ASSIGNMENT IN ANALYTICAL CHEMISTRY

Jeferlyn Martinez
BMLS I-A

ISOMERS
Isomers are two molecules with the same molecular formula but differ structurally. Therefore,
isomers contain the same number of atoms for each element, but the atomic arrangement differs.
Despite having the same molecular formula, the physical properties of each molecule may differ,
particularly if the functional groups associated with each molecule are different. Isomerization is
the process by which one molecule is converted into another molecule with the identical atoms.
This may occur spontaneously or a reaction may be required to achieve this effect.
EXAMPLES
Glucose and Fructose
Glucose and fructose are an example of C6H12O6 isomers, which differ based on the position of
a double bonded O atom. In glucose, the O is situated on the first C, whereas it is located on the
second C in fructose (the structures of each are shown below).

CHIRAL COMPOUND
Chiral Compound - An asymmetric carbon atom (chiral carbon) is a carbon atom that is attached
to four different types of atoms or groups of atoms, and the Compound called Chiral compound.
Lactic acid Tartaric acid

I
STEREOCENTERS
An atom with three or more different attachments, interchanging of two of these attachments
leads to another stereoisomer. Most commonly, but not limited to, an sp3 (tetrahedral) carbon
atom bearing four different attachments.

CHIRALITY CENTER
A chiral centre is an atom that has four different groups bonded to it in such a manner that it has
a nonsuperimposable mirror image.
The term "chiral centre" has been replaced by the term chirality centre.
In the molecule below, the carbon atom is a chirality centre.
It has four different groups attached, and the two structures are nonsuperimposable mirror
images of each other.
EXAMPLE

ENANTIOMERS
Enantiomers are mirror-image isomers with identical chemical and physical properties in an
achiral environment. To distinguish between a pair of enantiomers, one must either place them in
a chiral environment or use a probe that is inherently chiral in nature (like a polarized light
beam).
EXAMPLE
 RACEMIC MIXTURE
Racemic Mixtures A solution in which both enantiomers of a compound are present in equal
amounts is called a racemic mixture, or racemate. Racemic mixtures can be symbolized by a
(d/l)- or ()- prefix in front of the substance's name. Since enantiomers have equal and opposite
specific rotations, a racemic mixture exhibits no optical activity. Therefore it is impossible to tell
a racemic mixture apart from an achiral substance using polarimetry alone.
EXAMPLE

DIASTEREOMERS
Diastereomers are stereoisomers that are not mirror images of one another and are non-
superimposable on one another. Stereoisomers with two or more stereocenters can be
diastereomers. It is sometimes difficult to determine whether or not two molecules are
diastereomers.
EXAMPLE
MESO COMPOUND
A meso compound is a molecule with multiple stereocenters that is superimposable on its mirror
image. These particular traits lead to specific qualities that meso compounds do not share with
most other stereoisomers.

FISCHER PROJECTION
A Fischer projection is a way of showing a three dimensional structure in two dimensions. It
shows the absolute configuration at chiral centres. In a Fischer projection, the longest chain is
drawn vertically. The four bonds to a chiral carbon make a cross, with the carbon atom at the
intersection of the horizontal and vertical lines. The two horizontal bonds are pointing toward the
viewer. The two vertical bonds are directed away from the viewer.

ROTATING FISCHER PROJECTIONS

Rules for Handling Fischer Projections

The Fischer projection of 2-butanol (Abb. 1)  shows one of several possible Fischer projections of
the same enantiomer. Only specific manipulations of Fischer projections are allowed, otherwise
not a projection of the same but of the opposite enantiomer would be obtained. The allowed
manipulations are expressed as follows:

RULE 1
 A Fischer projection may be rotated 180° in the illustration plane. 90° and 270° rotations
are not allowed.

Explanation:
A 180° rotation of the Fischer projection means that substituents that initially pointed towards or
away from the viewer continue to point in these same directions. In addition, substituents that
initially lie directly opposite from each other are interchanged. The overall result is basically the
same as that of a 180° rotation of the whole molecule on an axis that is perpendicular to the
illustration plane and passes through the asymmetric carbon (run the animation). Therefore, the
new Fischer projection represents the same enantiomer.
In contrast, a 90° or 270° rotation of the Fischer projection is actually not equivalent to a 90° or
270° rotation of the whole molecule on the axis mentioned above. As a result of a 90° or 270°
rotation of the Fischer projection, the substituents that initially pointed towards or away from the
viewer now point in the opposite directions. In exchange, a 90° or 270° rotation of the whole
molecule on the formerly mentioned axis does not alter the orientation of the substituents in
relation to the illustration plane (run the animation of 90° and 270° rotation of the whole
molecule).
CYCLIC STEREOISOMERS
In the case of cyclic compounds, the free single bond rotation is restricted. It is therefore
important to note whether substituents are on the same side or on opposite sides of the ring.
Different stereoisomers arise from different substituent arrangements relative to the ring side,
because they are incapable of becoming superimposable through conformational changes. As a
result, cyclic compounds contain several specific characteristics.
DEFINITION
If the substituents are on the same side of the ring, they are called cis. If they are on opposite
sides, they are called trans.
1,2-Dimethylcyclopentane, for instance, consists of three stereoisomers:
NAMING CYCLIC STEREOISOMERS
Configurational Stereoisomers of Cycloalkanes

Stereoisomers are also observed

in certain disubstituted (and
higher substituted) cyclic
compounds. Unlike the relatively
flat molecules of alkenes,
substituted cycloalkanes must be
viewed as three-dimensional
configurations in order to
appreciate the spatial orientations
of the substituents. By agreement,
chemists use heavy, wedge-
shaped bonds to indicate a substituent located above the average plane of the ring (note that
cycloalkanes larger than three carbons are not planar), and a hatched line for bonds to atoms or
groups located below the ring. As in the case of the 2-butene stereoisomers, disubstituted
cycloalkane stereoisomers may be designated by nomenclature prefixes such as cis and trans.
The stereoisomeric 1,2-dibromocyclopentanes shown to the right are an example.

In general, if any two sp3 carbons in a ring have two different substituent groups (not counting
other ring atoms) stereoisomerism is possible. This is similar to the substitution pattern that gives
rise to stereoisomers in alkenes; indeed, one might view a double bond as a two-membered ring.
Four other examples of this kind of stereoisomerism in cyclic compounds are shown below.
If more than two ring carbons have different substituents (not counting other ring atoms) the
stereochemical notation distinguishing the various isomers becomes more complex.

Examples of the IUPAC Rules in Practice

When one substituent and one hydrogen atom are attached at each of more than two positions of
a monocycle, the steric relations of the substituents may be expressed by first identifying a
reference substituent (labeled r) followed by a hyphen and the substituent locator number and
name. The relative configuration of other substituents are then reported as cis (c) or trans (t) to
the reference substituent.

When two different substituents are attached at the same position of a monocycle, then the
lowest-numbered substituent named as a suffix is selected as reference group. If none of the
substituents is named as a suffix, then that substituent of the pair of substituents having the
lowest number, and which is preferred by the sequence rule, is chosen as the reference group.
The relationship of the sequence-rule-preferred substituent at geminally substituted positions,
relative to the reference group, is cited as c- or t-, as appropriate.

An alternative system which specifies the absolute configuration of substituted carbon atoms
may also be used. This system, known as the Cahn-Ingold-Prelog rules, uses and elaborates the
priority rules developed earlier.

PROCHIRAL CARBONS

When a tetrahedral carbon can be converted to a chiral center by changing only one of the
attached groups, it is referred to as a ‘prochiral' carbon. The two hydrogens on the prochiral
carbon can be described as 'prochiral hydrogens'.

Note that if, in a 'thought experiment', we were to change either one of the prochiral hydrogens
on a prochiral carbon center to a deuterium (the 2H isotope of hydrogen), the carbon would now
have four different substituents and thus would be a chiral center.

Prochirality is an important concept in biological chemistry, because enzymes can distinguish

between the two ‘identical’ groups bound to a prochiral carbon center due to the fact that they
occupy different regions in three-dimensional space. Consider the isomerization reaction below,
which is part of the biosynthesis of isoprenoid compounds. We do not need to understand the
reaction itself (it will be covered in chapter 14); all we need to recognize at this point is that the
isomerase enzyme is able to distinguish between the prochiral 'red' and the 'blue' hydrogens on
the isopentenyl diphosphate (IPP) substrate. In the course of the left to right reaction, IPP
specifically loses the 'red' hydrogen and keeps the 'blue' one.
Prochiral hydrogens can be unambiguously designated using a variation on the R/S system for
labeling chiral centers. For the sake of clarity, we'll look at a very simple molecule, ethanol, to
explain this system. To name the 'red' and 'blue' prochiral hydrogens on ethanol, we need to
engage in a thought experiment. If we, in our imagination, were to arbitrarily change red H to a
deuterium, the molecule would now be chiral and the chiral carbon would have
the R configuration (D has a higher priority than H).

For this reason, we can refer to the red H as the pro-R hydrogen of ethanol, and label it HR.
Conversely, if we change the blue H to D and leave red H as a hydrogen, the configuration of the
molecule would be S, so we can refer to blue H as the pro-S hydrogen of ethanol, and label it HS.

Looking back at our isoprenoid biosynthesis example, we see that it is specifically the pro-
R hydrogen that the isopentenyl diphosphate substrate loses in the reaction.

Prochiral hydrogens can be designated either enantiotopic or diastereotopic. If either H R or HS on
ethanol were replaced by a deuterium, the two resulting isomers would be enantiomers (because
there are no other stereocenters anywhere on the molecule).
Thus, these two hydrogens are referred to as enantiotopic.

In (R)-glyceraldehyde-3-phosphate ((R)-GAP), however, we see something different:

R)-GAP already has one chiral center. If either of the prochiral hydrogens HR or HS is replaced
by a deuterium, a second chiral center is created, and the two resulting molecules will be
diastereomers (one is S,R, one is R,R). Thus, in this molecule, HR and HS are referred to
as diastereotopic hydrogens.

Finally, hydrogens that can be designated neither enantiotopic nor diastereotopic are
called homotopic. If a homotopic hydrogen is replaced by deuterium, a chiral center
is not created. The three hydrogen atoms on the methyl (CH3) group of ethanol (and
on any methyl group) are homotopic.
An enzyme cannot distinguish among homotopic hydrogens.