ORGANIC CHEMISTRY : MIDTERM EXAM

STUDENT NAME:
Duong Phuong Nam
2
Student ID : 20190635
CLASS ID: 128403
 ORGANIC
CHEMISTRY
Contents
▹ Organic chemistry
▹ Chemical bonding
▹ Effects Organic Chemistry
3
▹ Acid-Base in OC
▹ Hydrocarbons
▹ Halogen Directions
 1. Organic
chemistry
3 sources :
Carbonized organic /Living
organism/Invention , human
ingenuity
1. Characteristics: 2. Classifications
Organic compounds: + Open rings : saturated,
- Combustible unsaturated + Loop rings
compounds, easily : saturated, unsaturated ,
decomposed, volatile aromatic rings
- The covalent bond is
predominant.
- The reaction occurs 5

slowly, in the direction,

occurs incompletely,
under conditions
- Very rich in number,
types, complex in
structure
- Play an important role
in life.
I. Homogeneity
# Are substances with 2
characteristics:
- Have the same chemical
Structure; The molecular
composition is less than one or
more CH2 group
6

II. Isomer
l. Definition:
-Substances are said to be isomers if
they have 2 characteristics; They have
the same molecular structure; Structural
differences
II. Classify

#2.1. Structural isomers

- Isomers of carbon chain
- Site isomer
- Function group isomer
7
- Bonding isomer
- Mutative isomer

# 2.2 Stereoisomers
- Geometric isomers
- Optical isomers
IV. ATOMIC ORDER C AND
ORGANIC COMPOUNDS
Atomic C Order of organic Radical
compounds
Most are the order R: (CH2_R1)
of C atoms, except 8
for amines (which is
the order of N)
 V. TYPES OF ORGANIC
AGENTS AND REACTIONS
▹ 1. Types or agents
▹ a, Nucleophilic agent - Bearing sign includes anions:
molecules, groups of atoms attack the rich in (+) charge the
most
EX: Off. CT, NHS 9

▹ b. Free radical agent - Atoms and groups of atoms with an

odd charge, preferentially attack the sites rich
▹ 2. Types or organic reactions
▹ 2.1. Substitution reaction (S)
▹ Replace a group atom of one atom with a group of another
atom.
 V. TYPES OF ORGANIC
AGENTS AND REACTIONS
▹ a/ Electrophilic substitution reaction SE divorce break
(very important and common reaction in the substitution of
aromatic hydrocarbons)
▹ b/ Nucleophilic substituent (SN )
SNI : single molecule 10

SN2 : bimolecular
(This reaction is very important with halogen
derivatives and open-chain alcohols.)
▹ c. Free radical potential (SR )
 V. TYPES OF ORGANIC
AGENTS AND REACTIONS
▹ 2. Types of organic reactions
▹ 2.2. Addition reaction: 2 atoms of a molecule joined
together.
a, Addition electrophile AE
b, Addition nucleophile AN 11

c, Addition free radical AR

▹ 2.3. Elimination reaction (E)
▹ 2.4 polymerization reaction
▹ 2.5. Displacement reaction displacement of an atom or a
group of atoms.
* The reaction mechanism is all the detailed steps in the
reaction process.
 V. Basic Method
Simple Distillation
Fractional
Separation of one
Distillation
Distillation
liquid from another at reduce P
Distillation of many Separation of
completely soluble liquids with high V12
liquids based on a or at high t0that are
different decomposed
distribution
Steam-charismatic Extraction
Separation of It is a common
Crystallize
volatile liquids by method used to As a method to purify
steam, slightly purify and isolate solids. based on other
soluble or insoluble organic compounds; solubility of solid organic
Usually used for compound suitable solvent
extraction create a hot saturated
solution then cooled to
obtain a clean
2. CHEMICAL
BONDING
CHEMICAL BONDING
1.Directed valence 2. Bonding' s
theory : Hybridization:
The direction of the -3 bonds due to 3 orbitals px
chemical bond is , py, pz, bonded 14

determined such that: perpendicular to each other

the bonding e orbital are (according to coordinate
overlapped to the axis) and 1 bond due to-the
maximum extent within participation of orbs will
a given distance between have no definite direct with
the atomic nuclei less overlap
 “
. Link hybridization –
-Prior to bonding. the different bonding
orbs (s and p) of the C element have
create more stable and homogenous
hybridized orbs (greater overlapping
capacity) than those of C. orb has not yet
hybridized.
-Actually a combination of the orb wave
functions s and p
- When creating a new link. the shape of
the hybrid orbs will be different from the
original
15
 Hybrid types

2.1 Hybridization of (tetra-hybridization)

- It is a case where 1 orb s hybridizes with 3 orb p ( px ,py ,pz resulting in 4 identical hybrid orb s
directed from the center to the 4 vertices of regular tetrahedron with a vertex angle of 1090 28’.
- Sp3 hybridization is common in saturated compounds
- Maximum overlapping capacity (overlapping radius) =2
2.2 Hybridization sp2
- It is the case where I orb s hybridized With 2 orb p (px py creating 3 identify hybrid orb s lying
on a plane from the center to the vertex of an equilateral triangle with vertex angle of 1200
- Sp2 hybridization is common in unsaturated compounds containing double bond (alkenes )
- Interlayer ability (interlacing radius)
2.3 Hybridization sp (line hybridization)
- This is a case 1 orb s hybridizes with 1 p orb, creating 2 identical hybrid orb lying on a straight
Ime with a peak angle of 180
- Sp hybridization is common in unsaturated compounds containing triple bonds (alkenes...)
Ability to overlap (radius of overlap) = 1.93

16
CONCLUSION

17
3.Common types or bonds in organic chemistry
3.1 Bonds a
- Is a link created by the overlapping of orbs whose orientation
symmetry axis coin the bond axis. Therefore => overlap max at
the link axis
- This overlap is called axial overlap. Electrons that form bonds
are called e
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- Can be formed by overlapping s-s orbs; s-p; p-p - are
characteristic of saturated compounds
*Bonding properties
-The bond is very durable due to: axial interspersion . Large
interjecting capacity
 
3.Common types or bonds in organic chemistry
3.2 Bonds
- A link created by the overlapping of orbs with // or near //
symmetry axis to and perpendicular to the link axis.
Overlapping occurs off-axis.
-This overlap is called lateral overlap. Orb creates a link called
e
-The bond is formed by the overlap between the p-p orbs; p-d;
d-d - bonds are characteristic of unsaturated compounds 19

-Bonding properties + The bond is unstable due to: side

overlapping. so the ability to overlap is small + Orb has no axial
symmetry but only passes through mp nodes containing that
axis -> bond is easily polarized. easily broken +Because the
bond m is not stable. the e are very flexible 3.3 Bonds α :
Bond is very weak
- Conclude: About durability: σ> > α
3. EFFECTs ORGANIC
CHEMISTRY
INDUCTIVE
I. Concept of effects (theory of e -displacement in
molecules)

The properties of an atom or group of atoms are influenced

not *by the attached to it. but also by other indirect atoms
present in the molecule. 21
• Due to different causes (difference in electronegativity. to
the density of e covalent bond is unevenly distributed
causes e shift -> changes the density Conclusion
Introducing the concept of effects
 Definition: Effect is a concept that characterizes the
propagation of mutual influence between atoms in a
molecule causing an electron shift on the bonds to
polarize in molecule
 II. Inductive Effect

1/ Concept: Consider two simple molecules with bonds o,

propane and Il-propyl chloride.
We see that unlike propane. n-propyl chloride has a strongly
polarized C1-C1 bond t chlorine. which is more electronegative.
- Therefore. the chlorine atom caries a partial negative charge ϐ. 22
The C1 atom has a positive charge ϐ
- C bond is also polarized towards CI _ The C2-C3 bond turn is
also polarize towards C2, although the polarization is already
much weaker..
In addition, polarization also occurs at the C-H bonds in the
molecule. The overall result is that the molecule becomes polar
 II. Inductive Effect

1/ Concept
- The inductive effect (I) characterizes the displacement of
electrons along the bond (single bond), because an atom or of
atoms has a different electronegativity : the electronegativity
of the atom cause by C
23
- - Symbol I : Or for simplicity denoted by I (Inductive Effect)
- The direction of the density shift e in the inductive effect is
depicted by a straight ( —> ) along the bond axis, the
direction is from the atom with small atom with high
electronegativity
 II. Inductive Effect

2/Classify
2.1. Static inductive effect (Is ):
- is the inductive effect that forms in the molecule in the :
isolated State (static state) Cause: due to polarity
- Sign convention: to classify groups of atoms according to the 24
I effect, the convention that H bonded to c in has Is - O
- Atoms or groups of atoms X (C X) that have a stronger
electron attraction than H are considered —Is
- Those atoms or groups of atoms Y (Y C) that have the ability
to electrons strongly than H are said to be -Is
 II. Inductive Effect

2/Classify
2.1.1 Inductive effect +Is :
Appear :
+Charged group (-) / Alkyns
25

-In the ankyl group, the +Is effect increases by branching or

level of the group:

- CH3 <- CH3-CH2 <- CH (CH3)2 <- -C(CH3)3

 II. Inductive Effect

2/Classify
2.1.2 Inductive effect -Is :
-Appears commonly in groups: unsaturated, charged groups (+),
or groups with high electronegativity such as halogen groups.
- The variation in the strength and weakness of -Is in groups of 26
atoms obeys some of the following laws
- One of the most obvious manifestations of the Induction Effect
is the influence different substituents on the acid strength of
saturated carboxylic acids.
-For example. when replacing an H atom at position a in a
molecule of acetic acid with a halogen atom X the Ka of the acid
increases tens or even hundreds of time
 II. Inductive Effect
2/Classify
2.1.3 Characteristics Of Is : - Is the transfer of electrons o along
the C's chain and along the bond axis electronegative atom to the
more electronegative atom.
- The very important property of the inductive effect I is to
decrease very quickly when the chain of the bonds is
prolonged (usually through 3C, the inductive. effect loses its 27

effect.

2.1.4 Method Of determining the and mark of I: There two

methods.
 II. Inductive Effect

2/Classify
2.2. Dynamic inductive effects :Id
- Formed by the transfer of electrons in the molecule when there
is an external or an electrically charged reactant.
- Cause: Due to polarization 28

-Characteristics + Is ,+ ld changed in the same direction

-

- -Is , -Id with halogen group change in opposite directions

- When the agent is NaOH -> decide. Because – Id of l>- Id of
C1 -> Reaction (2) is more likely.
 II. Inductive Effect

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4/ Application
- Effect -I increases acidity and decreases basicity
- Effect +I reduce acidity and increases basicity
- Explain the act of OC
- Explain the acid and base properties of OC
4. EFFECTS IN
ORGANIC
CHEMISTRY
CONJUGATE EFFECT
HYPER-CONJUGATE
EFFECT
 Ill. Conjugate Effect

1. Conjugate system
2. These are systems that satisfy the following conditions: The
syst Single bonds and double bonds alternate, called a
bonding
3. A system with an undivided electron p (not in a bond) is 31
conjugate double bond through a single bond o, called the
conjugate system p-pi
 Ill. Conjugate Effect
1.2. Conjugation effect concept (C)
- Define: The conjugation effect characterizes the displacement
of the electrons p. along double bonds in a conjugated system.
either by a more electronegative atom or by an external force.
- Direction of electron displacement in conjugation effect:
• The conjugation effect that occurs in the pi—pi conjugate 32

system is called conjugation effect: pi -pi

- The direction of the curved allow goes from the bond z to the
more a, or - Conjugation effect occurs in p —pi conjugate
systems, called the p— pi conjugation effect multiple bond
- The direction of the curved among goes from the undivided
electron pair towards multiple bond.
 Ill. Conjugate Effect
1.3. Classify

• Similar l, conjugation effects are of two types: Cd - Static

conjugation effect occurs in a molecule in a stationary (isolate -
Static conjugation effects are also classified into 2 types +Cs &
-Cs 33

- Dynamic conjugation effects occur in molecules under the

influence o external conditions such as electric fields. light.
reactants...

- Dynamic conjugation effects are also classified into 2 types –

Cd & +Cd
 Ill. Conjugate Effect
1.3.1 positive conjugation effect (+C)
The X groups with the +C effect in general all have residual
electron pair participate in the e-shift in the direction of the pi
bond
-The X groups with the +Cs effect in general all have residual
electron participate in the e-shift in the direction of the bond pi 34
 Ill. Conjugate Effect
1.3.2 Negative conjugation effect.(-C)
- Effect groups - C are unsaturated groups containing C with the
C=Y, or some other group that doesn’t contain C like N02
group.
- The force of the -C effect depends on the electronegative
* There are a few rules: In groups C=Y : -C depends on Y 35

*The more electronegative Y is, the stronger the -C.

- -C: C=0 > C=NR > C=CR2
*Cations always have a —C effect greater than the
corresponding groups of neutral atoms:
• -C: C=N+R2 > C=NR
 Ill. Conjugate Effect
1.3.3 Characteristics and properties of the conjugation effect
- The conjugation effect is not attenuated or changed very 1itt1e
by conjugate chain
-

36

- Some substituents are unsaturated, the sign of the conjugation e

depending on the group of atoms associated with it:
 Ill. Conjugate Effect
1.3.3 Characteristics and properties of the conjugation effect
- Conjugation effect is valid only on planar conjugate systems:

37

1.4 Direction or application of the conjugate effect:

- Explain some reaction mechanisms
- Explain the high reactivity of some compounds
- Explain the suppression or reduction of basic properties of
some compounds containing N
- Explain the color properties of some compounds
IV. 38

Hyper-Conjugation
 IV: Hyperconjugation Effect

2. Define:

-The super conjugation effect occurs due to the interaction of a

electrons (in C-H, N-H bonds) with electrons through 1 o bond.

- +H is stronger the more H atoms in Ca: 39

 IV: Hyperconjugation Effect

# Positive hyperconjugation effect

*

40

* However, in fact, due to the effect of +H, the main product is

 IV: Hyperconjugation Effect

# Negative hyperconjugation effect (-H)

*

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Effect of super conjugation the stability of carbocations
• The more positive cations is released (the smaller), the more
stable the cation.
• • Strength due to electron repulsion of +H , +I:
 IV: Hyperconjugation Effect

Carbonation stability

+Because +C of-C6H5 is stronger than +I, +H of —C .

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+The more charge is released the more stable t carbocation.

 IV: Hyperconjugation Effect

4. Direction or application or hyperconjugation effect

- Explain the mobility of the Ha atom

- Explain the reactivity of some compounds with the H effect
- Explain the thermodynamic stability of some compounds H
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- Effect expands The thermodynamic stability increases.
- Explain reaction direction, some rules, laws..
 Chapter 5:
Acid-Base in organic
chemical
Bronsted Acids & Bases

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46
 “
Quotations are commonly
printed as a means of
inspiration and to invoke
philosophical thoughts
from the reader.

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Conjugate Acids and Bases

•A conjugate acid is the particle

formed when a base gains a 48

hydrogen ion.

•A conjugate base is the particle

that remains when an acid has
donated a hydrogen ion.
•A conjugate acid-base pair consists of two
substances related by the loss or gain of a
single hydrogen ion.
•A substance that can act as both an acid and a
base is said to be amphoteric.

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Ka - the Acidity Constant

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Want big impact? Use big image.
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 pKa - the Acid Strength Scale

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 And tables to compare data

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•A Lewis acid is a substance that can
accept a pair of electrons to form a
covalent bond.
•A Lewis base is a substance that can
donate a pair of electrons to form a
covalent bond.

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Summary

Bronsted-Lowry Lewis Theory

Theory Acids can accept a free 55
Acids are substances that pair of electrons
can donate protons H+
Bases can donate their
Bases are substances that free electron pair
can accept protons H+
When comparing acidity, Bronsted theory should be used:
The more readily protonated a substance is, the more acidic it
is.

When comparing basicity , Lewis’s theory should be used:

The more readily a substance gives a free electron pair, the stronger the basicity
due to the greater electron density on the heteroatom

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 Chapter 6:
Saturated & Unsaturated
Hydrocarbons
 Atoms are linked together
by single bonds
Part1: Alkanes
Open-chain saturated hydrocarbons with the
general formula

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 “
Butane

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Physical Properties of Alkanes

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Nomenclature
Nomenclature

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Nomenclature

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A picture is worth a thousand words

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The Most Common 65

Alkyl Substituents
and Their Names
Combustion Reactions of Alkanes

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 Substitution Reactions of Alkanes

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 Dehydrogenation Reactions of Alkanes

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Nitrification Reaction

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From unsaturated hydrocarbons

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 Salt pyrolysis of carboxylic acids

Aluminum Carbide
Al4C3 + 12H2O → 3CH4 + 4Al(OH)3

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 ▪ Alkenes: hydrocarbons that contain
at least one carbon–carbon double
Part2: Alkenes
bond. [CnH2n]
CH3–CH=CH2 propene

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 IUPAC Nomenclature

•Parent is longest chain containing the double

bond -ane changes to -ene (or -diene, -triene)
•Chains are numbered to give the double bond 73

the smallest possible number.

•In a ring, the double bond is assumed to be
between carbon 1 and carbon 2.
Nomenclature Examples

74
 Ethene ( The simplest Alkenes)

● Ethene has two sp2-

hybridized C atoms
● Each C has one
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unhybridized p orbital as
well
● The sp2 orbitals are in a
trigonal plane, 120°apart.
 2p Orbitals and the Pi (p) Bond
z
•One p orbital on each C of ethene
•Overlapping sp2 orbitals form form a bond known as a pi
bond. a sigma (s) bond.
•The p bond is formed at a 90°angle from the s bond.

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Derivatives and Isomers of Alkenes

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Derivatives and Isomers of Alkenes

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Addition Reactions

▪ Pi Bonds (which are weaker than the C—C bonds), are

broken, and new bonds are formed to the atoms being
added.
 Halogenation Reactions

▪ Addition of halogen atoms of alkenes

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 Addition to asymmetric alkenes

81
 Addition to asymmetric alkenes

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 Addition to asymmetric alkenes

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Polymerization reaction

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85
 ● Alkynes: hydrocarbons containing at least
one carbon–carbon triple bond. [CnH2n-2]

Part3: Alkynes
CH3–CH2–CΞC–CH3 2–pentyne

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 ▪ Alkenes: hydrocarbons that contain
at least one carbon–carbon double
Part4: Alkadienes
bond. [CnH2n]
CH3–CH=CH2 propene

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 Bonding in Conjugated Dienes

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96
 Halogen Addition to Dienes

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 A 𝝅 molecular orbital analysis of a dienes reaction

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From Butane

From 2-Methyl Butane

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Chapter 7: Aromatic
 

Hydrocarbons
 “
ARENS
Arens are cyclic hydrocarbons
containing at least one benzene
nucleus in the molecule: 
CnH2n-6 ( n ≥ 6 )
Aromatic hydrocarbons
containing one or many benzene
rings ( polynuclear compounds )

102
 Aromatic polynuclear
compound

Condensed compound Unconnected compound

( the benzene rings have mutual C ( the benzene rings bind
atoms; condensing at ortho pos (o-) directly by C-chains )

Straight polynuclear Diagonal polynuclear

( the ring’s centers ( the ring’s centers
make a straight line ) make broken lines )

103
SOME ARYL RADICALS
The common name for aromatic hydrocarbons with a benzene ring is aren. If
a hydrogen atom (H) is separated from aromatic hydrocarbons, the initial
aromatic hydrocarbon radicals are called aryl radicals (denoted Ar).

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STRUCTURE
- The structure of benzene according to classical theory: Benzene was discovered by
Michael Faraday in 1825, but it was not until 1866 that Kekulé suggested the
molecular formula for benzene was C6H6.

- According to Kekulé, the benzene ring is a ring made of 6 C- H groups, so each C

atom will have one valence remaining. The C atoms will use this valence to form 3
double bonds, like a cyclohexatriene. These three double bonds are not fixed, but
there are displacements between the double and single bonds.

105
- Kekulé's benzene ring formula is the most accepted because in the cyclic
system, the properties of the double bond are reduced, making it more difficult
to add than open-chain unsaturated compounds. However, due to the single
bond there is a substitution reaction.
- Since the length of C-C bonds is 1.54Å, is 1.34k, benzene will not be a regular
hexagon.
- This formula does not explain the chemical properties of benzene. which is
easy to participate in substitution reactions, difficult to participate in addition
reactions.

106
MODERN THEORY BENZENE STRUCTURE
The benzene ring is a regular hexagon with a symmetrical Structure.
C-C bond length is 1.39 Å; C-H is 1.08 Å,
6 carbon atoms have sp2 hybridization state, valence angle is 1200.
6 p electrons are not located on 3 separate π bonds but are released on all 6 bonds. These 6
bonds are completely identical and feature a partial double bond forming a hexagonal π
system that is released over the entire ring.
This release, which is completely symmetrical, covers the entire molecule and makes the
benzene ring exceptionally stable (energy 36 kcal/mol).

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108
THE CONCEPT OF AROMATICITY
The formation of the π-electron system is what causes benzene
and its homolog, as well as other planar aromatic polycyclic
systems, to be aromatic
Benzene is typical for aromatic systems (electron systems with a
special structure) exhibiting the following properties:
- Relative stability in terms of thermodynamics
10
- The electrons must be paired and the number Of electrons must 9
satisfy Hückers rule of having (4n+2) eπ
Formally very unsaturated (CnH2n-6) but actually satiated and
relatively inert
The tendency to participate in the substitution reaction is
dominant (because in the reaction the conjugate system is
preserved)
The tendency to participate in addition reactions is decreased
(because the addition reaction breaks the conjugate system in the
ring)
Hard to oxidize and no polymerization
NAPHTHALENE STRUCTURE (molecular, C10H8)
Naphthalene molecule consists of 2 benzene rings condensed at the ortho position:

Naphthalene has 2 condensate rings with the number of electrons π in the conjugate system is
10 (satisfying the Hückel formula for the number of electrons π
Because Of the uneven bond length and electron density, naphthalene is less aromatic than
benzene. Naphthalene is more active than benzene, readily participates in substitution, addition
oxidation reactions.

110
CHEMICAL PROPERTIES
Because the molecule with an electron system has a special
structure, is thermodynamically stable, and is aromatic, the
chemical properties of benzene and its homologue are
shown in the following reactions:
The electrophilic substitution reaction on the aromatic
nucleus (SEAr) and the substitution reaction occurs in a 11
1
regular manner
Addition and oxidation reactions take place under strict
conditions
The isomers of benzene, in addition to the substitution
reaction in the aromatic nucleus, also have the reaction in
the branch chain (alkyl radical) according to the SR
radical . substitution mechanism
Electrophilic substitution reaction (SE)
#General diagram of the reaction

+ The electrophilic agent is an cation or an X-Y polar molecule.

#The reactions of SE substitution into the aromatic ring depend on:

- Calculate the basicity of the benzene ring (electron density in the ring)
- Electrophilicity of the reactant
- Catalysts increase the generation of electrophilic agents

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113
SOME RESPONSIBILITIES OF BEZEN SE

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115
116
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118
119
120
ADDITIVE REACTION
+ Because of the closed conjugated π-electron system, the addition reaction to the benzene
ring is more difficult than that of the Opel-chain unsaturated hydrocarbons.
+ The reaction occurs at high temperature or with strong illumination and catalysis.

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122
OXIDATION
REACTION

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SUBSTITUENT REACTIONS IN THE BRANCH
CHAIN
+ The radical substitution reaction (SR) Of alkyl groups in alkylbenzenes occurs more
easily than in alkanes.
+ SR mechanism is similar to alkanes.

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 Chapter 8
 

Halogen directions
CONCEPT
Halogen derivatives are formed when the hydrogen atom(s) of a hydrocarbon are replaced
with halogen atoms
CLASSIFY
- Halogen derivatives Of open-chain hydrocarbons (saturated, unsaturated)
- Halogen derivatives of saturated cyclic hydrocarbons
- Halogen derivatives of aromatic cyclic hydrocarbons:
+ halogen atom directly bonded to the aromatic ring
+ halogen atom bonded to the branched carbon Of the ring

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NOMENCLATURE
Common name and IIJPAC name
Common name
Hydrocarbon name + Halogen name + ua

IUPAC name
- Number the carbon halogen group
- Name in order
Halogen position + Halogen name + Name of hydrocarbon

Some derivatives are used by IUPAC:

CHCl3 – Chloroform ; CHBr3 – Bromoform ; CCl4 – Carbon tetra chloride

127
For halogen derivatives of hydrocarbons with multiple bonds, the name must be given first before
the halogen atom

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129
130
 NUCLEOPHILIC SUBSTITUTION REACTION (SN)
Substitute the halogen atom by the nucleophilic agent Y-
General diaqram

R: Hydrocarbon
X: Halogen (Cl, Br, l)
Y-: nucleophil factor
Y- can be anions : OH-, RO-, HaI-, CN-, RCOO-, SCN-,
Y- can be molecules: H2O, NH3, ROH, RNH2,..

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Some nucleophilic substitution reactions of halogen
derivatives

Halogen derivatives hydrolysis

Williamson’s ete process
Kolbe’s nitril process
Este process
Alkyne process
Hoffmann’s amin process

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MECHANISM OF THE NUCLEOPHILIC SUBSTITUTION
REACTION
Depending on the number of molecules pancipating in the rate- determining
phase of the reaction (the slow phase forming an intermediate state)
Classification
+ Single-molecule nucleophilic reaction (S N1)
+ Bimolecular nucleophilic reaction (S N2)
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3
13
4
SN2 REACTION
The reaction occurs in one stage
The slow phase determines the rate of the
reaction involving nucleophilic agents and
reactants, so is called a bimolecular
nucleophilic substitution reaction (SN2).
Reaction speed equation
v = k[R-X].[Y-]
In the transition state, the break of the bond
and the formation of a new bond occur
simultaneously (the old bond C-X has not
completely broken and the new bond has not
completely formed)
The product has configuration rotation if the
original halogen derivative is photoactive
SN1 REACTION
The reaction occurs in two stages
The slow phase determines the rate of a
reaction with only reactants involved,
so it is call a single- molecule
nucleophilic substitution reaction (SN1)
Reaction speed equation
V = k[R-X]
Breaking old links and forming new 13
5
ones do not happen at the same time.
The intermediate product is a
carbocation with a planar structure, the
carbon in the sp2 hybridized state
The reaction for the mixture of
products due to the nucleophilic attack
on both sides of the carbonation is the
same. If the original halogen derivative
is photoactive, the product is the
Racemic variant
FACTORS AFFECTING THE NUCLEOPHILIC
SUBSTITUTION REACTION

The factors that determine (or facilitate) a reaction can be

quite a few, such as: the nature of the halogen derivative, the
nature of the nucleophilic agent, the nature of the solvent, the
concentration, the temperature, etc.
13
The nature of the halogen atom in R—X 6

Reactivity decreases with the sequence:

R—I > R—Br > R—Cl > R—F
Due to the -Id of the halogen arranged :
I > Br > Cl > F
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STRUCTURAL NATURE OF HYDROCARBON RADICALS IN
R-X

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STRUCTURAL NATURE OF HYDROCARBON
RADICALS IN R-X
Allyl- and benzyl- radicals: The allyl and benzyl halides, in
contrast, are more active than the alkyl halides

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THE NATURE OF THE NUCLEOPHILIC AGENT Y-

The weak nucleophilic agent promotes the S N1 response

Strong nucleophile favorable for SN2 reactions
The effect Of nucleophilic agents is mainly on the S N2 mechanism.
The SN2 reaction depends on the nucleophilic force and the
concentration of the nucleophilic agent Y- 14
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The nucleophilic force of agent Y- is arranged as follows
I- > Br- > Cl- > F-
NH2- > RO- > HO- > R2O- > ArO- > NH3 > H2O
SOLVENT
Without solvent, the SN1 and SN2 reactions do not occur
Polar solvents containing protons (water, ethanol, methanol...)
favoring the SN1 reaction due to the salvation of R + and halogen ions
by hydrogen bonding with the solvent

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Less polar solvents are favorable for SN2 reactions

LEAVING GROUP

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