimination octet. They are very reactive species.
reaction - Radicals don’t go rearrangement
- it has 2 sites: markonikov and anti-
markonikov addition Steps of a radical reaction
- it always favors the markonikov process

Markonokov’r rule  Initiation – two radicals on the right side of

the equation
 Markovnikov’s rule - the nucleophile is  Propagation – one radical on both sides of
added to the carbon that would have formed the equation
the most stable carbocation  Termination – two radical on the left side of
 Anti-markovnikov - follows the opposite of the equation
the markovnikov’s rule
 Chlorination of methane

 Chain reactions – reactions that have self-

sustaining propagation steps

Selectivity

- As the reactivity increases, the selectivity

decreases
 Selective – favors the secondary hydrogen
 Non-selective – favors non

Radical stability

- Tertiary radicals are the most stable

 Compilation of exercises

2.1

1. Determine which of the following works the same way as LEWIS BASE in an organic reaction

a.nucleophile b. Bronstead base c. electrophile d. Bronstead acid

2. Determine which product will be the MAJOR product formed when a strong Nuclephile/base will
react with secondary substrate?
a. Sn1 product b. E1 product c. Sn2 product d. E2 product

3. Determine which of the following patterns of mechanism involved in E1 reaction

a. nucleophile attact and loss of the leaving group at the same time
b. Proton transfer and loss of the leaving group at the same time
c. loss of the leaving group then nucleophile attack
d. loss of the leaving group then proton transfer

4. Determine which of the following will complete the sentence: In S N2 reaction, there is/are
a. transition state only b. none of the choices c. transition and intermediates d. intermedietes
only
5. Identify which organic reaction follows Zaitsev rule?
a. Addition b. Substitution c. Elimination d. Redox

6. Determine in which organic reaction will invoved an alkyl halide as one of the reactants?
a. Substitution b. Elimination c. all of the choices d. Addition

7. Determine which of the following will NOT act as nucleophile but always act as base.
a. RSH b. ROH c. H2O d. NaH

8. Determine which of the following patterns of mechanism involved in E2 reaction

a. loss of the leaving group then proton transfer
b. Proton transfer and loss of the leaving group at the same time
c. loss of the leaving group then nucleophile attack

9. Identify which organic reaction follows Markovnokov’s rule?

a. Substitution b. Elimination c. Redox d. Addition

10. Determine which of the following works the same way as LEWIS ACID in an organic reaction
a. nucleophile b. Bronstead base c. electrophile d. Bronstead acid

11. Determine which of the following will complete the sentence: In S N1 reaction, there is/are
a. transition state only b. none of the choices c. transition and intermediates d. intermedietes
only

12. Determine which of the following will affects the reaction as Sn1 or Sn2.
a. all of the choices b. solvent used c. nature of substrate d. strength of the nucleophile

13. Determine which of the following works the same way as ACID in an organic reaction
a. Bronstead base b. electrophile c. Bronstead acid d. nucleophile

14. Identify which of the following is an oxidation product?

a. methyl benzene b. alkene c. alcohol d. alkyne

15. Determine which of the following patterns of mechanism involved in Sn1 reaction
a. nucleophile attact and loss of the leaving group at the same time
 b. loss of the leaving group then nucleophile attack
c. loss of the leaving group then proton transfer
d. Proton transfer and loss of the leaving group at the same time
16. Determine which of the following patterns of mechanism involved in Sn2 reaction
a. loss of the leaving group then proton transfer
b. nucleophile attact and loss of the leaving group at the same time
c. Proton transfer and loss of the leaving group at the same time
d. loss of the leaving group then nucleophile attack

17.

Elimination

18.

D. nitrogen with double bond to carbon

19.

The second product

20.
Base

2.2

1. Syn co-planar arrangement of the leaving group and beta-hydrogen is prefered over anti-
coplanar
False
2. The term use to designate two Leaving Groups, such as two same halogen, attached to adjacent
carbon of substrate is known as geminal dihalides.
False
3. Zaitsev product is favored over Hoffman in the presence of methoxide (CH 3O -)
True
4. Ozonolysis of triple bond is an example of OXIDATION reaction of organic compounds.
True
5. Acid catalysed hydration in the triple bond of 1-Butyne involved anti-Markovnikov’s reaction.
False
6. A concerted, one-step reaction is involved between tert-Butyl bromide and sodium hydride at
50 o C.
True
7. Hydrogenation of triple bond of alkyne with Lindlar’s Catalyst will form trans (or E) alkene.
False
8. Anti- addition mechanism normally happens when a “cyclic” intermediates involved in the
substrate
True
9. The term use to designate two Leaving Groups, such as two same halogen, attached to adjacent
carbon of substrate is known as vicinal dihalides.
True
10. Addition reaction, just like Elimination Reaction, also follows Zaitsev Rule.
False
11. Vinylic radical is less stable than benzyllic radical.
True
12. Radical are formed via heterolytic bond cleavage.
False
13. Radical like carbocation, is proned to rearrangement.
False
14. In Elimination reaction, a nucleophile interacts with the subtsrate.
False
15. Syn- addition mechanism normally happens when a “planar” surface provided by other reactant
in the reaction.
True
 2.3

1. Consider [14]Annulene structure.Is this aromatic and follows Huckel’s Rule?

Yes

2. The IUPAC name of the structure below is 1-((1R, 3R)-3-methylcyclohexyl)benzene

False

3. The structure of 3,5-dimethylbenzoic acid is

False

4. The structure of 1-phenyl-3-methylpentane is:

True

5. The structure of (Z)-2,3-diphenyl-2-hexene is:

False

6. The structure of 2,4-diaminotoluene is also 1-methyl-2,4-benzenediamine

True

7. The IUPAC name of the structure below is p-bromoaniline

True

8. Consider [16]Annulene structure.Is this aromatic and follows Huckel’s Rule?

No
9. The IUPAC name of the structure below is o-fluoronitrobenzene
False

10. The IUPAC name of the structure below is 4-bromobenzaldehyde

False

11. The reactive electrophile in Friedel-Crafts acylation reactions

12. Consider the reaction below. What is the role of the AlCl3 in the reaction?
Lewis base

13. Arrange the following based on INCREASING reactivity toward Electrophilic Aromatic Substitution
Reaction:
I<III<II

14. Consider the reaction below. What is the role of the benzene in the reaction?
Nucleophile

15. Consider the reaction below. What is the role of the ethyl chloride in the reaction?
Electrophile

16. Arrange the following based on DECREASING reactivity toward Electrophilic Aromatic Substitution
Reaction:
II>I>III