ORGANIC COMPOUNDS I

ORGANIC CHEMISTRY

Organic chemistry is the chemistry of carbon compounds except for carbon dioxide and
the carbonates. Metallic cyanides also belong to the “inorganic realm”. Organic
compounds as we have seen last year (Classification of Substances: Organic and
Inorganic compounds) are essentially covalent, more than 99 % of them contain also
hydrogen and the other frequently found elements (called hetero-atoms) are oxygen,
nitrogen, sulphur, phosphorus and the halogens, mainly chlorine.
Because of the ability of carbon to form long chains and complex structures the
chemistry of these compounds posed extraordinary difficulties to the chemists of the
early nineteenth century.
At this time, chemists could identify the first pure chemical product obtained from a
living organism. It contained C, H, O and N in about the same proportion and was
called protein. Many questions arouse: How are thy made in the cell? Can the laws of
chemistry be applied to such compounds as “proteins”? Attempts to synthesise these
compounds from known chemicals had failed time after time.
Organic compounds (the compounds from living organisms) didn’t seem to follow some
of the laws of chemistry: as an example of these difficulties there was the fact that there
were many compounds having the same “formula” but different properties, and that
they couldn’t be prepared from just carbonates and other inorganic raw materials; a
“vital force” found in living organisms was thought to be necessary to form these
curious carbon compounds.
Finally in 1828, Wohler could get to a typical organic compound from ammonium
carbamate (a substance related to carbonates) and Berthelot later prepared acetylene
from carbon and hydrogen. The theory of the vital force was abandoned and at a steady
pace organic chemistry became the chemistry of carbon compounds no matter they were
natural compounds or absolutely artificial compounds as for example Diazepam, Teflon
or (poly) ethane.
The first step to the understanding of Organic Chemistry is to realise that the simple
formula obtained by elemental analysis is not enough to describe them.

CHEMICAL FORMULAE OF ORGANIC COMPOUNDS

When a new compound either natural or synthetic is isolated it is subjected to elemental

analysis to determine what elements are present and in what proportion. This
composition (usually expressed as a percentage) allows the calculation of the empirical
formula.

Empirical formulae

An empirical formula is the simplest formula that shows the ratio of the atoms in a
molecule.
Suppose that a compound is analysed and shows that is made by an 80,12 % of carbon
and 20,14 % of hydrogen (notice that the percentages do not add exactly to 100 because
of the inevitability of experimental errors). The relation expressed in a mole basis can
be found dividing each percentage into the Ar (relative atomic mass) of the
corresponding element:
80,12 : 12,01 = 6.67 and 20,14 : 1,008 = 19,98
These figures show that for every 6,67 moles of C there are 19,98 moles of H in the
compound. Dividing both results into the smallest (6,67) the least possible relation
between the elements, that is the empirical (also called the least) formula is found. In
this case
6,67 : 6, 67 = 1 19,98 : 6,67 = 2,99 (approx 3)
So the empirical formula for this compound is C1H3 or simply CH3
A further example follows.
Compound X has the following percentage composition: 40 % of C, 6,67 % of H and
53,3 of O. Calculate its empirical formula.
Dividing each percentage into the Mr of the element it belongs the Mr of its
corresponding element, we get:
40 : 12 = 3,33 for C 6,67 : 1 = 6,67 for H and 53,3 : 16 = 3,33 for O

If each of the results is divided into 3,33 (the lowest result) the relation turns to be
C = 1 H = 2 O = 1. The empirical formula is thus CH2O.

Molecular formulae

A molecular formula expresses not just the ratio but the exact number of atoms of
each element in a molecule. Obviously ionic compounds do not have a molecular
formula.
To find the molecular formula, the Mr (relative molecular mass) of the compound has to
be found experimentally. Suppose that for the substance of the previous example this
determination has been carried out and a Mr of 29,8 were found. Considering that the
mass of the empirical formula is 15 [(12 x 1) + (1 x 3)] it follows that the molecule is
twice as heavy so it contains twice as many C and H atoms as the empirical formula,
that is the molecular formula will be C2H6.
Regarding the second example above, at least three frequently found substances have
the same empirical formula:
• Formaldehyde (its 40 % aqueous solution is used to preserve biological material)
is simply CH2O
• Ethanoic (acetic) acid (a 3 to 5 % solution used for salad dressing, vinegar)
C2H4O2
• Glucose (syrup is used for making cakes) C6H12O6
If the Mr for compound X is 60: which of the three is X?

A molecular formula simply counts the numbers of each sort of atom present in the
molecule, but tells you nothing about the way they are joined together.

For example, the molecular formula of butane is C4H10, and the molecular formula of
ethanol is C2H6O.

Molecular formulae are very rarely used in organic chemistry, because they don't give
any useful information about the bonding in the molecule.
STRUCTURAL FORMULAE

A structural formula shows how the various atoms are bonded.

There are various ways of drawing this and you will need to be familiar with all of
them.

Displayed formulae

A displayed formula shows all the bonds in the molecule as individual lines. Each line
represents a pair of shared electrons.

For example, this is a model of methane together with its displayed formula:

Notice that the way the methane is drawn bears no

resemblance to the actual shape of the molecule. Methane
isn't flat with 90° bond angles.

Consider the simple molecule with the molecular

formula CH2Cl2. You might think that there were
two different ways of arranging these atoms if you
drew a displayed formula.

The chlorines could be opposite each other or at

right angles to each other. But these two
structures are actually exactly the same. Look at
how they appear as models. One structure is
actually a simple rotation of the other one

The commonest way to draw structural formulae

You can simplify the formula by writing, for

example, CH3 or CH2 instead of showing all
these bonds. So for example, ethanoic acid
would be shown in a fully displayed form and a
simplified form as shown in the figure (see left).
You could even condense it further to CH3COOH

The next three structures all

represent butane. All of these are just
versions of four carbon atoms joined
up in a line. The only difference is
that there has been some rotation
about some of the carbon-carbon bonds. We will choose the linear drawing as a
standard representation of its structure
 It doesn't matter in the least whether
you draw any side groups pointing up
or down. All of the following
represent exactly the same molecule.

If you made a model of one of them,

you could turn it into any other one
simply by rotating one or more of the
carbon-carbon bonds.

CARBON CHAINS AND FUNCTIONAL GROUPS: HOMOLOGOUS SERIES

Oversimplifying for the sake of simplicity, an organic molecule can be divided in two
parts: the carbon chain or carbon skeleton and the functional groups

The carbon chain works as a

scaffold to which the functional
groups are attached. It is made by a
series of carbon atoms linked by
single bonds. The links to atoms
other than carbon and the functional
groups are links to hydrogen atoms.
The figure shows linear, branched
and closed chains

The functional groups are atoms or groups of atoms

that provide the molecules with their specific physical
and chemical characteristics. Molecules that have the
same functional group belong to the same (or form a)
homologous series. Each of the members of the
series differs from the previous member because of a –
CH2– group. They are a family of compounds with
definite properties that gradually change as the size of
the chain increases (or the chain is branched).

UNSATURATION NUMBER

A compound has been considered to be saturated when it can add no H2. Unsaturation
indicates that there are double bonds in the compound, either C – C or C- Z (Z stands
for any other atom that could eventually form a double bond). A cycle (although not
being a double bond, formally could add a hydrogen molecule opening the cycle or ring
without splitting the molecule in two.

Unsaturation number is easily calculated for any molecule and gives worthy information
when you are given the molecular formula and have to find possible structures for it.

For calculating it a very simple “recipe” can be used after a short explanation:
 1- Remember that an unsaturation can be either a double bond (triple bonds show
two unsaturations), or a cycle or A dative bond
2- Hydrogen and the halogens are considered to be monovalent, i. e. they for just
one bond. The number of monovalent atoms call it (I)
3- Oxygen and sulphur are considered divalent (form two bonds).
4- Nitrogen and phosphorus are considered trivalent (three bonds). The number of
trivalent atoms call it (III)
5- Carbon and silicon are always tetravalent. Total number of them call it (IV)

Unsaturation Number (UN) = (IV) – (I)/2 + (III)/2 + 1

Thus, for C6H8 the unsaturation number is UN = 6 – 8/2 + 1 = 3. Its structure can
show a double and a triple bond, three double bonds, two double bonds and a cycle
and so on. Although there are still a lot of possibilities, much more structures can be
immediately discarded.

For C6H10O UN = 6 – 10/2 + 1 = 2 (notice that divalent atoms do not appear in

the “formula”

Finally; C2H7N UN = 2 – 7/2 + 1/2 + 1 = 0

STRUCTURAL ISOMERISM

What are isomers?

Isomers are molecules that have the same molecular formula, but have a different
arrangement of the atoms in space. That excludes any different arrangements which
are simply due to the molecule rotating as a whole, or rotating about particular bonds.

For example, both of the molecules (right)

are the same molecule. They are not
isomers. Both are butane. There are also
endless other possible ways that this
molecule could twist itself. There is
completely free rotation around all the
carbon-carbon single bonds.

If you had a model of a molecule in front of you, you would have to take break some
bonds and rebuild it if you wanted to make an isomer of that molecule. If you can make
an apparently different molecule just by rotating single bonds, it's not different - it's still
the same molecule.

What are structural isomers?

In structural isomerism, the atoms are arranged in a completely different order. This is
easier to see with specific examples.

What follows, looks at some of the ways that structural isomers can arise. The names of
the various forms of structural isomerism probably don't matter all that much, but you
must be aware of the different possibilities when you come to draw isomers.
TYPES OF STRUCTURAL ISOMERISM

Chain isomerism

These isomers arise because of the

possibility of branching in carbon
chains. For example, there are two
isomers of butane, C4H10. In one of them,
the carbon atoms lie in a "straight chain"
whereas in the other the chain is
branched.

Be careful not to draw "false" isomers which are just

twisted versions of the original molecule. For example,
this structure is just the straight chain version of butane
rotated about the central carbon-carbon bond. You could
easily see this with a model. This is the example we've
already used at the top of this page.

Pentane, C5H12, has three chain

isomers. If you think you can find any
others, they are simply twisted versions
of the ones below.

Position isomerism

In position isomerism, the basic carbon skeleton remains unchanged, but functional
groups are moved around on that skeleton.

For example, there are two position

isomers with the molecular formula
C3H7Br. In one of them the bromine atom
is on the end of the chain, whereas in the
other it's attached in the middle.

If you made a model, there is no way that you could twist one molecule to turn it into
the other one. You would have to break the bromine off the end and re-attach it in the
middle. At the same time, you would have to move a hydrogen from the middle to the
end.

Another similar example occurs

in alcohols such as C4H9OH
These are the only two possibilities
provided you keep to a four carbon chain
but you can easily have a mixture of chain
isomerism and position isomerism So two
other isomers of butanol are:

Functional group isomerism

In this variety of structural isomerism, the isomers contain different functional groups -
that is, they belong to different families of compounds (different homologous series).

For example, a molecular formula C3H6O could be either propanal (an aldehyde) or
propanone (a ketone).There are
other possibilities as well for this
same molecular formula: you
could have a carbon-carbon
double bond (an alkene) and an
-OH group (an alcohol) in the
same molecule

NOMENCLATURE OF ORGANIC COMPOUNDS

A modern organic name is simply a code. Each part of the name gives you some useful
information about the compound. To understand the name 2-methylpropan-1-ol you
need to take the name to pieces.

The prop in the middle tells you how many carbon atoms there are in the longest chain
(in this case, 3). The an which follows the "prop" tells you that there aren't any carbon-
carbon double bonds.

The other two parts of the name tell you about interesting things which are happening
on the first and second carbon atom in the chain. Any name you are likely to come
across can be broken up in this same way.

Counting the carbon atoms

You will need to remember the codes for the number of carbon atoms in a chain up to 6
carbons. There is no easy way around this - you have got to learn them. If you don't do
this properly, you won't be able to name anything!

code no of carbons code no of carbons

meth 1 but 4
eth 2 pent 5
prop 3 hex 6

Types of carbon-carbon bonds

Whether or not the compound contains a carbon-carbon double bond is shown by the
two letters immediately after the code for the chain length.

code means

an only carbon-carbon single bonds

contains a carbon-carbon double

en
bond

For example, butane means four carbons in a chain with no double bond.

Propene means three carbons in a chain with a double bond between two of the
carbons.

Alkyl groups

Compounds like methane, CH4, and ethane, CH3CH3, are members of a family of
compounds called alkanes. If you remove a hydrogen atom from one of these you get an
alkyl group.

For example:

• A methyl group is CH3.

• An ethyl group is CH3CH2.

These groups must, of course, always be attached to something else.

Numbering the chain

• Choose the longest possible chain no matter how twisted it seems to be. That
chain will give you the “root” of the name.
• If there is a double bond in the chain, choose the double bond containing chain
as the basis for your naming
• Then start numbering the C atoms from one of the ends of the chosen chain
• You can start from any of the two ends of the chain
• Choose the end that will allow the lowest possible number for the carbons to
which side –chains and/or functional groups are attached.
• If the functional group is placed at the beginning of the chain, assign number 1
to that carbon.

Functional groups

The ending of the name generally gives you the functional group or family to which the
compound belongs. In some cases the ending is just that of the hydrocarbon and a prefix
is used instead. The chart shows the code to different functional groups. The list is by
no means exhaustive. You are allowed to use this table with no scribbling during the
test and the exams (including December or March exams)
 FUNCTIONAL
FUNCTIONS ENDING EXAMPLE
GROUP
Alkanes -ane
Alkenes -ene
Alkynes -yne
Aromatic Non systematic with –
Hydrocarbons ene ending
Alcohols -ol
Ethers …yl ether

Aldehydes -al

Ketones -one

Carboxylic acids -oic acid

Esters …yl ….ate

…yl amine or
Amines
amino…ane

Amides -anoamide

Nitriles -anonitrile
Halo-alkanes Halo….ane (ene)

APPLYING THE CODES

The alkanes

Example 1: Write the structural formula for 2-methylpentane.

Start decoding the name from the bit that counts the number of carbon atoms in the
longest chain - pent counts 5 carbons.

Are there any carbon-carbon double bonds? No: an tells you there aren't any.

Now draw this carbon skeleton:

Put a methyl group on the number 2 carbon atom:

Does it matter which end you start counting from? No - if you

counted from the other end, you would draw the next structure. That's exactly the same
as the first one, except that it has been flipped over.
Finally, all you have to do is to put in the correct number of hydrogen atoms on each
carbon so that each carbon is forming four bonds.

If you had to name this yourself:

• Count the longest chain of carbons that you can find. Don't assume that you have
necessarily drawn that chain horizontally. 5 carbons means pent.
• Are there any carbon-carbon double bonds? No - therefore pentane.
• There's a methyl group on the number 2 carbon - therefore 2-methylpentane.
Why the number 2 as opposed to the number 4 carbon? In other words, why do
we choose to number from this particular end? The convention is that you
number from the end which produces the lowest numbers in the name - hence 2-
rather than 4-.

Example 2: Write the structural formula for 2,3-dimethylbutane.

Start with the carbon backbone. There are 4 carbons in the longest chain (but) with no

carbon-carbon double bonds (an).

This time there are two methyl groups (di) on the number 2 and
number 3 carbon atoms.

Completing the formula by filling in the hydrogen atoms gives:

The cycloalkanes

In a cycloalkane the carbon atoms are joined up in a ring – hence a cyclo prefix is added

Example 3: Write the structural formula for cyclohexane.

Hexane shows 6 carbons with no carbon-carbon double bonds. Cyclo

shows that they are in a ring. Drawing the ring and putting in the correct
number of hydrogens to satisfy the bonding requirements of the carbons
gives:

The alkenes

Example 5: Write the structural formula for but-1-ene.

But counts 4 carbon atoms in the longest chain and en tells you that there is a carbon-
carbon double bond. The number in the name tells you where the double bond starts.

No number would be necessary in the propene example above because the double bond
has to start on one of the end carbon atoms. In the case of butene, though, the double
bond could either be at the end of the chain or in the middle - and so the name has to
code for its position.
The carbon skeleton is:

And the full structure is:

Compounds containing halogens

Example 6: Write the structural formula for 1,1,1-trichloroethane.

This is a two carbon chain (eth) with no double bonds (an). There are three chlorine
atoms all on the first carbon atom.

Alcohols

All alcohols contain an -OH group. This is shown in a name by the ending ol.

Example 7: Write the structural formula for 2-methylpropan-1-ol.

The carbon skeleton is a 3 carbon chain with no carbon-carbon double bonds, but a
methyl group on the number 2 carbon.

The -OH group is attached to the number 1 carbon.

The structure is therefore:

PROBLEMS ON ORGANIC CHEMISTRY

1- Calculate the percent composition for acetone (C3H6O) and nitrobenzene

(C6H5O2N).
2- On analysis a compound shows 85,7 %C and 14,3 %H. At 100°C and 1 atm. 274
mg of this compound occupies 100 mL. Calculate its empirical and molecular
formulae.
3- 100mg of an organic liquid burn completely forming 314 mg of CO2 and 128,6
mg of H2O. Cryoscopic methods indicate that its Mr is 70. Find:
a- The mass of one mole of the substance
b- The mass of H2O and CO2 that would be formed from one mole of it.
c- The number of moles of C and H atoms in this calculated mass.
d- The molecular formula of the substance.
e- Write a possible structure foe it
4- Write the formulae and structures for the following compounds:
a- pentanal
b- 3-methyl-butanone
c- 2,3-dichlorobut-2-ene
d- 2-amino-pent-3-enoic acid
e- 3-chloro-cyclopentanol
5- Write and name:
a- two chain isomers to 4-a
b- two functional isomers to 4-a
 c- two position isomers to 4-e
6- Write and name:
a- a two carbon carboxylic acid
b- a branched 4 carbon alcohol
c- an amine that has Mr = 31
d- a cyclic ketone
7- Name the following structures: