Tutorial 6
1) 1,4-Diaminobenzene is used in the manufacture of a variety of materials
including dyes and polymers.
(a) Explain what is meant by the term 1,4-diamino in the name of this compound.
Diamino - two/2 amine groups
1,4 - their position on the ring / numbering of carbons around ring (or shown on a
diagram)
(b) 1,4-diaminobenzene can be manufactured from 1,4-dinitrobenzene.
(i) What type of reaction is this?
reduction / redox
(ii) State reagents and conditions that could be used to carry out this reaction.
tin and HCl
conc acid under reflux or H2 gas + Ni/Pd catalyst
(iii) Complete and balance the equation below for this reaction.
Answers
(c) 1,4-Diaminobenzene is used to make permanent black dye for hair. 1,4Diaminobenzene can irritate the skin because it is basic. Therefore, it is sometimes
neutralised with excess hydrochloric acid to give the salt.
(i) Explain how the amino groups in a primary amine such as 1,4-diaminobenzene
allow the molecule to act as a base.
accepts H+ using the lone pair (on N) which is donated/forms a (dative) covalent bond
(ii) Draw the structure of the salt formed in this reaction.
(iii) State whether you would expect hexane-1,6-diamine to be a stronger or weaker
base than 1,4-diaminobenzene. Explain your reasoning.
hexane-1,6-diamine is a stronger base because:
electrons move towards the N (due to the inductive effect) (in hexane-1,6-diamine)
the lone pair from N is (partially) delocalised around the ring (in diaminobenzene)
so the electron pair is more easily donated / H+ more easily accepted (in hexane-1,6
diamine) ora
2) The method below can be used to make phenylamine from nitrobenzene
in the laboratory. 3.69 g of nitrobenzene and 8 g of tin (an excess) were
placed into a flask. The flask was fitted with a reflux condenser.
Concentrated hydrochloric acid was then added dropwise to the flask. The
mixture was heated for 30 minutes to complete the reaction. Once the
mixture had cooled, concentrated sodium hydroxide solution was added
until the mixture was alkaline. Purification gave a 72.1% yield of
phenylamine.
(a) Reaction of nitrobenzene with the tin and hydrochloric acid produces
phenylammonium chloride as the organic product.
(i) Complete the equation for this reaction.
Answers
(ii) State what the symbol [H] in the equation represents.
reducing agent
(b) When the sodium hydroxide was added, the phenylammonium chloride was
converted to phenylamine. Write an equation for this reaction.
(c) Calculate the mass of phenylamine that was produced from the 3.69 g of
nitrobenzene in this experiment. Give your answer to three significant figures.
Mr: nitrobenzene,123; phenylamine, 93.1
moles C6H5NO2 used = 0.0300 (mol)
theoretical yield of C6H5NH2 = 2.79(3) (g) or ecf
actual 72.1% yield = 2.014 (g) / (calculator value 2.013753) or ecf
to three sig figs = 2.01 (g) or ecf
3) The diagram below shows some reactions of phenol.
(i) On the diagram above, identify suitable reagents that could be used to carry out
reactions I, II and III.
Answers
(ii) State a use for the compound formed in reaction IV.
dye / colouring / indicator
(iii) Outline how you could carry out reaction IV in the laboratory starting from
phenol and a suitable aromatic amine.
Phenylamine - NaNO2 / HNO2 + HCl
< 10C
add to alkaline phenol
4) Coloured organic compounds also include azo dyes. Describe how an
azo dye can be made from phenylamine. Show the structure of the azo dye
and the organic intermediate in your answer.
sodium nitrite + HCl / nitrous acid
<10C
phenol/named example (added to the products from above)
alkaline conditions / OH
example of an azo dye that could be formed from phenylamine,
5) A dye can be made from 4-methylphenylamine and 2,6-dimethylphenol,
shown below.
4-Methylphenylamine is dissolved in ice-cold hydrochloric acid and sodium nitrite is
added. This mixture is then slowly added to an alkaline solution of the phenol to
form the dye.
(i) Identify the inorganic nitrogen-containing compound formed by the mixture of
hydrochloric acid and sodium nitrite.
nitrous acid / HNO2
(ii) Draw the structure of the organic compound formed in the ice-cold acidic
mixture, showing a displayed formula of the nitrogen-containing group.
(iii) State the name of the type of organic compound drawn in (ii).
diazonium (ion /salt)
(iv) Suggest why the mixture must be kept at a low temperature.
to prevent decomposition / it reacting (diazonium ion) is unstable
(v) Suggest the structure of the dye.
6) E110 is a yellow colouring agent that is commonly added to a variety of
foods. E110 contains an azo dye made from an amine and a phenol.
(a) Describe how you would prepare a sample of an azo dye in the laboratory from
an amine, a phenol and any other necessary reagents.
Include in your answer
essential reagents and conditions for each stage
names of any functional groups formed during the process.
1st stage
aromatic amine / named aromatic amine / structure sodium nitrite / nitrous acid
HCl/H2SO4 (but not conc) /H+
at <10C
which forms a diazonium salt / ion
2nd stage
the product from the first stage mixed with the phenol AW (in excess) hydroxide / alkali
(b) The structure of E110 is shown below.
(i) On the structure above, draw a circle around the functional group that identifies
this molecule as an azo dye.
(ii) Deduce how many carbon and hydrogen atoms are in a molecule of E110.
16 carbon and 10.. hydrogen atoms
(c) The solubility of E110 in water can be improved by converting the phenolic OH
group into a charged O group. Suggest a suitable reagent that will convert the
OH group in E110 into an O group.
Na / NaOH / OH etc
(d) In the boxes below, draw the structures of a phenol and an amine that could be
used to make E110 by the method in part (a). Assume that the SO 3 Na+ groups do
not change during the process.
Amine
Phenol
7) Complete the reactions by drawing structural formulae in each of the
boxes provided.
(i)
CH3CH2CH2NH
(ii)
