Ilovepdf Merged 3

CEB1013 ORGANIC CHEMISTRY
NUCLEOPHILIC SUBSTITUTION
REACTION:
Alkyl Halide & The Basic of Organic Reaction
Course Learning Outcome:

CLO2: Interpret the important relationship between structure and reactivity of
organic molecules from knowledge of acid-base and nucleophile-electrophile
properties
CLO3: Outline reaction mechanism for synthesis of common organic compounds
1
LEARNING OUTCOME
By end of this lecture, student should be able to
1. To name alkyl halide from the given structure and to draw its chemical
structures from the given name.
2. To correlate the type of alkyl halide (primary, secondary, or tertiary)
and correlate it with their physical properties such as boiling point and
solubility in water.
3. To understand the different kinds of organic reactions.
2
ALKYL HALIDE
▪ Alkyl halides are organic molecules containing a halogen atom X bonded to an
sp3 hybridized carbon atom.
▪ Alkyl halides are classifi ed as primary (1°), secondary (2°), or tertiary (3°)
depending on the number of carbons bonded to the carbon with the halogen.
R X
3
ALKYL HALIDE - NOMENCLATURE
▪ An alkyl halide is named as an alkane with a halogen substituent—that is, as a
halo alkane.
▪ To name a halogen substituent, change the -ine ending of the name of the
halogen to the suffix –o (chlorine → chloro).
4
ALKYL HALIDE - COMMON NAME
▪ Common names for alkyl halides are used only for simple alkyl halides.
▪ To assign a common name:
i. Name all the carbon atoms of the molecule as a single alkyl group.
ii. Name the halogen bonded to the alkyl group.
iii. To name the halogen, change the -ine ending of the halogen name to the
suffix -ide; for example, bromine ã bromide.
iv. Combine the names of the alkyl group and halide, separating the words
with a space.
5
ALKYL HALIDE - COMMON NAME (C ONT.)
▪ Common name cannot be applied for complex alkyl halide.
6
ALKYL HALIDE - PHYSICAL PROPERTIES
▪ Alkyl halides are weakly polar molecules.
▪ They exhibit dipole–dipole interactions because of their polar C – X bond, but
because the rest of the molecule contains only C – C and C – H bonds they are
incapable of intermolecular hydrogen bonding.
7
ALKYL HALIDE - PHYSICAL PROPERTIES (C
ONT.)
8
CLASS ACTIVITY 4.1
1. Give the IUPAC name for each compound.
2. Name the following compounds using IUPAC method.
3. Classify each compounds in problem 1 and 2 as 1°, 2°, or 3°.
9
CLASS ACTIVITY 4.1 (C ONT.)
4. Give the structure corresponding to each name.

a. 3-chloro-2-methylhexane
b. 1,1,3-tribromocyclohexane
c. 4-ethyl-5-iodo-2,2-dimethyloctane
d. propyl chloride
e. cis-1,3-dichlorocyclopentane
f. sec-butyl bromide
5. Rank the compounds in each group in order of increasing boiling point.

a. CH3CH2CH2I, CH3CH2CH2Cl, CH3CH2CH2F
b. CH3(CH2)4CH3, CH3(CH2)5Br, CH3(CH2)5OH
6. Draw the eight constitutional isomers having the molecular formula C5H11Cl.
a. Give the IUPAC name for each compound.
b. Classify each isomer as 1°, 2°, or 3°.
c. Rank their boiling point.
10
WRITING EQUATIONS FOR ORGANIC REACTIONS
Like other reactions, equations for organic reactions are usually drawn with a single
reaction arrow (→) between the starting material and product, but other
conventions make these equations look different from those encountered in
general chemistry.
11
WRITING EQUATIONS FOR ORGANIC REACTIONS (CONT.)
▪ When two sequential reactions are carried out without drawing any
intermediate compound, the steps are usually numbered above or below the
reaction arrow. This convention signifies that the first step occurs before the
second, and the reagents are added in sequence, not at the same time.
12
WRITING EQUATIONS FOR ORGANIC REACTIONS (CONT.)
▪ More example:
13
ORGANIC REACTIONS MAP
14
KINDS OF ORGANIC REACTIONS
Substitution: a reaction in which an atom or a group of atoms is replaced
1 by another atom or group of atoms.
▪ In a general substitution reaction, Y replaces Z on a carbon atom.

▪ Substitution reactions involve σ bonds: one σ bond breaks and another forms at
the same carbon atom.
▪ The most common examples of substitution occur when Z is hydrogen or a
heteroatom that is more electronegative than carbon.
15
KINDS OF ORGANIC REACTIONS (C ONT.)
Substitution: a reaction in which an atom or a group of atoms is replaced

1 by another atom or group of atoms.
16
Elimination: a reaction in which elements of the starting material are “lost”

2 and a π bond is formed.
▪ In an elimination reaction, two groups X and Y are removed from a starting

material.
▪ Two σ bonds are broken, and a o bond is formed between adjacent atoms.
▪ The most common examples of elimination occur when X = H and Y is a
heteroatom more electronegative than carbon.
17
Elimination: a reaction in which elements of the starting material are “lost”

2 and a π bond is formed.
18
Addition: a reaction in which elements are added to a starting material.

3
▪ In an addition reaction, new groups X and Y are added to a starting material.

▪ A π bond is broken and two σ bonds are formed.
19
Addition: a reaction in which elements are added to a starting material.

3
20
Addition and elimination reactions are exactly opposite. A π bond is formed in

elimination reactions, whereas a π bond is broken in addition reactions
21
BOND BREAKING AND BOND MAKING
▪ A reaction mechanism is a detailed description of how bonds are broken and
formed as a starting material is converted to a product.
▪ A reaction can occur either in one step or in a series of steps:
1. A one-step reaction is called a concerted reaction. No matter how many

bonds are broken or formed, a starting material is converted directly to a
product.
2. A stepwise reaction involves more than one step. A starting material is first
converted to an unstable intermediate, called a reactive intermediate,
which then goes on to form the product.
22
BOND CLEAVAGE
▪ No matter how many steps there are in the reaction, however, there are only two
ways to break (cleave) a bond: the electrons in the bond can be divided equally
or unequally between the two atoms of the bond.
1. Breaking a bond by equally dividing the electrons between the two atoms
in the bond is called homolysis or homolytic cleavage.
23
BOND CLEAVAGE (C ONT.)
2. Breaking a bond by unequally dividing the electrons between the two

atoms in the bond is called heterolysis or heterolytic cleavage. Heterolysis
of a bond between A and B can give either A or B the two electrons in the
bond. When A and B have different electronegativities, the electrons
normally end up on the more electronegative atom.
24
▪ A full-headed curved arrow shows the movement of an electron pair.

▪ A half-headed curved arrow shows the movement of a single electron.
25
BOND CLEAVAGE (C
ONT.)
26
Homolysis and heterolysis generate radicals, carbocations, and carbanions, the

three most common reactive intermediates in organic chemistry.
▪ Radicals and carbocations are electrophiles because they contain an electron-

deficient carbon.
▪ Carbanions are nucleophiles because they contain a carbon with a lone pair.
27
BOND FORMATION
Like bond cleavage, bond formation occurs in two different ways.
1. Two radicals can each donate one electron to form a two-electron bond.
2. Alternatively, two ions with unlike charges can come together, with the
negatively charged ion donating both electrons to form the resulting two
electron bond.
28
ALL KINDS OF ARROWS
▪ Curved arrows are especially important because they explicitly show what
electrons are involved in a reaction, how these electrons move in forming and
breaking bonds, and if a reaction proceeds via a radical or polar pathway.
29
CLASS ACTIVITY 4.2
1. Classify each transformation as substitution, elimination, or addition.
2. Classify each transformation as substitution, elimination, or addition.
30
3. By taking into account electronegativity differences, draw the products formed

by heterolysis of the carbon–heteroatom bond in each molecule. Classify the
organic reactive intermediate as a carbocation or a carbanion.
4. Use full-headed or half-headed curved arrows to show the movement of

electrons in each equation.
31
5. Draw the products of each reaction by following the curved arrows.
32
WHAT HAVE YOU LEARNED?
33
REACTION:
Nucleophilic Substitution

properties
1
LEARNING OUTCOME
1. To construct nucleophilic substitution reaction from the given reactant

or target molecules.
2
Three components are necessary in any substitution reaction:
1. R—An alkyl group R containing an sp3 hybridized carbon bonded to X.

2. X—An atom X (or a group of atoms) called a leaving group, which is able to
accept the electron density in the C – X bond. The most common leaving groups
are halide anions (X–), but H2O (from ROH2+) and N2 (from RN2+) are also
encountered.
3. :Nu–—A nucleophile. Nucleophiles contain a lone pair or a π bond but not
necessarily a negative charge.
3
NUCLEOPHILIC SUBSTITUTION (C ONT.)
The R—X:
1 An alkyl group R containing an sp3 hybridized carbon bonded to X.
▪ Whether an alkyl halide is 1°, 2°, or 3° is the most important factor

in determining the course of its chemical reactions
4
The R—X:
These organic halides are These organic halides do

unreactive in the reactions. participate in the reactions.
5
The R—X:
▪ Alkyl halides undergo substitution reactions with nucleophiles.
▪ Alkyl halides undergo elimination reactions with Brønsted–Lowry bases.
6
The Nucleophile:
2 Nucleophiles and bases are structurally similar: both have a lone pair or a π
bond. They differ in what they attack
7
The Nucleophile vs Basicity:

2 1. For two nucleophiles with the same nucleophilic atom, the stronger
base is the stronger nucleophile.
2. A negatively charged nucleophile is always stronger than its conjugate
acid. –OH is a stronger base and stronger nucleophile than H2O, its
conjugate acid.
3. Right-to-left across a row of the periodic table, nucleophilicity increases
as basicity increases.
8
The Nucleophile vs Basicity – The Exception: Steric Hindrance

2
▪ For example, although pKa tables indicate that tert-butoxide

[(CH3)3CO–] is a stronger base than ethoxide (CH3CH2O–), ethoxide is
the stronger nucleophile. The three CH3 groups around the O atom of
tert-butoxide create steric hindrance, making it more difficult for this
big, bulky base to attack a tetravalent carbon atom.
9
The Leaving Group: The more stable the leaving group X:–, the better able
3 it is to accept an electron pair, giving rise to the following generalization:
▪ For example, H2O is a better leaving group than –OH because H2O is a
weaker base
10
The Leaving Group: The more stable the leaving group X:–, the better able
3 it is to accept an electron pair, giving rise to the following generalization:
▪ Left-to-right across a row of the periodic table, basicity decreases so

leaving group ability increases.
▪ Down a column of the periodic table, basicity decreases so leaving

group ability increases.
11
The Leaving Group:

3 All good leaving groups are weak bases with strong conjugate acids having
low pKa values.
12
▪ Curved arrow notation can be used to show the movement of electron pairs, as
shown in Equation [3] below.
13
▪ Negatively charged nucleophiles like –OH and –SH are used as salts with Li+, Na+,
or K+ counter ions to balance charge. The identity of the cation is usually
inconsequential, and therefore it is often omitted from the chemical equation.
14
▪ When a neutral nucleophile is used, the substitution product bears a positive

charge. Note that all atoms originally bonded to the nucleophile stay bonded to
it after substitution occurs. All three CH3 groups stay bonded to the N atom in
the given example.
15
▪ Furthermore, when the substitution product bears a positive charge and also
contains a proton bonded to O or N, the initial substitution product readily loses
a proton in a Brønsted–Lowry acid–base reaction, forming a neutral product.
16
All of these reactions are nucleophilic substitutions and have the same overall
result—replacement of the leaving group by the nucleophile, regardless of the
identity or charge of the nucleophile. To draw any nucleophilic substitution product:
▪ Find the sp3 hybridized carbon with the leaving group.
▪ Identify the nucleophile, the species with a lone pair or π bond.
▪ Substitute the nucleophile for the leaving group and assign charges (if
necessary) to any atom that is involved in bond breaking or bond formation.
17
CLASS ACTIVITY 4.3
1. Identify the nucleophile and leaving group and draw the products of each
reaction.
2. Draw the products of each nucleophilic substitution reaction.
18
3. Analyse which of the following nucleophilic substitution reactions will take

place? Hint: In each part involves an acid–base reaction
Compound pKa Compound pKa

HI -10 H2O 15.7
NH3 38 HCN 9.1
CH3OH 15.5 H3O+ -1.7
HF 3.2
19
MECHANISM FOR NUCLEOPHILIC SUBSTITUTION
▪ Nucleophilic substitution at an sp3 hybridized carbon involves two σ bonds: the
bond to the leaving group, which is broken, and the bond to the nucleophile,
which is formed.
▪ To understand the mechanism of this reaction, though, we must know the

timing of these two events; that is,
a. What is the order of bond breaking and bond making?
b. Do they happen at the same time, or
c. does one event precede the other?
There are three possibilities.
20
POSSIBLE MECHANISM
1 Bond breaking and bond making occur at the same time.
▪ If the C – X bond is broken as the C – Nu bond is formed, the

mechanism has one step. The rate of such a bimolecular reaction
depends on the concentration of both reactants; that is, the rate
equation is second order.
21
POSSIBLE MECHANISM (CONT.)
2 Bond breaking occurs before bond making.
▪ If the C – X bond is broken first and then the C – Nu bond is formed,

the mechanism has two steps and a carbocation is formed as an
intermediate. Because the first step is rate- determining, the rate
depends on the concentration of RX only; that is, the rate equation is
first order.
22
POSSIBLE MECHANISM (CONT.)
3 Bond making occurs before bond breaking.
▪ If the C – Nu bond is formed first and then the C – X bond is broken,

the mechanism has two steps, but this mechanism has an inherent
problem. The intermediate generated in the first step has 10
electrons around carbon, violating the octet rule. Because two other
mechanistic possibilities do not violate a fundamental rule, this last
possibility can be disregarded.
23
24
REACTION:
SN2 and SN1 Mechanism

properties
1
LEARNING OUTCOME
1. To compare and contrast SN1 and SN2 reactions mechanism.

2
SN2 MECHANISM
▪ SN2: Substitution Nucleophile Bimolecular.
▪ Example, the reaction of CH3Br with CH3COO– is an example of an SN2 reaction.
▪ What are the general features of this mechanism?
3
SN2 MECHANISM (C ONT.)
Kinetics:
1 An SN2 reaction exhibits second-order kinetics; that is, the reaction is
bimolecular and both the alkyl halide and the nucleophile appear in the
rate equation.
▪ Changing the concentration of either reactant affects the rate.

▪ For example, doubling the concentration of either the nucleophile or
the alkyl halide doubles the rate.
▪ Doubling the concentration of both reactants increases the rate by a
factor of four.
4
A One-Step Mechanism:
2 The most straightforward explanation for the observed second-order
kinetics is a concerted reaction—bond breaking and bond making
occur at the same time.
5
Stereochemistry of the SN2 Reaction

3 From what direction does the nucleophile approach the substrate in an
SN2 reaction? There are two possibilities.
▪ Frontside attack: The nucleophile approaches from the same side as
the leaving group.
▪ Backside attack: The nucleophile approaches from the side opposite
the leaving group.
6

3 From what direction does the nucleophile approach the substrate in an
SN2 reaction? There are two possibilities.
▪ Frontside attack: The nucleophile approaches from the same side as
the leaving group.
▪ Backside attack: The nucleophile approaches from the side opposite
the leaving group.
7

3 The products of front side and backside attack are different compounds.
A and B are stereoisomers that are non-superimposable—they are
enantiomers.
▪ All SN2 reactions proceed with backside attack of the nucleophile,

resulting in inversion of configuration at a stereogenic center.
8
4 The Identity of the R Group.

▪ As the number of R groups on the carbon with the leaving group
increases, the rate of an SN2 reaction decreases.
▪ Methyl and 1° alkyl halides undergo SN2 reactions with ease.

▪ Alkyl halides react more slowly.
▪ Alkyl halides do not undergo SN2 reactions.
9
4 The Identity of the R Group.

▪ This order of reactivity can be explained by steric effects.
10
5 How to draw the SN2 mechanism?
11
5 How to draw the SN2 mechanism?
12
SN2 MECHANISM (CONT.)
6 Summary.
13
APPLICATION: USEFUL SN2 REACTIONS
The SN2 reaction is a key step in the laboratory synthesis of many drugs including
ethambutol (trade name: Myambutol), used in the treatment of tuberculosis, and
fluoxetine (trade name: Prozac), an antidepressant
14
CLASS ACTIVITY 4.4
1. Rank the alkyl halides in each group in order of increasing SN2 reactivity.
2. Identify which SN2 reaction in each pair is faster?
15
3. Consider the following SN2 reaction:
a. Draw a mechanism using curved arrows.

b. Draw the structure of the transition state.
c. What is the rate equation?
d. What happens to the reaction rate in each of the following instances?
i. The leaving group is changed from Br– to I–
ii. The solvent is changed from acetone to CH3CH2OH
iii. The alkyl halide is changed from CH3(CH2)4Br to CH3CH2CH2CH(Br)CH3
iv. The concentration of –CN is increased
16
SN1 MECHANISM
▪ SN1: Nucleophilic substitution unimolecular
▪ Example, the reaction of (CH3)CBr with CH3COO– is an example of an SN1
reaction.
▪ What are the general features of this mechanism?
17
Kinetics:
1 The SN1 reaction exhibits first-order kinetics.
▪ The SN1 mechanism involves more than one step, and that the slow
step is unimolecular, involving only the alkyl halide.
▪ The identity and concentration of the nucleophile have no effect on
the reaction rate. For example, doubling the concentration of
(CH3)3CBr doubles the rate, but doubling the concentration of the
nucleophile has no effect.
18
A Two-Step Mechanism:
2 The most straightforward explanation for the observed first-order
kinetics is a two-step mechanism in which bond breaking occurs before
bond making.
▪ Heterolysis of the C – Br bond forms an intermediate carbocation.

This step is rate-determining because it involves only bond
cleavage.
19
A Two-Step Mechanism:
2 The most straightforward explanation for the observed first-order
kinetics is a two-step mechanism in which bond breaking occurs before
bond making.
▪ Nucleophilic attack of acetate on the carbocation forms the new C –

O bond in the product.
▪ This is a Lewis acid–base reaction; the nucleophile is the Lewis base
and the carbocation is the Lewis acid.
▪ Step [2] is faster than Step [1] because no bonds are broken and one
bond is formed.
20
Stereochemistry of the SN1 Reaction:

3 To understand the stereochemistry of the SN1 reaction, we must
examine the geometry of the carbocation intermediate.
▪ A carbocation (with three groups around C) is sp2 hybridized and

trigonal planar, and contains a vacant p orbital extending above and
below the plane.
21
Stereochemistry of the SN1 Reaction:

3
▪ SN1 reactions proceed with racemization at a single stereogenic

center.
▪ Racemization is the formation of equal amounts of two enantiomeric
products from a single starting material.
22
The Identity of the R Group.

4 ▪ As the number of R groups on the carbon with the leaving group
increases, the rate of an SN1 reaction increases.
▪ 3° Alkyl halides undergo SN1 reactions rapidly.

▪ 2° Alkyl halides react more slowly.
▪ Methyl and 1° alkyl halides do not undergo SN1 reactions..
This trend is exactly opposite to that observed for the SN2 mechanism
23
The Identity of the R Group.

4 ▪ Carbocation stability: as the number of R groups on the positively
charged carbon atom increases, the stability of the carbocation
increases.
▪ As R groups successively replace the H atoms in CH3+, the positive

charge is more dispersed on the electron donor R groups, and the
carbocation is more stabilized
24
The Hammond Postulate - The rate of an SN1 reaction depends on the rate of
formation of the carbocation (the product of the rate-determining step) via
heterolysis of the C – X bond.
▪ The rate of an SN1 reaction increases as the number of R groups on the carbon
with the leaving group increases.
▪ The stability of a carbocation increases as the number of R groups on the
positively charged carbon increases.
25
CLASS ACTIVITY 4.5
1. Classify each carbocation as 1°, 2°, or 3°.
2. Rank the carbocation in each group in order of increasing stability.
26
3. Rank the alkyl halides in each group in order of increasing SN1 reactivity.
4. Identify which SN1 reaction in each pair is faster?
27
28
REACTION:
SN2 or SN1 (Cont.)

properties
1
LEARNING OUTCOME
1. To compare and contrast SN1 and SN2 reactions mechanism.

2
WHEN IS THE MECHANISM SN1 OR SN2?
Given a particular starting material and nucleophile, how do we know whether a
reaction occurs by the SN1 or SN2 mechanism? Four factors are examined:
▪ The alkyl halide—CH3X, RCH2X, R2CHX, or R3CX. – The most important factor!
▪ The nucleophile—strong or weak.
▪ The leaving group—good or poor.
▪ The solvent—protic or aprotic
S N1
S N2
3
WHEN IS THE MECHANISM SN1 OR SN2? (CONT.)
The alkyl halide
1 ▪ Increasing alkyl substitution favours SN1.
▪ Decreasing alkyl substitution favours SN2.
▪ Methyl and 1° halides (CH3X and RCH2X) undergo SN2 reactions only.
▪ 3° Alkyl halides (R3CX) undergo SN1 reactions only.
▪ 2° Alkyl halides (R2CHX) undergo both SN1 and SN2 reactions. Other
factors determine the mechanism.
4
The alkyl halide
1 ▪ Increasing alkyl substitution favours SN1.
▪ Decreasing alkyl substitution favours SN2.
5
The alkyl halide
1 ▪ Methyl and 1° halides (CH3X and RCH2X) undergo SN2 reactions only.
▪ 3° Alkyl halides (R3CX) undergo SN1 reactions only.
▪ 2° Alkyl halides (R2CHX) undergo both SN1 and SN2 reactions. Other
factors determine the mechanism.
6
The nucleophile
2 ▪ Strong nucleophiles present in high concentration favour SN2
reactions.
▪ Weak nucleophiles favour SN1 reactions by decreasing the rate of any
competing SN2 reaction.
7
The nucleophile
reactions.
8
The nucleophile
reactions.
9
The leaving group
3 ▪ A better leaving group increases the rate of both SN1 and SN2 reactions.
The solvent
4 ▪ Polar protic solvents are especially good for SN1 reactions.
▪ Polar aprotic solvents are especially good for SN2 reactions.
10
11
CLASS ACTIVITY 4.6
1. Identify the most likely mechanism of nucleophilic substitution for each alkyl
halide?
2. For each alkyl halide and nucleophile:

I. Determine the likely mechanism (SN1 or SN2) for each reaction.
II. Draw the product of nucleophilic substitution.
12
3. Determine the mechanism of nucleophilic substitution of each reaction and

draw the products, including stereochemistry.
13
ORGANIC SYNTHESIS
Organic synthesis is the systematic preparation of a compound from a readily
available starting material by one or many steps.
▪ By thinking of nucleophilic substitution as a reaction that makes a particular

kind of organic compound, we begin to think about synthesis.
14
ORGANIC SYNTHESIS (C
ONT.)
15
ORGANIC SYNTHESIS (C ONT.)
To carry out synthesis we must think backwards. We examine a compound and ask:
What starting material and reagent are needed to make it?
16
ORGANIC SYNTHESIS (C ONT.)
▪ The carbon atoms come from the organic starting material, in this case a 1° alkyl
halide [(CH3)2CHCH2Br].
▪ The functional group comes from the nucleophile, –OH in this case. With these
two components, we can “fill in the boxes” to complete the synthesis.
17
CLASS ACTIVITY 4.7
1. Fill in the appropriate reagent or starting material in each of the following
reactions.
18
19

Ilovepdf Merged 3

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Ilovepdf Merged 3

Uploaded by

Copyright:

Available Formats

CEB1013 ORGANIC CHEMISTRY

Course Learning Outcome:

▪ Common name cannot be applied for complex alkyl halide.

2. Name the following compounds using IUPAC method.

3. Classify each compounds in problem 1 and 2 as 1°, 2°, or 3°.

4. Give the structure corresponding to each name.

5. Rank the compounds in each group in order of increasing boiling point.

▪ In a general substitution reaction, Y replaces Z on a carbon atom.

Substitution: a reaction in which an atom or a group of atoms is replaced

Elimination: a reaction in which elements of the starting material are “lost”

▪ In an elimination reaction, two groups X and Y are removed from a starting

Elimination: a reaction in which elements of the starting material are “lost”

Addition: a reaction in which elements are added to a starting material.

▪ In an addition reaction, new groups X and Y are added to a starting material.

Addition: a reaction in which elements are added to a starting material.

Addition and elimination reactions are exactly opposite. A π bond is formed in

1. A one-step reaction is called a concerted reaction. No matter how many

2. Breaking a bond by unequally dividing the electrons between the two

▪ A full-headed curved arrow shows the movement of an electron pair.

Homolysis and heterolysis generate radicals, carbocations, and carbanions, the

▪ Radicals and carbocations are electrophiles because they contain an electron-

2. Classify each transformation as substitution, elimination, or addition.

3. By taking into account electronegativity differences, draw the products formed

4. Use full-headed or half-headed curved arrows to show the movement of

5. Draw the products of each reaction by following the curved arrows.

Course Learning Outcome:

1. To construct nucleophilic substitution reaction from the given reactant

1. R—An alkyl group R containing an sp3 hybridized carbon bonded to X.

▪ Whether an alkyl halide is 1°, 2°, or 3° is the most important factor

These organic halides are These organic halides do

▪ Alkyl halides undergo substitution reactions with nucleophiles.

▪ Alkyl halides undergo elimination reactions with Brønsted–Lowry bases.

The Nucleophile vs Basicity:

The Nucleophile vs Basicity – The Exception: Steric Hindrance

▪ For example, although pKa tables indicate that tert-butoxide

▪ Left-to-right across a row of the periodic table, basicity decreases so

▪ Down a column of the periodic table, basicity decreases so leaving

The Leaving Group:

▪ When a neutral nucleophile is used, the substitution product bears a positive

2. Draw the products of each nucleophilic substitution reaction.

3. Analyse which of the following nucleophilic substitution reactions will take

Compound pKa Compound pKa

▪ To understand the mechanism of this reaction, though, we must know the

There are three possibilities.

▪ If the C – X bond is broken as the C – Nu bond is formed, the

▪ If the C – X bond is broken first and then the C – Nu bond is formed,

▪ If the C – Nu bond is formed first and then the C – X bond is broken,

Course Learning Outcome:

1. To compare and contrast SN1 and SN2 reactions mechanism.

▪ What are the general features of this mechanism?

▪ Changing the concentration of either reactant affects the rate.

Stereochemistry of the SN2 Reaction

Stereochemistry of the SN2 Reaction

Stereochemistry of the SN2 Reaction

▪ All SN2 reactions proceed with backside attack of the nucleophile,

4 The Identity of the R Group.

▪ Methyl and 1° alkyl halides undergo SN2 reactions with ease.

4 The Identity of the R Group.

5 How to draw the SN2 mechanism?

5 How to draw the SN2 mechanism?

2. Identify which SN2 reaction in each pair is faster?

3. Consider the following SN2 reaction:

a. Draw a mechanism using curved arrows.