Pines City Colleges

GENERAL EDUCATION DEPARTMENT

Second Semester, A.Y. 2023-2024

Course Number: CHEM 102

Course Title: ORGANIC CHEMISTRY

Modular Learning Guide #5

Topic: ORGANIC REACTIONS

Expected Time of Completion: 6 hours

A. Learning Outcomes
1. Identify and write organic reactions

B. Learning Content
Overview
MLG 5 introduces chemical reactions involving organic compounds. It starts with a simple recall of what
you know about chemical reactions, chemical equations, reactants, products, and how to write chemical
equations.

Recap/Review of the Past Lesson

In MLG #2, you learned about chemical bonding (forces that holds atoms together in compounds)
which will be your foundation in this new lesson. The formation or breaking down of chemical bonds to
forms various substances happens when there is a chemical reaction. You now need to read and
understand chemical reactions and chemical equations.

Concepts

Chemical reaction is a process in which one or more substances (called reactants) are converted to
one or more different substances (called products). Substances are either chemical
elements or compounds. A chemical reaction rearranges the constituent atoms of the reactants to create
different substances as products.

Chemical reactions are an integral part of technology, of culture, and indeed of life itself. Burning fuels,
smelting iron, making glass and pottery, brewing beer, and making wine and cheese are among many
examples of activities incorporating chemical reactions that have been known and used for thousands of
years. Chemical reactions abound in the geology of Earth, in the atmosphere and oceans, and in a vast
array of complicated processes that occur in all living systems.

Chemical reactions must be distinguished from physical changes. Physical changes include changes of
state, such as ice melting to water and water evaporating to vapor. If a physical change occurs, the
physical properties of a substance will change, but its chemical identity will remain the same. No matter
what its physical state, water (H 2O) is the same compound, with each molecule composed of two atoms of
hydrogen and one atom of oxygen. However, if water, as ice, liquid, or vapor, encounters sodium metal
(Na), the atoms will be redistributed to give the new substances molecular hydrogen (H 2) and sodium
hydroxide (NaOH). By this, we know that a chemical change or reaction has occurred.
2H2O + 2Na → 2NaOH + H2

A chemical equation is a concise way of representing a chemical reaction. The initial substances or
reactants are written first then an arrow, and the final substances or products. A chemical equation must
always follow the Law of Conservation of Mass. Therefore, the equation must be balanced. A balanced
chemical equation shows equal number of atoms of elements on the reactant side and product side.

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 How to Write Chemical Equations:
1. Know the facts about the chemical reaction (what is the type of chemical reaction involved, what are
the reactants and products)
2. Write the correct formula of the reactants and products
3. Balance the chemical equation (numerical coefficients are written before the formula of substances to
show how many moles of the substances are involved)

General Types of Organic Reactions:

There are five main types of organic reactions that can take place. They are as follows:
1. Substitution Reactions
Substitution reaction is any of a class of chemical reactions in which an atom, ion, or group of atoms
or ions in a molecule is replaced by another atom, ion, or group. An example is the reaction in which the
chlorine atom in the chloromethane molecule is displaced by the hydroxide ion, forming methanol:
CH3Cl + −OH→ CH3OH + Cl-

2. Elimination Reactions
Elimination reaction is any of a class of organic chemical reactions in which pair of atoms or groups of
atoms are removed from a molecule, usually through the action of acids, bases, or metals and, in some
cases, by heating to a high temperature. It is the principal process by which organic compounds
containing only single carbon-carbon bonds (saturated compounds) are transformed to compounds
containing double or triple carbon-carbon bonds (unsaturated compounds).

The reaction involves the elimination and removal of the adjacent atoms. After these multiple bonds are
simultaneously formed and there is a release of small molecules as products as a result. One of the examples
of a typical elimination reaction is the conversion of ethyl chloride to ethylene.
CH3CH2Cl → CH2 = CH2 + HCl

a. Dehydration – removal of water

H+ (acid)
CH3 – CH2 – CH2 – OH CH3 – CH = CH2 + H2O
∆
Note: ∆ means heat
b. Dehydrogenation – removal of hydrogen
Pt (catalyst)
CH3 – CH2 – CH2 – CH3 CH3 – CH = CH – CH3 + H2
∆
c. Dehalogenation – removal of halogen
Zn (catalyst)
CH3 – CH – CH2 CH3 – CH = CH2 + Cl2
∆
Cl Cl
d. Dehydrohalogenation – removal of hydrogen and halogen

CH3 – CH2 – CH – CH2 – CH3 + KOH CH3 – CH = CH – CH2 – CH3 + KBr + H2O
(in aqueous alcohol)
Br

3. Addition Reactions
Addition reaction, any of a class of chemical reactions in which an atom or group of atoms is added
to a molecule. An addition reaction is seems just the opposite of an elimination reaction. The components or
molecules of A and B are added to the carbon-carbon multiple bonds. In the reaction given below when
hydrochloric acid (HCl) is added to ethylene, it will give us ethylene chloride.
HCl + CH2 = CH2 → CH3CH2Cl

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 a. Hydration – addition of water

b. Hydrogenation – addition of hydrogen

c. Halogenation – addition of halogen (bromination, chlorination, or fluorination)

d. Hydrohalogenation – addition of hydrogen and halogen

4. Rearrangement Reactions
The term “rearrangement” is used to describe two different types of organic chemical reactions. A
rearrangement may involve the one step migration of an H atom or of a larger molecular fragment within
a relatively short lived intermediate.

On the other hand, a rearrangement may be a multi-step reaction that includes the migration of an H
atom or of a larger molecular fragment as one of its steps.

Curtius Rearrangement or Curtius Reaction

Curtius’ reaction involves the heating of an acyl azide which loses nitrogen and then rearranges to an
isocyanate.

If the reaction is performed in an alcoholic or aqueous medium, the isocyanate further reacts to
form urethane, amine or substituted urea.

Claisen Rearrangement
The classical Claisen rearrangement is the first and slow step of the isomerization of allyl aryl ethers to
ortho allylated phenols. A cyclohexadienone is formed in the actual rearrangement step which is a [3,3]-
sigmatropic rearrangement. Three valence electron pairs are shifted simultaneously.

Cyclohexadienone, a non-aromatic compound, cannot be isolated and tautomerizes immediately to

the aromatic and consequently more stable phenol.

Beckmann Rearrangement
In the Beckmann rearrangement, an oxime is converted to an amide. An oxime is easily obtained by
treatment of aldehyde or ketone with hydroxylamine. The OH group of ketoximes can become a leaving
group. The Beckmann rearrangement of cyclic oximes results in lactams.
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 The comparison of the structure of the starting ketone with those of the products reveals that the
combination of oxime formation and Beckmann rearrangement accomplishes the insertion of an NH
group between the carbonyl carbon and the alpha carbon.

Hofmann Rearrangement
The Hofmann rearrangement is well known reaction used to synthesize primary amines from amides
via one carbon degradation. In this reaction, amides react with bromine and strong base which
subsequently rearranges to give an isocyanate. Hydrolysis of the isocyanate affords an amine, whereas
carbamate is provided by treatment with an alcohol. These mechanistic steps lend well to utilizing the
Hoffman rearrangement as a method for amine protection.

The Hofmann rearrangement results from the treatment of a primary amide with bromine and
hydroxide ion in water, ultimately forming an amine in which the carbonyl group of the starting amide has
been lost.

Thus, the Hofmann rearrangement results in a shortening of the carbon chain by one atom and a
change in functional group from an amide to an amine. The Hofmann rearrangement occurs through a
pathway similar to that for the Beckmann rearrangement.

Pericyclic Rearrangement
Pericyclic reactions are defined as the reactions that occur by a concerted cyclic shift of electrons.
This definition states two key points that characterize a pericyclic reaction.

 First point is that reaction is concerted. In concerted reaction, reactant bonds are broken and
product bonds are formed at the same time without intermediates.

 Second key point in pericyclic reactions involves a cyclic shift of electrons. The word pericyclic means
around the circle. Pericyclic words come from the cyclic shift of electrons. Pericyclic reactions thus are
characterized by a cyclic transition state involving the pi bonds.

Photochemical rearrangements
Many photoreactions are known to interconvert isomeric compounds. The term “rearrangement” is
more general than “isomerization” but for the reactions under photochemical rearrangement will not be
concerned with a distinction between these terms.

For convenience, we shall classify primary photochemical rearrangements as the following types.
a. Cis-trans isomerization
b. Sigmatropic rearrangements
c. Electrocyclic rearrangements
d. Structural rearrangements which result from intramolecular cycloadditions.

5. Reduction-Oxidation Reactions
Oxidation-reduction reaction (also called redox reaction) is any chemical reaction in which
the oxidation number of a participating chemical species changes. The term covers a large
and diverse body of processes. Many oxidation-reduction reactions are as common and familiar as fire,
the rusting and dissolution of metals, the browning of fruits, and respiration and photosynthesis.
Note: This was discussed in high school chemistry.

Reaction Mechanisms
Every chemical reaction proceeds according to a reaction mechanism, which is a step-by-step
description of what occurs during a reaction on the molecular level. Each step of the mechanism is known
as an elementary process, which describes a single moment during a reaction in which molecules break
and/or form new bonds. It is important to keep in mind that every reaction mechanism is simply a proposed
version of what might be occurring at the molecular level; even if a mechanism agrees with experimental
results, it is impossible to prove a reaction mechanism for certain. That being said, there are two strict
requirements that must be fulfilled for a reaction mechanism to be valid. They are:
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 a. The sum of each elementary step in a reaction mechanism must yield the overall reaction equation.
b. The rate law of the rate-determining step must agree with the experimentally determined rate law.

Example of Reaction Mechanism; Benzoin Condensation

Cyanide ion (CN−) acts as a catalyst here, entering at the first step and leaving in the last step. Proton
(H+) transfers occur at (i) and (ii). The arrow pushing method is used in some of the steps to show where
electron pairs go.

Reaction Intermediate
Reaction mechanisms describe how the material in a chemical reaction gets from the initial reactants
to the final products. An intermediate is a species which appears in the mechanism of a reaction, but not in
the overall balanced equation. An intermediate is always formed in an early step in the mechanism and
consumed in a later step.

Chemical intermediate may also be defined as any chemical substance produced during the
conversion of some reactant to a product. Most synthetic processes involve transformation if some readily
available and often inexpensive substance to some desired product through a succession of steps. All
substances generated by one step and used for the succeeding step are considered intermediates.

Types of Reaction Intermediates

1. Carbanions
In organic chemistry, a carbanion is a reaction intermediate in which there is a negative one charge
located on a carbon atom. Carbanions are formed by treating an organic compound with a very strong
base.
Carbanions are extremely reactive, and once they are formed in a chemical reaction they typically
don't last very long. Usually they go on further to react with a positive species in the reaction to form the
final product of the reaction. This should make sense to us because we are forming a negatively charged
intermediate, meaning it will be attracted to something else that has some sort of positive character to it.

2. Carbocation
A carbocation is a molecule in which a carbon atom has a positive charge and three bonds. We can
basically say that they are carbon cations. Carbocation today is defined as any even-electron cation that
possesses a significant positive charge on the carbon atom.

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 3. Free Radicals
Free radicals contain a single, unpaired electron. They result when a covalent bond (a bond composed
of two electrons) is broken and each atom takes one electron from the bond. For example, when a
carbon-hydrogen bond in methane is broken, one of the electrons from the bond goes to carbon and the
other electron goes to hydrogen. Notice that when we are representing free radicals, we use single dots on
the atom in which the radical is located.

4. Carbenes
Carbenes are the least obvious of the four common intermediates; in most cases they have a six-
electron sp2 structure that has a lone pair but no overall charge. Although they are short of a full octet, they
also have a reactive lone pair, so (depending on structure) carbenes can be either electrophilic or
nucleophilic, or sometimes both – they just like to react with almost anything!

METHODS OF FORMING REACTION INTERMEDIATES

1. Homolytic Cleavage
Homolytic cleavage occurs when the bonding electrons are evenly divided between the two parting
atoms. This results into the formation of two reaction intermediates which are free radicals.

2. Heterolytic Cleavage
Heterolytic cleavage takes place when the bonding electrons are unevenly divided between the two
parting atoms. The reaction intermediates formed are cabocation and carbanion.

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 SITES OF ORGANIC REACTIONS
1. Multiple bonds
2. Polar bonds
3. Lewis acids and bases

PREDICTING THE PRODUCTS OF A REACTION

1. Markovnikov’s Rule
This rule states that when halogen acid (HX) is added to an unsymmetrical alkene, the negative com-
ponent of the halogen acid is attached to the carbon atom that is double-bonded and has the fewest hy-
drogen atoms.

2. Zaitsev’s rule
This is an empirical rule used to predict the major products of elimination reactions. It states that in an
elimination reaction the major product is the more stable alkene with the more highly substituted double
bond.

REACTIONS INVOLVING AROMATIC COMPOUNDS

1. BENZENE
Though benzene is an unsaturated molecule, it does not readily undergo addition reactions but rather
undergo substitution reactions.

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 2. Substituted benzenes
Substituents determine the reactivity of rings. The reaction of a substituted ring with an activating group
is faster than benzene. On the other hand, a substituted ring with a deactivated group is slower than
benzene.
When mono substituted benzene undergoes an electrophilic attack, the rate of reaction and the site of
attack vary with the functional group already attached to it. We further divide these groups into two
categories depending on the way they influence the orientation of attack by the incoming electrophile.
Those which increase the electron density at ”ortho” and “para” positions are known as ortho-para directors
while those which increase the electron density at “meta” position are known as meta directors.
Ortho-para directing group: As discussed earlier, these groups direct the electrophilic attack on “ortho”
and “para” positions. All activating groups are “ortho-para” directors, for example –NH2, –NHR, –NHCOCH3, –
OCH3, –CH3, –C2H5, etc.

Meta directing groups: These groups direct the electrophilic attack on “meta” positions of the
associated benzene ring. Generally deactivating groups are meta directors, for example –NO2, –CN, –CHO,
–COR, –COOH, –COOR, –SO3H, etc.

C. Learning Activities

This activity will be rated (20 points).

Define the following terms:
1. Pyrolysis
2. Cracking
3. Halohydrin
4. Dimerization
5. Alkylation
6. Epoxidation
7. Hydroxylation
8. Ozonolysis
9. Sulfonation
10. Oxirane ring

Note: You are required to write your answer on a piece of intermediate pad.

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D. Resources
The following materials are worthy references for you to understand organic chemistry better:
1. Chemical Reaction
https://www.britannica.com/science/chemical-reaction
2. Types of Organic Reactions
https://www.toppr.com/guides/chemistry/organic-chemistry/types-of-organic-reactions/
3. Common Types of Organic Reactions
https://brilliant.org/wiki/common-types-of-organic-reactions/
4. What is a Reaction Intermediate?
https://study.com/academy/lesson/what-is-a-reaction-intermediate-definition-examples.html

E. Assessment

Prepare for a 20-point quiz next meeting.

F. References
McMurry, John. (2006). Organic Chemistry. U.S.A. Brooks/Cole Publishing Company.
Carey, Francis and Richard Sundberg. (2007). Advanced Organic Chemistry. U.S.A.: Springer/Link Co.
Bettelheim, Frederick, William Brown, Mary Campbell, and Shawn Farrel. (2010). Introduction to General,
Organic, and Biochemistry (8th edition). U.S.A.: Thomson-Brooks/Cole Co.
Brown, William and Foote. (2001). Organic Chemistry (3rd ed). U.S.A.: Brooks/Cole Publishing Co.
Denniston, Katherine, Joseph Topping, and Robert Caret. (2004). General, Organic, and Biochemistry (4th
ed). U.S.A.: McGraw-Hill Book Co., Inc.
Hein, Morris, Leo Best, Scott Pattison, and Susan Arena. (2005). Introduction to General, Organic, and
Biochemistry (8th edition). U.S.A.: John Wiley and Sons, Inc.
Patrick, G.L. (2000). Organic Chemistry. U.S.A.: BIOS Scientific Publishers Limited.
Solomons, Graham and Craig Fryhle. Organic Chemistry (10th ed.). U.S.A.
Stoker, H. Stephen. (2013). Exploring General, Organic & Biological Chemistry (6th edition). Singapore:
Cengage Learning Co.

http://greenmedicine.ie/school/images/Library/A%20Brief%20History%20of%20Organic%20Chemistry.pdf
http://www.windows2universe.org/earth/water/co2_cycle.html
http://www.vision/learning.com/library/module_viewer.php?mid=95
http://sparkcharts.sparknotes.com/chemistry/organicchemistry1/section1.php

Prepared by
Cecilia L. Cabanilla
Instructor

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