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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.
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
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.
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-
– 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.
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.
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.
– All amino acids contain the base amine (-NH2) group which accepts protons and
contains the carboxylic acid (COOH) group which donates protons.
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 have the same structural formula but a different arrangement of atoms
in space. There are two types; E/Z isomerism and optical isomerism.
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.
– 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
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
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.
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 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.