FACULTY OF APPLIED SCIENCES

KUALA LUMPUR CAMPUS

Practical Submission Form

Course Code & Title: BACH2114 Kinetics, Mechanisms & Stereochemistry

Group: RBS 2 G1

Student’s Name (Registration number):

1. Chin Jia Yue (20WLR08551)

2. Ng Si Qi (20WLR08569)

3. Wong Pui Mun (20WLR08576)

4.

Submission Date: 14 August 2020

Title of Experiment: A study of molecular rearrangement: Preparation of one
diastereomeric form of 1,2-diphenylethane-diol by a stereoselective reaction

Lecturer: Dr Tan Siew San

Declaration:

We declare that this submitted coursework is our own work and that any material
presented in this coursework, whose authorship does not belong to us, has been
properly acknowledged of its source. If we are proven guilty of copying from any
source or colluding with others during the preparation of this coursework, we will be
punished with a zero mark for the whole or part of this coursework.

Signature(s):
Experiment 4:​ A study of molecular rearrangements: Preparation of one diastereomeric form
of 1,2-diphenyl-1,2-diol by a stereoselective reaction.

Objective:
To understanding the molecular arrangement
To determine whether the product of experiment is a racemic or meso compound

Introduction:
Molecular rearrangement is the term applied to any reaction that involves a change of
connectivity and interrupts the principle of minimum structural change. According to the
principle, chemical substances will not be isomerized during the transformation process. For
example, when replacing or changing the functional group of a chemical species to a different
functional group, it is expected that no more than the minimum number of bonds required to
achieve the conversion will be generated or destroyed. Besides that, the definition of
molecular rearrangement includes changes in which there is a bond migration of an atom or
bond (International Union of Pure and Applied 2014).
In stereochemistry, a stereocenter is a point on a molecule which attaches to four different
groups. When two molecules have the same molecular structure but different 3D
configurations, they can be defined as isomers. The stereoisomers are based on chirality.
Chiral molecules form nonsuperimposable mirror images, whereas, the achiral molecules
form mirror images that can be superposed. For a molecule to be chiral, it cannot contain a
plane of symmetry. A plane of symmetry divides an entire molecule into two pieces that
extract mirror images. The most common cause of chirality in an organic molecule is a
carbon atom with four different atoms or groups bonded to it (Houghton Mifflin Harcourt
2020). This carbon atom is called a stereogenic, chiral, or asymmetric center. Then, isomers
can further be defined as enantiomers, diastereomers, epimers and meso compounds. An
epimer is when a molecule is exactly the same except one stereocenter is different. A ​
diastereomer is a stereoisomer that is not mirror images and different compounds with
different physical properties. An enantiomer is a stereoisomer that is non-superimposable
mirror images. R and S is a pair of enantiomers and it is important to indicate the enantiomer.
The R/S system is based on the priority, it will follow the arrow from the highest priority
substituent to the lowest priority substituent. If the arrow points in a counter clockwise
direction, the configuration at stereocenter is considered S. If, however, the arrow points
clockwise, then the stereocenter is labeled R (LibreTexts [1] 2019). The only properties of
enantiomers different from each other are direction of optical rotation.
A meso compound is a molecule having more than one identical stereocenters and an
identical or superimposable mirror image. Therefore, a meso compound has many chiral
carbon centers, but the mirror image is superimposable. A meso compound also has the
mirror images when the internal plane of symmetry of the molecules is divided to half.
Hence, meso compounds are optically inactive. A racemic mixture is an enantiomer that the
mixture contains equal amounts of left-handed and right-handed enantiomer. A racemic
mixture is optically inactive due to the presence of equal amounts of non-superimposable
mirror images. Since this mixture is optically inactive, there is no net rotation of
plane-polarized light which is passed through a racemic mixture. Although the two types of
enantiomers rotate the light in opposite directions, rotations are cancelled due to the presence
of equal amounts of opposite enantiomers (Madhusha 2018).
Optical activity is an effect of an optical isomer's interaction with plane-polarized light. ​An
enantiomer that rotates plane-polarized light in the positive direction, or clockwise, is called
dextrorotatory [(+), or d-], while the enantiomer that rotates the light in the negative
direction, or counter clockwise, is called levorotatory [(-), or l-] (LibreTexts [2] 2019).
Optical activity is measured by a polarimeter.

Procedure:
Result:
Determination of yield
Experimental yield = 1.80 g
Benzil + Sodium Borohydride → 1,2-diphenylethane-1,2-diol (crystal)

Mass of benzil = 3g
Molar mass of benzil = 210.23 g/mol
3g
Mole of benzil =​ 210.23g/mol

​= 0.01427 mol
Mass of Sodium Borohydride = 1g
Molar mass of sodium borohydride = 37.83 g/mol
1g
Mole of sodium borohydride = 37.83 g/mol

= 0.02643 mol
Benzil is the limiting reagent ( smaller mole).

Molar mass of 1,2-diphenylethane-1,2-diol = 214.26 g/mol

Theoretical mass of 1,2-diphenylethane-1,2-diol = 0.01427 mol × 214.26 g/mol

= 3.0574 g

1.8 g
Percentage yield of 1,2-diphenylethane-1,2-diol = 3.0574 g x 100%

= 58.87%

Determination of IR spectrum

Figure 1: The FTIR spectrum of the product.

 Table 1: Analysis of FTIR spectrum of the product.

No. Wavenumber ( cm−1 ) Functional group

1 3499, 3394 O-H

2 2956, 2925 C-H

3 1452

4 1218, 1079 C-O

5 847, 706 C-H

Determination of Melting point

Melting point of product = 136 °C (meso compound)

Discussion：
After the sample had incubated in 0​o​C for 1 hour, the crystals formed were filtered off and
weighed on a laboratory scale and the mass that we obtained is 1.8g. In order to determine the
percentage yield, the theoretical mass of 1,2-diphenylethane-1,2-diol must be calculated. By
using the mass obtained, the mole of the substance benzil and sodium borohydride could then
be calculated. There is 0.01427 mol of benzil and 0.02643 mol of sodium borohydride being
used in preparing 1,2-diphenylethane-1,2-diol thus, benzil is the limiting reagent as it has a
lesser number of mol. Therefore, the mole of benzil was used to calculate the theoretical mass
of 1,2-diphenylethane-1,2-diol and we found that the percentage yield is 58.87%. The
percentage yield i​s the percent ratio of experimental yield to the theoretical yield. In this
experiment, the percentage yield is low because of incomplete or competing reactions and
loss of sample during recovery. However, to improve the percentage yield of the experiment,
operator error must be minimized such as calculating and weighing the amount of reagents
accurately and using clean glassware to avoid contamination of the pure reactants.

FTIR spectrometers are widely used in organic synthesis polymer science, petrochemical
engineering, pharmaceutical industry and food analysis. Traditionally, the application of IR
spectroscopy in mineralogy is reduced to the determination of wavelengths or frequencies of
discrete absorption maxima. These values are brought in correspondence with normal
vibrations of different chemical bonds or groups of atoms forming covalent bonds such as
complex anions, polyatomic cations, neutral molecules as well as lattice vibrations of infinite
chains, layers or frameworks as part of crystal structures minerals. In this experiment, FTIR
was used to identify the functional groups of the products formed based on the wavenumbers
which are the stretching frequencies that are caused by the vibration of covalent bonds are
shown in table 1. Based on the table, the wavenumber was highest between ​3499 cm−1 and
3394 cm−1 . This high wavenumber has indicated the presence of O-H bond as O-H bond has
an absorption between 3230 and 3550 cm−1 . ​The band appearance of the O-H stretching
appears strong where the band covers most of the y-axis and is broad with rounded tips. The
second highest wavenumber was between 2956 and 2925 cm−1 ​and also a number range
from 847 to 706 cm−1 . ​This is the set vibrations of C-H bond where the band of the
stretching also appears strong and broad The wavenumber between 847 and 706 cm−1 is the
bending frequencies of the C-H bond. The C-H stretching that below 3000 cm−1 ​indicate that
it is a sp​3 carbon-hydrogen bonding. Next, the wavenumber of 1492 cm−1 confirm the
presence of carbon-carbon double bonds which the range is below 1600 cm−1 . By right,
carbon-carbon double bond has a higher wavenumber however due to the conjugation of the
C=C bond to form a benzene ring, the wavenumber becomes lower. Lastly, the fingerprint
region shows the complex stretching of C-O bond where the expected vibrations is between
600-1400 cm−1 . ​Based on the IR spectrum shown in figure 1, the functional group ketone is
Aldehydes and ketones show a strong, prominent, stake-shaped band around 1710 - 1720
cm-1 (right in the middle of the spectrum). This band is due to the highly polar C=O bond.
Because of its position, shape, and size, it is hard to miss. Because aldehydes also contain a
C-H bond to the sp​2 carbon of the C=O bond, they also show a pair of medium strength bands
positioned about 2700 and 2800 cm-1. These bands are missing in the spectrum of a ketone
because the sp2 carbon of the ketone lacks the C-H bond.

Figure 2: Mechanism of reduction of benzil by sodium borohydride.

The mechanism in ​Figure 2 s​ hows that the nucleophile, which is the negatively charged
hydride on the BH​4​- species attacks the partial positive charge of carbonyl carbon which will
then produce a complex that the boron atom is chelated to 4 reduced carbonyl molecules at
the same time. Water is added to separate the bonding between boron and oxygen of the
complex to liberate up to 4 alcohols and B(OH)​4​- complex. Since the carbonyl has a π bond
which can break, no leaving group is involved. Benzyl is a yellow coloured compound, thus
the disappearance of yellow colour denoted the reaction is completed. Sodium borohydride is
a useful reducing agent for ketone and aldehyde. The reduction of a carbonyl group in ketone
and aldehyde can be completed with either lithium aluminum hydride or sodium borohydride.
Lithium aluminium is the more powerful and is capable of reducing aldehydes, ketones,
carboxylic acids, esters and amides, but NaBH​4 is more easier to be handled and more
selective, reducing only aldehydes and ketones. Moreover, NaBH​4 ​can be utilized under
non-anhydrous conditions and in alcoholic solutions, in contrast to lithium aluminum hydride
which reacts violently with both water and alcohol. Therefore, sodium borohydride was used
in this experiment.
Diastereomers are stereoisomers that are not related as objects and mirror images and are not
enantiomers. Unlike enantiomers, diastereomers do not have the same physical properties and
reactivity. In other words, the diastereomers can be differentiated by determining their
melting point and so on. Meso compound is an achiral compound that has more than one
identical stereocenter and an identical or superimposable mirror image, whereas racemic is a
mixture of enantiomers, which are the optical isomers that are non superimposable images of
each other (QS Study 2020). Meso compounds and enantiomers are diastereomers, thus their
melting point is different, and can be differentiated by checking their melting point in the
melting point apparatus. In this experiment, the reduction of benzil may result in two possible
products, one is the meso compound that has melting point about 136°C to 137°C, while
another is racemic that has melting point at 122°C to 123°C. One of the possible products
will have a much greater amount than another. Since the crystal formed has a melting point at
136°C, thus it is believed that the most abundant compound in the crystal is the meso
compound of 1,2-diphenylethane-1,2-diol.

Conclusion：
In conclusion, absorption of the energy radiation through the infrared spectroscopy causes
vibrational and rotational excitation of groups of atoms within the molecule. Due to their
characteristic absorption, identification of functional groups can then be easily accomplished.
The product of the experiment, which is 1,2-diphenylethane-1,2-diol is a meso compound as
the melting point is 136°C.

References:
1. International Union of Pure and Applied, 2014, molecular rearrangement, viewed on
31 July 2020, <​ ​https://goldbook.iupac.org/terms/view/M03997​>.
2. Houghton Mifflin Harcourt, 2020, Chirality, viewed on 31 July 2020, <
https://www.cliffsnotes.com/study-guides/chemistry/organic-chemistry-i/stereochemis
try/chirality​>.
3. LibreTexts [1], 2019, Absolute Configuration: R-S Sequence Rules, viewed on 31
July 2020, <
https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Supplemental_Modules_
(Organic_Chemistry)/Chirality/Absolute_Configuration_R-S_Sequence_Rules​>.
4. Madhusha, 2018, Difference Between Racemic Mixture and Meso Compound,
viewed on 31 July 2020, <
https://pediaa.com/difference-between-racemic-mixture-and-meso-compound/#Race
mic%20Mixture​>.
5. LibreTexts [2], 2019, Optical Activity, viewed on 31 July 2020, <
https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Supplemental_Modules_
(Organic_Chemistry)/Chirality/Optical_Activity​>.
6. QS Study 2020, ​‘Differences between Racemic Mixture and Meso Compound’,​
viewed 14 August 2020, <​https://www.qsstudy.com/chemistry/
differences-racemic-mixture-meso-compound​>.