FUNDAMENTALS OF ORGANIC MOLECULES

THE NATURE AND STRUCTURE OF ORGMOL

KEKULE (August Kekulé)

- a German Chemist and Couper a Scottish chemist were the two most important persons to
- Recognize that Carbon (C) is tetravalent.
- TETRAVALENT - means Carbon can form four covalent bonds with other atoms such as hydrogen(H),
oxygen(O), nitrogen(N) and with itself.
- Silicon having four valence electrons cannot bond easily with other atoms like that of carbon.
- Silicon -silicon easily cleaved off it is very strong but cannot resist the diversity of the carbon atom which is
the main component of organic molecules.

The illustration below is the nature of Carbon:

1.) It can form linear, branched and cyclic bonds with a wide array of organic substances.

2.) It can form more diverse molecular structure if the carbon atom will have single, double and triple bonds.

Look at the structure below what will happen if the carbon is link to one another using this framework?

This is not only for carbon atom but also for other atoms like nitrogen, oxygen which will form small and simple
molecules and to its greater extent of biomolecules which is found in living organisms.

The Lewis Structure

• Gilbert N. Lewis
- Notion about the chemical inertness of the noble gases indicated a high degree of stability of the electron
configuration of these elements (the noble gases have completely filled valence shells).
- Lewis then devised a model of bonding that unified many of the observations about chemical reactions of the
elements.

The table below are examples of elements and their electron dots as well as the noble gas structure that can explain
the concept of how to write Lewis’ dot symbol and its combination.
 Lewis dot
Name of the element Symbol Atomic number Electronic configuration

Li .
Lithium Li 3 1s2 2s1

Be :
Berellium Be 4 1s2 2s2

B: .
Boron Al 5 1s2 2s2 2p1

:C:
Carbon C 6 1s2 2s2 2p2

:N:.
Nitrogen N 7 1s2 2s2 2p3

::O:
Oxygen O 8 1s2 2s2 2p4

::F:.
Fluorine F 9 1s2 2s2 2p5

::Ne::
Neon Ne 10 1s2 2s2 2p6
• Chemical bonding
- Chemical bonding of a molecule happens when it acquire the complete (octet) Eight electrons in the outer
most shell of an atom.
- An atom becomes negatively charged (-) when it loses an electron. It becomes positively charged (+) when it
gains an electron. When this happens the bond formed between them is ionic bond. While when the two
atoms shared their electrons it forms a covalent bond.
• Covalent bond
- Polar - if the electrons shared are not equal
- Non polar - if the electrons shared are equal.
- We can also cite the electronegativity difference of the atoms in this case.

Writing chemical bonds using Lewis Structure

1.) Identify the number of electrons to be used in connecting the atoms. This is done by adding all the numbers
of valence electrons of the atoms in the molecule.

Let us do it with carbon dioxide (CO2)

-
Carbon ( C ) has four valence electrons
x 1 carbon = 4 e
-
Oxygen ( O ) has six valence electrons
x 2 oxygen = 12 e

There are exactly 16 e - to be placed in the Lewis structure. -

Total = 16 e

2.) Draw the connectivity and determine the central atom. Avoid long chains. Connect the central atom to the
other atoms in the molecule with single bonds. Carbon is the central atom, the two oxygen are bound to it
and put a dash.

O —C —O

3.) Complete the octet by writing the dots of all the atoms in the structure.

4.) Remove electrons, from the central atom, in excess of the number stipulated in step 1 (16 -e). There are 20
electrons in this example, but only is 16 needed and required. Remove 2 pairs from the carbon.

5.) If the valence shell of the central atom is complete, you have drawn an acceptable Lewis structure. If not, the
electron deficiency (below an octet) is made up by sharing lone pair electrons from the outer atoms to make
double or triple bonds. Continue this process of making multiple bonds between the outer atoms and the
central atom until the valence shell of the central atom is complete.
 6.) Carbon lacks electron it has only four electrons around it. This is not an acceptable Lewis structure.

7.) The central atom is still electron deficient, so share another pair. Make it right by putting eight electrons in
each atom.

8.) The best Lewis structure that can be drawn for carbon dioxide is:

Classification of Organic Molecules

a.) Classes of Organic Molecules and its functional groups

Organic Compounds are classified into two big groups;

• Hydrocarbons - are organic compounds containing hydrogen and carbon. This can also be classified into two the
saturated composed of single bonds and unsaturated composed of double or triple bonds.
• Heteroatoms - Elements aside from carbon and hydrogen which is incorporated in organic compounds are called
heteroatoms. Among the most common heteroatoms are oxygen, nitrogen and the halogens (Cl, Br, I and F). Along
these, sulfur and phosphorus are also found in some organic compounds.

The concept map above shows the most common classes of organic compounds and their relationships with one
another. (See concept map)

The hydrocarbons, which contain only carbon and hydrogen, are of two types;

• Aliphatics - what belongs to the aliphatic are alkanes, alkenes, alkynes and their cyclic analogs. They can be
linear, branched or cyclic compounds.
• Aromatics - Aromatic hydrocarbons are organic compounds composed of carbon and hydrogen atoms,
arranged in ring structures with delocalized pi electrons.

With halogens With oxygen with nitrogen with sulfur

organic halides Alkyl Alcohols, phenols, ethers, Amines, amides, amino thiols, sulfides
and aryl halides aldehydes and ketones, carboxylic acids
acids, anhydrides, esters.
SUMMARY

There are millions of organic compounds-much more than the combined compounds of the rest of the
elements in the periodic table. This number is increasing tremendously as more new compounds are isolated from
natural resources and synthesized in the laboratory.

Carbon is tetravalent, i.e., it can form four covalent bonds with other carbon atoms as well as other elements,
mainly H, O, N.

Carbon atoms can link with each other to form linear, branched or cyclic chains. In addition, carbon atoms
may participate in single, double or triple bonds. These properties of carbon atoms plus the fact that organic
compounds exhibit isomerism, explain the huge number of organic compounds and the great diversity in their
structure.

Atoms bond together in such a way that each atom participating in the bond acquires the very stable electronic
configuration of the noble gases. Carbon atoms acquire an octet of electrons by sharing electrons with other atoms.
Thus organic compounds are mostly covalent compounds having low melting points and limited solubility in water.

Organic compounds are classified according to their functional groups. The functional group defines the
structure as well as the chemical and physical properties of an organic compound.
REACTION MECHANISMS OF ORGANIC MOLECULES

TYPES OF ORGANIC MOLECULES REACTIONS

There are four important kinds of organic reaction - addition, elimination, substitution and rearrangement.
Another category, oxidation and reduction may fall naturally into one of the four types mentioned above.

• Reactants
• Used in a chemical reaction consists of a substrate and reagent.
• These are transformed into products under the proper reaction conditions.
• The substrate is the reactant that is acted upon or attacked by the reagent; it is the molecule which contains
the carbon atom(s) to which bonds are broken and made.

• The organic reactions such addition, elimination, substitution and rearrangement is based on the changes that
occur in bonding to carbon atoms in the substrate.

1.) The addition reaction

• The addition reactions can be identified if there is an increase in the number of atoms or groups attached to
a carbon(s) in the substrate. (A saturated compound contains single bonds only while an unsaturated
compound contains double or triple bonds.)
• Each carbon atom in the unsaturated (double bond) substrate gets one more atom resulting in a saturated
product.
• If you compare the structure of the substrate with that of the product, you can see quite clearly that each
carbon atom in the unsaturated substrate gets one more atom (one carbon atom gets an H and the other a Cl
atom) resulting in a saturated product.

2.) The Elimination Reaction

• In elimination reactions, an atom or a group of atoms is removed from the substrate, thus there is a decrease
in the number of atoms or groups attached to carbon. The substrate is transformed to a more unsaturated
(single bond) product. Let us examine the reaction below:

An unsaturated (double bond) organic

product is obtained through the removal of an
H atom and OH group from the saturated
substrate.
3.) The Substitution Reaction
• They involve the replacement of an atom or a group of atoms in the substrate by another atom or group of
atoms. Check the example is given below:

The organic product results from the

replacement of the chlorine atom in the
substrate by the hydroxyl group. The Cl is
replaced by the OH.

4.) The rearrangement Reaction

• Reactions involve migration of an atom or group of atoms from one atom to another. To illustrate:

In this reaction, bromine migrates from an

outer carbon atom to the inner carbon
atom.

5.) Oxidation and reduction reactions

• The most common type of reaction which is also found in the above reactions are the Oxidation and
reduction reactions in organic chemistry they are defined according to the increase or decrease in oxygen
or hydrogen content because the transfer of electrons cannot be easily monitored as in inorganic
reactions.

• An oxidation reaction occurs when there is an increase in the oxygen content and/or a decrease in the
hydrogen content of the substrate. For example:

Comparing the structure of the organic

product with the substrate, notice that there
is an increase in the oxygen content (by one
oxygen) as well as a decrease in the hydrogen
content (by two hydrogens).

• In a reduction reaction, there is an

increase in the hydrogen content and/or a decrease in the oxygen content of the substrate. Consider the
following reaction:
MECHANISMS FOR REACTIONS of Organic Molecules

• The reaction mechanism is the step by step events by which a substrate is converted to products at a given
set of conditions.
• The order and breaking of bond are described including the bonds that is formed its relative rate by the action
of the catalyst.
• Reaction intermediates - are formed in one step and then consumed in a later step of the reaction
mechanism.
• Rate determining or rate-limiting step - the slowest step in the mechanism
• Products - are formed from the transformation of reactants and reagents. During the reaction products could
not proceed and form right away it will still undergo this process. Along with it the covalent bond can break.
• It can form either homolytic or heterolytic cleavage when bond to Carbon atom.
• homolytic - bond to carbon it can form carbon radical
• heterolytic - it can be a trivalent carbon anion, or carbanions or can be carbon cation or carbocations.

An example of carbo cation:

CLASSIFICATION OF REACTANTS

Type of bond cleavage that will occur in a reaction

➢ Reactants - are classified into two, the substrate and reagents.
➢ Reagents - have three types, the nucleophilic, electrophilic and radical-like.
a.) Nucleophilic reagents (nucleus loving) or nucleophiles are substances who loves electrons they are consist of pairs
of electrons that can be used for bond formation. They attack positively charged atoms or low electron density.

b.) Electrophilic Reagents (electron loving) or electrophiles they are electron deficient, capable of forming new bonds
by accepting a pair of electrons, they attack negatively charged electrons or high electron density.
c.) Radical Like reagents they have odd number of electrons react easily and attack high electron density atoms.
SUMMARY OF TERMS and CONCEPTS

Organic reactions may be classified as addition, elimination, substitution, rearrangement, oxidation or

reduction. This classification depends upon what kind of reactions or transformations occur. The products formed will
undergo reaction intermediates this is the process called reaction mechanisms. There are two types of reactants the
substrate and the reagents. Reagents have three types, the nucleophiles loves nucleus, electrophiles loves
electrons,and the radical like has odd number of electrons. Each of which has its own role to play during chemical
reactions.

The heterolytic cleavage during reaction, either carbocation or carbanion. While the homolytic cleavage can form
charged carbon intermediate known as radical. It gives in understanding and controlling chemical reactions.

The substance ethanol can be converted to ethane by dehydration process and ethanol can be converted to
propene using dehydration process. These chemical reactions we encounter everyday suggest some reaction
mechanisms in order to produce certain products.
ALKANES and CYCLOALKANES

Nomenclature and writing structure of Alkanes and Cycloalkanes

CONCEPT MAP

ALKANES

Are saturated hydrocarbons, contain only single covalent bonds between carbon atoms. Each of the carbon atoms
in an alkane has sp3 hybrid orbitals and is bonded to four other atoms, each of which is either carbon or hydrogen.
List of Alkanes Molecular Formula Structure

Methane (CH4)

Ethane
(C2H6)

Propane (C3H8)

Butane (C4H10)

Pentane (C5H12)

Hexane (C6H14)

Heptane (C7H16)

Octane (C8H18)

Nonane (C9H20)

Decane (C10H22)
STRUCTURE of Alkanes

Skeletal structure (also called a line-angle structure)

• In this type of structure, carbon atoms are not symbolized with a C, but represented by each end of a line
or bend in a line. Hydrogen atoms are not drawn if they are attached to a carbon. Other atoms besides
carbon and hydrogen are represented by their elemental symbols.

EXAMPLES

Cycloalkanes

They are cyclic hydrocarbons, meaning that the carbons of the molecule are arranged in the form of a ring.
Cycloalkanes are also saturated, meaning that all of the carbons atoms that make up the ring are single bonded to
other atoms (no double or triple bonds).

STRUCTURE of Cycloalkanes

Cycloalkanes are composed of sp3 hybridized carbon and hydrogen atoms connected by sigma bonds. However,
unlike linear hydrocarbons, which can achieve a more stable tetrahedral configuration around each carbon atom in
the backbone, the bond angles in cycloalkanes are constrained, producing ring strain.

• ANGLE STRAIN
is molecular instability resulting from carbon atoms bonded in alkanes at angles other than 109.5°.
• RING STRAIN
is a combination of angle and torsional strain that determines a molecule's stability.
Cycloalkanes- with the exception of cyclopropane, are nonplanar.
Cyclopropane - has a large angle strain because the carbon-carbon bonds have an angle of 60°, which is far from
the ideal angle of 109.5°. Since rotation around the carbon-carbon bonds is impossible, cyclopropane has torsional
strain because of eclipsed hydrogen in the cyclic structure.

Ring Strain in Cyclopropane

Three-dimensional models of cyclopropane, such as the ball-and-stick model and the Newman projection, can help to
visualize ring strain caused by the eclipsed conformation.

NOMENCLATURE of ALKANES AND CYCLOALKANES

NOMENCLATURE OF ALKANES Unbranched Chain Alkanes

 Alkane nomenclature requires vocabulary that you will use throughout Organic Chemistry. This includes
formal systems ("IUPAC" nomenclature) and names that have a historical origin without necessarily a systematic
structural meaning ("common" names).

All organic compounds, alkanes especially, are named using a root name that reflects the number of carbons in the
longest carbon chain.

These are derived from Greek words, and from pentane up all are related specifically to Greek words for the
corresponding number of carbons in the chain.

HOW TO NAME Unbranched Alkyl Group

If we remove one hydrogen atom from an alkane,

we obtain what is called the ALKYL GROUP. These
alkyl groups have names that end in -YL.

When the alkane is unbranched, the

hydrogen atom that is removed is a terminal
hydrogen atom making the names more
straightforward.
HOW TO NAME Branched Chain Alkanes

1.) Locate the longest contiguous carbon chain and name it--this is the base name of the compound. When there is a
choice of two equivalent-length chains to provide the base name, choose the one that has the least number of
substituents.
Note: The longest chain may not always be

obvious from the way the formula is written.

continuous

2.) Number the chain starting with the end nearest a substituent.

3.) Name each alkyl substituent based on the number of carbons in it.

4.) List multiple groups in alphabetic order.

Note: When two substituents are

present on the same carbon atom, use
that number twice.

EXAMPLE

Step 1: Find the longest carbon chain and count the number of carbons

Step 2: Number the chain so that the substituents have the lowest aggregate numbered positions: This is an octane (8
carbons).

Step 3: Name each alkyl substituent based on the number of carbons in it.
HOW TO NAME MONOCYCLIC CYCLOALKANES

Cycloalkanes are named by adding “cyclo” before the parent name.

1.) CYCLOALKANES WITH ONE RING AND NO SUBSTITUENTS:

Count the number of carbon

atoms in the ring, then add
“cyclo” to the beginning of
the name of the alkane with
that number of carbons.

2.) CYCLOALKANES WITH ONE RING AND ONE SUBSTITUENTS:

Add the name of the substituent to the beginning

of the parent name. Ex. - cyclohexane with an
attached isopropyl group is isopropylcyclohexane.
For compound with only one substituent, it is not
necessary to specify a number (locant) for the
carbon bearing the substituent.

3.) CYCLOALKANES WITH ONE RING AND TWO OR MORE SUBTITUENTS:

For a ring with two substituents, begin by numbering the carbons in the ring, starting at the carbon with the
substituent that is first in the alphabet and number in the direction that gives the next substituent the lower number
possible. When there are three or more substituents, begin at the substituent that leads to the lowest set of numbers
(locants). The substituents are listed in alphabetical order, not according to the number of carbon atom.

NOTE: When a single ring system is attached to

a single chain with a greater number of carbon
atoms, or when more than one single ring
system is attached to a single chain, then it is
appropriate to name the compounds as
cycloalkylalkanes.
HOW TO NAME Bicyclic Cycloalkanes

Bicyclic cycloalkanes are compounds containing two fused or bridged rings.

1.) We use the name of the alkane corresponding to the total number of carbon atoms in the rings as the parent
name.

Example: Contains 7 carbon atoms, and is,

therefore, a bicycloheptane. The carbon atoms
common to both rings are called bridgeheads, and
each bond, or each chain of atoms connecting the
bridgehead atoms, is called the bridge.

2.) We then interpose an expression in brackets within the name that denotes the number of carbon atoms in
each bridge (in order of decreasing length). Fused rings have zero carbon in their bridge.

3.) In bicycloalkanes with substituents, we number the bridge ring system beginning at one bridgehead,
proceeding first along the longest bridge to the other bridgehead, then along the next longest bridge back to
the first bridgehead; the shortest bridge is numbered last.
PHYSICAL PROPERTIES of ALKANES and CYCLOALKANES

PHYSICAL PROPERTIES OF ALKANES

a.) Melting and Boiling Point

• BOILING POINT

-The boiling points shown are for the "straight chain" isomers of which
there is more than one. The first four alkanes are gases at room
temperature, and solids do not begin to appear until about C17H36 ,
but this is imprecise because different isomers typically have
different melting and boiling points.

-The boiling points for the "straight chain" isomers and isoalkanes
isomers are shown to demonstrate that branching decreases the
surfaces area, weakens the IMFs, and lowers the boiling point.

• MELTING POINT

The boiling points for the "straight chain" isomers and isoalkanes isomers are shown to demonstrate that branching
decreases the surfaces area, weakens the IMFs, and lowers the boiling point.

b.) Solubility

Alkanes (both alkanes and cycloalkanes) are virtually insoluble in water, but dissolve in organic solvents. However,
liquid alkanes are good solvents for many other non-ionic organic compounds.
SOLUBILITY IN WATER

When a molecular substance dissolves in water, the following must occur:

- Break the intermolecular forces within the substance. In the case of the alkanes, these are the Van der Waals
dispersion forces.
- Break the intermolecular forces in the water so that the substance can fit between the water molecules. In
water, the primary intermolecular attractions are hydrogen bonds.
- Breaking either of these attractions requires energy, although the amount of energy to break the Van der
Waals dispersion forces in something like methane is relatively negligible; this is not true of the hydrogen
bonds in water.

NOTE: a substance will dissolve if there is enough energy released when new bonds are made between the substance
and the water to compensate for what is used in breaking the original attractions.

SOLUBILITY IN ORGANIC SOLVENTS

In most organic solvents, the primary forces of attraction between the solvent
molecules are Van der Waals - either dispersion forces or dipole-dipole
attractions. Therefore, when an alkane dissolves in an organic solvent, the Van
der Waals forces are broken and are replaced by new Van der Waals forces. The
two processes more or less cancel each other out energetically; thus, there is no
barrier to solubility.

c.) Density

Alkanes have densities between 0.6 and 0.8 g/cm3, so they are less dense than
water.

NOTE: The density of the alkanes usually increases with the number of carbon atoms but remains less than that of
water.

PHYSICAL PROPERTIES OF CYCLOALKANES

a.) Melting and Boiling Point

Generally, the melting point, the boiling point and the density of cycloalkanes increase as the number of carbons
increases. This trend occurs because of the greater number of bonds that are in higher membered rings, thus making
the bonds harder to break.

NOTE: The physical properties of cycloalkanes are similar to those of alkanes, but they have higher boiling points,
melting points and higher densities due to the greater number of London forces that they contain
 b.) Solubility

Alkanes (both alkanes and cycloalkanes) are virtually insoluble in water, but dissolve in organic solvents. However,
liquid alkanes are good solvents for many other non-ionic organic compounds.

REACTIONS of ALKANES

-All alkanes have similar chemical properties because they belong to the same homologous series.

-Alkanes are rather unreactive: They don’t react with most chemicals. However, they undergo 2 main types of reaction.

c.) Combustion of Alkanes

1. COMPLETE COMBUSTION REACTION

-Alkanes are called saturated hydrocarbons because they

only have single bonds between carbon atoms (C-C).

-Alkanes burn in a plentiful supply of air to release energy.

(This is why they are used as fuels).

-Burning or combustion also produces: Carbon dioxide (CO2), water vapor and heat.

EXAMPLE

OBSERVE WHAT HAPPENS WHEN YOU LIGHT A BUNSEN BURNER

1.) Methane gas (CH4) exits from the mouth of the Bunsen Burner and mixes with the
oxygen gas (O) in the atmosphere.

2.) A flame is placed near the mouth of the Bunsen Burner

3.) Methane gas (CH4 burns in oxygen gas O) surrounding atmosphere process:
combustion

4.) The products of the combustion are CO and H O

5.) Complete combustion Blue, non-luminous flame.

NOTE: Heat is always produced during combustion of

hydrocarbons ---> exothermic reaction.
2. INCOMPLETE COMBUSTION REACTION

- When there is insufficient oxygen gas, incomplete combustion occurs.

NOTE: Incomplete combustion also occurs for larger alkanes (ex. Candle wax)

-It means that the alkanes are not burned completely and gives more sooty flame (orange yellow in color)

- The black soot is carbon and the yellow comes from glowing carbon atoms.

EXAMPLE: METHANE GAS

d.) Halogenation of Alkanes

The replacement of one or more hydrogen atoms in an organic compound by a halogen (fluorine, chlorine, bromine
or iodine).

- Alkanes react with halogens, such as chlorine and bromine, in the presence of ultraviolet light (UV light).

METHANE REACTS WITH CHLORINE TO FORM CHLOROMETHANE AND HYDROGEN CHLORIDE GAS

-This is substitution reaction. Notice that the hydrogen atom in the methane is replaced by chlorine atom.

GENERAL EQUATION
-More hydrogen atom can be replaced with chlorine atoms to produce a mixture of four organic compounds.

THE EXTRA REACTIVITY OF CYCLOPROPANE

- The reactions of the cycloalkanes are generally just the same as the alkanes, with the exception of the very
small ones - particularly cyclopropane.
- In the presence of UV light, cyclopropane will undergo substitution reactions with chlorine or bromine just
like a non-cyclic alkane. However, it also has the ability to react in the dark.

In the absence of UV light, cyclopropane can undergo addition reactions in which the ring is broken. For example, with
bromine, cyclopropane gives 1,3-dibromopropane.

NOTE: This can still happen in the presence of light - but you will get substitution reactions as well.
- The ring is broken because cyclopropane suffers badly from ring strain.

- The bond angles in the ring are 60° rather than the normal value of about 109.5° when the carbon makes four single
bonds.

- The overlap between the atomic orbitals in forming the carbon-carbon bonds is less good than it is normally, and
there is considerable repulsion between the bonding pairs. The system becomes more stable if the ring is broken.
SUMMARY

Alkanes and cycloalkanes. The attraction between alkanes and cycloalkanes are weak because of the solely
govern by Van der Waals forces they are both non polar molecules. Their boiling points are low among similar
molecular masses.

They both undergo combustion and halogenation. The combustion has several applications in home and industry. The
fuel we use are products of fractional distillation from crude petroleum.

Consist of non-polar molecules which are attracted to each other solely by the weak dispersion or Van der Waals
forces. Thus, among organic compounds of similar molecular masses, alkanes and cycloalkanes would have the lowest
boiling points.

The major reactions, alkanes and cycloalkanes undergo are combustion and halogenation. Combustion, which
gives off a tremendous amount of heat, has several practical applications in home and in industry and has given us the
opportunity to have a comfortable life. The halogenation of alkanes and cycloalkanes often time yields a mixture of
products.

Aliphatic HC

Alkanes has a general formula of CnH2n + 2, it is a saturated HC a straight chain or branched HC. They are
systematically named using IUPAC nomenclature and rules.

Alkyl Group- are group of alkanes that one hydrogen atom is removed. In naming it replaces the name -ane to -yl it is
usually represented by R radical. Prefixes sec for secondary carbon and tert for tertiary carbon atoms.

Cycloalkanes has a general formula of CnH2n. They are rings of Carbon atoms can exist as cis -trans isomers. In a cis
both constituents are in the same side and on the transit is at the opposite side of the ring. It also exists as a strain
free chair confirmation with 109o bond angles on all sides. The chair confirmation the two kinds of bonding the Axial
bonds are directed up and down while the equatorial bonds are band along the plane like a belt. Substituents along
the plane are more stable or when they are in an equatorial plane.

Bicycloalkanes are cycloalkanes that are having two fused rings. The carbon atoms common to both rings are called
bridgeheads, and each bond, or each chain of atoms connecting the bridgehead atoms, is called the bridge.

APPLICATION

What do you take when your muscles are aching or when you are sick? Do you take drugs or medicines to
relieve the pain? The trend of the people now is to just take medicine the natural way. Going back to the olden times
medicines are just taken from the plants and eventually developed into drugs. Our medicines and drugs are not at all
natural some of these are 33% synthetic according to the study of the US National Cancer Institute. To date drugs are
still tested and screed in order to gain approval. When tested to human it takes five to seven years. The recent problem
we have today is the cure for COVID 19 and it is not easy to simply administer it right away to the humans. Alkanes
has given us the opportunity to enjoy things in life and makes our life easy and comfortable.

Butane or n-butane is an alkane with the formula C₄H₁₀. Butane is a gas at

room temperature and atmospheric pressure. Butane is highly flammable, colorless,
easily liquefied gas that quickly vaporize at room temperature. The name butane comes
from the roots but- and -ane.

Formula: C4H10 Molar mass: 58.12 g/mol

Boiling point: -1 °C IUPAC ID: Butane

Density: 573 kg/m³ Melting point: -138 °C

ALKENES

INTRODUCTION

• Alkenes are aliphatic hydrocarbons whose molecules contain double bond carbon-carbon atom. An old name
for this family of compounds that is still often used is the name olefins. Ethene (ethylene), the simplest olefin
(alkene), was called olefiant gas (Latin: oleum, oil + facere, to make) because gaseous ethene (C2H4) reacts
with chlorine to form C2H4Cl2, a liquid (oil). Unlike ethane the, ethene the lowest form of alkene is planar angles
between bonds is 120o. It is sp2 hybrid orbital.

DOUBLE BOND CARBON

• Alkenes are family of hydrocarbons containing at least one Carbon-Carbon double bond.
• Double bond carbon are unsaturated hydrocarbons with the molecular formula is CnH 2n, which is also the
same molecular formula as cycloalkanes.

a.) THE SP2 HYBRID ORBITAL

• A sp2 hybrid orbital is an orbital formed by the linear combination of one s and two p orbitals of
comparable energy (such 2s and 2p orbitals) on a same atom. The three sp 2 hybrid orbitals lie in a
plane with angle of 120 degrees

b.) THE PI BOND STURCTURE OF ALKENES

• These are formed by end-on overlap of orbitals. This still leaves a singularly occupied p orbital on each
carbon atom. These then overlap side on to produce a pi (π) bond which occupies a position above
and below the plane of the molecule.

c.) THE FEATURE OF C=C BOND

• A carbon–carbon bond is a covalent bond between two carbon atoms. The most common form is
the single bond.
• The carbon–carbon single bond is a sigma bond and is formed between one hybridized orbital from
each of the carbon atoms.
MOLECULAR FORMULA OF ALKENES

• GENERAL FORMULA: CnH2n (where n equals any integer greater than one.)
• MOLECULAR FORMULA: C2H4
• STRUCTURAL FORMULA:

• EXAMPLE: Ethene

NOMENCLATURE OF ALKENES AND CYCLOALKENES

Many of the same rules for alkanes apply to alkenes.

1.) Name the parent hydrocarbon by locating the longest carbon chain that contains the double bond and
name it according to the number of carbons with the suffix (-ene).

2.) Number the carbons of the parent chain so the double bond carbons have the lowest possible numbers.

• If the double bond is equidistant from each end, number so the first substituent has the lowest number.

3.) Write out the full name, numbering the substituents according to their position in the chain and list them
in alphabetical order.
 4.) Indicate the double bond by the number of the first alkene carbon.
5.) If more than one double bond is present, indicate their position by using the number of the first carbon of
each double bond and use the suffix -diene (for 2 double bonds), -triene (for 3 double bonds), -tetraene
(for 4 double bonds), etc.

6.) Cycloalkenes are named in a similar way. Number the cycloalkene so the double bond carbons get
numbers 1 and 2, and the first substituent is the lowest possible number.

• If there is a substituent on one of the double bond carbons, it gets number 1.

ALKENES AS SUBSTITUENTS

NON-IUPAC ALKENES
STRUCTURES OF ALKENES AND CYCLOALKENES

ALKENES

• Alkenes are also called olefins.

• Alkenes contain a carbon—carbon double bond.
• Terminal alkenes have the double bond at the end of the carbon chain.
• Internal alkenes have at least one carbon atom bonded to each end of the double bond.

• A carbon carbon triple bond thus consists of one ơ bond and two π bonds. The remaining sp hybrid orbital of
each carbon atom in ethyne forms a sigma bond with the s orbital of hydrogen. In higher alkynes, the
remaining sp hybrid orbitals may overlap with the sp3 hybrid orbitals of the other carbon atoms in the
hydrocarbon chain.

CYCLOALKENES

• Cycloalkenes contain a double bond in a ring.

• General formula is: CnH2n-2

PHYSICAL PROPERTIES OF ALKENES

• Melting and Boiling Point - The physical properties of alkenes and alkynes are very similar to those of alkanes
primarily because these three hydrocarbons have same types of bond present: C-H and C-C bonds, both of
which are nonpolar and only weak Van der Waals or dispersion forces exist between their molecules.

• Density - Alkenes are lighter than water and are insoluble in water due to their non-polar characteristics.
Alkenes are only soluble in nonpolar solvents.
• Solubility - Alkenes are virtually insoluble in water, but dissolve in organic solvents. The reasons for this are
exactly the same as for the alkanes.
PREPARATION OF ALKENES: CRACKING OF PETROLEUM

• Alkenes are prepared (synthesized) industrially by thermal cracking of petroleum.

• Cracking - a reaction that literally cracks or breaks alkane into smaller ones. In addition, alkenes are also
produced together with hydrogen gas which are very valuable commercial products.

NOTE: Another type of cracking is catalytic cracking used to improve the quality of gasoline bye producing highly
branched alkanes with higher octane rating from straight-run petroleum fractions.

• In the laboratory, preparation of alkenes is accomplished by elimination rations.

- converts a single bond to a double bond by removal of atoms or groups of atoms from adjacent carbon
atoms in the substrate.
• Alkenes can be prepared from alkyl halides and alcohols via elimination reactions.
• EXAMPLE:

NATURALLY OCCURING ALKENES

• Alkenes occur abundantly in nature where they perform many important biological roles. The simplest of the
alkenes, ethene, is a plant hormone that induces ripening of fruits.

REACTIVITY OF ALKENES

• Alkenes are a family of hydrocarbons (compounds containing carbon and hydrogen only) containing a
carbon-carbon double bond. Alkenes are relatively stable compounds, but are more reactive than alkanes
because of the reactivity of the carbon–carbon π-bond. Most reactions of alkenes involve additions to this π
bond, forming new single bonds.
• ADDITION REACTION
- The characteristic reaction of alkenes is addition—the π bond is broken and two new σ bonds are formed.
 - Alkenes are electron rich, with the electron density of the π bond concentrated above and below the plane of
the molecule.
- Because alkenes are electron rich, simple alkenes do not react with nucleophiles or bases, reagents that are
themselves electron rich. Alkenes react with electrophiles.
- Because the carbon atoms of a double bond are both trigonal planar, the elements of X and Y can be added to
them from the same side or from opposite sides.

NOTE: Syn addition takes place when both X and Y are added from the same side. Anti addition takes place when
X and Y are added from opposite sides.

- Most alkene addition reactions are exothermic--the products are more stable (lower in energy) than the
reactants.
H H H H
Reaction D escriptive N ame(s ) are replaced by
C C + H H HC C H + heat
H Cl
+ hydrochlorin ation H H H H
C C HCl C C three single bond s
one d ou ble bond
and on e single bond
H OH
C C + H2 O C C hydration

Br Br
NOTE:
C C + Br C C bromination
2
- Exothermic doesn’t mean rapid.
H H
hydrogenation - Reaction rate depends on activation
C C + H
2 C C
(red uction) energy.

-a catalyst is often required

ADDITION OF HX

• Addition of HX (HCl, HBr, or HI) to an alkene gives a haloalkane.

• Reaction is regioselective. (process that favors bond formation at a particular atom over other possible
atoms.)
H Cl NOTE:
CH2 =CH2 + HCl CH2 -CH2 - H adds to one carbon and X
to the other.
Ethylene Chloroethan e
(Ethyl chloride)
MARKONIKOV’S RULE

• states that, in hydrohalogenation of an unsymmetrical alkene, the hydrogen atom in the hydrogen halide
forms a bond with the doubly bonded carbon atom in the alkene, bearing the greater number of hydrogen
atoms.
Cl H H Cl
CH3 CH=CH2 + HCl CH3 CH-CH2 CH3 CH-CH2
Prop ene 2-Ch loroprop ane 1-Chlorop ropan e
(not formed)
ADDITION OF H2O

• Addition of water is called hydration.

• Hydration is acid catalyzed, usually by H2SO4.
• Hydration follows Markovnikov’s rule; H adds to the less substituted carbon and OH adds to the more
substituted carbon.

ADDITION OF Cl2 AND Br2

• Addition reaction can be carried out at room temperature with the use of pure reagents and mixing them
with organic solvent which is nonreactive.
• Addition of Br2 is a useful qualitative test for the presence of a carbon-carbon double bond.
• Br2 has a deep red color; dibromoalkanes are colorless.

ADDITION OF H2 – REDUCTION

• Virtually all alkenes add H2 in the presence of a transition metal catalyst, commonly Pd, Pt, or Ni.

H3 C H Pd
Pd + H2
C C + H2 CH3 CH2 CH2 CH3
25°C, 3 atm 25°C, 3 atm
H CH3 Butane
trans-2-Buten e Cycloh exene Cyclohexan e
OXIDATION REACTION OF ALKENES

• The reaction which increases the oxygen content and/or decreases the hydrogen content of an organic
substrate. Due to the presence of carbon-carbon multiple bonds, alkenes and alkynes are very
susceptible to oxidation.
• Alkenes react with potassium manganate (VII) solution in the cold. The color change depends on whether
the potassium manganate (VII) is used under acidic or alkaline conditions.
• EXAMPLE: OXIDATION OF ALKENES WITH COLD DILUTE POTASSIUM MANGANATE (VII) SOLUTION.
• If the potassium manganate (VII) solution is acidified with dilute sulfuric acid, the purple solution becomes
colorless.
• If the potassium manganate (VII) solution is made slightly alkaline (often by adding sodium carbonate
solution), the purple solution first becomes dark green and then produces a dark brown precipitate.

CHEMISTRY OF THE REACTION

• We'll look at the reaction with ethene. Other alkenes react in just the same way. Manganate(VII) ions are a
strong oxidizing agent, and in the first instance oxidize ethene to ethane-1,2-diol (old name: ethylene glycol).
• Point of view of the organic reaction:

NOTE: THE FULL EQUATION DEPENDS ON

THE CONDITIONS.

- Under acidic conditions, the manganate (VII) ions are reduced to manganese (II) ions.

- Under alkaline conditions, the manganate (VII) ions are first reduced to green manganate (VI) ions.

- And then further to dark brown solid manganese (IV) oxide (manganese dioxide).
 NOTE: This last reaction is also the one you would get if the reaction was done under neutral conditions. You will
notice that there are neither hydrogen ions nor hydroxide ions on the left-hand side of the equation.

BAEYER'S TEST: HYDROXYLATION

• Alkenes when treated with cold, dilute, neutral or basic KMnO 4 (Baeyer’s reagent), readily cause the
decolorization of the purple color of KMnO4 and formation of brown precipitate. This is known as the
Baeyer’s test which is used to detect the presence of unsaturation in a molecule.

• In this reaction, each carbon atom in the double bond of the alkene gets a hydroxyl group resulting in a
compound called a glycol or 1,2-diol. This reaction is not synthetically useful due to the poor yield of the
glycol - the glycol forms only under mild conditions. Under stranger conditions so many side reactions set
in. However, the reaction is very useful in detecting the presence of alkenes and alkynes.

EXAMPLE OF MILD OXIDATION OF ALKENES:

• The formation of a glycol may be a prelude to the eventual cleavage of the double bond. When this
happens, the oxidation is classified as the oxidative cleavage.

OXIDATIVE CLEAVAGE

• Both alkenes and alkynes undergo oxidative cleavage depending on the reagents and conditions used.
• Alkene oxidative cleavage occurs when the alkene is reacted with either the follwing:
• Hot KMnO4
• O3 followed by H2O and Zn (ozonolysis)
• The products formed from oxidative cleavage may either be aldehydes, ketones, carbon dioxide, or even
acids, depending on the structure of the starting materials.

• A terminal doubly-bonded carbon atom which contains two hydrogen atoms is cleaved by hot KMnO 4 to
form CO2 and by ozonolysis to form formaldehyde. A doubly bonded carbon atom with only one hydrogen
atom is cleaved by hot KMnO4 to form carboxylic acid, and by ozonolysis to form an aldehyde. On the
other hand, a doubly-bonded carbon atom which has no hydrogen atom is cleaved by both hot KMnO 4
and ozonolysis to yield a ketone.
 • The carbon atoms involved in the double bonds may have two hydrogens, one hydrogen, or no hydrogen
at all and each type produces different cleavage products shown below:

COMBUSTION

• Alkenes and alkynes undergo combustion in much the same way as alkanes do. However, they are not
ordinarily burned for their fuel value. Their combustion reactions are important since the combustion data
may be used for molecular and empirical formula determinations.

APPLICATION

• Ethylene gas cause physiological changes one is fruit ripening it may also be affected by other gases, such as
carbon dioxide and oxygen, and varies from fruit to fruit. Fruits such as apples and pears emit a greater amount
of ethylene gas in fruits, which affects their ripening. Other fruits, like cherries or blueberries, produce very
little ethylene gas. The effect of ethylene gas upon fruit is a resulting change in texture (softening), color, and
other processes. Ethylene as an aging hormone can damage and destroy plants not only ripening it. Other
effects of ethylene gas are loss of chlorophyll, abortion of plant foliage and stems, shortening of stems, and
bending of the stems (epinasty). Ethylene gas can be either a good guy when used to hasten ripening of fruit
or a bad guy when it yellows vegetables, damages buds, or causes abscission in ornamental specimens.
Hydration of ethene produce tons and tons of alcohol in the US.

SUMMARY

• Alkenes are substances having a general formula of CnH2n, also known as unsaturated HC. It is composed of
a double bond structure which has an angle of 120o. One bond is sigma and the other one is called pi bond.
• Isomerism is the term used for the substances with the same molecular formula but different structures. In
the case of Alkenes they exhibit, skeletal isomerism where the functional group and its position is the same
but carbon skeleton is different.
• Positional isomerism differs in the position of the functional group.
• Geometrical Isomers because of its double bond the alkene can have the cis and trans isomerism.
• Naming of alkenes uses IUPAC, instead of -ane for alkanes -ene for alkenes.
• Alkenes undergo addition and oxidation reactions just like alkanes. The addition of hydrogen to alkenes may
lead to the production of alkanes. May transform to alcohol if added with water. Petroleum industry benefit
more to the alkylation of alkenes. Formation of bigger alkanes is possible just like preparation of octane gas.
• Addition of hydrogen halides to alkenes becomes well known and this is formulated by Vladimir Marconikov
a Russian Chemist in 1869, betterknown as Marconikov’s rule. Which states that the hydrogen is added to the
carbon of the double bond with the greater number of hydrogen atoms.
• Alkenes are prepared by thermal cracking. It breaks longer alkane into smaller ones. The other process is
called catalytic cracking it is use to produce more branched chain alkenes to produce a high-quality petroleum
product from straight chain petroleum products.