UNIDAD CURRICULAR: QUÍMICA IV

MODULO: QUÍMICA ORGÁNICA

DOCENTE: YAVIELY CASTILLO

TEMA I
Reacciones de sustitución

Mechanism of the Reaction of Alcohols with

Hydrogen Halides
¿Qué relación tiene esta imagen con un mecanismo de
reacción?
Contents

 Alcohols and Alkyl Halides

 Preparation of Alkyl Halides from Alcohols and Hydrogen Halides

 Mechanism of the Reaction of Alcohols with Hydrogen Halides

 Potential Energy Diagrams for Multistep Reactions: The SN1 Mechanism

 Structure, Bonding, and Stability of Carbocations

 Effect of Alcohol Structure on Reaction Rate

 Reaction of Methyl and Primary Alcohols with Hydrogen Halides: The

SN2 Mechanism

 Ejercicios
Alcohols and alkyl halides

The conversion of alcohols to alkyl halides by reaction with

hydrogen halides:

4
Alcohols and alkyl halides

https://www.chemistrysteps.com/introduction-alkyl-halides/

5
Preparation of Alkyl Halides from Alcohols
and Hydrogen Halides

6
Mechanism of the Reaction of Alcohols with
Hydrogen Halides

Step 1: Proton Transfer

7
Mechanism of the Reaction of Alcohols with
Hydrogen Halides

Step 2: Carbocation Formation

the step is unimolecular

8
Mechanism of the Reaction of Alcohols with
Hydrogen Halides
Step 3: Reaction of tert-Butyl Cation with
Chloride Ion

The transition state

9
Mechanism of the Reaction of Alcohols with
Hydrogen Halides

10
Potential Energy Diagrams for Multistep Reactions:
The SN1 Mechanism

Potential energy diagram

for the reaction of tert-
butyl alcohol and hydrogen
chloride according to the
SN1 mechanism

11
Structure, Bonding, and Stability of Carbocations

12
Structure, Bonding, and Stability of Carbocations

Electrostatic potential maps of carbocations. The positive charge (blue) is most

concentrated in CH3+ and most spread out in (CH3) 3C +.

13
Effect of Alcohol Structure on Reaction Rate

Energies of activation for formation of carbocations from alkyloxonium ions of methyl,

primary, secondary, and tertiary alcohols.

14
Reaction of Methyl and Primary Alcohols with Hydrogen
Halides: The SN2 Mechanism

Problema 1 1-Butanol and 2-butanol are converted to

their corresponding bromides on being
heated with hydrogen bromide. Write a
suitable mechanism for each reaction, and
assign each the appropriate symbol (SN1 or
SN2).

15
Reaction of Methyl and Primary Alcohols with Hydrogen
Halides: The SN2 Mechanism

16
Ejercicios
2) Although useful in agriculture as a soil fumigant, methyl bromide is an ozone-
depleting chemical, and its production is being phased out. The industrial
preparation of methyl bromide is from methanol, by reaction with hydrogen
bromide. Write a mechanism for this reaction and classify it as SN1 or SN2.

3) Deuterium oxide (D2O) is water in which the protons (1H) have been replaced
by their heavier isotope deuterium (2H). It is readily available and is used in a
variety of mechanistic studies in organic chemistry and biochemistry. When D2O
is added to an alcohol (ROH), deuterium replaces the proton of the hydroxyl
group.

The reaction takes place extremely rapidly, and if D2O is present in excess, all the
alcohol is converted to ROD. This hydrogen–deuterium exchange can be catalyzed
by either acids or bases. If D3O+ is the catalyst in acid solution and DO the
catalyst in base, write reasonable reaction mechanisms for the conversion of ROH
to ROD under conditions of (a) acid catalysis and (b) base catalysis.

17
Ejercicios

18
Ejercicios
4) Classify the elementary steps in the mechanism according to their molecularity.

A. Step 1 is unimolecular; step 2 is bimolecular.

B. Step 1 is bimolecular; step 2 is unimolecular.
C. Both steps are unimolecular.
D. Both steps are bimolecular.

5) By applying Hammond’s postulate to the potential energy diagram for this

reaction, we can say that:

A. the structure of 2 is more carbocation-like than 4

B. the structure of 2 is less carbocation-like than 4
C. the structure of 2 resembles 1 more than it resembles 3
D. the structure of 4 resembles 5 more than it resembles 3

19
 UNIDAD CURRICULAR: QUÍMICA IV
MODULO: QUÍMICA ORGÁNICA
DOCENTE: YAVIELY CASTILLO

TEMA 2
Reacciones con radicales libres

Mechanism of the Reaction of Alcohols with

Hydrogen Halides
Contents

 Halogenation of Alkanes

 Chlorination of Methane

 Structure and Stability of Free Radicals

 Mechanism of Methane Chlorination

 Halogenation of Higher Alkanes

 Ejercicios
Halogenation of Alkanes

Describes a completely different

method for preparing alkyl
halides, one that uses alkanes as
reactants.
The reactivity of the
halogens decreases in the
It involves substitution of a
halogen atom for one of the order F2 > Cl2 > Br2 > I2
alkane’s hydrogens.

22
Chlorination of Methane

Alcohols are converted to

alkyl halides in reactions
involving ionic (or “polar”)
intermediates—
alkyloxonium ions and
carbocations.

The intermediates in the

chlorination of methane
and other alkanes are
quite different;
they are neutral
(“nonpolar”) species
called free radicals

23
Structure and Stability of Free Radicals

24
Structure and Stability of Free Radicals

Homolytic cleavage

Heterolytic cleavage

25
 Structure and Stability of Free Radicals

The bond dissociation

enthalpies of
methylene and methyl
COH bonds in
propane reveal a
difference in stabilities
between two isomeric
free radicals. The
secondary radical is
more stable than
the primary.

26
Mechanism of Methane Chlorination

27
Mechanism of Methane Chlorination

28
Mechanism of Methane Chlorination

The elementary steps (1) through (3) describe a free-radical chain

mechanism for the reaction of an alkane with a halogen.

29
TIPS

30
Ejercicios
1) Cyclopropyl chloride has been prepared by the free-radical chlorination of
cyclopropane. Write a stepwise mechanism for this reaction.

2) In both the following exercises, assume that all the methylene groups in the
alkane are equally reactive as sites of free-radical chlorination.

(a) Photochemical chlorination of heptane gave a mixture of monochlorides

containing 15% 1-chloroheptane. What other monochlorides are present?
Estimate the percentage of each of these additional C7H15Cl isomers in the
monochloride fraction.

(b) Photochemical chlorination of dodecane gave a monochloride fraction

containing 19% 2-chlorododecane. Estimate the percentage of 1-chlorododecane
present in that fraction.

31
 UNIDAD CURRICULAR: QUÍMICA IV
MODULO: QUÍMICA ORGÁNICA
DOCENTE: YAVIELY CASTILLO

TEMA III
Reacciones de eliminación

Structure and Preparation of Alkenes

Contents

 Structure and Bonding in Alkenes

 Preparation of Alkenes: Elimination Reactions

 Dehydration of Alcohols

 Regioselectivity in Alcohol Dehydration: The Zaitsev Rule

 The E1 and E2 Mechanisms of Alcohol Dehydration

 Rearrangements in Alcohol Dehydration

 Anti Elimination in E2 Reactions: Stereoelectronic Effects

 Ejercicios
Structure and Bonding in Alkenes

(a) The planar framework of bonds in ethylene showing bond distances and
angles.
(b) and (c) The p orbitals of two sp2-hybridized carbons overlap to produce a
bond.
(d) The electrostatic potential map shows a region of high negative potential
due to the electrons above and below the plane of the atoms.

34
Structure and Bonding in Alkenes

35
Preparation of Alkenes: Elimination Reactions

Alkene formation requires that X and Y be

substituents on adjacent carbon atoms.

36
Dehydration of Alcohols

In the dehydration of alcohols, the H and

OH are lost from adjacent carbons. An
acid catalyst is necessary.

37
Regioselectivity in Alcohol Dehydration: The Zaitsev Rule

Here, a double bond can be generated

between C-1 and C-2 or between C-2 and C-3.
Both processes occur but not nearly to the Dehydration of this alcohol is
same extent. Under the usual reaction selective in respect to its
conditions 2-methyl-2-butene is the major direction.
product, and 2-methyl-1-butene the minor
one.

38
Regioselectivity in Alcohol Dehydration: The Zaitsev Rule

Zaitsev’s rule stated that the alkene

formed in greatest amount is the one
that corresponds to removal of the
hydrogen from the carbon having the
fewest hydrogens.
elimination reactions of alcohols yield
the most highly substituted alkene as
the major product.

39
The E1 and E2 Mechanisms of Alcohol Dehydration

40
Rearrangements in Alcohol Dehydration

41
Rearrangements in Alcohol Dehydration
Methyl migration in
1,2,2-trimethylpropyl
cation.
Structure (a) is the
initial secondary
carbocation; structure
(b) is the transition
state for methyl
migration, and
structure (c) is the final
tertiary carbocation.

42
Rearrangements in Alcohol Dehydration

Hydride shift

43
Anti Elimination in E2 Reactions: Stereoelectronic Effects
Although both stereoisomers yield 4-tert-
butylcyclohexene as the only alkene, they do so at
quite different rates. The cis isomer reacts over 500
times faster than the trans.

44
Anti Elimination in E2 Reactions: Stereoelectronic Effects

The trans stereoisomer has no hydrogens anti to Br in its most stable

conformation; all four are gauche. Strain increases significantly in
going to the E2 transition state, and the rate of elimination is slower
than for the cis stereoisomer.

45
Ejercicios
1) (a) Write the structures of all the isomeric alcohols having the molecular
formula C5H12O.
(b) Which one will undergo acid-catalyzed dehydration most readily?
(c) Write the structure of the most stable C5H11 carbocation.
(d) Which alkenes may be derived from the carbocation in part (c)?
(e) Which alcohols can yield the carbocation in part (c) by a process involving
a hydride shift?
(f) Which alcohols can yield the carbocation in part (c) by a process involving
a methyl shift?

46
Ejercicios
2) Predict the major organic product of each of the following reactions. In spite of
the structural complexity of some of the starting materials, the functional group
transformations are all of the type described in this chapter.

47
Ejercicios
2) Predict the major organic product of each of the following reactions. In spite of
the structural complexity of some of the starting materials, the functional group
transformations are all of the type described in this chapter.

48
Ejercicios
3) Evidence has been reported in the chemical literature that the reaction

proceeds by the E2 mechanism. Use curved arrows to represent the flow of

electrons for this process.

4) In the acid-catalyzed dehydration of 2-methyl-1-propanol, what carbocation

would be formed if a hydride shift accompanied cleavage of the carbon–oxygen
bond in the alkyloxonium ion? What ion would be formed as a result of a methyl
shift? Which pathway do you think will predominate, a hydride shift or a methyl
shift?

49
Ejercicios
5) Write a sequence of steps depicting the mechanisms of each of the following
reactions. Use curved arrows to show electron flow.

50