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NOTTINGHAM TRENT UNIVERSITY

CHEM10161 Coursework Portfolio Template


(2016/17)
Maryim Almutairi
Experiment 5: The Purification of Cholesterol

1. In the space below, give your risk assessment from Experiment 5 (Purification
of Cholesterol) by noting
the H and P codes for all chemicals and reagents used, and explaining the
meanings of those H and P
codes.

Chemicals and Hazardous Precautionary


reagents being used statement(s) (H code) statement(s) (P code)
and the meaning and the meaning
Diethyl ether ((CH3CH2)2O) H224 Extremely flammable P210 Keep away from heat,
Volume: 7 cm3 liquid and vapour. hot surfaces, sparks, open
H302 Harmful if swallowed. flames and other ignition
H336 May cause sources. No smoking.
drowsiness or dizziness. P261 Avoid breathing
vapours.
A solution of bromine and No components need to be
sodium ethanoate disclosed according to the
Volume: 5 cm3 applicable regulations.
Ethanoic acid known as H226 Flammable liquid and P280 Wear protective
Acetic acid (CH3CO2H) vapour. gloves/ protective clothing/
Volume: 7 cm3 H314 Causes severe skin eye protection/ face
5 cm3 burns and eye damage. protection.
P305 + P351 + P338
IF IN EYES: Rinse cautiously
with water for several
minutes. Remove contact
lenses, if present and easy
to do. Continue rinsing.
P310 Immediately call a
POISON CENTER or doctor/
physician.
Cholesterol dibromide No components need to be
disclosed according to the
applicable regulations.
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Diethyl ether-ethanoic acid No components need to be
mixture disclosed according to the
For washing the product on applicable regulations.
the filter paper
H225 Highly flammable P210 Keep away from heat,
Methanol (CH3OH) liquid and vapour. hot surfaces, sparks, open
H301 + H311 + H331 flames and other ignition
Volume: 2 x 5 cm3 Toxic if swallowed, in sources. No smoking.
contact with skin or if
inhaled P260 Do not breathe dust/
H370 Causes damage to fume/ gas/ mist/ vapours/
organs. spray.
P280 Wear protective
gloves/ protective clothing.
P301 + P310 IF
SWALLOWED: Immediately
call a POISON CENTER or
doctor/ physician.
P311 Call a POISON
CENTER or doctor/
physician.
The air-dried crude No components need to be
dibromocholesterol disclosed according to the
applicable regulations.
diethyl ether ((CH3CH2)2O) H224 Extremely flammable P210 Keep away from heat,
Volume: 20 cm3 liquid and vapour. hot surfaces, sparks, open
H302 Harmful if swallowed. flames and other ignition
H336 May cause drowsiness sources. No smoking.
or dizziness P261 Avoid breathing
vapours.
Fresh zinc dust (Zn) No components need to be No components need to be
weight: 0.2 g disclosed according to the disclosed according to the
applicable regulations. applicable regulations.
Water (H2O) No components need to be No components need to be
Volume: 2 x 10 cm3 disclosed according to the disclosed according to the
applicable regulations. applicable regulations.
Dilute sodium hydroxide H290 May be corrosive to P280 Wear protective
solution (NaOH) metals. gloves/ protective clothing/
Volume: 2 x 10 cm3 H314 Causes severe skin eye protection/ face
burns and eye damage. protection.
P305 + P351 + P338 IF IN
EYES: Rinse cautiously with
water for several minutes.
Remove contact lenses, if
present and easy to do.
Continue rinsing.
P310 Immediately call a
POISON CENTER or doctor/
physician.
saturated sodium chloride No components need to be

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solution (NaCl) disclosed according to the
Volume: 20 cm3 applicable regulations.
Anhydrous magnesium No components need to be
sulphate (MgSO4) disclosed according to the
For collecting and dry the applicable regulations.
organic layer
2.

(i) Attach your IR spectra for cholesterol and dibromocholesterol to this report.

IR Spectrum for Cholesterol

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IR spectrum for Dibromocholesterol (this IR spectrum was taken
from Georgia)

(ii) In the tables below highlight the significant IR peaks for each
compound, and assign each peak to a specific functional group.

*TIP*: If any peaks involved in the key functional group (FG) transformation prove hard
to spot, you should make a note of this, and estimate the peak position instead.

Dibromocholesterol Cholesterol

Peak Assignment Peak Assignment


position position
(cm-1) (cm-1)
3300 -OH 3257.89 -OH
2929.87 C-H 2935.82 C-H
2860 C-H 2865.89 C-H
NOT exist C=C 1692.89 C=C

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(ii) Give a brief discussion of how the information gained from IR spectroscopy
can be used in conjunction with other methods to confirm the structure
of a compound.

By using IR spectroscopy, it can be distinguished between Cholesterol and


Dibromocholesterol, because in Cholesterol there is a double bond C=C that mostly appears
in 1692.89 cm-1 while in Dibromocholesterol this bond does not exist and disappears. The
other method includes the melting point because there will be a difference between the
different products (Cholesterol and Dibromocholesterol).

3. Choose one of the experiments that you carried out (Experiments 5-7) and give
a brief write-up of the
experimental method that you followed. This should include enough information
to allow another
person to repeat this work, and should be written in the third person and past
tense (i.e. not I did this,
and I did that but rather the reagent was added to the solvent).

*TIP*: This is not an exercise in simply reproducing a verbatim copy of the procedure already
provided.

Experiment (7) Reduction of benzophenone with sodium Borohydride


A 0.356g of the benzophenone was dissolved in 5 cm 3 ethanol in a 25 cm3 round
bottomed flask, and then the solution was stirred with a magnetic stirrer bar. In a small test
tube, the sodium borohydride (0.084g) was dissolved in 1.5 cm 3 cold water, and this
solution was added as one drop at a time to the stirred ethanoic solution of benzophenone
at room temperature. After all the sodium borohydride has been added, the mixture was
continued to stir for a further 40 min. Slowly the mixture was poured into a 50 cm 3 beaker

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containing a mixture of 10 cm3 ice-water and 1 cm3 concentration hydrochloric acid. After a
few minutes the precipitated product was collected by suction filtration using a Buchner
apparatus, and was washed with 2 portions of 5 cm 3 portions of water. The crude product
was dried by suction at the filter pump for 10 min., and then was recrystallised from
petroleum ether.
The yield and melting point of the pure product were recorded. IR spectra of the product
was recorded and of the benzophenone starting material for comparison. The IR spectra
was Interpreted, any significant changes were noted between starting material and product.
The IR spectrum of the product should be kept to help you with the report. The purity of the
product was checked by TLC. Dilute samples of the obtained product was spotted and the
starting material (benzophenone) onto a TLC plate and elute using a 9:1 mixture of
petroleum ether and ethyl acetate. The developed plate was visualised under UV light,
then, the spots was circled using a pencil, and the R f value of the two compounds were
worked out. A picture of an annotated TLC plate was taken.

Experiment 6: Synthesis of 5-nitrosalicylic acid

4.
(i) Provide an original drawing for the full reaction mechanism for the
nitration of benzene.

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(ii) Show your calculation for working out the percentage yield of the final
product.

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5-Nitrosalysilic acid
Salicylic acid
M.wt 138 gmol-1 183 gmol-1
From the 1 mol 1 mol
equation
1.38 g
138 g X
mol

0.01 mol X
Number of 0.01 mol of 5-Nitrosalysilic X183.118 gmol-1 = 1.83g
mol (Theoretically)
5-
Nitrosalysilic Actual yield = 0.91g
acid (X) =
Percentage Actual yield 0.91 g
= x 100 = 49.73%
yield Theoretical yield 1.83 g

The maximum theoretical mass of product in a certain reaction is 1.83g, but only 0.91g is
actually obtained. The low percentage of yield obtained might be due to several reasons such
as: some product may be lost when it is removed from the reaction mixture or some of the
reactants may react in an unexpected way.

(iii) By consideration of the inductive effects of both the CO 2H and OH


substituents on the
aromatic ring in salicylic acid (starting material), explain why 5-
nitrosalicylic acid is the
major product of this reaction. All possible regioisomers should be
considered, but
resonance forms are not required.

When we have two functional groups on benzene ring such as CO 2H and OH as salicylic
acid compound, the orientation of electrophile ( NO 2+) will be directed to 5-position of
salicylic acid because of the OH is strongly activating group ( Ortho-Para director) while
CO2H is moderately deactivating group (Meta-director). Therefore, the major product is 5-
nitrosalicylic acid. As illustrated in next equation:

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Major product
minor product

Experiment 7: Reduction of Benzophenone

5.

(i) Either sketch or insert a picture of the TLC for this reaction, including
as much detail as possible. Fully explain the relative positions of the
spots for the starting material and product.

Distance from baseline travelled by solute (a) (Diphenylmethanol) = 0.7cm


Distance from baseline travelled by solute (a) (Benzophenone) = 1.6cm
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Distance travelled by solvent (Solvent form) = 5.1 cm
0.7 cm
Rf product (Diphenylmethanol )= =0.137 cm
5.1 cm
1.6 cm
Rf benzophenone= =0.314 cm
5.1cm

Diphenymethanol (alcohol product) has higher polarity than the ketone such as
benzophenone (starting material). In fact, polar compounds such as alcohol stick to the
adsorbent/ being interacted with (the stationary phase) more readily, and thus do not elute
as far and have a lower value for Rf compared with compounds with less polarity such as
ketones; therefore a higher value of Rf because of the faster elution. Moreover, TLC plate is
a given set of conditions where the Rf values of two spots on it may provide some
indications or an evidence as the identity of a compound, and the success or even failure of
a reaction. In terms of TLC being used as an indicator for purity, usually a pure compound
when spotted and developed on a TLC plate appears as a single spot, while two or more
spots in a single (lane) might indicate that the compound is impure.

(ii) Report the melting point of your diphenylmethanol product and show
how you were able to use this as an indicator of purity.
m.p. = 66oC
m.p. = 65-67 C (Literature) (Sigma Aldrich)
Clearly, diphenylmethanol which is formed in the experiment is highly pure solid. Since
the presence of a small amount of impurity substances will lower a compounds melting
point by a few degrees and widen the melting point temperature range. Defects in the
crystalline lattice results from impurity substances, it is easier to overcome the
intermolecular interactions between the molecules.
The desired compound (diphenylmethanol) is a very pure organic crystal. Pure compounds
have all of the molecules the same; they are arranged and packed together in a very
orderly array. In this array, the attractive forces between the molecules are maximized. All
of the molecules are identical, and adhere tightly together in an orderly, three-dimensional
array. Thus, the structure is strong, and it is not easily can be overcome by an input of
energy. On the other hand, impure compounds require a lower temperature in order to be
melted than is required to melt the pure structure where no impurities present. Moreover,
impure solids melts over a wider temperature range due to regions within the crystal that
contain different amounts of the impurity, and therefore different numbers of distorts in the
crystalline molecules wall occur.

(iii) By consideration of the methods and reagents that you used in


Experiment 7, suggest how might you prepare the following target
compound (starting from benzophenone):

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By using Grignard reagent As following :

Grignard reagent is used in the purpose of preparing the () compound.


Benzophenone + Grignard reagent (CH 3MgCl) using dry ether in order to prevent the
break down (distort) of the Grignard reagent resulting in formation of the product

6. Briefly explain how you could use IR spectroscopy to differentiate between the
following groups of
compounds. For each compound predict where you would expect the main peaks
in the IR spectrum of
that compound to appear (in the range 500-4000 cm-1).

Compou
nd

Mean
peak C=O : 1740- C=O : 1750- C=O :1670- NH : 3500- S=O : 1050
v cm-1 1720 1730 1640 3100

In compound # 1 the C=O band appears between 1740-1720 cm-1 and the intensity is
strong
In compound # 2 the C=O band appears between 1750-1730 cm -1 and the intensity is
strong
In compound # 3 the C=O band appears between 1670-1640 cm-1 and the intensity is
strong
In compound # 4 the NH band appears between 3500-3100 cm-1 and the intensity is
moderate
In compound # 5 the S=O band appears near 1050 cm-1 and the intensity is strong.

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Skills Competency Grid

Fill out the following grid giving brief reflections on where you acquired
the following skills during Section 2 (Synthetic Organic Chemistry,
Experiments 5-7) of the laboratory course:

Competency / Skill Developed Evidence (Experiment number and


brief description)
Understanding and assessing safety Hazard and precautionary statements have
hazards in the chemical laboratory. been noted before conducting the
expirements (5,6 and 7) by using Sigma
Aldrich website. This allows the student to
be aware of the hazards in the chemical
laboratory and being able to follow the
appropriate method for responding to urgent
cases.

Stereochemistry of organic compounds. 5

Separation of insoluble impurities from a In Experiment (5) where recrystalistion


compound. technique depends on different solubilities of
the solutes present in a solvent. The more
the compounds are less able to be soluble,
the more they will be recrystalised .
Purification occurs once the crystals formed
after applying slow cooling technique to the
substances, which promotes the formation
of purer crystals. The molecule of the
impurities do not fit well with the newly
forming crystals. Then, crystals select the
right molecule where they can fit into the

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crystal lattice. This results in the increase in
the purity of the desired product.
Determination of a melting point, and (Experiments (5,6 & 7). During these
implications for assessing product purity. experiments, the melting points have been
determinated and this technique increases
the ability to indicate to the purity of the
desired products. Moreover, the filter paper
used to filtrate the product obtained from
the impurities.

Analytical tests for product purity. In Experiments (5,6 &7). The spectrum
technique was used. the observation made
was when The desired constituent has Rf~
0.7cm. IT has been observed that when Rf is
too low, then the solvent system is too non-
polar. As a result, it will take very long time
for the material to come up to the column.
Alternatively, if f is too high, then the
solvent system is too polar and the material
will come up to the column too quickly with
pore separation.

Work-up and extraction of a chemical The solvent extraction, washing with


product from a reaction. organic solvent.

Understanding of the Percentage Yield In Experiments (5,6 &7). This represents the
of a reaction. actual recovery amount obtained. The
formula of Percentage Yield (Actual amount
Theoretical amount) X100

Understanding of reaction mechanisms In Experiments (6) The reaction inserted in


for explaining the formation of products the portfolio.
from starting materials.
Determination of Organic Structure IR is spectroscopic method or NMR is
through Spectroscopic Methods. spectroscopic method
Real World applications of organic Synthesis of new compounds that can be
chemistry or organic products. used as drugs to treat disease.
Applying your organic chemistry 7
experience and knowledge to the
synthesis of new target compounds.

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