A guide for A level students KNOCKHARDY PUBLISHING AN INTRODUCTION TO ORGANIC CHEMISTRY A guide for A level students KNOCKHARDY PUBLISHING

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.argonet.co.uk/users/hoptonj/sci.htm Navigation is achieved by... either clicking on the grey arrows at the foot of each page or using the left and right arrow keys on the keyboard CONTENTS

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

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

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 CONTENTS

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 ATOMIC RADIUS BOND ENTHALPY C-C 0.077 nm +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. CONTENTS

CHAINS AND RINGS THE SPECIAL NATURE OF CARBON CARBON ATOMS CAN BE ARRANGED IN STRAIGHT CHAINS BRANCHED CHAINS and RINGS You can also get a combination of rings and chains CONTENTS

THE SPECIAL NATURE OF CARBON MULTIPLE BONDING AND SUBSTITUENTS CARBON-CARBON COVALENT BONDS CAN BE SINGLE, DOUBLE OR TRIPLE CONTENTS

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

MULTIPLE BONDING AND SUBSTITUENTS 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 CONTENTS

TYPES OF FORMULAE - 1 MOLECULAR FORMULA C4H10 The exact number of atoms of each element present in the molecule EMPIRICAL FORMULA C2H5 The simplest whole number ratio of atoms in the molecule STRUCTURAL FORMULA CH3CH2CH2CH3 CH3CH(CH3)CH3 The minimal detail using conventional groups, for an unambiguous structure there are two possible structures DISPLAYED FORMULA Shows both the relative placing of atoms and the number of bonds between them THE EXAMPLE BEING USED IS... BUTANE CONTENTS

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 for CYCLOHEXANE THALIDOMIDE CONTENTS

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 GENERAL FORMULA Represents any member of for alkanes it is... CnH2n+2 a homologous series possible formulae... 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 H’s for CYCLOHEXANE THALIDOMIDE CONTENTS

ALCOHOLS - FIRST THREE MEMBERS OF THE SERIES 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 C2H5OH C3H7OH METHANOL ETHANOL PROPAN-1-OL CONTENTS

FUNCTIONAL GROUPS H H H H H H C C C C C NH2 H H H H H H C C C C C OH 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 NH2 H H H H H H C C C C C OH Carbon Functional Carbon Functional skeleton Group = AMINE skeleton Group = ALCOHOL CONTENTS

COMMON FUNCTIONAL GROUPS GROUP ENDING GENERAL FORMULA EXAMPLE ALKANE - ane RH C2H6 ethane ALKENE - ene C2H4 ethene ALKYNE - yne C2H2 ethyne HALOALKANE halo - RX C2H5Cl chloroethane ALCOHOL - ol ROH C2H5OH ethanol ALDEHYDE -al RCHO CH3CHO ethanal KETONE - one RCOR CH3COCH3 propanone CARBOXYLIC ACID - oic acid RCOOH CH3COOH ethanoic acid ACYL CHLORIDE - oyl chloride RCOCl CH3COCl ethanoyl chloride AMIDE - amide RCONH2 CH3CONH2 ethanamide ESTER - yl - oate RCOOR CH3COOCH3 methyl ethanoate NITRILE - nitrile RCN CH3CN ethanenitrile AMINE - amine RNH2 CH3NH2 methylamine NITRO nitro- RNO2 CH3NO2 nitromethane SULPHONIC ACID - sulphonic acid RSO3H C6H5SO3H benzene sulphonic acid ETHER - oxy - ane ROR C2H5OC2H5 ethoxyethane CONTENTS

COMMON FUNCTIONAL GROUPS ALKANE ALKENE ALKYNE HALOALKANE AMINE NITRILE ALCOHOL ETHER ALDEHYDE KETONE CARBOXYLIC ACID ESTER ACYL CHLORIDE AMIDE NITRO SULPHONIC ACID CONTENTS

HOW MANY STRUCTURES? C2H6 ONE C3H9Br TWO 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 4 covalent bonds surrounding them oxygen atoms 2 nitrogen atoms 3 hydrogen 1 halogen atoms 1 C2H6 ONE C3H9Br TWO C4H8 FIVE - 3 with C=C and 2 ring compounds with all C-C’s C2H6O TWO - 1 with C-O-C and 1 with C-O-H C3H6O SIX - 2 with C=O, 2 with C=C and 2 with rings C2H7N TWO C2H4O2 SEVERAL - Only 2 are stable C2H3N TWO CONTENTS

HOW MANY STRUCTURES? C2H6 ONE C3H9Br TWO 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 4 covalent bonds surrounding them oxygen atoms 2 nitrogen atoms 3 hydrogen 1 halogen atoms 1 C2H6 ONE C3H9Br TWO C4H8 FIVE - 3 with C=C and 2 ring compounds with all C-C’s C2H6O TWO - 1 with C-O-C and 1 with C-O-H C3H6O SIX - 2 with C=O, 2 with C=C and 2 with rings C2H7N TWO C2H4O2 SEVERAL - Only 2 are stable C2H3N TWO CONTENTS

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 : 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). HOMOLOGOUS SERIES trivial name systematic name example(s) paraffin alkane methane, butane olefin alkene ethene, butene fatty acid alkanoic (carboxylic) acid ethanoic acid INDIVIDUAL COMPOUNDS trivial name derivation systematic name methane methu = wine (Gk.) methane (CH4) butane butyrum = butter (Lat.) butane (C4H10) acetic acid acetum = vinegar (Lat.) ethanoic acid (CH3COOH) CONTENTS

A systematic name has two main parts. 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. The list of alkanes demonstrate the use of prefixes. The ending -ane is the same as they are all alkanes. Prefix C atoms Alkane meth- 1 methane eth- 2 ethane prop- 3 propane but- 4 butane pent- 5 pentane hex- 6 hexane hept- 7 heptane oct- 8 octane non- 9 nonane dec- 10 decane Working out which is the longest chain can pose a problem with larger molecules. CONTENTS

I.U.P.A.C. NOMENCLATURE CH3 CH3 CH2 CH2 CH2 CH3 CH2 CH3 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 CH2 CH3 CH2 CH3 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. CONTENTS

How long is the longest chain? 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. CH2 CH3 CH THE ANSWERS ARE ON THE NEXT SLIDE CH2 CH3 CH CH3 CH CH2 CONTENTS

How long is the longest chain? 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. CH2 CH3 CH LONGEST CHAIN = 5 CH2 CH3 CH LONGEST CHAIN = 6 CH3 CH CH2 LONGEST CHAIN = 6 CONTENTS

A systematic name has two main parts. 1-CHLOROBUTANE 2-CHLOROBUTANE 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 Suffix ALKANE - ANE ALKENE - ENE ALKYNE - YNE ALCOHOL - OL ALDEHYDE - AL KETONE - ONE ACID - OIC ACID 1-CHLOROBUTANE 2-CHLOROBUTANE SUBSTITUENTS Many compounds have substituents (additional atoms, or groups) attached to the chain. Their position is numbered. CONTENTS

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). Number the principal chain from one end to give the lowest numbers. Side-chain names appear in alphabetical order butyl, ethyl, methyl, propyl 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 e.g. 2-methylheptane Numbers are separated from numbers by a COMMA e.g. 2,3-dimethylbutane Alkyl radicals methyl CH3 - CH3 ethyl CH3- CH2- C2H5 propyl CH3- CH2- CH2- C3H7 CONTENTS

I.U.P.A.C. NOMENCLATURE CH3 CH2 CH 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 to give the lowest numbers. Side-chain names appear in alphabetical order butyl, ethyl, methyl, propyl 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 e.g. 2-methylheptane Numbers are separated from numbers by a COMMA e.g. 2,3-dimethylbutane 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 Alkyl radicals methyl CH3 - CH3 ethyl CH3- CH2- C2H5 propyl CH3- CH2- CH2- C3H7 CH3 CH2 CH CONTENTS

I.U.P.A.C. NOMENCLATURE CH2 CH3 CH CH2 CH3 CH CH3 CH CH2 Apply the rules and name these alkanes THE ANSWERS ARE ON THE NEXT SLIDE CH2 CH3 CH CH2 CH3 CH CH3 CH CH2 CONTENTS

Apply the rules and name these alkanes I.U.P.A.C. NOMENCLATURE I.U.P.A.C. NOMENCLATURE Apply the rules and name these alkanes CH2 CH3 CH CH2 CH3 CH CH3 CH CH2 CONTENTS

Apply the rules and name these alkanes I.U.P.A.C. NOMENCLATURE 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 CH2 CH3 CH CH2 CH3 CH CH3 CH CH2 CONTENTS

Apply the rules and name these alkanes I.U.P.A.C. NOMENCLATURE 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 CH2 CH3 CH Longest chain = 6 so it is a hexane A CH3, methyl, group is attached to the second carbon from one end... 2-methylhexane CH2 CH3 CH CH3 CH CH2 CONTENTS

Apply the rules and name these alkanes I.U.P.A.C. NOMENCLATURE 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 CH2 CH3 CH Longest chain = 6 so it is a hexane A CH3, methyl, group is attached to the second carbon from one end... 2-methylhexane CH2 CH3 CH 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 CH3 CH CH2 CONTENTS

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 Position 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 CH3CH2CH=CHCH3 is pent-2-ene (NOT pent-3-ene) Side-chain 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 CH2 = CHCH(CH3)CH3 2-methylbut-1-ene 3-methylbut-1-ene CONTENTS

Elucidation of the structures of organic compounds - a brief summary 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 = 12/44 of the mass of CO2 produced mass of hydrogen = 2/18 of the mass of H2O produced CONTENTS

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. CONTENTS

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. CONTENTS

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 . CONTENTS

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. CONTENTS

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. CONTENTS

INVESTIGATING MOLECULES Chemical Chemical reactions can 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 IR or NMR spectra and mass spectrometry CONTENTS

What should you be able to do? 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 CONTENTS

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© 2003 JONATHAN HOPTON & KNOCKHARDY PUBLISHING AN INTRODUCTION TO ORGANIC CHEMISTRY THE END © 2003 JONATHAN HOPTON & KNOCKHARDY PUBLISHING