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F324: Rings, Polymers and Analysis

1. Rings, Acids and Amines


Arenes
Arenes
–– Aromatic
Aromatic hydrocarbons
hydrocarbons containing
containing one
one or
or more
more benzene
benzene rings
rings

Structure of Benzene
– Kekulé suggested that benzene was a cyclic molecule with alternating C=C
double bonds.
BUT,
– Benzene was more stable than expected 
– Bromine doesn’t decolourise bromine water
– All bonds in Benzene are the same length
– Different enthalpy change than expected reacting with hydrogen
SO THE CURRENT MODEL:
– Each carbon atom contributes 1 electron to π-delocalised ring
of electrons above and below the carbons.
– Each carbon has one p-orbital perpendicular to the carbon plane.
Each p-orbital overlaps with adjacent ones so the delocalisation
is spread over 6 carbon atoms.
MEANING
– The π-delocalised ring accounts for increased stability of benzene.

Electrophilic Substitution reactions of Benzene

NITRATION OF BENZENE with Conc. H2SO4 and HNO3


– Reagents are H2SO4 and HNO3 and conditions of 60oc
OVERALL: C6H6 + HNO3 C6H5NO2 + H2O
MECHANISM:
The electrophiles is generated:

The Electrophiles attack at the benzene ring:

The catalyst is re-generated


H+ + HSO4  H2SO4
Remember this can be made into an aromatic amine. (See amines)
HALOGENATION OF BENZENE
– Reagents are Cl2 and AlCl3 and anhydrous conditions
OVERALL: C6H6 + Cl2  C6H5Cl + HCl
MECHANISM:
The electrophiles is generated
Cl2 + AlCl3  Cl+ + AlCl4-
The electrophile attacks the benzene ring

Regeneration of the catalyst


Cl2 + AlCl3-  AlCl3 + HCl.

The relative ease of reaction with a cycloalkenes rather than benzene is of the high
electron density in the C=C double bonds which can induce a dipole in the Br-Br
bond making an electrophile. The electrophile is then attracted to the high electron
density in the C=C bond.
 Benzene doesn’t undergo bromination easily.

Phenols
– In phenols, the OH is directly attached to the benzene

Reactions with sodium hydroxide and sodium


– When dissolved in water, phenol forms a weak acid solution by losing the H+
from the –OH group.
– C6H5OH + aq  C6H5O- + H+
– Phenol is neutralised by aqueous sodium hydroxide to
form the salt sodium phenoxide.
C6H5OH + NaOH  C6H5O-Na+ + H2O
– With sodium, phenol gives sodium phenoxide and
hydrogen gas
Na + C6H5OH  C6H5O-Na+ + 12H2
Electron- pair donation of the oxygen p orbital
– The lone-pair electrons on the oxygen p-orbital of
the –OH group can be delocalised on the benzene ring.
– This increases the electron density on the ring (especially
at sites 2,4,6) , making phenols more reactive than
Benzene!

– Therefore Substitution occurs at the sites indicated on the


diagram because of the increased electron density at these sites compared with
the others.
– Substitution usually occurs at ALL THREE of these sites because of the extra
reactivity
e.g. REACTS WITH BROMINE to form 2,4,6-tribromophenol
C6H5OH + 3Br2  C6H2Br3OH + 3HBr where the product is 2,4,6-
tribromophenol
Phenolic Compounds; the uses!
– Production of plastics
– Antiseptics
– Disinfectants -
Resins/Paints
Carbonyl compounds (C=O)

RECAP: The presence of this C=O carbonyl group means the molecule is unsaturated.
The position of the carbonyl group determines whether it is an aldehyde or ketone.

Aldehydes are formed by oxidation of primary alcohols (not too long though!)
2CH3CH2OH + [O]  2CH3CHOH + H2O
Ketones are formed by oxidation of secondary alcohols
CH3CHOHCH3 + [O]  CH3COCH3 + H2O

Both use acidified potassium dichromate K2Cr2O7/H2SO4 is the ‘in’ one to remember.
Orange  Green.
Reduction
Aldehydes and ketones can be reduced to their respective alcohols. NaBH4 is a
suitable reducing agent. [H] is used to represent this reducing agent.

Aldehyde: CH3CH2COH + 2[H]  CH3CH2CH2OH


Ketones: CH3COCH3 + 2[H]  CH3CHOHCH3

This is a nucleophillic addition reaction


The carbonyl group is unsaturated and polar and consequently undergoes
nucleophillic addition reactions.
This occurs in the reduction reactions.
NaBH4 is the source of the hydride ion H- which is the nucleophile for the reaction. The
intermediate formed reacts with the solvent H2O to form the alcohol.

If the compound was a ketone it would make no difference.

Reactions with 2,4-dinitrophenulhydrazine (we can call it 2,4-DNPH)


These reactions are important because:
1. Carbonyls react with 2,4-DNPH to produce distinctive orange precipitates.
Therefore this reaction can be used to identify an carbonyl group.
2. The organic product is relatively easy to purify by recrystillisation. Therefore
the melting point of the brightly coloured precipitate can be measured. Each
derivative has a different melting point and the value of the melting point can
be used to identify the specific carbonyl.
e.g. Ethanal at 142-43 oc, 2-Methylpropanal at 180-81oc etc.

Dude; is this chemical here an aldehyde?


1. Aldehydes are readily oxidised to carboxylic acids. We take advantage of this
with our Tollen’s test.
2. Infra-red spectrum.

3. Tollen’s reagent identifies an aldehyde group, (It is an aqueous solution of


Ag+ ions in an excess of ammonia, Ag(NH3)2+). When Tollen’s reagent is reacted
with aldehyde and warmed gently in a water bath at about 60oc, silver metal is
precipitated which forms a silver mirror. This is a redox reaction whereby the
Ag+ is reduced to Ag metal and the aldehyde oxidised to a carboxylic acid.

Ag+ + e- ---reduction---> Ag (silver mirror)


H3CCOH + [O] ---oxidation--->
H3CCOOH
Tollen’s reagent does not react with a ketone or carboxylic acids, because ketones are
not oxidised.

Carboxylic acids and esters


Carboxylic acids are soluble in water. This is due to the
hydrogen bonds formed between the OH in the carboxylic
acid and the water molecule.

The solubility of carboxylic acids decreases with increasing molecular mass.


Carboxylic acids are weak acids so they donate protons, but they only partially
dissociate into their ions:
CH3COOH(aq) ↔CH3COO-(aq) + H+(aq)
The carboxylic acid group can be attached to a chain (aliphatic) or a ring (aromatic).
Makes sense!

Carboxylic acids display typical reactions of an acid and form salts.


• Acid + base  salt + water
CH3COOH(aq) + NaOH(aq)  CH3COO-Na+(aq) + H2O(l)

• Acid + metal  Salt + Hydrogen


CH3COOH(aq) + Na(s)  CH3COO-Na+ + 12H2

• Acid + Carbonate  Salt + Water + Hydroxide


CH3COOH(aq) + Na2CO3(aq)  2CH3COO-Na+(aq) + H2O(l) + CO2(g)

This reaction with a carbonate can be used as a test for a carboxylic acid. When an
acid is added to a solution of carbonate, bubbles of carbon dioxide are seen.
Carboxylic acids can also react with alcohols to form esters. This type of reaction is
esterification. Reversible and carried out with acid catalyst such as concentrated
H2SO4. Esters are used in flavourings and perfumes.
Esters, trigylercerides, unsaturated and saturated fats

Esters react with water. The hydrolysis react is slow and is carried out in presence of
either an acid H+ or a base OH-.
(Hot aqueous acid) Acid-catalysed hydrolysis leads to the formation of the
carboxylic acid and the alcohol.
H3CCOOCH3 + H2O ---H+---> H3CCOOH + HOCH3

(Hot aqueous alkali) Base-catalysed hydrolysis forms the salt (of the carboxylic
acid) and the alcohol.
H3CCOOCH3 + OH-

– Fats/Triglycerides are esters of long-chain carboxylic acids (fatty acids)


and the alcohol glycerol.
– Fats are hence also called triglycerides.
– The fatty acids that form the esters with glycerol can be either saturated or
unsaturated.

– The greater the number of carbon-carbon double bonds, the lower the
melting point of the fatty acid and hence the triglycerides.
– Unsaturated fatty acids make up triglycerides found in vegetable and fish oils
whilst saturated fatty acids make up triglycerides in animal fats.
– Esters are used in Biodiesel as they increase the quality of the fuel.
Trans fatty acids (Transfats) are formed when manufacturers add hydrogen to
vegetable oil.

Amines (derivatives of ammonia)


The functional group is the amino (-NH2) group.

The naming goes like this:


CH3CH2NH2 + H+  CH3CH2NH3+
Ethylamine ethylammonium ion
C6H5NH2 + H+  C6H5NH3+
Pheylamine phenylammonium ion

Because of the nitrogen lone pair, they are proton acceptors, they are bases.
With water, they NICK the H+ and so they form OH- ions so they are weak alkalis
CH3CH2NH2 + H2O  CH3CH2NH3+ + OH-

Because they act as bases, primary amines react with acids to form salts.
The names of these salts come from the ions formed from the amine and the acid.
For example, ethylammonium chloride are formed by the reactions of the bases
ethylamine and phenylamine with hydrochloric acid.
e.g.
NH3 + HCl  NH4+Cl-
Ammonium chloride CH3CH2NH2 + HCl  CH3CH2NH3+Cl-
Ethylammonium chloride C6H5NH2 + HCl 
C6H5NH3 Cl
+ -

Phenylammonium chloride
Preparation of amines
There are 2 methods; one for straight-chain amines and one for aromatic amines.

1. Preparation of straight-chain (aliphatic) amines:


Excess ammonia is refluxed with a halogenoalkanes (e.g.
bromoalkane) with ethanol as the solvent.
RBr + NH3  RNH2 + HBr

2. Preparation of aromatic amines:


Nitrobenzene is reduced by refluxing with the reducing agent; tin and
concentrated hydrochloric acid.
C6H6NO2 + 6[H]  C6H6NH2 + 2H2O (Aromatic amine; AZO DYE!)

Azo Dyes
Phenylamine and other aromatic amines are the stating compounds for azo dyes.

Stage 1
Nitrous acid (HNO2) (which is formed from NaNO2 and excess HCl) and
temperature below 10oc. The reaction is kept below 10oc because otherwise the
product, benzenediazonium chloride decomposes.

Stage 2
The benzenediazonium chloride is added to phenol in the presence of an alkali;
an azo dye is formed.

The azo group N=N is responsible


for the colour of the dye.
The formation of azo-dye
compounds is the basis of the dye
industry

Polymers and Synthesis


Amino acids, polypeptides and proteins
The general formula for an α-amino acid is
RCH(NH2)COOH
If R is not H, the C is attached to 4 different atoms/groups so it is a chiral carbon and
hence amino acids exhibit optical isomerism (Linkage!).

– All amino acids contain the base amine (-NH2) group which accepts protons and
contains the carboxylic acid (COOH) group which donates protons.

Amino acids have higher melting points than expected.


Zwitterions are formed because of the movement of the hydrogen
from the carboxylic acid to the amine. At solid state, the amino acid
exists as this.

If we add an basic solution (OH- ions), it


forms a negative ion. The proton (H+)
moves to the hydroxide ion to form
water.

If we add an acidic solution (H+) ions,


it forms a positive ion. The proton
moves to the O- ion. +HHHdsddsf

Suppose we start with the positive ion produced under acidic conditions and slowly
add alkali to it until you get back to the zwitterion.
So when you have added just the right
amount of alkali, the amino acid no
longer has a net positive or negative
charge. That means that it wouldn't move towards either the cathode or anode during
electrophoresis.
The pH at which this lack of movement during electrophoresis happens is known as
the isoelectric point of the amino acid. This pH varies for each amino acid and can
depend on the R group.
Peptide bonds and polypeptides/proteins!
Amino acid react to form peptides with
peptide bonds.
If two different amino acids such as glycine and
alanine react, two different dipeptides could be
formed depending on which gives the OH (from
COOH) and H form (NH2) in the peptide bond.
All dipeptides react further with other amino
acids, extending their chain length. Proteins
are polypeptides; chains of amino acids linked
by peptide bonds. Because of the loss of H2O
when proteins are put together, proteins are
considered condensation polymers (Like
polyesters and polyamides as well)
Hydrolysis back to amino acids
To get the individual amino acids back from a polypeptide, water has to be added
back to the polypeptide and the peptide bonds are broken.
This process requires HCl (to mimic stomach conditions) and H2O . The process can
also be carried out with alkalis, but a COO- is formed rather than the COOH.

Stereoisomers; E/Z and optical

Stereoisomers have the same structural formula but a different arrangement of atoms
in space. There are two types; E/Z isomerism and optical isomerism.

E/Z isomerism requires a C=C double bond.


If the 2 highest priority groups are on the zame side,
they are Z isomers
If the 2 highest priority groups are oppositE, they are E
isomers.

If 2 of substituent groups one on each carbon are the same, it is cis-


trans isomerism.
If the groups are on the cis same side they are cis.
If the groups are on the opposite side they are trans;
TRANSEXUAL

Optical isomerism requires a chiral carbon (4 different


groups). Optical isomers are non-superimposable
mirror images of each other.
The optical isomers react in exactly the same way
but show different biological activity.
The solutions or crystals of optical isomers can be
distinguished from one another because they rotate in plane-polarised light. The
isomer rotating the light clockwise is called the (+) isomer, whilst the anticlockwise
one is the (-) isomer.

Polyesters and Polyamides


We studied addition polymerisation at AS where alkenes became polymers.
In a condensation reaction, two large molecules join to make a larger molecule +
water. The two main types are polyesters and polyamides.

Polyesters
Formed when a di-alcohol and dicarboxylic acid.
Remember the H2O made as a product. Used as
fibres in clothing.

Polyamides
Formed when a diamine and dicarboxylic
acid.
e.g. Nylon-6,6 is made from 1,6-
diaminohexane and hexane-1,6-
dicarboxylic acid.
Nylon-6,6 forms a strong flexible fibre when strung. Kevlar is another polyamide. It is
stronger than steel and used for making bulletproof vests.
Used as fibres in clothing.

Polyesters and polyamides can be acid or base hydrolysed like the


polypeptides before.
Polyesters (-ol) are more easily hydrolysed by bases and Polyamides by .
– Polyamides acid hydrolyse by reacting with H2O with H2SO4 (as a catalyst) to
form the constituent dicarboxylic acid and diamine.
– Polyesters base hydrolyse with NaOH. A metal salt of the carboxylic acid is
formed and the diol.

Minimising environmental waste

– The C=O bond absorbs radiation. When they are in the polymer chain, the
energy causes the
breakdown of the chain. This makes them photodegradable which is desirable
for chemists.
– The esters and amide bonds can be hydrolysed by acids and alkalis helping
their breakdown (See above)
– Producing polymers formed from plant feedstock such as starch. E.g. Lactic
acid which can be extracted from corn starch and sugar cane. Degradable
polymers

Pharmaceuticals and organic synthesis


– Enzymes in the body only recognise one optical isomer of a chiral
compound. Therefore pharmaceutical products acting on living systems require
synthesis of these single optical isomers.
– But the molecules prepared synthetically in the laboratory often contain a
mixture of optical isomers, whereas the molecules of the same compound
produced naturally by enzymes in living systems will only be on one optical
isomer.
– Separating the single optical isomer has costs due to separation, but increases
the pharmacological activity and rules out possible side effects from the
other optical isomer .

– Nowadays, modern synthesis of a pharmaceutical is carried out:


➢ Using enzymes or bacteria to promote stereoselectivity.
➢ Using natural chiral molecules as starting materials
➢ Using chemical chiral synthesis (Using carefully chosen reagents
and conditions so as only 1 isomer made)

Organic Synthesis
3. Analysis
Chromatography; Thin Layer (TLC) and Gas (GC)
Small scale analytical technique that separates components in a mixture between a
mobile phase (liquid in TLC and gas in GC) and a stationary phase (solid in TLC
and liquid on solid support in GC). The mobile phase moves through the stationary
phase and
the

components in the mixture separate out between the phases.


• Different types of chromatography separate the components in a mixture by
either adsorption or partition.

Thin layer (TLC); Solid stationary phase separating by


adsorption.
– The mobile phase is a solvent e.g. ethanol that passes over the
stationary phase.
– The stationary phase is a thin layer of solid e.g. Silica Gel or
alumina on a glass/plastic plate.
As the solvent spreads up the plate, the different substances in the
mixture move with it but at different rates so they separate out.

A value of Rf is worked out where Rf= distance travelled by SPOTdistance


travelled by solvent and compared to the known value of Rf for different
substances.
How far each part of the mixture moves depends on how strongly it’s attracted to the
stationary phase. The attraction between a substance and the surface of the
stationary phase is called absorption. A substance that is strongly absorbed will
move slowly and not travel very far as one that’s weakly absorbed.

Gas (GC); Liquid stationary phase separating by relative solubility.


– The stationary phase is a viscous liquid, such as an oil, which coats the inside
of the long tube.
– The mobile phase is an unreactive carrier gas, such as nitrogen or helium.
Sample injected into stream of carrier gas, so passes over stationary phase.
Components of the mixture dissolve in the stationary phase, evaporate into the
mobile phase, dissolve again etc.

The solubility of each component in the mixture


determines how long it spends. The time taken is
called the retention time and can identify the
substance.
Each peak corresponds to the substance with the
particular retention time.

Retention times are measured from zero to the centre


of each peak, and can be looked up in a reference
table to identify the substances present.

The area under each peak is proportional to the


amount of substance. Tallest peak doesn’t always
have the greatest area.

Limitations
– Similar compounds often have similar retention times so difficult to identify. A
mixture of 2 similar substances may only produce 1 peak so you can’t tell how
much there is.
– There must already be a recorded reliable reference retention time.

Combining Gas chromatography and mass spectroscopy (GC-MS)


The combination of these two A2 and AS techniques makes a powerful analytical took
that is used in forensics.
Gas chromatography is good at separating a mixture into its individual components,
but not so good at identifying those compounds. Mass spectroscopy is good at
identifying the unknown compounds.

The mixture is separated using gas chromatography and the different components
are sent to the mass spectroscopy to be identified.

Spectroscopy
NMR spectroscopy involves interaction of atomic nuclei with radio waves that
are at the low-energy end of the electromagnetic spectrum.
– The sample is placed in a strong magnetic field and exposed to a range of
different frequencies of low-energy radio waves.
– The nuclei of certain atoms within the molecule absorb energy from the
radio waves.
– The amount of energy that a nucleus absorbs at each frequency depends on the
environment they are in.
– The 2 types of NMR spectroscopy are carbon-12 NMR (tells you about the
number of carbon atoms that there are in a molecule and the environments
they are in) and high resolution proton NMR (Information about the number
of hydrogen atoms that are in a molecule and the environments they are in)
An Atom’s environment depends on all the groups it’s connected to. The
environment makes the nuclei absorb different amounts of energy at different
frequencies.

The chemical shift, δ is the difference in radio frequency and runs along the x-axis. =>
The number of peaks determines the number of environments. The differences in
adsorption are relative to tetramethylsilane, TMS which produces a single peak
because it has 1 environment and is used as a reference point.

13
C NMR spectra tells us about
the carbon environments.
– The number of peaks
(excluding TMS peak) is
the number of
environments for the
carbons.
– The chemical shift tells
us what bond the C (or
pair of C’s) belongs to
– The area under the peak
tells us the number of
carbon atoms in that environment.
1
H (Proton) NMR Spectra tells us about hydrogen environments.
– Works as carbon-13 NMR works but with respect to hydrogen’s.
– The number of peaks (excluding TMS peak) is the number of environments
for the hydrogen’s.

– The chemical shift tells us what bond the H involved belongs to

– The area under the peak tells us how many hydrogen atoms are in the
environment.
– The splits is caused by hydrogen atoms bonded to neighbouring carbons. This
effect is called spin-spin coupling. Only hydrogen nuclei on adjacent carbon
atoms effect. Follows n+1 rule.

⇒ The solvent the thing is dissolved in WOULD add peaks to NMR (both proton and
carbon-13) spectra. Hence, deuterated solvents, CDCl3 is used which doesn’t
absorb wave energy.

⇒ In Proton NMR OH and NH protons can be identified using D2O. The problem is
OH and NH have a huge range so are hard to spot. Hence making another
spectra with D2O will get rid of the OH or NH by replacing the O or N with D,
which does not show up. Clever.

⇒ NMR spectroscopy is used is MRI (Magnetic resonance imaging) to obtain


information about internal structures in body scanners in casualty.

Infrared Spectroscopy from F322


A beam of infra-red radiation is passed through the chemical. The IR radiation is
absorbed by the covalent bonds in the molecules increasing their vibrational energy.
Bonds between different atoms absorb different frequencies of IR radiation.
So the bonds in a molecule can be determined.

Using the combined techniques of infrared spectroscopy, mass spectrometry, thin


layer chromatography, gas chromatography and both NMR spectrums, it is easy to
deduce the molecule you have.

F324 ; Rings, Polymers and Analysis; Robbie Peck ‘09/’10