Organic Chemistry - Introduction F322 1

Basic definitions for organic chemistry

Scope Organic chemistry is a vast subject so is split it into small sections for study. This
is done by studying compounds which behave in a similar way because they have
a particular atom, or group of atoms, (FUNCTIONAL GROUP) in their structure.

Catenation The ability to form bonds between atoms of the same element. Carbon
catenates to form chains and rings, with single, double or triple covalent bonds.

Q.1 • Why does carbon form so many catenated compounds ?

• Why does silicon undergo catenation to a lesser extent than carbon ?

Homologous
Series A series of organic compounds having the same functional group and each
member differs from the next by CH2 .

• all share the same general formula

• formulae differ from their neighbours by CH2. (e.g. CH4, C2H6, . . . etc )
• contain the same functional group(s)
• have similar chemical properties
• show a gradual change in physical properties as molar mass increases
• can usually be prepared by similar methods.

Functional
Group A group of atoms responsible for the characteristic reactions of a compound.
• can consist of - one atom — Br
- a group of atoms — OH
- multiple bonds between carbon atoms C=C

• each functional group has its own distinctive properties

Q.2 The followingH listHcontains

H H some
H molecular formulae. DrawH outHas many
H Hlegitimate
H structures
for each and classify each compound made according to the functional group present.
H C C C atoms
C CwillOH H C C C Cthem, NH 2
C oxygen
Remember that carbon have four covalent bonds surrounding atoms
will have two,H nitrogen atoms three and hydrogen atoms and
H H H H H halogen atoms just one.
H H H H
carbon skeleton functional
carbon skeleton functional group
group
C2H6 C4H10 C4H8 C2H6O C3H6O C2H7N C2H4O2 C2H3N

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2 F322 Organic Chemistry - Introduction

Some common functional groups

GROUP ENDING GEN. FORMULA / STRUCTURE EXAMPLE

ALKANE - ane RH C C C2H6 ethane

ALKENE - ene C C C2H4 ethene

C C
ALKYNE - yne C2H2 ethyne

HALOALKANE halo - RX C − Cl C2H5Cl chloroethane

ALCOHOL - ol ROH O H C2H5OH ethanol

H
ALDEHYDE -al RCHO C CH3CHO ethanal
O

C
KETONE - one RCOR C O CH3COCH3 propanone
C

O H
CARBOXYLIC - oic acid RCOOH C CH3COOH ethanoic acid
ACID O

Cl
ACYL - oyl chloride RCOCl C CH3COCl ethanoyl chloride
O
CHLORIDE

NH2
AMIDE - amide RCONH2 C CH3CONH2 ethanamide
O

O R
ESTER - yl - oate RCOOR C CH3COOCH3 methyl ethanoate
O

NITRILE - nitrile RCN C N CH3CN ethanenitrile

AMINE - amine RNH2 C − NH2 CH3NH2 methylamine

+ O
NITRO - nitro RNO2 N CH3NO2 nitromethane
-
O
O
SULPHONIC - sulphonic RSO3H S OH C6H5SO3H benzene sulphonic
ACID acid O acid

ETHER - oxy - ane ROR R-O-R C2H5OC2H5 ethoxyethane

The symbol R represents groups of carbon and hydrogen atoms in the rest of the molecule

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Organic Chemistry - Introduction F322 3

Use of different formulae in organic chemistry

General the simplest algebraic formula for a

member of a homologous series CnH2n+2 for an alkane
CnH2n for an alkene

Molecular shows the exact number of atoms

of each element in a molecule C4H10 for butane

Empirical shows the simplest whole number ratio

of atoms of each element in a molecule C2H5 for butane

Structural the minimal detail that shows the

arrangement of atoms in a molecule CH3CH2CH2CH3 butane

CH3CHOHCH3 propan-2-ol

H H H H
Displayed shows the relative positioning of atoms
and the number of bonds between them H C C C C H butane

H H H H

Skeletal used to show a simplified organic formula

by removing hydrogen atoms from alkyl
chains, leaving just a carbon skeleton and cyclohexane
associated functional groups.

• each covalent bond is shown by a line cyclohexene

• a carbon atom is at the join of lines
• functional groups are shown OH
• the number of hydrogen atoms on cyclohexanol
each carbon atom is the difference
between the number of lines and 4

OH butan-1-ol

Skeletal formulae tend to be used with

N
larger organic molecules - e.g. thalidomide
O N O
O

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4 F322 Organic Chemistry - Introduction

Nomenclature in organic chemistry

Systems A naming system must tell you everything about a structure without ambiguity.
There are two types of naming system commonly found in organic chemistry;

Trivial : based on some property or historical aspect;

the name tells you little about the structure

Systematic : based on an agreed set of rules (I.U.P.A.C);

exact structure can be found from the name (and vice-versa).

Series trivial name systematic name example(s)

paraffin alkane methane, butane
olefin alkene ethene, butene
fatty acid alkanoic (carboxylic) acid ethanoic acid

Compounds trivial name derivation systematic name

acetic acid acetum = vinegar (Lat.) ethanoic acid (CH3COOH)

Systematic (IUPAC) Nomenclature

STEM Shows the number of carbon atoms in longest chain bearing the functional group
+ (if necessary) a prefix showing the position and identity of any substituents

Nomenclature Apart from the first four, which retain trivial names, Prefix C atoms Alkane
the number of carbons atoms is indicated by a
prefix derived from the Greek numbering system. meth- 1 methane
eth- 2 ethane
prop- 3 propane
• the list of alkanes demonstrate the use of prefixes but- 4 butane
pent- 5 pentane
• the ending is the same as they are all alkanes hex- 6 hexane
hept- 7 heptane
oct- 8 octane
non- 9 nonane
dec- 10 decane

SUFFIX The ending tells you which functional group is present

Nomenclature If any functional groups are present, add relevant ending to the basic stem. The
position of the functional group must be given to avoid any ambiguity.

In many cases the chain of carbon atoms is branched so one must include the ...

Substituents Many compounds have substituents (additional atoms, or groups of atoms)

attached to the chain. Their position is numbered according to a set of rules.

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Organic Chemistry - Introduction F322 5

NOMENCLATURE - GENERAL RULES

Stem • look for the longest chain of carbon atoms containing the functional group.
• the carbon atoms must be in a continuous row.
• use prefixes as shown on previous page
• ending tells you what type of carbon structure you have; alkanes end in ANE

Side-chain • carbon based substituents are named before the chain name.
• they have the prefix -yl added to the basic stem (e.g. CH3 is methyl).
• Number the principal chain from one end so that the side chain is attached
to a carbon atom with the lowest possible number.

CH3
e.g. 2-methylhexane CH3 CH 2 CH CH 2 CH CH
2 3

If there is more than one side-chain the following rules apply:-

• side-chain names appear in alphabetical order i.e. butyl, ethyl, methyl, propyl.
• number the principal chain from one end to give the lowest numbers.
• each side-chain is given its own number.
• if identical side-chains appear more than once, prefix with di, tri, tetra etc
• numbers are separated from names by a HYPHEN 2-methylheptane
• numbers are separated from numbers by a COMMA 2,3-dimethylbutane

Example CH 3
CH2 CH3
• longest chain 8 (it is an octane)
CH3 CH2 CH2
• 3,4,6 are the numbers NOT 3,5,6 CH3 CH 2 CH CH2 CH CH CH2 CH3
• order is ethyl, methyl, propyl 6 5 4 3 2 1
NOT 1 2 3 4 5 6

3-ethyl-6-methyl-4-propyloctane

Q.3 Name these alkanes

CH3 CH3

CH2 CH2

CH3 CH CH2 CH3 CH3 CH CH2 CH2 CH2 CH CH3

2

CH3
CH3 CH3 CH2 CH3
CH3 CH CH CH CH2 CH CH3 CH3 CH CH2 CH2 CH CH2 CH3
2 2

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6 F322 Organic Chemistry - Introduction

ALKENES / ALCOHOLS

Length In alkenes and alcohols the principal chain is not always the longest chain.

Alkenes It must contain the C=C bond. The name ends in -ENE
Alcohols It must contain the OH group. The name ends in -OL

Position Alkenes Indicated by the lower numbered carbon atom on one end of the
double bond. Count from one end to give lowest number.

CH3 CH CH CH2 CH 3 is pent-2-ene ( NOT pent-3-ene )

Alcohols Count from one end to give lowest number.

CH3 CH 2 CH2 CH CH 3 is pentan-2-ol ( NOT pentan-4-ol )

OH

Side-chain Position is based on the number allocated to the C=C bond or OH group.

CH3 CH3 OH
CH3 CH2 C CH2 CH3 CH CH CH3

2-methylbut-1-ene 3-methylbutan-2-ol

Q.4 Draw structures for . . . • 4-methylhex-2-ene

• 3,3-dimethyloct-1-ene • 4-ethyl-3-methylhexan-1-ol

Q.5 Name these compounds.

CH3 CH CH3
CH3 CH2
CH3 CH OH CH3 CH2 CH CH CH2
CH3 CH2 CH CH2 CH CH 3 CH2 CH 2

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Organic Chemistry - Introduction F322 7

PERCENTAGE YIELD

Yield • the mass of a product obtained in reaction

Percentage • the mass of product obtained expressed as a percentage of what you ought
yield to get assuming complete conversion

Example 1 What mass of salicylic acid will make 5g of aspirin (assuming 100% conversion)?

Aspirin can be made by the reaction between salicylic acid and ethanoic
anhydride. If one mole of each of the reactants is used the masses involved are...

COOH COOH
OH OOC CH3
+ (CH3CO)2O ——> CH3COOH +

Mr = 138 Mr = 102 Mr = 60 Mr = 180

In order to make 180g of aspirin you will need a minimum of 138g of salicylic acid.

If you only want 5g of aspirin you will need to scale the masses accordingly...

molar scale 138g 102g 60g 180g

divide by 180 138g/180 102g/180 60g/180 1g

multiply by 5 5 x 138g/180 5 x 102g/180 5 x 60g/180 5g

3.833g salicylic acid will produce 5g of aspirin

Example 2 When an experiment was carried out using 3.833g of salicylic acid, only 3.75g
of aspirin was produced. What is the percentage yield of aspirin?

If there is a 100% yield then... 3.833g salicylic acid ——> 5g of aspirin

If 3.75g of aspirin is made, the percentage yield = 3.75g / 5g x 100 = 75%

Q.6 The equation for the synthesis of N-ethyl ethanamide from ethylamine and ethanoyl chloride is
CH3COCl + C2H5NH2 ——> CH3CONHC2H5 + HCl
• What mass of ethanoyl chloride is required to make 3g of N-ethyl ethanamide?
• If only 1.8g are produced, what is the percentage yield?

Q.7 Ethyl ethanoate can be synthesised from ethanoyl chloride and ethanol.
CH3COCl + C2H5OH ——> CH3COOC2H5 + HCl
• What mass of ethanoyl chloride will react with 2.3g of ethanol?
• If only 1g of ethyl ethanoate is produced, what is the percentage yield from 2.3g of ethanol?

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8 F322 Organic Chemistry - Introduction

ATOM ECONOMY

Background • In most reactions you only want to make one of the resulting products
• atom economy is a measure of how much of the products are useful

ATOM ECONOMY = MOLECULAR MASS OF DESIRED PRODUCT x 100

SUM OF MOLECULAR MASSES OF ALL PRODUCTS

Example 1 Calculate the atom economy for the formation of 1,2-dichloroethane, C2H4Cl2
C2H4 + Cl2 ——> C2H4Cl2
Mr 28 71 99

atom economy = molecular mass of C2H4Cl2 x 100 = 99 x 100 = 100%

molecular mass of all products 99

Example 2 Calculate the atom economy for the formation of nitrobenzene, C6H5NO2
C6H6 + HNO3 ——> C6H5NO2 + H2O
Mr 78 63 123 18

atom economy = molecular mass of C6H5NO2 x 100 = 123 x 100 = 87.2%

molecular mass of all products 141

Notes • addition reactions will have 100% atom economy

• substitution reactions will have less than 100% atom economy
• elimination reactions will have less than 100% atom economy
• high atom economy = fewer waste materials
• reactions may have a high yield but a low atom economy

Q.8 Calculate the atom economy of the following reactions (required product is in bold);

• CH3COCl + C2H5NH2 ——> CH3CONHC2H5 + HCl

• C2H5Cl + NaOH ——> C2H5OH + NaCl
• C2H5Cl + NaOH ——> C2H4 + H2O + NaCl

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Organic Chemistry - Introduction F322 9
Elucidation of the structures of organic compounds - a brief summary

Introduction Traditionally, working out the identity was a long-winded process but, with the use
of modern analytical instruments, the process is much quicker.

ELEMENTAL COMPOSITION PERCENTAGE COMPOSITION EMPIRICAL FORMULA

STRUCTURAL FORMULA MOLECULAR FORMULA MOLECULAR MASS

Elemental
composition The presence of carbon and hydrogen can be proved by letting the compound undergo
combustion. Carbon is converted to carbon dioxide and hydrogen to water. Other
elements can also be identified.

Percentage
composition The percentage composition by mass is found by dividing the mass of an element present
by the mass of the compound present, then multiplying by 100. Elemental mass of C and
H can be found by allowing the substance to undergo complete combustion.

• mass of carbon = 12/44 of the mass of CO2 produced

• mass of hydrogen = 2/18 of the mass of H2O produced

Empirical
formula Gives the simplest ratio of elements present in the substance. It can be calculated by
dividing the mass or percentage mass of each element present by its molar mass and
finding the simplest ratio between the answers. Empirical formula is converted to the
molecular formula using molecular mass.

Molecular
mass Nowadays mass spectrometry is used. The position of the last m/z signal is due to the
molecular ion and gives the molecular mass. The fragmentation pattern also gives
information about the compound.

Molecular
formula The molecular formula is an exact multiple of the empirical formula. Comparing the
molecular mass with the empirical mass allows one to find the true formula.

if the empirical formula is CH (relative mass = 13) and the molecular mass is 78
the molecular formula will be 78/13 or 6 times the empirical formula i.e. C6H6 .

Structural
formula Because of the complexity of organic molecules, there can be more than one structure for
a given molecular formula. To work out the structure, one can carry out different tests...

Chemical Use chemical reactions to identify the functional group(s) present.

Spectroscopy IR detects bond types due to absorbance of i.r. radiation

NMR gives information about the position and relative
numbers of hydrogen atoms present in a molecule

Confirmation By comparison of spectra and melting point or boiling point.

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