Organic 1

A2 ORGANIC Chemistry
Isomerism & Naming organic compounds Naming compounds has been covered in the AS course make sure you know how to name compounds using the IUPAC rules. Isomerism has been covered in the AS syllabus. Make sure you know the following:
know and understand the meaning of the term structural isomerism know that E-Z isomerism and optical isomerism are forms of stereoisomerism know that an asymmetric carbon atom is chiral and gives rise to optical isomers which exist as non super-imposable mirror images and differ only in their effect on plane polarised light understand the meaning of the terms enantiomer and racemate understand why racemates are formed be able to draw the structural formulae and displayed formulae of isomers Appreciate that drug action may be determined by the stereochemistry of the molecule and that different optical isomers may have very different effects e.g Thalidomide

Carbonyl Compounds
Compounds that contain the (C=O) functional group. Aldehydes & Ketones Carboxylic Acids Esters Anhydrides Acyl halides(chlorides)

Making Carbonyl compounds:

Aldehydes and Ketones

These are also known as carbonyl compounds and contain the carbonyl (C=O) functional group.

Functional Group:

O C H

O C C KETONE C

ALDEHYDE

Organic 2

Oxidation Primary and secondary alcohols may be oxidised using an oxidising agent such as acidified potassium dichromate(VI) or acidified potassium manganate(VII). Primary Alcohols Primary alcohols are oxidised first of all to an aldehyde (partial oxidation) and then the aldehyde is oxidised further to a carboxylic acid (complete oxidation). Carboxylic acids have the 2-/H+ Cr2O72-/H+ O Cr2O7 Carboxylic Primary Aldehyde C acid alcohol HEAT HEAT O H Aldehydes contain the functional group O
C H functional group

Cr2O72- is the oxidising agent and is therefore reduced during the reaction. Cr 2O72- is orange and it is reduced to the green Cr3+(aq) ion. The half equation for the reduction is: Cr2O72- + 14H+ + 6e- 2Cr3+ + 7H2O Colour change: ORANGE GREEN Aldehydes have a lower boiling point than alcohols as they do not have an H attached directly to an O and therefore do not participate in hydrogen bonding.

If the reaction mixture is heated under reflux ethanoic acid is obtained as the main product and the aldehyde is not usually isolated. However, it is possible to set up the experiment so that the aldehyde is distilled off as soon as it is formed and before it can be oxidised further.

If we look at the reactions in terms of the functional group change it is easier to generalise the reaction to other molecules:

OH C H H

Cr2O72-/H+ HEAT

O Cr2O72-/H+ C H HEAT

O C O H

Secondary Alcohols Secondary alcohols are also oxidised by acidified potassium dichromate(VI). They are oxidised to ketones, which cannot be oxidised any further.
Secondary alcohol Cr2O72-/H+ Ketone HEAT Cr2O72-/H+ HEAT

Ketones contain the O

C C C functional group

In terms of functional group change the reaction can be represented as:

OH C C H C

Cr2O72-/H+ HEAT

O C C C

Organic 3

Tertiary Alcohols Tertiary alcohols are resistant to oxidation.

H OH H H C C C H H CH3 H 2-methylpropan-2-ol

Cr2O72-/H+ HEAT

No Reaction

Identification test for the carbonyl group

Addition-Elimination reactions
The reaction of aldehydes and ketones with 2,4-dinitrophenylhydrazine (2,4-DNPH) is an example of an addition-elimination reaction and is used as a test for the presence of the carbonyl (C=O) group in aldehydes and ketones.

Water is eliminated.

This reaction may be used to distinguish aldehydes and ketones from other species. The product of the reaction with aldehydes and ketones is yellow/orange crystals. If the melting point of these crystals is determined and the values compared with those in tables exactly which aldehyde/ketone was originally present may be determined.

Yellow-orange crystals produced test for carbonyl group

Draw out the structures of the organic products formed when the following aldehydes/ketones react with 2,4-dinitrophenylhydrazine. 1 butanone

2-methylpentanal

Organic 4

Distinguishing between Aldehydes and Ketones. Use is made of the oxidation reaction to tell the difference between Aldehydes (can be oxidised) and ketones(cannot be oxidised) 1. Tollens Reagent silver mirror(Ag) Uses ammonical silver nitrate solution (AgNO3/NH3)

2. Fehlings solution Brick red precipitate (Cu2O) Uses copper(II) chloride in sodium hydroxide (CuCl2/NaOH)

Reduction of Aldehydes and Ketones (H) Using (H- ion ) HYDRIDE ION , aldehydes and ketones can be reduced back into alcohols. Reducing agent: sodium borohydride (NaBH4) or lithium aluminium hydride (LiALH4) **(LiAlH4 reaction is carried out in a non aqueous environment at low temperature (exothermic)) *(NaBH4 can be carried out in water) Reaction is an example of NUCLEOPHILLIC ADDITION Carboxylic acids can also be reduced back into primary alcohols. Example

Organic 5

Aldehydes and ketones reaction with HYDROGEN CYANIDE (HCN) Another example of nucleophillic addition involving the carbonyl group involves reacting aldehydes and ketones with hydrogen cyanide. The product is a HYDROXYNITRILE or CYANOHYDRIN. ** (HCN is a very weak acid In practice a KCN/H2SO4 solution is used) NOTE!! KCN is extremely toxic!!! (HCN is also VERY toxic and flammable) Death = 100ppm Mechanism

Nitrile groups may be hydrolysed to form a carboxylic acid:

CH3 C N + H2O + H3O
+

H2O/H reflux hydrolysis

O CH3 C O H + NH4+

Or hydrolysis of a cyanohydrin: Hydrolysis is also brought about by refluxing with aqueous alkali. In this case the product is the salt of the acid and ammonia: OH OH H2O/OH reflux CH C H + NH3 3 CH3 C H + H2O + NaOH hydrolysis + COO Na CN

Organic 6

Carboxylic acids
O
Functional Group:

C O H

Physical properties of carboxylic acids

Boiling point / oC

Boiling Point of carboxylic acids, aldehydes and alcohols 250 200 150 100 alcohols 50 0
aldehydes

carboxylic acids

-50 0 20 40 60 80 100 120 140 relative molecular mass

Lower relative molecular mass carboxylic acids are generally soluble in water because However, the solubility decreases as the length of the hydrocarbon chain increases because Carboxylic acids readily liberate CO2 from carbonate compounds Carboxylic acids react with alcohols in the presence of an acid catalyst to give an ESTER.

Condensation Reactions
These are reactions in which two molecules join together with the elimination of the elements of water. They are part of a more general class of reactions called addition-elimination reactions, where molecules other than H2O are eliminated.

Esterification
When an alcohol is heated with a carboxylic acid in the presence of a small amount of concentrated sulphuric acid as a catalyst an ester is formed: conc H2SO4 alcohol carboxylic acid ester + + water heat

For example:

The alcohol and the carboxylic acid have been joined together and water has been eliminated 1 H atom from the alcohol and OH from the carboxylic acid molecule.

Organic 7

Complete the table:

Alcohol
H H H C O H H H H H H C C C O H H H H OH H

Carboxylic Acid
O H O H H H C C C C H H H H
O H C O H
H H H C C H H C C C O H
O O H

Ester

H C C

C H

H H H CH2OH H H

H CH3 H H
H CH3 H C C C CH3 H

C H

H C H

CH3 H

H C C CH3 H
H H C C C H H H C H H

H3C C O CH3
H CH3 H H C C H CH3 H O

C O

CH3 H3C C CH3

O O

H C C H H

Organic 8

Naming Esters Esters are named according to the carboxylic acid from which they are derived. H H H H H H O O O H H H H H C C C C H C C C H C C CH3 H C C C O H C O H3C C O H H H H H H H H H H H

H C C H H

H3C C O CH2 CH3

C C C CH3 H2 H C O H H

CH3
H CH3 H H C C H CH3 H

H H C C C H H

H C H H

C O

Uses of esters Esters often have a sweet-fruity smell and they are used as artificial flavours and odours. Other uses are as plasticizers (added to polymers to make them easier to process and reduce brittleness) and as solvents. Animal Fats and Vegetable oils are esters of propane-1,2,3-triol (glycerol) and long chain carboxylic acids (fatty acids). (Vegetable oils and animal fats can be hydrolysed to give soap, glycerol and long chain carboxylic(fatty) acids) Esters can be HYDROLYSED back into carboxylic acid and alcohol. This is done by heating(refluxing) with either an acid or a base (H2SO4 or NaOH) Biodiesel is a mixture of methyl esters of long chain carboxylic acids Vegetable oils can be converted into biodiesel by reaction with methanol in the presence of an acid catalyst

Polyesters
Polyesters may be formed in a condensation polymerisation reaction when a dicarboxylic acid reacts with dihydric alcohol (alcohol with 2 OH groups). It is the presence of two functional groups on each monomer that allows the production of a polymer chain as an ester is formed on both sides of both monomers. The type of polymerisation is condensation polymerisation as a water molecule is eliminated each time two monomers are joined together.

Organic 9

It can be seen from this reaction that, when four monomer molecules join together three water molecules are produced. The total number of water molecules is always one less than the total number of monomer molecules that join together. If we then look at a specific example

The polymer chain as a whole can be represented by the unit shown in brackets in the equation. This is called the repeat unit or repeating unit of the polymer. The whole polymer chain could be built up by just joining these units together

Organic 10

From which monomers could the following polymers be formed?

O H H O H H H H H H H H H H H H O H H O H H H H H H H H H H H H O H H O O C C C C H H

C C C C O C C C C C

O C C C C O C C C C C

O H H CH3 H H C C C C H H H C C H H

O C O

H H CH3 H H C C C H H CH3 H H

O H H CH3 H H C C H H H H H

O C O

H H CH3 H H C C C C C O H H CH3 H H

C C O C C C C

Acylation reactions Reactions involving Anhydrides and Acid Chlorides (Acylating agents)
Acid Anhydrides
The basic structure of an acid anhydride is:

O R C O R C O

This can be regarded as being formed from two molecules of carboxylic acid with water removed:

Naming acid anhydrides:

O H3C C O H3C C O

O CH3CH2 CH3CH2 C O C O
O R C

Acid anhydrides are acylating agents, that is they react by adding the acyl group to other species. The reactions are called addition-elimination

Organic 11

reactions Acid anhydrides react with nucleophiles: 1 Reaction with water

Acid anhydrides react violently with water to from carboxylic acids

Reaction with alcohols

Acid anhydrides react with alcohols to form esters.

Organic 12

Phenol does not react directly with acid anhydrides but must first be dissolved in sodium hydroxide solution, to generate the phenoxide ion, which reacts readily with the anhydride to form an ester.

This reaction is used in the formation of aspirin from 2-hydroxybenzoic acid

OH O C OH

H3C C O

O O C OH

2-hydroxybenzoic acid

aspirin

** Ethanoic anhydride is used instead of ethanoyl chloride on an industrial scale because it is cheaper, easier to handle, reacts more slowly and does not produce HCl as a by product.

Reactions with ammonia

When concentrated ammonia solution is added to an acid anhydride a primary amide is formed.

Reactions with amines

When acid anhydrides are reacted with amines substituted amides are formed.

Organic 13

This reaction is used in the formation of paracetamol.

OH

OH

H3C

NH2

C O

paracetamol Draw out equations, using structural formulae for the following reactions: 1 Butanoic anhydride + ammonia

Propanoic anhydride + water

Ethanoic anhydride + 2-methylbutylamine

Organic 14

Acyl chlorides
O

The basic structure of an acyl chloride is:

R C Cl

These are extremely reactive and react in basically the same way as acid anhydrides to add an acyl groups to nucleophiles with the elimination of HCl.

Reaction with water

Acyl chlorides react violently with water to from carboxylic acids

Reaction with alcohols

Acyl chlorides react with alcohols to form esters.

Phenol does not react directly with acyl chlorides but must first be dissolved in sodium hydroxide solution, to generate the phenoxide ion, which reacts readily with the acyl chloride to form an ester.

*This reaction may also be used in the formation of aspirin from 2-hydroxybenzoic acid.
(Frequent exam question)

Organic 15

Reactions with ammonia

When concentrated ammonia solution is added to an acyl chloride a primary amide is formed.

Reactions with amines

When acyl chlorides are reacted with amines substituted amides are formed.

The addition-elimination mechanism The mechanism of these reactions involves two steps: 1 initial addition of a nucleophile 2 elimination of a molecule/ion

IB Further Organic Option 16

AROMATIC CHEMISTRY
Benzene and Aromatic compounds
Benzene has the formula C6H6 and is usually represented by a skeletal formula: Compounds which contain a benzene ring are called aromatic whereas compounds without benzene rings are called aliphatic. When determining molecular formulae or condensed structural formulae for compounds containing benzene rings it must be remembered that there is a C and, if there is nothing else attached, an H atom at each vertex.

Therefore methyl benzene Has the molecular formula

The condensed structural formula may be written as C6H5CH3 or may be shown as a benzene ring with CH3 attached.

As long as a particular functional group is not attached directly to the benzene ring the reactions of compounds containing a benzene ring will be basically the same as the reactions encountered in other sections.

Benzene and Aromatic Compounds

The structure originally proposed for benzene (C6H6) was due to Kekul: Kekul Benzene The structure was accepted for many years but eventually the weight of evidence against it became too great and a modified structure was proposed.

Evidence for a different structure of benzene:

X-ray crystallographic data
C-C bond lengths may be determined by x-ray crystallography.

Bond C=C C-C C--C

Compound ethene ethane BENZENE

Bond length /nm 0.133 0.154 0.139

All C-C bond lengths are equal in benzene

IB Further Organic Option 17

Thermochemical evidence
+ H2

cyclohexane (C6H12) H = -120 kJ mol-1

+
1,3,5-cyclohexatriene

3H2

H =

3H2

H = -207 kJ mol-1

Actual benzene

Therefore actual benzene is 153 kJ mol-1 more stable than expected if it were made up of 3 C=C double bonds.

IB Further Organic Option 18

Heat of Combustion Data

The enthalpy change for the combustion of Kekul benzene may be worked out from the following bond enthalpies:

Bond C=C C=O (CO2) O-H O=O C-H C-C

Energy /kJ mol-1 612 805 464 496 413 347

This value can be compared with the heat of combustion of actual benzene (in the gaseous state), -3242 kJ mol-1.

The value for the extra stability of benzene here is not exactly the same as the value from hydrogenation data. Why not? Which value is more reliable?

The extra stability of benzene comes from the

delocalised electron system

The spreading out of electrons (delocalisation) stabilises the molecule.

IB Further Organic Option 19

Reactions of Benzene
A feature of the extra stability associated with the benzene aromatic ring is that benzene does not react like alkenes, i.e. it does not undergo addition reactions under normal conditions (and will not decolourise bromine water).
The stability of the aromatic ring means that it is regenerated in reactions, therefore benzene undergoes SUBSTITUTION reactions. e.g. benzene reacts with chlorine at room temperature in the presence of a catalyst such as aluminium chloride:

Naming aromatic compounds

CH3 NO2 OH

O C OH
Cl

O C CH3

Organic 20

Relative rates of nucleophilic substitution in halogenated benzene compounds

Chlorobenzene does not undergo nucleophilic substitution (hydrolysis) reactions with sodium hydroxide under normal conditions.
Cl + NaOH NO REACTION under normal conditions

Halogen atom attached directly to the ring

Chloroethane undergoes the reaction much more readily:

To all extents and purposes halogenated benzene compounds with the halogen atom attached directly to the ring are inert to nucleophilic substitution.

overlap of a lone pair on the halogen with the benzene system.

strengthens the C-Cl bond nucleophiles are repelled from the C attached to the Cl.

When the halogen atom is not attached directly to the benzene ring but is rather in the side-chain, hydrolysis occurs much more readily, e.g.

H C C

H H Cl

What is the organic product formed when the following compound is heated with excess sodium hydroxide solution

H Cl

H H H C C C H H Cl

Cl

Organic 21

Electrophilic Substitution Reactions General mechanism

The Nitration of Benzene

+ HNO3

Reflux 60 oC conc. HNO3 conc. H2SO4

NO2 + H2O pale yellow liquid

The electrophile is the NO2+ ion

C6H6 + HNO3 C6H5NO2 + H2O

Formation of the electrophile:

Mechanism:

HNO3 + 2H2SO4 NO2+ + H3O+ + 2HSO4Or HNO3 + H2SO4 NO2+ + H2O + HSO4-

Organic 22

Chlorination of benzene
Overall equation:

Benzene does not react with halogens in the dark because the halogen molecule is non-polar. Therefore a catalyst is required which polarises the molecule. The catalysts used are AlCl3 or FeCl3, these are known as HALOGEN CARRIERS. Aluminium chloride is electron deficient and accepts a pair of electrons from the Cl 2: Formation of the electrophile

Cl2 + AlCl3 AlCl4- + Cl+

Mechanism: For bromination FeBr3 would be used.

Alkylation (also known as Friedel Crafts alkylation)

Halogenoalkanes react with benzene in the presence of a halogen carrier catalyst: Overall Reaction:

Formation of the electrophile: The mechanism is the same as for halogenation.

Organic 23

Acylation (also known as Friedel Crafts acylation)

Acyl halides react with benzene in the presence of a halogen carrier: Overall Reaction:

Formation of the electrophile:

The mechanism is the same as for alkylation.

Organic 24

Naming substituted benzene rings

When more than one group is present in a benzene ring the groups are first of all numbered to give the lowest possible numbers and then in alphabetical order.

CH3 CH3

CH3 H3C

CH3 Cl

CH3 O2N

OH
OH O2N

Cl

Organic 25

Reactions of methylbenzene
Methylbenzene reacts in the same way as benzene, via an electrophilic substitution mechanism. The conditions for the reactions of methylbenzene are slightly milder than those for the reactions of benzene and the methyl group is an activating group. The methyl group donates electron density into the benzene ring (positive inductive effect). This increase the amount of electron density in the ring so that it is more attractive to electrophiles and reacts more readily. The methyl group is a 2,4-directing group and so the major products of substitution are: CH3 CH3
X

Nitration of methylbenzene
The methylbenzene is heated under reflux with a mixture of concentrated sulphuric and concentrated nitric acid:

Mono nitration occurs readily easily, further nitration is possible but because of the deactivating effect of the nitro group the 2nd and 3rd nitrations are slow and more difficult to achieve. Multiple nitrated compounds: 2,4,6, trinitromethylbenzene(trinitrotoluene/TNT)

2,4,6 trinitrohydroxybenzene(trinitrophenol/picric acid)

Organic 26

Chlorination of methylbenzene
Methylbenzene is reacted with chlorine in the presence of a halogen carrier catalyst (AlCl 3) at room temperature. This is chlorination in the ring.

If methylbenzene is reacted with chlorine in the presence of UV light then side chain substitution occurs. This involves a free radical substitution mechanism as for alkanes.

Alkylation of methylbenzene
Methylbenzene is reacted with a halogenoalkane in the presence of a halogen carrier catalyst (AlCl3) at room temperature.

Acylation of methylbenzene
Methylbenzene is reacted with an acyl chloride in the presence of a halogen carrier catalyst (AlCl 3) at room temperature.

Organic 27

***Reactions of Substituted Benzene Rings (NOT IN THE SYLLABUS) Substituted benzene rings undergo basically the same reactions as a benzene ring, i.e. electrophilic substitution. The nature of the substituent determines the position of further substitution and the rate of the reaction relative to unsubstituted benzene. Substituents on a benzene ring may be divided into two group: those which cause substitution predominantly at positions 2 and 4 (and 6) (ortho and para) and those which cause substitution at position 3 (and 5) (meta). Substituents that cause substitution faster than with benzene are called activating groups and those that cause substitution to occur more slowly than with benzene are called deactivating groups.

Substituent

Main Product of Halogenation

CH3 CH3 Cl

Rate of Substitution relative to benzene

-CH3

FASTER
Cl
OH OH Cl Cl OH Cl

-OH

FASTER
Cl Cl

NO2

-NO2
Cl

SLOWER

2,4-directing groups normally cause substitution faster than in benzene and 3-directing groups normally react more slowly than benzene Rate of substitution The rate determining step in the reaction is the attack of the electrophile on the ring. Attack, and hence the reaction, occurs more quickly when there is more electron density in the ring so that an electrophile is attracted more strongly. When the ring is deactivated by the withdrawal of electron density the electrophile is attracted less strongly and reaction occurs more slowly. Thus methylbenzene reacts more readily than benzene due to the electronreleasing effect of the -CH3 group (positive inductive effect). The methyl group activates the ring towards electrophilic substitution by donating electron density into the ring. This makes the ring more negative, i.e. more attractive towards electrophiles and the reaction occurs more quickly than with benzene.

CH3

Organic 28

- Back to syllabus

Phenol is a significantly stronger acid than aliphatic alcohols such as ethanol

Dissociation of phenol: H O
+ H2O

Consider the anion (phenoxide ion) Delocalisation of negative charge from O- into ring H+ not attracted back as strongly Anion (conjugate base) stabilised Greater dissociation Stronger acid

Delocalisation results in stabilisation of the anion, making it more likely to be formed than the corresponding ion with ethanol, where no delocalisation can take place.

OH

In general, for compounds of the form shown, if X (in any position) is an electronwithdrawing group the compound will be a stronger acid than phenol. The electronwithdrawing group reduces the amount of electron density on the O in the conjugate + base the charge is more delocalised in the anion meaning that the H is less strongly attracted. If X is an electron-donating group the compound will be a weaker acid than phenol. In this case the charge is less delocalised in the anion with the charge more localised on the O the H+ is attracted back more strongly.

AZODYES The nitration of aromatic compounds, followed by the reduction of the nitro group to an amine are the first steps to producing organic dyes. Step 1. Nitration

Step 2. Reduction

Organic 29

Step3. Producing the diazonium salt

Step4. Making the Azodyes

Organic 30

Amines
Functional Group: -NH2 or -NHR or -NR2 or NR3+ Solubility: Boiling Points: Acidity: Preparation:
Nucleophilic Substitution:
CH3 CH2Br + NH3 conc. NH 3 Heat in sealed tube CH3 CH2NH2 + HBr

Lower members are soluble in water (H-bonding). Higher members increasingly less soluble.

HYDROGEN BONDING

Higher than alkanes of similar Mr (H-bonding) but lower than corresponding alcohols.

BASIC

Mechanism:

Further substitution is also possible to give secondary and tertiary amines and quaternary ammonium salts(cationic surfactant). Aliphatic amines can also be made by the reduction of nitriles:
(Nitriles made by substitution of haloalkane with CN-)

(i)LiAlH4/dry ether then H2O CH3CN + 4[H] (ii) H2 and Ni catalyst **Carbon chain extended by one carbon unit Aromatic amines are made by the reduction of nitro compounds: (i)Sn/HCl(conc) C6H5NO2 (ii) H2/Ni C6H5NH2 CH3CH2NH2

Amides
Functional Group:
C NH2 O

Organic 31

Solubility: Boiling Points: Acidity:

Soluble but solubility decreases as length of hydrocarbon chain increases. Solids except for methanamide. Higher boiling points than corresponding carboxylic acids. Very weakly basic

HYDROGEN BONDING

Basicity (General )
B: +

A base (Brnsted-Lowry definition) is a proton acceptor: H+ HB+

The order of basicity for nitrogen-containing compounds is:

Compound Structure

ethylamine

ammonia

phenylamine

ethanamide

pKb Kb /mol dm-3

3.33 5.4x10-4

4.75 1.8x10-5

9.38 5x10-10

14.5 1x10-15

Amides are very weak bases and will not affect red litmus paper. The base strength depends on:

The charge on the N atom. A greater negative charge means

that the H+ is more strongly attracted and the compound is a stronger base.

The availability of the lone pair. The less available the lone
pair for donation, the weaker the base.

Ethylamine is a stronger base than NH3 because of the electron-donating effect of the ethyl
group:
CH3 CH2 > N
-

H H

H H N

ETHYLAMINE alkyl group electron-donating N more H+ attracted more strongly

Phenylamine and ethanamide are weak bases due to unavailability of the lone pair:

Organic 32

Delocalisation of the lone pair makes it less available for donation to H+ Amides: the N is also less - due to electron-withdrawing effect of the adjacent O atom

Formation of SALTS NH3 + HCl NH4 Cl

+ -

Amines, like ammonia, form salts with acids, e.g.

CH3NH2 + HCl CH3NH3+Clmethylammonium chloride (Surfactant)

Syntheses of amines actually often result in the formation of a salt. CH3NH3+Cl- + NaOH CH3NH2 + H2O + NaCl The alkylammonium ion is acting as a Brnsted-Lowry acid.

The free amine may be released by adding a stronger base (e.g. NaOH)

Thus, if sodium hydroxide solution is added to a salt of an amine the free amine is released. This will be noticed by a fishy smell or can be tested for by using moist litmus paper (amines are basic).

Peptides and Proteins

Peptides and proteins are naturally occurring polyamide polymers formed from amino acids ( bifunctional compounds.)

2-amino acids

(-amino acids) contain an amine and an carboxylic acid functional group.

H H
H N H H C H C O

H N C C R

O O H

All 2-amino acids except glycine (aminoethanoic acid) are (all naturally occurring optically active amino acids in proteins are L-isomers)
H N H H C C H O

optically active

O H

CH3 O

AMINOETHANOIC ACID glycine

2-AMINOPROPANOIC ACID Alanine

Organic 33

Zwitterions The carboxylic acid in amino acids donates its proton to the amine. This makes a doubly charged ion which can act as both acid and base:

+ OHH2NCH2CO2H + H+ At an intermediate pH it will exist as simultaneously as a cation and anion Zwitterion. Each amino acid has a unique pH value when this happens Isoelectric pH. (The existence of the zwitterion makes amino acids crystalline solids at room temperature) Separating amino acids: simple chromatography is used to separate mixtures of amino acids, as they are colourless compounds a staining agent is used to develop the chromatogram (ninhydrin) amino acids stain purple. This technique can be extended to a more sophisticated separative technique Electrophoresis. In living organisms enzymes catalyse the polymerisation of amino acids to form peptides and proteins: CH2O H CH2O H H O H H H O O H + H2O N C C O N C C + N C C N C C H H H O H H H CH3 O H H CH3 O H SERINE ALANINE a dipeptide
CH2OH H O C C N H O H H O H H O H O CH2OH O C C N H H H C C N CH3 H H + H2O

H3N+CH2CO2Zwitterion

+ C C N H O CH3 H

The dipeptides are different depending on which way round the amino acids are joined together. The functional group present in peptides and proteins is an amide group called a peptide link. Proteins are macromolecules (large long chain molecules) formed when amino acids polymerise. The simplest level of protein structure is the sequence of the amino acids in the chain. This is known as primary structure. There are 20 naturally occurring amino acids and, if just 100 are joined together to make a polymer, there are 20100 combinations.
H O C R1 C N H O C C N H H R2 H C R3 O C N H

part of a protein chain

There are three further levels of protein structure; secondary, tertiary, quaternary.

Organic 34

Polymerisation
Addition Polymerisation
H C H C H H

O2 200 oC 2000 atm.

[ ]
H H C C H H
H H C C H H H H C C H H

MONOMER Ethene
H H C C H H H H C C H H H H C C H H H H C C H H H H C C H H H H C C H H H H C C H H

POLYMER poly(ethene)
H H C C H H H H C C H H

This is an example of addition polymerisation. The mechanism is free radical addition involving opening of the double bond:
H C H C H H

H H C C H H

HOMOLYTIC FISSION

PVC [Poly(vinylchloride)]
This is more properly known as poly(chloroethene)

Cl C H C

H H

HEAT peroxide initiator

[ ]
H Cl C C H H

chloroethene

poly(chloroethene)

Poly(propene)
Write an equation for the formation of poly(propene) and draw a length of the polymer chain showing three repeat units.

** Addition polymers are non-biodegradeable

Organic 35

Condensation Polymerisation
Polyesters
The mechanism involved is addition-elimination, where a molecule of water is eliminated as each monomer is linked to the chain.

O C H O C

O H O O H CONDENSATION POLYMERISATION HEAT acid cat.

H H C C O H H H
ethane-1,2-diol

benzene-1,4-dicarboxylic acid

NEED 2 FUNCTIONAL GROUPS ON THE MONOMERS

[
H H O C C H H

O C C

O H H O TERYLENE
O C O C O O H H C C

+ (2n-1)H2O

H H

n
O C C O H H C C O H H

O O

H H TERYLENE

The functional group present is the

ester group and the polymer is a polyester.

In general, an diol and an dioic acid are required for formation of a polyester.

Polyamides
H H H H H H NH2 C C C C C C NH2 H H H H H H H O O C H H H H C C C C C O H H H H H O

CONDENSATION P OLYMERISATION H H H H C C C C C C H H H H

H H H H H H C C C C

C C N N H H H H H H H H

NYLON-6,6

+ (2n-1) H2O

amide link

Organic 36
H H H H C C C C C C N H H H H H H H H H H H C C C C C O C H H H H C C C C C N H H H H H O H H H H H H C N H H H H H H H C C C C C

C N H H H H H H H

The functional group present is the amide group, therefore nylon is a polyamide.
** Condensation polymers are biodegradeable, the ester and amide link can be broken by acid hydrolysis (and bioorganisms) Note: Know the arguments for and against the recycling of plastics The advent of biodegradable plastics Different methods used to dispose of plastics