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H H H
Amines H2N O
These end in amine. H C C C NH2 If there is another CH C
There is, however, rather confusingly
priority functional group
two ways of using this suffix. H H H
as well as the amine H3C O H
The exam board tend to use the propylamine group then the prefix
common version where the name Or propan-1-amine 2-aminopropanoic acid.
amino is used.
stem ends in -yl propylamine.
The IUPAC version of the same
chemical is propan-1-amine. (This is
used in the same way as naming
alcohols)
H H
N (CH2)6 N It could also be named
H H 1,6-diaminohexane
hexane-1,6-diamine
Amides
O CH3
CH3 O CH3
H3C CH2 C N CH3
H3C CH C N CH3
N,N-dimethylpropanamide N,N,2-trimethylpropanamide
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Properties of Amines
Amines have a characteristic fishy smell H +
- + -
Small amines can form hydrogen bonds with water
CH3 N H O
+
and therefore can dissolve readily in water.
H
Base Properties
H +
Primary aliphatic amines act as Bronsted-Lowry Bases because the
lone pair of electrons on the nitrogen is readily available for forming a CH3NH2 +H2O CH3NH3+ +OH-
dative covalent bond with a H+ and so accepting a proton.
Secondary amines are stronger bases than primary amines because they have more alkyl groups that are
substituted onto the N atom in place of H atoms. Therefore more electron density is pushed onto the N atom (as
the inductive effect of alkyl groups is greater than that of H atoms).
One might expect using the same trend that tertiary amine would be the strongest amine base but the trend does
not hold. The tertiary amines and corresponding ammonium salts are less soluble in water and this makes them
less strong bases than the secondary amines. (This point will not be examined)
Primary aromatic amines such as Phenylamine do not form basic solutions because the
lone pair of electrons on the nitrogen delocalise with the ring of electrons in the benzene
ring. This means the N is less able to accept protons. phenylamine
This is a similar ligand exchange reaction to the one where ammonia acts as the ligand
Amines will react with halogenoalkanes in a similar way to the reaction of ammonia with
halogenoalkanes via a nucleophilic substitution reaction
H
+
H3C CH2 NH2 CH2 CH3
H3C C Br Br -
H
:
CH3CH2NH2
+
H3C CH2 NH CH2 CH3 H3C CH2 NH CH2 CH3 + CH3CH2NH3Br
:NH2CH2CH3
H Diethylamine
The secondary amine formed can also then react with more halogenoalkane to form a tertiary
amine and subsequently on to what is called a quaternary ammonium salt
Where RX is the haloalkane
H R R
H
RX RX RX +
H N: R N: R N: R N R
R R R R
O O
CH 3 C + 2CH3NH2 CH 3 C NH CH 3 + CH3NH3+Cl-
Cl N-methylethanamide
Paracetamol
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Reducing nitroarenes to aromatic amines
The nitro group on an arene can be reduced an amine group as follows
NO 2 NH2
Reagent: Sn and HCl or Fe and HCl
Conditions: Heating + 6[H] + 2H2O
Mechanism:reduction
phenylamine
nitrobenzene
As the reaction is carried out in HCl the salt C6H5NH3+Cl- will be formed.
Reacting this salt with NaOH will give phenylamine.
Step 1: reaction of an aromatic amine with nitrous acid at Nitrous acid is generated in
<10 C, forming a diazonium ion, situ from NaNO2/HCl.
NaOH
+
N N + OH N N OH
4-hydroxyazobenzene
C6H5N2+ Cl +C6H5OH C6H5N2C6H4OH +HCl
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Polymers
There are two types of polymerisation: addition and condensation
Addition Polymerisation
An addition polymer forms when unsaturated Poly(alkenes) are chemically inert due to the strong C-C
monomers react to form a polymer and C-H bonds and non-polar nature of the bonds and
Monomers contain C=C bonds therefore are non-biodegradable.
Chain forms when same basic unit is
repeated over and over.
H CH3
You should be able e.g. For but-2-ene H CH3
to draw the polymer C C
H3C CH CH CH3 C C
repeating unit for any
alkene H3C H
CH3 H n
It is best to first draw out
the monomer with groups
O of atoms arranged around O O
the double bond
C H C NH2 H C NH2
H2C CH NH2
C C C C H
e.g. For propenamide H H H H
poly(propenamide)
Poly(ethenol)
H OH H OH
The addition polymer poly(ethenol) has good solubility in
n C C H C C water because it can form many strong hydrogen bonds
with water. The makes it a useful polymer for uses such
H H H H n as soluble laundry bags and liquid detergent capsules .
poly(ethenol)
Condensation Polymerisation
In condensation polymerisation there are two different monomers
The two most common types of that add together and a small molecule is usually given off as a
condensation polymers are side-product e.g. H2O or HCl.
polyesters and polyamides which
involve the formation of an ester The monomers usually have the same functional group on both ends
linkage or an amide linkage. of the molecule e.g. di-amine, di carboxylic acid, diol, diacyl chloride.
Forming polyesters and polyamide uses these reactions we met earlier in the course
Carboxylic Acid + Alcohol Ester + water Carboxylic Acid + Amine amide + water
Acyl chloride + Alcohol Ester + HCl Acyl chloride + Amine amide + HCl
If we have the same functional group on each end of molecule we can make polymers so we have the
analogous equations:
dicarboxylic acid + diol poly(ester) + water dicarboxylic acid + diamine poly(amide) + water
diacyl dichloride + diol poly(ester) + HCl diacyl dichloride + diamine poly(amide) + HCl
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Using the carboxylic acid to make the ester or amide would need an acid catalyst and would only give an
equilibrium mixture. The more reactive acyl chloride goes to completion and does not need a catalyst but does
produce hazardous HCl fumes.
O O O O
n C (CH2)3 C + n HO OH
C (CH2)3 C + 2n-1 HCl
O O
Cl Cl n
Pentanedioyl dichloride Benzene-1,4-diol
O O
n HO2C CO2H + n H2N NH2 + 2n-1 H2O
N N C C
H H n
O O O O
HO (CH2)3 C O (CH2)3 C O (CH2)3 C O (CH2)3 C
Cl
3 repeating units
O O O O
H2N C
N C N C N C
OH
H H H
3 repeating units
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Chemical reactivity of condensation polymers The reactivity can be explained by the presence of
polyesters and polyamides can be broken down by polar bonds which can attract attacking species
hydrolysis and are, therefore, biodegradable such as nucleophiles and acids
:
O O- O
bonding between the lone pairs on oxygen in -
-
N C N C N C
C+=O- groups and the H in the N- H+ + +
H H + H +
groups in the different chains.
There are also Permanent dipole-permanent
:
dipole forces because the polar C=O O - O- O
bond and polar C-N bond
N C N- C N - C
There are also London forces which are large + +
because there are many electrons in the H H H+
+
molecule
Polyamides will therefore have higher melting
points than polyesters.
Amino Acids
General structure of an amino acid The simplest amino acid is NH2 CH2 CO2H
glycine, where the R is an H
NH2 CH CO2H
R
The R group can be a variety of
different things depending on what
amino acid it is.
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Zwitterions
R R
The no charge form of an amino acid never occurs. + -
The amino acid exists as a dipolar zwitterion. H2N C CO2H H3N C CO2
H H
Amino acids are often solids Zwitterion
The ionic interaction between zwitterions explains the relatively high melting points of amino acids as
opposed to the weaker hydrogen bonding that would occur in the no charge form.
-
COO
The extra carboxylic acid or amine groups
on the R group will also react and change CH2 Aspartic acid in high pH
form in alkaline and acid conditions -
NH 2 C COO
H
If ninhydrin is sprayed on an amino acid and then heated for 10 minutes then red to blue spots appear.
This is done because amino acids are transparent and cannot be seen.
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Proteins CH3
H3C CH3 S
Proteins are polymers made from
combinations of amino acids. CH HS CH2
The amino acids are linked by peptide links, CH3 O CH2 CH2 O CH2 O
O
which are the amide functional group.
H N CH C N CH C N CH C N CH C O H
O O O H H H H
NH CH C NH CH C NH CH C
R R R
Dipeptides
Dipeptides are simple combination molecules of For any two different amino acids there are two possible
two amino acids with one amide (peptide) link. combinations of the amino acids in the dipeptide.
HO HO
HO
CH3 H
Can make CH3 H CH2 CH2 CH3
CH2 or
H2N C CO2H +
H2N C C N C CO2H H2N C C N C CO2H
H H2N C CO2H
H H H O H
O
H
O - O
Importance of hydrogen bonding in proteins
:
-
N CH C N CH C
The 3D arrangement of amino acids with the +
polypeptide chain in a corkscrew shape is held in H R H+ R
place by Hydrogen bonds between the H of N-
:
H+ group and the O of C+=O-
O - O
-
N CH + C N CH C
H R H R
Hydrolysis of di-peptides/proteins
If proteins are heated with dilute acid or alkali they can be The composition of the protein
hydrolysed and split back in to their constituent amino acids. molecule may then be deduced by
using paper chromatography
H3C CH3
CH H3C CH3
CH
CH3 O CH2 O CH3 O
H+
H N CH C N CH C O H + CH2 O
H3N CH C O H + +
H3N CH C O H
H H
H H
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