ORGANIC CHEMISTRY

A guide for A level students

AN INTRODUCTION TO

KNOCKHARDY PUBLISHING

2008
SPECIFICATIONS

KNOCKHARDY PUBLISHING

ORGANIC CHEMISTRY
INTRODUCTION
This Powerpoint show is one of several produced to help students understand selected topics at AS and A2 level Chemistry. It is based on the requirements of the AQA and OCR specifications but is suitable for other examination boards. Individual students may use the material at home for revision purposes or it may be used for classroom teaching if an interactive white board is available. Accompanying notes on this, and the full range of AS and A2 topics, are available from the KNOCKHARDY SCIENCE WEBSITE at... www.knockhardy.org.uk/sci.htm

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ORGANIC CHEMISTRY
CONTENTS
Scope of organic chemistry
Special nature of carbon Types of formulae Homologous series Functional groups Nomenclature Investigating molecules Revision check list

ORGANIC CHEMISTRY
Before you start it would be helpful to Recall how covalent bonding arises Recall simple electron pair repulsion theory

ORGANIC CHEMISTRY
Organic chemistry is the study of carbon compounds. It is such a complex branch of chemistry because...

CARBON ATOMS FORM STRONG COVALENT BONDS TO EACH OTHER

THE CARBON-CARBON BONDS CAN BE SINGLE, DOUBLE OR TRIPLE

CARBON ATOMS CAN BE ARRANGED IN

STRAIGHT CHAINS BRANCHED CHAINS and RINGS

OTHER ATOMS/GROUPS OF ATOMS CAN BE PLACED ON THE CARBON ATOMS

GROUPS CAN BE PLACED IN DIFFERENT POSITIONS ON A CARBON SKELETON

SPECIAL NATURE OF CARBON - CATENATION

CATENATION is the ability to form bonds between atoms of the same element. Carbon forms chains and rings, with single, double and triple covalent bonds, because it is able to FORM STRONG COVALENT BONDS WITH OTHER CARBON ATOMS

Carbon forms a vast number of carbon compounds because of the strength of the C-C covalent bond. Other Group IV elements can do it but their chemistry is limited due to the weaker bond strength.
BOND C-C ATOMIC RADIUS 0.077 nm BOND ENTHALPY +348 kJmol-1

Si-Si

0.117 nm

+176 kJmol-1

The larger the atoms, the weaker the bond. Shielding due to filled inner orbitals and greater distance from the nucleus means that the shared electron pair is held less strongly.

THE SPECIAL NATURE OF CARBON

CHAINS AND RINGS

CARBON ATOMS CAN BE ARRANGED IN

STRAIGHT CHAINS

BRANCHED CHAINS

and

RINGS

You can also get a combination of rings and chains

THE SPECIAL NATURE OF CARBON

MULTIPLE BONDING AND SUBSTITUENTS

CARBON-CARBON COVALENT BONDS CAN BE SINGLE, DOUBLE OR TRIPLE

THE SPECIAL NATURE OF CARBON

MULTIPLE BONDING AND SUBSTITUENTS

CARBON-CARBON COVALENT BONDS CAN BE SINGLE, DOUBLE OR TRIPLE

DIFFERENT ATOMS / GROUPS OF ATOMS CAN BE PLACED ON THE CARBONS The basic atom is HYDROGEN but groups containing OXYGEN, NITROGEN, HALOGENS and SULPHUR are very common.

CARBON SKELETON

FUNCTIONAL GROUP

CARBON SKELETON

FUNCTIONAL GROUP

The chemistry of an organic compound is determined by its FUNCTIONAL GROUP

THE SPECIAL NATURE OF CARBON

MULTIPLE BONDING AND SUBSTITUENTS

ATOMS/GROUPS CAN BE PLACED IN DIFFERENT POSITIONS ON A CARBON SKELETON THE C=C DOUBLE BOND IS IN A DIFFERENT POSITION

PENT-1-ENE

PENT-2-ENE

THE CHLORINE ATOM IS IN A DIFFERENT POSITION

1-CHLOROBUTANE

2-CHLOROBUTANE

TYPES OF FORMULAE - 1
MOLECULAR FORMULA The exact number of atoms of each element present in the molecule

C4H10

THE EXAMPLE BEING

USED IS...

BUTANE

EMPIRICAL FORMULA The simplest whole number ratio of atoms in the molecule

C2H5

STRUCTURAL FORMULA The minimal detail using conventional groups, for an unambiguous structure

CH3CH2CH2CH3

CH3CH(CH3)CH3

there are two possible structures

DISPLAYED FORMULA Shows both the relative placing of atoms and the number of bonds between them

H H C H

H C H

H C H

H C H H H

H C

H C

H C H

H H H C H H

TYPES OF FORMULAE - 2
SKELETAL FORMULA A skeletal formula is used to show a simplified organic formula by removing hydrogen atoms from alkyl chains, leaving just a carbon skeleton and associated functional groups
CH2 CH2 CH2 CH2 CH2

for
CH2

CYCLOHEXANE

THALIDOMIDE

TYPES OF FORMULAE - 2
SKELETAL FORMULA A skeletal formula is used to show a simplified organic formula by removing hydrogen atoms from alkyl chains, leaving just a carbon skeleton and associated functional groups
CH2 CH2 CH2 CH2 CH2

for
CH2

CYCLOHEXANE

THALIDOMIDE

GENERAL FORMULA Represents any member of a homologous series

for alkanes it is... possible formulae...

CnH2n+2 CH4, C2H6 .... C99H200

The formula does not apply to cyclic compounds such as cyclohexane is C6H12 - by joining the atoms in a ring you need fewer Hs

HOMOLOGOUS SERIES
A series of compounds of similar structure in which each member differs from the next by a common repeating unit, CH2. Series members are called homologues and...
all share the same general formula.

formula of a homologue differs from its neighbour by CH2. (e.g. CH4, C2H6, ... etc ) contain the same functional group have similar chemical properties. show a gradual change in physical properties as molar mass increases. can usually be prepared by similar methods.

ALCOHOLS - FIRST THREE MEMBERS OF THE SERIES

CH3OH METHANOL

C2H5OH ETHANOL

C3H7OH PROPAN-1-OL

FUNCTIONAL GROUPS
Organic chemistry is a vast subject so it is easier to 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.
Functional groups can consist of one atom, a group of atoms or multiple bonds between carbon atoms. Each functional group has its own distinctive properties which means that the properties of a compound are governed by the functional group(s) in it.

H H H H H H C C C C C H H H H H
Carbon skeleton Functional Group = AMINE

H H H H H NH2 H C C C C C H H H H H
Carbon skeleton Functional Group = ALCOHOL

OH

COMMON FUNCTIONAL GROUPS

GROUP
ALKANE ALKENE ALKYNE

ENDING
- ane - ene - yne

GENERAL FORMULA
RH C2H6 C2H4 C2H2

EXAMPLE
ethane ethene ethyne

HALOALKANE
ALCOHOL ALDEHYDE KETONE CARBOXYLIC ACID ACYL CHLORIDE AMIDE ESTER NITRILE AMINE NITRO SULPHONIC ACID ETHER

halo - ol -al - one - oic acid - oyl chloride - amide - yl - oate - nitrile - amine nitro- sulphonic acid - oxy - ane

RX
ROH RCHO RCOR RCOOH RCOCl RCONH2 RCOOR RCN RNH2 RNO2 RSO3H ROR

C2H5Cl
C2H5OH CH3CHO CH3COCH3 CH3COOH CH3COCl CH3CONH2 CH3COOCH3 CH3CN CH3NH2 CH3NO2 C6H5SO3H C2H5OC2H5

chloroethane
ethanol ethanal propanone ethanoic acid ethanoyl chloride ethanamide methyl ethanoate ethanenitrile methylamine nitromethane benzene sulphonic acid ethoxyethane

COMMON FUNCTIONAL GROUPS

ALKANE ALKENE ALKYNE HALOALKANE AMINE NITRILE ALCOHOL ETHER ALDEHYDE SULPHONIC ACID ACYL CHLORIDE ESTER CARBOXYLIC ACID

AMIDE

NITRO

KETONE

HOW MANY STRUCTURES?

Draw legitimate structures for each molecular formula and classify each one according to the functional group present. Not all the structures represent stable compounds. carbon atoms have oxygen atoms nitrogen atoms hydrogen halogen atoms 4 covalent bonds surrounding them 2 3 1 1

C2H6 C3H7Br C4H8 C2H6O C3H6O C2H7N C2H4O2 C2H3N

ONE TWO FIVE - 3 with C=C and 2 ring compounds with all C-Cs TWO - 1 with C-O-C and 1 with C-O-H SIX - 2 with C=O, 2 with C=C and 2 with rings TWO SEVERAL - Only 2 are stable TWO

HOW MANY STRUCTURES?

Draw legitimate structures for each molecular formula and classify each one according to the functional group present. Not all the structures represent stable compounds. carbon atoms have oxygen atoms nitrogen atoms hydrogen halogen atoms 4 covalent bonds surrounding them 2 3 1 1

C2H6 C3H7Br C4H8 C2H6O C3H6O C2H7N C2H4O2 C2H3N

ONE TWO FIVE - 3 with C=C and 2 ring compounds with all C-Cs TWO - 1 with C-O-C and 1 with C-O-H SIX - 2 with C=O, 2 with C=C and 2 with rings TWO SEVERAL - Only 2 are stable TWO

NOMENCLATURE
Ideally a naming system should tell you everything about a structure without ambiguity. There are two types of naming system commonly found in organic chemistry; Trivial : Systematic : based on some property or historical aspect; the name tells you little about the structure based on an agreed set of rules (I.U.P.A.C); exact structure can be found from the name (and vice-versa). HOMOLOGOUS SERIES systematic name example(s) alkane methane, butane alkene ethene, butene alkanoic (carboxylic) acid ethanoic acid

trivial name paraffin olefin fatty acid

trivial name methane butane acetic acid

INDIVIDUAL COMPOUNDS derivation systematic name methu = wine (Gk.) methane (CH4) butyrum = butter (Lat.) butane (C4H10) acetum = vinegar (Lat.) ethanoic acid (CH3COOH)

I.U.P.A.C. NOMENCLATURE
A systematic name has two main parts.
STEM number of carbon atoms in longest chain bearing the functional group + a prefix showing the position and identity of any side-chain substituents.

Apart from the first four, which have trivial names, the number of carbons atoms is indicated by a prefix derived from the Greek numbering system.

Prefix methethpropbutpenthexheptoctnondec-

C atoms 1 2 3 4 5 6 7 8 9 10

Alkane methane ethane propane butane pentane hexane heptane octane nonane decane

The list of alkanes demonstrate the use of prefixes. The ending -ane is the same as they are all alkanes.

Working out which is the longest chain can pose a problem with larger molecules.

I.U.P.A.C. NOMENCLATURE
How long is a chain?
Because organic molecules are three dimensional and paper is two dimensional it can confusing when comparing molecules. This is because...

1. It is too complicated to draw molecules with the correct bond angles 2. Single covalent bonds are free to rotate
All the following written structures are of the same molecule - PENTANE C5H12

CH3 CH2 CH2 CH2 CH3 CH3 CH2 CH2 CH2

CH3

CH2 CH2 CH2 CH3

CH3 CH2 CH3 CH2 CH2

CH3

A simple way to check is to run a finger along the chain and see how many carbon atoms can be covered without reversing direction or taking the finger off the page. In all the above there are... FIVE CARBON ATOMS IN A LINE.

I.U.P.A.C. NOMENCLATURE
How long is the longest chain?
Look at the structures and work out how many carbon atoms are in the longest chain.

CH3 CH2 CH3 CH CH2 CH3 CH3 CH3 CH2 CH2 CH2 CH CH3 CH3 CH3 CH2 CH3 CH2 CH CH CH3

THE ANSWERS ARE ON THE NEXT SLIDE

I.U.P.A.C. NOMENCLATURE
How long is the longest chain?
Look at the structures and work out how many carbon atoms are in the longest chain.

CH3 CH2 CH3 CH CH2 CH3 CH3 CH3 CH2 CH2 CH2 CH CH3 CH3 CH3 CH2 CH3 CH2 CH CH CH3
LONGEST CHAIN = 6 LONGEST CHAIN = 5

LONGEST CHAIN = 6

I.U.P.A.C. NOMENCLATURE
A systematic name has two main parts.
SUFFIX An ending that tells you which functional group is present See if any functional groups are present. Add relevant ending to the basic stem. In many cases the position of the functional group must be given to avoid any ambiguity

Functional group ALKANE ALKENE ALKYNE ALCOHOL ALDEHYDE KETONE ACID

Suffix - ANE - ENE - YNE - OL - AL - ONE - OIC ACID

1-CHLOROBUTANE

2-CHLOROBUTANE

SUBSTITUENTS

Many compounds have substituents (additional atoms, or groups) attached to the chain. Their position is numbered.

I.U.P.A.C. NOMENCLATURE
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). Alkyl radicals methyl ethyl propyl CH3 CH3- CH2CH3- CH2- CH2CH3 C2H5 C3H7

Number the principal chain from one end to give the lowest numbers. Side-chain names appear in alphabetical order Each side-chain is given its own number. If identical side-chains appear more than once, prefix with di, tri, tetra, penta, hexa Numbers are separated from names by a HYPHEN Numbers are separated from numbers by a COMMA e.g. 2-methylheptane e.g. 2,3-dimethylbutane butyl, ethyl, methyl, propyl

I.U.P.A.C. NOMENCLATURE
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). Alkyl radicals methyl ethyl propyl CH3 CH3- CH2CH3- CH2- CH2CH3 C2H5 C3H7

Number the principal chain from one end to give the lowest numbers. Side-chain names appear in alphabetical order Each side-chain is given its own number. If identical side-chains appear more than once, prefix with di, tri, tetra, penta, hexa Numbers are separated from names by a HYPHEN Numbers are separated from numbers by a COMMA
Example longest chain 8 (it is an octane) 3,4,6 are the numbers NOT 3,5,6 order is ethyl, methyl, propyl 3-ethyl-5-methyl-4-propyloctane

butyl, ethyl, methyl, propyl

e.g.

2-methylheptane

e.g. 2,3-dimethylbutane

CH3 CH3 CH3 CH2 CH2 CH CH3 CH2 CH2 CH CH2 CH CH2 CH3

I.U.P.A.C. NOMENCLATURE
Apply the rules and name these alkanes
THE ANSWERS ARE ON THE NEXT SLIDE

CH3
CH2 CH3 CH CH2 CH3 CH3 CH3 CH2 CH2 CH2 CH CH3

CH3 CH3 CH2

CH3 CH2 CH CH CH3

I.U.P.A.C. NOMENCLATURE
Apply the rules and name these alkanes

CH3
CH2 CH3 CH CH2 CH3

CH3
CH3 CH2 CH2 CH2 CH CH3

CH3 CH3 CH2 CH3 CH2 CH CH CH3

I.U.P.A.C. NOMENCLATURE
Apply the rules and name these alkanes
Longest chain = 5 so it is a pentane A CH3, methyl, group is attached to the third carbon from one end... 3-methylpentane

CH3
CH2 CH3 CH CH2 CH3

CH3
CH3 CH2 CH2 CH2 CH CH3

CH3 CH3 CH2 CH3 CH2 CH CH CH3

I.U.P.A.C. NOMENCLATURE
Apply the rules and name these alkanes
Longest chain = 5 so it is a pentane A CH3, methyl, group is attached to the third carbon from one end... 3-methylpentane

CH3
CH2 CH3 CH CH2 CH3

CH3
CH3 CH2 CH2 CH2 CH CH3

Longest chain = 6 so it is a hexane A CH3, methyl, group is attached to the second carbon from one end... 2-methylhexane

CH3 CH3 CH2 CH3 CH2 CH CH CH3

I.U.P.A.C. NOMENCLATURE
Apply the rules and name these alkanes
Longest chain = 5 so it is a pentane A CH3, methyl, group is attached to the third carbon from one end... 3-methylpentane

CH3
CH2 CH3 CH CH2 CH3

CH3
CH3 CH2 CH2 CH2 CH CH3

Longest chain = 6 so it is a hexane A CH3, methyl, group is attached to the second carbon from one end... 2-methylhexane

CH3 CH3 CH2 CH3 CH2 CH CH CH3

Longest chain = 6 so it is a hexane

CH3, methyl, groups are attached to the third and fourth carbon atoms (whichever end you count from). 3,4-dimethylhexane

NAMING ALKENES
Length In alkenes the principal chain is not always the longest chain It must contain the double bond the name ends in -ENE Count from one end as with alkanes. Indicated by the lower numbered carbon atom on one end of the C=C bond
5 4 3 2 1

Position

CH3CH2CH=CHCH3
Side-chain

is pent-2-ene

(NOT pent-3-ene)

Similar to alkanes position is based on the number allocated to the double bond
1 2 3 4 1 2 3 4

CH2 = CH(CH3)CH2CH3
2-methylbut-1-ene

CH2 = CHCH(CH3)CH3
3-methylbut-1-ene

WHICH COMPOUND IS IT?

Elucidation of the structures of organic compounds - a brief summary
Organic chemistry is so vast that the identification of a compound can be involved. The characterisation takes place in a series of stages (see below). Relatively large amounts of substance were required to elucidate the structure but, with modern technology and the use of electronic instrumentation, very small amounts are now required.

Elemental composition One assumes that organic compounds contain carbon and hydrogen but it can be proved by letting the compound undergo combustion. Carbon is converted to carbon dioxide and hydrogen is converted to water. Percentage composition by mass 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. From this one can find... mass of carbon mass of hydrogen = = 12/44 of the mass of CO2 produced 2/18 of the mass of H2O produced

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

INVESTIGATING MOLECULES
Empirical formula The simplest ratio of elements present in the substance. It is calculated by dividing the mass or percentage mass of each element 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 Traditionally found out using a variety of techniques such as ... volumetric analysis or molar volume methods (Dumas, Victor-Meyer or gas syringe experiments). Mass spectrometry is now used. The m/z value of the molecular ion and gives the molecular mass. The fragmentation pattern gives information about the compound.

INVESTIGATING MOLECULES
Empirical formula The simplest ratio of elements present in the substance. It is calculated by dividing the mass or percentage mass of each element 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 Traditionally found out using a variety of techniques such as ... volumetric analysis or molar volume methods (Dumas, Victor-Meyer or gas syringe experiments). Mass spectrometry is now used. The m/z value of the molecular ion and gives the molecular mass. The fragmentation pattern 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. e.g. 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 .

INVESTIGATING MOLECULES
Empirical formula The simplest ratio of elements present in the substance. It is calculated by dividing the mass or percentage mass of each element 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 Traditionally found out using a variety of techniques such as ... volumetric analysis or molar volume methods (Dumas, Victor-Meyer or gas syringe experiments). Mass spectrometry is now used. The m/z value of the molecular ion and gives the molecular mass. The fragmentation pattern 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. e.g. 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, different tests are carried out.

INVESTIGATING MOLECULES
Empirical formula The simplest ratio of elements present in the substance. It is calculated by dividing the mass or percentage mass of each element 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 Traditionally found out using a variety of techniques such as ... volumetric analysis or molar volume methods (Dumas, Victor-Meyer or gas syringe experiments). Mass spectrometry is now used. The m/z value of the molecular ion and gives the molecular mass. The fragmentation pattern 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. e.g. 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, different tests are carried out.

INVESTIGATING MOLECULES
Chemical Chemical reactions can identify the functional group(s) present.

Spectroscopy

IR NMR

detects bond types due to absorbance of i.r. radiation gives information about the position and relative numbers of hydrogen atoms present in a molecule

Confirmation

By

comparison of IR or NMR spectra and mass spectrometry

REVISION CHECK

What should you be able to do?

Recall and explain the reasons for the large number of carbon based compounds Be able to write out possible structures for a given molecular formula Recognize the presence of a particular functional group in a structure

Know the IUPAC rules for naming alkanes and alkenes

Be able to name given alkanes and alkenes when given the structure Be able to write out the structure of an alkane or alkene when given its name Recall the methods used to characterise organic molecules

CAN YOU DO ALL OF THESE?

YES

NO

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WELL DONE!
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ORGANIC CHEMISTRY
THE END

AN INTRODUCTION TO

2008 JONATHAN HOPTON & KNOCKHARDY PUBLISHING